TWI676508B - Al-based plated steel sheet and method of producing the same - Google Patents
Al-based plated steel sheet and method of producing the same Download PDFInfo
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Abstract
一種Al系鍍敷鋼板,其特徵在於:Al系鍍敷層所含之Al的平均組成以質量%計為85%以上,Si以質量%計為4%以上且在12%以下,鍍敷附著量為30g/m 2以上,鍍敷表面的Si面積率為12%以下,Al系鍍敷層之厚度方向的Si濃度分布之最大值以質量%計為15%以下,且厚Al系鍍敷層之厚度方向的Si濃度分布之最大值與Fe濃度在4質量%以下時的Si濃度之最小值的比為1.0以上且在2.0以下。 An Al-based plated steel sheet characterized in that the average composition of Al contained in the Al-based plating layer is 85% or more by mass%, and Si is 4% or more and 12% or less by mass%. The amount is 30 g / m 2 or more, the Si area ratio of the plating surface is 12% or less, the maximum value of the Si concentration distribution in the thickness direction of the Al-based plating layer is 15% or less by mass%, and the thick Al-based plating is The ratio of the maximum value of the Si concentration distribution in the layer thickness direction to the minimum value of the Si concentration when the Fe concentration is 4% by mass or less is 1.0 or more and 2.0 or less.
Description
本發明有關能充分展現塗裝後耐蝕性之以熱壓用而言較佳之Al系鍍敷鋼板及其製造方法。The present invention relates to an Al-based plated steel sheet which is capable of sufficiently exhibiting corrosion resistance after painting and is suitable for hot pressing, and a method for producing the same.
近年,為了保護環境及抑制地球暖化,抑制消耗化石燃料的訴求不斷高漲,且此訴求已對各種製造業造成影響。製造對於日常生活等不可欠缺的移動手段之汽車產業也無例外地尋求利用車體之輕量化等來抑制消耗燃料。有許多汽車零件係由鐵,尤其是由鋼板形成,減低所使用之鋼板的總重量對車體輕量化進而抑制消耗燃料而言相當重要。In recent years, in order to protect the environment and suppress global warming, the demand for suppressing the consumption of fossil fuels has been increasing, and this demand has affected various manufacturing industries. The automobile industry, which manufactures indispensable means of movement for daily life, has also sought to suppress the consumption of fuel by reducing the weight of the car body without exception. Many automobile parts are made of iron, especially steel plates. Reducing the total weight of the steel plates used is very important for reducing the weight of the car body and suppressing fuel consumption.
然而,對於汽車而言必須確保安全性,故不容許單僅減少鋼板的板厚,還會要求維持鋼板的機械強度。如上述之對於鋼板的訴求不僅在汽車產業中逐漸高漲,在各種製造業中也同樣逐漸攀高。因此,正藉由提高鋼板的機械強度,來針對即便使以往所使用之鋼板變薄,仍能維持或提升機械強度之鋼板進行研究開發。However, for automobiles, safety must be ensured, so it is not allowed to reduce the thickness of the steel sheet alone, and it is also required to maintain the mechanical strength of the steel sheet. As mentioned above, the demand for steel plates has gradually increased not only in the automotive industry, but also in various manufacturing industries. Therefore, by increasing the mechanical strength of steel plates, research and development are being performed on steel plates that can maintain or improve the mechanical strength even if the steel plates used in the past are thinned.
一般而言,具有優異機械強度的材料在彎曲加工等成形加工中有成形性、形狀凍結性降低的傾向,當要加工成複雜形狀時,加工本身即有困難。作為解決此一有關成形性的問題之手段之一,可舉例所謂的「熱壓方法(亦稱為熱壓印法、熱壓製法、模具淬火法、加壓硬化)」。此熱壓方法係將成形對象之材料先加熱到高溫(沃斯田鐵區),並在對因加熱而軟化的鋼板進行壓製加工而成形後進行冷卻。In general, materials with excellent mechanical strength tend to have reduced formability and shape freezing properties during forming processes such as bending, and when they are processed into complex shapes, the processing itself is difficult. As one of the means for solving such a problem related to formability, a so-called "hot pressing method (also referred to as a hot stamping method, a hot pressing method, a mold quenching method, and pressure hardening)" can be cited. In this hot pressing method, the material to be formed is first heated to a high temperature (Vostian Iron Zone), and the steel sheet softened by the heating is pressed and formed, and then cooled.
根據該熱壓方法會先將材料加熱到高溫而使其軟化,故可輕易壓製加工該材料,並且可利用成形後之冷卻所帶來的淬火效果來提高材料的機械強度。因此,利用此熱壓可獲得兼具良好的形狀凍結性及高機械強度的成形品。According to this hot pressing method, the material is first heated to a high temperature to soften it, so the material can be easily pressed and processed, and the quenching effect brought by the cooling after forming can be used to improve the mechanical strength of the material. Therefore, by this hot pressing, a molded product having both good shape freezing properties and high mechanical strength can be obtained.
然而,當熱壓鋼板時,若加熱至例如800℃以上之高溫,表面的鐵會氧化而生成鏽皮(氧化物)。因此,在熱壓後,必須進行去除鏽皮的步驟(去鏽步驟),而生產性降低。並且,若為有耐蝕性之需求的成形品,因在熱壓後會於成形品表面施行防鏽處理或形成金屬皮膜,而須有表面淨化步驟或表面處理步驟,生產性會更為降低。However, when the steel sheet is hot-pressed, if it is heated to a high temperature of, for example, 800 ° C. or higher, iron on the surface is oxidized to generate scale (oxide). Therefore, after the hot pressing, a step of removing scale (a step of removing rust) must be performed, and productivity is reduced. In addition, if a molded product is required to have corrosion resistance, the surface of the molded product is subjected to rust prevention treatment or a metal film is formed after hot pressing. Therefore, a surface purification step or surface treatment step is required, and productivity is further reduced.
抑制這種生產性降低的例子可舉出於鋼板形成皮膜的方法。一般而言,鋼板上之皮膜是使用有機系材料或無機系材料等各種材料。其中又以對鋼板具有犧牲性防蝕作用的鋅系鍍敷鋼板,基於其本身的防蝕性能及鋼板生產技術的觀點,而被廣泛使用於汽車用鋼板等。An example of suppressing such reduction in productivity is a method of forming a film on a steel sheet. Generally, the film on the steel sheet is made of various materials such as organic materials and inorganic materials. Among them, a zinc-based plated steel sheet, which has a sacrificial anticorrosive effect on a steel sheet, is widely used in automotive steel sheets and the like from the viewpoint of its own corrosion resistance and steel sheet production technology.
然而,熱壓之加熱溫度(700℃以上且1000℃以下)較有機系材料的分解溫度或Zn(鋅)的沸點等更高。因此,當為了熱壓而加熱鋼板時,鋼板表面的鍍敷層便會蒸發,而有表面性狀明顯劣化之虞。However, the heating temperature of hot pressing (700 ° C. to 1,000 ° C.) is higher than the decomposition temperature of the organic material or the boiling point of Zn (zinc). Therefore, when the steel sheet is heated for hot pressing, the plating layer on the surface of the steel sheet may evaporate, and the surface properties may be significantly deteriorated.
因此,在熱壓之際,對於會加熱至高溫的鋼板宜形成例如沸點較有機系材料皮膜或Zn系金屬皮膜高之Al(鋁)系金屬皮膜,以作成所謂的Al系鍍敷鋼板。藉由形成Al系金屬皮膜,可防止鏽皮附著於鋼板表面而不需去鏽步驟等的步驟,故生產性會提升。此外,Al系金屬皮膜也有防鏽效果,故塗裝後的耐蝕性亦會提升。 Therefore, when hot-pressing, it is desirable to form an Al (aluminum) -based metal film having a higher boiling point than an organic-based material film or a Zn-based metal film, for a steel plate that is heated to a high temperature, to form a so-called Al-based plated steel plate. By forming the Al-based metal film, the scale can be prevented from adhering to the surface of the steel sheet without the need for steps such as a rust-removing step, and thus the productivity is improved. In addition, Al-based metal film also has anti-rust effect, so the corrosion resistance after coating will also be improved.
如上述之於具有預定鋼成分的鋼上形成有Al系金屬皮膜之Al系鍍敷鋼板,其課題之一為改善熱壓時的加工性。針對熱壓方法之加工性,有於加熱時生成之Fe-Al-Si鍍敷層為硬質而導致會咬入模具、或因摩擦係數大而導致會堆積於模具中等有疑慮之事項。因該些有疑慮之事項,而有製品表面有損傷,使得外觀品級變差之虞。 As described above, in an Al-based plated steel sheet in which an Al-based metal film is formed on a steel having a predetermined steel composition, one of the problems is to improve the workability during hot pressing. Regarding the workability of the hot pressing method, there are some doubtful matters such as that the Fe-Al-Si plating layer generated during heating is hard and may bite into the mold, or may be accumulated in the mold due to a large friction coefficient. Due to these doubtful matters, the surface of the product may be damaged, which may cause the appearance grade to deteriorate.
作為解決上述課題之手段之一,已提案有一種使含有氧化鋅(ZnO)的皮膜層附著於鍍敷表面之方法(參照譬如文獻1(國際公開第2013/157522號)、文獻2(國際公開第2014/171417號)、文獻3(國際公開第2009/131233號)、文獻4(國際公開第2015/087921號))。 As one of the means to solve the above-mentioned problems, a method has been proposed in which a coating layer containing zinc oxide (ZnO) is attached to a plating surface (see, for example, Document 1 (International Publication No. 2013/157522) and Document 2 (International Publication 2014/171417), Document 3 (International Publication No. 2009/131233), Document 4 (International Publication No. 2015/087921)).
文獻1至4所揭示之方法具體而言為下述方法:使為了抑制ZnO之脫落而含有樹脂成分或矽烷偶合劑等作為黏合劑的皮膜層附著於鋼板表面,並於熱壓時使黏合劑的有機溶劑成分揮發而使僅ZnO殘存。藉由所述方法,因有機溶劑燃燒、蒸發而生成的空隙使得ZnO與模具金屬成為點接觸,而潤滑性提升。 The methods disclosed in Documents 1 to 4 are specifically methods for attaching a film layer containing a resin component or a silane coupling agent as an adhesive agent to the surface of a steel sheet to suppress ZnO from falling off, and making the adhesive agent during hot pressing Of the organic solvent component was volatilized and only ZnO remained. According to the method, voids generated due to the combustion and evaporation of the organic solvent cause ZnO to come into point contact with the mold metal, and the lubricity is improved.
藉由在Al系鍍敷層上形成含有ZnO的表面 皮膜層,熱壓時的滑動性便會提升。然而,最近因壓製形狀複雜化,而在加工時Al系鍍敷層容易剝離,此外為了高加工性及延長材料之壽命,而要求有更高的耐蝕性。尤其,在藉由熔融鍍敷來形成Al系鍍敷層時,鋼與Al的合金層之生成有時會成為問題,而為了抑制合金層的成長,會在鍍敷浴中添加Si。在通常的熔融Al系鍍敷中,從鍍敷浴拉起後會以10℃/秒進行冷卻,此時,鍍敷的表層為非平衡凝固,且被有Si濃化之共晶覆蓋。 By forming a ZnO-containing surface on an Al-based plating layer The coating layer will improve the sliding properties during hot pressing. However, recently, because the pressed shape is complicated, the Al-based plating layer is easily peeled off during processing. In addition, in order to improve the workability and extend the life of the material, higher corrosion resistance is required. In particular, when an Al-based plating layer is formed by hot-dip plating, generation of an alloy layer between steel and Al may be a problem. To suppress growth of the alloy layer, Si is added to the plating bath. In ordinary molten Al-based plating, after being pulled up from the plating bath, cooling is performed at 10 ° C./sec. At this time, the surface layer of the plating is non-equilibrium solidified, and is covered by eutectic with Si concentration.
發明概要 Summary of invention
本發明是有鑑於上述情事而作成者,其目的在於提供一種能使塗裝後耐蝕性充分展現之熱壓用Al系鍍敷鋼板及其製造方法。 The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide an Al-based plated steel sheet for hot pressing that can sufficiently exhibit corrosion resistance after coating and a method for producing the same.
本發明中之Al系鍍敷鋼板係Al-Si系鍍敷鋼板,且係以鍍敷浴中之Si濃度在6質量%以上且12質量%以下製造而得之物。藉此製造而得之鍍敷鋼板其Al系鍍敷層整體中的Si濃度,基本上會與鍍敷浴組成同樣成為6質量%以上且12質量%以下之組成。 The Al-based plated steel sheet in the present invention is an Al-Si-based plated steel sheet, and is a product produced by having a Si concentration in a plating bath of 6 mass% or more and 12 mass% or less. The Si concentration in the entire Al-based plating layer of the plated steel sheet manufactured by this method basically has a composition of 6 mass% or more and 12 mass% or less as the composition of the plating bath.
