DE1521439A1 - Autocatalytic bath and process for the production of metal coatings - Google Patents
Autocatalytic bath and process for the production of metal coatingsInfo
- Publication number
- DE1521439A1 DE1521439A1 DE19651521439 DE1521439A DE1521439A1 DE 1521439 A1 DE1521439 A1 DE 1521439A1 DE 19651521439 DE19651521439 DE 19651521439 DE 1521439 A DE1521439 A DE 1521439A DE 1521439 A1 DE1521439 A1 DE 1521439A1
- Authority
- DE
- Germany
- Prior art keywords
- bath
- metal
- liter
- group
- metals
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 27
- 239000002184 metal Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 11
- 238000000576 coating method Methods 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000003839 salts Chemical class 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- -1 water Chemical class 0.000 claims description 5
- 238000001465 metallisation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 229910000085 borane Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- 229960003330 pentetic acid Drugs 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001649081 Dina Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000089409 Erythrina poeppigiana Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000009776 Rathbunia alamosensis Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- KEBHLNDPKPIPLI-UHFFFAOYSA-N hydron;2-(3h-inden-4-yloxymethyl)morpholine;chloride Chemical compound Cl.C=1C=CC=2C=CCC=2C=1OCC1CNCCO1 KEBHLNDPKPIPLI-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Description
-B1Ur diese iinmeldung wira die Priorität der entsprechenden US-Anmeldung oerial i\lo. 377 509 vom ^4. Juni 1^)64 in Anspruch g-B 1 For this registration, the priority of the corresponding US application is oerial i \ lo. 377 509 of ^ 4. June 1 ^) 64 in claim g
Die Erfindung oetrixit ein ijad una Verfahren zum abscheiden von Metallen der Axru^^e lü des periodischen öystems ohne Stromzufuhr von außen, wobei di.e überf'iächen auge&chiedener Metalle "seiDüt katalytisch auf den Abscheidungsvorgang wirken also praktiscn unbegrenzte Schichtdicken erzielt werden können.The invention oetrixit an ijad una method for deposition of metals of the axru ^^ e lü of the periodic system without Power supply from the outside, whereby the surface of the eyes & different Metals "are catalytically involved in the deposition process thus practically unlimited layer thicknesses are achieved can be.
Ziel der Erfindung ist exn Verfahren und eine dazu benutzte Badlösung für die besonders wirtschaftliciie, sichere Metallabsclieidung auf verschiedenartigsten Oberflächen und üas Erzielen von glänzenden, dichten Metallschichten»The aim of the invention is a method and a method used for this purpose Bathroom solution for the particularly economical, safe Metal coating on a wide variety of surfaces and achieving glossy, dense metal layers »
Bäder zur stromlosen i»ietailabsoneidung wurden Dereits in großer Zahl vorgeschlagen, iiach den erfindungsgeiuäßenBaths for electroless separation of details have already been proposed in large numbers, after those according to the invention
· I· I
0098 13/1340098 13/134
Untersuchungen der Anmelder in hat sich eroeLen, dcai al ο 'Reduktionsmittel in sulcneii rädern Borohyuride uesundero geeignet sina. Im ^usaiiimenwirker: nit geeigneten Aomplexbildnern zull iviadicieren des betreffenden iviett-iliünes führen Borohydride zur wirtscn^itlicnen j£.&au.rctiuii ueö ivj.ec allocations au katalytiscnen uDerfläcnen oei germfcer l'enaenz zur Spontanreaktion.Investigations by the applicant in has he o eLen, dcai al ο 'reducing agents in sulcneii wheels Borohyuride uesundero suitable sina. In ^ usaiiimenwirker: nit suitable Aomplexbildnern Zull iviadicieren the relevant iviett-iliünes lead Borohydride for wirtscn ^ j £ itlicnen & au.rctiuii ueö ivj.ec allocations au katalytiscnen uDerfläcnen oei germ fc he l'enaenz to spontaneous reaction..
Geeignet si na alle wasserlöslicneii Boronydriae mic einem guten Löslicnkeitsprodukt una -ausreicn'ender btaoilität in wässrigen Lösungen, bevorzugt vorgeschlagen weraen uie i\iatrium- Dzw. KaliumDoronydride. Gleichfalls gut brauchbar dina suostituierte Bodohydride, wie oeispielsweise Natriumxrimethoxyborohydrid, WaB (OCH,),H} dies gilt auch z.rs. für Amineboraneiwie Isopropylemin und jjimethylaiainboran.All water-soluble Boronydriae are suitable good solubility product and sufficient btaoility in aqueous solutions, preferably suggested were uie i \ iatrium or potassium doronhydride. Also useful dina substituted bodohydrides, such as sodium xrimethoxyborohydride, WaB (OCH,), H} this also applies to the right for amineboranes such as isopropylemine and jjimethylaiaainborane.
