JPH0353053A - Production of zn-al alloy plated steel sheet - Google Patents
Production of zn-al alloy plated steel sheetInfo
- Publication number
- JPH0353053A JPH0353053A JP18835489A JP18835489A JPH0353053A JP H0353053 A JPH0353053 A JP H0353053A JP 18835489 A JP18835489 A JP 18835489A JP 18835489 A JP18835489 A JP 18835489A JP H0353053 A JPH0353053 A JP H0353053A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- alloy
- plated steel
- plating
- resistance
- 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.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 43
- 239000010959 steel Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 title 1
- 238000007747 plating Methods 0.000 claims abstract description 42
- 229910007570 Zn-Al Inorganic materials 0.000 claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 238000007598 dipping method Methods 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 23
- 238000005275 alloying Methods 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 abstract description 21
- 238000005260 corrosion Methods 0.000 abstract description 21
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 235000005074 zinc chloride Nutrition 0.000 abstract description 2
- 239000011592 zinc chloride Substances 0.000 abstract description 2
- 239000011686 zinc sulphate Substances 0.000 abstract description 2
- 235000009529 zinc sulphate Nutrition 0.000 abstract description 2
- 238000003853 Pinholing Methods 0.000 abstract 2
- 229910001297 Zn alloy Inorganic materials 0.000 abstract 1
- 239000010960 cold rolled steel Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012733 comparative method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 241000473391 Archosargus rhomboidalis Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Coating With Molten Metal (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、建材用、自動車車体用等に用いられるＺｎ−
Ａｊ！合金めっき鋼板の製造方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to Zn-
Aj! This invention relates to a method for producing alloy plated steel sheets.
（従来の技術）
近年、建材用鋼板あるいは自動車車体用鋼板の分野にお
いて表面処理鋼板の採用が増加しているが、それに伴い
それらの鋼板の防錆性の向上に対する要求が高まりつつ
ある。自動車防錆鋼板の場合、特に冬季に融雪塩を敗布
する北米においてその要求が非常に強い。(Prior Art) In recent years, the use of surface-treated steel sheets has been increasing in the fields of steel sheets for building materials and steel sheets for automobile bodies, and along with this, there has been an increasing demand for improved rust prevention properties of these steel sheets. In the case of automobile rust-proof steel sheets, there is a strong demand for this, especially in North America, where snow melting salt is used in the winter.
従来より、自動車車体の防錆力を強化するため表面処理
鋼板が多量に使用されているが、最近では車体用鋼板の
耐孔あき性をｌＯ年間保証することが要求されており、
このような要求に対しては、従来の表面処理鋼板では対
応が極めて難しい。即ち、従来よりＮｉ−Ｚｎｆｌ気め
っき鋼板や、Ｆｅ−Ｚｎ電気めっき鋼仮、さらには電気
亜鉛めっき鋼板等が防錆鋼板として用いられているが、
これらの電気めっき鋼仮においては、めっき付着量は一
般に２０〜３０ｇ／ｍ”で、耐孔あき性に対する前記の
要求を満たすにはその倍以上の付着量が必要とされてい
る．なお、孔あきとは、塗装欠陥部、めっき欠陥部、あ
るいは傷つき部分、もしくは塗装付き廻りの不十分な部
分から鋼板の腐食が進行して孔食を生し、場合によって
は鋼板を貫通する現象である．ところで、電気めっき調
板はめっき付着量の増加と共に製造費が著しく上昇する
ため、電気めっき鋼板のめっき付着量を増加させて耐孔
あき性を向上させることはコスト面から極めて難しい．
これに対して、溶融めっきプロセスで製造される溶融め
っき鋼板（以下、ＨＤＳと略記する）あるいはめっき後
更に加熱合金化処理を施した合金化溶融亜鉛めっき鋼板
（以下、ＧＡと略記する）は、電気めっきｍ仮に比較す
るとめっき付着量の増加に伴うコストの増加が比較的少
ない，ＨＤＳは溶接性の点などから自動車用に使用され
ることは少ないが、ＧＡは従来より４５ｇ／ｍ”程度の
付着量のものがかなり使用されてきた経緯もあり、厚目
付化によって（例えば、付着量を片面当たり６０ｇ／ｓ
＋”とする）上記の耐孔あき性に対する要求に対応しよ
うとする試みもなされている．
しかし、ＧＡは従来からプレス戒形性において比較的難
点の多い素材とされており、事実戒形時に生じるフレー
キング、パウダリングと称されるめっき皮膜の剥離が問
題視されてきた．この加工時の剥離は一般にめっき付着
量の増加と共に著しくなるため、ＧＡの厚日付化は従来
にも増して戒形過程におけるトラブルの増加を招く可能
性が大きい。そのうえスポット溶接性の観点からも付着
量の増加はあまり好ましいものと言えない。Conventionally, surface-treated steel sheets have been used in large quantities to strengthen the rust prevention ability of automobile bodies, but recently there has been a demand for the perforation resistance of steel sheets for car bodies to be guaranteed for 10 years.
