JP3135818B2 - Manufacturing method of zinc-tin alloy plated steel sheet - Google Patents
Manufacturing method of zinc-tin alloy plated steel sheetInfo
- Publication number
- JP3135818B2 JP3135818B2 JP07073140A JP7314095A JP3135818B2 JP 3135818 B2 JP3135818 B2 JP 3135818B2 JP 07073140 A JP07073140 A JP 07073140A JP 7314095 A JP7314095 A JP 7314095A JP 3135818 B2 JP3135818 B2 JP 3135818B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- zinc
- bath
- steel sheet
- tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating With Molten Metal (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は亜鉛−錫系合金めっき鋼
板の製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a zinc-tin alloy plated steel sheet.
【０００２】[0002]
【従来の技術】従来、亜鉛−錫合金めっき鋼板は例え
ば、特開昭５２−１３０４３８号公報のように亜鉛およ
び錫イオンを含む溶液中で電解する電気めっき法で主と
して製造されてきた。また亜鉛−錫合金めっき鋼板は亜
鉛以外に錫を含むため耐蝕性や半田性に優れており、電
子部品等に多く使用されてきた。溶融めっき法ではめっ
き付着量を比較的容易に厚くすることができるため、溶
融めっき法で製造された製品は屋外用途等厳しい環境で
使用されている。例えば特開平４−２１４８４８号公報
では鉄系被めっき物に錫７０〜９８重量％の亜鉛−錫合
金めっきした被覆物やその製造法が開示されている。2. Description of the Related Art Conventionally, zinc-tin alloy plated steel sheets have been mainly produced by an electroplating method in which electrolysis is carried out in a solution containing zinc and tin ions as disclosed in Japanese Patent Application Laid-Open No. 52-130438. Zinc-tin alloy plated steel sheets have excellent corrosion resistance and solderability because they contain tin in addition to zinc, and have been widely used for electronic parts and the like. Since the coating weight can be relatively easily increased by the hot-dip plating method, products manufactured by the hot-dip plating method are used in severe environments such as outdoor applications. For example, Japanese Patent Application Laid-Open No. Hei 4-214848 discloses a coating obtained by plating an iron-based material with a zinc-tin alloy of 70 to 98% by weight of tin and a method for producing the same.
【０００３】特開平５−２６３２０８号公報では、鉄系
基材に溶融亜鉛または溶融亜鉛合金めっき層として錫を
含む合金層、または亜鉛とアルミニウムを含む合金層の
上にクロムめっき層で順次被覆された亜鉛系めっき被覆
物および製造法が開示されている。特開平３−２２９８
４６号公報では鉄系被めっき物が少なくても鉄および亜
鉛を含む合金層を介して亜鉛皮膜または亜鉛合金皮膜に
よって被覆されている溶融亜鉛めっき被覆物およびめっ
き方法を開示している。一方燃料タンク材料としてこれ
まで耐蝕性、加工性、ハンダ性、溶接性等の優れたＰｂ
−Ｓｎめっき鋼板等が主として用いられ実燃料タンクと
して使用実績を積み重ねてきた。[0003] In Japanese Patent Application Laid-Open No. 5-263208, an iron-based substrate is coated with a tin-containing alloy layer as a hot-dip zinc or hot-dip zinc alloy plating layer, or a chromium plating layer sequentially coated on an alloy layer containing zinc and aluminum. Zinc-based plating coatings and methods of manufacture are disclosed. JP-A-3-2298
No. 46 discloses a hot-dip galvanized coating material and a plating method in which an iron-based material to be plated is coated with a zinc film or a zinc alloy film via an alloy layer containing at least iron and zinc. On the other hand, as a fuel tank material, Pb with excellent corrosion resistance, workability, solderability, weldability, etc.
-Sn-plated steel sheets and the like are mainly used and have been used as actual fuel tanks.
