JPS63230896A - Bright aluminum plating bath and plating method using same - Google Patents
Bright aluminum plating bath and plating method using sameInfo
- Publication number
- JPS63230896A JPS63230896A JP6267287A JP6267287A JPS63230896A JP S63230896 A JPS63230896 A JP S63230896A JP 6267287 A JP6267287 A JP 6267287A JP 6267287 A JP6267287 A JP 6267287A JP S63230896 A JPS63230896 A JP S63230896A
- Authority
- JP
- Japan
- Prior art keywords
- bath
- plating
- aluminum
- mol
- bright
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 97
- 229910052782 aluminium Inorganic materials 0.000 title claims description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 60
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims 2
- 238000009713 electroplating Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 description 9
- 239000010960 cold rolled steel Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- -1 aluminum halide compound Chemical class 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 101100323029 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) alc-1 gene Proteins 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QAIGYXWRIHZZAA-UHFFFAOYSA-M 1-methylpyridin-1-ium;chloride Chemical group [Cl-].C[N+]1=CC=CC=C1 QAIGYXWRIHZZAA-UHFFFAOYSA-M 0.000 description 1
- 229910000680 Aluminized steel Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910000149 boron phosphate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZTHNOZQGTXKVNZ-UHFFFAOYSA-L dichloroaluminum Chemical compound Cl[Al]Cl ZTHNOZQGTXKVNZ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は浴寿命が長く、危険性も小さく、しかも安価で
電流効率も高い電気アルミニウムめっき浴およびそのめ
っき浴によるめっき方法を開発したものであるが、とく
に表面は均一でち密な光沢アルミニウムめっきが得られ
るため、金属アルミニウムの特性の生かせる幅広い分野
に応用可能である。[Detailed Description of the Invention] (Field of Industrial Application) The present invention has developed an electrolytic aluminum plating bath that has a long bath life, is less dangerous, is inexpensive, and has high current efficiency, and a plating method using the plating bath. However, it can be applied to a wide range of fields where the characteristics of metal aluminum can be utilized, especially since it produces a uniform, dense, and glossy aluminum plating on the surface.
（従来技術）
アルミニウムの電気めっきは、アルミニウムの酸素に対
する親和力が大きく、電位が水素より卑であるので、水
溶液系のめっき浴で行うことは困難である。このため従
来よりアルミニウムの電気めっきは非水溶液系のめっき
浴、特に有機溶媒系のめっき浴で行われている。(Prior Art) It is difficult to perform electroplating of aluminum in an aqueous plating bath because aluminum has a large affinity for oxygen and its potential is less noble than that of hydrogen. For this reason, electroplating of aluminum has conventionally been carried out in a non-aqueous plating bath, particularly an organic solvent-based plating bath.
この有機溶媒系のめっき浴としては、ＡｌＣ１ｘとＬｉ
Ａ ＩＩ ｌ、又はＬｉＨとをエーテルに溶解したもの
や、ＡｌＣｌ、とＬｉＡ Ｉ Ｈ，とをＴＨＦ （テト
ラヒドロフラン）に溶解したもの、あるいは西ドイツの
シーメンス・リサーチ・ラボラトリ−によって１９７５
年に工業化の検討が進められ、１９８０年オランダのヘ
ギン・ガルバノ・アルミニウムによって工業用パイロッ
トプラントが完成した５ＩＧＡＬ ＰＲＯＣＥＳＳなど
がある。これらのめっき浴によれば、純度、加工性およ
び外観の優れたアルミニウムめっきを行うことができる
とされている。This organic solvent-based plating bath includes AlC1x and Li
AlCl or LiH, dissolved in ether, AlCl and LiA IH, dissolved in THF (tetrahydrofuran), or 1975 by the Siemens Research Laboratory in West Germany.
In 1980, consideration of industrialization progressed, and in 1980, an industrial pilot plant was completed by Hagin Galvano Aluminum of the Netherlands, including 5IGAL PROCESS. According to these plating baths, it is said that aluminum plating with excellent purity, workability, and appearance can be performed.
