JPH0331796B2 - - Google Patents
Info
- Publication number
- JPH0331796B2 JPH0331796B2 JP12508083A JP12508083A JPH0331796B2 JP H0331796 B2 JPH0331796 B2 JP H0331796B2 JP 12508083 A JP12508083 A JP 12508083A JP 12508083 A JP12508083 A JP 12508083A JP H0331796 B2 JPH0331796 B2 JP H0331796B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- bath
- alloy
- strip
- electroplating
- 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
Links
- 238000007747 plating Methods 0.000 claims description 123
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 31
- 229910000831 Steel Inorganic materials 0.000 claims description 29
- 238000009713 electroplating Methods 0.000 claims description 29
- 239000010959 steel Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 21
- 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 claims description 15
- 210000004027 cell Anatomy 0.000 description 19
- 239000000203 mixture Substances 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000007664 blowing Methods 0.000 description 8
- 238000010422 painting Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 210000002287 horizontal cell Anatomy 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】
この発明は、安定した品質（性能）をもつFe
−Zn系合金メツキ鋼板を連続的に得ることがで
きる合金電気メツキ方法に関する。[Detailed Description of the Invention] This invention provides Fe with stable quality (performance).
- It relates to an alloy electroplating method that can continuously obtain Zn-based alloy plated steel sheets.
Fe−Zn系合金メツキ鋼板としては、いわゆる
合金化処理溶融Znメツキ鋼板（以下、単に合金
化処理鋼板と云う）が古くからよく知られてい
る。云う迄もなくこれは、溶融Znメツキ鋼板を
加熱処理することによりFe−Zn合金層を形成し
めたものであるが、これはとくに塗装後耐食性に
すぐれるメリツトがあることから、自動車部品や
家電製品等に適用されるものである。しかしなが
らこの合金化処理鋼板はその一方で、加工性に劣
りしかも薄目付が不可能でカチオン電着塗装で通
電ブツ疵が発生するという弱点がある。 As Fe--Zn alloy plated steel sheets, so-called alloyed hot-dip Zn plated steel sheets (hereinafter simply referred to as alloyed steel sheets) have been well known for a long time. Needless to say, this is a Fe-Zn alloy layer formed by heat-treating a molten Zn-plated steel sheet, and this has the advantage of excellent corrosion resistance after painting, so it is used in automobile parts and home appliances. This applies to products, etc. However, on the other hand, this alloyed steel sheet has the disadvantage that it is inferior in workability, cannot be applied to a thin coating, and is prone to electrical conduction defects when coated with cationic electrodeposition.
かかる事情を背景に近時、Fe−Zn合金メツキ
鋼板を電気メツキ法にて直接製造することが提案
された。電気メツキ法では、前記合金化処理鋼板
より加工性、カチオン電着塗装性の点ですぐれし
かも塗装後耐食性並びに電気抵抗溶接性も良好な
Fe−Zn合金メツキ鋼板を得ることができるもの
である。 Against this background, it has recently been proposed to directly produce Fe--Zn alloy plated steel sheets by electroplating. In the electroplating method, the alloyed steel sheet is superior to the above-mentioned alloyed steel sheet in terms of workability and cationic electrodeposition coating properties, and also has good corrosion resistance and electric resistance weldability after coating.
A Fe-Zn alloy plated steel plate can be obtained.
ところで、Fe−Zn系合金メツキを得る鋼板の
連続電気メツキにおいては、メツキ浴として通
常、FeおよびZnの硫酸塩または塩化物と、電解
支持塩としてNaまたはNH3硫酸塩もしくは塩化
物の混合溶液が使用されるが、このような場合、
成品のメツキ皮膜組成、つまり皮膜中のFe含有
量は電流密度、メツキ浴PHや組成等、メツキ条件
の影響を強く受けることとなる。一方、実際の連
続電気メツキラインでは稼働中、操業因子である
メツキ浴組成やPHの変動は避けられない。すなわ
ち、連続電気メツキの場合には、メツキ進行に伴
う浴組成、PHの変化に対し、これに応じて金属イ
オン酸や補給を行うようにしているが、高精度の
管理は現実問題として不可能であり、現在のとこ
ろ上記メツキ条件のある程度の変動は殆んど不可
避なものとされているのが実状である。また、用
途に応じメツキ付着量を変えたり、通板速度の変
動に対処するために、電流密度の積極的な変更を
強いられることも少なくない。このように実際の
連続電気メツキでは、メツキ浴組成やPH、電流密
度といつた条件の変動は避けられないものであ
り、したがつてメツキ皮膜組成の安定した品質の
よいFe−Zn系合金電気メツキ鋼板を連続的に得
ることは容易なことではない。 By the way, in continuous electroplating of steel sheets to obtain Fe-Zn alloy plating, a mixed solution of Fe and Zn sulfates or chlorides is usually used as the plating bath, and Na or NH 3 sulfate or chloride as the electrolytic supporting salt. is used, but in such cases,
The plating film composition of the finished product, that is, the Fe content in the film, is strongly influenced by plating conditions such as current density, plating bath PH and composition. On the other hand, in an actual continuous electroplating line, fluctuations in the plating bath composition and pH, which are operational factors, are unavoidable during operation. In other words, in the case of continuous electroplating, metal ion acid and replenishment are performed in response to changes in bath composition and pH as plating progresses, but highly accurate control is practically impossible. At present, the actual situation is that some variation in the plating conditions is almost inevitable. Furthermore, in order to change the amount of plating deposited depending on the application or to cope with fluctuations in the sheet passing speed, it is often necessary to actively change the current density. As described above, in actual continuous electroplating, fluctuations in conditions such as the plating bath composition, pH, and current density are unavoidable. It is not easy to continuously obtain plated steel sheets.
このFe−Zn合金電気メツキにおける皮膜組成
の安定化を目的として、本出願人は先に、メツキ
浴中に硫酸アルミニウム塩を添加することを提案
した（特願昭57−1962号）。この方法によれば、
上記したメツキ浴PH、電流密度等のメツキ条件が
変動する条件下においてもメツキ皮膜中のFe量
を効果的に安定させることができるものである。 For the purpose of stabilizing the film composition in this Fe-Zn alloy electroplating, the present applicant previously proposed adding an aluminum sulfate salt to the plating bath (Japanese Patent Application No. 1987-1962). According to this method,
The amount of Fe in the plating film can be effectively stabilized even under conditions where the plating conditions such as the above-mentioned plating bath PH and current density fluctuate.
