EP0423005A1 - Hydrazinbad zur stromlosen Plattierung mit Platin und/oder Palladium, sowie Verfahren zur Herstellung eines solchen Bades - Google Patents
Hydrazinbad zur stromlosen Plattierung mit Platin und/oder Palladium, sowie Verfahren zur Herstellung eines solchen Bades Download PDFInfo
- Publication number
- EP0423005A1 EP0423005A1 EP90402778A EP90402778A EP0423005A1 EP 0423005 A1 EP0423005 A1 EP 0423005A1 EP 90402778 A EP90402778 A EP 90402778A EP 90402778 A EP90402778 A EP 90402778A EP 0423005 A1 EP0423005 A1 EP 0423005A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- palladium
- ethylenediamine
- platinum
- solution
- 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.)
- Withdrawn
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 86
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 74
- 229910052763 palladium Inorganic materials 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000126 substance Substances 0.000 title description 3
- 238000007747 plating Methods 0.000 title 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 58
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 35
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 51
- 229910052697 platinum Inorganic materials 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 33
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 28
- 238000000151 deposition Methods 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 24
- 239000011550 stock solution Substances 0.000 claims description 24
- -1 oxalate anions Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 239000010413 mother solution Substances 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 6
- 239000001230 potassium iodate Substances 0.000 claims description 6
- 229940093930 potassium iodate Drugs 0.000 claims description 6
- 235000006666 potassium iodate Nutrition 0.000 claims description 6
- 238000005234 chemical deposition Methods 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003252 NaBO2 Inorganic materials 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent 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
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WMNIETDRLRTYFX-UHFFFAOYSA-N ethane-1,2-diamine;platinum Chemical compound [Pt].NCCN WMNIETDRLRTYFX-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HNKLPNDFOVJIFG-UHFFFAOYSA-N oxalic acid;platinum Chemical compound [Pt].OC(=O)C(O)=O HNKLPNDFOVJIFG-UHFFFAOYSA-N 0.000 description 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent 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
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Definitions
- the invention relates to the chemical deposition of platinum and / or palladium on a substrate, by autocatalytic reduction.
- the industrial utility of a metal deposition bath depends to a large extent on the following three parameters: - absence of annoying impurities in the deposit; - Possibility of obtaining deposits with a thickness of several microns in a reasonable time, which implies both autocatalytic properties and a deposition rate of several microns per hour; - long bath life, preferably unlimited with periodic refills.
- European Patent 0 227 518 in the name of the Applicant relating to a nickel and / or cobalt deposition bath, explains the advantage of choosing hydrazine as a reducing agent, which does not provide any impurity in the deposit.
- This same patent also indicates that many anions, and in particular chloride, sulfate and nitrate anions, disturb the functioning of hydrazine baths.
- US Patent No. 3,562,911 describes hydrazine baths for the chemical deposition of platinum, containing hexachloroplatinic acid and hydrochloric acid, and therefore chloride ions. These baths are not autocatalytic and operate until exhaustion without the reaction can be stopped. The platinum yield is at most 91%, that is to say that at least 9% of the platinum ions contained in the bath are lost.
- the object of the invention is to provide a hydrazine autocatalytic bath, not containing chloride ions and which can be recharged to operate for long periods of time.
- the subject of the invention is an aqueous bath for the chemical deposition of platinum and / or palladium, containing a compound of the metal or of each of the metals to be deposited and of hydrazine as reducing agent, characterized in that said compound is an oxalate and that the bath contains ethylenediamine as complexing agent and at least one stabilizer, this bath being strongly basic and having an autocatalytic action.
- a bath according to the invention for the deposition of platinum advantageously contains platinum II at a concentration of between 0.05 and 0.15 g / l ion approximately, and a bath for the deposition of palladium, palladium at a concentration between 0.01 and 0.3 ion g / l approximately.
- the invention also relates to a method for preparing a bath as defined above, in which a mother solution containing platinum II or palladium, ethylenediamine and oxalate anions is first prepared and therein then add the stabilizer (s) and hydrazine.
- the platinum, ethylenediamine and oxalate concentrations and the pH of the stock solution are substantially the same as for the final bath.
- the mother solution is concentrated, that is to say that the palladium ions, ethylenediamine and the oxalate anions are present there at higher concentrations than in the bath, and the stock solution is diluted and its pH possibly adjusted before introduction of the stabilizer and hydrazine.
- a stock solution containing platinum, a stock solution containing palladium and dilution water are mixed in an amount suitable for obtaining the desired concentrations of platinum and palladium, and the stabilizer (s) and hydrazine are added.
