JPS6215635B2 - - Google Patents
Info
- Publication number
- JPS6215635B2 JPS6215635B2 JP54016928A JP1692879A JPS6215635B2 JP S6215635 B2 JPS6215635 B2 JP S6215635B2 JP 54016928 A JP54016928 A JP 54016928A JP 1692879 A JP1692879 A JP 1692879A JP S6215635 B2 JPS6215635 B2 JP S6215635B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- corrosion resistance
- alloy
- concentration
- current density
- 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 54
- 238000005260 corrosion Methods 0.000 claims description 21
- 230000007797 corrosion Effects 0.000 claims description 20
- 229910000831 Steel Inorganic materials 0.000 claims description 19
- 239000010959 steel Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 7
- 238000009713 electroplating Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910007567 Zn-Ni Inorganic materials 0.000 claims 2
- 229910007614 Zn—Ni Inorganic materials 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000011701 zinc Substances 0.000 description 23
- 229910018605 Ni—Zn Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Description
【発明の詳細な説明】
この発明は、高耐食性Ni−Zn合金メツキ鋼板
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a highly corrosion resistant Ni-Zn alloy plated steel sheet.
耐食性メツキとしては、亜鉛メツキが一般的で
ある。しかし亜鉛メツキは亜鉛自身の犠牲防食効
果を期待するものであり、耐食性の良否はメツキ
付着量にかかつているので、高い耐食性を賦与し
ようとして厚くメツキすると、いきおい製品コス
トが高くつき、また溶接性が悪化する。従つて近
時上記欠点を解消するためにNi−Zn等の合金メ
ツキが提案されている。例えば英国特許第548184
号には、線材を対象としたNi−Zn合金メツキの
有用性について報告されており、なかでも合金組
成のNi含有量が11〜18％で最も優れた耐食性の
得られることが発表されている。しかしメツキラ
インでは、不可避とされるメツキ条件（メツキ電
流密度等）の変動による析出合金組成の変化のた
めに、常にこのような所定成分に合金を析出させ
ることは極めて困難で、安定した耐食性並びに外
観性状（光沢）が得られ難い。 Zinc plating is commonly used as a corrosion-resistant plating. However, zinc plating is expected to have a sacrificial anti-corrosion effect from the zinc itself, and the quality of corrosion resistance depends on the amount of plating deposited. Therefore, if the plating is thick in an attempt to impart high corrosion resistance, the product cost will be high, and weldability will be reduced. becomes worse. Therefore, recently, alloy plating such as Ni--Zn has been proposed to overcome the above-mentioned drawbacks. For example UK Patent No. 548184
The issue reports on the usefulness of Ni-Zn alloy plating for wire rods, and it is announced that the best corrosion resistance can be obtained when the Ni content in the alloy composition is 11 to 18%. . However, in the plating line, it is extremely difficult to always precipitate the alloy with such predetermined components because the deposited alloy composition changes due to unavoidable fluctuations in the plating conditions (plating current density, etc.), and it is difficult to maintain stable corrosion resistance and appearance. It is difficult to obtain good properties (gloss).
このNi−Zn合金メツキにおける析出合金組成
のバラツキについては、一部改善策が出されてい
る。すなわち、比較的低電流密度での電子部品等
のNi−Zn合金メツキにおいて、メツキ用電解液
として従来の酸性或いはアルカリ浴に代えてシア
ン浴を用いる方法（特開昭51−28533）がそれで
ある。しかしこの方法は、鋼板のようにメツキ面
積が大きく、しかも生産性をあげるため高電流密
度で行わねばならないような場合には、あまり有
効ではなく、同時に排水処理等の問題もあつて、
鋼板のNi−Zn合金メツキへの適用の可能性は極
めて薄いと云わなければならない。このため現在
鋼板の表面処理としてのNi−Zn合金メツキは、
殆んど工業化されていないのが実状である。 Some measures have been taken to improve the variation in the composition of the precipitated alloy in Ni--Zn alloy plating. That is, in the plating of Ni-Zn alloys such as electronic parts at relatively low current density, there is a method in which a cyanide bath is used instead of the conventional acidic or alkaline bath as the electrolyte for plating (Japanese Patent Laid-Open No. 51-28533). . However, this method is not very effective in cases where the plating area is large, such as steel plates, and high current density must be used to increase productivity, and at the same time there are problems such as wastewater treatment.