ところがこの方法では、確かに組成という面で
は安定したメツキ皮膜を得ることはできるが、メ
ツキ皮膜の性能そのものは必ずしも良好には維持
されず、加工性（耐パウダリング性）や溶接性、
塗装後耐食性等が不安定となることがある。これ
は、メツキ皮膜の性能は、その組成のみならず、
メツキ皮膜中のFe−Zn金属関化合物、つまりΓ
相、δ1相、ζ相、η相の状態にも少なからず依存
しており、とくにメツキ浴中に硫酸アルミニウム
塩を添加する上記の方法では、この金属間加工物
の析出状態に問題があると考えられる。 However, with this method, although it is possible to obtain a plating film that is stable in terms of composition, the performance of the plating film itself is not necessarily maintained well, and the processability (powdering resistance), weldability,
Corrosion resistance etc. may become unstable after painting. This means that the performance of the plating film is determined not only by its composition but also by its composition.
Fe-Zn metal-related compounds in the plating film, that is, Γ
It depends to some extent on the state of the phase, δ 1 phase, ζ phase, and η phase, and in particular, the above method of adding aluminum sulfate salt to the plating bath has problems with the state of precipitation of this intermetallic workpiece. it is conceivable that.
本発明は、この硫酸アルミニウム含有浴を利用
して、高性能Fe−Zn系合金メツキを安定的に得
ることができる鋼板の合金電気メツキ方法を提供
しようとするものである。 The present invention aims to provide an alloy electroplating method for steel sheets that can stably obtain high-performance Fe--Zn alloy plating using this aluminum sulfate-containing bath.
硫酸アルミニウム含有浴からFe−Zn系合金を
電析させる方法の問題は、先に述べたとおりメツ
キ皮膜を形成する金属間化合物の析出状態にある
と考えられる。 The problem with the method of electrodepositing Fe-Zn alloy from an aluminum sulfate-containing bath is thought to lie in the state of precipitation of intermetallic compounds that form the plating film, as described above.
本発明者らは、この考え方を踏まえた上で、硫
酸アルミニウム含有浴からのFe−Zn系合金電気
メツキの性能を安定化させる方法の開発を意図し
て、とくに各種メツキ条件が上記メツキ性能に及
ぼす影響について、詳細に実験、調査を行なつ
た。その結果、メツキ浴におけるメツキ液の走行
ストリツプに対する相対的な流動状態がFe−Zn
系合金電気メツキ皮膜の性能の良否と深く係わつ
ており、具体的にはメツキ液流と走行ストリツプ
との相対平均速度VR（以下、メツキ液の相対速度
と云えばこれを指す）と、走行ストリツプと陽極
との平均電極間距離ｈ（以下、単に電極間距離と
云えばこれを指す）の積VR・ｈを指標としてメ
ツキ液の流動状態を規制することにより、上記メ
ツキ性能の安定管理が可能であることを見い出し
た。すなわち、鋼板の連続電気メツキの方式とし
ては現在、実に多くのものが知られているが、そ
れらは何れも、その方式に違いこそあれ、メツキ
液を操業中連続的に浴中へ供給し同時にその一方
でこれを抜取りメツキ液を循環せしめつつメツキ
を行うようになつている。これは、メツキの進行
に伴う浴PHや組成の変化に対処するためと、更に
は操業中メツキ浴においてメツキ液を強制的に流
動させて、ストリツプ走行による流動と合成して
流動状態を制御することがその目的であるが、本
発明者らの詳細な実験調査の結果、このメツキ液
の相対速度VRと更に電極間距離ｈとが上記Fe−
Zn系合金電気メツキ皮膜の性能に係わつており、
これらの積VR・ｈの管理をもつてそのメツキ性
能を良好に安定させることが可能であることが判
明したものである。この点については次のように
考察できる。すなわち、まずFe−Zn系合金電気
メツキ皮膜は形成する金属間化合物の析出相の状
態は、メツキ時陰極としてのストリツプ表面上に
おいて起こる水素発生の現象との関連が深い。つ
まり、Fe−Zn系合金電気メツキにおける陰極で
の電流効率は60〜90％程度であつて、陰極上では
つねに多量の水素ガスの泡が核発生→凝集→脱離
という現象を繰返すことになるが、この陰極上で
の水素ガスの挙動が、Fe−Zn系合金メツキ皮膜
の析出相（Γ相、δ1相、ζ相、η相）の混合状態
のはじめ、これら金属間化合物の析出結晶方位や
結晶粒径、更にはそれら結晶の内部歪の状態等に
複雑に関係してくる。メツキ浴中に硫酸アルミニ
ウム塩の添加があると、メツキ液の粘度が増し、
また同時に界面張力が変化して泡の発生が起り易
くなる。したがつてこの場合には上記した陰極面
上での水素ガスの泡成長や脱離が抑制される傾向
となる。このような関係で、とくに硫酸アルミニ
ウム含有浴の場合には、メツキ皮膜中の金属間化
合物の析出状態がメツキ性能上望ましくないもの
となり易くなる。 Based on this idea, the present inventors aimed to develop a method to stabilize the performance of Fe-Zn alloy electroplating from an aluminum sulfate-containing bath, and in particular, various plating conditions were developed to improve the above plating performance. We conducted detailed experiments and investigations into the effects of As a result, the flow state of the plating liquid relative to the running strip in the plating bath is
It is closely related to the quality of the performance of the electroplating film of the electroplating film based on the alloy, and specifically, the relative average velocity V R between the plating liquid flow and the running strip (hereinafter referred to as the relative velocity of the plating liquid refers to this). By regulating the flow state of the plating liquid using the product V R h of the average inter-electrode distance h (hereinafter simply referred to as the inter-electrode distance) between the running strip and the anode as an index, the plating performance described above can be stabilized. We have found that it is possible to manage In other words, there are currently many methods known for continuous electroplating of steel sheets, but all of them, although they differ in their methods, are capable of continuously supplying the plating solution into the bath during operation, and at the same time. On the other hand, plating is performed while removing this and circulating the plating liquid. This is done in order to cope with changes in bath pH and composition as plating progresses, and also to control the flow state by forcing the plating liquid to flow in the plating bath during operation and combining it with the flow caused by strip running. However, as a result of detailed experimental investigation by the present inventors, it was found that the relative velocity V R of the plating liquid and the distance h between the electrodes were
It is concerned with the performance of Zn-based alloy electroplated coating.