【０００４】[0004]
【発明が解決しようとする課題】このような電気亜鉛−
錫めっき鋼板の使用によって耐蝕性や半田性は改善され
たものの、燃料タンクのような長期耐蝕性の要求される
環境には付着量を厚くしためっき鋼板が必要であるが、
電気めっき法における付着量の制御は時間と電流の大き
さに依存するため、付着量を厚くはできるが処理時間を
長くしたり、電流をたくさん流す必要があり、生産性や
経済的に大きな問題を生ずる。SUMMARY OF THE INVENTION
Corrosion resistance and solderability have been improved by using tin-plated steel sheets, but in environments where long-term corrosion resistance is required, such as fuel tanks, plated steel sheets with a large amount of adhesion are required.
Since the control of the amount of adhesion in the electroplating method depends on the time and the magnitude of the current, the amount of adhesion can be increased, but the processing time must be lengthened and a large amount of current needs to be applied, which is a major problem in terms of productivity and economy. Is generated.
【０００５】また溶融めっき法による錫−亜鉛めっき鋼
板の使用によって塩水噴霧においてもかなりの耐蝕性を
示しているが、そのめっき層の構造は棚状晶と柱状晶と
いった特徴のある鉄−亜鉛合金層が通常５〜３５μｍ
（その外側のめっき被覆層が５〜４０μｍ、好ましくは
１０〜３０μｍ）とめっき被覆層と同等以上も厚みがあ
って素地腐食抑制に関して合金層の寄与が非常に大きい
と共に、燃料タンクのような厳しい加工に関しては合金
層はめっき被覆層よりも硬度が高いためにこのような合
金層のめっき被覆層に対する比率が高く厚みが厚い場合
にはクラック等が入りやすく燃料タンク内外面の腐食進
展が遥かに起こりやすくなり、燃料タンク材料としては
不向きである。これらの製造に際しては３０秒〜３分程
度と長時間浴中に浸漬することが必要であり生産性や経
済的にも大きな問題を生ずる。[0005] The use of tin-zinc-coated steel sheets by hot-dip plating has shown considerable corrosion resistance even when sprayed with salt water, but the structure of the plating layer is an iron-zinc alloy having characteristics such as shelf crystals and columnar crystals. The layer is usually 5-35 μm
(The outer plating coating layer is 5 to 40 μm, preferably 10 to 30 μm) and has a thickness equal to or greater than that of the plating coating layer, and the contribution of the alloy layer with respect to the base corrosion inhibition is very large. Regarding the processing, since the alloy layer has higher hardness than the plating coating layer, when the ratio of such an alloy layer to the plating coating layer is high and the thickness is large, cracks and the like are likely to occur, and the corrosion progress on the inner and outer surfaces of the fuel tank is far It is easy to occur and is not suitable as a fuel tank material. In the production of these, it is necessary to immerse them in the bath for a long time of about 30 seconds to 3 minutes, which causes great problems in productivity and economy.
【０００６】さらに鉄系基材が亜鉛または亜鉛合金層と
クロムめっき層の順次被覆された場合についてはクロム
被覆層も加わり耐蝕性等がさらに向上するが、亜鉛また
は亜鉛合金層の厚みが５〜７５μｍ、好ましくは１０〜
５０μｍ、さらに好ましくは１０〜３０μｍと非常に厚
く、上記と同様に、合金層による耐蝕性の確保と共に、
溶融亜鉛めっき時に素地鉄が合金層中に含有され亜鉛−
鉄合金層が厚く生成するため硬度が上昇し、加工性が大
幅に低下し燃料タンク材料には不向きである。これらの
製造に際して浴浸漬時間は例えば、１秒〜５分程度、好
ましくは１５秒〜２分程度である。これは耐蝕性を確保
することが主目的であることから厚みは耐蝕性を損なわ
ない程度確保する必要があり、めっき金属での被覆後の
プレス加工等の成形性を考慮したものではない。Further, when the iron-based substrate is coated with a zinc or zinc alloy layer and a chromium plating layer sequentially, a chromium coating layer is added to further improve the corrosion resistance and the like, but the thickness of the zinc or zinc alloy layer is 5 to 5. 75 μm, preferably 10
50 μm, more preferably 10 to 30 μm, which is very thick.