It must be said that the possibility of application to Ni-Zn alloy plating of steel sheets is extremely slim. For this reason, Ni-Zn alloy plating is currently used as a surface treatment for steel sheets.
The reality is that almost none of it has been industrialized.
上記状況に鑑み本発明者らは、鋼板に均一な品
質のNi−Zn合金メツキを形成させ得る連続電気
メツキ方法について、種々実験、研究した結果、
メツキ浴中のNi2+濃度とZn2+濃度のモル比Ni2+／
Zn2+、PH並びにメツキ液と鋼板の相対移動速度、
の３つの条件を適正化することにより、メツキ条
件の変動に拘らず、高速、高電流密度においても
Ni含有量が９〜20％で安定した品質のNi−Zn合
金メツキを得ることに成功した。 In view of the above circumstances, the present inventors conducted various experiments and research on continuous electroplating methods that can form Ni-Zn alloy plating of uniform quality on steel sheets.
Molar ratio of Ni 2+ concentration to Zn 2+ concentration in plating bath Ni 2+ /
Zn 2+ , PH and relative movement speed between plating liquid and steel plate,
By optimizing the following three conditions, it can be used at high speeds and high current densities regardless of variations in plating conditions.
We succeeded in obtaining stable quality Ni-Zn alloy plating with a Ni content of 9 to 20%.
すなわち本発明は、メツキ液中のNi2+濃度が
20g／以上、Zn2+濃度が10g／以上の条件下
でNi2+とZn2+のモル濃度比を1.5〜４、PHを１〜
4.5に調整し、同時に前記メツキ液と鋼板の相対
移動速度を10m／min以上に維持して5A／ｄm2以
上の電流密度で連続メツキする点を特徴とする。
この方法により、耐食性、光沢ともに良好なNi
−Zn合金メツキ鋼板を得ることができる。 That is, in the present invention, the Ni 2+ concentration in the plating solution is
The molar concentration ratio of Ni 2+ and Zn 2+ is 1.5 to 4 , and the pH is 1 to 20 g/min, and the Zn 2+ concentration is 10 g/min or more.
4.5, and at the same time maintain the relative moving speed between the plating liquid and the steel plate at 10 m/min or more, and perform continuous plating at a current density of 5 A/dm 2 or more.
This method allows Ni to have good corrosion resistance and gloss.
- Zn alloy plated steel sheets can be obtained.
第１図は上記Ni2+及びZn2+濃度、Ni2+とZn2+の
モル濃度比Ni2+／Zn2+が、Ni−Znメツキ鋼板に及
ぼす影響を示す。図中○，△，×は、メツキの耐
食性並びに外観の良否を表わしており、○：外観
良・耐食性良、△：外観不良・耐食性良、×：外
観不良・耐食性不良、を各示している。本発明に
おけるNi2+／Zn2+の限定範囲に斜線を施して示
す。 FIG. 1 shows the effects of the Ni 2+ and Zn 2+ concentrations and the molar concentration ratio of Ni 2+ and Zn 2+ , Ni 2+ /Zn 2+ , on the Ni-Zn plated steel sheet. In the figure, ○, △, and × represent the corrosion resistance and appearance quality of plating. ○: Good appearance and good corrosion resistance, △: Poor appearance and good corrosion resistance, ×: Poor appearance and poor corrosion resistance. . The limited range of Ni 2+ /Zn 2+ in the present invention is indicated by diagonal lines.