一般而言,若Al系鍍敷層中含有Si,在製造Al系鍍敷鋼板的鍍敷步驟時,鍍敷係Al作為初晶而從鋼板側凝固,因此在Al系鍍敷層表面中,Si會在最後凝固的表面側濃化成高濃度。於圖1中顯示利用一般手法對鋼板施以含Si之Al系鍍敷後,藉由EPMA(測定機器係使用日本電子製之JXA8500F。分布模式係step數為500點×500點、step間隔為1μm、光束直徑為1μm)來測定Al系鍍敷層表面而得之Si面積率。橫軸表示鍍敷浴中的Si濃度(Al系鍍敷層整體的Si濃度),且縱軸表示Al系鍍敷層表面之Si表面積率。由圖1明白可知:相較於Al系鍍敷層整體的Si濃度,表面的Si面積率約濃化為3倍左右。Generally speaking, if the Al-based plating layer contains Si, the plating-based Al solidifies from the steel sheet side as the primary crystal during the plating step of manufacturing the Al-based plating steel sheet. Therefore, on the surface of the Al-based plating layer, Si is concentrated to a high concentration on the surface side of the final solidification. Fig. 1 shows that after applying a Si-containing Al-based plating to a steel plate by a general method, EPMA (the measuring equipment is JXA8500F made by Japan Electronics Co., Ltd.). The distribution pattern is 500 points × 500 points, and the step interval is 1 μm, beam diameter is 1 μm) to measure the Si area ratio obtained from the surface of the Al-based plating layer. The horizontal axis represents the Si concentration in the plating bath (the Si concentration of the entire Al-based plating layer), and the vertical axis represents the Si surface area ratio on the surface of the Al-based plating layer. As is clear from FIG. 1, compared with the Si concentration of the entire Al-based plating layer, the Si area ratio on the surface is about 3 times as thick.
若以用以熱壓如上述之於Al系鍍敷層中含有Si之Al系鍍敷鋼板的加熱條件(爐溫900℃以上且950℃以下×爐内滯留時間0.5分鐘以上且6分鐘以下)來加熱,則如圖2、3會有Al、Si及Fe濃度相異的5層形成。最表層即第1層係Si濃度稀薄的AlFe層,其下之第2層(5層中從表面數來第2層)則成為Si濃度高的層。該高Si層(第2層)顯示出5層内最高之電位,並且會促進腐蝕的陰極反應(溶氧之還原反應)。因此,若該第2層露出,則有促進腐蝕之傾向。If the heating conditions are used to hot press an Al-based plated steel sheet containing Si in the Al-based plating layer as described above (furnace temperature 900 ° C or higher and 950 ° C or lower × furnace residence time 0.5 minutes to 6 minutes) To heat, as shown in Figures 2 and 3, five layers with different Al, Si, and Fe concentrations are formed. The first surface layer is an AlFe layer with a thin Si concentration. The second layer (the second layer from the surface of the five layers) is a layer with a high Si concentration. This high Si layer (second layer) shows the highest potential among the five layers, and promotes the cathodic reaction (reduction reaction of dissolved oxygen) of corrosion. Therefore, if this second layer is exposed, there is a tendency to promote corrosion.
亦即發現到:若在熱壓加熱前的鍍敷階段中鍍敷表面的Si面積率變高,在熱壓的加熱階段中就會變得容易生成Si濃度高之第2層,一旦生成第2層便會形成與第1層之腐蝕電路而塗裝後耐蝕性變差。In other words, it was found that if the area ratio of Si on the plating surface becomes higher during the plating stage before hot pressing and heating, the second layer with a higher Si concentration will be easily formed during the heating stage of hot pressing. Two layers will form a corrosion circuit with the first layer and the corrosion resistance will deteriorate after coating.
此外,如先前所述,在製造Al系鍍敷鋼板製造的鍍敷步驟時,Al系鍍敷會從鋼板側開始凝固,且Si會在最後凝固的表面側濃化成高濃度。可知會因該現象而使鍍敷表面中之Si面積率增加。In addition, as described above, in the plating step for manufacturing an Al-based plated steel sheet, the Al-based plating starts to solidify from the steel sheet side, and Si is concentrated to a high concentration on the surface side that is finally solidified. It is found that the Si area ratio in the plating surface increases due to this phenomenon.
並且,還可知即便在Si並非於表面而係在内部濃化之情況下,仍會在熱壓時形成第2層。It was also found that even when Si is not concentrated on the surface but is internally concentrated, the second layer is formed during hot pressing.
本發明人等究明了藉由以酸洗去除該鍍敷凝固後之Si濃化部,則加工性及熱壓時之塗裝後耐蝕性會明顯提升。The inventors have found that by removing the Si-concentrated portion after the plating and solidification by pickling, the workability and the corrosion resistance after coating during hot pressing are significantly improved.
根據以上知識見解,本發明人等完成了發明。其要旨如下。Based on the above knowledge, the present inventors have completed the invention. The gist is as follows.
[1].一種Al系鍍敷鋼板,其特徵在於:Al系鍍敷層所含之Al的平均組成以質量%計為85%以上,Si以質量%計為4%以上且在12%以下,鍍敷附著量為30g/m 2以上,鍍敷表面的Si面積率為12%以下,Al系鍍敷層之厚度方向的Si濃度分布之最大值以質量%計為15%以下,且Al系鍍敷層之厚度方向的Si濃度分布之最大值與Fe濃度在4質量%以下時的Si濃度之最小值的比為1.0以上且在2.0以下。 [1]. An Al-based plated steel sheet characterized in that the average composition of Al contained in the Al-based plating layer is 85% or more by mass%, and Si is 4% or more and 12% or less by mass% , The plating adhesion amount is 30 g / m 2 or more, the Si area ratio of the plating surface is 12% or less, the maximum value of the Si concentration distribution in the thickness direction of the Al-based plating layer is 15% or less by mass%, and Al The ratio of the maximum value of the Si concentration distribution in the thickness direction of the plating layer to the minimum value of the Si concentration when the Fe concentration is 4% by mass or less is 1.0 or more and 2.0 or less.
[2].如[1]之Al系鍍敷鋼板,其中前述Al系鍍敷層之表面粗度以算術平均粗度Ra計為0.1μm以下。[2]. The Al-based plated steel sheet according to [1], wherein the surface roughness of the aforementioned Al-based plated layer is 0.1 μm or less based on the arithmetic average roughness Ra.
[3].如[1]或[2]之Al系鍍敷鋼板,其中前述Al系鍍敷層之厚度方向的Si濃度分布之最大值與Fe濃度在4質量%以下時的Si濃度之最小值的比為1.0~1.5。[3]. The Al-based plated steel sheet according to [1] or [2], wherein the maximum Si concentration distribution in the thickness direction of the aforementioned Al-based plating layer and the minimum Si concentration when the Fe concentration is 4% by mass or less The value ratio is 1.0 ~ 1.5.
[4].如[1]至[3]中任1項之Al系鍍敷鋼板,其具備表面皮膜層,該表面皮膜層係設置於前述Al系鍍敷層之上,且含有ZnO粒子與有機樹脂,並且前述ZnO粒子之附著量以金屬Zn換算計為0.5g/m 2以上且在10.0g/m 2以下。 [5].一種Al系鍍敷鋼板的製造方法,其特徵在於實施以下步驟: 鍍敷步驟,將鋼板浸漬於以質量%計含有6%以上且15%以下的Si之Al鍍敷浴中,以形成鍍敷層; 冷卻步驟,冷卻浸漬後之前述鋼板; 蝕刻步驟,將冷卻後之前述鋼板浸漬於pH1以下的酸性溶液中,蝕刻表層直至下述深度為止:鍍敷表面的Si面積率為12%以下,Al系鍍敷層之厚度方向的Si濃度分布之最大值以質量%計為15%以下,且Al系鍍敷層之厚度方向的Si濃度分布之最大值與Fe濃度在4質量%以下時的Si濃度之最小值的比為1.0以上且在2.0以下。 [4]. The Al-based plated steel sheet according to any one of [1] to [3], comprising a surface coating layer provided on the Al-based plating layer and containing ZnO particles and organic resin, and the deposition amount of ZnO to Zn metal particles in terms of 0.5g / m 2 or more and 2 or less at 10.0g / m. [5]. A method for manufacturing an Al-based plated steel plate, characterized in that the following steps are performed: a plating step of immersing the steel plate in an Al plating bath containing Si in an amount of 6% to 15% by mass, To form a plating layer; a cooling step to cool the aforementioned steel sheet after immersion; an etching step to immerse the cooled steel sheet in an acidic solution below pH 1 to etch the surface layer to the following depth: the Si area ratio of the plating surface Below 12%, the maximum value of the Si concentration distribution in the thickness direction of the Al-based plating layer is 15% or less in terms of mass%, and the maximum value of the Si concentration distribution in the thickness direction of the Al-based plating layer and the Fe concentration are 4 mass The ratio of the minimum value of the Si concentration at% or less is 1.0 or more and 2.0 or less.
根據本發明,以提供一種能使塗裝後耐蝕性充分展現之熱壓用Al系鍍敷鋼板及其製造方法為目的。According to the present invention, it is an object of the present invention to provide an Al-based plated steel sheet for hot pressing that can sufficiently exhibit corrosion resistance after coating and a method for manufacturing the same.
以下詳細說明作為熱壓用而言較佳之本發明Al系鍍敷鋼板(以下有時僅稱為「鋼板」)的實施形態。惟,以下實施形態並非限定本發明者。並且,上述實施形態之構成要素包含所屬技術領域中具有通常知識者能夠輕易取代之要素、或實質上為相同之要素。此外,所屬技術領域中具有通常知識者可在顯而易見之範圍内任意組合上述實施形態所包含之各種形態。Hereinafter, embodiments of the Al-based plated steel sheet of the present invention (hereinafter sometimes referred to simply as "steel sheet"), which is preferable for hot pressing, will be described in detail. However, the following embodiments are not limited to the present inventors. In addition, the constituent elements of the above-mentioned embodiment include elements that can be easily replaced by those with ordinary knowledge in the technical field to which they belong, or substantially the same elements. In addition, those having ordinary knowledge in the technical field can arbitrarily combine various forms included in the above-mentioned embodiments within a scope that is obvious.
於圖4中顯示本發明之Al系鍍敷鋼板100之一例。本發明Al系鍍敷鋼板100係於母材101表面形成Al系鍍敷層103而構成。或者是如圖5所示,進一步於Al系鍍敷層103表面形成表面皮膜層107而構成,且該表面皮膜層107係由利用有機樹脂111接合的ZnO粒子109所構成。關於各層,於以下詳細說明。惟,圖4、5係於Al系鍍敷鋼板100之單面形成有Al系鍍敷層103、表面皮膜層107之例,但亦可於兩面分別形成。 <Al系鍍敷鋼板100> [母材101]An example of the Al-based plated steel sheet 100 of the present invention is shown in FIG. 4. The Al-based plated steel sheet 100 of the present invention is configured by forming an Al-based plated layer 103 on the surface of a base material 101. Alternatively, as shown in FIG. 5, a surface coating layer 107 is further formed on the surface of the Al-based plating layer 103, and the surface coating layer 107 is composed of ZnO particles 109 bonded by an organic resin 111. Each layer is described in detail below. However, FIGS. 4 and 5 are examples in which an Al-based plating layer 103 and a surface coating layer 107 are formed on one side of the Al-based plated steel sheet 100, but they may be formed on both sides. <Al-based plated steel sheet 100> [Base material 101]
本實施形態之Al系鍍敷鋼板100所用的母材101(用以形成Al系鍍敷層103之構件),係使用即便在形成鍍敷層後進行熱壓,仍會具有優異機械強度(意指拉伸強度、降伏點、延伸率、引深率、硬度、衝撃值、疲勞強度、潛變強度等有關機械性的變形及破壞之各種性質)的構件。譬如使用藉由添加C(碳)或合金元素而提高了淬火性的構件。藉此,在對形成如後所述的Al系鍍敷層103及表面皮膜層107而製得的Al系鍍敷鋼板100施行熱壓而得之汽車零件中,可展現出優異機械強度。The base material 101 (the member used to form the Al-based plating layer 103) for the Al-based plated steel sheet 100 of this embodiment is used even if it is hot-pressed after the plating layer is formed. Refers to various properties related to mechanical deformation and damage such as tensile strength, yield point, elongation, depth of penetration, hardness, impact value, fatigue strength, creep strength, etc.). For example, a member having a hardenability improved by adding C (carbon) or an alloy element is used. Thereby, an automotive component obtained by hot-pressing an Al-based plated steel sheet 100 prepared by forming an Al-based plated layer 103 and a surface coating layer 107 described later can exhibit excellent mechanical strength.
