NL8105601A - COMPOSITIONS AND METHODS FOR ELECTROLYTIC DEPOSITION OF PALLADIUM AND PALLADIUM ALLOYS. - Google Patents
COMPOSITIONS AND METHODS FOR ELECTROLYTIC DEPOSITION OF PALLADIUM AND PALLADIUM ALLOYS. Download PDFInfo
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- NL8105601A NL8105601A NL8105601A NL8105601A NL8105601A NL 8105601 A NL8105601 A NL 8105601A NL 8105601 A NL8105601 A NL 8105601A NL 8105601 A NL8105601 A NL 8105601A NL 8105601 A NL8105601 A NL 8105601A
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- Prior art keywords
- palladium
- metal
- bath
- bath according
- amine
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 82
- 229910052763 palladium Inorganic materials 0.000 title claims description 42
- 239000000203 mixture Substances 0.000 title claims description 12
- 229910001252 Pd alloy Inorganic materials 0.000 title claims description 6
- 230000008021 deposition Effects 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- -1 amine palladium halide Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 238000005275 alloying Methods 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000009713 electroplating Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910002065 alloy metal Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- ONBDEXUUNGGFRN-UHFFFAOYSA-N amino nitrite Chemical compound NON=O.NON=O ONBDEXUUNGGFRN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 238000005282 brightening Methods 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000002028 premature Effects 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 150000001642 boronic acid derivatives Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- HMRJQTZQGGNCCJ-UHFFFAOYSA-M zinc azanide acetate Chemical compound C(C)(=O)[O-].N[Zn+] HMRJQTZQGGNCCJ-UHFFFAOYSA-M 0.000 description 2
- FMYBFLOWKQRBST-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid;nickel Chemical compound [Ni].OC(=O)CN(CC(O)=O)CC(O)=O FMYBFLOWKQRBST-UHFFFAOYSA-N 0.000 description 1
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- HOGKWLXRMABQDU-UHFFFAOYSA-N OB(O)OB(O)O.N.N.N.N Chemical compound OB(O)OB(O)O.N.N.N.N HOGKWLXRMABQDU-UHFFFAOYSA-N 0.000 description 1
- 101150072055 PAL1 gene Proteins 0.000 description 1
- 102100035031 Palladin Human genes 0.000 description 1
- 101710128215 Palladin Proteins 0.000 description 1
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- CBSHTDMWCFIHLH-UHFFFAOYSA-N acetic acid cobalt ethane-1,2-diamine Chemical compound [Co].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN CBSHTDMWCFIHLH-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- ADPUQRRLAAPXGT-UHFFFAOYSA-M sodium;2-formylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=O ADPUQRRLAAPXGT-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
- * * VO 2568.- * * VO 2568.
Samenstellingen en werkwijzen voor het elektrolytisch af zetten van •palladium en nalladiumlegeringen._Compositions and methods for electrolytic deposition of palladium and • nalladium alloys.
De uitvinding heeft "betrekking op samenstellingen en werkwijzen voor het elektrolytisch afzetten van palladiummetaal of legeringen daarvan op substraten uit baden, waarin gebruik wordt gemaakt van palladium in de vorm van palladiumamineverbindingen, zoals palladiumamine-5 chloride, dat wil zeggen PdClIH^)^01^.The invention relates to compositions and methods for the electrolytic deposition of palladium metal or alloys thereof on bath substrates, which use palladium in the form of palladium amine compounds, such as palladium amine 5 chloride, i.e. PdClIH ^) ^ .
Het elektrolytisch afzetten van palladiummetaal en legeringen daarvan op substraten is bekend. Er wordt onder andere verwezen naar de volgende Amerikaanse octrooischriften 3-530.050, 3.580.820, 3.6771909» 066.517 en ^.098.656.The electrolytic deposition of palladium metal and its alloys on substrates is known. Reference is made, inter alia, to the following U.S. Patents 3-530,050, 3,580,820, 3,67771909, 066,517, and 1,098,656.