（発明が解決しようとする問題点）
しかし、これらのめっき浴からのめっき状態は白色を呈
するもので、実際的には光沢鏡面を示さない、さらに、
５ＩＧＡＬ ＰＲＯＣＥＳＳでは、良質な八ｌめっきが
得られるが、８μ−以上めっき厚がないと無孔とならな
い。(Problems to be Solved by the Invention) However, the plating state from these plating baths is white and does not actually show a glossy mirror surface.
In 5IGAL PROCESS, high-quality 8L plating can be obtained, but unless the plating thickness is 8μ or more, it will not be porous.
（問題点を解決するための手段）
本発明者らは上記のような光沢表面を示す八！めっき浴
を開発すべく、種々研究した結果、塩化アルミニウムと
メチル−およびブチル−ピリジニウムクロリド（前者を
ＭＰＣ，後者をＢＰＣと略記する）とからなる溶融塩浴
にトルエンを含む有機溶媒を添加した浴を開発した（Ｍ
ＰＣの場合、合成法などに若干の問題があるので、ここ
ではＢＰＣに代表させてのべである。）のであるが、さ
らに効率よく光沢鏡面を有する外観良好な高純度のアル
ミニウムめっきを行うには、特定の電解条件で行う必要
のあることを知見した。すなわち本発明者らは、ＡｌＣ
ｌ１ｓ ５０〜７５モル％とＢＰＣ２５〜５０モル％と
を溶融してなる溶融塩浴に、トルエンあるいはトルエン
＋ベンゼン混合溶媒を添加したことを特徴とする光沢ア
ルミニウムめっき浴およびこのめっき浴を用い、乾燥無
酸素雰囲気中で直流電流またはパルス電流により、浴温
０〜８０℃、電流密度０．１〜１０ Ａ／ｄａ＋”の電
解条件でめっきすることを特徴とする光沢アルミニウム
めっき方法を開発したのである。なお、トルエン＋ベン
ゼンなどの混合溶媒の添加により、高箪流密度でのアル
ミニウムの光沢めっきが可能となった。(Means for Solving the Problems) The present inventors have developed an 8! As a result of various studies to develop a plating bath, we developed a bath in which an organic solvent containing toluene was added to a molten salt bath consisting of aluminum chloride and methyl- and butyl-pyridinium chloride (the former is abbreviated as MPC, and the latter as BPC). developed (M
In the case of PC, there are some problems with the synthesis method, so BPC will be used as a representative example here. ), but it has been found that in order to more efficiently perform high-purity aluminum plating with a glossy mirror surface and a good appearance, it is necessary to perform plating under specific electrolytic conditions. That is, the present inventors discovered that AlC
A bright aluminum plating bath characterized by adding toluene or a mixed solvent of toluene and benzene to a molten salt bath formed by melting 50 to 75 mol% of l1s and 25 to 50 mol% of BPC, and drying using this plating bath. We have developed a bright aluminum plating method that uses direct current or pulsed current in an oxygen-free atmosphere under electrolytic conditions at a bath temperature of 0 to 80°C and a current density of 0.1 to 10 A/da+. By adding a mixed solvent such as toluene and benzene, bright plating of aluminum at a high flow density became possible.
本発明のめっき浴を使用することにより、常温で光沢ア
ルミニウムの電気めっきが可能となる。By using the plating bath of the present invention, bright aluminum can be electroplated at room temperature.
このめっき浴は有機溶媒を添加しているため、引火性は
あるが、著しく活性な成分を添加してないため、安定し
ており、酸素や水分と接触しても爆発などの心配がない
。This plating bath contains an organic solvent, so it is flammable, but since it does not contain any extremely active ingredients, it is stable, and there is no risk of explosion if it comes into contact with oxygen or moisture.