亦即,本實施形態之Al系鍍敷鋼板100用之母材101只要係具有優異機械強度者,則可利用周知之物 。可利用譬如具有以下成分之物來作為母材101,惟母材101之成分並不限於此。That is, as long as the base material 101 for the Al-based plated steel sheet 100 of the present embodiment has excellent mechanical strength, a well-known thing can be used. As the base material 101, for example, a material having the following components can be used, but the components of the base material 101 are not limited thereto.
本實施形態之母材101譬如以質量%計含有C:0.01%以上且0.5%以下、Si:2.0%以下、Mn:0.01%以上且3.5%以下、P:0.1%以下、S:0.05%以下、Al:0.001%以上且0.1%以下、N:0.01%以下,並且可任意選擇含有以下之1種或2種以上元素:Ti:0.005%以上且0.1%以下、B:0.0003%以上且0.01%以下、Cr:0.01%以上且1.0%以下、Ni:0.01%以上且5.0%以下、Mo:0.005%以上且2.0%以下、Cu:0.005%以上且1.0%以下,可更含有W、V、Nb、Sb等元素,且剩餘部分由Fe及無法避免之不純物所構成。以下詳述母材101中添加之各成分。以下記載中,各成分之單位%皆指質量%。 (C:0.01%以上且0.5%以下)The base material 101 in the present embodiment contains, for example, mass: C: 0.01% or more and 0.5% or less, Si: 2.0% or less, Mn: 0.01% or more and 3.5% or less, P: 0.1% or less, and S: 0.05% or less. , Al: 0.001% or more and 0.1% or less, N: 0.01% or less, and optionally one or more of the following elements: Ti: 0.005% or more and 0.1% or less, B: 0.0003% or more and 0.01% or less Below, Cr: 0.01% or more and 1.0% or less, Ni: 0.01% or more and 5.0% or less, Mo: 0.005% or more and 2.0% or less, Cu: 0.005% or more and 1.0% or less, and may further contain W, V, and Nb , Sb and other elements, and the remainder is composed of Fe and unavoidable impurities. Hereinafter, each component added to the base material 101 will be described in detail. In the following description, the unit% of each component refers to mass%. (C: 0.01% or more and 0.5% or less)
碳(C)係無法避免會含有於鋼中,且係為了確保母材101之作為目的之機械強度而含有。過度使C含量減低會使冶煉成本增加,故以含有0.01%以上為宜。並且,若C含量在0.1%以上,即會變得不須為了提升機械強度而大量添加其他合金元素,故藉由添加C所帶來的提升強度的效果大。另一方面,若C含量大於0.5%,雖可使母材101更加硬化,但會變得容易產生熔融破裂。因此,C以含有0.01%以上且0.5%以下為宜,且由提升強度與防止熔融破裂的觀點看來,較宜以0.1%以上且0.4%以下之含量來作添加。又,C含量更宜設為0.15%以上且0.35%以下。 (Si:2.0%以下)Carbon (C) is unavoidably contained in steel, and is contained to ensure the mechanical strength of the base material 101 for the purpose. Excessively reducing the C content will increase the smelting cost, so it is preferable to contain more than 0.01%. In addition, if the C content is 0.1% or more, it becomes unnecessary to add a large amount of other alloy elements in order to improve the mechanical strength, so the effect of increasing the strength by adding C is large. On the other hand, if the C content is more than 0.5%, the base material 101 can be hardened more, but melt cracking easily occurs. Therefore, C is preferably contained in an amount of 0.01% or more and 0.5% or less, and from the viewpoint of improving strength and preventing melt fracture, it is more preferable to add C in an amount of 0.1% to 0.4%. The C content is more preferably 0.15% to 0.35%. (Si: 2.0% or less)
矽(Si)係作為脫氧劑而被添加等在鋼的精煉過程中無法避免會含有的元素。然而,過度添加Si會造成在鋼板製造時的熱軋步驟中延展性降低、或是作為其結果而損害表面性狀等,故宜設為2.0%以下。Silicon (Si) is an element which is added as a deoxidizer and cannot be avoided during the refining of steel. However, excessive addition of Si may cause a reduction in ductility in a hot-rolling step at the time of steel sheet production, or as a result, may deteriorate surface properties. Therefore, it is preferably set to 2.0% or less.
並且,Si係可提升母材101之機械強度的強化元素之一,亦可添加其以與C同樣確保作為目的之機械強度。若Si含量小於0.01%,則不易發揮提升強度的效果,而難以獲得充分的機械強度之提升。另一方面,Si也是易氧化性元素,因此若Si含量大於0.6%,在進行熔融Al系鍍敷時,濡濕性會降低,而有產生未鍍(unplated)之可能性。因此,Si較宜以0.01%以上且0.6%以下的含量作添加。又,Si含量更宜設為0.05%以上且0.5%以下。 (Mn:0.01%以上且3.5%以下)In addition, Si is one of the reinforcing elements that can increase the mechanical strength of the base material 101, and it may be added to ensure the same mechanical strength as C. If the Si content is less than 0.01%, it is difficult to exert the effect of increasing the strength, and it is difficult to obtain a sufficient increase in mechanical strength. On the other hand, Si is also an easily oxidizable element. Therefore, when the Si content is more than 0.6%, the wettability is reduced when molten Al-based plating is performed, and there is a possibility that unplating may occur. Therefore, Si is preferably added at a content of 0.01% to 0.6%. The Si content is more preferably set to 0.05% or more and 0.5% or less. (Mn: 0.01% or more and 3.5% or less)
錳(Mn)係作為脫氧劑而被添加等在鋼的精煉過程中無法避免會含有的元素。然而,過度添加Mn會因鑄造時之Mn偏析導致損害品質之均一性,且鋼板會過度硬化而致使熱加工、冷加工時的延展性降低,故宜設為3.5%以下。另一方面,若Mn含量降低至小於0.01%,去除Mn之步驟或成本便會增加,故Mn含量宜為0.01%以上。從而,Mn宜設為0.01%以上且3.5%以下。Manganese (Mn) is an element which cannot be avoided during the refining process of steel, such as being added as a deoxidizer. However, excessive addition of Mn may impair the uniformity of quality due to Mn segregation during casting, and the steel sheet may be excessively hardened, resulting in a reduction in ductility during hot working and cold working. Therefore, it should be set to 3.5% or less. On the other hand, if the Mn content is reduced to less than 0.01%, the step or cost of removing Mn will increase, so the Mn content should be more than 0.01%. Therefore, Mn is preferably set to 0.01% to 3.5%.
除此之外,Mn為母材101的強化元素之一,亦為可提高淬火性的元素之一。而且,對於將無法避免之不純物之一即S(硫)所導致的熱脆性抑制得較低這一點,Mn亦為有效。因此,藉由將Mn含量設為0.5%以上,便能獲得提升淬火性或抑制熱脆性之效果。另一方面,若Mn含量大於3%,會有殘留γ相變得過多而強度降低之虞。因此,Mn較宜以0.5%以上且3%以下的含量來作添加。又,Mn含量更宜設為1%以上且2%以下。 (P:0.1%以下)In addition, Mn is one of the strengthening elements of the base material 101 and one of the elements that can improve the hardenability. Furthermore, Mn is also effective in suppressing the thermal brittleness caused by S (sulfur), which is one of the unavoidable impurities. Therefore, by setting the Mn content to 0.5% or more, the effect of improving hardenability or suppressing hot brittleness can be obtained. On the other hand, if the Mn content is more than 3%, the residual γ phase may become excessive and the strength may be reduced. Therefore, Mn is preferably added at a content of 0.5% to 3%. The Mn content is more preferably 1% or more and 2% or less. (P: 0.1% or less)
磷(P)係無法避免會含有的元素,另一方面亦為固溶強化元素,且係可較廉價地使母材101強度提升之元素。然而,基於經濟面上的精煉極限,宜設含量下限為0.001%。另一方面,若P含量大於0.1%,則有母材101的韌性降低之虞。因此,P含量較宜為0.001%以上且0.1%以下。又,P含量更宜設為0.01%以上且0.08%以下。 (S:0.05%以下)Phosphorus (P) is an element that cannot be avoided, on the other hand, it is a solid solution strengthening element, and it is an element that can increase the strength of the base material 101 relatively inexpensively. However, based on the economic refining limit, the lower limit of the content should be set to 0.001%. On the other hand, if the P content is more than 0.1%, the toughness of the base material 101 may decrease. Therefore, the P content is more preferably 0.001% to 0.1%. The P content is more preferably 0.01% to 0.08%. (S: 0.05% or less)
硫(S)係無法避免會含有的元素,且會作為MnS而成為母材101中的夾雜物並成為破壞的起點,會阻礙延展性或韌性而成為加工性劣化的主要原因。故,S含量越低越好,宜設含量上限為0.05%。另一方面,為了使S含量降低可預想到製造成本的上升,故含量下限宜設為0.001%。又,S含量更宜設為0.01%以上且0.02%以下。 (Al:0.001%以上且0.1%以下)Sulfur (S) is an unavoidable element, and as MnS, it becomes an inclusion in the base material 101 and becomes a starting point of destruction, which hinders ductility and toughness and becomes a cause of deterioration of workability. Therefore, the lower the S content, the better, and the upper limit of the content should be set to 0.05%. On the other hand, in order to reduce the S content, an increase in manufacturing costs can be expected, so the lower limit of the content should be 0.001%. The S content is more preferably 0.01% to 0.02%. (Al: 0.001% or more and 0.1% or less)
鋁(Al)係作為脫氧劑而被含有於母材101中之成分,但亦為會阻礙鍍敷性之元素。故,Al含量上限宜設為0.1%。另一方面,Al含量下限並未特別規定,但基於經濟面上的精煉極限,宜設為例如0.001%。又,Al含量更宜設為0.01%以上且0.08%以下。 (N:0.01%以下)Aluminum (Al) is a component contained in the base material 101 as a deoxidizer, but it is also an element that hinders plating properties. Therefore, the upper limit of the Al content should be set to 0.1%. On the other hand, the lower limit of the Al content is not particularly specified, but is preferably set to, for example, 0.001% based on the economical refining limit. The Al content is more preferably 0.01% to 0.08%. (N: 0.01% or less)
氮(N)係無法避免會含有的元素,由使母材101的各種特性穩定化之觀點看來,宜固定其含量,具體而言可根據Ti、Al等元素之含量來固定。另一方面,若N含量過多,因Ti、Al等的含量會變多而可預想母材101的製造成本的增加,故N含量上限宜設為0.01%。 (Ti:0.005%以上且0.1%以下、B:0.0003%以上且0.01%以下、Cr:0.01%以上且1.0%以下、Ni:0.01%以上且5.0%以下、Mo:0.005%以上且2.0%以下、Cu:0.005%以上且1.0%以下之1種或2種以上) (Ti:0.005%以上且0.1%以下)Nitrogen (N) is an unavoidable element. From the viewpoint of stabilizing various characteristics of the base material 101, its content should be fixed. Specifically, it can be fixed according to the content of elements such as Ti and Al. On the other hand, if the content of N is too large, since the content of Ti, Al, etc. will increase and the manufacturing cost of the base material 101 can be expected to increase, the upper limit of the content of N should be set to 0.01%. (Ti: 0.005% or more and 0.1% or less, B: 0.0003% or more and 0.01% or less, Cr: 0.01% or more and 1.0% or less, Ni: 0.01% or more and 5.0% or less, Mo: 0.005% or more and 2.0% or less , Cu: 0.005% or more and 1.0% or less or 1 or more) (Ti: 0.005% or more and 0.1% or less)
鈦(Ti)為母材101之強化元素之一,亦為可提升形成於母材101表面之Al系鍍敷層103的耐熱性之元素。若Ti含量小於0.005%,則無法充分獲得提升強度之效果或耐熱性。另一方面,若過度添加Ti,便會形成譬如碳化物或氮化物,而有使母材101軟質化之虞。尤其,若Ti含量大於0.1%,無法獲得作為目的之機械強度的可能性就高。從而,Ti宜以0.005%以上且0.1%以下的含量來作添加。又,Ti含量更宜設為0.03%以上且0.08%以下。 (B:0.0003%以上且0.01%以下)Titanium (Ti) is one of the strengthening elements of the base material 101 and is an element that can improve the heat resistance of the Al-based plating layer 103 formed on the surface of the base material 101. If the Ti content is less than 0.005%, the effect of improving strength or heat resistance cannot be sufficiently obtained. On the other hand, if Ti is excessively added, carbides or nitrides are formed, for example, and the base material 101 may be softened. In particular, if the Ti content is more than 0.1%, there is a high possibility that the intended mechanical strength cannot be obtained. Therefore, Ti is preferably added at a content of 0.005% to 0.1%. The Ti content is more preferably 0.03% or more and 0.08% or less. (B: 0.0003% or more and 0.01% or less)
硼(B)係會在淬火時作用而具有提升母材101的強度之效果的元素。Boron (B) is an element that acts during quenching and has the effect of increasing the strength of the base material 101.