10 Uit deze referenties blijkt, dat de palladiummetaalcomponent van het elektrolytische bekledingsbad, hetzij als zodanig toegepast of tezamen met een legerend metaal, het best in de vorm van aminecomplex-zouten wordt toegepast, zoals bijvoorbeeld palladiumaminechloride en palladiumdiaminedinitriet.These references show that the palladium metal component of the electrolytic plating bath, whether used as such or together with an alloying metal, is best used in the form of amine complex salts, such as, for example, palladium amine chloride and palladium diamine dinitrite.
15 Be aminepalladium- en palladiumlegeringselektrolyten of elektro lytische bekledingsbaden als beschreven in de stand van de techniek worden normaal toegepast bij een pH in het gebied van ongeveer 6,5 tot 10,0. Wanneer deze baden bij bedrijf worden verhit tot temperaturen Φ 1 van ongeveer 20 - 70 C, ontstaan echter moeilijkheden, omdat de pH de 20 neiging heeft te dalen tot 5 of lager. Wanneer eenmaal de pH tot deze niveaus is gedaald, vindt een voortijdige precipitatie van het palla-diummetaalzout alsmede van het legerende metaalzout plaats. Men heeft reeds voorgesteld deze ongewenste pH-daling te vermijden door gebruik te maken van buffers, zoals ammonium- of alkalimetaalfosfat en. Het ge-25 bruik van dergelijke buffers heeft echter weer het nadeel dat een ongewenste precipitatie van deze metalen als fosfaten wordt veroorzaakt.Be amine palladium and palladium alloy electrolytes or electrolytic plating baths as described in the prior art are normally used at a pH in the range of about 6.5 to 10.0. However, when these baths are heated to temperatures Φ 1 of about 20-70 ° C during operation, difficulties arise because the pH tends to drop to 5 or less. Once the pH has dropped to these levels, a premature precipitation of the palladium metal salt and of the alloying metal salt occurs. It has already been proposed to avoid this undesired drop in pH by using buffers such as ammonium or alkali metal phosphates. However, the use of such buffers again has the disadvantage that an undesired precipitation of these metals as phosphates is caused.
Aldus blijft als hoofdprobleem bij toepassing van aminepalladiumcomplex-elektrolyten de noodzaak van herhaalde pH-instelling en het vermijden van voortijdige precipitatie van het palladium en/of het legerende metaal 30 daarvan bestaan.Thus, the main problem with the use of amine palladium complex electrolytes remains the need for repeated pH adjustment and avoidance of premature precipitation of the palladium and / or its alloying metal.
Het is een hoofddoel van de uitvinding te voorzien in middelen voor het overwinnen van de problemen die verbonden zijn bij de toepassing van pal 1 adiιττηρττη n^nrnpl&xan als elektrolyt bij de elektrolytische afzetting van palladiummetaal op verschillende substraten.It is a main object of the invention to provide means for overcoming the problems associated with the use of pal 1 adiιττηρττη n ^ nrnpl & xan as electrolyte in the electrolytic deposition of palladium metal on various substrates.
35 Het is een ander doel van de uitvinding te voorzien in elektroly tische bekledingsbaden, die padladiumaminecomplexen op zichzelf of met 8 1 0 5 6 0 1 .................... ~ _ ' *' *c -2- een legerende met aal'verb inding "bevatten, welke baden gedurende bedrijf geen ongewenste pH-daling vertonen.It is another object of the invention to provide electrolytic plating baths comprising padladium amine complexes by themselves or with 8 1 0 5 6 0 1 .................... ~ Contains an alloy with eel compound, which baths do not exhibit an undesirable drop in pH during operation.
Het is een verder doel van de uitvinding te voorzien in palladium-aminecomplex-bevattende elektrolytische bekledingsbaden, waarbij de voor-' 5 tijdige precipitatie van de palladium- of legerende metaalzouten wordt voorkomen.It is a further object of the invention to provide electrolytic plating baths containing palladium-amine complex, whereby the premature precipitation of the palladium or alloying metal salts is prevented.
Het is nog een ander doel van de uitvinding te voorzien in een verbeterde werkwijze voor het bekleden van palladium of legeringen daarvan op substraten onder toepassing van speciale elektrolytische be-10 kledingsbaden.It is yet another object of the invention to provide an improved method of coating palladium or alloys thereof on substrates using special electrolytic coating baths.