本発明のめっき浴の場合も、従来のめっき浴と同様アル
ミニウムめっきはアルミニウムハロゲン化合物により行
うのであるが、本発明の場合、アルミニウムハロゲン化
合物はＡｌＣｌ２．に限定されず、Ａｊ！Ｂｒｓ、 Ａ
ｎ！Ｉｓも使用可能である。しかしＡｌＩＣｌ１．は安
価であるほか、刺激性、腐食性なども少ないことから、
安全面からも好ましい。In the case of the plating bath of the present invention, aluminum plating is performed using an aluminum halide compound as in the conventional plating bath, but in the case of the present invention, the aluminum halide compound is AlCl2. Not limited to Aj! Brs, A
n! Is can also be used. However, AlICl1. In addition to being inexpensive, it is also less irritating and corrosive.
This is preferable from a safety standpoint.
浴中の塩化アルミニウム濃度は５０〜７５モル％にする
のが好ましい。これはアルミニウムハロゲン化合物が５
０モル％未満であると、アルキルピリジニウムカチオン
濃度が高くなり、アルミニウム電析の際、アルキルピリ
ジニウムカチオン還元反応が同時に進行し、浴の劣下、
電流効率の低下およびめっき層の表面外観不良を招くか
らである。また７５モル％を越えると、浴に溶は難くな
るとともに、浴の導電率が低くなり、蒸気圧も高くなる
。The aluminum chloride concentration in the bath is preferably 50 to 75 mol%. This is an aluminum halide compound with 5
If it is less than 0 mol%, the alkylpyridinium cation concentration will be high, and during aluminum electrodeposition, the alkylpyridinium cation reduction reaction will proceed at the same time, resulting in bath deterioration and
This is because this results in a decrease in current efficiency and poor surface appearance of the plating layer. Moreover, if it exceeds 75 mol%, it becomes difficult to dissolve in the bath, the conductivity of the bath becomes low, and the vapor pressure becomes high.
アルミニウムハロゲン化合物の濃度をこのようにした場
合、アルキルピリジニウムハロゲン化合物はその残部で
あるので、濃度は２５〜５０モル％となる。When the concentration of the aluminum halogen compound is set in this manner, the alkylpyridinium halogen compound is the remainder, so the concentration is 25 to 50 mol %.
また、アルミニウムハロゲン化合物とアルキルピリジニ
ウムハロゲン化合物との合計量に対するトルエンおよび
ベンゼン＋トルエン混合溶媒の添加割合は、有機溶媒の
割合が１０〜７５ｖｏｌ％（従って両ハロゲン化合物の
合計量は２５〜９０ｖｏｌ％となる）になるようにする
のが好ましい。In addition, the addition ratio of toluene and benzene + toluene mixed solvent to the total amount of the aluminum halogen compound and the alkylpyridinium halogen compound is such that the ratio of the organic solvent is 10 to 75 vol% (therefore, the total amount of both halogen compounds is 25 to 90 vol%). It is preferable to do so.
有機溶媒の割合が１０ｖｏｌ％未満であると、特性が溶
融塩浴とほとんど変らず、鏡面光沢めっきが得られない
。また有機溶媒の割合が７５ｖｏｌ％を越えると、溶融
塩浴と有機溶媒が均一混合しなくなるとともに、浴中の
アルミニウムハロゲン化合物の濃度が低くなるため、ア
ルミニウム電析の際の電流効率が著しく低くなる。If the proportion of the organic solvent is less than 10 vol %, the properties will be almost the same as those of a molten salt bath, and a specular gloss plating will not be obtained. Furthermore, if the proportion of the organic solvent exceeds 75 vol%, the molten salt bath and the organic solvent will not mix uniformly, and the concentration of the aluminum halide compound in the bath will decrease, resulting in a significant decrease in current efficiency during aluminum electrodeposition. .