- Platinum II compounds and Platinum IV compounds are commercially available. The latter are much more stable and therefore easier to handle than the former. Their industrial use therefore leads to lower costs.
- the most common platinum IV compounds are hexachloroplatinic acid H2PtCl6 and hexahydroxoplatinic acid H2Pt (OH) 6.
- An intermediate complex is therefore formed with oxalate ions in an acid medium.
- the acid medium suppresses the repulsive electrostatic effect with the amino ligand.
- the platinum-ethylenediamine complex is obtained by neutralizing the acidic solution of platinum oxalate II by an excess of anhydrous ethylenediamine.
- the pH can then be adjusted to a higher value by adding potassium hydroxide.
- the manufacturing of the palladium stock solution uses palladium chloride PdCl2, which is the only compound practically available, as starting material.
- This salt is soluble in an aqueous solution of hydrochloric acid.
- a solution of potassium hydroxide in an amount sufficient to obtain a pH greater than 8 is added to the solution obtained, so as to precipitate the palladium in the form of hydroxide Pd (OH) 2, which is collected by filtration under vacuum.
- This solution is neutralized by adding anhydrous ethylenediamine to a pH of about 10.
- the mother solution is thus obtained in which the palladium is complexed with ethylenediamine.
- This solution is concentrated and contains at least 0.1 gram ion of palladium, or at least 10 g / l of palladium metal.
- the procedure for obtaining a palladium bath is as follows: - Diluted with deionized water, to the desired volume of bath, a volume of stock solution containing the desired amount of palladium ions. - We put in solution a primary stabilizer, for example arsenic pentoxide. - One or more secondary stabilizers chosen from imidazole, benzotriazole, copper sulphate, lead acetate, iodic acid and glycine are placed in solution. - The reducing agent (hydrated hydrazine) is added.
- the mother solution obtained contains, for 1 liter, 0.1 gram ion of platinum, 1.2 mole of ethylenediamine and approximately 0.1 gram ion of oxalate.
- a typical concentrated stock solution contains, for 1 liter, 0.1 to 0.2 gram ion of palladium and 0.1 to 0.19 gram ion of oxalate, its pH being between 9 and 12, depending on the quantities of reagent used and the final degree of concentration.
- the ethylenediamine concentration is adjusted to 1M.
- Example 1 To the stock solution of Example 1, the following constituents are added at the following concentrations: - primary stabilizer: arsenic pentoxide 6,5.10 ⁇ 4M - secondary stabilizer: imidazole 0.3M - reducing agent: hydrazine hydrate 1M
- the pH of this bath is 13. It is used at 90 ° C. to coat an IN100 nickel-based alloy plate of dimensions approximate 10 mm x 13 mm x 2 mm. A constant deposition rate of 1 micron / hour is obtained for 2 hours, by recharging the bath periodically, after dosing, in a known manner. The deposit obtained is light gray and semi-gloss. Its surface appearance is dense and nodular, observations confirmed by metallographic examination on a polished section.
- a bath is prepared having the following composition: Pt 0.1 ethylenediamine 3.1 oxaldate About 0.1 (remaining amount after precipitation) potassium hydroxide QSPP pH greater than 13 arsenic pentoxide 6.5 10 ⁇ 4 imidazole 0.5 hydrated hydrazine 4.1
- the treated substrate is a Z10 NCD18-10 stainless steel plate previously nickel-plated and measuring approximately 20 mm x 20 mm x 2 mm. At a temperature of 82 ° C., a deposition rate of 1 micron / hour is obtained for 1 hour 40 minutes.
- Example 2 From the stock solution of Example 2, a bath is prepared having the following composition in molarities: palladium 0.02 ethylenediamine 1.5 oxalate 0.19 arsenic pentoxide 10 ⁇ 3 imidazole 0.2 hydrazine 1 The pH of this bath is 10.5.
- This bath is used to coat a nickel plate measuring approximately 10 mm x 10 mm x 2 mm at the temperature of 70 ° C. The speed obtained is 2 microns / hour for 1 hour.
- the bath differs from the previous one in that the ethylenediamine concentration is 2M.
- the concentration of ethylenediamine in the bath is brought to 3M, all other things being equal.
- the deposition rate is 4 microns / hour for 1 hour.
- the bath is similar to the previous ones, the ethylenediamine concentration being brought to 4M.
- the deposition rate at 70 ° C goes to 5 microns / hour for 1 hour.
- Example 5 A bath similar to that of Example 5 is prepared, except with regard to the imidazole concentration which is 0.3M.
- the bath differs from those of Examples 1 and 9 by an imidazole concentration of 0.4M.