The base iron is contained in the alloy layer during hot-dip galvanizing and zinc-
Since the iron alloy layer is formed to be thick, the hardness increases, the workability is greatly reduced, and it is not suitable for a fuel tank material. In these productions, the bath immersion time is, for example, about 1 second to 5 minutes, preferably about 15 seconds to 2 minutes. Since the main purpose is to ensure the corrosion resistance, the thickness needs to be secured to the extent that the corrosion resistance is not impaired, and does not consider the formability such as press working after coating with the plated metal.
【０００７】Ｐｂ−Ｓｎめっき鋼板の使用においては、
車の寿命を満足する耐蝕性、車底部の複雑な構造に合っ
た加工のできること、燃料タンク部品を接合できるハン
ダ性、溶接性が確保されたもののシュレッダーダスト等
の産業廃棄物からのＰｂ溶出規制等の環境規制に対して
はＰｂが含まれていることから使用は好ましくない。そ
こで本発明では安価にかつ性能に優れた亜鉛−錫系合金
めっき鋼板の溶融めっき法を提供するものである。[0007] In the use of Pb-Sn plated steel sheet,
Corrosion resistance that satisfies the service life of the car, ability to process in accordance with the complex structure of the bottom of the car, solderability for joining fuel tank parts, and Pb elution regulation from industrial waste such as shredder dust, while ensuring weldability It is not preferable to use Pb due to environmental regulations such as Pb. Therefore, the present invention provides a hot-dip galvanizing method of a zinc-tin-based alloy-coated steel sheet which is inexpensive and excellent in performance.
【０００８】[0008]
【課題を解決するための手段】本発明者らは安価でかつ
性能に優れた亜鉛−錫合金めっき鋼板の提供を目的に種
々検討したところ、前処理法および冷却条件を検討する
ことによって溶融めっき法にて亜鉛−錫合金めっき鋼板
を製造できることを見いだしたものである。その要旨
は、 （１） 焼鈍済の鋼板に、ＮｉまたはＮｉ−Ｆｅ系プレ
めっきをＮｉ含有量で片面当たり０．１〜３．０ｇ／m2
行い、塩酸を含有した塩素換算量で２〜４５ｗｔ％のフ
ラックスを塗布し、錫：４０〜９８ｗｔ％残部亜鉛およ
び不可避的不純物からなる浴で、融点＋２０〜＋３００
℃の浴温で浴中に１．５〜１５秒未満浸漬しめっきする
ことを特徴とする亜鉛−錫合金めっき鋼板の製造法にあ
る。The present inventors have conducted various studies with the aim of providing a zinc-tin alloy-coated steel sheet which is inexpensive and excellent in performance. It has been found that a zinc-tin alloy plated steel sheet can be manufactured by the method. The gist is as follows: (1) Ni or Ni-Fe-based pre-plating is applied to an annealed steel sheet at a Ni content of 0.1 to 3.0 g / m 2 per one side.
Then, a flux of 2 to 45 wt% in terms of chlorine containing hydrochloric acid is applied, and tin: 40 to 98 wt% in a bath composed of zinc and unavoidable impurities, melting point +20 to +300.
A method for producing a zinc-tin alloy-plated steel sheet, characterized by immersing in a bath at a bath temperature of 1.5 ° C for less than 1.5 to 15 seconds and plating.
