JPH04157166A - Method for chemically plating aluminum stock - Google Patents
Method for chemically plating aluminum stockInfo
- Publication number
- JPH04157166A JPH04157166A JP28220190A JP28220190A JPH04157166A JP H04157166 A JPH04157166 A JP H04157166A JP 28220190 A JP28220190 A JP 28220190A JP 28220190 A JP28220190 A JP 28220190A JP H04157166 A JPH04157166 A JP H04157166A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- stock
- complexing agent
- chemical
- soln
- 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 70
- 238000000034 method Methods 0.000 title claims description 14
- 229910052782 aluminium Inorganic materials 0.000 title claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 22
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 5
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 5
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 5
- 229940033123 tannic acid Drugs 0.000 claims abstract description 5
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 5
- 229920002258 tannic acid Polymers 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 31
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 238000007772 electroless plating Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- GIXWDMTZECRIJT-UHFFFAOYSA-N aurintricarboxylic acid Chemical compound C1=CC(=O)C(C(=O)O)=CC1=C(C=1C=C(C(O)=CC=1)C(O)=O)C1=CC=C(O)C(C(O)=O)=C1 GIXWDMTZECRIJT-UHFFFAOYSA-N 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000002585 base Substances 0.000 description 16
- 230000008018 melting Effects 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- -1 aircraft Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006174 pH buffer Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229910004729 Na2 MoO4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- AIPNSHNRCQOTRI-UHFFFAOYSA-N aluminon Chemical compound [NH4+].[NH4+].[NH4+].C1=C(C([O-])=O)C(O)=CC=C1C(C=1C=C(C(O)=CC=1)C([O-])=O)=C1C=C(C([O-])=O)C(=O)C=C1 AIPNSHNRCQOTRI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、アルミニウム（Ａρ）素材の新規な化学めっ
き方法に関し、特に、モリブデン（Ｍ。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel chemical plating method for aluminum (Aρ) material, and in particular, to a method for chemically plating aluminum (Aρ) material.
）、タングステン（Ｗ）等の高融点金属をＡβ素材に化
学めっきするのに好適な方法に関する。), relates to a method suitable for chemically plating a high melting point metal such as tungsten (W) onto an Aβ material.
〈従来の技術〉
従来から、Ａρ素材は融点が６６０℃と低いため、その
ままでは、高温雰囲気にさらされる製品には、使用が制
限された。Ａｌ１の耐熱性を向上させる手段として別の
高融点金属を被覆することが考えられる。特に、被覆手
段として、化学めっきは、電気めっきに比して、均一な
かつピンホールの少ないめっき膜を容易にかつ安価に形
成できる利点を有する。<Prior Art> Conventionally, Aρ material has a low melting point of 660° C., so its use as it is in products exposed to high-temperature atmospheres has been restricted. A possible means of improving the heat resistance of Al1 is to coat it with another high melting point metal. In particular, as a coating means, chemical plating has an advantage over electroplating that it can easily and inexpensively form a uniform plating film with fewer pinholes.
従来、Ａｌ１の耐熱・耐食性を向上させるために、Ｚｎ
置換めっきを介してＮｉ（融点１４５５℃）などを無電
解めっきしてきたが、Ａβの低融点に加えてＮｉなとの
融点もさほど高くないため、耐熱性を著しく向上するま
でには至っていない。Conventionally, in order to improve the heat resistance and corrosion resistance of Al1, Zn
Electroless plating of Ni (melting point: 1455° C.) has been performed through displacement plating, but in addition to the low melting point of Aβ, the melting point of Ni is not very high, so heat resistance has not been significantly improved.
理想的には、さらに高融点で耐火金属の部類に入るＭｏ
（融点： ２６２２℃）やＷ（融点： ３４００℃）で
、Ａ℃素材に直接被覆することである。この際ＭＯの場
合、充分な耐熱・耐食性を得るのには、０、２〜１．
Ｏｒａｇ／ ｃｍ”厚のＭｏ膜が必要とされており、一
方、Ａβは、化学的に活性であるため短時間にめっきす
ることが要望されている。Ideally, Mo, which has a higher melting point and is classified as a refractory metal, would be ideal.