若B含量小於0.0003%,則無法充分獲得上述提升強度之效果。另一方面,若B含量大於0.01%,母材101中會形成夾雜物(譬如,BN、碳硼化物等)並脆化,而有使疲勞強度降低之虞。因此,B宜以0.0003%以上且0.01%以下的含量來作添加。又,B含量更宜設為0.001%以上且0.008%以下。 (Cr:0.01%以上且1.0%以下)If the B content is less than 0.0003%, the above-mentioned effect of increasing the strength cannot be obtained sufficiently. On the other hand, if the B content is more than 0.01%, inclusions (for example, BN, boron carbide, etc.) are formed in the base material 101 and become brittle, which may reduce the fatigue strength. Therefore, B should be added at a content of 0.0003% or more and 0.01% or less. The B content is more preferably 0.001% to 0.008%. (Cr: 0.01% or more and 1.0% or less)
鉻(Cr)具有在將Al系鍍敷層103合金化以形成Al-Fe合金層時,使Al系鍍敷層103生成於與母材101之界面,藉此抑制會成為Al系鍍敷層103剝離之原因的AlN生成的效果。並且,Cr為可提升耐磨耗性的元素之一,亦為可提高淬火性的元素之一。若Cr含量小於0.01%,則無法充分獲得上述效果。另一方面,若Cr含量大於1.0%,不僅上述效果會飽和,鋼板的製造成本亦會上升。因此,Cr宜以0.01%以上且1.0%以下的含量來作添加。又,Cr含量更宜設為0.5%以上且1.0%以下。 (Ni:0.01%以上且5.0%以下)Chromium (Cr) suppresses formation of an Al-based plating layer by forming the Al-based plating layer 103 at the interface with the base material 101 when the Al-based plating layer 103 is alloyed to form an Al-Fe alloy layer. Effect of AlN generation due to 103 peeling. In addition, Cr is one of the elements that can improve the wear resistance and one of the elements that can improve the hardenability. If the Cr content is less than 0.01%, the above effects cannot be sufficiently obtained. On the other hand, if the Cr content is more than 1.0%, not only the above-mentioned effects will be saturated, but also the manufacturing cost of the steel sheet will increase. Therefore, Cr is preferably added at a content of 0.01% to 1.0%. The Cr content is more preferably 0.5% to 1.0%. (Ni: 0.01% or more and 5.0% or less)
鎳(Ni)具有提升熱壓時之淬火性的效果。而且,Ni還具有提高母材101之耐蝕性的效果。但若Ni含量小於0.01%,則無法充分獲得上述效果。另一方面,若Ni含量大於5.0%,不僅上述效果會飽和,鋼板的製造成本亦會上升。因此,Ni宜以0.01%以上且5.0%以下的含量來作添加。 (Mo:0.005%以上且2.0%以下)Nickel (Ni) has the effect of improving the hardenability during hot pressing. In addition, Ni has the effect of improving the corrosion resistance of the base material 101. However, if the Ni content is less than 0.01%, the above effects cannot be sufficiently obtained. On the other hand, if the Ni content is more than 5.0%, not only the above-mentioned effects will be saturated, but also the manufacturing cost of the steel sheet will increase. Therefore, Ni is preferably added at a content of 0.01% to 5.0%. (Mo: 0.005% or more and 2.0% or less)
鉬(Mo)具有提升熱壓時之淬火性的效果。而且,Mo還具有提高母材101之耐蝕性的效果。但若Mo含量小於0.005%,則無法充分獲得上述效果。另一方面,若Mo含量大於2.0%,不僅上述效果會飽和,鋼板的製造成本亦會上升。因此,Mo宜以0.005%以上且2.0%以下的含量來作添加。 (Cu:0.005%以上且1.0%以下)Molybdenum (Mo) has the effect of improving hardenability during hot pressing. In addition, Mo also has the effect of improving the corrosion resistance of the base material 101. However, if the Mo content is less than 0.005%, the above effects cannot be sufficiently obtained. On the other hand, if the Mo content is more than 2.0%, not only the aforementioned effects will be saturated, but also the manufacturing cost of the steel sheet will increase. Therefore, Mo is preferably added in an amount of 0.005% to 2.0%. (Cu: 0.005% or more and 1.0% or less)
銅(Cu)具有提升熱壓時之淬火性的效果。而且,Cu還具有提高母材101之耐蝕性的效果。若Cu含量小於0.005%,則無法充分獲得上述效果。另一方面,若Cu含量大於1.0%,不僅上述效果會飽和,鋼板的製造成本亦會上升。因此,Cu宜以0.005%以上且1.0%以下的含量來作添加。 (W、V、Nb、Sb)Copper (Cu) has the effect of improving the hardenability during hot pressing. Cu also has the effect of improving the corrosion resistance of the base material 101. If the Cu content is less than 0.005%, the above effects cannot be sufficiently obtained. On the other hand, if the Cu content is more than 1.0%, not only the above-mentioned effects will be saturated, but also the manufacturing cost of the steel sheet will increase. Therefore, Cu should preferably be added in an amount of 0.005% to 1.0%. (W, V, Nb, Sb)
又,除了上述的多數個元素之外,本實施形態之母材101還可選擇性添加鎢(W)、釩(V)、鈮(Nb)、銻(Sb)等元素。該等元素的添加量只要在周知範圍內,則可採用任一個添加量。 (剩餘部分)In addition to the above-mentioned many elements, the base material 101 of the present embodiment can optionally add elements such as tungsten (W), vanadium (V), niobium (Nb), and antimony (Sb). As long as these elements are added in a known range, any of them may be used. (The remaining part)
母材101之剩餘部分僅為鐵(Fe)與無法避免之不純物。所謂無法避免之不純物是指原材料中所含成分、或是在製造過程中混入的成分,且指不是刻意含有於母材101中的成分之成分。The remainder of the base material 101 is only iron (Fe) and unavoidable impurities. The unavoidable impurities refer to the components contained in the raw materials or the components mixed in the manufacturing process, and the components that are not the components intentionally contained in the base material 101.
上述成分所形成之母材101會藉由熱壓等之加熱來淬火,而能具有約1500MPa以上的機械強度。雖是像這樣具有優異機械強度的鋼板,但只要利用熱壓來加工的話,便能在因加熱而軟化的狀態下進行壓製,故可輕易成形。並且,在壓製後,從高溫冷卻下來的母材101可實現高機械強度,進而即便為了輕量化而使厚度變薄,仍可維持甚或提升機械強度。 [Al系鍍敷層103]The base material 101 formed by the above components is quenched by heating such as hot pressing, and can have a mechanical strength of about 1500 MPa or more. Although it is a steel sheet with excellent mechanical strength like this, if it is processed by hot pressing, it can be pressed in a softened state by heating, so it can be easily formed. In addition, after pressing, the base material 101 cooled from a high temperature can achieve high mechanical strength, and even if the thickness is reduced for weight reduction, the mechanical strength can be maintained or even improved. [Al-based plating layer 103]
Al系鍍敷層103是形成於母材101之至少單面。於Al系鍍敷層103中,Si係作為抑制熔融鍍敷時Fe-Al合金層之生成的元素而被添加。若Al系鍍敷層103中的Si含量小於4質量%,在熔融鍍敷時Fe-Al合金層會過度成長,因此會在壓製加工時助長鍍敷層破裂。另一方面,當該Si含量大於12質量%,就算使表面的Si量減低,Al系鍍敷層103的加工性和耐蝕性仍會降低。因此,Al系鍍敷層103中的Si含量係設為4質量%以上且在12質量%以下。另,Al系鍍敷層103中的Si含量更宜為4質量%以上且在10質量%以下。Al系鍍敷層103只要含有85質量%以上的Al即可。Al、Si以外的成分並未特別限定,但Zn會因熱壓前的加熱而蒸發,故宜為10質量%以下或宜不被含有大於無法避免之不純物量的量。並且,因與母材中的Fe之合金化等,而亦含有Fe。此外,其宜為Al、Si以外係無法避免之不純物之JIS 4000系鋁合金等的Al-Si系合金(係由Al及Si所構成之Al合金,且為Al、Si以外係無法避免之不純物之鋁合金)組成。The Al-based plating layer 103 is formed on at least one side of the base material 101. In the Al-based plating layer 103, Si is added as an element that suppresses the formation of the Fe-Al alloy layer during hot-dip plating. If the Si content in the Al-based plating layer 103 is less than 4% by mass, the Fe-Al alloy layer excessively grows during the hot-dip plating, and thus the cracking of the plated layer is promoted during the pressing process. On the other hand, when the Si content is more than 12% by mass, even if the amount of Si on the surface is reduced, the workability and corrosion resistance of the Al-based plating layer 103 are still reduced. Therefore, the Si content in the Al-based plating layer 103 is set to 4% by mass or more and 12% by mass or less. The Si content in the Al-based plating layer 103 is more preferably 4% by mass or more and 10% by mass or less. The Al-based plating layer 103 only needs to contain 85% by mass or more of Al. The components other than Al and Si are not particularly limited, but Zn will evaporate due to heating before hot pressing, so it is preferably 10% by mass or less, and should not be contained in an amount greater than the amount of unavoidable impurities. In addition, Fe is also contained due to alloying with Fe in the base material. In addition, it is preferably an Al-Si-based alloy such as JIS 4000 series aluminum alloy, which is an unavoidable impurity other than Al and Si. (It is an Al alloy composed of Al and Si, and is an unavoidable impurity other than Al, Si. Aluminum alloy).
此處所謂之Si含量為平均組成。The Si content referred to here is an average composition.
含80質量%以上的Al之Al系鍍敷層103可防止母材101的腐蝕。而且,Al系鍍敷層103可防止在熱壓前的加熱時,於鋼板表面上生成鏽皮(鐵之氧化物)。因此,藉由於母材101之至少單面存在有Al系鍍敷層103,便能省略鏽皮去除步驟、表面淨化步驟及表面處理步驟等,進而可使汽車零件等的生產性提升。此外,與有機系材料之皮膜或其他金屬系材料(例如Zn系材料)之皮膜相較,Al系鍍敷層103的熔點較高,故在熱壓時可進行在高溫下之加工。The Al-based plating layer 103 containing 80% by mass or more of Al can prevent corrosion of the base material 101. In addition, the Al-based plating layer 103 can prevent scale (oxide of iron) from being formed on the surface of the steel sheet during heating before hot pressing. Therefore, since the Al-based plating layer 103 is present on at least one side of the base material 101, the scale removal step, the surface purification step, the surface treatment step, and the like can be omitted, and the productivity of automobile parts and the like can be improved. In addition, the Al-based plating layer 103 has a higher melting point than a film of an organic-based material or a film of another metal-based material (for example, a Zn-based material), so that it can be processed at a high temperature during hot pressing.
並且,於Al系鍍敷層表面會有Al氧化物系的鈍化皮膜生成。此鈍化皮膜會防止ZnO在熱壓時被Al系鍍敷層中的成分還原而消失的情形。In addition, an Al oxide-based passivation film is formed on the surface of the Al-based plating layer. This passivation film prevents ZnO from being reduced and disappeared by components in the Al-based plating layer during hot pressing.
另,Al系鍍敷層103所含Al之一部分會在熔融鍍敷時或在熱壓時與母材101中的Fe合金化。從而,Al系鍍敷層103並不一定是以成分固定之單一的層形成,也有為含經局部性合金化的層(合金層)或濃度梯度較表面有變化之鋼-鋁傾斜合金層之物的情形。 (鍍敷附著量)In addition, a part of Al contained in the Al-based plating layer 103 is alloyed with Fe in the base material 101 during hot-dip plating or hot pressing. Therefore, the Al-based plating layer 103 is not necessarily formed as a single layer with a fixed composition, but may also be a layer containing a locally alloyed layer (alloy layer) or a steel-aluminum inclined alloy layer whose concentration gradient changes from the surface. Things. (Plating deposit)
Al系鍍敷層103之附著量為30g/m 2以上。當小於30g/m 2時,鍍敷厚會變得過薄,致使於熱壓時會有鏽皮生成而耐蝕性惡化。較佳係在50g/m 2以上。 (Al系鍍敷層103表面的Si面積率) The adhesion amount of the Al-based plating layer 103 is 30 g / m 2 or more. When it is less than 30 g / m 2 , the thickness of the plating becomes too thin, and rust is generated during hot pressing, which deteriorates the corrosion resistance. It is preferably 50 g / m 2 or more. (Si area ratio of the surface of the Al-based plating layer 103)
如前所述,若為因非平衡凝固而形成之Al系鍍敷層103,則Si易於表面濃化。若在熱壓加熱前的鍍敷階段中,Si於鍍敷表面濃化而造成Si面積率變高,則在熱壓的加熱階段中會變得容易生成Si濃度高之第2層,一旦生成第2層便會形成與第1層之腐蝕電路而塗裝後耐蝕性變差。As described above, if the Al-based plating layer 103 is formed by non-equilibrium solidification, Si is easily surface-concentrated. If Si is concentrated on the plating surface during the plating stage before hot pressing and heating, and the Si area ratio becomes high, the second layer with a high Si concentration will be easily formed in the hot pressing and heating stage. The second layer will form a corrosion circuit with the first layer and the corrosion resistance will deteriorate after coating.