It is extremely difficult to meet such demands with conventional surface-treated steel sheets. That is, conventionally Ni-Znfl galvanized steel sheets, Fe-Zn electroplated steel sheets, and even electrogalvanized steel sheets have been used as rust-proof steel sheets.
For these electroplated steels, the coating weight is generally 20 to 30 g/m'', and in order to meet the above requirements for porosity resistance, a coating weight of more than twice that is required. Perforation is a phenomenon in which corrosion of a steel plate progresses from paint defects, plating defects, scratched areas, or areas with insufficient coating, resulting in pitting corrosion, and in some cases penetrating the steel plate. By the way, the manufacturing cost of electroplated plates increases significantly as the coating weight increases, so it is extremely difficult from a cost perspective to improve the pitting resistance of electroplated steel sheets by increasing the coating weight.
On the other hand, hot-dip galvanized steel sheets (hereinafter abbreviated as HDS) manufactured by a hot-dip galvanizing process or alloyed hot-dip galvanized steel sheets (hereinafter abbreviated as GA) that are further heat-alloyed after plating, If we compare electroplating, the increase in cost due to the increase in plating weight is relatively small. HDS is rarely used for automobiles due to its weldability, but GA is about 45g/m" There is also a history in which products with a high adhesion rate have been used, and by increasing the thickness (for example, the adhesion rate has been increased to 60g/s per side)
Attempts have been made to meet the above-mentioned requirements for perforation resistance. However, GA has traditionally been considered to be a material with relatively many problems in press forming, and in fact it Peeling of the plating film, called flaking and powdering, that occurs has been viewed as a problem.This peeling during processing generally becomes more significant as the amount of plating increases, so increasing the thickness of GA is becoming more of a concern than ever before. There is a strong possibility that troubles will increase during the forming process.In addition, an increase in the amount of adhesion is not very desirable from the viewpoint of spot weldability.
一方、ＧＡの耐食性を向上させる手段として、例えば特
開昭５４−１５９３４０号公報ではｈｇ添加のＧＡが提
案されている．しかしながら、このめっき皮膜は、めっ
き皮膜自体の耐食性には優れるものの、自動車用電着塗
装を施した後のスクランチ傷部における耐孔あき性に関
しては、従来の成分系のＧＡと比較してほとんど改善効
果が′認められない。On the other hand, as a means to improve the corrosion resistance of GA, for example, GA with added hg has been proposed in Japanese Patent Application Laid-Open No. 159340/1983. However, although this plating film has excellent corrosion resistance of the plating film itself, compared to conventional component-based GA, there is little improvement in porosity resistance at the scratch scratched area after applying electrodeposition coating for automobiles. No effect observed.