めっき浴は、酸素や水分に触れても安全であるが、アル
ミニウム錯イオンの酸化、あるいはめっきされたＡｌの
酸化を防止するため、めっきは乾燥無酸素雰囲気中（た
とえば乾燥ＮＺやＡｒ中）で行うのが好ましい。また電
解条件は浴温０〜８０℃で、直流またはパルス電流を用
いて、０．１〜１０Ａ／ｄｍ”にすると効率よ（高純度
で、均一なめっきを行うことができる。１〜３Ａ／ｄａ
”では鏡面光沢めっきも得られる。電流は直流よりパル
ス電流の方が結晶が微細になり、めっき性が良好になる
。なお、ジェット噴流、超音波かくはん等の使用により
、電流密度をＩＯＡ／ｄｗ！以上にすることが可能であ
る。The plating bath is safe even if it comes into contact with oxygen or moisture, but in order to prevent the oxidation of aluminum complex ions or the oxidation of the plated Al, plating should be performed in a dry oxygen-free atmosphere (for example, in dry NZ or Ar). It is preferable to do so. The electrolysis conditions are a bath temperature of 0 to 80°C, a direct current or a pulsed current, and a flow rate of 0.1 to 10 A/dm. da
", mirror-like gloss plating can also be obtained. When using a pulsed current, the crystals become finer than when using a direct current, resulting in better plating properties. By using a jet stream, ultrasonic stirring, etc., the current density can be increased to IOA/dw. It is possible to do more than !
浴温は０℃より低くすると、めっき浴の凝固が起こった
り、高電流密度でめっきすることができない。また、８
０℃より高くすると、溶剤の蒸発が激しく、均一なめっ
きも得にくい。If the bath temperature is lower than 0° C., coagulation of the plating bath may occur or plating cannot be performed at high current density. Also, 8
If the temperature is higher than 0°C, the solvent will evaporate rapidly and it will be difficult to obtain uniform plating.
一般に連続めっきで均一なめっきを施すには、めっき浴
に＾ｌイオンを補給して、浴中のＡＪイオン濃度を一定
に管理する必要があるが、本発明のめっき浴では、陽極
をアルミニウム製可溶性陽極にすると、通電量に応じて
Ａβイオンが補給さ・れるので好都合である。たとえば
、１４１ｃＩｌｘ −ＢＰＣ系めっき浴でアルミニウム
製陽極を使用してめっきすると、ｌイオンは陽極より次
のようにして自動的に補給される。Generally, in order to achieve uniform plating through continuous plating, it is necessary to replenish the plating bath with ^l ions and control the AJ ion concentration in the bath at a constant level, but in the plating bath of the present invention, the anode is made of aluminum. A soluble anode is advantageous because Aβ ions are replenished according to the amount of current applied. For example, when plating is performed using an aluminum anode in a 141cIlx -BPC-based plating bath, l ions are automatically replenished from the anode as follows.
Ａｌ ＋４Ｃ１−→ＡｌＣｌ＜−＋３ｅ−Ａｌ ＋７Ａ
ｊ２ＣＪ４− ＝４ＡＩ！ｚＣ１ｑ−＋３８−陽極にＴ
ｉ−Ｐｔ系などの不溶性陽極を使用して連続めっきする
場合のＡＩ！イオンの補給は、ＡｌＣ１！、、Ａ ｌ
１３ｒ ３、Ａ Ｉ Ｉ ｘなどのハロゲン化合物を補
給すればよい。しかし不溶性陽極使用による連続めっき
の場合、電解時に陽極界面でハロゲンガス発生反応が起
こって、浴中のハロゲン成分が減少する。Al +4C1-→AlCl<-+3e-Al +7A
j2CJ4− =4AI! zC1q-+38-T on anode
AI when performing continuous plating using an insoluble anode such as i-Pt type! Ion replenishment is AlC1! ,,A l
A halogen compound such as 13r 3 or A I I x may be supplied. However, in the case of continuous plating using an insoluble anode, a halogen gas generation reaction occurs at the anode interface during electrolysis, reducing the halogen component in the bath.
このため、浴組成が変動し、浴の寿命が短くなる。This causes the bath composition to fluctuate and shortens the life of the bath.