此外,若在熱壓加熱前的鍍敷階段中,Si於鍍敷表面濃化而造成Si面積率變高,則Al氧化物系的鈍化皮膜之生成會變得不充分,而有在熱壓時ZnO被Al系鍍敷層中的成分還原而消失之虞。In addition, in the plating stage before hot pressing heating, if Si is concentrated on the plating surface and the Si area ratio becomes high, the formation of an Al oxide-based passivation film becomes insufficient. At this time, ZnO may be reduced and disappeared by components in the Al-based plating layer.
因此,必須令Al系鍍敷層103表面的Si面積率為12%以下。為了獲得明顯效果,設Si面積率為8%以下較佳,設為6%以下更佳。Si面積率之下限並未特別限定,雖然理想係Si面積率為0%,但在實用面上1%為實質下限。Therefore, the Si area ratio on the surface of the Al-based plating layer 103 must be 12% or less. In order to obtain a significant effect, the Si area ratio is preferably 8% or less, and more preferably 6% or less. The lower limit of the Si area ratio is not particularly limited. Although the ideal Si area ratio is 0%, the practical lower limit is 1%.
Al系鍍敷層103表面的Si面積率,可在鍍敷後藉由EPMA(Electron Probe Micro Analyzer)之區域分析、或歐傑電子能譜術(Auger Electron Spectroscopy, AES)之區域分析來測定。此時,若為EPMA,以測定機器係使用日本電子製之JXA8500F,且測定點為500點×500點、以1μm間距且以光束直徑為1μm來測定為理想,而若為歐傑電子能譜術,則以光束直徑為10μm以下且測定點為500點×500點、以10μm間距在5mm×5mm視野中進行測定為理想。另,Si面積率亦能由從表面起在深度方向之非常薄的區域中的Si濃度(原子%)來求取。若形成有後述之表面皮膜層107,當在之後要測定Al系鍍敷層103表面的Si面積率時,亦可以高頻輝光放電分光分析法(高頻GDS)從表面進行深度方向之定量分析,並設定如下而求取。The Si area ratio on the surface of the Al-based plating layer 103 can be measured by area analysis after EPMA (Electron Probe Micro Analyzer) or area analysis by Auger Electron Spectroscopy (AES) after plating. In this case, if it is EPMA, the measurement equipment is JXA8500F made by Japan Electronics, and the measurement point is 500 points × 500 points, and the measurement is performed at a pitch of 1 μm and the beam diameter is 1 μm. The measurement is preferably performed with a beam diameter of 10 μm or less, a measurement point of 500 points × 500 points, and a 10 μm pitch in a 5 mm × 5 mm field of view. The Si area ratio can also be determined from the Si concentration (atomic%) in a very thin region in the depth direction from the surface. If the surface coating layer 107 described later is formed, when the Si area ratio of the surface of the Al-based plating layer 103 is to be measured later, the depth-wise quantitative analysis can also be performed from the surface by high-frequency glow discharge spectrometry (high-frequency GDS). And set it as follows.
高頻輝光放電分光分析法(高頻GDS)中宜進行直徑4mm範圍之測定。藉由高頻GDS,將鍍敷成分之Al、Si以外的成分為5元素%的部分規定為鍍敷表面,並求取該部位中的各構成成分濃度(原子%)後,根據各構成成分的比重與原子量(分子量)來計算Si的體積分率。根據定量組織學的觀點,體積分率等於面積率,故令以前述方式求得之Si的體積分率為Si面積率。In the high-frequency glow discharge spectroscopic analysis method (high-frequency GDS), it is suitable to measure a diameter of 4mm. A high-frequency GDS is used to specify a portion of the plating component other than Al and Si with a content of 5 element% as the plating surface. After determining the concentration of each constituent component (atomic%) in the portion, the component is determined based on the constituent components. The specific gravity and the atomic weight (molecular weight) were used to calculate the volume fraction of Si. From the viewpoint of quantitative histology, the volume fraction is equal to the area ratio, so the volume fraction of Si obtained in the foregoing manner is the Si area ratio.
作為使Al系鍍敷層103表面的Si面積率降低的方法,有於鍍敷後蝕刻表面以去除有Si濃化之部分的方法。As a method of reducing the Si area ratio of the surface of the Al-based plating layer 103, there is a method of etching the surface after plating to remove a portion where Si is concentrated.
譬如,若將凝固溫度附近的冷卻速度設成10℃/秒使Si濃化後,在pH1以下的酸性溶液中溶解表面的Si濃化共晶,便能使表面的Si面積率降低至10%左右。並且,當令凝固時的冷卻速度為20℃/秒時,共晶的Si濃度就會變成在20%以上,若使該部分在酸性溶液中溶解,便能使Si面積率降低至8%以下。For example, if the cooling rate near the solidification temperature is set to 10 ° C / sec to condense Si, the Si-concentrated eutectic on the surface is dissolved in an acidic solution with a pH of 1 or less, and the Si area ratio on the surface can be reduced to 10%. about. In addition, when the cooling rate during solidification is set to 20 ° C./sec, the eutectic Si concentration becomes 20% or more. If this part is dissolved in an acidic solution, the Si area ratio can be reduced to 8% or less.
作為在鍍敷後蝕刻表面以去除有Si濃化之部分的方法,可舉例以硫酸等的酸來蝕刻Al鍍敷層表面的方法。 (厚度方向的Si濃度分布)As a method of etching the surface after plating to remove a portion where Si is concentrated, a method of etching the surface of the Al plating layer with an acid such as sulfuric acid can be exemplified. (Si concentration distribution in thickness direction)
Al系鍍敷層103之厚度方向的Si濃度分布之最大值以質量%計為15%以下(較佳為12質量%以下),且厚度方向的Si濃度分布之最大值與Fe濃度在4質量%以下時的Si濃度之最小值的比為1.0以上且在2.0以下,前述之理由如下。The maximum value of the Si concentration distribution in the thickness direction of the Al-based plating layer 103 is 15% or less (preferably 12% by mass or less) in terms of mass%, and the maximum value of the Si concentration distribution in the thickness direction and the Fe concentration are 4 mass The ratio of the minimum value of the Si concentration at% or less is 1.0 or more and 2.0 or less, and the reason described above is as follows.
首先,若表面的Si面積率高,便如圖6所示會在表層產生Si濃度高的部分,在熱壓的加熱階段中就會變得容易生成Si濃度高之第2層的情況已於前說明。First, if the surface area ratio of Si is high, as shown in FIG. 6, a high Si concentration portion is generated in the surface layer, and it becomes easy to form a second layer with a high Si concentration during the heating stage of hot pressing. Before description.
另一方面,即便如圖7上段所示並非在表層而是於內部有Si濃度高的部分,該部分在熱壓的加熱階段中仍如圖7下段所示會變得容易生成Si濃度高之第2層。On the other hand, even if there is a part with a high Si concentration not in the surface layer but in the interior as shown in the upper part of FIG. 7, in the heating stage of hot pressing, it will become easy to generate a high Si concentration as shown in the lower part of FIG. Layer 2.
因此,如圖8中段所示,就連不是表面而是内部也不可有Si濃度高的部分。Therefore, as shown in the middle part of FIG. 8, not even the surface but the inside may have a portion having a high Si concentration.
此即為規定厚度方向的Si濃度分布之理由。另,作為最小值,使用Fe濃度在4質量%以下時的Si濃度之理由係因考量到鍍敷層與母材之界面有合金化之情況之故。This is the reason for specifying the Si concentration distribution in the thickness direction. The reason for using the Si concentration at a Fe concentration of 4% by mass or less as a minimum value is to consider that the interface between the plating layer and the base material may be alloyed.
理想係厚度方向的Si濃度分布之最大值與Fe濃度在4質量%以下時的Si濃度之最小值的比為1.0~1.5。The ratio of the maximum value of the Si concentration distribution in the ideal thickness direction to the minimum value of the Si concentration when the Fe concentration is 4% by mass or less is 1.0 to 1.5.
厚度方向的Si濃度分布只要利用EPMA等來進行Al鍍敷鋼板之垂直截面的組成分析即可求取。The Si concentration distribution in the thickness direction can be obtained by analyzing the composition of the vertical section of the Al-plated steel sheet using EPMA or the like.
獲得此種濃度分布的方法可舉例蝕刻表面之方法。譬如,若係鍍敷層中的Si顯示出圖8上段所示濃度分布的鍍敷鋼板的話,只要以蝕刻去除鍍敷層至表層的Si濃度為15%以下之位置為止,便會成為如圖8中段所示之濃度分布。若為該濃度分布,則在熱壓之後,如圖8下段所示,於鍍敷層中也不會生成Si濃度高之第2層。A method for obtaining such a concentration distribution may be a method of etching a surface. For example, if the Si in the plating layer exhibits a concentration distribution as shown in the upper section of FIG. 8, as long as the plating layer is removed by etching to a position where the Si concentration of the surface layer is 15% or less, it will become as shown in the figure. The concentration distribution shown in the middle 8 section. With this concentration distribution, as shown in the lower stage of FIG. 8, after the hot pressing, a second layer having a high Si concentration is not formed in the plating layer.
作為蝕刻液,只要係添加有鐵系抑制劑之pH1以下之酸性溶液的話便無特別限定,而可舉例添加有鐵系抑制劑之2莫耳%濃度以上的H 2SO 4水溶液。若為大於pH1之酸性溶液,則有蝕刻不會進行,或是即便有進行但蝕刻速率過慢而生產性惡化之虞。 The etching solution is not particularly limited as long as it is an acidic solution having a pH of 1 or less to which an iron-based inhibitor is added, and examples thereof include an H 2 SO 4 aqueous solution having a concentration of 2 mol% or more of the iron-based inhibitor. If it is an acidic solution with a pH greater than 1, the etching may not proceed, or even if it does, the etching rate may be too slow and productivity may deteriorate.
且可舉例以下方法:浸漬於其他蝕刻液即2莫耳%濃度以上的氫氧化鈉水溶液之鹼溶液中,將鍍敷之金屬Al、Si溶解,接著以上述酸性溶液來溶解殘留的Al-Si-Fe合金層。In addition, the following method can be exemplified: immersion in other etching solution, that is, an alkali solution of an aqueous sodium hydroxide solution having a concentration of 2 mol% or more, dissolving the plated metals Al and Si, and then dissolving the remaining Al-Si with the above acid solution -Fe alloy layer.
蝕刻時間係可去除Si濃度高的部分且鍍敷之附著量會成為30g/m 2以上之時間。具體而言,係進行蝕刻直至下述深度為止:鍍敷表面的Si面積率為12%以下,Al系鍍敷層之厚度方向的Si濃度分布之最大值以質量%計為15%以下,且最大值與最小值的比為1.0以上且在2.0以下。藉由將譬如鍍敷附著量50g/m 2的鍍敷鋼板於60℃的10%硫酸溶液中進行30~60秒浸漬處理,即可獲得本發明之鍍敷鋼板。且藉由控制浸漬液的溫度或硫酸濃度便能縮短浸漬處理時間。並且亦可磨削鍍敷表面以去除表面之Si濃化層。 The etching time is a time when a portion having a high Si concentration can be removed and the adhesion amount of the plating becomes 30 g / m 2 or more. Specifically, etching is performed to a depth where the Si area ratio of the plating surface is 12% or less, and the maximum value of the Si concentration distribution in the thickness direction of the Al-based plating layer is 15% or less by mass%, and The ratio of the maximum value to the minimum value is 1.0 or more and 2.0 or less. The plated steel sheet of the present invention can be obtained by, for example, immersing a plated steel sheet having a plating adhesion of 50 g / m 2 in a 10% sulfuric acid solution at 60 ° C. for 30 to 60 seconds. And by controlling the temperature or the sulfuric acid concentration of the immersion liquid, the immersion treatment time can be shortened. In addition, the plating surface can be ground to remove the Si-concentrated layer on the surface.