また、特開昭５２−１３１９３４号公報では３〜２２重
量％のＡｌを添加したＺｎ浴中でＺｎ−Ａｌ溶融めっき
を行う方法が開示されているが、Ａｌ添加量が１５％を
超えると融点が上昇し操業が困難になること、および、
この方法で製造したＧＡは、腐食環境によっては耐食性
が必ずしも十分ではない、等の問題がある．
（発明が解決しようとする課題）
本発明は、上記の問題点を解決することを課題としてな
されたものであって、前記従来のＺｎ−Ａｌ溶融めっき
において、めっき浴中のｌ／！′ａ度の増加に伴う操業
性の低下を回避し、耐食性、特に耐孔あき性に優れため
っき鋼板の製造方法を提供することを目的とする．
（課題を解決するための手段）
本発明者等は、Ｚｎ−Ａｌ合金めっき鋼板のめっき皮膜
の特性を多面的に検討した結果、下記１）および２）の
事実を知見した．
ｌ） めっき層を電解液中で陽極電解処理すると、選択
的にＺｎのみがアノード溶解してめっき層の表層のＡｌ
ｆｉ度が増加し、ＨＤＳの耐食性が大幅に向上する．
２）前記の陽極電解処理しためっき鯛仮を加熱合金化処
理してＧＡとすると、従来のＧＡに比較して耐食性が飛
躍的に向上する。Furthermore, JP-A-52-131934 discloses a method of performing Zn-Al hot-dip plating in a Zn bath to which 3 to 22% by weight of Al is added, but if the amount of Al added exceeds 15%, the melting point increases, making operations difficult, and
GA manufactured by this method has problems such as not necessarily having sufficient corrosion resistance depending on the corrosive environment. (Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned problems, and in the conventional Zn-Al hot-dip plating, l/! The object of the present invention is to provide a method for producing a plated steel sheet that has excellent corrosion resistance, especially porosity resistance, and avoids the decrease in operability that accompanies an increase in a degree. (Means for Solving the Problems) The present inventors investigated the characteristics of the plating film of Zn-Al alloy plated steel sheets from multiple angles, and as a result, they discovered the following facts 1) and 2). l) When the plating layer is subjected to anodic electrolysis treatment in an electrolytic solution, only Zn is selectively dissolved in the anode, and Al on the surface layer of the plating layer is dissolved.
The fi degree increases and the corrosion resistance of HDS is greatly improved. 2) When the plated sea bream temporarily subjected to the anodic electrolytic treatment is heated and alloyed to form GA, the corrosion resistance is dramatically improved compared to conventional GA.
本発明は、上記の知見に基づいてなされたもので、その
要旨は下記のおよび■の方法にある。The present invention has been made based on the above findings, and its gist lies in the following methods and (2).
■ 鋼板を２％（以下、％は重量％を意味する）以上１
５％以下のＡ２を含有するＺｎ−Ａｌめっき浴で溶融め
っきした後、電解液中で１５０００ク−ｏン／ ｍ ２
以上の？電電気量（通電量）により陽極電解を施すこと
を特徴とするＺｎ−Ａｌ合金めっき鋼板の製造方法。■ 2% (hereinafter, % means weight%) or more of steel plate1
After hot-dip plating in a Zn-Al plating bath containing up to 5% A2, 15000 Coon/m2 in electrolyte
More than? A method for producing a Zn-Al alloy plated steel sheet, characterized by performing anodic electrolysis using the amount of electricity (amount of current applied).
■ 前記■の方法で製造したＺｎ−Ａｌ合金めっき鋼仮
に、更に加熱合金化処理を施すことを特徴とするＺｎ−
Ａｊ２合金めっき鋼板の製造方法。(2) The Zn-Al alloy plated steel produced by the method (2) above is further subjected to heat alloying treatment.
A method for producing an Aj2 alloy plated steel sheet.