Deze en andere doeleinden van de uitvinding zullen nu nader worden toegelicht.These and other objects of the invention will now be explained in more detail.
Volgens de uitvinding is nu gevonden dat de pH kan worden gestabiliseerd onder vermijding van voortijdige precipitatie van palladium-15 metaal- of legerende metaalzouten, wanneer men gebruik maakt van een boraatbuffer bij het samenstellen van het elektrolytische bekledingsbad.According to the invention it has now been found that the pH can be stabilized avoiding premature precipitation of palladium-15 metal or alloying metal salts when using a borate buffer in the composition of the electrolytic coating bath.
De boraatbuffer wordt in een voldoende hoeveelheid toegepast om het bad op een pH in het.gebied van ongeveer 6,5 — 9,5 te brengen. Deze pH zal niet dalen tot 5 of lager bij de praktische bedrijfsomstandigheden, be-20 staande uit gebruikelijke palladiummetaalbekledingsteraperaturen van ongeveer 20 - T5°C en'.stroomdichtheden‘variërende van ongeveer 0,11 - 11 2 2 A/dm , bij voorkeur 0,33 - 5,5 A/dm .The borate buffer is used in an amount sufficient to bring the bath to a pH in the range of about 6.5-9.5. This pH will not drop to 5 or less under the practical operating conditions, consisting of conventional palladium metal cladding temperatures of about 20 DEG-5 DEG C. and current densities ranging from about 0.11-11 2 A / dm, preferably 0 33 - 5.5 A / dm.
Aldus wordt de voortijdige precipitatie van het palladium- of legerende metaalzout vermeden doordat de pH in het bad in het gewenste 25 traject wordt gehandhaafd; terwijl tevens de bij de uitvoering van de uitvinding toegepaste speciale boraten geen neiging vertonen metaalzou-hen te vormen die anders zouden neerslaan en de normale functionering van het elektrolytische bekledingsbad zouden verstoren.Thus, the premature precipitation of the palladium or alloying metal salt is avoided by maintaining the pH in the bath in the desired range; while also the special borates used in the practice of the invention do not tend to form metal salts which would otherwise precipitate and interfere with normal operation of the electrolytic plating bath.
De boraten, die voor de onderhavige doeleinden worden toegepast, 30 worden gevormd door neutralisatie van boorzuur met een alkalimetaal, ammonia, ammoniumhydroxyde of een amine. De neutralisatie kan hetzij in situ, dat wil zeggen gedurende de samenstelling van het bad worden uitgevoerd of als een afzonderlijke trap waarbij het aldus gevormde boraat als een component van het bad wordt toegepast. De neutralisatie van het " 35 boorzuur kan als bovenbeschreven worden uitgevoerd met de volgende stoffen: ammoniak, aramoniumhydroxyde, alkali- of aardalkalimetaalverbin-dingen, zoals natriumhydroxyde, kaliumhydroxyde en dergelijke of een amine., zoals ethyleendiamine, diëthyleentriamine en dergelijke. Voor- 8 ΐ Ó § 6 01.......... —‘ “ ' li -3- keursboraten zijn natriumtetraboraat en ammoniumdiboraat.The borates used for the present purposes are formed by neutralizing boric acid with an alkali metal, ammonia, ammonium hydroxide or an amine. The neutralization can be carried out either in situ, i.e. during the composition of the bath, or as a separate step using the borate thus formed as a component of the bath. The neutralization of the boric acid can be carried out as described above with the following substances: ammonia, aramium hydroxide, alkali or alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide and the like or an amine such as ethylenediamine, diethylene triamine and the like. Ó § 6 01 .......... - '' 'li -3- approved borates are sodium tetraborate and ammonium diborate.