為了不在Al系鍍敷層103内部形成Si濃度高的部分,亦有將鍍敷浴浸漬後的冷卻條件設為15℃/秒以下的方法。 (表面粗度)In order not to form a portion with a high Si concentration inside the Al-based plating layer 103, there is also a method in which the cooling conditions after the immersion of the plating bath are set to 15 ° C / sec or less. (Surface roughness)
Al系鍍敷層103之表面粗度以算術平均粗度Ra計宜為0.1μm以下。當大於0.1μm時,表面凹凸會變得過大且會產生局部較薄的區域,而有在熱壓時生成鏽皮之虞。此外,當有設置表面皮膜層107時,亦會產生局部較薄的區域,而變得無法充分獲得作為表面皮膜層107之效果。The surface roughness of the Al-based plating layer 103 is preferably 0.1 μm or less in terms of the arithmetic average roughness Ra. When it is larger than 0.1 μm, the surface unevenness may become too large and a locally thin area may be generated, and there is a concern that rust may be generated during hot pressing. In addition, when the surface film layer 107 is provided, a locally thin area is also generated, and the effect as the surface film layer 107 cannot be sufficiently obtained.
較理想係表面粗度以算術平均粗度Ra計在0.1μm以下。 [表面皮膜層107]The ideal surface roughness is 0.1 μm or less in terms of the arithmetic average roughness Ra. [Surface coating layer 107]
為了使熱壓時的熱潤滑性更加提升,會於Al系鍍敷鋼板100的Al系鍍敷層103表面形成含ZnO粒子109之表面皮膜層107。In order to further improve the thermal lubricity during hot pressing, a surface film layer 107 containing ZnO particles 109 is formed on the surface of the Al-based plating layer 103 of the Al-based plated steel sheet 100.
表面皮膜層107宜含有譬如平均粒徑0.10μm以上且5.00μm以下的ZnO粒子109與有機樹脂111,並且,上述ZnO粒子109的附著量以金屬Zn換算計宜為0.5g/m 2以上且10.0g/m 2以下。另,於母材101之兩面形成有Al系鍍敷層103時,可於至少單側的該鍍敷層上形成表面皮膜層107。 The surface coating layer 107 preferably contains, for example, ZnO particles 109 and organic resin 111 having an average particle size of 0.10 μm to 5.00 μm, and the adhesion amount of the ZnO particles 109 is 0.5 g / m 2 to 10.0 in terms of metal Zn. g / m 2 or less. When an Al-based plating layer 103 is formed on both sides of the base material 101, a surface film layer 107 can be formed on the plating layer on at least one side.
表面皮膜層107可使用譬如在水或有機溶劑等各種溶劑中混合上述各成分而得之液體來形成。 (ZnO粒子109)The surface film layer 107 can be formed using a liquid obtained by mixing the above components in various solvents such as water or an organic solvent. (ZnO particles 109)
為了在熱壓中獲得良好熱潤滑性,在Al系鍍敷層103上,平均粒徑0.10μm以上且5.00μm以下的ZnO粒子109以金屬Zn換算計宜以0.5g/m 2以上且10.0g/m 2以下的附著量來形成。ZnO粒子109會與模具點接觸,致使動摩擦係數降低而使熱潤滑性提升。然而,若ZnO粒子109的平均粒徑小於0.10μm,在壓製加工時ZnO粒子109與模具的接觸點會過多,而熱潤滑性不會充分提升。 In order to obtain good thermal lubricity during hot pressing, on the Al-based plating layer 103, the ZnO particles 109 having an average particle size of 0.10 μm or more and 5.00 μm or less are preferably 0.5 g / m 2 or more and 10.0 g in terms of metal Zn. / m 2 or less. The ZnO particles 109 will come into point contact with the mold, resulting in a reduction in the dynamic friction coefficient and an improvement in thermal lubricity. However, if the average particle diameter of the ZnO particles 109 is less than 0.10 μm, there will be too many contact points between the ZnO particles 109 and the mold during press processing, and the thermal lubricity will not be sufficiently improved.
另一方面,若ZnO粒子109的平均粒徑大於5.00μm,熔接性會惡化。雖然ZnO為絕緣性,但當粒徑小時,於熔接加壓時會被壓毀而能充分確保通電點。然而,若ZnO粒子109的平均粒徑變大且大於5μm,於熔接加壓時ZnO粒子109會變得不易被壓毀。其結果,會變得無法充分確保通電點且容易產生粉塵,故熔接性會惡化。On the other hand, if the average particle diameter of the ZnO particles 109 is larger than 5.00 μm, the weldability is deteriorated. Although ZnO is insulating, when the particle diameter is small, it will be crushed during welding and pressurization, which can sufficiently ensure the energization point. However, if the average particle diameter of the ZnO particles 109 becomes larger than 5 μm, the ZnO particles 109 become difficult to be crushed during welding and pressing. As a result, the energization point cannot be sufficiently secured and dust is easily generated, so that the weldability is deteriorated.
又,ZnO粒子109的平均粒徑之測定方法並無特別限定。只要利用譬如掃描型電子顯微鏡(SEM, Scanning Electron Microscope)等,以2000倍觀察任意10個以上的ZnO粒子109並測定各粒子的最大粒徑後,算出平均值而求取即可。或者亦可使用粒度分布測定裝置來求取ZnO粒子109的平均粒徑。The method for measuring the average particle diameter of the ZnO particles 109 is not particularly limited. For example, a scanning electron microscope (SEM, Scanning Electron Microscope) or the like may be used to observe arbitrary 10 or more ZnO particles 109 at 2000 times, measure the maximum particle size of each particle, and calculate the average value. Alternatively, the average particle diameter of the ZnO particles 109 may be determined using a particle size distribution measuring device.
而且,若表面皮膜層107的所有ZnO粒子109的附著量以金屬Zn換算計小於0.5g/m 2,在熱壓時便無法獲得充分的潤滑性。 In addition, if the adhesion amount of all the ZnO particles 109 in the surface coating layer 107 is less than 0.5 g / m 2 in terms of metal Zn, sufficient lubricity cannot be obtained during hot pressing.
另,於Al系鍍敷層103上之ZnO粒子109的附著量可藉由使用有XRF(螢光X射線,X-ray Fluorescence)之校準曲線法來測定。The amount of ZnO particles 109 deposited on the Al-based plating layer 103 can be measured by a calibration curve method using XRF (X-ray Fluorescence).
又,此處所謂的附著量係指在熱壓時,載置於輸送帶上加熱之前的附著量。 (有機樹脂111)The term "adhesion amount" used herein refers to the amount of adhesion before being placed on a conveyor belt and heated during hot pressing. (Organic resin 111)
表面皮膜層107之構成要素的有機樹脂111,只要是可發揮作為將ZnO粒子109保持於該皮膜中的黏合劑之機能之物,則無特別限定。這是因為有機樹脂111會在熱壓前的加熱時燃燒消失,而不會影響其後之處理即壓製加工或熔接等。當令有機樹脂111為水系之藥劑時,宜使用與ZnO同樣為弱鹼性且穩定的陽離子樹脂,可使用例如陽離子系胺甲酸酯樹脂或陽離子系丙烯酸樹脂。另,藥劑中之有機樹脂的濃度(g/kg)比率並未特別規定。此外,可作為有機樹脂111使用的樹脂為陽離子系胺甲酸酯樹脂(第一工業製藥公司製,製品名SUPERFLEX650)等。The organic resin 111 as a component of the surface film layer 107 is not particularly limited as long as it can function as a binder that holds the ZnO particles 109 in the film. This is because the organic resin 111 burns and disappears during heating before hot pressing, and does not affect subsequent processing such as pressing processing or welding. When the organic resin 111 is a water-based agent, a cationic resin that is weakly alkaline and stable like ZnO is preferably used. For example, a cationic urethane resin or a cationic acrylic resin can be used. The concentration (g / kg) ratio of the organic resin in the pharmaceutical is not particularly specified. The resin usable as the organic resin 111 is a cationic urethane resin (manufactured by Daiichi Kogyo Co., Ltd., product name SUPERFLEX650), and the like.
為了使有機樹脂111充分展現作為黏合劑之作用,以質量%計,宜設有機樹脂111相對於表面皮膜層107整體之含量為10%以上且在60%以下。若上述含量小於10%,便無法充分展現作為黏合劑之作用,致使加熱前的塗膜變得容易剝離。又,為了要穩定獲得作為黏合劑之作用,更宜設有機樹脂111之上述含量為15%以上。另一方面,若有機樹脂111的含量大於60%,加熱時產生令人不愉快之臭味的情形會變得明顯。In order for the organic resin 111 to fully exhibit its role as an adhesive, it is preferable to provide the organic resin 111 with a content of 10% or more and 60% or less with respect to the entire surface coating layer 107 in terms of mass%. If the content is less than 10%, the effect as an adhesive cannot be fully exhibited, and the coating film before heating becomes easily peeled. In addition, in order to stably obtain the effect as an adhesive, the above-mentioned content of the organic resin 111 is more preferably 15% or more. On the other hand, if the content of the organic resin 111 is more than 60%, it becomes obvious that an unpleasant odor is generated during heating.
於Al系鍍敷層103上形成表面皮膜層107的方法並無特別限定。表面皮膜層107可藉由以輥塗機或噴灑器等周知手法,將使上述各主成分溶解而得之水溶液或溶劑塗佈於Al系鍍敷層103上,並加以乾燥而形成。並且,在形成表面皮膜層107時,針對塗佈後的乾燥方法亦無特別限定,可使用熱風、IH(感應加熱)、NIR(近紅外線)、通電加熱等各方式。此外,針對乾燥之際的升溫溫度,宜考慮黏合劑即有機樹脂111之玻璃轉移溫度(Tg)作適當設定。 <製造方法>The method for forming the surface coating layer 107 on the Al-based plating layer 103 is not particularly limited. The surface film layer 107 can be formed by applying an aqueous solution or a solvent obtained by dissolving each of the main components described above to the Al-based plating layer 103 by a well-known method such as a roll coater or a sprayer, and drying it. In addition, when the surface coating layer 107 is formed, the drying method after coating is not particularly limited, and various methods such as hot air, IH (induction heating), NIR (near infrared), and electric heating can be used. In addition, for the heating temperature during drying, the glass transition temperature (Tg) of the organic resin 111, which is a binder, should be appropriately set. < Manufacturing method >
在此,簡單說明本發明之Al系鍍敷鋼板100的製造方法。Here, the manufacturing method of the Al-based plated steel sheet 100 of the present invention will be briefly described.
首先,將鋼板浸漬於以質量%計含有6%以上且15%以下的Si之Al鍍敷浴中,以形成鍍敷層(鍍敷步驟)。First, a steel plate is immersed in an Al plating bath containing Si in an amount of 6% to 15% by mass to form a plating layer (plating step).
母材的條件係與在[母材101]中所說明的條件相同。The conditions of the base material are the same as those described in [Base Material 101].
接著,將浸漬後的前述鋼板冷卻(冷卻步驟)。冷卻宜為氣冷。其係因為若為水霧冷卻,則表面粗度會變得過大,在蝕刻時要去除的鍍敷量就會增加。冷卻速度並無特別限定,但以5~15℃/秒為佳。Next, the steel sheet after the immersion is cooled (cooling step). Cooling should be air-cooled. This is because if the water mist is used for cooling, the surface roughness will become too large, and the amount of plating to be removed during etching will increase. The cooling rate is not particularly limited, but it is preferably 5 to 15 ° C / second.
接下來,將冷卻後之前述鋼板浸漬於pH1以下的酸性溶液中,蝕刻表層直至下述深度為止:鍍敷表面的Si面積率為12%以下,Al系鍍敷層之厚度方向的Si濃度分布之最大值以質量%計為15%以下,且Al系鍍敷層之厚度方向的Si濃度分布之最大值與Fe濃度在4質量%以下時的Si濃度之最小值的比為1.0以上且在2.0以下(蝕刻步驟)。Next, the aforementioned steel sheet after cooling is immersed in an acidic solution having a pH of 1 or less, and the surface layer is etched to the following depth: the Si area ratio of the plating surface is 12% or less, and the Si concentration distribution in the thickness direction of the Al-based plating layer The ratio of the maximum value by mass% is 15% or less, and the ratio of the maximum value of the Si concentration distribution in the thickness direction of the Al-based plating layer to the minimum value of the Si concentration when the Fe concentration is 4% by mass or less is 1.0 or more and less than 2.0 or less (etching step).
規定蝕刻條件之理由係如(厚度方向的Si濃度分布)中所說明。The reason for specifying the etching conditions is as described in (Si concentration distribution in the thickness direction).