上記の電解液としては、塩化亜鉛（ＺｎＣ ｌ ！）、
硫酸亜鉛（ＺｎＳＯ４）、塩化アルミニウム（ＡｌＣｌ
，）、硫酸アルミニウム（Ａ２■（Ｓｏｎ）ｚ）等の塩
を単独または２種以上含む溶液が目的に通うものである
．特に、Ｚｎ２゜を３ ｇ／ １ 〜２００ｇ／ ｌ含
有する電解液が液性の長時間安定性の点から望ましいが
、必ずしもこれに限定されるものではない．
また、前記のＺｎ−Ａｊ！めっき浴には、合計１％以下
のＭｇ， Ｍｎ， Ｃｒ、Ｔ＋％ ＣＱ％ Ｃｕｚ Ｎ
ｌ％ Ｚｒが含有されていてもよい．
（作用）
Ｚｎ−ＡＩ！合金めっき鋼板を製造するにあたり、前記
■の本発明方法を通用するには、まず、通常の、ゼンジ
マー法や無酸化炉法等で行われる前処理により清浄化さ
れた鋼板をＺｎ−Ａｎめっき浴で７容融めっきする．こ
のとき、めっき浴中のＡｌａ度が２％以下では、引き続
き実施される陽極電解において、めっき層中のＡｌの相
対的濃度の上昇が小さく、耐食性向上効果に乏しいため
、ＡＩ４度の下限を２％とした．一方、Ａ２の耐食性向
上効果はＡｌｄ度が１５％以上で飽和し、かつＡｌ４度
の上昇に伴い合金化が困難となるので、ＡＡ？ａ度の上
限を１５％とした。The above electrolyte includes zinc chloride (ZnCl!),
Zinc sulfate (ZnSO4), aluminum chloride (AlCl
, ), aluminum sulfate (A2■(Son)z), and other salts, either singly or in combination, are suitable for this purpose. In particular, an electrolytic solution containing 3 g/1 to 200 g/l of Zn2° is desirable from the viewpoint of long-term stability of the liquid, but it is not necessarily limited to this. Moreover, the above-mentioned Zn-Aj! The plating bath contains a total of 1% or less of Mg, Mn, Cr, T+% CQ% Cuz N
It may contain 1% Zr. (Effect) Zn-AI! In manufacturing an alloy-plated steel sheet, in order to apply the method of the present invention described in (1) above, first, a steel sheet that has been cleaned by pretreatment performed by the usual Sendzimer method or non-oxidation furnace method is subjected to a Zn-An plating bath. 7 volumes of hot-dip plating. At this time, if the Ala degree in the plating bath is 2% or less, the increase in the relative concentration of Al in the plating layer is small in the subsequent anodic electrolysis, and the effect of improving corrosion resistance is poor. %. On the other hand, the corrosion resistance improvement effect of A2 is saturated when the Ald degree is 15% or more, and alloying becomes difficult as the Al4 degree increases, so AA? The upper limit of degree a was set at 15%.
上記の方法で溶融めっきした鋼板に、前記の電解質溶液
中で陽極電解を施す。電解時の通電量としては片面当た
り少なくとも１５０００クーロン／ ｍ ２が必要であ
り、１５０００クーＵシ／ ｍ ２以下の通電量ではＺ
ｎ溶解量が少ないためめっき層の平均組成の変化が小さ
く、耐食性の向上効果はあまり７ｖ２められない。The steel plate hot-dipped by the above method is subjected to anodic electrolysis in the above electrolyte solution. The amount of current applied during electrolysis must be at least 15,000 coulombs/m2 per side, and if the amount of current is less than 15,000 coulombs/m2, Z
Since the amount of n dissolved is small, the change in the average composition of the plating layer is small, and the corrosion resistance improvement effect of 7v2 is not noticeable.