It has been found that it is possible to satisfactorily stabilize the plating performance by managing these products V R ·h. This point can be considered as follows. That is, first of all, the state of the precipitated phase of the intermetallic compound formed in the electroplated Fe--Zn alloy film is closely related to the phenomenon of hydrogen generation that occurs on the surface of the strip as a cathode during plating. In other words, the current efficiency at the cathode in Fe-Zn alloy electroplating is about 60 to 90%, and a large amount of hydrogen gas bubbles constantly repeat the phenomenon of nucleation → agglomeration → desorption on the cathode. However, the behavior of hydrogen gas on the cathode is not limited to the mixed state of the precipitated phases (Γ phase, δ 1 phase, ζ phase, and η phase) of the Fe-Zn alloy plating film, as well as the precipitated crystals of these intermetallic compounds. It is intricately related to orientation, crystal grain size, and the state of internal strain in those crystals. When aluminum sulfate is added to the plating bath, the viscosity of the plating solution increases.
At the same time, the interfacial tension changes, making it easier to generate bubbles. Therefore, in this case, the bubble growth and desorption of hydrogen gas on the cathode surface described above tends to be suppressed. Due to this relationship, particularly in the case of a bath containing aluminum sulfate, the state of precipitation of intermetallic compounds in the plating film tends to be undesirable in terms of plating performance.
一方、上記陰極面上で水素ガスの挙動には、メ
ツキ浴中のメツキ液のストリツプに対する相対的
な意味での流動状態の影響が大きい。水素ガスの
挙動への影響は物理的なものと考えられるが、そ
の意味においては、上記メツキ液の流動状態は積
VR・ｈで規定できるものである。すなわち、流
体力学によれば、一般に流体の流れの力学的状態
は、
Ｒ＝υd／ν
ここに、ν：流体の動粘性係数
：流体の平均粒速
ｄ：代表長さ
上式で定義される、いわゆるレイノルズ数Ｒを
もつて規定できるとされるが、ここで流体をメツ
キ液に限つたとすれば、上記流体の動粘性係数は
殆ど変動がなく実際上Ｒ数への影響は無視できる
こととなり、したがつてＲ数は・ｄにて支配さ
れることになる。このような理由から、物理的意
味におけるメツキ液の流動状態として積VR・ｈ
をもつて規定できるものである。 On the other hand, the behavior of hydrogen gas on the cathode surface is greatly influenced by the fluidity state of the plating solution relative to the strip in the plating bath. The influence on the behavior of hydrogen gas is considered to be physical, but in that sense, the flow state of the plating liquid described above is a cumulative effect.
It can be defined by V R h. In other words, according to fluid mechanics, the mechanical state of fluid flow is generally as follows: R=υd/ν Where, ν: Kinematic viscosity coefficient of fluid: Average particle velocity of fluid d: Representative length Defined by the above formula It is said that it can be defined by the so-called Reynolds number R, but if the fluid here is limited to plating liquid, the kinematic viscosity coefficient of the fluid will hardly change and its effect on the R number can be ignored in practice. , therefore the R number is dominated by d. For this reason, the fluid state of the liquid in a physical sense is expressed as the product V R h
It can be defined as follows.
以上に説明した理由から、とくに硫酸アルミニ
ウム含有浴からのFe−Zn系合金電気メツキにつ
いても、そのメツキ性能を積VR・ｈの管理によ
つてつねに安定した良好なものとなすことができ
ると考えられるものである。 For the reasons explained above, it is believed that the plating performance of Fe-Zn alloy electroplating from a bath containing aluminum sulfate can always be kept stable and good by controlling the product V R h. It is something that can be considered.
すなわち本発明は、鋼板にFe−Zn系合金を連
続的に電析される場合において、メツキ浴中に硫
酸アルミニウム塩をAl重量で３〜20ｇ／添加
するとともに、メツキ液流と走行ストリツプとの
平均相対速度VRおよび走行ストリツプと陽極と
の平均電極間距離ｈを、
500VR・ｈ6500
但し、VR：〔ｍ／min〕
ｈ：〔mm〕
上記の条件を満たすように管理することを特徴
とする鋼板のFe−Zn系合金電気メツキ方法を要
旨とする。ここに、メツキ液の相対速度VRとは、
ノズル等により浴中へ吸込み、供給されるメツキ
液流の速度ベクトルをVF、ストリツプ走行速度
ベクトルをVSとすれば｜VF−VS｜として定義さ
れるものである。すなわち現在、メツキ液の吹込
み式としては、メツキ液吹込み方向がストリツプ
走行方向と平行で対向する向流（counter
flow）、同じく同一方向である順流（co−flow）、
更には両者が直角の横流（cross−flow）やメツ
キ液吹込みをストリツプと陽極間とは無関係なと
ころで行うもの（この場合はVF≒０となる）等、
種々なものが公知であるが、上記VRはこれらの
何れにも適用され得るわけである。 That is, in the case of continuous electrodeposition of Fe-Zn alloy on a steel plate, the present invention adds aluminum sulfate salt of 3 to 20 g/Al weight to the plating bath, and also controls the plating liquid flow and the running strip. The average relative speed V R and the average interelectrode distance h between the running strip and the anode are 500V R h6500, however, V R : [m/min] h: [mm] The characteristic is that the above conditions are managed to be satisfied. This paper summarizes the Fe-Zn alloy electroplating method for steel sheets. Here, the relative velocity V R of the mesh liquid is
If the velocity vector of the plating liquid flow sucked and supplied into the bath by a nozzle or the like is V F and the strip running velocity vector is V S , then it is defined as |V F −V S |. In other words, currently, the plating liquid blowing method is a counter-current (counterflow) method in which the plating liquid is blown in parallel to and opposite the strip running direction.
flow), co-flow, which is also in the same direction;
Furthermore, there are cases where the two sides are perpendicular to each other, such as cross-flow, or where the plating liquid is injected at a location unrelated to the space between the strip and the anode (in this case, V F ≒0), etc.
Although various types are known, the above-mentioned VR can be applied to any of them.
電極間距離ｈは、走行ストリツプ（パスライ
ン）と陽極とが完全平行型の場合には云う迄もな
くストリツプと陽極面とのセパレーシヨン・ギヤ
ツプに当り、ストリツプと陽極との距離が陽極面
の位置によつて多少変化した形式では、その電極
間距離の平均をとればよい。 Needless to say, when the running strip (pass line) and the anode are completely parallel, the distance h between the electrodes corresponds to the separation gap between the strip and the anode surface, and the distance between the strip and the anode is equal to the separation gap between the strip and the anode surface. If the format varies somewhat depending on the position, the distance between the electrodes may be averaged.