Het boraat "wordt bij voorkeur in situ gevormd, waarbij de alkalische reactant wordt toegepast in een hoeveelheid die niet alleen voldoende is om het boorzuur in het overeenkomstige boraat om te zetten, 5 gewoonlijk ongeveer 10 - 50 g/1, maar tevens voldoende om de begin-pH van het nieuw gevormde elektrolytische bekledingsbad op te voeren of in te stellen in het gebied van ongeveer 6,5 - 9,5.The borate is preferably formed in situ, the alkaline reactant being used in an amount not only sufficient to convert the boric acid to the corresponding borate, usually about 10 - 50 g / l, but also sufficient to raise or adjust the initial pH of the newly formed electrolytic plating bath in the range of about 6.5-9.5.
Eet palladiumaminecomplex kan hetzij het halogenide, nitriet, nitraat, sulfaat of sulfamaat zijn. Illustratieve complexen omvatten 10 de volgende: palladiumdiaminechloride [PdfïïH^gClg] palladiumdiaminedinitriet [PdCïïH^gCliOg^] palladiumtetraminenitraat [PdiliH^) palladiumdiaminesulfaat [PdClIH^JgSO^] 15 Andere bruikbare palladiumzouten zijn dichloordiaminepalladium- chloride en dergelijke.The palladium amine complex can be either the halide, nitrite, nitrate, sulfate or sulfamate. Exemplary complexes include the following: palladium diamine chloride [Pdf] H ^ gClg] palladium diamine dinitrite [PdCIH ^ gCliOg ^] palladium tetramine nitrate [PdilHH4] palladium diamine sulfate [PdClIH ^ JgSO ^] salts and other useful palladium chloride.
Het palladiummetaal in het aminecomplex wordt toegepast in een hoeveelheid die ligt in het gebied van ongeveer 1 - 50 g/1, welke hoeveelheid bij voorkeur ongeveer 5-35 g/1 is.The palladium metal in the amine complex is used in an amount in the range of about 1 - 50 g / l, which amount is preferably about 5-35 g / l.
20 Aangezien het dikwijls wenselijk is het werkstuk of het substraat 0 te bekleden met een palladium!egering, worden als legeringsmetalen in de uitvinding onder andere toegepast de aminozouten van koper, kobalt, cadmium, goud, ijzer, indium, nikkel, zilver, tin en zink. Voorbeelden van legeringsmetaalcomponenten omvatten nikkelaminechloride, aminozink-25 acetaat, ethyleendiaminetetraazijnzuurkobaltcomplex, nitrilotriazijn-zuurnikkelcomplex, enz.Since it is often desirable to coat the workpiece or substrate with a palladium alloy, the alloy metals used in the invention include the amino salts of copper, cobalt, cadmium, gold, iron, indium, nickel, silver, tin and zinc. Examples of alloy metal components include nickel amine chloride, amino zinc acetate, ethylenediamine tetraacetic acid cobalt complex, nitrilotriacetic acid nickel complex, etc.
De legerende metaalcomponent kan in het elektrolytische bekledingsbad aanwezig zijn in een hoeveelheid tot ongeveer 0-50 g/1, waarbij hoeveelheden van ongeveer 5-20 g/1, indien de component aanwezig is, 30 de voorkeur hebben.The alloying metal component may be present in the electrolytic plating bath in an amount of up to about 0-50 g / l, with amounts of about 5-20 g / l if the component is present.
Het bad zal tevens ongeveer 5-150 g/1, bij voorkeur 10 - 100 g/1 van het geleidingszout bevatten. Voor de onderhavige doeleinden zijn bruikbare geleidingszouten, ammonium- of alkali metaalhalogeniden, carbonzuur zout en, sulfaten, nitraten en sulfamaten. Voorbeelden van dergelijke 35 zouten omvatten ammoniumchloride, ammoniumcitraat, ammoniumnitraat, na- triumnitraat, ammoniumsulfamaat, kaliumsulfaat enz. alsmede mengsels ' daarvan?. In het bijzonder de voorkeur hebben als geleidings zouten ammoniumchloride, ammoniumcitraat, kaliumcitraat en mengsels daarvan.The bath will also contain about 5-150 g / l, preferably 10-100 g / l, of the guide salt. Useful for the present purposes are conductive salts, ammonium or alkali metal halides, carboxylic acid salts, sulfates, nitrates and sulfamates. Examples of such salts include ammonium chloride, ammonium citrate, ammonium nitrate, sodium nitrate, ammonium sulfamate, potassium sulfate etc. as well as mixtures thereof. Especially preferred as the guiding salts are ammonium chloride, ammonium citrate, potassium citrate and mixtures thereof.