(melting point: 2622°C) or W (melting point: 3400°C) to directly coat the A°C material. At this time, in the case of MO, in order to obtain sufficient heat resistance and corrosion resistance, 0.2 to 1.
A Mo film with a thickness of 1.5 cm is required, while Aβ is chemically active and needs to be plated in a short time.
〈発明が解決しようとする課題〉
へβ素材にＭｏめっきを、前述の直付は化学めっきを行
なった場合、途中で析出量が頭打ちとなり（比較例１参
照）、一方、汎用の無電解めっきで行なった場合、めっ
きの速度が遅い（比較例２参照）、従って、両者とも所
要厚のＭＯめっき膜を短時間に形成することは困難であ
ることがわかった。さらに、両者とも、Ａρ母材がめつ
き中に浸食されてめっき面が荒れたり、また、めっき膜
のＡβ母材に対する密着力も充分でないことが分った。<Problems to be Solved by the Invention> When Mo plating is applied to the β material and chemical plating is applied to the above-mentioned direct attachment, the amount of precipitation reaches a ceiling midway through (see Comparative Example 1).On the other hand, when general-purpose electroless plating It was found that in both cases, it was difficult to form an MO plating film of the required thickness in a short time because the plating speed was slow (see Comparative Example 2). Furthermore, in both cases, the Aρ base material was eroded during plating, resulting in roughened plating surfaces, and the adhesion of the plating film to the Aβ base material was also found to be insufficient.
本発明は、上記にかんがみて、ＭＯ等の高融点金属を高
速度で継続めっきができ、かつ、Ａβ母材をできるだけ
浸食しない化学めっき方法を提供することにある。In view of the above, it is an object of the present invention to provide a chemical plating method that allows continuous plating of a high melting point metal such as MO at a high speed and that does not erode the Aβ base material as much as possible.
〈課題を解決するための手段〉
本発明者は、上記課題を解決するために、鋭意開発に努
力をした結果、下記構成のへβ素材の化学めっき方法に
想到した。<Means for Solving the Problems> In order to solve the above problems, the inventors of the present invention have made extensive efforts in development, and as a result, have come up with a method for chemical plating of β material having the following configuration.
アルミノンおよびタンニン酸の少なくとも一方を錯化剤
として含む錯化剤水溶液で、へβ素材を表面処理した後
、還元剤および錯化剤を実質的に含まない化学めっき浴
で中性に制御して化学めっきを行なった後、化学還元剤
を実質的に不要な中性の化学めっき浴に浸漬して化学め
っきを行なうことを特徴とする。After surface-treating the Heβ material with an aqueous complexing agent solution containing at least one of aluminone and tannic acid as a complexing agent, the material is controlled to be neutral in a chemical plating bath that does not substantially contain reducing agents and complexing agents. The method is characterized in that after chemical plating is performed, chemical plating is performed by immersing the method in a neutral chemical plating bath that does not substantially require a chemical reducing agent.
〈手段の詳細な説明〉
（１）Ａβ素材としては、通常の、航空機・車両・建材
等の各種構造材用、および、自動車部品、光学部品、電
気部品等の各種非構造材用、充填材用のもの、さらには
、Ａρ被覆鋼板等を素材として適用可能である。<Detailed explanation of means> (1) Aβ materials can be used as ordinary materials for various structural materials such as aircraft, vehicles, and building materials, as well as for various non-structural materials such as automobile parts, optical parts, electrical parts, and fillers. It is also possible to use Aρ-coated steel plates or the like as the material.