Um die Oxydation des Borohyariaes zu vermeia&n, sollte aie Badlösung bei relativ hohem pü., vorzugöweise zwiscnen 10 und 14 benutzt weraen.To avoid the oxidation of Borohyariaes, should aie bath solution with a relatively high pu., preferably between 10 and 14 are used.
Grundsätzlich bestehen erfindungsgemäße Baulöäungen aus einem wasserlöslichen ketallsatz der Gruppe IB, »vasser, einem komplexbildner zum kaskieren des ketc.llSalzes und einem Borohydrid als _.eduktiunömittel, wobei das pxi beispielsweise vermittels von Katriumhydroxyd auf einenBasically, construction solutions according to the invention consist of a water-soluble metal set of group IB, »vasser, a complexing agent to mask the ketc.ll salt and a borohydride as a reducing agent, the pxi for example by means of sodium hydroxide on one
0 0 9 8 13/13 A U 0 0 9 8 13/13 A U
SADSAD
geeigneten „ert, vorzugswei&e zwioonen 10 und 14 eingestellt wix-vi. Die Mengen der einzelnen, wesentlichen BadbestcJidteile können in .eilen Frenzen variiert weraen. Typische Bäder entsprecnen jedoch etwa den folgenden Angabenι suitable "ert, preferably set between 10 and 14 wix-vi. The quantities of the individual, essential bath components can be varied within quick limits. However, typical baths entsprecnen about the following information ι
Wasserlösliches Metallsalz 0,002 bis 0,60 Mol/LiterWater soluble metal salt 0.002 to 0.60 mol / liter
Komplexbildner 0,7 bis 10 mal die ZahlComplexing agent 0.7 to 10 times the number
Mole des MetallsalzesMoles of metal salt
Reduktionsmittel 0,0002 bis 2,5 Mol/LiterReducing agent 0.0002 to 2.5 moles / liter
AlkalimetcJLlhydroxyd um ein pH zwischen 10 una 14Alkali metal hydroxide around a pH between 10 and 14
einzustellen.to adjust.
Theoretisch wird 1/4 bis 1/8 Mol Borohydrid pro Mol Metal· salz benötigt und diese Menge kann als untere Grenze Getrachtet werden. Die Menge an Komplexbildner hängt von dessen ^rt weitgehend ab» ebenso notwendigerweise von der Konzentration des Metallsalzes. In alkalischer Lösung liegt uas bevorzugte Verhältnis zwiscnen Metallsalz und Komplexbildner etwa zwiscnen lsi und 1:10. Ein geringer Überschuß an Komplexbildner, berechnet auf die Menge an vorhandenen Metallsalz, ist grundsätzlich vorteilhaft.Theoretically 1/4 to 1/8 mole of borohydride per mole of metal salt is required and this amount can be used as a lower limit To be considered. The amount of complexing agent depends largely from its place »just as necessarily on the concentration of the metal salt. In alkaline Solution is the preferred ratio between the metal salt and complexing agents between about 1 and 1:10. A small excess of complexing agent, calculated on the The amount of metal salt present is generally advantageous.
Π H S ΰ 1 3 / 1 3 A 'Ii Π HS ΰ 1 3/1 3 A 'Ii
BADBATH
Mit den erfindungsgemäßen Bädern ist die Abscheidung von Metallen der Gruppe IB mit konstanter Abscheidungsgeschwindigkeit auf allen katalytischen Oberflächen einwandfrei möglich. Als besonderen Vorzug derartiger autokatalytischer Bäder ist zu vermerken, daß die Dicke der abgeschiedenen Metallschicht über die ganze mit der Badflüssigkeit in Berührung stehende Oberfläche konstant , und zwar vollkommen unabhängig von der räumlichenWith the baths according to the invention, the deposition of metals of group IB is perfectly possible with a constant deposition rate on all catalytic surfaces. It should be noted as a particular advantage of such autocatalytic baths that the thickness of the deposited metal layer is constant over the entire surface in contact with the bath liquid, completely independent of the spatial one
. Das erfindungsgemäße Verfahren kann daher mit Vorteil zum Metallisieren von kompliziert geformten Bauteilen benutzt werden, deren Galvanisieren nur ^schwierig oder kaum möglich ist. . ■ , .. The method according to the invention can therefore advantageously be used for metallizing components with a complex shape are used whose electroplating is only ^ difficult or is hardly possible. . ■,.
