JPH0488188A - Al alloy electroplating bath and plating method using this bath - Google Patents
Al alloy electroplating bath and plating method using this bathInfo
- Publication number
- JPH0488188A JPH0488188A JP20174590A JP20174590A JPH0488188A JP H0488188 A JPH0488188 A JP H0488188A JP 20174590 A JP20174590 A JP 20174590A JP 20174590 A JP20174590 A JP 20174590A JP H0488188 A JPH0488188 A JP H0488188A
- Authority
- JP
- Japan
- Prior art keywords
- halide
- bath
- alloy
- plating bath
- plating
- 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 81
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 6
- 238000009713 electroplating Methods 0.000 title abstract description 11
- -1 aluminum halide Chemical class 0.000 claims abstract description 58
- 150000004820 halides Chemical class 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 150000001491 aromatic compounds Chemical class 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000002635 aromatic organic solvent Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 239000010960 cold rolled steel Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910001080 W alloy Inorganic materials 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910001257 Nb alloy Inorganic materials 0.000 description 4
- 229910001362 Ta alloys Inorganic materials 0.000 description 4
- 229910000756 V alloy Inorganic materials 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- OOKUTCYPKPJYFV-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;bromide Chemical compound [Br-].CN1C=C[NH+]=C1 OOKUTCYPKPJYFV-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- XNSAROHFORHQRR-UHFFFAOYSA-M 1,3-dimethylbenzimidazol-3-ium;chloride Chemical compound [Cl-].C1=CC=C2N(C)C=[N+](C)C2=C1 XNSAROHFORHQRR-UHFFFAOYSA-M 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- ISWZUFUYWWUREQ-UHFFFAOYSA-M 1-ethyl-3-methylbenzimidazol-3-ium;bromide Chemical compound [Br-].C1=CC=C2N(CC)C=[N+](C)C2=C1 ISWZUFUYWWUREQ-UHFFFAOYSA-M 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910001295 No alloy Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000005005 aminopyrimidines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LETVJWLLIMJADE-UHFFFAOYSA-N pyridazin-3-amine Chemical compound NC1=CC=CN=N1 LETVJWLLIMJADE-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、常温もしくは比較的低温でめっきできる電気
Ａｌ合金めっき浴およびその浴によるめっき方法に関す
る
（従来技術）
Ａｌ合金は、一般に軽量で、耐食性、耐熱性に優れてい
るが、組み合わせ元素によってはさらに他の特性を付与
することができる。しかし、Ａｌ合金は、高価であるの
で、安価な用途に使用する場合にはＡｌ合金をめっきし
た部材が適している。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an electrolytic Al alloy plating bath that can perform plating at room temperature or relatively low temperature, and a plating method using the bath (prior art) Al alloys are generally lightweight; It has excellent corrosion resistance and heat resistance, but depending on the combination of elements, other properties can be imparted. However, since Al alloy is expensive, members plated with Al alloy are suitable for use in inexpensive applications.
Ａｌ合金めっきは、溶融めっきや蒸着めっきでも可能で
あるが、工業的に溶融めっきで行うには、容量が数百ト
ンのめっき浴を必要とするため、多量の合金元素を必要
とする。また、めっき合金を変更する場合、溶融合金を
全量かき出さなければならないので、めっき浴の変更に
多くの困難を伴う。Al alloy plating can be performed by hot-dip plating or vapor deposition plating, but industrially performing hot-dip plating requires a plating bath with a capacity of several hundred tons, and thus requires a large amount of alloying elements. Furthermore, when changing the plating alloy, the entire amount of the molten alloy must be scraped out, so changing the plating bath is accompanied by many difficulties.
一方、蒸着めっきにはこのような問題がないが、生産性
が劣り、蒸着金属は直進しかしないため、被めっき材の
形状が複雑なものの場合、めっきできない部分が生じる
。On the other hand, although vapor deposition plating does not have such problems, it has poor productivity and the vapor-deposited metal only moves in a straight line, so if the shape of the material to be plated is complex, there will be parts that cannot be plated.
また、溶融めっき、蒸着めっきはともに被めっき材の加
熱を伴うため、形状や寸法に゛変動が生じる。Furthermore, since both hot-dip plating and vapor deposition plating involve heating of the material to be plated, variations occur in shape and dimensions.
このようなことから、Ａｌ合金を常温もしくは低温で電
気めっきで施すことができれば、非常に好都合である。For this reason, it would be very convenient if Al alloy could be applied by electroplating at room temperature or low temperature.
（発明が解決しようとする問題点）
しかしながら、Ａｌ合金をこのような条件で電気めっき
できるめっき浴はまだ開発されていなかった。(Problems to be Solved by the Invention) However, a plating bath capable of electroplating an Al alloy under such conditions has not yet been developed.
本発明は、このようなことから、常温もしくは比較的低
温で電気めっき可能な電気Ａｌ合金めっき浴およびその
浴によるめっき方法を提供するものである。For this reason, the present invention provides an electrolytic Al alloy plating bath that allows electroplating at room temperature or relatively low temperature, and a plating method using the bath.