（２）錯化剤水溶液は、アルミノン（化学名：アラリン
トリカルボン酸アンモニウム）およびタンニン酸の少な
くとも一方を錯化剤として含む水溶液である。(2) The aqueous complexing agent solution is an aqueous solution containing at least one of aluminone (chemical name: ammonium alarintricarboxylate) and tannic acid as a complexing agent.
■上記必須成分は、Ａρの化学活性を低減させ、Ａｌ母
材の溶出を置換めっき必要量の範囲に止めることができ
て、継続めっきできる作用を奏すると推定される。(2) The above essential components are presumed to have the effect of reducing the chemical activity of Aρ, keeping the elution of the Al base material within the amount required for displacement plating, and allowing continuous plating.
■錯化剤の配合量は、アルミノン（Ｍ：４７３）の場合
、０．０００５〜Ｏ，Ｏｌｍｏｌ ／ Ｒ，濃度の範囲
が有効で、好ましくは０．００１〜０．００４２ｍｏｌ
／βの範囲が最適である。おなじく処理液にタンニン
酸を用いるときは、ｌ−１０ｇ／β濃度の範囲が有効で
、好ましくは２〜７ｇ／Ｉ２の範囲が適している。上記
数値より小さいと、充分なＡｌに対する錯体形成能が得
られず、上記数値を超えると逆にＡβ母材表面がＡｊ２
錯体で完全に被覆されてしまい、それぞれ望ましくない
。■For aluminon (M: 473), the amount of the complexing agent is effective in the concentration range of 0.0005 to O,Olmol/R, preferably 0.001 to 0.0042 mol.
/β range is optimal. Similarly, when tannic acid is used in the treatment liquid, a concentration range of 1-10 g/β is effective, preferably a range of 2 to 7 g/I2. If it is smaller than the above value, sufficient complex forming ability for Al cannot be obtained, and if it exceeds the above value, the Aβ base material surface becomes Aj2
complete coverage with the complex, which is undesirable.
■上記ｐＨ緩衝剤としてアンモニウム塩、はう酸塩、有
機酸塩などを用いることができるが、塩化アンモニウム
、硫酸アンモニウム、はう酸塩、グルコン酸塩が好まし
く、特にほう酸やほう酸塩が最適である。ｐＨ緩衝剤の
濃度は０．０８〜１．６ｍｏｌ／ｇの範囲が有効で、好
ましくは０．１６〜１．２１ｍｏｌ ／ Ｉ２である。■Ammonium salts, balates, organic acid salts, etc. can be used as the above pH buffering agent, but ammonium chloride, ammonium sulfate, balates, and gluconates are preferable, and boric acid and borates are particularly optimal. . The effective concentration of the pH buffer is in the range of 0.08 to 1.6 mol/g, preferably 0.16 to 1.21 mol/I2.
■本処理液のｐＨ調整は、アンモニアや苛性アルカリな
らびに硫酸または塩酸でおこない、処理液をｐＨ７±０
．５の範囲にすることが、表面処理時のへβ母材への化
学的攻撃（腐食）を抑制することができ望ましい。また
、処理温度・時間は、液温７０〜１００℃の範囲とする
が、好ましくは、８０〜９０℃の範囲に設定する。この
場合の表面処理時間は５〜１０ｍｊｎである。■The pH of the treatment liquid is adjusted using ammonia, caustic alkali, sulfuric acid or hydrochloric acid, and the treatment liquid is adjusted to pH 7±0.
．． A range of 5 is desirable because it can suppress chemical attack (corrosion) on the β base material during surface treatment. Further, the treatment temperature and time are set within a range of liquid temperature of 70 to 100°C, preferably within a range of 80 to 90°C. The surface treatment time in this case is 5 to 10 mjn.
（２）化学めっき浴は、化学還元剤および錯化剤を実質
的に含有しない中性浴とする０通常、めっき金属成分、
ｐＨ調整剤、ｐＨ緩衝剤、添加剤を含有する。(2) The chemical plating bath should be a neutral bath that does not substantially contain chemical reducing agents and complexing agents. Usually, plating metal components,
Contains pH adjusters, pH buffers, and additives.