8 1 0 5 5 0 1 ...... ............... ^ s.8 1 0 5 5 0 1 ...... ............... ^ s.
Λ -k-Λ -k-
Bij het samenstellen van de elektrolytxs ehe bekledingsbaden volgens de uitvinding is het tevens gewenst voor "bepaalde toepassingen een glansmiddel toe te voegen. De glansmiddelen die voor de onderhavige doeleinden het "best bruikbaar zijn, zijn aromatische gesulfoneerde amiden, 5 aromatische gesulfoneerde imiden, alkalimetaal-aromat is che sulfonaten en aromatische sulfonzuren, alsmede mengsels daarvan. Speciale glansmiddelen zijn natriumnaftaleensulfonaat, mtriumsaceharine en mengsels ervan.When formulating the electrolyte coating baths of the invention, it is also desirable to add a brightener for "certain applications. The brighteners most useful for the present purposes are aromatic sulfonated amides, aromatic sulfonated imides, alkali metals. aromatic is sulfonates and aromatic sulfonic acids, as well as mixtures thereof. Special brighteners are sodium naphthalene sulfonate, sodium aceharine and mixtures thereof.
De glansmiddelen zullen in het algemeen worden toegepast in hoeveelheden die variëren van ongeveer 0,1 tot 5 g/1» waarbij de voorkeurshoeveelheid 10 ongeveer 0,5 - 4 g/1 bedraagt.·The brighteners will generally be used in amounts ranging from about 0.1 to 5 g / l, with the preferred amount of 10 being about 0.5-4 g / l.
In sommige gevallen is het wenselijk een leverancier van "vrije" of niet gecompleteerde nitrietionen in het bad aanwezig te hebben. De -leverancier van de vrije nitrietionen is bij voorkeur een wateroplosbare anorganische nitrietverbinding, zoals een alkalimetaalnitriet. In het 15 ' bijzonder de voorkeur hebben natriumnitriet, kaliumnitriet, ammonium-nitriet enz. De hoeveelheid toegepaste nitrietionen kan ruim variëren en is tenminste ongeveer 0,05 gew.% betrokken op de palladium!onen in het bad. Aanvankelijk kan de concentratie van de nitrietionen variëren van ongeveer 0,1 tot ongeveer 50 gew./5 betrokken op het gewicht van de 20 palladium! onen.In some cases it is desirable to have a supplier of "free" or incomplete nitrite ions in the bath. The supplier of the free nitrite ions is preferably a water-soluble inorganic nitrite compound, such as an alkali metal nitrite. Especially preferred are sodium nitrite, potassium nitrite, ammonium nitrite, etc. The amount of nitrite ions used can vary widely and is at least about 0.05 wt% based on the palladium ones in the bath. Initially, the concentration of the nitrite ions can range from about 0.1 to about 50 weight percent based on the weight of the palladium! onen.
De baden volgens de uitvinding kunnen worden toegepast tezamen met onoplosbare platina, platina-beklede, tantaal- of columbiumanoden.The baths of the invention can be used in conjunction with insoluble platinum, platinum-coated, tantalum or columbium anodes.
In het algemeen wordt bekleding op rekken toegepast en hebben de werkstukken, bijvoorbeeld doos en pencontacten; contacten van gedrukte scha-25 kelingenplaten, decoratieve juwelen., enz. oppervlakken van metalen, zoals koper, messing, brons, nikkel, zilver, staal enz. De palladium-metaal- of palladiummetaallegeringsbekledingen bleken van hoge kwaliteit te zijn. ·Generally, cladding is applied to racks and the workpieces have, for example, box and pin contacts; printed circuit board contacts, decorative jewelry, etc. metal surfaces such as copper, brass, bronze, nickel, silver, steel, etc. The palladium metal or palladium metal alloy coatings were found to be of high quality. ·
De uitvinding zal nu verder worden toegelicht door de volgende 30 illustratieve uitvoeringsvormen.The invention will now be further elucidated by the following illustrative embodiments.