【０００９】（２） 焼鈍済の鋼板に、ＮｉまたはＮｉ
−Ｆｅ系プレめっきをＮｉ含有量で片面当たり０．１〜
３．０ｇ／m2を行い、塩酸を含有した塩素換算量で２〜
４５ｗｔ％のフラックスを塗布し、錫：４０〜９８ｗｔ
％残部亜鉛および不可避的不純物からなる浴で、融点＋
２０〜＋３００℃の浴温で浴中に１．５〜１５秒未満浸
漬しめっきを行い、前記浴中のＺｎ含有量が８．８ｗｔ
％より多い場合、冷却速度２０℃/sec以上の冷却速度で
冷却することを特徴とする亜鉛−錫合金めっき鋼板の製
造法にある。(2) Ni or Ni is added to the annealed steel sheet.
-Fe-based pre-plating with Ni content of 0.1 to 0.1 per side
3.0 g / m 2 , and 2 to 2 in terms of chlorine containing hydrochloric acid
45wt% flux is applied, tin: 40-98wt
% Bath with zinc and unavoidable impurities, melting point +
The bath is immersed in a bath at a bath temperature of 20 to + 300 ° C. for less than 1.5 to 15 seconds to perform plating, and the Zn content in the bath is 8.8 wt.
%, The cooling rate is at a cooling rate of 20 ° C./sec or more.
【００１０】以下に本発明について詳細に説明する。鋳
片から熱間圧延、酸洗、冷間圧延等の熱処理、圧延等を
行った後、焼鈍を行った、焼鈍済の鋼板を通常脱脂、酸
洗して被めっき材として使用し、前処理を行った後、亜
鉛−錫めっきを行い、付着量の制御、冷却をして亜鉛−
錫めっき鋼板を製造する。亜鉛−錫めっきでは錫中の亜
鉛含有量が増加することによって濡れ性が低下し、特に
亜鉛が８．８ｗｔ％の共晶点近傍では濡れにくい為、亜
鉛−錫合金めっき浴と鋼板の濡れ性を向上させる必要が
ある。濡れ性を向上させるためには浴温を高めること、
通板速度を遅くすること、鋼板表面を活性にする前処理
をすることが上げられる。この中では鋼板表面を活性化
するための前処理が特に重要である。Hereinafter, the present invention will be described in detail. After performing heat treatment such as hot rolling, pickling, and cold rolling from a slab, rolling, etc., annealed, the annealed steel sheet is usually degreased, pickled, used as a material to be plated, and pre-treated. After that, zinc-tin plating is performed, the amount of coating is controlled, and cooling is performed.
Manufactures tin-plated steel sheets. In the zinc-tin plating, the wettability decreases due to the increase of the zinc content in the tin, and the wettability between the zinc-tin alloy plating bath and the steel sheet is particularly difficult because the zinc is hardly wet near the eutectic point of 8.8 wt%. Need to be improved. Raise the bath temperature to improve wettability,
It is possible to reduce the passing speed and perform a pretreatment for activating the steel sheet surface. Among them, pretreatment for activating the steel sheet surface is particularly important.
【００１１】前処理法としてプレめっきおよびフラック
ス種類、条件が影響する。プレめっきではＮｉまたはＮ
ｉ−Ｆｅ系が亜鉛−錫合金めっき浴との組み合わせにお
いて濡れ性向上効果が極めて大きい、付着量はＮｉ含有
量で０．１ｇ／m2未満では被覆性が充分でないため濡れ
性向上効果が小さい。３．０ｇ／m2を超えて付着すると
濡れ性が飽和すると共にめっき層と鋼界面に合金層が厚
く生成しタンクに成形した時のめっき密着性が低下す
る。従ってプレめっき量はＮｉ含有量で０．１〜３．０
ｇ／m2とした。[0011] As a pretreatment method, the type of pre-plating, flux and conditions are affected. Ni or N for pre-plating
When the i-Fe system is used in combination with a zinc-tin alloy plating bath, the effect of improving wettability is extremely large. When the amount of Ni is less than 0.1 g / m 2 in Ni content, the effect of improving wettability is small because coverage is insufficient. . If the adhesion exceeds 3.0 g / m 2 , the wettability will be saturated, and a thick alloy layer will be formed at the interface between the plating layer and the steel, and the plating adhesion when molded into a tank will decrease. Therefore, the pre-plating amount is 0.1 to 3.0 in Ni content.
g / m 2 .