第１図、第２図は、積VR・ｈと硫酸アルミニ
ウム含有浴からのFe−Zn系合金電気メツキ皮膜
の性能との関係を示す実験結果である。実験の要
領を以下に記す。矩形断面を有する平行平板電極
系のフロー・チヤネル槽を用い、0.75mm厚×100
mm巾×100mm長のキルド鋼冷延鋼板を素材として、
下記の条件にてZn−Fe系合金メツキを付着量20
ｇ／m2で施した。 FIGS. 1 and 2 are experimental results showing the relationship between the product V R ·h and the performance of an electroplated Fe--Zn alloy film from a bath containing aluminum sulfate. The outline of the experiment is described below. Using a flow channel tank with parallel plate electrodes with a rectangular cross section, 0.75 mm thick x 100
Made of cold-rolled cold-rolled steel plate with a width of mm x 100 mm,
The amount of Zn-Fe alloy plating was 20 under the following conditions.
g/m 2 .
＜電解条件＞
電流密度60〜100A／ｄm2、メツキ浴：浴温45
〜60℃、浴PH1.0〜2.0、Fe2+濃度0.8〜1.2kmol／
m3、〔Fe2+〕／〔Fe2+〕＋〔Zn2+〕）のモル比0.3〜
0.8、Al2（SO4）・xH2OをAl換算濃度で15ｇ／
添加、電極間距離ｈは５〜100mmの間で、またメ
ツキ液の相対速度VRは２〜1800ｍ／minの間でそ
れぞれ変更。<Electrolytic conditions> Current density 60 to 100 A/dm 2 , plating bath: bath temperature 45
~60℃, bath PH1.0~2.0, Fe 2+ concentration 0.8~1.2kmol/
m 3 , [Fe 2+ ]/[Fe 2+ ]+[Zn 2+ ]) molar ratio 0.3~
0.8, Al 2 (SO 4 ) xH 2 O at an Al equivalent concentration of 15g/
The distance h between the addition and electrodes was varied between 5 and 100 mm, and the relative velocity V R of the plating solution was varied between 2 and 1800 m/min.
得られたメツキ鋼板について、以下の３つの試
験を実施した。 The following three tests were conducted on the obtained plated steel plate.
＜耐パウダリング性（加工性）試験＞
巾50mm、長さ200mmの試験片のメツキ面にセロ
テープを貼付し、10mmφ直径の丸棒に沿わせて
180°内曲げを行い、その後この試験片を曲げ戻し
てテープをはがし、この際テープ面に付着したメ
ツキ粉末の量にて調査する。評価は○：メツキ粉
の付着殆どなし、△：やや薄く細かくメツキ着、
●：濃く大きくメツキ粉付着、の３段階による。<Powdering resistance (workability) test> Attach sellotape to the plating surface of a test piece with a width of 50 mm and a length of 200 mm, and place it along a round bar with a diameter of 10 mm.
After bending the specimen 180° inwards, the test piece is bent back and the tape is removed. At this time, the amount of plating powder adhering to the tape surface is examined. Evaluation: ○: Almost no plating powder attached, △: Slightly thin and fine plating,
●: Three stages: thick and large plating powder adhesion.
＜塗装後耐食性試験＞
リン酸塩処理（フオスフオエライト結晶促進剤
含有の処理液の浸漬）→カチオン電着塗装（20μ
ｍ）の後、塗膜にクロスカツトを入れ、360時間
の塩水噴霧試験にかけてクロスカツト部からの剥
離幅を調査する。評価は、Ａ：剥離巾１mm未満、
Ｂ：同じく１〜２mm、Ｃ：同じく２mmをこえるも
の、で行う。<Corrosion resistance test after painting> Phosphate treatment (immersion in treatment solution containing phosphorite crystal accelerator) → cationic electrodeposition coating (20μ
After m), crosscuts are made in the coating film, and a 360-hour salt water spray test is conducted to investigate the peeling width from the crosscuts. Evaluation: A: peeling width less than 1 mm;
B: Same as 1 to 2 mm, C: Same as above 2 mm.
＜スポツト溶接性試験＞
連続5000打点を行なつたのち、5001〜5010打点
目の形成ナゲツト径を調べる。評価は、Ａ：ナゲ
ツト径良、Ｂ：ナゲツト径やや小、Ｃ：ナゲツト
径小さく溶込み不足、による。<Spot weldability test> After performing 5000 consecutive dots, the diameter of the nugget formed at the 5001st to 5010th dots is examined. The evaluation is based on A: Nugget diameter is good, B: Nugget diameter is slightly small, and C: Nugget diameter is small and penetration is insufficient.
第１図は耐パウダリング性についての調査結果
であるが、同図に示すように、積VR・ｈが500以
上では良好は耐パウタリング性が得られ、これ未
満で耐パウダリング性は著しく劣ることになる。
合金メツキ皮膜のパウダリングの発生機構につい
ては未だ不明な部分が多く、したがつて積VR・
h500未満において耐パウダリング性が悪化する
その理由についても明確なことは云えないが、メ
ツキ皮膜中の結晶粒径や結晶内歪に関係があり、
これらが、電析界面において発生する水素の皮膜
中への吸蔵拡散、脱離する水素ガスの粒径や脱離
率（＝１−〔被膜率〕）等に依存する因子であるこ
とから、積VR・ｈが小さい場合陰極面よりの水
素の脱離が不十分となることに原因があるものと
考察される。 Figure 1 shows the results of a study on powdering resistance.As shown in the figure, when the product V R h is 500 or more, good powdering resistance is obtained, and when it is less than this, powdering resistance is extremely poor. It will be inferior.
There are still many unknowns about the mechanism of powdering in alloy plating films, and therefore the product V R
Although it is not possible to say for sure why the powdering resistance deteriorates below h500, it is related to the crystal grain size and intracrystalline strain in the plating film.
These are factors that depend on the absorption and diffusion of hydrogen generated at the electrodeposition interface into the film, the particle size of desorbed hydrogen gas, the desorption rate (=1 - [coating rate]), etc. The reason for this is considered to be that when V R ·h is small, hydrogen is not sufficiently desorbed from the cathode surface.