Voorbeeld I.Example I.
Een waterig palladiummetaal-bevattend elektrolytisch bekledings-bad werd als volgt samengesteld: component g/l 35 palladinmaminechloride 10 (Pd metaal) ammoniumchlori-de .50 boorzuur 30 ~ ammoniumhydrozyde tot pH 8,2 water ^__________________________________rest, —-— 8105601 -5-An aqueous palladium metal-containing electrolytic plating bath was formulated as follows: component g / l 35 palladin amine chloride 10 (Pd metal) ammonium chloride .50 boric acid 30 ~ ammonium hydroxide to pH 8.2 water.
Het bad verd toegepast bij een temperatuur van ongeveer 20 tot 70° C en bij een stroomdichtbeid van 1,1 A/dm . Ha k uur bedrijf vas de pH nog niet gedaald beneden 7»5.The bath is used at a temperature of about 20 to 70 ° C and at a current density of 1.1 A / dm. After an hour of operation, the pH has not yet fallen below 7 »5.
Voorbeeld II.Example II.
5 Een vaterig palladiummetaal-bevattend elektrolytis ch bekledings- bad -werd als volgt samengesteld: component g/1 palladiumdiaminodinitriet 10 - 30 (Pd metaal) natriumnitriet 10 ' 10 ammoniumnitraat 30 boorzuur 20 ammoniak tot pH 7,0 - 7,5 vat er rest.5 A palatal palladium metal-containing electrolytic plating bath was composed as follows: component g / 1 palladium diamino dinitrite 10 - 30 (Pd metal) sodium nitrite 10 '10 ammonium nitrate 30 boric acid 20 ammonia to pH 7.0 - 7.5 barrel left over .
Het bad verd toegepast bij een temperatuur van ongeveer 50 - 70°CThe bath is used at a temperature of about 50-70 ° C
2 15 en bij een stroomdichtbeid van 11 tot 110 A/dm . Er verd na 4 uur bedrijf geen daling van de piï beneden 7,5 vaargenomen.2 15 and with a current density of 11 to 110 A / dm. After 4 hours of operation, no drop of the PI below 7.5 was observed.
Voorbeeld III.Example III.
Een vaterig, palladium-nikkelmetaallegering-bevattend elektroly— tiscb bekledingsbad verd als volgt samengesteld: 20 component g/1 " Φ paHadiumaminechloride 10 (Pd metaal) nikkelaminechloride 12 (Ui metaal) ammoniumchloride 30 ammoniumcitraat 10 25 boorzuur 15 ammoniumhydroxyde tot pH 9,0 vater rest.An aqueous palladium-nickel metal alloy containing electrolyte coating bath composed as follows: 20 component g / 1 "Φ paHadium amine chloride 10 (Pd metal) nickel amine chloride 12 (Onion metal) ammonium chloride 30 ammonium citrate 10 25 boric acid 15 ammonium hydroxide to pH 9.0 more rest.
Het bad verd toegepast bij een temperatuur van ongeveer 20 - 50°C en bij een stroomdichtbeid van ongeveer 2,2 A/dm . Ua U uur bedrijf vas 30 de pH niet beneden 7,5 gedaald*The bath is used at a temperature of about 20-50 ° C and at a current density of about 2.2 A / dm. Ua Hour operation vas 30 the pH has not dropped below 7.5 *
Voorbeeld IV.Example IV.
Proef A.Trial A.
Het bad van voorbeeld II verd opnieuv samengesteld, vaarbij bet palladiummetaalgehalte verd verminderd tot 2h gil en 5 g/1 zilvermetaal 35 aanwezig vas in de vorm van gilverdinitrietallralimetaalzout. De temperatuur van bet bad verd tussen 20 en 25°C gehandhaafd.The bath of Example II is further reconstituted, with the palladium metal content reduced to 2 g / g and 5 g / l of silver metal vas present in the form of giltin nitrite allral metal salt. The bath temperature is maintained between 20 and 25 ° C.
8 10 5 6 0 1 -6- %8 10 5 6 0 1 -6-%
Proef B.Trial B.