【００１２】フラックスではＺｎＣｌ2、ＨＣｌ等の塩
素イオンを含むフラックスが濡れ性向上に効果的であっ
た。フラックス中の塩素換算量が２ｗｔ％未満では被め
っき材表面の酸化皮膜溶解性が低く濡れ性の向上効果は
小さい。４５ｗｔ％を超えて濃度が高いと効果が飽和す
ると共に使用薬品量が多くなりすぎ不経済である。この
時望ましくはＨＣｌを０．１％以上添加すると被めっき
材表面の酸化皮膜が溶解しやすく濡れ性が更に向上す
る。従ってフラックス中に塩酸を含有した塩素換算量で
２〜４５ｗｔ％のフラックスを塗布とした。The flux containing chlorine ions such as ZnCl 2 and HCl was effective in improving the wettability. If the amount of chlorine in the flux is less than 2 wt%, the solubility of the oxide film on the surface of the material to be plated is low, and the effect of improving the wettability is small. If the concentration is higher than 45 wt%, the effect is saturated and the amount of chemicals used is too large, which is uneconomical. At this time, if 0.1% or more of HCl is desirably added, the oxide film on the surface of the material to be plated is easily dissolved, and the wettability is further improved. Therefore, a flux containing 2-45 wt% in terms of chlorine containing hydrochloric acid in the flux was applied.
【００１３】浴温についてはかなり適正範囲が広いが濡
れ性は高い方が有利である。融点＋２０℃未満では反応
性が低く、不めっきや密着性不良が発生しやすい。＋３
００℃超では濡れ性は飽和すると共に、めっきが流れや
すく外観不良を起こしやすい。従って浴温は融点＋２０
〜＋３００℃とした。浴中浸漬時間はめっき浴と鋼との
めっき反応程度と関連し、浸漬時間が長い方が合金層が
厚く生成し耐蝕性確保の点では有利であるが、加工時の
めっき密着性を逆に低下させる原因となるため、燃料タ
ンク用には極力薄くする必要がある。したがってめっき
密着性を確保する程度の薄い合金層であることが望まし
く、浸漬時間の上限を定め１５秒未満とした。The bath temperature has a fairly wide range, but a higher wettability is advantageous. If the melting point is lower than + 20 ° C., the reactivity is low, and non-plating and poor adhesion are likely to occur. +3
If the temperature is higher than 00 ° C., the wettability is saturated, and the plating is liable to flow, resulting in poor appearance. Therefore, the bath temperature is melting point +20.
To + 300 ° C. The immersion time in the bath is related to the degree of the plating reaction between the plating bath and the steel, and a longer immersion time is more advantageous in terms of forming a thicker alloy layer and ensuring corrosion resistance. It is necessary to make it as thin as possible for fuel tanks, because it causes a decrease. Therefore, it is desirable that the alloy layer be thin enough to secure plating adhesion, and the upper limit of the immersion time is set to less than 15 seconds.
【００１４】浴成分に関しては、燃料タンク内外面耐蝕
性、加工時のめっき密着性、ハンダ性、溶接性を考慮す
ると、亜鉛含有量が６０ｗｔ％より多い場合、劣化ガソ
リン等燃料タンク内の耐蝕性およびハンダ性が懸念され
る。亜鉛含有量が２ｗｔ％未満ではＺｎ含有量が少ない
ためタンク外面の耐蝕性が懸念される。従って錫：４０
〜９８ｗｔ％残部亜鉛および不可避的不純物からなる浴
とした。冷却速度については、図１の様にめっき浴中Ｚ
ｎ含有量が８．８ｗｔ％より多い場合、２０℃/sec未満
ではめっき後の冷却過程で粗大な亜鉛晶が析出するた
め、加工時のめっき層の割れや粗大な亜鉛晶の優先腐食
によってタンク内外面の局部的に腐食が懸念される。従
って冷却速度は２０℃/sec以上とした。Regarding the bath components, considering the corrosion resistance inside and outside the fuel tank, plating adhesion during processing, solderability and weldability, when the zinc content is more than 60 wt%, the corrosion resistance in the fuel tank such as deteriorated gasoline is considered. And solderability is a concern. If the zinc content is less than 2 wt%, the Zn content is small, and there is concern about the corrosion resistance of the tank outer surface. Therefore tin: 40
The bath was made up of ~ 98 wt% balance zinc and unavoidable impurities. As for the cooling rate, as shown in FIG.