■めっき金属成分としては、Ｍｏの場合、モリブデン酸
（Ｈｚ ＭｏＯ４） 、三酸化モリブデン（ＭｏＯ５）
、モリブデン酸ナトリウムニ水和物（Ｎａ２ ＭｏＯ４
・２ Ｈ２０） 、モリブデン酸アンモニウム四水和物
（（ＮＨ４）ｓ ＭＯｙ Ｏ＊ａ・４Ｈ２０）を用いる
ことができ、その濃度は、０．００３〜０．３ｍｏｌ／
βの範囲が有効で、好ましくは０．０３〜０．２ｍｏｌ
／βの範囲が適している。Ｗの場合も、各種Ｗ化合物を
使用できる。■As plating metal components, in the case of Mo, molybdic acid (Hz MoO4), molybdenum trioxide (MoO5)
, sodium molybdate dihydrate (Na2 MoO4
・2H20), ammonium molybdate tetrahydrate ((NH4)sMOyO*a・4H20) can be used, and its concentration is 0.003 to 0.3 mol/
A range of β is effective, preferably 0.03 to 0.2 mol
/β range is suitable. In the case of W, various W compounds can also be used.
■ｐｌ（調製剤としては、前記錯化剤水溶液と同様のも
のを使用できる。これらのｐＨ調整剤で、化学めっき浴
を中性、通常、ｐｈ濃度をｐｌ（７±０．２の範囲に保
つ。■ pl (As a preparation agent, the same one as the complexing agent aqueous solution can be used. With these pH adjusting agents, the chemical plating bath is kept neutral, and the pH concentration is usually kept in the range of pl (7 ± 0.2). keep.
■めっき浴温度は、めっき浴がアンモニア基を含むとき
は８０℃で作動させることが望ましく、またそのほかの
Ｎａ塩などで構成されているときには、９０℃で作動さ
せると析出速度を上げてめっきができる。■If the plating bath contains an ammonia group, it is desirable to operate it at 80°C, and if it is composed of other Na salts, operating it at 90°C will increase the deposition rate and improve plating. can.
■上記ｐＨ緩衝剤として、前記錯化剤水溶液と同様のも
を使用できるが、塩化アンモニウム、硫酸アンモニウム
、はう酸、グルコン酸ナトリウムが好ましい、濃度は０
．０８〜１．６ｍｏｌ／ρの範囲が有効で、好ましくは
０．１６〜１．２１ｍｏ＋ ／ １２を用いる。■As the above pH buffer, the same ones as the complexing agent aqueous solution can be used, but ammonium chloride, ammonium sulfate, oxalic acid, and sodium gluconate are preferable, and the concentration is 0.
．． A range of 0.8 to 1.6 mol/ρ is effective, and preferably 0.16 to 1.21 mo+/ρ is used.
■上記添加剤として、ＭＯの析出効率や密着を良くする
ために、酒石酸アンチモニルカリウムを用いることがで
き、０．１−１０ｍｇ／ １２の範囲が有効で、好まし
くは０．５〜５ｍｇ／Ｉ２が適している。■ As the above additive, potassium antimonyl tartrate can be used to improve the precipitation efficiency and adhesion of MO, and the range of 0.1-10 mg/I2 is effective, preferably 0.5-5 mg/I2. is suitable.
さらに添加剤としては、めっき界面の状態を改善するた
めに界面活性剤を挙げることができる。Furthermore, as an additive, a surfactant can be mentioned in order to improve the condition of the plating interface.
この界面活性剤は、極微量の添加で十分である。Addition of this surfactant in a very small amount is sufficient.
界面活性剤としてはめつき浴が中性ｐＨのため、陰イオ
ン系、非イオン系、陽イオン系、両性イオン系のいずれ
も使用することができる。Since the plating bath has a neutral pH, any of anionic, nonionic, cationic, and amphoteric surfactants can be used as the surfactant.