（問題点を解決するための手段）
本発明者らは、電気Ａｌ合金めっき浴として次のような
めっき浴を開発した。(Means for Solving the Problems) The present inventors have developed the following plating bath as an electrolytic Al alloy plating bath.
（１）下記（Ａ）、（Ｂ）および（Ｃ）成分を含有する
電気Ａｌ合金めっき浴。(1) An electrolytic Al alloy plating bath containing the following components (A), (B) and (C).
（Ａ）アルミニウムハロゲン化物 ３３〜６７モル％
（Ｂ）次の（イ）〜（へ）から選んだ１種 ０．０１〜
６７モル％
（イ）リチウムハロゲン化物、
（ロ）バナジウムハロゲン化物またはフルオロバナジウ
ム酸のアルカリ金属塩あるいはこれらの両方、
（ハ）ニオブハロゲン化物またはフルオロニオブ酸のア
ルカリ金属塩あるいはこれらの両方、
（ニ）タンタルハロゲン化物またはフルオロタンタル酸
のアルカリ金属塩あるいはこれらの両方
（ホ）モリブデンハロゲン化物
（へ）タングステンハロゲン化物
（Ｃ）アルキルピリジニウムハロゲン化物またはアルキ
ルイミダゾリウムハロゲン化物（但し、いずれの化合物
ともアルキル基の炭素数は１〜１２） ３３〜６７モ
ル％
（２）上記（１）のめっき浴に芳香族有機溶媒を添加し
た電気Ａｌ合金めっき浴。(A) Aluminum halide 33 to 67 mol% (B) One type selected from the following (a) to (f) 0.01 to
67 mol% (a) Lithium halide, (b) Vanadium halide or alkali metal salt of fluoroniobic acid, or both, (c) Niobium halide or alkali metal salt of fluoroniobic acid, or both. ) Tantalum halide or alkali metal salt of fluorotantalic acid, or both (e) Molybdenum halide (f) Tungsten halide (C) Alkylpyridinium halide or alkylimidazolium halide (However, neither compound has an alkyl group carbon number is 1 to 12) 33 to 67 mol% (2) An electric Al alloy plating bath obtained by adding an aromatic organic solvent to the plating bath of (1) above.
（３）前記（１）のめっき浴に窒素原子を有する芳香族
化合物を添加した電気Ａｌ合金めっき浴。(3) An electrolytic Al alloy plating bath in which an aromatic compound having a nitrogen atom is added to the plating bath of (1) above.
そして、これらのめっき浴による電気めっき方法として
、浴温２５〜１８０℃、電流密度０．０１〜１００ Ａ
／ｄａ＋”で直流またはパルス電流によりめっきする方
法を開発した。Electroplating methods using these plating baths include bath temperatures of 25 to 180°C and current densities of 0.01 to 100 A.
/da+'' plating method using direct current or pulsed current was developed.
本発明のめっき浴の前記３成分は、いずれも固体である
が、混合すると溶融し、常温でも液体の溶融塩浴となり
、電気めっきで合金元素含有量が０．０二〜９３％のＡ
ｌ合金をめっきすることができる。具体的には、Ａｌ−
Ｌｉ合金およびＡｌ−Ｔａ合金めっきの場合はＬｉまた
はＴａ含有量が０．０１〜７０％のものを、Ａｌ−Ｖ合
金めっきの場合はＶ含有量が０．１〜４０％のものを、
また、Ａｌ−Ｎｂ合金およびＡｌ−Ｗ合金めっきの場合
はＮｂまたはＷ含有量が０．１〜９３％のものをめっき
することができる。The three components of the plating bath of the present invention are all solids, but when mixed, they melt and form a molten salt bath that is liquid even at room temperature.
1 alloy can be plated. Specifically, Al-
In the case of Li alloy and Al-Ta alloy plating, the Li or Ta content is 0.01 to 70%, and in the case of Al-V alloy plating, the V content is 0.1 to 40%.
Furthermore, in the case of Al-Nb alloy and Al-W alloy plating, those having a Nb or W content of 0.1 to 93% can be plated.
本発明のめっき浴では、アルミニウムハロゲン化物を３
３〜６７モルに含有させる。この化合物の含有量が３３
モル％未満になると、アルキルピリジニウムイオンやア
ルキルイミダゾリウムイオンが多くなり、それがめつき
層に付着し、６７モル％を越えると、めっき浴の融点が
高くなり、好ましくない。このアルミニウムハロゲン化
物は、一般式ＡｌＸ５（Ｘはハ（＋ゲン原子でＦ、 Ｃ
ｌ５Ｂｒ、 １など）で示されるものである。In the plating bath of the present invention, aluminum halide is
The content is 3 to 67 moles. The content of this compound is 33
If it is less than 67 mol%, alkylpyridinium ions and alkylimidazolium ions will increase and adhere to the plating layer, and if it exceeds 67 mol%, the melting point of the plating bath will become high, which is not preferable. This aluminum halide has the general formula AlX5 (X is Ha (+gen atom is F, C
15Br, 1, etc.).