Het laad van voorbeeld II werd opnieuw samengesteld, waarbij het palladiummetaalgehalte werd verminderd tot 5 g/l en een legerend zinkniet aal (1 g/l) aanwezig was in de vorm van aminozinkacetaat.The charge of Example II was reconstituted, reducing the palladium metal content to 5 g / L and an alloying zinc eel (1 g / L) was present in the form of amino zinc acetate.
5 Proef C.5 Trial C.
Het elektrolyt!sche bekledingsbad van voorbeeld III werd opnieuw samengesteld, waarbij 3 g/l benzaldehyde-O-natriumsulfonaat en 0,1 g/l van het natriumzout van naftaleensulfonaat werden toegevoegd. Dit bad werd toegepast bij 30°C en met een-stroomdichtheid tussen 1,1 en 5,5 10 A/dm2.The electrolytic coating bath of Example III was reconstituted, adding 3 g / l of benzaldehyde-O-sodium sulfonate and 0.1 g / l of the sodium salt of naphthalene sulfonate. This bath was operated at 30 ° C and with a current density between 1.1 and 5.5 10 A / dm2.
Proef D.Trial D.
Het bad van voorbeeld III werd opnieuw samengesteld, waarbij 0,1-10 g/l natriumsaccharine werd toegevoegd. Dit bad werd geëlektro- o 2 lyseerd bij 35°C en "bij stroomdichtheden tussen 0,5 en 5,5 A/dm om 15 nikkel-paUadiumbekledingen te geven met lage spanningen*.The bath of Example III was reconstituted, adding 0.1-10 g / l sodium saccharin. This bath was electrolyzed at 35 ° C and "at current densities between 0.5 and 5.5 A / dm to give 15 nickel-plating coatings with low voltages *.
Bij de gebruikelijke bedrijfsomstandigheden vertoonde geen van de baden, proeven A - D, een overmatige pH-daling, dat wil .zeggen van 7,5 tot 5· Wanneer daarentegen deze baden, alsmede de baden van voorbeelden I - III in bedrijf werden genomen zonder de voorgeschreven boraatbuffer, 20 dat wil zeggen het alkalimetaal- of ammoniumhydroxyde-geneutraliseerd boor zuur, of wanneer andere buffers., .zoals citraten, fosfaten, tar-traten enz. in plaats van de boraten werden toegepast., daalde de pH in U uur of minder tot een ongewenste waarde van 5, hetgeen leidde tot de precipitatie van het palladium en/of de andere of legerende metalen.Under the usual operating conditions none of the baths, tests A - D, showed an excessive drop in pH, that is to say from 7.5 to 5. When, on the other hand, these baths and the baths of Examples I - III were put into operation without the prescribed borate buffer, ie the alkali metal or ammonium hydroxide neutralized boric acid, or when other buffers such as citrates, phosphates, tartrates, etc. were used in place of the borates, the pH dropped in 1 hour or less to an undesirable value of 5 leading to the precipitation of the palladium and / or the other or alloying metals.