- the concentration of imidazole in the bath is brought to 0.5M, without any other change.
- the deposition rate increases to 4.5 microns / hour for 2 hours.
- Example 2 From the stock solution of Example 2, a bath is prepared having the following composition, in molarities: palladium 0.1 ethylenediamine 3 oxalate 0.5 arsenic pentoxide 10 ⁇ 3 imidazole 0.4 hydrazine 1 Its pH is equal to 9.
- the bath differs from that of Example 12 by replacing the arsenic pentoxide with copper sulphate at a concentration of 1.7.10 ⁇ 4M, the pH being equal to 9.5.
- the bath differs from that of Example 12 by replacing the arsenic pentoxide with potassium iodate at the same concentration, the pH here again being equal to 9.5.
- the bath differs from that of the previous example in that the potassium iodate concentration is reduced to 10 ⁇ 4M.
- a deposition rate of 2.5 microns / hour for 10 hours is observed under the usual conditions of use.
- the bath differs from those of the two previous examples in that the potassium iodate concentration is reduced to 10 ⁇ 5M.
- the same bath at a temperature of 60 ° C provided a deposition rate of 1.5 microns / hour for 3 hours.
- a bath is prepared having the following composition, in molarities: palladium 0.19 ethylenediamine 1 oxalate 0.19 arsenic pentoxide 6.5.10 ⁇ 4 imidazole 0.3 hydrazine 0.14 the pH being brought to a value greater than or equal to 13 by potassium hydroxide.
- This bath can be used in a temperature range from 75 to 90 ° C, the deposition rate varying between 4 and 25 microns / hour.
- the deposit obtained, whose growth is of the columnar type, has a very healthy surface appearance and slightly cracked in its external part (rapid growth deposit).
- the bath of Example 16 is used to coat a plate te silicon carbide ceramic measuring approximately 10 mm x 8 mm x 3 mm having previously undergone an appropriate surface treatment.
- this surface treatment comprises the following stages: a) chemical degreasing for 10 min in a solution having the following composition, at 90 ° C: sodium hydroxide 120 g / l trisodium phosphate 100 g / l sodium perborate NaBO2.H2O2.H2O 50 g / l wetting agent (Teepol type) 100 ml / l b) After careful rinsing with deionized water, immersion in a hydrochloric solution containing 5 g / l of palladium chloride, for 10 to 15 minutes. c) Rinsing again with deionized water then immersion in pure hydrated hydrazine for 3 to 5 minutes. d) Rinsing again with deionized water.
- the wafer is then introduced into the bath according to the invention and the deposition reaction starts as soon as its surface temperature reaches that of the bath.
- a deposition rate of 4.5 microns / hour is obtained for 2 hours.
- the deposit is healthy and adherent.
- a bath is prepared having the following composition, in molarities: palladium 0.03 platinum II 0.06 ethylenediamine 2.7 oxalate 0.2 arsenic pentoxide 10 ⁇ 3 imidazole 0.4 hydrazine 1
- the pH of this bath is equal to 10.5. Under the conditions of use of Examples 5 to 15, a deposition rate of 3 microns / hour for 1 hour is obtained. Analysis of the deposit shows that it is an alloy composed of 80% palladium and 20% platinum by mass.
- the baths according to the invention have a practically unlimited lifetime with periodic recharging.
- Tables 1 and 2 indicate the ranges of compositions and conditions of use of the platinum and palladium baths respectively.
- the load of the bath is the ratio between the surface to be coated and the volume of the bath.
- the minimum and maximum columns indicate the limit values.
- the "optimal" column indicates the preferred value or range of values for each parameter.
- the stability of the baths according to the invention makes it possible to introduce therein particles to be included in the deposits, as described in the aforementioned Patent No. 2,590,595.