以下実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
（実施例）
実施例１
冷延鋼板（板厚０．５ｍ）に、常法により溶剤蒸気洗浄
、アルカリ脱脂および酸洗などのめっき前処理を施した
後、乾燥して、直ちにあらかじめＮ２雰囲気に保ってお
いたＡｌＣ２，６７モル％とＲＰＣ３３モル％からなる
溶融塩浴に、トルエンをその割合が６０ｖｏｌ％となる
ように添加しためっき浴（浴温：２０℃）に浸漬し、ア
ルミニウムめっきを行った。めっきは、冷延鋼板を陰極
、アルミニウム板（純度９９．９９ ｗｔ％、板厚５鶴
）を陽極として、直流により電流密度０．５Ａ／ｄｍ”
で約３０分間行った。電流効率は通電量、めっき付着量
より計算してみると、１００％であった。(Example) Example 1 A cold-rolled steel plate (thickness: 0.5 m) was subjected to plating pretreatment such as solvent vapor cleaning, alkaline degreasing, and pickling using a conventional method, then dried and immediately placed in an N2 atmosphere in advance. Aluminum plating was performed by immersing the molten salt bath containing 67 mol% AlC and 33 mol% RPC into a plating bath (bath temperature: 20°C) in which toluene was added at a ratio of 60 vol%. Ta. The plating was performed using a direct current with a current density of 0.5 A/dm using a cold rolled steel plate as a cathode and an aluminum plate (purity 99.99 wt%, plate thickness 5 mm) as an anode.
It lasted about 30 minutes. The current efficiency was calculated from the amount of current applied and the amount of plating deposited, and was 100%.
このようにして得られたアルミニウムめっき鋼板のめっ
き層は、厚みが均一で像鮮映性り／Ｉ値（ＡＳＴＭ ｆ
！ ４３０による）が６０以上を示す鏡面光沢を呈し、
結晶はち密であった。The plating layer of the aluminized steel sheet obtained in this way has a uniform thickness and a good image sharpness/I value (ASTM f
! 430) exhibits a specular luster of 60 or more,
The crystals were dense.
第１図は本実施例におけるアルミニウムめっきした状態
における表面状況を示す走査型電子顕微鏡写真、第２図
はめっき層並びに素材金属の断面状況を示す金属断面写
真を示す。第１図より、めっき表面は極めて平滑であり
、また第２図、断面写真より、良好なめっき密着状況と
なっていることが示されている。また鋼板に繰り返し折
り曲げを施しても、クランクや剥離は発生せず、加工性
、密着性とも良好であった。FIG. 1 is a scanning electron microscope photograph showing the surface condition of the aluminum plated state in this example, and FIG. 2 is a metal cross-sectional photograph showing the cross-sectional condition of the plating layer and the raw metal. From FIG. 1, the plating surface is extremely smooth, and from the cross-sectional photograph in FIG. 2, it is shown that the plating has good adhesion. Further, even when the steel plate was repeatedly bent, no cracking or peeling occurred, and both workability and adhesion were good.
実施例２
実施例１と同要領で、あらかじめＮ２雰囲気に保ってお
いたＡＩＣＪｓ６７モル％とＢＰＯ４３モル％からなる
溶融塩浴にトルエン中ベンゼン（配合モル比は１：１）
をその割合が６０ｖｏｌ％となるように添加しためっき
浴（浴温２０℃）に浸漬し、アルミニウムめっきを行っ
た。めっきは冷延鋼板を陰極、アルミニウム板（純度９
９．９９ ｗｔ％、板厚５鰭）を陽極として、直流によ
り、電流密度２Ａ／ｄｍ”で８分間行った。Example 2 In the same manner as Example 1, benzene in toluene (mixed molar ratio 1:1) was added to a molten salt bath consisting of 67 mol% AICJs and 43 mol% BPO, which had been kept in an N2 atmosphere in advance.
Aluminum plating was performed by immersing the sample in a plating bath (bath temperature: 20° C.) to which 60 vol % of aluminum was added. For plating, a cold-rolled steel plate is used as the cathode, and an aluminum plate (purity 9
9.99 wt%, plate thickness: 5 fins) was used as an anode, and the test was carried out for 8 minutes using direct current at a current density of 2 A/dm''.