如以上所說明,根據本發明之Al系鍍敷鋼板100(鋼板),可抑制Al系鍍敷層103表面的Si面積率,藉此便能抑制熱壓之加熱階段中生成Si濃度高之第2層,而可防止熱加工後塗裝後耐蝕性的惡化。而且,根據附加有表面皮膜層107之本實施形態之Al系鍍敷鋼板100,會因潤滑性優異之表面皮膜層107的存在,而可抑制於模具之黏附。就算Al系鍍敷層103因加熱而粉化,因潤滑性優異之表面皮膜層107的存在,而仍可抑制粉末(Al-Fe粉等)黏附於後續的壓製所使用之模具上。因此,當熱壓本實施形態之鋼板時,便不需要有去除黏附於模具上之Al-Fe粉之步驟等,而可實現優異生產性。As described above, according to the Al-based plated steel sheet 100 (steel sheet) of the present invention, the Si area ratio on the surface of the Al-based plated layer 103 can be suppressed, thereby suppressing the formation of a high Si concentration in the heating stage of hot pressing. Two layers to prevent deterioration of corrosion resistance after coating after hot working. In addition, according to the Al-based plated steel sheet 100 of the present embodiment to which the surface film layer 107 is added, the presence of the surface film layer 107 having excellent lubricity can suppress adhesion to the mold. Even if the Al-based plating layer 103 is pulverized by heating, the presence of the surface film layer 107 having excellent lubricity can prevent powder (Al-Fe powder, etc.) from adhering to the mold used for subsequent pressing. Therefore, when the steel sheet of this embodiment is hot-pressed, there is no need to remove the Al-Fe powder adhering to the mold and the like, and excellent productivity can be achieved.
實施例以下,藉由發明例更具體說明本發明之效果。惟,本發明並非僅限定於以下發明例所用之條件。 Examples Hereinafter, the effects of the present invention will be described more specifically with reference to the invention examples. However, the present invention is not limited only to the conditions used in the following invention examples.
使用表1所示化學成分(剩餘部分為Fe及無法避免之不純物)的冷軋鋼板(板厚1.4mm),以森吉米爾法於其兩面形成了Al系鍍敷層103。形成Al系鍍敷層103時的退火溫度約為800℃。於Al系鍍敷浴中,以質量%計係添加有0%以上且19%以下之Si,另外還含有從母材101溶出之Fe。以添加有抑制劑之鹽酸水溶液來使Al系鍍敷層103溶解後,利用高頻感應耦合電漿發光分光分析法(ICP)測定溶液中Al系鍍敷層103的Si量,而確認到分別為表2中記載之量。 [表1] An Al-based plating layer 103 was formed on both sides of the cold-rolled steel sheet (plate thickness of 1.4 mm) using the chemical composition shown in Table 1 (the remainder was Fe and unavoidable impurities) by the Senzimir method. The annealing temperature when forming the Al-based plating layer 103 is about 800 ° C. In the Al-based plating bath, Si is added in an amount of 0% to 19% by mass, and Fe is eluted from the base material 101. After the Al-based plating layer 103 was dissolved in an aqueous solution of hydrochloric acid to which an inhibitor was added, the amount of Si in the Al-based plating layer 103 in the solution was measured by high-frequency inductively coupled plasma emission spectrometry (ICP), and it was confirmed that The amounts are shown in Table 2. [Table 1]
以氣體抹拭法將Al系鍍敷層103對於母材101之附著量調整成單面160g/m 2。鍍敷凝固溫度區(凝固溫度±20℃間)中的平均冷卻速度,試樣編號1至18、20至22、24、25、28至33係以10℃/秒,試樣編號19、23係以22℃/秒來實施。試樣編號1至13係在形成前述Al系鍍敷層103後,不施行以鍍敷凝固後之酸洗所進行的溶解處理之物。另一方面,針對試樣編號14至25,係在將形成有Al系鍍敷層103之母材101冷卻後,於10%的硫酸溶液中浸漬30秒,試樣編號28係浸漬300秒,試樣編號29係浸漬250秒,試樣編號30係浸漬200秒,試樣編號31係浸漬150秒,試樣編號32係浸漬15秒,試樣編號33則浸漬5秒。 The adhesion amount of the Al-based plating layer 103 to the base material 101 was adjusted to 160 g / m 2 on one side by a gas wiping method. The average cooling rate in the plating solidification temperature zone (solidification temperature ± 20 ° C), sample numbers 1 to 18, 20 to 22, 24, 25, 28 to 33 are at 10 ° C / sec, and sample numbers 19, 23 It was performed at 22 ° C / sec. Sample Nos. 1 to 13 were obtained after forming the aforementioned Al-based plating layer 103, and were not subjected to a dissolution treatment by pickling after solidification of the plating. On the other hand, for sample numbers 14 to 25, after cooling the base material 101 on which the Al-based plating layer 103 was formed, it was immersed in a 10% sulfuric acid solution for 30 seconds, and sample number 28 was immersed for 300 seconds. Sample number 29 was immersed for 250 seconds, sample number 30 was immersed for 200 seconds, sample number 31 was immersed for 150 seconds, sample number 32 was immersed for 15 seconds, and sample number 33 was immersed for 5 seconds.
試樣編號26係設為水霧冷卻,並使用TiO粒子懸浮液、藉由粒子之凝固核生成與以水溶液進行之急冷來加快凝固速度,而促進了凝固。Sample No. 26 is water mist-cooled, and uses TiO particle suspension to accelerate the coagulation rate by coagulation nucleation of particles and rapid cooling with an aqueous solution to promote coagulation.
試樣編號27也係設為水霧冷卻,並使用VO粒子懸浮液,藉由粒子之凝固核生成與以水溶液進行之急冷來加快凝固速度,而促進了凝固。Sample No. 27 was also water mist-cooled, and VO particle suspension was used. The coagulation nucleation of particles and rapid cooling with an aqueous solution were used to accelerate the coagulation rate and promote coagulation.
試樣編號34係設為使用了蒸餾水的水霧冷卻。Sample No. 34 is water mist cooling using distilled water.
另,Al系鍍敷層103表面的Si面積率係以AES之區域分析進行了測定。The Si area ratio on the surface of the Al-based plating layer 103 was measured by AES region analysis.
之後,形成了表面皮膜層107。要形成表面皮膜層107之際,係將ZnO粒子109及有機樹脂111於溶劑中混合並調整而得溶液,將該溶液塗佈於Al系鍍敷層103上,並以到達板溫度80℃加以乾燥。如上述進行,而製得各試驗例之Al系鍍敷鋼板100。Thereafter, a surface coating layer 107 is formed. To form the surface coating layer 107, a solution was prepared by mixing and adjusting ZnO particles 109 and organic resin 111 in a solvent, and applying the solution to the Al-based plating layer 103, and applying the solution at a plate temperature of 80 ° C. dry. As described above, the Al-based plated steel sheet 100 of each test example was prepared.
接著,以以下方法評估如上述進行而製得之各試驗例鋼板的各種特性等。 (1)鍍敷粗度Next, various characteristics and the like of the steel sheets of each test example produced as described above were evaluated by the following methods. (1) Plating thickness
使用東京精密股份有限公司製之三維粗度計(製品名:SURFCOM 1900DX-3DF-12)來測定了算術平均粗度Ra。測定距離係設為30mm,並以3處測定點的平均值為鍍敷粗度。 (2)鍍敷附著量The arithmetic average roughness Ra was measured using a three-dimensional roughness meter (product name: SURFCOM 1900DX-3DF-12) manufactured by Tokyo Precision Co., Ltd. The measurement distance was set to 30 mm, and the average of three measurement points was used as the plating thickness. (2) Plating adhesion
依據JIS H 8672測定鍍敷前後之各試驗例的鋼板質量,並以將質量差除以試樣面積而得之值為鍍敷附著量g/m 2。 (3)Si面積率 The mass of the steel sheet of each test example before and after plating was measured in accordance with JIS H 8672, and the value obtained by dividing the difference in mass by the area of the sample was the plating adhesion amount g / m 2 . (3) Si area ratio
Al系鍍敷層103表面的Si面積率,係在鍍敷後使用日本電子製之JXA8500F,在5mm×5mm的視野中進行了EPMA(Electron Probe Micro Analyzer)之區域分析。此時,測定點為500點×500點,並以10μm間距且光束直徑為10μm來進行了測定。 (4)Si濃度The Si area ratio on the surface of the Al-based plating layer 103 was determined by performing area analysis of EPMA (Electron Probe Micro Analyzer) in a field of view of 5 mm × 5 mm using JXA8500F manufactured by Japan Electronics after plating. At this time, the measurement points were 500 points × 500 points, and the measurement was performed at a pitch of 10 μm and a beam diameter of 10 μm. (4) Si concentration
將切出為寬50mm×長50mm之各試驗例鋼板浸漬於添加有0.5質量%之抑制劑(杉村化學工業製HIBIRON Y-30)而成之10%硫酸水溶液中使鍍敷溶解後,以ICP將該溶解液作定量分析並利用校準曲線法測定了Si濃度。The steel plates of each test example cut out to a width of 50 mm by a length of 50 mm were immersed in a 10% sulfuric acid aqueous solution prepared by adding a 0.5% by mass inhibitor (HIBIRON Y-30 manufactured by Sugiura Chemical Industries) to dissolve the plating. The dissolved solution was quantitatively analyzed, and the Si concentration was measured by a calibration curve method.
以高頻GDS採取將Si強度換算成Si濃度之深度方向分布圖,並設最大值為鍍敷中厚度方向的Si濃度分布之最大值,且設Fe濃度在4質量%以下之區域中的最小值為鍍敷中的Si濃度分布之最小值。求取最大值與最小值的比為最大值/最小值。 (5)合金層厚度A high-frequency GDS is used to convert the Si intensity into the Si concentration depth distribution map, and set the maximum value to the maximum value of the Si concentration distribution in the thickness direction of the plating, and set the minimum Fe concentration in the area below 4% by mass. The value is the minimum value of the Si concentration distribution in the plating. Find the ratio of the maximum value to the minimum value as the maximum value / minimum value. (5) Alloy layer thickness
將切出為寬10mm×長30mm之各試驗例鋼板埋入樹脂中後,研磨截面並觀察了長方向的垂直截面。在20mm寬度中選出任意20點並測定合金層厚度後,以20點之平均值為合金層厚度。 (6)合金層剝離率Each test example steel plate cut out into a width of 10 mm × length of 30 mm was embedded in a resin, and then the cross section was ground to observe the vertical cross section in the longitudinal direction. After selecting any 20 points in a 20 mm width and measuring the thickness of the alloy layer, the average value of the 20 points was taken as the thickness of the alloy layer. (6) Stripping rate of alloy layer
在拉伸試驗中將寬30mm×長300mm之各試驗例鋼板加工成L方向延伸率為10%後,從L方向中央部將試樣切出寬10mm×長30mm並埋入樹脂中,然後研磨截面並觀察了L方向的垂直截面。統計在20mm寬度中散布的合金層剝離部位之寬度,並以下式所示之剝離率來進行評估。 合金層剝離率=(100×合金層剝離長度<mm>合計)/20<mm>In the tensile test, each test example steel plate having a width of 30 mm and a length of 300 mm was processed to have an elongation of 10% in the L direction. Then, a sample was cut from the central portion of the L direction to a width of 10 mm and a length of 30 mm and was embedded in the resin. Cross section and observed the vertical cross section in the L direction. The width of the peeling part of the alloy layer spread over a width of 20 mm was counted, and the peeling rate shown by the following formula was used for evaluation. Peeling rate of alloy layer = (100 × peeling length of alloy layer <mm> total) / 20 <mm>
合金剝離率係以小於15%為合格。 (7)ZnO消失試驗The alloy peeling rate is qualified as less than 15%. (7) ZnO disappearance test
將各試驗例之鋼板衝孔成30mmφ後,重疊於70mm×70mm的SiC製爐内台座上,並在載置有已加熱為900℃之50mm×50mm×70mm的SUS304鋼塊的狀態下,以900℃在爐加熱6分鐘,並於取出後立即夾於不鏽鋼製模具中進行急冷。利用XRF來測定加熱之前與之後的Zn附著量以測定Zn換算之Zn附著量,並算出了Zn換算之ZnO殘存率。The steel sheet of each test example was punched into 30 mmφ, and was superposed on a SiC furnace base of 70 mm × 70 mm, and a SUS304 steel block of 50 mm × 50 mm × 70 mm heated at 900 ° C. was placed in a state of It was heated in a furnace at 900 ° C. for 6 minutes, and immediately after being taken out, it was clamped in a stainless steel mold for rapid cooling. The amount of Zn deposited before and after heating was measured by XRF to measure the amount of Zn deposited in Zn conversion, and the ZnO residual ratio was calculated.