Die Überfläche von Metallen, wie Mckel, Kobalt, Eisen, Stahl, Palladium, Platin, Kupfer, Bronze, Mangan, Chrom, Molybdän, Wolfram, Titan, Zinn, Gold und Silber wirkt katalytisch} Materialien, wie Glas, Keramik, diverse Kunststoffe, Papier u. dgl. sind in der Hegel nicht katalytisch. Sie können jedoch leicht oberflächlich katalytisch gemacht werden· Hierzu wurden bereits zahlreiche Verfahren in der Praxis vorgeschlagen und benutzt. Grundsätzlich wird hierbei entweder die Oberfläche mit einem extrem dünnen Film eines katalytischen Metalles, wie z.B. Palladium, überzogen oder mit Partikeln, die^^ katalytische Eigenschaften besitzen, ausgerüstet oder in anderer WeiseThe surface of metals such as mckel, cobalt, iron, Steel, palladium, platinum, copper, bronze, manganese, chromium, molybdenum, tungsten, titanium, tin, gold and silver work catalytic} Materials such as glass, ceramics, various plastics, paper and the like are not catalytic in Hegel. However, they can easily be made superficially catalytic. There have already been numerous Procedure proposed and used in practice. Basically, either the surface with a extremely thin film of a catalytic metal, e.g. Palladium, coated or with particles, the ^^ catalytic Own properties, equipped or otherwise
9813/13449813/1344
SADSAD
152U39152U39
aktive Zentren hergestellt. Sobald auf einer katalytischen Oberfläche eine erste Schicht des abzuscheidenden IB-Metalles vorhanden ist, wirkt dann diese selbst katalytisch für den weiteren Metallabscheidungsvorgang. Das nach der Erfindung vorgeschlagene Verfahren eignet sich daher auch zum Metallisieren einer großen Vielzahl verschiedener, nichtmetallischer Oberflächen, wie beispielsweise solcher von Silikonen, Phenolen, Epoxyd-^arzen, Styrenen, Acrylharzen, Cinylchlriden, Polyamiden, Mylar, Acriylnitril-Butadienstyren u. dgl. mehr.active centers established. Once on a catalytic Surface a first layer of the IB metal to be deposited is present, then this itself acts catalytically for the further metal deposition process. That after The method proposed by the invention is therefore also suitable for metallizing a large number of different, non-metallic surfaces, such as those made of silicones, phenols, epoxies, styrenes, Acrylic resins, cynyl chloride, polyamides, Mylar, acrylnitrile-butadiene-styrene and the like more.
■Pur den praktischen Betrieb hat es sich als zweckdienlich erwiesen, die Metallsalzkonzentration sowie jene anderer verbrauchter Bestandteile entsprechend der abgeschiedenen Metallmenge zu ergänzen und die Badkonzentrationen konstan zu halten.■ It has proven to be useful for practical operation proved the metal salt concentration as well as that of others consumed components according to the deposited To replenish the amount of metal and to keep the bath concentrations constant to keep.
Es hat sich auch als zweckmäßig erwiesen, der Badlösung eine geringe Menge, beispielsweise von weniger als 5 g/l einer Öberflächenwirksamen Verbindung zuzusetzen} typische Verbindungen dieser Art sind organische Phosphateater sowie Natriumoxyälaylate.It has also proven useful to use the bath solution add a small amount, for example less than 5 g / l of a surface-active compound} typical compounds of this type are organic phosphateatres as well as sodium oxyalaylates.
Im folgenden sollen Beispiele für erfindungsgemäße Badkompositionen zur besseren Verdeutlichung der Erfindung dienernThe following are examples of bath compositions according to the invention serve to better illustrate the invention
009813/1344009813/1344
essigsäureDiethylenetriaminepenta-
acetic acid
einer iiatriumborohydridlösungpH before addition
an iiatrium borohydride solution
pentaessigsaureDiethylenetriamine
pentaacetic acid
einer totriumborohydridlösungpH before addition "
a totrium borohydride solution
pentaessigsäureDiethylenetriamine
pentaacetic acid
009813/1344009813/1344
1521.43?1521.43?