得られたアルミニウムめっき層は、厚みが均一で、光沢
を呈し、結晶はち密であった。また鋼板に繰り返し折り
曲げを施しても、クラックや剥離は発生せず、加工性、
密着性とも良好であった。The obtained aluminum plating layer had a uniform thickness, was shiny, and had dense crystals. In addition, even if the steel plate is repeatedly bent, no cracks or peeling will occur, and the processability will be improved.
Adhesion was also good.
電流効率は通電量、めっき付着量より計算してみると、
１００％であった。Current efficiency is calculated from the amount of current flowing and the amount of plating deposited.
It was 100%.
実施例３
板厚０．５ ｍの冷延鋼板に、実施例１と同要領でアル
ミニウムめっきを行った。めっきは、Ａｒ雰囲気に保っ
た浴温２０℃のＡβＢｒｊ！：＋６７モル％とＢＰＯ４
３モル％からなる溶融塩浴に、トルエンを６０ｖｏｌ％
添加しためっき浴に、冷延鋼板を浸漬し、該鋼板を陰極
、アルミニウム板（実施例１と同じ）を陽極として、直
流により電流密度０．５Ａ／ｄｍ”で３０分間行った。Example 3 A cold rolled steel plate having a thickness of 0.5 m was aluminum plated in the same manner as in Example 1. Plating was performed using AβBrj at a bath temperature of 20°C maintained in an Ar atmosphere. : +67 mol% and BPO4
60 vol% toluene was added to a molten salt bath consisting of 3 mol%.
A cold-rolled steel plate was immersed in the plating bath containing the additives, the steel plate was used as a cathode, and the aluminum plate (same as in Example 1) was used as an anode, and the plating was carried out using direct current at a current density of 0.5 A/dm for 30 minutes.
得られたアルミニウムめっき鋼板のめっき層高質は、実
施例１と同様厚みが均一で、光沢を呈し、結晶はち密で
あった。The high-quality plating layer of the obtained aluminum-plated steel sheet had a uniform thickness, was glossy, and had dense crystals as in Example 1.
このように、実施例１と同様の結果を得た。In this way, the same results as in Example 1 were obtained.
実施例４
板ＦＥ ０．５ ｍの冷延鋼板に、実施例１と同要領で
アルミニウムめっきを行った。めっきは、Ａｒ雰囲気に
保った浴温２５℃のＡｊ？Ｂｒｊ！ｚ６７モル％とＢＰ
Ｃ３３モル％からなる溶融塩浴に、ベンゼン＋トルエン
混合溶媒を６０ｖｏｌ％添加しためっき浴に、冷延鋼板
を浸漬、該鋼板を陰極、アルミニウム板（実施例１と同
じ）を陽極として、直流を用いて電流密度１．５Ａ／ｄ
ｍ”で１０分間行った。Example 4 A cold-rolled steel sheet with a plate FE of 0.5 m was aluminum plated in the same manner as in Example 1. Plating was carried out in an Ar atmosphere with a bath temperature of 25°C. Brj! z67 mol% and BP
A cold-rolled steel plate was immersed in a plating bath containing 60 vol% of benzene + toluene mixed solvent in a molten salt bath consisting of 33 mol% of C, and a direct current was applied using the steel plate as a cathode and an aluminum plate (same as in Example 1) as an anode. using a current density of 1.5A/d
m” for 10 minutes.
得られたアルミニウムめっき鋼板のめっき層高質は、実
施例１と同様厚みが均一で、光沢を呈し、結晶はち密で
あった。The high-quality plating layer of the obtained aluminum-plated steel sheet had a uniform thickness, was glossy, and had dense crystals as in Example 1.