在表4所示評價中,係以Zn殘存率計在75%以上為合格,且以Zn殘存量計在0.40g/m 2以上為合格。 (8)點熔接性 In the evaluations shown in Table 4, a pass rate of 75% or more based on the Zn residual rate was acceptable, and a pass rate of 0.40 g / m 2 or more based on the Zn residual rate was acceptable. (8) Point welding
點熔接性係如以下進行評估。The spot weldability was evaluated as follows.
將所製作之各試驗例鋼板放入加熱爐内,以900℃在爐加熱6分鐘,並於取出後立即以不鏽鋼製模具夾住進行急冷。此時的冷卻速度約為150℃/秒。接著,將冷卻後之各鋼板剪切成30×50mm,並測定點熔接適當電流範圍(上限電流-下限電流)。測定條件如以下所示。下限電流係設為熔核徑成為3×(t) 0.5時的電流值,上限電流則設為發生噴濺之電流。 電流:直流 電極:鉻銅製、DR(前端6mmφ為40R) 加壓:400kgf(1kgf為9.8N) 通電時間:240毫秒 Each of the produced steel plates of the test examples was put into a heating furnace and heated in a furnace at 900 ° C. for 6 minutes, and immediately after being taken out, it was clamped in a stainless steel mold for rapid cooling. The cooling rate at this time was about 150 ° C / second. Next, each steel sheet after cooling was cut into 30 × 50 mm, and the appropriate current range (upper limit current-lower limit current) for point welding was measured. The measurement conditions are shown below. The lower limit current is set to a current value when the nugget diameter becomes 3 × (t) 0.5 , and the upper limit current is set to a current at which a splash occurs. Current: DC electrode: chrome-copper, DR (front end 6mmφ is 40R) pressure: 400kgf (1kgf is 9.8N) energizing time: 240 ms
上述之值越大意味著點熔接性越優異,且在表4所示評價中係以1.0kA以上為合格。 (9)熱加工後塗裝後耐蝕性The larger the value is, the better the spot weldability is. In the evaluation shown in Table 4, a pass of 1.0 kA or more is considered acceptable. (9) Corrosion resistance after coating after hot working
將200mm×200mm之各試驗例鋼板插入爐内,並以使評估面不接觸於SiC製之爐内台座上之方向來設置後,以900℃在爐加熱6分鐘再從爐內取出後,立即夾於不鏽鋼製模具(衝頭直徑50mm、肩部R3mm、壓料壓力500kg)中進行杯型加工至引深高度50mm為止,再進行急冷。此時之凸緣部冷卻速度約為150℃/秒。接下來,以日本帕卡濑精(股)有限公司製化學轉化處理液(PB-SX35)將冷卻後之杯狀的各鋼板進行化學轉化處理後,塗裝日本油漆(股)有限公司製電沉積塗料(Powernics110)使膜厚成為20μm,並以170℃進行燒附。另,將熔接有熱電偶的70mm×150mm之各鋼板插入已設定成900℃的大氣爐内,測量至變成900℃為止的溫度,並算出平均升溫速度而為5℃/秒。After inserting 200 mm × 200 mm steel plates of each test example into the furnace, and setting the evaluation surface so as not to contact the pedestal of the SiC furnace, it was heated at 900 ° C for 6 minutes and then taken out of the furnace. Clamped in a stainless steel mold (50mm punch diameter, shoulder R3mm, pressure of 500kg), cup-shaped processing to a depth of 50mm, and then quenched. The flange portion cooling rate at this time was about 150 ° C / second. Next, each of the cooled cup-shaped steel plates was subjected to chemical conversion treatment with a chemical conversion treatment liquid (PB-SX35) manufactured by Japan Pakase Seiki Co., Ltd., and then coated with electricity manufactured by Japan Paint Co., Ltd. The coating material (Powernics 110) was deposited to a thickness of 20 μm, and was fired at 170 ° C. In addition, each steel plate of 70 mm × 150 mm to which a thermocouple was fused was inserted into an atmospheric furnace set at 900 ° C., and the temperature until the temperature became 900 ° C. was measured, and the average temperature rise rate was calculated to be 5 ° C./second.
塗裝後耐蝕性評估係以汽車技術協會制定之JASO M609所規定之方法進行。亦即,事先以壓克力切刀於塗膜施以橫切,並測量腐蝕試驗180循環(60日)後的起自橫切之塗膜膨脹寬度(單側最大值)。The post-painting corrosion resistance evaluation is performed by the method prescribed by JASO M609 formulated by the Automobile Technology Association. That is, the coating film was cross-cut with an acrylic cutter in advance, and the swelling width (unilateral maximum value) of the coating film from the cross-cut after 180 cycles (60 days) of the corrosion test was measured.
熱加工後塗裝後耐蝕性係以小於7mm為合格。The corrosion resistance after coating after hot working is less than 7mm.
於表2顯示以上結果。 [表2] The above results are shown in Table 2. [Table 2]
結果顯示於表2。由表2明白可知:試樣編號14至25、31中,Al系鍍敷層103所含之Si量平均值在6%以上而合金層厚度變薄,其結果,合金層剝離率小於15%而加工性良好。並且,可知:Al系鍍敷層103表面的Si面積率在12%以下,鍍敷附著量在30g/m 2以上,Al系鍍敷層之厚度方向的Si濃度分布之最大值以質量%計為15%以下,且鍍敷中厚度方向的Si濃度之最大值與Fe濃度在4質量%以下之區域中之最小值的比為1.0以上且在2.0以下,故熱加工後塗裝後耐蝕性會小於7mm,而獲得良好結果。 The results are shown in Table 2. It is clear from Table 2 that in the sample numbers 14 to 25 and 31, the average amount of Si contained in the Al-based plating layer 103 is 6% or more and the alloy layer thickness is reduced. As a result, the alloy layer peeling rate is less than 15% The processability is good. In addition, it can be seen that the Si area ratio on the surface of the Al-based plating layer 103 is 12% or less, the plating adhesion amount is 30 g / m 2 or more, and the maximum value of the Si concentration distribution in the thickness direction of the Al-based plating layer is expressed as mass%. 15% or less, and the ratio of the maximum value of the Si concentration in the thickness direction to the minimum value of the Fe concentration in the region of 4% by mass or less in the plating is 1.0 or more and 2.0 or less, so the corrosion resistance after coating after hot working Will be less than 7mm, and good results are obtained.
此外,在熱壓後ZnO並未消失,而熔接性亦優異。In addition, ZnO did not disappear after hot pressing, and the weldability was also excellent.
相對於此,試樣編號1至3因Al系鍍敷層103所含之Si量平均值小於6%,致使合金層厚度變厚,其結果,合金層剝離率大於15%而加工性不良。並且,可知:試樣編號4至13因Al系鍍敷層103表面的Si面積率大於12%,故就熱加工後塗裝後耐蝕性而言並未獲得良好結果。試樣編號26、27因進行了水霧冷卻,導致表面粗度變得過大,而塗裝後耐蝕性惡化。On the other hand, in sample numbers 1 to 3, the average amount of Si contained in the Al-based plating layer 103 was less than 6%, which resulted in a thicker alloy layer. As a result, the peeling rate of the alloy layer was greater than 15% and the workability was poor. In addition, it can be seen that the sample numbers 4 to 13 do not give good results in terms of corrosion resistance after coating after hot working because the area ratio of Si on the surface of the Al-based plating layer 103 is greater than 12%. Sample Nos. 26 and 27 were subjected to water mist cooling, which caused the surface roughness to become too large, and the corrosion resistance after coating was deteriorated.
試樣編號28、29、30因鍍敷層是以酸洗而去除,故在加熱時有鏽皮生成,而熔接性與塗裝後耐蝕性惡化。Sample Nos. 28, 29, and 30, because the plating layer was removed by pickling, rust was formed during heating, and the weldability and corrosion resistance after coating deteriorated.
試樣編號32之厚度方向的Si濃度分布之最大值過大,而塗裝後耐蝕性不合格。The maximum value of the Si concentration distribution in the thickness direction of Sample No. 32 was too large, and the corrosion resistance after coating was unsatisfactory.
此外,試樣編號4至13、26、27、33、34,因鍍敷中厚度方向的Si濃度之最大值與Fe濃度在4質量%以下之區域中之最小值的比大於2.0,故熱壓後在熱壓時就會形成第2層,致使塗裝後耐蝕性惡化。In addition, for sample numbers 4 to 13, 26, 27, 33, and 34, the ratio of the maximum value of the Si concentration in the thickness direction to the minimum value of the Fe concentration in the region of 4% by mass or less in the plating is greater than 2.0, so it is hot. After pressing, a second layer is formed during hot pressing, which deteriorates the corrosion resistance after coating.
另,實施例1至3,雖然鍍敷中厚度方向的Si濃度之最大值與Fe濃度在4質量%以下之區域中之最小值的比大於2.0,但鍍敷中的Si濃度平均值低,因此並未形成第2相。但,合金層發生了剝離。In Examples 1 to 3, although the ratio of the maximum value of the Si concentration in the thickness direction to the minimum value in the region where the Fe concentration was 4% by mass or less was greater than 2.0, the average Si concentration in the plating was low. Therefore, the second phase is not formed. However, the alloy layer was peeled.
100‧‧‧Al系鍍敷鋼板100‧‧‧Al series plated steel plate
101‧‧‧母材101‧‧‧ mother material
103‧‧‧Al系鍍敷層103‧‧‧Al-based plating
107‧‧‧表面皮膜層107‧‧‧ surface coating
109‧‧‧ZnO粒子109‧‧‧ZnO particles
111‧‧‧有機樹脂111‧‧‧Organic resin
圖1係含Si之Al系鍍敷浴中的Si濃度與表面Si面積率之關係。Figure 1 shows the relationship between the Si concentration in the Si-containing Al-based plating bath and the surface Si area ratio.
圖2係在950℃下加熱0.5分鐘後的Al系鍍敷層截面之顯微鏡照片。Fig. 2 is a microscope photograph of a cross section of an Al-based plating layer after being heated at 950 ° C for 0.5 minutes.
圖3係針對Al、Si及Fe之圖2的深度方向之濃度分布圖,且從1至5之數值係表示與圖2中附有相同號碼之區域相對應之區域。FIG. 3 is a concentration distribution map in the depth direction of FIG. 2 for Al, Si, and Fe, and the values from 1 to 5 indicate the areas corresponding to the areas with the same numbers in FIG. 2.
圖4係於母材表面設置有Al系鍍敷層之本發明Al系鍍敷鋼板的截面示意圖。4 is a schematic cross-sectional view of an Al-based plated steel sheet of the present invention in which an Al-based plated layer is provided on the surface of a base material.
圖5係設置有Al系鍍敷層與表面皮膜層之本發明Al系鍍敷鋼板的截面示意圖。5 is a schematic cross-sectional view of an Al-based plated steel sheet of the present invention provided with an Al-based plated layer and a surface coating layer.
圖6係顯示鍍敷層之厚度方向的Si濃度分布的圖。FIG. 6 is a graph showing the Si concentration distribution in the thickness direction of the plating layer.
圖7係顯示鍍敷層之厚度方向的Si濃度分布的圖。FIG. 7 is a diagram showing the Si concentration distribution in the thickness direction of the plating layer.
圖8係顯示鍍敷層之厚度方向的Si濃度分布的圖。FIG. 8 is a graph showing the Si concentration distribution in the thickness direction of the plating layer.
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CN105051238A (en) * | 2013-03-27 | 2015-11-11 | 日新制钢株式会社 | Hot-dip galvanized steel plate with excellent coating adhesion and process for producing same |
WO2017168958A1 (en) * | 2016-03-31 | 2017-10-05 | Jfeスチール株式会社 | Thin steel sheet, plated steel sheet, method for producing hot-rolled steel sheet, method for producing cold-rolled full hard steel sheet, method for producing thin steel sheet, and method for producing plated steel sheet |
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TWI236968B (en) * | 1999-05-24 | 2005-08-01 | Nippon Steel Corp | Plated steel material, plated steel sheet and coated steel sheet excellent in corrosion resistance, and a method of producing the same |
CN105051238A (en) * | 2013-03-27 | 2015-11-11 | 日新制钢株式会社 | Hot-dip galvanized steel plate with excellent coating adhesion and process for producing same |
WO2017168958A1 (en) * | 2016-03-31 | 2017-10-05 | Jfeスチール株式会社 | Thin steel sheet, plated steel sheet, method for producing hot-rolled steel sheet, method for producing cold-rolled full hard steel sheet, method for producing thin steel sheet, and method for producing plated steel sheet |
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