- These particles (ceramic such as alumina or yttrine, metal or alloy) are obtained by grinding in the presence of the mother solution and a deflocculant.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8913294A FR2652822B1 (fr) | 1989-10-11 | 1989-10-11 | Bain a l'hydrazine pour le depot chimique de platine et/ou de palladium, et procede de fabrication d'un tel bain. |
| FR8913294 | 1989-10-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0423005A1 true EP0423005A1 (de) | 1991-04-17 |
Family
ID=9386293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90402778A Withdrawn EP0423005A1 (de) | 1989-10-11 | 1990-10-05 | Hydrazinbad zur stromlosen Plattierung mit Platin und/oder Palladium, sowie Verfahren zur Herstellung eines solchen Bades |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5085693A (de) |
| EP (1) | EP0423005A1 (de) |
| JP (1) | JPH03134178A (de) |
| FR (1) | FR2652822B1 (de) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5882736A (en) * | 1993-05-13 | 1999-03-16 | Atotech Deutschland Gmbh | palladium layers deposition process |
| DE102005046351A1 (de) * | 2005-09-28 | 2007-04-05 | Knorr-Bremse Systeme für Nutzfahrzeuge GmbH | Bremsbelag, insbesondere für eine Scheibenbremse eines Nutzfahrzeugs |
| US9101915B2 (en) | 2012-12-18 | 2015-08-11 | Umicore Ag & Co. Kg | Catalyst particles comprising a layered core-shell-shell structure and method of their manufacture |
| US9440224B2 (en) | 2012-12-18 | 2016-09-13 | Umicore Ag & Co. Kg | Catalyst particles comprising hollow multilayered base metal-precious metal core/shell particles and method of their manufacture |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AUPN705195A0 (en) * | 1995-12-08 | 1996-01-11 | Cardiac Crc Nominees Pty Limited | Electroless deposition of metallic coatings on non-conducting substrates |
| FR2787472B1 (fr) | 1998-12-16 | 2001-03-09 | Onera (Off Nat Aerospatiale) | Procede pour produire une poudre d'alliage metallique de type mcraly et revetements obtenus avec cette poudre |
| KR20070118073A (ko) * | 2005-01-12 | 2007-12-13 | 유미코아 갈바노테히닉 게엠베하 | 팔라듐층들을 증착하는 방법 및 이를 위한 팔라듐 배스 |
| JP4662039B2 (ja) * | 2005-07-08 | 2011-03-30 | 上村工業株式会社 | ダイレクトプレーティング方法 |
| JP5327494B2 (ja) * | 2005-11-16 | 2013-10-30 | 日立化成株式会社 | 無電解めっき用触媒濃縮液の製造方法とそれを用いためっき触媒付与方法 |
| DE102006029947B4 (de) * | 2006-06-29 | 2013-01-17 | Basf Se | Verfahren zum Aufbringen einer metallischen Deckschicht auf einen Hochtemperatursupraleiter |
| EP2080822B1 (de) * | 2006-11-06 | 2017-03-29 | C. Uyemura & Co., Ltd. | Verfahren zur direkten metallabscheidung und lösung zur bildung einer palladiumleiterschicht |
| JP2008184679A (ja) * | 2007-01-31 | 2008-08-14 | Okuno Chem Ind Co Ltd | 無電解パラジウムめっき用活性化組成物 |
| JP6012132B2 (ja) * | 2011-12-20 | 2016-10-25 | メタローテクノロジーズジャパン株式会社 | 無電解白金めっき液、その製造方法、及び白金皮膜の形成方法 |
| DE102013207045A1 (de) * | 2012-10-05 | 2014-06-12 | Heraeus Precious Metals Gmbh & Co. Kg | Verfahren zur Herstellung von Edelmetalloxalat-Komplexen |
| JP6352879B2 (ja) * | 2015-10-15 | 2018-07-04 | 小島化学薬品株式会社 | 無電解白金めっき液 |
| CN114702527B (zh) * | 2022-03-08 | 2024-06-04 | 徐州浩通新材料科技股份有限公司 | 一种由钯粉制备硫酸乙二胺钯（ⅱ）的方法 |
| CN114773181B (zh) * | 2022-03-08 | 2024-06-11 | 徐州浩通新材料科技股份有限公司 | 一种水合双草酸根钯(ⅱ)酸的制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1771053A1 (de) * | 1968-03-28 | 1971-11-25 | Telefunken Patent | Verfahren zum stromlosen Abscheiden von Metallschichten der Platinmetallgruppe auf Oberflaechen metallischer und nichtmetallischer Teile |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2915406A (en) * | 1958-03-03 | 1959-12-01 | Int Nickel Co | Palladium plating by chemical reduction |
| US3704156A (en) * | 1970-07-13 | 1972-11-28 | Du Pont | Catalyst solution for electroless plating on nonconductors |
| US4006047A (en) * | 1974-07-22 | 1977-02-01 | Amp Incorporated | Catalysts for electroless deposition of metals on comparatively low-temperature polyolefin and polyester substrates |
-
1989