If the n content is more than 8.8 wt%, if the temperature is less than 20 ° C./sec, coarse zinc crystals will precipitate during the cooling process after plating, so the tank will be damaged by cracking of the plating layer during processing and preferential corrosion of the coarse zinc crystals. There is a concern about local corrosion of the inner and outer surfaces. Therefore, the cooling rate was set to 20 ° C./sec or more.
【００１５】[0015]
【実施例】以下に本発明法により製造される亜鉛−錫合
金めっき鋼板の実施例を述べる。鋳片から熱間圧延、酸
洗、冷間圧延した後、焼鈍した材料を被めっき材とし
た。また一部は焼鈍後、プレめっきした材料を被めっき
材とした。その後、フラックスを塗布しＳｎ−Ｚｎ浴に
通じ付着量を調整し、巻き取った。表１〜表３に各種操
業条件とめっき後の不めっき状態、めっき密着性を示
す。なおめっき後の冷却は２０℃/sec以上で行ってい
る。表１〜表３に示す様なＮo.１〜Ｎo.５２の操業条件
の基に製造した試料は不めっき、めっき剥離も無く良好
な結果であった。一方、Ｎo.５３〜Ｎo.６３の操業条件
で製造した試料は不めっき、めっき密着性に何らかの問
題があった。EXAMPLES Examples of zinc-tin alloy plated steel sheets produced by the method of the present invention will be described below. After hot rolling, pickling and cold rolling from the slab, the annealed material was used as the material to be plated. In addition, a material that was partially pre-plated after annealing was used as a material to be plated. Thereafter, a flux was applied, and the flux was applied to a Sn-Zn bath to adjust the amount of the applied flux, and the resultant was wound. Tables 1 to 3 show various operating conditions, unplated state after plating, and plating adhesion. The cooling after plating is performed at 20 ° C./sec or more. Samples manufactured under the operating conditions of Nos. 1 to 52 as shown in Tables 1 to 3 showed good results without non-plating and plating peeling. On the other hand, the samples manufactured under the operating conditions of No. 53 to No. 63 had some problems in non-plating and plating adhesion.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】[0018]
【表３】 [Table 3]
【００１９】・不めっき評点／肉眼観察 ◎ 不めっきなし △ 微小不めっきあり × 小さな不めっきあり ・めっき密着性評点／円筒プレス（ブランク系７０mm、
絞り深さ１５mm）の外側面のテーピング ◎ めっき剥離なし △ 微小めっき剥離あり × 小さなめっき剥離あり ＊プレめっき量はＮｉ含有量で示した。Non-plating rating / visual observation ◎ No plating △ Small non-plating × Small non-plating ・ Plating adhesion rating / Cylinder press (blank 70mm,
Taping of the outer surface with a drawing depth of 15 mm) ◎ No plating peeling △ Small plating peeling × Small plating peeling * Pre-plating amount is indicated by Ni content.