Ni2+濃度が20g／より少なくなると、または
Zn2+濃度について10g／未満では、電流密度が
大きくなつた場合正常なメツキが行われず、図示
する如く△或は×となつてしまう。また、これら
両濃度についての上限は特に限定しない。 When the Ni 2+ concentration is less than 20 g/
If the Zn 2+ concentration is less than 10 g/, normal plating will not be performed when the current density becomes large, resulting in △ or × as shown in the figure. Further, the upper limits for both these concentrations are not particularly limited.
Ni2+／Zn2+が1.5未満になると、電流密度の変
動によつてメツキ中にNiが充分含有されない場
合があり、均一な耐食性や良好な外観が得られな
い。またこの値が４を越えた場合には、上記とは
逆にメツキ中のNi含有量が必要以上に多くな
り、その結果Zn固溶のNi相（α相）が析出し、
耐食性に劣化がみられる。なおメツキ浴の温度に
ついては、40〜70℃程度が最適で、低過ぎると
Niの析出量が低下し、逆に高過ぎる場合はこれ
が多くなるとともに、メツキ浴での液蒸発量が増
して操業上不経済である。またメツキ液のPHは、
１〜4.5前後に調整しておくのが好ましく、低く
なる程メツキ中水素ガスの発泡が多くなつてメツ
キ表面に気泡ムラが生じ、同時に電流効率も悪化
し得策ではない。他方必要以上に高いとメツキの
外観が黒灰色となる傾向がある。 When Ni 2+ /Zn 2+ is less than 1.5, Ni may not be sufficiently contained in the plating due to fluctuations in current density, and uniform corrosion resistance and good appearance cannot be obtained. If this value exceeds 4, contrary to the above, the Ni content in the plating will be higher than necessary, and as a result, the Ni phase (α phase) in solid solution with Zn will precipitate.
Deterioration in corrosion resistance is observed. Regarding the temperature of the plating bath, the optimum temperature is between 40 and 70 degrees Celsius, and if it is too low,
The amount of Ni precipitated decreases, and conversely, if it is too high, it increases, and the amount of liquid evaporated in the plating bath increases, which is uneconomical in terms of operation. In addition, the PH of Metsuki liquid is
It is preferable to adjust the value to about 1 to 4.5. The lower the value, the more hydrogen gas bubbles during plating, causing uneven bubbles on the plating surface, and at the same time, the current efficiency deteriorates, which is not a good idea. On the other hand, if it is higher than necessary, the appearance of the plating tends to be blackish gray.
メツキ槽内のメツキ液と鋼板の相対的な速度
は、メツキ浴通過中の鋼板近傍のNi2+／Zn2+のバ
ランスに影響を与えるもので、本発明者らの実験
によればこの相対移動速度が10m／min未満にな
ると、鋼板近傍のNi2+／Zn2+の比率がバルクの組
成よりくずれてしまい、電流密度の変動によつて
メツキ合金組成が適正範囲から外れた耐食性等の
劣化を来たすことが明かとなつた。従つてこれを
10m／min以上に限定した。この相対速度の設定
は、ライン速度（鋼板移動速度）がその他の条件
で先に決められてしまう場合には、メツキ液の給
排によつて槽内のメツキ液に流れを与え、流れ速
さの調節によつて行うことができる。 The relative speed between the plating liquid and the steel plate in the plating bath affects the balance of Ni 2+ /Zn 2+ near the steel plate passing through the plating bath, and according to experiments conducted by the present inventors, this relative speed If the moving speed is less than 10 m/min, the Ni 2+ /Zn 2+ ratio near the steel plate will deviate from the bulk composition, and changes in current density will cause the plating alloy composition to deviate from the appropriate range, resulting in poor corrosion resistance, etc. It became clear that this would lead to deterioration. Therefore this
Limited to 10m/min or more. When the line speed (steel plate movement speed) is determined in advance by other conditions, this relative speed setting is done by supplying and discharging the plating liquid to give a flow to the plating liquid in the tank, and to adjust the flow speed. This can be done by adjusting the
電流密度は5A／ｄm2以下であるとメツキ浴の
PHによつてはメツキがつかない部分を生じること
があるのでこれ以上とした。また上限は特に限定
しないが、100A／ｄm2以下程度が望ましい。 If the current density is less than 5A/ dm2 , the plating bath
Depending on the pH, some parts may not be plated, so a higher value was chosen. The upper limit is not particularly limited, but it is preferably about 100 A/dm 2 or less.