〈発明の作用〉
本発明の如く、特定の錯化剤水溶液でＡｌ素材を表面処
理した後、還元剤および錯化剤を実質的に含まない化学
めっき浴で中性に制御して化学めっきを行なうと、Ａβ
母材に対する化学めっき処理時における化学的攻撃が必
要最小限に抑制され、かつ、高速度の化学めっき（置換
めっき）が可能となった。その理由は、断定できないが
、下記ごとくであると推定される。<Operation of the invention> As in the present invention, after surface-treating the Al material with a specific complexing agent aqueous solution, chemical plating is performed by controlling the neutrality in a chemical plating bath that does not substantially contain a reducing agent or a complexing agent. When done, Aβ
Chemical attack on the base material during chemical plating processing is suppressed to the necessary minimum, and high-speed chemical plating (displacement plating) is now possible. Although the reason cannot be determined, it is presumed to be as follows.
上記のＭＯ化学めっき浴は、還元剤を使用していないた
め、
の反応による直接的な電子授受だけでＭＯがＡｌＩ２上
に析出する。この際、上記表面処理剤中の錯化剤が、Ａ
ｒ１の化学活性を抑制して、ＡρをＡｌ２３０に必要量
だけイオン化させる作用を奏するものと推定される。一
般に用いられる酸化剤である硝酸によりＡ℃母材が不動
態化される如く、置換めっきに必要なＡβのイオン化ま
で完全に阻止されることはない。このめっき反応は、実
質的に置換めっきであり、還元剤を使用する化学めっき
（無電解めっき）の如く、水素発生は観察されず、静粛
にめっきが進行する。Since the above MO chemical plating bath does not use a reducing agent, MO is deposited on AlI2 only by direct electron transfer through the reaction. At this time, the complexing agent in the surface treatment agent is
It is estimated that it suppresses the chemical activity of r1 and ionizes Aρ into Al230 in the required amount. Just as the A.degree. C. base material is passivated by nitric acid, which is a commonly used oxidizing agent, the ionization of A.beta., which is necessary for displacement plating, is not completely prevented. This plating reaction is essentially displacement plating, and unlike chemical plating (electroless plating) using a reducing agent, hydrogen generation is not observed and plating proceeds quietly.
この水素発生を伴なわない方法が、異種金属間の強い金
属結合を可能にしたことが考えられる。It is thought that this method, which does not involve hydrogen generation, made it possible to form strong metallic bonds between dissimilar metals.
即ち、■第１に、めっきのはじめにＭｏ金属がしばらく
の間は、ＡＪ２母材の格子定数にあわせて伸びるように
成長し、だんだんとＭｏ金属固有の格子定数になること
が考えられる。That is, (1) First, it is considered that at the beginning of plating, Mo metal grows for a while to match the lattice constant of the AJ2 base material, and gradually becomes a lattice constant unique to Mo metal.
■第２に、八βのイオン化を最小限に抑えて、過剰かつ
不測の電子供給をなくしたことが、Ｍｏ金属の結晶核成
長の発端となる空間を与えることにつながり、Ｍｏ金属
がＡβ母材の結晶の方向を受は継いでエピタキシー成長
するのに役立つためと考えられる。■Secondly, minimizing the ionization of 8β and eliminating excessive and unexpected electron supply provides space for the growth of Mo metal crystal nuclei, allowing Mo metal to become the Aβ host. This is thought to be because it helps in epitaxial growth by following the direction of the crystal of the material.
■第３に、Ａβの硬度の軟らかさも、双方金属の結晶構
造や格子定数の違いによるストレスを、吸収することに
一役かつているものと思われる。■Thirdly, the softness of Aβ's hardness also seems to play a role in absorbing the stress caused by the difference in crystal structure and lattice constant of both metals.