【００２０】表４〜表６に各種操業条件とめっき層中の
亜鉛結晶状態を示す。表４〜表６に示す様なＮo.１〜Ｎ
o.５２の操業条件の基に製造した試料はめっき層表面の
Ｚｎ分布状況を観察したところ、めっき密着性、耐蝕性
に影響を及ぼす長さ２５０μｍ以上のＺｎ晶が２０個以
下／０．０１mm2と非常に少なかった。Ｎo.５３〜６３
の操業条件で造られた試料は長さの長いＺｎ結晶の密度
が高かった。Tables 4 to 6 show various operating conditions and zinc crystal states in the plating layer. Nos. 1 to N as shown in Tables 4 to 6
Observation of the Zn distribution on the surface of the plating layer of the sample manufactured under the operating conditions of o.52 showed that the number of Zn crystals having a length of 250 μm or more that affected plating adhesion and corrosion resistance was 20 or less / 0.01 mm. 2 and very few. No.53-63
The sample made under the above operating conditions had a high density of long Zn crystals.
【００２１】[0021]
【表４】 [Table 4]
【００２２】[0022]
【表５】 [Table 5]
【００２３】[0023]
【表６】 [Table 6]
【００２４】・めっき層中Ｚｎ分布状況の評点／ＳＥＭ
によるめっき層表面観察による粗大Ｚｎ晶の面積率 ◎ 長さ２５０μｍ以上のＺｎ晶が２０個以下／０．２
５mm2 △ 長さ２５０μｍ以上のＺｎ晶が２０〜５０個以下／
０．２５mm2 × 長さ２５０μｍ以上のＺｎ晶が５０個より多／０．
２５mm2 ＊プレめっき量はＮｉ含有量で示した。Rating of Zn distribution in plating layer / SEM
Area ratio of coarse Zn crystals observed by plating layer surface observation by ◎ 20 Zn crystals having a length of 250 μm or more / 20 or less / 0.2
5 mm 2 △ 20 to 50 Zn crystals with a length of 250 μm or more /
0.25 mm 2 × More than 50 Zn crystals with a length of 250 μm or more / 50.
25 mm 2 * Pre-plating amount is indicated by Ni content.
【００２５】[0025]
【発明の効果】以上述べたように、本発明により安価
で、かつめっき密着性等性能の極めて優れた亜鉛−錫系
合金めっき鋼板を溶融めっき法で製造することが可能と
なった。As described above, according to the present invention, it is possible to manufacture a zinc-tin-based alloy-coated steel sheet which is inexpensive and has extremely excellent performance such as plating adhesion by a hot-dip plating method.
【図１】めっき後の冷却過程で粗大な亜鉛晶の析出する
状況を示す顕微鏡写真である。FIG. 1 is a photomicrograph showing a situation in which coarse zinc crystals precipitate during a cooling process after plating.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡田 伸義 福岡県北九州市戸畑区飛幡町１番１号 新日本製鐵株式会社 八幡製鐵所内 (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 2/00 - 2/40 ──────────────────────────────────────────────────続 き Continued from the front page (72) Inventor Nobuyoshi Okada 1-1, Hibata-cho, Tobata-ku, Kitakyushu-shi, Fukuoka Nippon Steel Corporation Yawata Works (58) Fields surveyed (Int. Cl. 7 , DB Name) C23C 2/00-2/40
Claims (2)
系プレめっきをＮｉ含有量で片面当たり０．１〜３．０
ｇ／m2行い、塩酸を含有した塩素換算量で２〜４５ｗｔ
％のフラックスを塗布し、錫：４０〜９８ｗｔ％残部亜
鉛および不可避的不純物からなる浴で、融点＋２０〜＋
３００℃の浴温で浴中に１．５〜１５秒未満浸漬しめっ
きすることを特徴とする亜鉛−錫合金めっき鋼板の製造
法。1. An annealed steel sheet is made of Ni or Ni-Fe.
System pre-plating 0.1 to 3.0 per one side in Ni content
g / m 2 , 2 to 45 wt.
% Flux, tin: 40-98 wt% in a bath consisting of zinc and unavoidable impurities, melting point + 20- +
A method for producing a zinc-tin alloy-plated steel sheet, comprising immersing in a bath at a bath temperature of 300 ° C. for 1.5 to less than 15 seconds and plating.