実施例５
板厚０．５鶴の冷延鋼板に、実施例１と同様にめっき前
処理、乾燥を施して、実施例１〜３の各めっき浴でパル
ス電流によりアルミニウムめっきを行った。パルス電流
によるめっきは、いずれのめっき浴の場合もデユーティ
−比１／１０〜１ ／１００、平均電流密度０．１〜Ｉ
ＯＡ／ｄａ”で行ったが、めっき層の厚みは均一で、外
観、加工性、密着性とも直流によりめっきした場合と同
一であった。Example 5 A cold-rolled steel plate with a thickness of 0.5 mm was subjected to plating pretreatment and drying in the same manner as in Example 1, and aluminum plating was performed using pulsed current in each of the plating baths of Examples 1 to 3. Plating using pulsed current is performed at a duty ratio of 1/10 to 1/100 and an average current density of 0.1 to I for any plating bath.
The thickness of the plating layer was uniform, and the appearance, workability, and adhesion were the same as those obtained by direct current plating.
なお、Ｃｕｓ Ｃｕ合金、Ｎｉ合金へも上記同様にめっ
きを試みたところ、優れたＡｌめっきが可能であった。In addition, when plating was also attempted on Cu alloy and Ni alloy in the same manner as above, excellent Al plating was possible.
（効 果）
以上の本発明のめっき浴は、酸素や水分と激しく反応す
るような成分を含んでいないので、浴寿命が長く、危険
性が小さい、またアルキルピリジニウムハロゲン化合物
は、ＬｉＡ ｊｌ ＨａやＬｉＨより安価で、電流効率
も高いので、浴寿命の長いことと相まって、めっき費を
著しく低減させることができる。しかも有機溶媒の添加
により、電流密度を上げることかで゛き、さらにトルエ
ンおよびベンゼン＋トルエン混合溶媒添加で、光沢鏡面
を有するアルミニウムめっきが可能となった。(Effects) The plating bath of the present invention as described above does not contain any components that react violently with oxygen or moisture, so it has a long bath life and is less dangerous. Since it is cheaper than LiH and has higher current efficiency, combined with a longer bath life, plating costs can be significantly reduced. Moreover, by adding an organic solvent, it is possible to increase the current density, and furthermore, by adding toluene or a mixed solvent of benzene and toluene, aluminum plating with a glossy mirror surface has become possible.
従って、本発明のめっき浴を使用すれば、耐熱性、耐酸
化性、耐食性などの点から、電気アルミニウムめっき素
材や製品を必要とする家電部品、ＩＣリードフレーム、
磁気ディスク等の電子部品、自動車部品、航空部品、燃
料電池などの分野に、それらを安価に供給することがで
きる。Therefore, if the plating bath of the present invention is used, it will be possible to improve the heat resistance, oxidation resistance, corrosion resistance, etc. of home appliance parts, IC lead frames, etc. that require electrolytic aluminum plating materials and products.
They can be supplied at low cost to fields such as electronic parts such as magnetic disks, automobile parts, aircraft parts, and fuel cells.
第１図は、本発明のめっき浴でアルミニウムめっきした
表面状況を示した走査型電子顕微鏡による倍率３０００
の金属組織を示す写真。
第２図は、本発明の実施例であるアルミニウムめっきさ
れた軟鋼板の断面状況を示した倍率５０００の金属組織
を示す写真である。図中、中間層の灰色部は、アルミめ
っき層であり、その下層の白っぽい部分が鋼素地である
。Figure 1 shows the surface condition of aluminum plated with the plating bath of the present invention using a scanning electron microscope at a magnification of 3000.
Photograph showing the metallographic structure of. FIG. 2 is a photograph showing the metal structure at a magnification of 5000, showing the cross-sectional state of an aluminum-plated mild steel plate according to an example of the present invention. In the figure, the gray part of the intermediate layer is the aluminum plating layer, and the whitish part below it is the steel base.
Claims (7)
ル％とブチルピリジニウムクロリド２５〜５０モル％と
を溶融してなる溶融塩浴にトルエンを添加することを特
徴とする光沢電気アルミニウムめっき浴。(1) A bright electrolytic aluminum plating bath characterized by adding toluene to a molten salt bath prepared by melting 50 to 75 mol% of aluminum chloride (AlCl_3) and 25 to 50 mol% of butylpyridinium chloride.