本発明では、上記アルミニウムハロゲン化物とともに、
前記（イ）〜（へ）の１種を００１〜６７モル％含有さ
せる。これらの化合物は、含有量が０．０１モル％未満
であると、合金元素イオンが不足し、電解条件によって
は合金元素が電析しない場合が生じる。一方、６７モル
％を越えると、めっき浴の融点が高くなり、好ましくな
い。In the present invention, together with the above aluminum halide,
One of the above (a) to (f) is contained in an amount of 001 to 67 mol%. If the content of these compounds is less than 0.01 mol %, alloying element ions will be insufficient, and depending on the electrolytic conditions, the alloying element may not be electrodeposited. On the other hand, if it exceeds 67 mol%, the melting point of the plating bath will become high, which is not preferable.
ここで、リチウムハロゲン化物とは、一般式ＬｉＸ（Ｘ
はハロゲン原子で、Ｆ、Ｃ１、Ｂｒ、 Ｉなどである）
で示される化合物である。Here, lithium halide refers to the general formula LiX(X
is a halogen atom, such as F, C1, Br, I)
This is a compound represented by
また、周期律表第Ｖａ族に属するバナジウム、ニオブ、
タンタルなどのハロゲン化物は、一般式ＭＩＸ、（Ｍｌ
はＶ、 Ｎｂ５Ｔａであり、Ｘはハロゲン原子でＦ 、
Ｃ１，Ｂｒ、 １など、ｎは２〜５）で示される原
子価が■価、■価、■価、７価のハロゲン化物であり、
また、フルオロ金属酸のアルカリ金属塩は、フルオロバ
ナジウム酸塩の場合、一般式Ｍ ！、Ｖ Ｆ 、（Ｍ
２はアルカリ金属でＬｉ、 Ｎａ、 Ｋ、 Ｒｂなどで
あり、１マ１〜２、ｎは５〜６である）で示され、フル
オロニオブ酸塩の場合は一般式Ｍ ２ｍＮｂＦ 、（Ｍ
”はアルカリ金属で、ｍは１〜２、ｎは６〜７である
）で示され、さらに、フルオロタンタル酸塩の場合は一
般式Ｍ ” ｎ Ｔ ａ Ｆ ｎ （Ｍ ２はアルカリ
金属で、ｍは１〜３、ｎは６〜８である）で示される。In addition, vanadium, niobium, which belongs to Group Va of the periodic table,
Halides such as tantalum have the general formula MIX, (Ml
is V, Nb5Ta, X is a halogen atom and F,
C1, Br, 1, etc., where n is 2 to 5), and the valence is ■, ■, ■, or heptavalent, and
Moreover, in the case of a fluorovanadate, the alkali metal salt of a fluorometallic acid has the general formula M! , V F , (M
2 is an alkali metal such as Li, Na, K, Rb, etc., where 1 is 1 to 2 and n is 5 to 6), and in the case of fluoroniobate, the general formula is M
" is an alkali metal, m is 1 to 2, n is 6 to 7), and in the case of fluorotantalate, the general formula M "n TaF n (M2 is an alkali metal, m is 1-3, n is 6-8).
さらに、周期律表第Ｖｌａ族に属するモリブデン、タン
グステンなどのハロゲン化物は、一般弐Ｍ３Ｘ、（Ｍ３
はＭｏ、 Ｗであり、Ｘはハロゲン原子でＦＳＣｌ、Ｂ
ｒ、 Ｉなど、ｎは２〜６）で示される原子価が■価
、■価、■価、７価、■価のハロゲン化物である。Furthermore, halides such as molybdenum and tungsten, which belong to Group Vla of the periodic table, are generally 2M3X, (M3
are Mo, W, X is a halogen atom, FSCl, B
r, I, etc., where n is 2 to 6) and the valence is ■, ■, ■, hepta, or ■.
本発明では、前記２種の化合物とともに、アルキルピリ
ジニウムハロゲン化物またはアルキルイミダゾリウムハ
ロゲン化物を３３〜６７モル％含有させる。これらの化
合物は、含有量が３３モル％未満になると、めっき浴の
融点が高（なり、６７モル％を越えると、アルキルピリ
ジニウムイオンやアルキルイミダゾリウムイオンが多（
なり、それがめつき層に付着し、好ましくない。なお、
ピリジン環やイミダゾール環に導入したアルキル基の炭
素数が１３以上のものを使用すると、常温で液体になり
に＜（、粘性も高くなるので、１〜１２のものを使用す
る。In the present invention, 33 to 67 mol % of an alkylpyridinium halide or an alkylimidazolium halide is contained together with the above two types of compounds. If the content of these compounds is less than 33 mol%, the melting point of the plating bath will be high, and if it exceeds 67 mol%, the content of alkylpyridinium ions and alkylimidazolium ions will be high (
This is undesirable because it adheres to the plating layer. In addition,
If an alkyl group introduced into the pyridine ring or imidazole ring has 13 or more carbon atoms, it will become liquid at room temperature and the viscosity will become high, so use one with 1 to 12 carbon atoms.