〈発明の効果〉
本発明のＡβ素材の化学めっき方法は、ＭＯ等の高融点
金属を高速度で継続めっきができ、かつ、Ａｌ母材がめ
つき処理中に化学的攻撃を受ない。<Effects of the Invention> The chemical plating method for Aβ material of the present invention allows continuous plating of high melting point metals such as MO at high speed, and the Al base material is not chemically attacked during the plating process.
すなわち、めっき浴を中性にし、錯化剤を削除し、さら
に還元材を削除した高融点金属の化学めっき浴をつくり
、Ａβ母材表面を特定の錯化剤で表面処理して化学活性
を弱めてからめつきすると、へβ基質の溶解を最小限に
して継続めっきできるため、Ａβ直接に強く金属結合し
た高融点金属膜を形成することが可能になった。In other words, the plating bath is made neutral, the complexing agent is removed, and a chemical plating bath of a high melting point metal is created by removing the reducing agent, and the surface of the Aβ base material is treated with a specific complexing agent to increase the chemical activity. By weakening Aβ and then plating, it is possible to continue plating with minimal dissolution of the Aβ substrate, making it possible to form a high melting point metal film with strong metal bonding directly to Aβ.
本発明によりＡｌ基材の表層に、簡単な方法でしかも安
価にＭＯ膜をコートでき、しかもそれがＡβ基材が細線
、微粉体、蒸着膜、溶融Ａβめつき鋼板などのへβ部分
にも施せる大きな特徴がある。また八βめっき鋼板の溶
接や熱加工でＡβ表皮の熱損傷を防げるため、鋼板の防
錆を保つことができる。そのほか自動車、航空機などの
高温部分で使用する材料や、熱を遮蔽するＡρ箔、Ａｌ
耐熱繊維など多彩な分野へ提供できるので、その効果は
大きい。According to the present invention, it is possible to coat the surface layer of an Al base material with an MO film using a simple method and at low cost.Moreover, it is possible to coat the surface layer of an Al base material with an MO film, and it is also possible to coat the surface layer of an Aβ base material on a thin β part of a thin wire, fine powder, vapor deposited film, hot-dip Aβ plated steel plate, etc. There are great features that can be applied. Furthermore, since thermal damage to the Aβ skin can be prevented by welding or heat processing of the 8β-plated steel sheet, the steel sheet can be kept rust-proof. In addition, materials used in high-temperature parts such as automobiles and aircraft, Aρ foil for heat shielding, and Al
The effect is great because it can be applied to a variety of fields such as heat-resistant fibers.
〈実施例〉
本発明の効果を確認するために行なった、化学めっき浴
の実施例について説明をする。<Example> An example of a chemical plating bath conducted to confirm the effects of the present invention will be described.
各実施例は、めっき素材を、脱脂処理後、錯化剤水溶液
（アルミノン０．００１ ｍａｔ／β、はう酸０．４８
５ ｍｏｌ／ １２、ｐＨ７）を使用して、８０℃Ｘｌ
０ｍ１ｎの条件で、表面処理（浸漬）した後、第１表に
示す組成のめつき浴・条件で化学めっきを行なった。各
比較例は、上記表面処理を行なわずに、脱脂処理後、第
１表に示す各組成のめつき浴条件で化学めっきを行なっ
た。In each example, the plating material was degreased and then treated with a complexing agent aqueous solution (aluminone 0.001 mat/β, oxalic acid 0.48
5 mol/12, pH 7) at 80°C
After surface treatment (immersion) under the conditions of 0 mln, chemical plating was performed using a plating bath having the composition and conditions shown in Table 1. In each comparative example, chemical plating was performed under the plating bath conditions of each composition shown in Table 1 after degreasing treatment without performing the above-mentioned surface treatment.
なお、めっき素材は、東洋アルミ社製の１００μｍｔの
硬質アルミ箔を使用した。As the plating material, 100 μm hard aluminum foil manufactured by Toyo Aluminum Co., Ltd. was used.