系プレめっきをＮｉ含有量で片面当たり０．１〜３．０
ｇ／m2行い、塩酸を含有した塩素換算量で２〜４５ｗｔ
％のフラックスを塗布し、錫：４０〜９８ｗｔ％残部亜
鉛および不可避的不純物からなる浴で、融点＋２０〜＋
３００℃の浴温で浴中に１．５〜１５秒未満浸漬しめっ
きを行い、前記浴中のＺｎ含有量が８．８ｗｔ％より多
い場合、冷却速度２０℃/sec以上の冷却速度で冷却する
ことを特徴とする亜鉛−錫合金めっき鋼板の製造法。2. An annealed steel sheet is made of Ni or Ni-Fe.
System pre-plating 0.1 to 3.0 per one side in Ni content
g / m 2 , 2 to 45 wt.
% Flux, tin: 40-98 wt% in a bath consisting of zinc and unavoidable impurities, melting point + 20- +
When the Zn content in the bath is more than 8.8 wt%, the plating is performed at a cooling rate of 20 ° C./sec or more when the bath is immersed in the bath at a bath temperature of 300 ° C. for less than 1.5 to 15 seconds for plating. A method for producing a zinc-tin alloy-plated steel sheet.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07073140A JP3135818B2 (en) | 1995-03-30 | 1995-03-30 | Manufacturing method of zinc-tin alloy plated steel sheet |
| DE1996637118 DE69637118T2 (en) | 1995-03-28 | 1996-03-28 | CORROSION-RESISTANT STEEL SHEET FOR FUEL TANK AND METHOD FOR PRODUCING THE LEAD |
| US08/750,073 US5827618A (en) | 1995-03-28 | 1996-03-28 | Rust-proofing steel sheet for fuel tanks and production method thereof |
| EP96907700A EP0763608B1 (en) | 1995-03-28 | 1996-03-28 | Rust-preventive steel sheet for fuel tank and process for producing the sheet |
| PCT/JP1996/000835 WO1996030560A1 (en) | 1995-03-28 | 1996-03-28 | Rust-preventive steel sheet for fuel tank and process for producing the sheet |
| EP20040018756 EP1477582A3 (en) | 1995-03-28 | 1996-03-28 | Rust-proofing steel sheet for fuel tanks and production method thereof |
| AU51219/96A AU686502B2 (en) | 1995-03-28 | 1996-03-28 | Rust-preventive steel sheet for fuel tank and process for producing the sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07073140A JP3135818B2 (en) | 1995-03-30 | 1995-03-30 | Manufacturing method of zinc-tin alloy plated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08269662A JPH08269662A (en) | 1996-10-15 |
| JP3135818B2 true JP3135818B2 (en) | 2001-02-19 |
Family
ID=13509608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07073140A Expired - Lifetime JP3135818B2 (en) | 1995-03-28 | 1995-03-30 | Manufacturing method of zinc-tin alloy plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3135818B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284122B1 (en) * | 1998-06-09 | 2001-09-04 | International Lead Zinc Research Organization, Inc. | Production of a zinc-aluminum alloy coating by immersion into molten metal baths |
| KR20080019265A (en) * | 2005-07-05 | 2008-03-03 | 신닛뽄세이테쯔 카부시키카이샤 | Hot-dip sn-zn system coated steel sheet having good corrosion resistance |
| JP5779847B2 (en) * | 2009-07-29 | 2015-09-16 | Ｊｆｅスチール株式会社 | Manufacturing method of high-strength cold-rolled steel sheets with excellent chemical conversion properties |
| JP6260413B2 (en) * | 2014-04-01 | 2018-01-17 | 新日鐵住金株式会社 | Tin-galvanized steel sheet and its manufacturing method |
| WO2019122959A1 (en) * | 2017-12-19 | 2019-06-27 | Arcelormittal | A hot-dip coated steel substrate |
-
1995
- 1995-03-30 JP JP07073140A patent/JP3135818B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08269662A (en) | 1996-10-15 |
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