また第２図は塗装後耐食性とスポツト溶接性に
関する試験結果であり、図中○：両特性とも評価
Ａ、△：何れかの特性が評価Ｂ或いはＣ、●：何
れも評価Ｃ、を表わすものであるが、同図から明
らかなように、塗装後耐食性、スポツト溶接性と
しては、VR・ｈが6500以下において良好な性能
が得られ、これが6500ごえでは劣化することとな
る。すなわち、硫酸アルミニウム含有浴の場合、
積VR・ｈが過大となると、メツチ皮膜中にη相
の混入比率が増加してくる傾向がみられ、メツキ
皮膜を形成する他のδ1相、Γ相、ζ相等との間で
局部腐食電池が形成されることになるため耐食性
が悪化するものと考えられる。またη相それ自体
はスポツト溶接を連続的に繰返し行う場合に、溶
接電極チツプの損耗を早めて溶接の連行を阻害す
るものとして働くものと思われる。 In addition, Figure 2 shows the test results regarding post-painting corrosion resistance and spot weldability. However, as is clear from the figure, good performance is obtained in terms of post-painting corrosion resistance and spot weldability when V R h is 6500 or less, but this deteriorates when V R h is 6500 or less. That is, in the case of a bath containing aluminum sulfate,
When the product V R h becomes too large, there is a tendency for the ratio of η phase to increase in the plating film, and there is a tendency for the ratio of η phase to increase in the plating film. It is thought that corrosion resistance deteriorates because a corrosion battery is formed. It is also believed that the η phase itself acts as a barrier to welding by accelerating wear of the welding electrode tip when spot welding is performed repeatedly.
すなわち、メツキ性能が何れの面でも良好とな
るのは、第３図にハツチングで示したVR・h500
〜6500の範囲においてであることが分る。積
VR・ｈに関する本発明の限定は、以上の理由に
よるものである。 In other words, the plating performance is good in all respects at V R h500, which is shown by the hatching in Figure 3.
~6500. product
The limitations of the present invention regarding V R ·h are based on the above reasons.
なお、本発明においてメツキ浴中に添加する硫
酸アルミニウム塩をAl重量換算で３〜20ｇ／
と限定したのは、Al重量が３ｇ／未満では析
出するメツキ皮膜の組成の安定化が十分に得られ
ず、一方これが20ｇ／ごえでは電流効率の低下
がみれら、経済面から不利となるからである。因
みにAl重量20ｇ／以下において80％以上の電
流効率が確保されるものである。 In addition, in the present invention, the amount of aluminum sulfate salt added to the plating bath is 3 to 20 g/Al weight equivalent.
The reason for this limitation is that if the Al weight is less than 3 g/weight, the composition of the precipitated plating film will not be sufficiently stabilized, while if it is 20 g/g/weight, the current efficiency will decrease, which is disadvantageous from an economic point of view. It is from. Incidentally, a current efficiency of 80% or more is ensured when the Al weight is 20 g/or less.
なお実ライン操業において、積VR・ｈの管理
は、ライン速度（ストリツプ走行速度）VSの変
化に応じ、メツキ液吹込み速度VFをその吹込み
流量の増減調整で制御する、或いは陽極の位置調
整機構により電極間距離ｈを調節する、若しくは
これらを併用する等の方法で行うことができる。 In actual line operation, the product V R h can be managed by controlling the plating liquid blowing speed V F by increasing or decreasing the blowing flow rate according to changes in the line speed (strip running speed) V S , or by controlling the plating liquid blowing speed V F by increasing or decreasing the blowing flow rate. This can be done by adjusting the inter-electrode distance h using a position adjustment mechanism, or by using these methods in combination.
本発明の方法は、最も通例的なZnを主成分と
する（Zn60〜95wt％程度）Fe−Zn合金メツキを
得る電気メツキばかりでなく、メツキ皮膜中に主
成分としてのFe、Znの他に少量のNi、Mn、Ti、
Co、Cr、Sn、Pb、Mg、Al等の１種以上を含有
した合金メツキ等を電析させる場合にも同様に適
用し得るものである。 The method of the present invention is applicable not only to electroplating to obtain Fe-Zn alloy plating mainly composed of Zn (approximately 60 to 95 wt% Zn), but also to Small amounts of Ni, Mn, Ti,
It can be similarly applied to the case of electrodepositing alloy plating containing one or more of Co, Cr, Sn, Pb, Mg, Al, etc.
因みに、実ラインにおいては近年、ストリツプ
走行速度は10〜700ｍ／min、メツキ液吹込み供
給速度も10〜300ｍ／minと高速化の傾向にあり、
したがつてメツキ液の相対速度VRとしては、20
〜1000ｍ／minの間でメツキ設備毎に大きく異な
り、また同一メツキライン内でも、操業中上相対
速度は大きな巾をもつて変動するようになつてき
ている。またストリツプと陽極との電極間距離ｈ
についても、電極槽の種類（タテ型槽、ヨコ型
槽、ラデイアル槽等がある）や陽極の長さをはじ
め、ストリツプの板厚や板巾、更には平坦度（中
伸び、ヘリのび、巾そり、長手そり、カテナリー
そり等による平坦不良がある）、ライン速度やス
トリツプ張力等の条件がメツキ設備毎に様々であ
ることから、メツキ設備毎に５〜100mm程度の範
囲で種々異なつている。また同一のメツキ設備に
おいても、可溶性陽極使用の場合には電極間距離
ｈは陽極の溶解の進行につれ変化することにな
り、更にはライン内張力の変動に起因して変動す
るようなこともある。加えてメツキ電力節減の目
的で、電極間距離ｈを積極的に縮めた特殊なメツ
キ装置なども開発されている。このように従来に
おいて、メツキ液の相対速度VP、電極間距離ｈ
は種々の都合によつてまちまちであり、つまりこ
れらの条件設定に関し確立された考え方は存在し
なかつたものである。 Incidentally, in recent years on actual lines, the strip running speed has been increasing to 10 to 700 m/min, and the plating liquid blowing speed has been increasing to 10 to 300 m/min.
Therefore, the relative velocity V R of the mesh liquid is 20
~1000m/min, which varies greatly depending on the plating equipment, and even within the same plating line, the upper relative speed has begun to fluctuate over a wide range during operation. Also, the distance h between the strip and the anode
There are also various factors such as the type of electrode tank (vertical tank, horizontal tank, radial tank, etc.), the length of the anode, the thickness and width of the strip, and even the flatness (medium elongation, edge extension, width, etc.). (There may be flatness defects due to warping, longitudinal warping, catenary warping, etc.), and conditions such as line speed and strip tension vary from plating equipment to plating equipment, so they vary by about 5 to 100 mm from plating equipment to plating equipment. Furthermore, even in the same plating equipment, if a soluble anode is used, the distance h between the electrodes will change as the anode melts, and may even change due to fluctuations in line tension. . In addition, for the purpose of reducing plating power, special plating devices have been developed in which the distance h between electrodes is actively reduced. In this way, in the past, the relative velocity V P of the plating liquid, the inter-electrode distance h
The conditions vary depending on various circumstances, and in other words, there is no established way of thinking regarding the setting of these conditions.