次に本発明の実施例について述べる。 Next, embodiments of the present invention will be described.
メツキ槽２つを備える水平式連続メツキライン
で、0.8mm厚×300mm巾の冷延鋼板ストリツプに下
記の条件で、連続メツキを施した。 On a horizontal continuous plating line equipped with two plating tanks, continuous plating was applied to a cold-rolled steel strip with a thickness of 0.8 mm and a width of 300 mm under the following conditions.
(1) メツキ浴：硫酸ニツケル（NiSO4・6H2O）
265g／と硫酸亜鉛（ZnSO4・7H2O）145g／
を添加してNi2+／Zn2+を1.99に調整（Ni2+濃
度59.1g／、Zn2+濃度33.1g／）し、これに
Na2SO475g／を加えてPH2.1〜2.5としたも
の、浴温50〜55℃
(2) 電流密度：20A／ｄm2
(3) ストリツプ速度：4m／min
(4) 給液方法：ストリツプの進行方向と逆方向に
向かつて供給循環
(5) 上記(3)と(4)に基くストリツプと浴との相対速
度：
15m／min〜18m／min
(6) 鋼板へのメツキ付着量：20g／m2
メツキ後、鋼板のメツキ面の光沢を全長に亘つ
て調べたが、無光沢部分は全くなく極めて良好で
あつた。またメツキ合金組成を同じく全長につい
て調査したところ、Ni含有量が12.8〜13.1％で適
正範囲９〜20％内に収まつており、耐食性につい
ても塩水噴霧試験を実施して赤錆発生時間が192
時間にも及び極めて優れたものであつた。(1) Plating bath: Nickel sulfate (NiSO 4 6H 2 O)
265g/ and zinc sulfate (ZnSO 4 7H 2 O) 145g/
was added to adjust Ni 2+ /Zn 2+ to 1.99 (Ni 2+ concentration 59.1 g/, Zn 2+ concentration 33.1 g/), and to this
75g of Na 2 SO 4 was added to adjust the pH to 2.1-2.5, bath temperature 50-55℃ (2) Current density: 20A/dm 2 (3) Stripping speed: 4m/min (4) Liquid supply method: Supply circulation in the direction opposite to the direction in which the strip travels (5) Relative speed between the strip and the bath based on (3) and (4) above: 15 m/min to 18 m/min (6) Amount of plating deposited on the steel plate: After plating at 20 g/m 2 , the gloss of the plated surface of the steel plate was examined over the entire length, and it was found to be extremely good with no matte areas. In addition, when we investigated the entire length of the metal alloy composition, we found that the Ni content was 12.8% to 13.1%, which was within the appropriate range of 9% to 20%, and for corrosion resistance, we conducted a salt spray test and found that the red rust generation time was 192%.
It lasted a long time and was extremely good.
このように本発明方法は、特別な設備を用いる
ことなく通常の電気メツキラインにて高速、高電
流密度で常に安定した品質のNi−Zn合金メツキ
鋼板を得ることができ、従つて鋼板のNi−Zn合
金メツキ処理の工業化を低コストに実現させるも
のである。 In this way, the method of the present invention can produce Ni-Zn alloy-plated steel sheets of consistently stable quality at high speed and high current density using ordinary electroplating lines without using any special equipment. This enables industrialization of Zn alloy plating processing at low cost.