Ｊｉ電量の上限は溶融めっき時のめっき付着量に依存し
て決定されるべきもので、限定はできないが、通常、溶
融めっき時のめっき付着量の６０％程度まで電解除去し
ても大きな悪影響は認められない
電解電７Ｍ密度は１〜ＩＯＯＡ／ｄ−の範囲で設備の能
力に応して設定できるが、低電流密度の方がめつき層の
表層におけるＡｌ冨化の効果が大きい．前記■の方広は
、■の方法に加熱合金化処理を付隨させたものであり、
合金化処理温度としては３００〜６５０゜Ｃが適当であ
る．
（実施例１）
Ｃ ：０．０３８％、Ｓｉ：＜０．０１％、Ｍｎ：０．
２２％、Ｐ：ｏ．ｏｉ％、ｓ ：０．００８％、Ｓｏｌ
．＾Ｎ ：０．０２６％を含有する低炭素Ａｌキルド鋼
板（厚さ０． ７６ｍｎ＋の未焼鈍材）を供試素材とし
、脱脂後、溶融めっきシくユレーターを用いて２６％Ｈ
ｚ十Ｎｚ雰囲気中で７２０’ＣＸ９０秒の焼鈍加熱を行
い、５００゜Ｃまで冷却後、所定の組或および温度に設
定したＺｎ−Ａｌめっき浴に３秒間浸漬し、試験用のめ
っき綱板を作威した．めっき付着量は１２０〜１５０ｇ
／ｍ”である。このめっき鋼仮について、めっきままの
状態（比較法）および電解処理を行った状態（本発明方
法）で塩水噴霧試験（ＪＩＳ Ｚ ２８６７）を実施し
、４８時間後の腐食減量を測定した．なお、電解液とし
てはρ１１３．５に調整した硫酸亜鉛（ＺｎＳＯｎ ・
７ＨｚＯ：１８０ｇ／ Ｅ ）と硫酸ナトリウム（Ｎａ
ｚＳＯａ：７５ｇ／ｉ！．）とのｄ合溶液（液温４５゜
Ｃ）を用い、電解電流密度２ＱＡ／ｄｍ”で２０秒間（
通電量４００００クーロン／ｍ２）陽極電解を行った。The upper limit of the amount of Ji electric current should be determined depending on the amount of plating deposited during hot-dip plating, and cannot be limited, but normally, even if electrolytic removal of about 60% of the amount of plating deposited during hot-dip plating is not performed, there will be no major adverse effect. The 7M density of electrolytic current that cannot be recognized can be set in the range of 1 to IOOA/d- according to the capacity of the equipment, but the effect of Al enrichment on the surface layer of the plating layer is greater at lower current densities. The above-mentioned method (■) is a method in which heat alloying treatment is added to the method (■),
The appropriate alloying temperature is 300 to 650°C. (Example 1) C: 0.038%, Si: <0.01%, Mn: 0.
22%, P:o. oi%, s: 0.008%, Sol
．． ＾N: A low carbon Al killed steel plate (thickness 0.76mm+ unannealed material) containing 0.026% was used as the test material, and after degreasing, it was heated to 26%H using a hot-dip plating urator.
After annealing and heating at 720'C for 90 seconds in a Z10Nz atmosphere and cooling to 500°C, the plated steel sheet for testing was immersed in a Zn-Al plating bath set at a predetermined composition and temperature for 3 seconds. I created it. Plating amount is 120-150g
/m”. Salt spray tests (JIS Z 2867) were conducted on this pre-plated steel in the as-plated state (comparative method) and in the state after electrolytic treatment (method of the present invention), and the corrosion after 48 hours was The weight loss was measured.The electrolyte was zinc sulfate (ZnSOn.
7HzO: 180g/E) and sodium sulfate (Na
zSOa: 75g/i! ．． ) for 20 seconds at an electrolytic current density of 2QA/dm'' (solution temperature: 45°C).
Anodic electrolysis was performed at a current flow rate of 40,000 coulombs/m2.