無論従来においても、技術としてはライン速度
VSやメツキ液吹込み速度VFを規定した例は種々
あるが、とくにFe−Zn系合金メツキに関しては、
これらの両者間の相対速度VRとして規定したも
のは殆どなく、ましてやそこに電極間距離ｈの関
連規定を導入したようなものは全くみられなかつ
たものである。 Of course, in the past, the line speed was
There are various examples of specifying V S and plating liquid injection speed V F , but especially regarding Fe-Zn alloy plating,
There are almost no regulations that define the relative velocity V R between these two, and even more so, there are no regulations that introduce a related regulation for the distance h between the electrodes.
次に本発明の実施例について説明する。 Next, examples of the present invention will be described.
実施例 １
第４図はタテ型メツキ槽を有する連続電気メツ
キ装置を示し、１はメツキ槽、２はストリツプ、
３ａ，３ｂはそれぞれダウンパス側とアツプパス
側の陽極、であるが、同図図示のような装置にお
いて、板厚0.3mm、板巾200mmの冷延鋼板コイルを
素材として、Fe−Zn系合金電気メツキを行なつ
た。メツキ装置の陽極３ａ，３ｂは、Znもしく
はFe陽極で、有効電極長1.5ｍであり、これを図
示の如くストリツプ２に対し約0.3〜0.5°勾配で上
拡がりの傾斜状態に配置したものである。電解条
件は、電流密度80〜120A／ｄm2、メツキ浴：浴
温40〜55℃、浴PH1.5〜2.5、Fe2+濃度0.8〜
1.2kmol／m3、〔Fe2+〕／｛〔Fe2+〕＋〔Zn2+〕｝モ
ル比0.5〜0.7、硫酸アルミニウム酸をAl換算濃度
で10ｇ／添加、硫酸塩と塩化物の混合浴、とし
た。Embodiment 1 FIG. 4 shows a continuous electroplating device having a vertical plating tank, 1 is a plating tank, 2 is a strip,
3a and 3b are anodes on the down-path side and up-path side, respectively. In the device shown in the same figure, a Fe-Zn alloy electric I performed the metsuki. The anodes 3a and 3b of the plating device are Zn or Fe anodes, and have an effective electrode length of 1.5 m, which are arranged in an upwardly expanding manner at an angle of about 0.3 to 0.5° relative to the strip 2, as shown in the figure. . Electrolysis conditions are: current density 80-120 A/dm 2 , plating bath: bath temperature 40-55°C, bath PH 1.5-2.5, Fe 2+ concentration 0.8-
1.2 kmol/m 3 , [Fe 2+ ]/{[Fe 2+ ] + [Zn 2+ ]} molar ratio 0.5 to 0.7, addition of 10 g/aluminum acid sulfate in terms of Al concentration, mixture of sulfate and chloride I took a bath.
上記電気メツキにおいて、メツキ槽１の非駆動
側の側面からストリツト状開口を有する横流
（cross−flow）ノズル（図示せず）によりメツキ
液をライン駆動側へ向けて電極間へ吹込み、その
吹込量を０〜40m3／minの範囲で変化させメツキ
液の流速VFをコントロールした。また、平均電
極間距離ｈを25mm、50mm、75mmの３種類に調整
し、ライン速度VSも２〜200ｍ／minの範囲で変
動させた。なお、メツキ付着量としては、上記ラ
イン速度毎に通電時間を制御して20ｇ／m2目付と
した。 In the above electroplating, the plating liquid is blown from the non-drive side side of the plating tank 1 toward the line drive side and between the electrodes using a cross-flow nozzle (not shown) having a strip-shaped opening. The flow rate V F of the plating solution was controlled by changing the amount in the range of 0 to 40 m 3 /min. Furthermore, the average interelectrode distance h was adjusted to three types: 25 mm, 50 mm, and 75 mm, and the line speed V S was also varied within a range of 2 to 200 m/min. The amount of plating deposited was set to 20 g/m 2 basis weight by controlling the current application time at each line speed.
上記種々の条件で得たFe−Zn系合金メツキ鋼
板について先に示した３つの試験を行い、耐パウ
ダリング性、塗装後耐食性およびスポツト溶接性
を調査し、総合的に評価した。第５図は、その結
果をメツキ条件（VR、ｈ）と対応させて示した
ものである。図中、○：良好、△：やや不良、
●：悪劣、を各示している。 The three tests described above were conducted on the Fe--Zn alloy plated steel sheets obtained under the various conditions described above, and the powdering resistance, post-painting corrosion resistance, and spot weldability were investigated and comprehensively evaluated. FIG. 5 shows the results in correspondence with the plating conditions (V R , h). In the figure, ○: Good, △: Slightly poor.
●: Indicates poor quality.
同図に明らかなように、積VR・ｈが500〜6500
の間でつねに安定して良好なメツキ性能を得るこ
とができた。積VR・ｈが500未満或いは6500ごえ
の条件で得たものはその殆どが著しく劣る性能し
か示さなかつた。 As is clear from the figure, the product V R h is 500 to 6500
It was possible to always obtain stable and good plating performance between the two. Most of the products obtained under conditions where the product V R h was less than 500 or more than 6500 showed significantly inferior performance.
実施例 ２
第６図乃至第８図は何れも水平型メツキセルを
もつ電気メツキ装置を示す。全ての図に共通して
１はセル全体、２はストリツプ（進行方向を矢印
で示す）、３は陽極、４はメツキ液吹込み供給口
であり、第６図のものはメツキ液をストリツプ２
進行方向と正反対の方向に吹込む向流セル方式、
第７図のものはメツキ液をセル１中からストリツ
プ信号方向及びそれと対向する方向に振分けて吹
込む中央垂直吹込み（順流＋向流）セル方式、、
第８図のもの方式的には前出第７図同様順流＋向
流セル方式であるが、これはセル１中央付近から
のメツキ液の吹込めで流体クツシヨンを形成しス
トリツプ２のカテナリー（鎖線図示）を抑えて電
極間距離ｈを接近可能にして中央クツシヨンパツ
ドセル方式になつている。Embodiment 2 FIGS. 6 to 8 each show an electroplating device having a horizontal plating cell. Common to all the figures, 1 is the entire cell, 2 is the strip (the direction of movement is indicated by an arrow), 3 is the anode, and 4 is the plating liquid injection supply port.
Countercurrent cell method that blows in the opposite direction to the direction of travel.
The one in Fig. 7 is a central vertical blowing (forward flow + countercurrent) cell system in which the plating liquid is distributed and blown into the strip signal direction and the opposite direction from inside the cell 1.
The cell system shown in Fig. 8 is a forward flow + countercurrent cell system similar to the previous Fig. The center cushion pad cell type is used, which allows the distance h between the electrodes to be reduced while suppressing the distance h (as shown in the figure).