このとき、各実施例においては、Ａｌ母材の腐食はなく
、光沢のある平滑なＭｏめっき面が得られた。At this time, in each Example, there was no corrosion of the Al base material, and a glossy and smooth Mo-plated surface was obtained.
（１）第１表に各実施例・比較例におけるめっきの時間
ごとの析出量を示すとともに、それらの結果を第１図に
示す。(1) Table 1 shows the amount of precipitation for each plating time in each Example and Comparative Example, and the results are shown in FIG.
第１図から、Ｍｏが継続めっきされていることがわかる
。From FIG. 1, it can be seen that Mo is continuously plated.
実施例と比較例の析出速度を比較すると、第１表におい
て、同一浴組成でめっきした実施例２（錯化）／比較例
１ （裸）のめつき時間別の比較で、 ２．０ 、２．
１ 、３．１ 、３．６ 、４．５．５．５ 、５．４
倍という飛躍的に析出速度が増大する結果が得られた。Comparing the deposition rates of Examples and Comparative Examples, Table 1 shows that Example 2 (complexed)/Comparative Example 1 (bare), which were plated with the same bath composition, was 2.0, 2.
1, 3.1, 3.6, 4.5.5.5, 5.4
The results showed that the precipitation rate increased dramatically by twice as much.
比較例１の浸漬めっき浴を中性ｐ）Ｉにした比較例３、
ならびに比較例２の無電解めっき浴をさらに中性ｐＨに
して、酸、アルカリの影響を小さくした比較例４の場合
は、析出量と速度をあまり向上させることができなかっ
た。さらに溶解因子となる錯化剤を排除しかつ必要のな
い還元剤を除いた、比較例５〜７の場合は、比較例６だ
けが僅かに析出量と析出速度が向上しただけで、各めっ
き浴とも途中で析出が頭打ちとなりめっきが停止した。Comparative Example 3, in which the immersion plating bath of Comparative Example 1 was changed to neutral p)I,
In addition, in the case of Comparative Example 4, in which the electroless plating bath of Comparative Example 2 was further adjusted to a neutral pH to reduce the effects of acids and alkalis, it was not possible to significantly improve the amount and rate of precipitation. Furthermore, in the case of Comparative Examples 5 to 7, in which the complexing agent as a solubility factor and the unnecessary reducing agent were removed, only Comparative Example 6 showed a slight improvement in the precipitation amount and precipitation rate, and each plating In the middle of the bath, precipitation reached a peak and plating stopped.
このときＡｌ母材は腐食をうけて荒れが認められ、ＭＯ
めっき面が粗雑になり、かつＭｏ膜の強い結合も得られ
なかった。At this time, the Al base material was corroded and roughened, and the MO
The plated surface became rough, and strong bonding of the Mo film could not be obtained.
（２）実施例２および裸のアルミニウム素材の耐熱試験
を行なった。(2) A heat resistance test was conducted on Example 2 and the bare aluminum material.
耐熱試験には幅３ｃｍＸ６ｃ＋ｎの試料を長手方向の一
端を片持ち梁に支持し、先端から２ｃｎ＋の位置を下側
からガスバーナーで加熱し、ガス焔計測温度７５０℃の
位置で試料がどれだけの時間で溶融して変形するかを調
べた。For the heat resistance test, a sample with a width of 3cm x 6c+n was supported on a cantilever at one end in the longitudinal direction, and heated with a gas burner from below at a position 2cm+ from the tip. We investigated whether it would melt and deform over time.