第１図は、メツキ浴中のNi2+及びZn2+濃度、
Ni2+とZn2+のモル濃度比Ni2+／Zn2+が、Ni−Zn合
金メツキに及ぼす影響を示し、横軸はNi2+濃度、
縦軸はZn2+濃度で、図中○，△，×は、メツキの
耐食性並びに外観光沢の良否を表わしており、
○：外観良・耐食性良、△：外観不良・耐食性
良、×：外観不良・耐食性不良、を各示してい
る。
Figure 1 shows the Ni 2+ and Zn 2+ concentrations in the plating bath,
The influence of the molar concentration ratio Ni 2+ /Zn 2+ of Ni 2+ and Zn 2+ on Ni−Zn alloy plating is shown, and the horizontal axis is the Ni 2+ concentration,
The vertical axis is the Zn 2+ concentration, and ○, △, and × in the figure represent the corrosion resistance of the plating and the quality of the appearance gloss.
○: Good appearance and good corrosion resistance, △: Poor appearance and good corrosion resistance, ×: Poor appearance and poor corrosion resistance.
Claims (1)
て、メツキ浴中のNi2+濃度を20g／以上、Zn2+
濃度を10g／以上とし、かつNi2+とZn2+のモル
濃度比を1.5〜４に、PHを１〜4.5に調整すると共
に、メツキ浴でのメツキ液と鋼板の相対移動速度
を10m／min以上に設定し、5A／ｄm2以上の電流
密度でメツキを行なうことを特徴とする高耐食性
Zn−Ni合金メツキ鋼板の製造方法。1 In the Zn-Ni alloy electroplating method for steel sheets, the Ni 2+ concentration in the plating bath is set to 20 g/or more, and the Zn 2+
The concentration was set to 10 g/or more, the molar concentration ratio of Ni 2+ and Zn 2+ was adjusted to 1.5 to 4, and the pH was adjusted to 1 to 4.5, and the relative movement speed between the plating solution and the steel plate in the plating bath was set to 10 m//. High corrosion resistance characterized by plating at a current density of 5 A/dm 2 or more with a current density of 5 A/dm 2 or more.
A method for producing Zn-Ni alloy plated steel sheets.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1692879A JPS55110791A (en) | 1979-02-15 | 1979-02-15 | Preparation of plated steel plate with high corrosion resistance |
| US06/118,962 US4313802A (en) | 1979-02-15 | 1980-02-05 | Method of plating steel strip with nickel-zinc alloy |
| GB8004471A GB2046790B (en) | 1979-02-15 | 1980-02-11 | Method of plating steel strip |
| DE3005159A DE3005159C2 (en) | 1979-02-15 | 1980-02-12 | Process for the plating of steel strips with a zinc-nickel alloy |
| FR8003275A FR2449140A1 (en) | 1979-02-15 | 1980-02-14 | METHOD OF PLACING A STEEL STRIP |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1692879A JPS55110791A (en) | 1979-02-15 | 1979-02-15 | Preparation of plated steel plate with high corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55110791A JPS55110791A (en) | 1980-08-26 |
| JPS6215635B2 true JPS6215635B2 (en) | 1987-04-08 |
Family
ID=11929785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1692879A Granted JPS55110791A (en) | 1979-02-15 | 1979-02-15 | Preparation of plated steel plate with high corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55110791A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5861292A (en) * | 1981-10-05 | 1983-04-12 | Sumitomo Metal Ind Ltd | Painted steel plate |
| JPS5890951A (en) * | 1981-11-26 | 1983-05-30 | 住友金属工業株式会社 | Laminated board having excellent corrosion-resistant property |
| JPS58130299A (en) * | 1982-01-26 | 1983-08-03 | Nisshin Steel Co Ltd | Production of zn-ni alloy electroplated steel plate having high corrosion resistance in worked part |
| JPS58204195A (en) * | 1982-05-25 | 1983-11-28 | Nippon Kokan Kk <Nkk> | Manufacture of steel plate electroplated with ni-zn alloy and provided with superior workability and corrosion resistance |
-
1979
- 1979-02-15 JP JP1692879A patent/JPS55110791A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| METAL FINISHING#M12=1972 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55110791A (en) | 1980-08-26 |
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