これら３種類の水平型セル式のメツキ装置にお
いて、鋼板のFe−Zn系合金メツキ（メツキ付着
量：20ｇ／m2）を行なつた。使用した各装置の電
極間距離ｈは、向流セル方式（第６図）では30
mm、中央垂直吹込みセル方式（第７図）では15
mm、中央クツシヨンパツドセル方式（第８図）で
は7.5mmで、陽極は全でPb−In−Tl系不溶性陽極
である。電解条件としては、電流密度120〜
150A／ｄm2、メツキ浴：浴温50〜65℃、浴PH1.2
〜1.8、Fe2+濃度1.0〜1.5kmol／m3、〔Fe2+〕／
｛〔Fe2+〕＋〔Zn2+〕｝のモル比0.4〜0.6、硫酸アル
ミニウム塩をAl濃度換算で20ｇ／添加、硫酸
アンモニウムを電導性支持塩として30ｇ／含有
した硫酸塩浴、とした。 Fe--Zn alloy plating (plating deposit: 20 g/m 2 ) of steel plates was performed using these three types of horizontal cell plating devices. The distance h between the electrodes of each device used was 30 in the countercurrent cell method (Figure 6).
mm, 15 for the central vertical blow cell system (Figure 7)
mm, 7.5 mm for the central cushion pad cell system (Fig. 8), and the anodes are all Pb-In-Tl insoluble anodes. The electrolytic conditions are a current density of 120~
150A/dm 2 , plating bath: bath temperature 50-65℃, bath PH1.2
~1.8, Fe 2+ concentration 1.0 ~ 1.5 kmol/m 3 , [Fe 2+ ]/
A sulfate bath was prepared in which the molar ratio of {[Fe 2+ ]+[Zn 2+ ]} was 0.4 to 0.6, aluminum sulfate was added at 20 g/in terms of Al concentration, and ammonium sulfate was added at 30 g/containing as a conductive supporting salt.
上記した電気メツキにおいて、ライン速度VS
を２〜200ｍ／minの間で変化させるとともに、
電極間へのメツキ液吹込の量を０〜40m3／minの
範囲で変化させ、メツキ液の相対速度VFをコン
トロールした。 In the electroplating described above, line speed V S
While changing between 2 and 200m/min,
The relative velocity V F of the plating liquid was controlled by changing the amount of plating liquid injected between the electrodes in the range of 0 to 40 m 3 /min.
上記種々の条件で得たFe−Zn系合金メツキ鋼
板について、実施例１と同様の方法で性能を評価
した。第９図はその結果を示す。 The performance of the Fe-Zn alloy plated steel sheets obtained under the various conditions described above was evaluated in the same manner as in Example 1. Figure 9 shows the results.
同図の試験結果でも、積VR・ｈが500〜6500の
範囲においてのみ良好な性能が得られている。 Also in the test results shown in the figure, good performance was obtained only in the range of product V R ·h from 500 to 6500.
実施例 ３
第１０図、第１１図はラデイアルセルを有する
片面電気メツキ装置を示し、第１０図のものは、
ストリツプ２を回転ドラム５に巻付けて片面がメ
ツキ浴１′と接触するように送り、回転ドラム５
の周面に沿つて配置されたダウンパス側、アツプ
パス側の可溶性陽極３ａ，３ｂによつてメツキを
施す可溶性陽極式（CAROSEL式）ラデイアルセ
ル方式であり、メツキ液は上記両陽極３ａ，３ｂ
の間に位置する供給口４からダウンパス、アツプ
パスの各側の陽極３ａ，３ｂと回転ドラムに巻付
いたストリツプ２間に振分け供給される。第１１
図のものも基本的には同様の形式であるが、これ
は陽極３ａ，３ｂが不溶性陽極で、回転ドラム５
の周面に沿つて設けたメツキセル１に内張りされ
た形になつている不溶性陽極式のものである。Embodiment 3 FIGS. 10 and 11 show a single-sided electroplating device having a radial cell, and the one in FIG.
The strip 2 is wound around the rotating drum 5 and fed so that one side is in contact with the plating bath 1'.
This is a soluble anode type (CAROSEL type) radial cell method in which plating is performed using soluble anodes 3a and 3b on the down-path side and up-path side arranged along the circumferential surface of the anodes 3a and 3b, and the plating liquid is applied to both the anodes 3a and 3b.
From a supply port 4 located between them, the anodes 3a and 3b on each side of the down path and up path are distributed and supplied between the strip 2 wound around the rotating drum. 11th
The one in the figure is basically of the same type, but in this case, the anodes 3a and 3b are insoluble anodes, and the rotating drum 5
It is of an insoluble anode type and is lined with a mesh cell 1 provided along the circumferential surface of the cell.
このような２種類のメツキ装置において、板厚
0.4mm、板巾200mmの薄鋼板を素材として、Fe−
Zn系合金メツキを行なつた。電解条件は、電流
密度50〜90A／ｄm2、メツキ浴：浴温60〜75℃、
浴PH1.5〜2.0、Fe2+濃度0.7〜1.0kmol／m2、
〔Fe2+〕／｛〔Fe2+〕＋〔Zn2+〕｝のモル比0.4〜0.8、
硫酸アルミニウム塩をAl濃度換算で10ｇ／添
加のもので、不溶性陽極式ラデイアルセル方式
（第１１図）では、上記メツキ浴は電導性支持塩
として硫酸ナトリウム80ｇ／、硫酸マグネシウ
ム10ｇ／を含む硫酸塩浴とした。可溶性陽極式
（第１０図）の方は、陽極３ａ，３ｂにZnとFeを
面積比で適宜分配した混合可溶性陽極を採用し、
上記メツキ浴としては、陽極の溶解を促進し不働
態化を抑制するため多量の塩化物（NH4Cl100
ｇ／、NaCl30ｇ／）を含有せしめた硫酸塩
と塩化物の混合浴を使用した。 In these two types of plating equipment, the plate thickness
Fe-
Zn alloy plating was carried out. Electrolysis conditions were: current density 50-90A/ dm2 , plating bath: bath temperature 60-75℃,
Bath pH 1.5-2.0, Fe 2+ concentration 0.7-1.0 kmol/m 2 ,
[Fe 2+ ]/{[Fe 2+ ] + [Zn 2+ ]} molar ratio 0.4 to 0.8,
In the insoluble anode radial cell method (Fig. 11), the plating bath is a sulfate bath containing 80 g of sodium sulfate and 10 g of magnesium sulfate as conductive supporting salts. And so. The soluble anode type (Figure 10) uses a mixed soluble anode in which Zn and Fe are appropriately distributed in the area ratio for the anodes 3a and 3b.