ル％とブチルピリジニウムクロリド２５〜５０モル％と
を溶融してなる溶融塩浴にトルエン＋ベンゼンを添加す
ることを特徴とする光沢電気アルミニウムめっき浴。(2) A bright electrolytic aluminum plating bath characterized by adding toluene and benzene to a molten salt bath made by melting 50 to 75 mol% of aluminum chloride (AlCl_3) and 25 to 50 mol% of butylpyridinium chloride.
ことを特徴とする特許請求の範囲第１項に記載の光沢電
気アルミニウムめっき浴。(3) The bright electrolytic aluminum plating bath according to claim 1, wherein the blending ratio of toluene is 25 to 75 vol%.
ｌ％であることを特徴とする特許請求の範囲第２項に記
載の光沢電気アルミニウムめっき浴。(4) The blending ratio of toluene + benzene is 25 to 75vo
1% of the bright electrolytic aluminum plating bath according to claim 2.
ル％とブチルピリジニウムクロリド２５〜５０モル％と
を溶融してなる溶融塩浴に対してトルエンを２５〜７５
ｖｏｌ％添加した電気アルミニウムめっき浴を用い、乾
燥無酸素雰囲気中で、直流電流又はパルス電流により浴
温０〜８０℃、電流密度０．１〜３Ａ／ｄｍ＾２の電解
条件でめっきすることを特徴とする光沢電気アルミニウ
ムめっき方法。(5) Add 25 to 75 mol% of toluene to a molten salt bath made by melting 50 to 75 mol% of aluminum chloride (AlCl_3) and 25 to 50 mol% of butylpyridinium chloride.
Using an electrolytic aluminum plating bath with vol% addition, in a dry oxygen-free atmosphere, plating is carried out under the electrolytic conditions of a bath temperature of 0 to 80 °C and a current density of 0.1 to 3 A/dm^2 by direct current or pulse current. Features a bright electrolytic aluminum plating method.
ル％とブチルピリジニウムクロリド２５〜５０モル％と
を溶融してなる溶融塩浴に対して、トルエン＋ベンゼン
を２５〜７５ｖｏｌ％添加した電気アルミニウムめっき
浴を用い、乾燥無酸素雰囲気中で、直流電流又はパルス
電流により浴温０〜８０℃、電流密度０．１〜１０Ａ／
ｄｍ＾２の電解条件でめっきすることを特徴とする光沢
電気アルミニウムめっき方法。(6) An electrolytic aluminum plating bath in which 25 to 75 vol% of toluene + benzene is added to a molten salt bath formed by melting 50 to 75 mol% of aluminum chloride (AlCl_3) and 25 to 50 mol% of butylpyridinium chloride. In a dry oxygen-free atmosphere, the bath temperature is 0 to 80°C and the current density is 0.1 to 10 A/
A bright electrolytic aluminum plating method characterized by plating under dm^2 electrolytic conditions.
を特徴とする特許請求の範囲第５項又は第６項に記載の
光沢電気アルミニウムめっき方法。(7) The bright electrolytic aluminum plating method according to claim 5 or 6, characterized in that plating is performed using an aluminum anode as an anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6267287A JPS63230896A (en) | 1987-03-19 | 1987-03-19 | Bright aluminum plating bath and plating method using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6267287A JPS63230896A (en) | 1987-03-19 | 1987-03-19 | Bright aluminum plating bath and plating method using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63230896A true JPS63230896A (en) | 1988-09-27 |
Family
ID=13207012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6267287A Pending JPS63230896A (en) | 1987-03-19 | 1987-03-19 | Bright aluminum plating bath and plating method using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63230896A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423389B1 (en) * | 1997-04-10 | 2002-07-23 | Occ Corporation | Metal tube armored linear body, metal tube armoring linear body, method and apparatus for manufacturing metal tube armored linear body |
-
1987
- 1987-03-19 JP JP6267287A patent/JPS63230896A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423389B1 (en) * | 1997-04-10 | 2002-07-23 | Occ Corporation | Metal tube armored linear body, metal tube armoring linear body, method and apparatus for manufacturing metal tube armored linear body |
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