アルキルピリジニウムハロゲン化物は、モノアルキル置
換体、ジアルキル置換体、トリアルキル置換体が好まし
く、これらの１種または２種以上の混合物であってもよ
い。また、ハロゲン原子としては、フッ素、塩素、臭素
、ヨウ素でもよい。The alkylpyridinium halide is preferably a monoalkyl-substituted product, a dialkyl-substituted product, or a trialkyl-substituted product, and may be one type or a mixture of two or more of these. Further, the halogen atom may be fluorine, chlorine, bromine, or iodine.
このような化合物を具体的に示せば、ブチルピリジニウ
ムハロゲン化物、１．２−ジメチルピリジニウムハロゲ
ン化物、■−エチルー２−メチルピリジニウムハロゲン
化物、１−ｎ−ブチル−２−メチルピリジニウムハロゲ
ン化物、１−イソブチル−２−メチルピリジニウムハロ
ゲン化物、１−ｎ−オクチル−２−メチルピリジニウム
ハロゲン化物、１−ベンジル−２−メチルピリジニウム
ハロゲン化物、１−エチル−３−メチルピリジニウムハ
ロゲン化物、１−シクロヘキシル３−メチルピリジニウ
ムハロゲン化物、１−エチル−２−エチルピリジニウム
ハロゲン化物、１−ブチル−２−エチルピリジニウムハ
ロゲン化物、１−エチル−４メチルピリジニウムハロゲ
ン化物、１−エチル−２，４−ジメチルピリジニウムハ
ロゲン化物、１−エチル２．６−ジメチルピリジニウム
ハロゲン化物、１−ｎ−ブチル−２，４−ジメチルピリ
ジニウムハロゲン化物などを挙げることができる。Specific examples of such compounds include butylpyridinium halide, 1,2-dimethylpyridinium halide, ■-ethyl-2-methylpyridinium halide, 1-n-butyl-2-methylpyridinium halide, 1- Isobutyl-2-methylpyridinium halide, 1-n-octyl-2-methylpyridinium halide, 1-benzyl-2-methylpyridinium halide, 1-ethyl-3-methylpyridinium halide, 1-cyclohexyl 3-methyl Pyridinium halide, 1-ethyl-2-ethylpyridinium halide, 1-butyl-2-ethylpyridinium halide, 1-ethyl-4methylpyridinium halide, 1-ethyl-2,4-dimethylpyridinium halide, 1 -ethyl 2,6-dimethylpyridinium halide, 1-n-butyl-2,4-dimethylpyridinium halide, and the like.
また、アルキルイミダゾリウムハロゲン化物は、１−ア
ルキル、１，３−ジアルキル、１．２．３−１−リアル
キルイミダゾリウムハロゲン化物が好ましく、ハロゲン
原子は、フッ素、塩素、臭素、ヨウ素でもよい。これら
は単独でも２種以上を混合使用してもよい。これらの化
合物を具体的に示せば、１−メチルイミダゾリウムブロ
マイド、１−エチルイミダゾリウムハロゲン化物、１−
ブチルイミダゾリウムハロゲン化物、１．３−ジメチル
イミダゾリウムハロゲン化物、■−メチルー３−エチル
イミダゾリウムハロゲン化物、１−メチル−３−ｎ−ブ
チルイミダゾリウムハロゲン化物、１−メチル−３−ベ
ンジルイミダゾリウムハロゲン化物、１−メチル−３−
エチルベンゾイミダゾリウムハロゲン化物、１．２．３
− トリメチルイミダゾリウムハロゲン化物、１．２−
ジメチル−３−エチルイミダゾリウムハロゲン化物、１
．２−ジメチル−３−ブチルイミダゾリウムハロゲン化
物などを挙げることができる。Further, the alkylimidazolium halide is preferably a 1-alkyl, 1,3-dialkyl, or 1.2.3-1-realkylimidazolium halide, and the halogen atom may be fluorine, chlorine, bromine, or iodine. These may be used alone or in combination of two or more. Specific examples of these compounds include 1-methylimidazolium bromide, 1-ethylimidazolium halide, and 1-methylimidazolium bromide.
Butylimidazolium halide, 1,3-dimethylimidazolium halide, ■-Methyl-3-ethylimidazolium halide, 1-methyl-3-n-butylimidazolium halide, 1-methyl-3-benzylimidazolium Halide, 1-methyl-3-
Ethylbenzimidazolium halide, 1.2.3
- Trimethylimidazolium halide, 1.2-
Dimethyl-3-ethylimidazolium halide, 1
．． Examples include 2-dimethyl-3-butylimidazolium halide.