試験結果を第１図に示す。同図から、めっき浴中のＡｌ
ａ度が２％以上では、電解処理を施した本発明方法を適
用することにより、めっきままで電解処理をしていない
比較法にくらべて耐食性が大幅に向上していることがわ
かる．
（実施例２）
実施例１で作威した試験用めっき鋼板のうち、ｉ４度５
％のＺｎ−Ａｌめっき浴でめっきした鋼板を、電解’ｔ
ｌｃＡ ＩＣＩ ｓ：６０ｇ／ ｌ ， ＺｎＣｌ ｚ
：８０ｇ／ Ｎ、ＮａＣ ｌ ：１０ｇ／ ｌ ， ｐ
ｌ！ ３．０、２５゜Ｃ）中で、電解電流密度２ＯＡ／
ｄ−で通電量を変えて陽極電解処理を施し、実施例ｌと
同様の塩水噴霧試験を行い、４８時間後の腐食減量を測
定した。The test results are shown in Figure 1. From the same figure, Al in the plating bath
It can be seen that when the a degree is 2% or more, the corrosion resistance is significantly improved by applying the method of the present invention in which electrolytic treatment is applied, compared to the comparative method in which electrolytic treatment is not performed in the as-plated state. (Example 2) Among the test plated steel sheets produced in Example 1, i4 degree 5
% Zn-Al plating bath, electrolytic 't
lcA ICI s: 60g/l, ZnCl z
:80g/N, NaCl:10g/l, p
l! 3.0, 25°C), electrolytic current density 2OA/
Anodic electrolytic treatment was performed by changing the amount of current applied in d-, and the same salt water spray test as in Example 1 was conducted, and the corrosion weight loss after 48 hours was measured.
その結果を第２図に示す．同図から、通電量が１５００
ＯＡ／ｄｉ”以上においては、耐食性の著しい向上効果
が肥められる。The results are shown in Figure 2. From the same figure, the amount of current is 1500
At OA/di'' or more, the effect of significantly improving corrosion resistance is enhanced.
（実施例３）
実施例１と同一の供試素材を用いて、／８融めっきシミ
ュレーターで種々のＡｎ濃度を有するＺｎＡｐ．めっき
浴で溶融めっきを行い、めっき付着量を５０〜６０ｇ／
ｍ”に調整した．このめっき綱仮を５００゜Ｃで合金化
処理したＧＡ（比較法）、およびめっき後、実施例１と
同じ電解戒中で４５０００ク−ｏン／ｍＺの通電量で陽
極電解処理した後、合金化処理したＧＡ（本発明方法）
を作威した．前記合金化処理において、めっき皮膜中の
ＦｅｉＪ度はいずれも８〜Ｘ２％となるように調整した
。得られたＧＡにりん酸亜鉛処理を施し、更に２０μｍ
のカチオン電着塗装を行い、以下の方法で耐孔あき性を
評価した．耐孔あき性は、試験片にスクラッチ疵を入れ
、この試験片を演温が３５゜Ｃの５％ＮａＣ ｅの溶液
中に１時間浸漬し、６０’Ｃの熱風で１時間乾燥する試
験を繰り返し行い、２００日経過後の孔あき深さを測定
して評価した。(Example 3) Using the same test material as in Example 1, ZnAp. Perform hot-dip plating in a plating bath, and reduce the amount of plating to 50 to 60 g/
This plated rope was alloyed at 500°C with GA (comparative method), and after plating, it was anodized at a current flow rate of 45,000 Coon/mZ in the same electrolytic condition as in Example 1. GA subjected to electrolytic treatment and then alloyed (method of the present invention)
was created. In the alloying treatment, the FeiJ degree in the plating film was adjusted to be 8 to X2%. The obtained GA was treated with zinc phosphate and further 20 μm thick.
A cationic electrodeposition coating was applied, and the puncture resistance was evaluated using the following method. Puncture resistance was tested by making a scratch on a test piece, immersing the test piece in a 5% NaC e solution with an effective temperature of 35°C for 1 hour, and drying it with hot air at 60°C for 1 hour. The test was repeated, and the perforation depth was measured and evaluated after 200 days.