" λ "■■■■. - 7 -"λ" ■■■■. - 7 -
Die Bäder nach, den aufgeführten Rezepturen geben glänzende Metallniederschläge und arbeiten an sich zufriedenstellend sie neigen jedoch bereits nach relativ kurzen Betriebszeiten zur Selbstzersetzung. Außerdem weisen die abgeschiedenen Metallschichten Sprödigkeit und gerichte Duktilität auf. Um diese .Nachteile zu vermeiden, kann den Badlösungen nach einer Ausgestaltung der Erfindung eine geringe Menge eines Syanides zugesetzt werden. Besonders geeignet sind hierfür anorganische Cyanide, Nitrile, beispielsweise llatrium- oder Kaliumcyanid, Glyeolnitril, Lactronitril und Alpha-Hydroxynitrile, wie Alphahydroxyiso butyronitrile. Die Konzentration des Cyansalzes liegt in der Regel etwa zwischen 5 nic$ogram/Lit er und 500 Milligram, Liter. In jedem Falle muß darauf geachtet werden, die Konzentration so geriig zu halten, daß der gewünschte Metal abscheidungsvorgang an katalytisehen Zentren nicht behindert oder zum Stillstand gebracht wird. Bäder, die ■einen Gyanidzusatζ enthalten, sind außerordentlich stabil und liefern duktile Metallabscheidungen.The baths according to the recipes listed give brilliant Metal precipitates and work on themselves satisfactorily, however, they tend already after relatively short periods of operation to self-decomposition. In addition, the deposited metal layers show brittleness and specific ductility on. In order to avoid these disadvantages, the bath solutions according to one embodiment of the invention can have a low Amount of a syanide can be added. Inorganic cyanides, nitriles, for example, are particularly suitable for this purpose sodium or potassium cyanide, glyeolnitrile, Lactronitrile and alpha-hydroxynitriles, such as alphahydroxyiso butyronitrile. The concentration of the cyan salt is in usually between about 5 nic $ ograms / liter and 500 milligrams, Liter. In any case, care must be taken to ensure that the Keep concentration so low that the desired metal deposition process at catalytic centers not hindered or brought to a standstill. Baths that contain ■ a gyanide additive are extremely stable and provide ductile metal deposits.
Als Beispiel für ein solches Bad mag die folgende Formel dienen:The following formula may serve as an example for such a bath:
009813/1344009813/1344
Kupfersalz
ΗΕΰΐΑCopper salt
ΗΕΰΐΑ
Natriumcyanid
iiatriumboröhydridSodium cyanide
iiatrium borohydride
Abscheidungsgeschwindigkeit Deposition rate
0,05 Mol/Liter 0,12 Mol/Liter 0,008 Mol/Liter 80 mg/Liter0.05 mol / liter 0.12 mol / liter 0.008 mol / liter 80 mg / liter
0,1 /u/h0.1 / u / h
Autokatalytische Metallisierungsverfahren nach der Erfindung finden einen weiten Anwendungsbereich,der von Idetallbeschichtungen für dekorative Zwecke, zur Verbesserung der mechanischen Eigenschaften, als Zeichen und bis zur Herstellung von metallischen Leibern für den Stromtransport auf Nichtleitern reicht.Autocatalytic metallization processes according to the Invention find a wide field of application, that of metal coatings for decorative purposes, for improvement of mechanical properties, as a sign and extends to the manufacture of metallic bodies for the transport of electricity on non-conductors.
9813/13449813/1344
SAD ORIGINALSAD ORIGINAL
Claims (4)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US37750964A | 1964-06-24 | 1964-06-24 | |
| US37750964 | 1964-06-24 | ||
| DEP0037111 | 1965-06-23 | ||
| US87705269A | 1969-11-14 | 1969-11-14 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1521439A1 true DE1521439A1 (en) | 1970-03-26 |
| DE1521439B2 DE1521439B2 (en) | 1975-03-06 |
| DE1521439C3 DE1521439C3 (en) | 1976-11-11 |
Family
ID=
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3622090C1 (en) * | 1986-07-02 | 1990-02-15 | Blasberg-Oberflaechentechnik Gmbh, 5650 Solingen, De |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3622090C1 (en) * | 1986-07-02 | 1990-02-15 | Blasberg-Oberflaechentechnik Gmbh, 5650 Solingen, De |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1521439B2 (en) | 1975-03-06 |
| US3589916A (en) | 1971-06-29 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| 8339 | Ceased/non-payment of the annual fee |