このアルキルピリジニウムハロゲン化物の場合、アミノ
基が導入されたものでもよい。例えば、１メチル−４−
ジメチルアミノピリジニウムハロゲン化物、１−エチル
−４−ジメチルアミノピリジニウムハロゲン化物、１−
エチル−４−（Ｎ−エチル、Ｎ−メチル）アミノピリジ
ニウムハロゲン化物、１−エチル−４−アミノピリジニ
ウムハロゲン化物、１−ｎ−ブチル−４−ジメチルアミ
ノピリジニウムハロゲン化物、１−ベンジル−４−ジメ
チルアミノピリジニウムハロゲン化物、１−ｎ−オクチ
ル−４−ジメチルアミノピリジニウムハロゲン化物、１
−エチル−４−ピペリジノピリジニウムハロゲン化物、
■−エチルー４ピロリジノピリジニウムハロゲン化物な
どが挙げられる。In the case of this alkylpyridinium halide, an amino group may be introduced. For example, 1 methyl-4-
Dimethylaminopyridinium halide, 1-ethyl-4-dimethylaminopyridinium halide, 1-
Ethyl-4-(N-ethyl, N-methyl)aminopyridinium halide, 1-ethyl-4-aminopyridinium halide, 1-n-butyl-4-dimethylaminopyridinium halide, 1-benzyl-4-dimethyl Aminopyridinium halide, 1-n-octyl-4-dimethylaminopyridinium halide, 1
-ethyl-4-piperidinopyridinium halide,
(1)-Ethyl-4-pyrrolidinopyridinium halide and the like.
アルキルイミダゾリウムハロゲン化物は、縮合環を形成
していてもよい。この縮合複素環化合物の代表的なもの
は、ジアルキルベンズイミダゾリウムハロゲン化物で、
具体例としては、１．３−ジメチルベンズイミダゾリウ
ムクロライド、１−メチル３−エチルベンズイミダゾリ
ウムブロマイドなどを挙げることができる。The alkylimidazolium halide may form a fused ring. A typical example of this fused heterocyclic compound is dialkylbenzimidazolium halide.
Specific examples include 1,3-dimethylbenzimidazolium chloride and 1-methyl3-ethylbenzimidazolium bromide.
以上挙げた化合物のうち、好ましい組み合わせは、Ａｌ
Ｃｌ３− ＭＣＩ、−ブチルピリジニウムクロライド系
またはＡｌＣｌ３− ＭＣＩ、 −１−エチル−３−メ
チルイミダゾリウムクロライド系（Ｍは合金元素、ｎは
２〜６）であるが、後者の組成のめっき浴の方が導電率
が高く、粘性も低いので、特に好ましい。Among the compounds mentioned above, a preferable combination is Al
Cl3-MCI, -butylpyridinium chloride system or AlCl3-MCI, -1-ethyl-3-methylimidazolium chloride system (M is an alloying element, n is 2 to 6), but the latter composition is preferable. is particularly preferred because it has high conductivity and low viscosity.
本発明のめっき浴は、芳香族系有機溶媒を添加して、め
っき液の粘性を低下させると、導電率が向上し、めっき
電流密度を増大させることができ、かつ、めっき層をも
平滑化できる。この有機溶媒の添加は、めっき浴の総量
に対して、５ Ｖｏ１％未満であると、添加効果が認め
られず、８ＱＶｏ１％を越えると、めっき液との均一混
合が困難になり、分離するので、５〜ｇＱＶｏ１％にす
るのが好ましい。By adding an aromatic organic solvent to the plating bath of the present invention to reduce the viscosity of the plating solution, the conductivity can be improved and the plating current density can be increased, and the plating layer can also be smoothed. can. When adding this organic solvent to the total amount of the plating bath, if it is less than 1% of 5Vo, no effect will be observed, and if it exceeds 1% of 8QVo, it will be difficult to mix uniformly with the plating solution and it will separate. , 5 to 1% of gQVo is preferable.
また、本発明のめっき浴に窒素を有する芳香族化合物を
添加すると、厚めつきの際にめっき層がデンドライト状
になるのを抑制できる。この添加剤を添加すると、３０
μｍ以上の厚めつきにしても、表面は光沢を呈し、電流
密度を広範囲に変動させても平滑なめっき層になり、ま
た、均一電着性も向上する。Furthermore, when an aromatic compound containing nitrogen is added to the plating bath of the present invention, it is possible to suppress the plating layer from becoming dendrite-like during thick plating. When this additive is added, 30
Even if the coating is thicker than μm, the surface will be glossy, and even if the current density is varied over a wide range, a smooth plating layer will be obtained, and uniform electrodeposition will be improved.
この芳香族化合物には、環内に窒素原子を２個以上有す
る不飽和複素環化合物、アミン基を有する芳香族化合物
などが挙げられるが、これらの化合物は、単環化合物、
縮合環化合物であってもよい。環内に窒素原子を２個以
上有する不飽和複素環化合物としては、ピリミジンやバ
ルビッル酸などのジアジン、ナフチリジン、フェナジン
、フェナントロリン、ピリダジン、ピラジンなどが、ま
た、アミノ基を有する芳香族化合物としては、ジフェニ
ルアミン、アミノピリミジンのようなアミノジアジンな
どを挙げることができ、これらは２種以上併用すること
も可能である。Examples of the aromatic compound include unsaturated heterocyclic compounds having two or more nitrogen atoms in the ring, aromatic compounds having an amine group, etc., but these compounds include monocyclic compounds,
It may also be a fused ring compound. Examples of unsaturated heterocyclic compounds having two or more nitrogen atoms in the ring include diazine, naphthyridine, phenazine, phenanthroline, pyridazine, pyrazine, etc. such as pyrimidine and barbylic acid, and aromatic compounds having an amino group include: Examples include diphenylamine and aminodiazine such as aminopyrimidine, and two or more of these can be used in combination.