The above plating bath contains a large amount of chloride (NH 4 Cl100
A mixed sulfate and chloride bath was used containing 30 g/g/, NaCl 30 g/).
上記の電気メツキにおいて、電極間距離ｈを、
可溶性陽極式（第１０図）では５mmと10mmに、ま
た不溶性陽極式（第１１図）では20mmと30mmにそ
れぞれ設定し、ライン速度VSを５〜200ｍ／min
の間で、またメツキ液吹込みの量を１〜40m3／
minの範囲でそれぞれ変化させてメツキ液の相対
速度VRコントロールした。 In the above electroplating, the distance h between the electrodes is
The soluble anode type (Figure 10) is set to 5 mm and 10 mm, and the insoluble anode type (Figure 11) is set to 20 mm and 30 mm, and the line speed V S is set from 5 to 200 m/min.
Between 1 and 40 m 3 /
The relative speed of the plating liquid V R was controlled by changing each within the range of min.
前出の〔実施例〕同様、上記種々の条件で得た
メツキ鋼板について、性能の評価を行なつたその
結果を第１２図に示す。 As in the above-mentioned [Example], the performance of the plated steel plates obtained under the various conditions described above was evaluated, and the results are shown in FIG.
同図の評価結果も、積VR・h500〜6500の範囲
において良好なメツキ性能が安定して得られるこ
とを明らかに示している。 The evaluation results in the figure also clearly show that good plating performance can be stably obtained in the range of product V R ·h 500 to 6500.
以上に詳述したとおり本発明の方法によれば、
硫酸アルミニウム含有浴を使用して、加工性、塗
装後耐食性、溶接性の何れの点でもすぐれた性能
を示すFe−Zn系合金電気メツキ鋼板を連続的に
安定して得ることができ、したがつて本発明は
Fe−Zn系合金メツキ鋼板の品質向上、製造歩留
りの改善に寄与するところ大なるものと云うこと
ができる。 According to the method of the present invention as detailed above,
Using a bath containing aluminum sulfate, it was possible to continuously and stably obtain Fe-Zn alloy electroplated steel sheets that exhibit excellent performance in terms of workability, post-painting corrosion resistance, and weldability. Therefore, the present invention
It can be said that this greatly contributes to improving the quality and manufacturing yield of Fe-Zn alloy plated steel sheets.
第１図、第２図は硫酸含有浴によるFe−Zn系
合金電気メツキにおける積VR・ｈとその製品と
してのFe−Zn系合金メツキ鋼板の性能との関係
を示す実験結果であり、第１図は耐パウダリング
性、第２図は塗装後耐食性、スポツト溶接性につ
いての調査結果を示す。第３図は積VR・ｈに関
する本発明の条件範囲を示す図、第４図はタテ型
メツキ槽式電気メツキ装置の模式図、第５図は第
４図図示のメツキ装置で得たFe−Zn系合金メツ
キ鋼板の性能を評価した結果であり、第６図〜第
８図は水平型メツキセル式電気メツキ装置を３種
類示す模式図、第９図は第６図〜第８図のメツキ
装置で得たFe−Zn系合金電気メツキ鋼板の性能
を評価した結果であり、第１０図、第１１図はラ
デイアルメツキセル式電気メツキ装置を２種類示
す模式図、第１２図は第１０図、第１１図の装置
で得たFe−Zn系合金電気メツキ鋼板の性能の評
価結果である。
図中、１：メツキ槽、２：ストリツプ、３：陽
極、４：メツキ液吹込み供給口、５：回転ドラ
ム。
Figures 1 and 2 show the experimental results showing the relationship between the product V R h in Fe-Zn alloy electroplating using a sulfuric acid-containing bath and the performance of Fe-Zn alloy plated steel sheets as products. Figure 1 shows the results of an investigation on powdering resistance, and Figure 2 shows the results of an investigation on post-painting corrosion resistance and spot weldability. Fig. 3 is a diagram showing the condition range of the present invention regarding the product V R h, Fig. 4 is a schematic diagram of a vertical plating bath type electroplating device, and Fig. 5 is a diagram showing Fe obtained with the plating device shown in Fig. 4. - The results of evaluating the performance of Zn-based alloy plated steel sheets. Figures 6 to 8 are schematic diagrams showing three types of horizontal type plating cell type electroplating equipment, and Figure 9 is a schematic diagram showing the plating equipment shown in Figures 6 to 8. These are the results of evaluating the performance of Fe-Zn alloy electroplated steel sheets obtained with the equipment. Figures 10 and 11 are schematic diagrams showing two types of radial mesh cell type electroplating equipment, and Figure 12 is a schematic diagram showing two types of radial mesh cell type electroplating equipment. 10 and 11 are the performance evaluation results of the Fe-Zn alloy electroplated steel sheet obtained with the apparatus shown in FIG. 11. In the figure, 1: plating tank, 2: strip, 3: anode, 4: plating liquid blowing supply port, 5: rotating drum.
Claims (1)
場合において、メツキ浴中に硫酸アルミニウム塩
をAl重量換算で３〜20ｇ／添加するとととも
に、メツキ液流と走行ストリツプとの平均相対速
度VRおよび走行ストリツプと陽極との平均極間
距離ｈを、 500VR・ｈ6500 但し、VR：〔ｍ／min〕 ｈ：〔mm〕 上記の条件を満たすように管理することを特徴
とする鋼板のFe−Zn系合金電気メツキ方法。[Claims] 1. In the case of continuously electrodepositing Fe-Zn alloy on a steel plate, 3 to 20 g of aluminum sulfate is added to the plating bath in terms of Al weight, and the plating liquid flow and running strip are The average relative speed V R between the running strip and the anode and the average distance h between the running strip and the anode are 500V R・h6500 However, V R : [m/min] h: [mm] Manage to satisfy the above conditions. A method for electroplating Fe-Zn alloy on steel sheets, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12508083A JPS6017093A (en) | 1983-07-08 | 1983-07-08 | Electroplating method of fe-zn alloy to steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12508083A JPS6017093A (en) | 1983-07-08 | 1983-07-08 | Electroplating method of fe-zn alloy to steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6017093A JPS6017093A (en) | 1985-01-28 |
| JPH0331796B2 true JPH0331796B2 (en) | 1991-05-08 |
Family
ID=14901332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12508083A Granted JPS6017093A (en) | 1983-07-08 | 1983-07-08 | Electroplating method of fe-zn alloy to steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6017093A (en) |
-
1983
- 1983-07-08 JP JP12508083A patent/JPS6017093A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6017093A (en) | 1985-01-28 |
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