' · i ~~ 810TF01 " “T-" 'I ~~ 810TF01 "" T- ""
Claims (13)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21521280A | 1980-12-11 | 1980-12-11 | |
| US21521280 | 1980-12-11 |
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| Publication Number | Publication Date |
|---|---|
| NL8105601A true NL8105601A (en) | 1982-07-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL8105601A NL8105601A (en) | 1980-12-11 | 1981-12-11 | COMPOSITIONS AND METHODS FOR ELECTROLYTIC DEPOSITION OF PALLADIUM AND PALLADIUM ALLOYS. |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS609116B2 (en) |
| BE (1) | BE891319A (en) |
| BR (1) | BR8108038A (en) |
| CH (1) | CH649582A5 (en) |
| DE (1) | DE3147823A1 (en) |
| DK (1) | DK548881A (en) |
| ES (1) | ES8304617A1 (en) |
| FR (1) | FR2496130A1 (en) |
| GB (1) | GB2089374B (en) |
| HK (1) | HK67186A (en) |
| IT (1) | IT8149859A0 (en) |
| NL (1) | NL8105601A (en) |
| SE (1) | SE8106867L (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512963A (en) * | 1982-12-10 | 1985-04-23 | At&T Bell Laboratories | Palladium compound synthesis procedure |
| IN164233B (en) * | 1984-12-14 | 1989-02-04 | Oronzio De Nora Impianti | |
| GB2171721B (en) * | 1985-01-25 | 1989-06-07 | Omi Int Corp | Palladium and palladium alloy plating |
| US4628165A (en) * | 1985-09-11 | 1986-12-09 | Learonal, Inc. | Electrical contacts and methods of making contacts by electrodeposition |
| DE3935664C1 (en) * | 1989-10-26 | 1991-03-28 | W.C. Heraeus Gmbh, 6450 Hanau, De | Palladium-silver alloys for electrical contacts - deposited from ammoniacal bath contg. palladium tetramine complex, silver di:amine complex and organic sulphur cpd. |
| DE4444232C1 (en) * | 1994-07-21 | 1996-05-09 | Heraeus Gmbh W C | Bath for the galvanic deposition of palladium-silver alloys |
| DE19528800C2 (en) * | 1995-08-04 | 1999-05-06 | Ami Doduco Gmbh | Alkaline or neutral bath for the galvanic deposition of palladium or alloys of palladium |
| US5976344A (en) * | 1996-05-10 | 1999-11-02 | Lucent Technologies Inc. | Composition for electroplating palladium alloys and electroplating process using that composition |
| JP4598782B2 (en) | 2006-03-03 | 2010-12-15 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Palladium plating solution |
| GB201200482D0 (en) * | 2012-01-12 | 2012-02-22 | Johnson Matthey Plc | Improvements in coating technology |
| IT202000000391A1 (en) * | 2020-01-13 | 2021-07-13 | Italfimet Srl | Galvanic process, and relative bath, of electrodeposition of palladium with high corrosion resistance. |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE2839360C2 (en) * | 1978-09-09 | 1982-11-04 | Oxy Metal Industries Corp., Detroit, Mich. | Aqueous bath for the galvanic deposition of shiny coatings made of palladium or its alloys |
-
1981
- 1981-11-18 SE SE8106867A patent/SE8106867L/en not_active Application Discontinuation
- 1981-12-01 BE BE0/206712A patent/BE891319A/en not_active IP Right Cessation
- 1981-12-03 DE DE19813147823 patent/DE3147823A1/en not_active Ceased
- 1981-12-09 JP JP56198322A patent/JPS609116B2/en not_active Expired
- 1981-12-09 IT IT8149859A patent/IT8149859A0/en unknown
- 1981-12-10 DK DK548881A patent/DK548881A/en unknown
- 1981-12-10 ES ES507865A patent/ES8304617A1/en not_active Expired
- 1981-12-10 CH CH7901/81A patent/CH649582A5/en not_active IP Right Cessation
- 1981-12-10 FR FR8123097A patent/FR2496130A1/en not_active Withdrawn
- 1981-12-10 BR BR8108038A patent/BR8108038A/en unknown
- 1981-12-11 GB GB8137456A patent/GB2089374B/en not_active Expired
- 1981-12-11 NL NL8105601A patent/NL8105601A/en not_active Application Discontinuation
-
1986
- 1986-09-11 HK HK671/86A patent/HK67186A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HK67186A (en) | 1986-09-18 |
| CH649582A5 (en) | 1985-05-31 |
| DE3147823A1 (en) | 1982-06-24 |
| GB2089374B (en) | 1983-11-30 |
| ES507865A0 (en) | 1983-03-01 |
| BR8108038A (en) | 1982-09-21 |
| JPS57123992A (en) | 1982-08-02 |
| DK548881A (en) | 1982-06-12 |
| GB2089374A (en) | 1982-06-23 |
| BE891319A (en) | 1982-06-01 |
| JPS609116B2 (en) | 1985-03-07 |
| SE8106867L (en) | 1982-06-12 |
| ES8304617A1 (en) | 1983-03-01 |
| FR2496130A1 (en) | 1982-06-18 |
| IT8149859A0 (en) | 1981-12-09 |
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