窒素原子を有する芳香族化合物の添加量は、めっき浴に
対して、通常０．００１〜１モルにである。The amount of the aromatic compound having a nitrogen atom added is usually 0.001 to 1 mol to the plating bath.
添加量が０．００１モル％より少ないと添加効果がなく
、１モル％より多くなると高電流密度でめっきした場合
、めっき焼けが発生する。If the amount added is less than 0.001 mol %, there will be no effect of the addition, and if it is more than 1 mol %, plating burn will occur when plating is performed at a high current density.
本発明のめっき浴を用いてのめっきは、乾燥無酸素雰囲
気中で、直流もしくはパルス電流で浴温２５〜１８０℃
、電流密度０．０１〜１００Ａ／ｄｍ”で行うと、電流
効率がよく、均一にめっきできる。Plating using the plating bath of the present invention is carried out in a dry oxygen-free atmosphere at a bath temperature of 25 to 180°C using direct current or pulsed current.
, current density is 0.01 to 100 A/dm'', the current efficiency is good and uniform plating can be achieved.
浴温が２５℃より低いと、めっき液の粘性が高（、電流
密度が極端に小さくなり、１８０°Ｃより高くすると、
有機物成分の分解が心配される。この浴温は、１００℃
以上にしなくても、常温〜６０°Ｃで十分めっき可能で
ある。電流は、パルス電流を使用すると、めっき層が緻
密になる。めっき浴は、超音波撹拌、ジェット噴流撹拌
などを施すと、電流密度を高くすることができる。If the bath temperature is lower than 25°C, the viscosity of the plating solution will be high (and the current density will be extremely low; if the bath temperature is higher than 180°C,
There is concern about the decomposition of organic components. This bath temperature is 100℃
Even if the temperature is not higher than that, plating can be sufficiently performed at room temperature to 60°C. When a pulsed current is used, the plating layer becomes denser. The current density of the plating bath can be increased by subjecting it to ultrasonic stirring, jet stirring, or the like.
（実施例）
実施例１
第１表に示す組成の電気Ａｌ−Ｌｉ合金めっき浴を調製
し、このめっき浴を用いて板厚が０ 、５ ａｍの冷延
鋼板にＡｌ合金を電気めっきした。めっきは、冷延鋼板
を常法により溶剤蒸気洗浄、アルカリ脱脂および酸洗を
施した後、乾燥して、直ちに不活性雰囲気に保っておい
ためっき浴に浸漬し、冷延鋼板を陰極、アルミニウム板
（純度９９．９９％、板厚１ 、 Ｏａｒｍ）またはリ
チウム板（純度９９％以上、板厚１ 、０ ｍｍ）を陽
極にし、直流で電解した。第２表に得られたＡｌ−Ｌｉ
合金めっき鋼板の性能を示す。(Example) Example 1 An electric Al--Li alloy plating bath having the composition shown in Table 1 was prepared, and using this plating bath, a cold rolled steel plate having a thickness of 0.5 am was electroplated with an Al alloy. For plating, cold-rolled steel sheets are subjected to solvent vapor cleaning, alkaline degreasing, and pickling using conventional methods, then dried and immediately immersed in a plating bath kept in an inert atmosphere. A plate (purity 99.99%, plate thickness 1.0 mm) or a lithium plate (purity 99% or more, plate thickness 1.0 mm) was used as an anode, and electrolysis was performed with direct current. Al-Li obtained in Table 2
This shows the performance of alloy plated steel sheets.
実施例２
第３表に示す組成の電気Ａｌ−Ｖ合金めっき浴を調製し
、実施例１と同要領でＡｌ−Ｖ合金を板厚０．５１の冷
延鋼板に電気めっきした。なお、陽極にはチタン板（純
度９９９９％、板厚１ 、０ ｆｆｍ）またはバナジウ
ム板（純度９９．５％、板厚１．０ｍｍ）を使用した。Example 2 An electrolytic Al-V alloy plating bath having the composition shown in Table 3 was prepared, and an Al-V alloy was electroplated on a cold rolled steel sheet having a thickness of 0.51 mm in the same manner as in Example 1. Note that a titanium plate (purity 9999%, plate thickness 1,0 ffm) or a vanadium plate (purity 99.5%, plate thickness 1.0 mm) was used as the anode.
第４表に得られたＡｌ−Ｖ合金めっき鋼板の性能を示す
。Table 4 shows the performance of the obtained Al-V alloy plated steel sheet.