- 1989-10-11 FR FR8913294A patent/FR2652822B1/fr not_active Expired - Fee Related
-
1990
- 1990-10-05 EP EP90402778A patent/EP0423005A1/de not_active Withdrawn
- 1990-10-10 US US07/597,647 patent/US5085693A/en not_active Expired - Fee Related
- 1990-10-11 JP JP2270648A patent/JPH03134178A/ja active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1771053A1 (de) * | 1968-03-28 | 1971-11-25 | Telefunken Patent | Verfahren zum stromlosen Abscheiden von Metallschichten der Platinmetallgruppe auf Oberflaechen metallischer und nichtmetallischer Teile |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5882736A (en) * | 1993-05-13 | 1999-03-16 | Atotech Deutschland Gmbh | palladium layers deposition process |
| DE102005046351A1 (de) * | 2005-09-28 | 2007-04-05 | Knorr-Bremse Systeme für Nutzfahrzeuge GmbH | Bremsbelag, insbesondere für eine Scheibenbremse eines Nutzfahrzeugs |
| US9101915B2 (en) | 2012-12-18 | 2015-08-11 | Umicore Ag & Co. Kg | Catalyst particles comprising a layered core-shell-shell structure and method of their manufacture |
| US9440224B2 (en) | 2012-12-18 | 2016-09-13 | Umicore Ag & Co. Kg | Catalyst particles comprising hollow multilayered base metal-precious metal core/shell particles and method of their manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2652822B1 (fr) | 1993-06-11 |
| US5085693A (en) | 1992-02-04 |
| FR2652822A1 (fr) | 1991-04-12 |
| JPH03134178A (ja) | 1991-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0423005A1 (de) | Hydrazinbad zur stromlosen Plattierung mit Platin und/oder Palladium, sowie Verfahren zur Herstellung eines solchen Bades | |
| CN104028773B (zh) | 制备高纯铂粉末的方法、可根据所述方法得到的铂粉末及其用途 | |
| CH622829A5 (de) | ||
| JP2004018923A (ja) | 金属微粉末の製造方法 | |
| KR20180090267A (ko) | 마그네슘 합금용 복합 화성 처리 필름을 위한 필름 형성 처리제 및 필름 형성 방법. | |
| BE1004650A3 (fr) | Synthese directe de peroxyde d'hydrogene par catalyse heterogene, catalyseur pour ladite synthese et procede de preparation dudit catalyseur. | |
| KR20140020829A (ko) | 고 알칼리성 도금 욕을 이용하는 금속의 무전해 증착 방법 | |
| EP0304315B1 (de) | Bad für das Elektroplattieren einer Gold-Kupfer-Zink-Legierung | |
| EP1268347B1 (de) | Komplexes palladiumsalz und seine verwendung zur anpassung der palladiumkonzentration in elektrolytischen bädern bestimmt für die abscheidung von palladium oder einer seiner legierungen | |
| FR2807450A1 (fr) | Bain electrolytique destine au depot electrochimique du palladium ou de ses alliages | |
| KR20010007134A (ko) | 전기도금욕용 팔라듐 보충제의 개선된 합성 방법 | |
| EP0227518B1 (de) | Hydrazin enthaltendes Bad zum stromlosen Abscheiden von Nickel und/oder Kobalt und Verfahren zu dessen Herstellung | |
| EP2730682B1 (de) | Alkalische, cyanidfreie lösung zur elektroplattierung von goldlegierungen, verfahren zur elektroplattierung und substrat mit einer heller, korrosionsfreien ablagerung einer goldlegierung | |
| EP1048618B1 (de) | Verfahren zur Herstellung eines Goldsalzes für die Galvanotechnik | |
| FR2515212A1 (fr) | Procede pour affiner l'or | |
| JP4992434B2 (ja) | 金メッキ液および金メッキ方法 | |
| KR20200008113A (ko) | 무전해 백금 도금액 및 그것을 사용하여 얻어진 백금 피막 | |
| FR2619371A1 (fr) | Uranate plutonate d'ammonium, son procede de preparation et son utilisation pour l'elaboration d'oxyde mixte (u, pu)o2 | |
| JP4463972B2 (ja) | 無電解白金めっき液の製造方法及び無電解白金めっき液並びに無電解白金めっき方法 | |
| JP2008174796A (ja) | 金メッキ液および金メッキ方法 | |
| BE842679A (fr) | Procede de preparation de nitrate d'argent | |
| FR2652823A1 (fr) | Bain a l'hydrazine pour le depot chimique de palladium, et procede de fabrication d'un tel bain. | |
| CN1308493C (zh) | 硫代硫酸金铵络合物及其制备方法 | |
| JPH07166392A (ja) | 金めっき液及び金めっき方法 | |
| EP0149830B2 (de) | Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE GB IT SE |
|
| 17P | Request for examination filed |
Effective date: 19910628 |
|
| K1C3 | Correction of patent application (complete document) published |
Effective date: 19910417 |
|
| 17Q | First examination report despatched |
Effective date: 19930914 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 19940426 |