結果を第３図に示す．図示のとおり、本発明方法による
合金化処理材においては、耐孔あき性に対する大きな向
上効果が認められる。なお、第３図の比較法というのは
、陽極電解処理を行わないこと以外は本発明方法と同じ
処理を行ったものである．
（発明の効果）
Ｚｎ−Ａｊ！合金めっきｆｉＩ板の製造において、溶融
めっき後、陽極電解処理を施す本発明方法、あるいは陽
極電解処理を施した後、加熱合金化処理を行う本発明方
法を適用することによりめっき面の耐食性、特に耐孔あ
き性は著しく向上する．The results are shown in Figure 3. As shown in the figure, the material alloyed by the method of the present invention shows a significant improvement in porosity resistance. Note that the comparative method shown in FIG. 3 is a method in which the same treatment as the present invention method was performed except that no anodic electrolytic treatment was performed. (Effect of the invention) Zn-Aj! In the production of alloy plated fiI plates, the corrosion resistance of the plated surface can be improved, especially by applying the method of the present invention in which anodic electrolytic treatment is performed after hot-dip plating, or the method of the present invention in which heat alloying treatment is performed after anodic electrolytic treatment. Puncture resistance is significantly improved.
第１図はＺｎ−Ａｌｆｉ合金めっき鋼板の耐食性に対す
るめっき浴中のＡｉＡ濃度の影響を示すグラフ、第２図
はＺｎ−Ａｊ！合金めっき鋼板の耐食性に対する陽極電
解処理時の通電量の影響を示すグラフ、第３図はＺｎ−
＾ｌ合金めっき綱板の耐孔あき性に対する加熱合金化処
理の影響を示すグラフ、である．Figure 1 is a graph showing the influence of the AiA concentration in the plating bath on the corrosion resistance of Zn-Alfi alloy plated steel sheets, and Figure 2 is a graph showing the influence of the AiA concentration in the plating bath on the corrosion resistance of Zn-Alfi alloy plated steel sheets. A graph showing the influence of the amount of current applied during anodic electrolytic treatment on the corrosion resistance of alloy-plated steel sheets.
^l This is a graph showing the influence of heat alloying treatment on the pitting resistance of alloy plated steel sheets.
Claims (2)
有するＺｎ−Ａｌめっき浴で溶融めっきした後、電解液
中で１５０００クーロン／ｍ＾２以上の通電電気量によ
り陽極電解を施すことを特徴とするＺｎ−Ａｌ合金めっ
き鋼板の製造方法。(1) After hot-dipping a steel plate in a Zn-Al plating bath containing 2% or more and 15% or less Al by weight, anodic electrolysis is performed in an electrolytic solution with a current flow of 15,000 coulombs/m^2 or more. A method for producing a Zn-Al alloy plated steel sheet, characterized in that:
ｌ合金めっき鋼板に、更に加熱合金化処理を施すことを
特徴とするＺｎ−Ａｌめっき鋼板の製造方法。(2) Zn-A produced by the method according to claim (1)
1. A method for producing a Zn-Al plated steel sheet, which comprises further subjecting the L-alloy plated steel sheet to a heat alloying treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18835489A JPH0353053A (en) | 1989-07-20 | 1989-07-20 | Production of zn-al alloy plated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18835489A JPH0353053A (en) | 1989-07-20 | 1989-07-20 | Production of zn-al alloy plated steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0353053A true JPH0353053A (en) | 1991-03-07 |
Family
ID=16222161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18835489A Pending JPH0353053A (en) | 1989-07-20 | 1989-07-20 | Production of zn-al alloy plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0353053A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2248662A1 (en) * | 2009-05-01 | 2010-11-10 | Fujifilm Corporation | Metal composite substrate and method of producing the same |
-
1989
- 1989-07-20 JP JP18835489A patent/JPH0353053A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2248662A1 (en) * | 2009-05-01 | 2010-11-10 | Fujifilm Corporation | Metal composite substrate and method of producing the same |
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