実施例３
第５表に示す組成の電気Ａｌ−Ｎｂ合金めっき浴を調製
し、実施例１と同要領でＡｌ−Ｎｂ合金を板厚０．５Ｉ
ＩｌｌＩの冷延鋼板に電気めっきした。なお、陽極には
チタン板（純度９９．９９％、板厚１ 、０ ｍｍ）ま
たはニオブ板（純度９９％、板厚１ 、０ ｍｍ）を使
用した。第６表に得られたＡｌ−Ｎｂ合金めっき鋼板の
性能を示す。Example 3 An electric Al-Nb alloy plating bath having the composition shown in Table 5 was prepared, and the Al-Nb alloy was plated to a thickness of 0.5I in the same manner as in Example 1.
Electroplated on IllI cold rolled steel sheet. Note that a titanium plate (purity 99.99%, plate thickness 1.0 mm) or a niobium plate (purity 99%, plate thickness 1.0 mm) was used as the anode. Table 6 shows the performance of the obtained Al-Nb alloy plated steel sheet.
実施例４
第７表に示す組成の電気Ａｌ−Ｔａ合金めっき浴を調製
し、実施例１と同要領でＡｌ−Ｔａ合金を板厚Ｑ 、
５ ｍｍの冷延鋼板に電気めっきした。なお、陽極には
チタン板（純度９９．９９％、板厚１ 、０ ｍｍ）ま
たはタンタル板（純度９９．５％、板厚１ 、０ ｍｍ
）を使用した。第８表に得られたＡｌ−Ｔａ合金めっき
鋼板の性能を示す。Example 4 An electric Al-Ta alloy plating bath having the composition shown in Table 7 was prepared, and the Al-Ta alloy was plated in the same manner as in Example 1 with a plate thickness of Q,
Electroplated on 5 mm cold rolled steel sheet. The anode was made of titanium plate (purity 99.99%, plate thickness 1.0 mm) or tantalum plate (purity 99.5%, plate thickness 1.0 mm).
)It was used. Table 8 shows the performance of the obtained Al-Ta alloy plated steel sheet.
実施例５
第９表に示す組成の電気Ａｌ−Ｎｏ合金めっき浴を調製
し、実施例１と同要領でＡｌ−Ｍｏ合金を板厚０ 、５
ｃｍの冷延鋼板に電気めっきした。なお、陽極にはチ
タン板（純度９９．９９％、板厚１ 、０ ｍｍ）また
はモリブデン板（純度９９％、板厚１ 、０ ｍｍ）を
使用した。第１０表に得られたＡｌ−Ｍｏ合金めっき鋼
板の性能を示す。Example 5 An electric Al-No alloy plating bath having the composition shown in Table 9 was prepared, and Al-Mo alloy was coated with plate thicknesses of 0 and 5 in the same manner as in Example 1.
Electroplated on cold rolled steel sheet. Note that a titanium plate (purity 99.99%, plate thickness 1.0 mm) or a molybdenum plate (purity 99%, plate thickness 1.0 mm) was used as the anode. Table 10 shows the performance of the obtained Al-Mo alloy plated steel sheet.
実施例６
第１１表に示す組成の電気Ａｌ−Ｗ合金めっき浴を調製
し、実施例１と同要領でＡＩ−Ｗ合金を板厚０．５Ｈの
冷延鋼板に電気めっきした。なお、陽極にはチタン板（
純度９９．９９％、板厚１ 、 Ｏａａ＋）またはタン
グステン板（純度９９．７５％、板厚１ 、０ ｍｍ）
を使用した。第１２表に得られたＡＩ−Ｗ合金めっき鋼
板の性能を示す。Example 6 An electrolytic Al-W alloy plating bath having the composition shown in Table 11 was prepared, and an AI-W alloy was electroplated on a cold rolled steel sheet having a thickness of 0.5H in the same manner as in Example 1. In addition, the anode is a titanium plate (
Purity 99.99%, plate thickness 1, Oaa+) or tungsten plate (purity 99.75%, plate thickness 1, 0 mm)
It was used. Table 12 shows the performance of the obtained AI-W alloy plated steel sheet.
第
表（ＡＩ−Ｗ合金めっき）
（発明の効果）
以上のように、本発明のめっき浴によれば、電気めっき
法によりＡｌ合金をめっきてきる。また、めっき浴は、
常温もしくは比較的低温でめっきてきるので、取り扱い
操作は容易で、被めっき材に熱歪を生じさせるようなこ
とがない。Table 1 (AI-W alloy plating) (Effects of the invention) As described above, according to the plating bath of the present invention, an Al alloy can be plated by electroplating. In addition, the plating bath is
Since plating is carried out at room temperature or relatively low temperature, handling is easy and the material to be plated does not suffer from thermal distortion.