このとき標準とした裸の試料は６秒間で変形して溶は落
ちた。これに対して、実施例２の試料は０、１３９ｍｇ
／ ｃｍ”のものは３分間経過で部分的にシワの発生
が認められたが、原形はそのまま保持しており、さらに
それ以上のＭｏを盛り上げた試料は、１５分間以上の加
熱で赤熱状態になっても溶融したり変形することがなか
った。At this time, the standard bare sample was deformed in 6 seconds and the melt was removed. In contrast, the sample of Example 2 was 0.139 mg
/ cm'' was partially wrinkled after 3 minutes, but the original shape remained as it was, and samples with more Mo than that became red-hot after being heated for 15 minutes or more. It did not melt or deform even when
これらの結果から、１００μｍ厚のＡ２箔にＭ。From these results, M was applied to 100 μm thick A2 foil.
膜を０．２ｍｇ ／ ｃｍ”以上盛り上げたものは、７
５０℃のガス焔による長時間加熱でも十分な耐熱性を発
揮でき、さらにそれ以上にＭｏを盛り上げたものは７５
０℃よりさらに高温の耐熱性が得られることが類推でき
る。さらに上記ＡＪ２箔の代わりに、十分な剛性を持つ
例えば鋳物、グイキャスト、八βめっき鋼板などにＭＯ
めっきすると、例えば溶接などで瞬間的に高温に曝され
ても、最表皮ＭＯの耐熱・耐食性によってＭＯ皮膜下の
Ａｌ母材またはＡＡ皮膜部分を高温から保護できること
が期待できる。If the membrane is raised by 0.2mg/cm” or more,
It can exhibit sufficient heat resistance even when heated for a long time with a gas flame at 50°C, and the one with Mo raised even further is 75.
It can be inferred that heat resistance even higher than 0° C. can be obtained. Furthermore, instead of the AJ2 foil mentioned above, MO can be made of a material with sufficient rigidity, such as casting, Guicast, or 8β-plated steel plate.
When plated, it can be expected that even if it is momentarily exposed to high temperatures during, for example, welding, the heat resistance and corrosion resistance of the outermost MO layer will protect the Al base material or AA layer portion under the MO layer from high temperatures.
第１図は第１表をもとに作成した析出量の変化を比較し
たグラフ図である。
特 許 出 願 人
津 １） 穣
第 １ 図
＋０ １５ ｆｆ１０
２５ ３０めっき時間（分）FIG. 1 is a graph comparing changes in the amount of precipitation created based on Table 1. Patent application Hitotsu 1) Jodai 1 Figure +0 15 ff10
25 30 Plating time (min)
Claims (2)
化剤として含む錯化剤水溶液でＡｌ素材を表面処理した
後、 還元剤および錯化剤を実質的に含まない化学めつき浴で
中性に制御して化学めつきを行なう、ことを特徴とする
アルミニウム素材の化学めつき方法。1. After surface-treating the Al material with an aqueous complexing agent solution containing at least one of aluminone and tannic acid as a complexing agent, it is controlled to be neutral in a chemical plating bath that does not substantially contain reducing agents and complexing agents, and then chemically treated. A chemical plating method for aluminum materials, which is characterized by plating.
リブデンであることを特徴とするアルミニウム素材の化
学めつき方法。2. 2. A method for chemically plating an aluminum material according to claim 1, wherein the plating component of the chemical plating bath is molybdenum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28220190A JPH04157166A (en) | 1990-10-19 | 1990-10-19 | Method for chemically plating aluminum stock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28220190A JPH04157166A (en) | 1990-10-19 | 1990-10-19 | Method for chemically plating aluminum stock |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04157166A true JPH04157166A (en) | 1992-05-29 |
Family
ID=17649386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28220190A Pending JPH04157166A (en) | 1990-10-19 | 1990-10-19 | Method for chemically plating aluminum stock |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04157166A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08302475A (en) * | 1995-05-10 | 1996-11-19 | Sumitomo Metal Mining Co Ltd | Production of metal-coated rare-earth element-containing powder |
-
1990
- 1990-10-19 JP JP28220190A patent/JPH04157166A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08302475A (en) * | 1995-05-10 | 1996-11-19 | Sumitomo Metal Mining Co Ltd | Production of metal-coated rare-earth element-containing powder |
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