Claims (6)
電気Ａｌ合金めっき浴。 （Ａ）アルミニウムハロゲン化物３３〜６７モル％ （Ｂ）次の（イ）〜（ヘ）から選んだ１種０．０１〜６
７モル％ （イ）リチウムハロゲン化物、 （ロ）バナジウムハロゲン化物またはフルオロバナジウ
ム酸のアルカリ金属塩あるいはこれらの両方、 （ハ）ニオブハロゲン化物またはフルオロニオブ酸のア
ルカリ金属塩あるいはこれらの両方、 （ニ）タンタルハロゲン化物またはフルオロタンタル酸
のアルカリ金属塩あるいはこれらの両方 （ホ）モリブデンハロゲン化物 （ヘ）タングステンハロゲン化物 （Ｃ）アルキルピリジニウムハロゲン化物またはアルキ
ルイミダゾリウムハロゲン化物（但し、いずれの化合物
ともアルキル基の炭素数は１〜１２）３３〜６７モル％(1) An electrolytic Al alloy plating bath containing the following components (A), (B) and (C). (A) 33-67 mol% aluminum halide (B) 0.01-6 mol% of one selected from the following (a) to (f)
7 mol% (a) Lithium halide, (b) Vanadium halide or alkali metal salt of fluorovanadate, or both, (c) Niobium halide or alkali metal salt of fluoroniobic acid, or both. ) Tantalum halide or alkali metal salt of fluorotantalic acid, or both (e) Molybdenum halide (f) Tungsten halide (C) Alkylpyridinium halide or alkylimidazolium halide (However, neither compound has an alkyl group carbon number is 1 to 12) 33 to 67 mol%
ル、ジアルキル、トリアルキルピリジニウムハロゲン化
物のうちの１種または２種以上の混合物であることを特
徴とする特許請求の範囲第１項に記載の電気Ａｌ合金め
っき浴。(2) The electrolytic Al alloy plating according to claim 1, wherein the alkylpyridinium halide is one or a mixture of two or more of monoalkyl, dialkyl, and trialkylpyridinium halides. bath.
キル、１，３−ジアルキル、トリアルキルイミダゾリウ
ムハロゲン化物のうちの１種または２種以上の混合物で
あることを特徴とする特許請求の範囲第１項に記載の電
気Ａｌ合金めっき浴。(3) Claim 1, characterized in that the alkylimidazolium halide is one or a mixture of two or more of 1-alkyl, 1,3-dialkyl, and trialkylimidazolium halides. The electrolytic Al alloy plating bath described in .
とを特徴とする電気Ａｌ合金めっき浴。(4) An electrolytic Al alloy plating bath, characterized in that an aromatic organic solvent is added to the plating bath of item 1.
物を添加したことを特徴とする電気Ａｌ合金めっき浴。(5) An electrolytic Al alloy plating bath, characterized in that an aromatic compound having a nitrogen atom is added to the plating bath of item 1.
〜１８０℃、電流密度０．０１〜１００Ａ／ｄｍ＾２で
直流またはパルス電流によりめっきすることを特徴とす
る電気Ａｌ合金めっき方法。(6) Using the plating bath described in items 1 to 5, the bath temperature is 25
An electric Al alloy plating method characterized by plating with direct current or pulsed current at ~180°C and a current density of 0.01 to 100 A/dm^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20174590A JPH0488188A (en) | 1990-07-30 | 1990-07-30 | Al alloy electroplating bath and plating method using this bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20174590A JPH0488188A (en) | 1990-07-30 | 1990-07-30 | Al alloy electroplating bath and plating method using this bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0488188A true JPH0488188A (en) | 1992-03-23 |
Family
ID=16446242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20174590A Pending JPH0488188A (en) | 1990-07-30 | 1990-07-30 | Al alloy electroplating bath and plating method using this bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0488188A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5751854A (en) * | 1992-08-03 | 1998-05-12 | Ricoh Company, Ltd. | Original-discrimination system for discriminating special document, and image forming apparatus, image processing apparatus and duplicator using the original-discrimination system |
| US6368486B1 (en) * | 2000-03-28 | 2002-04-09 | E. I. Du Pont De Nemours And Company | Low temperature alkali metal electrolysis |
| US6787019B2 (en) | 2001-11-21 | 2004-09-07 | E. I. Du Pont De Nemours And Company | Low temperature alkali metal electrolysis |
| JP2018521451A (en) * | 2015-05-11 | 2018-08-02 | ブローミン コンパウンズ リミテッド | Flow battery additives |
-
1990
- 1990-07-30 JP JP20174590A patent/JPH0488188A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5751854A (en) * | 1992-08-03 | 1998-05-12 | Ricoh Company, Ltd. | Original-discrimination system for discriminating special document, and image forming apparatus, image processing apparatus and duplicator using the original-discrimination system |
| US6368486B1 (en) * | 2000-03-28 | 2002-04-09 | E. I. Du Pont De Nemours And Company | Low temperature alkali metal electrolysis |
| US6730210B2 (en) | 2000-03-28 | 2004-05-04 | E. I. Du Pont De Nemours And Company | Low temperature alkali metal electrolysis |
| US6787019B2 (en) | 2001-11-21 | 2004-09-07 | E. I. Du Pont De Nemours And Company | Low temperature alkali metal electrolysis |
| JP2018521451A (en) * | 2015-05-11 | 2018-08-02 | ブローミン コンパウンズ リミテッド | Flow battery additives |
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