EP0329877A1 - Bain de dépôt électrolytique et procédé pour maintenir stable la composition de l'alliage déposé - Google Patents
Bain de dépôt électrolytique et procédé pour maintenir stable la composition de l'alliage déposé Download PDFInfo
- Publication number
- EP0329877A1 EP0329877A1 EP88301636A EP88301636A EP0329877A1 EP 0329877 A1 EP0329877 A1 EP 0329877A1 EP 88301636 A EP88301636 A EP 88301636A EP 88301636 A EP88301636 A EP 88301636A EP 0329877 A1 EP0329877 A1 EP 0329877A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- palladium
- bath
- nickel
- plating
- salt
- 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
Images
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
- C25D3/56—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
Definitions
- This invention relates to coatings of electroplated palladium-nickel alloys and in particular to a plating bath process for controlling the stability of the alloy composition in such coating over a wide variation of electroplating current densities.
- Gold has historically been the plating material of choice for electrical contacts because of its resistance to corrosion, good solderability properties and low electrical contact resistance at low loads. Since gold platings are expensive, lower cost substitutes have been sought.
- the coatings in the aforenoted 4,463,060 patent are prepared by electroplating in a bath of palladium (II) amine chloride, nickel ammine sulfate, a small amount of brighteners, and a conductive salt. Electroplating is carried out at a current density ranging from about 5 to 25 amps/sq.dm., or 50 to 250 amps/sq.ft. (asf). At current densities in the upper portion of this range, above about 100 asf, the Pd-Ni composition of the plated coating can be fairly readily controlled. As current densities decrease below this level, controlling the alloy composition becomes increasingly difficult.
- Pd-Ni alloy composition Controlling the Pd-Ni alloy composition during electroplating is extremely important.
- the stability of the alloy composition as a function of current density.
- current density in the commercial plating of formed terminals, there can be variations in current density as high as a factor of four depending upon location on the connector. The magnitude of the current density variation is dependent upon the part geometry, the plating cell design, and other factors.
- a typical range of current densities for most formed terminals is 25-100 asf. Locations on a few terminals might be plated as low as 10 asf or as high as 150 asf.
- the stability parameter for evaluation of Pd-Ni alloy plating process performance is defined as the difference between the Pd content in weight percent of an alloy deposited at 100 asf and that for an alloy deposited at 25 asf. This difference, which is illustrated for Curve A on Figure 1, will be referred to and indicated by the symbol ⁇ Wt% Pd (100-25) .
- Plating baths formulated with typical commercially available palladium ammine chloride salts and organic brightener systems have a ⁇ Wt% Pd (100-25) in the approximate range of 12 to 22 as shown in Examples 1, 2, and 3.
- Example 1 identical plating runs with respect to bath chemistry and plating conditions were conducted with palladous ammine dichloride salts from six different commercial sources.
- Iodide ions act as a brightener when added to a palladium-nickel alloy plating bath containing no organic additives.
- the iodide ion addition not only results in the plating of a mirror bright coating, but it also increases the maximum current density for the deposition of smooth, dense, nonporous coatings.
- Example 5 shows the effect of iodide ion additions ranging from 6 to 100 ppm on the constancy of alloy composition plated by a process based on a sodium vinyl sulfonate brightener.
- the stability parameter for runs in Example 5 plotted versus iodide ion concentration appears in Figure 2.
- Example 6 shows the effect of iodide ion additions ranging from 23 to 300 ppm on the constancy of alloy composition plated by a process based on technical grade N-benzyl niacin internal salt as brightener.
- This salt is CAS Registry No.
- Palladium salts used in Examples 7, 8 and 9 were purified by utilizing the fact that palladium diammine chloride, Pd(NH3)2Cl2, is insoluble in water and will form a precipitate when a solution of palladium tetrammine chloride is treated with an excess of hydrochloric acid, as per the following reaction: Pd(NH3)4Cl2 + HCl ⁇ 1/2 Pd(NH3)2Cl2 + 1/2 H2PdCl4 + 3NH3 Ammonia is liberated and chloropalladous acid is formed.
- Pd(NH3)2Cl2 palladium diammine chloride
- Palladium diammine chloride can be solubilized by treating with ammonia (dissolving in NH4OH), as follows: Pd(NH3)2Cl2 + 2NH3 ⁇ Pd(NH3)4Cl2
- Palladium tetrammine chloride salt is readily solubilized in water.
- one cycle of purification is defined as the series of steps which will repeat the chemical identity of the original entity treated (e.g., palladium diammine chloride back to palladium diammine chloride).
- a palladium balance made on this series of steps verified the above stiochiometry.
- Examples 8 and 9 also show the powerful effect of purification by precipitation as described above combined with the addition of iodide to the palladium-nickel plating bath.
- a one-cycle purification of a palladous tetrammine chloride salt, formulated into a plating bath with the addition of 31 ppm iodide ion resulted in a ⁇ Pd (100-25) of 4.2.
- ⁇ Pd (100-25) was 0.4, essentially a constant alloy composition over the current density range of 25 asf to 100 asf.
- the present invention has broad applicability with respect to all palladium-nickel alloy plating processes.
- the effectiveness of iodide additions in establishing constancy of plated alloy composition in the range of current densities from 25 to 100 amps/sq. ft. has been demonstrated for a variety of nickel salt types (see Example 10), different conductive salts (see Example 11), a broad range of agitation levels (see Example 12), and a broad range of Pd/Ni molar concentration ratios which result in the deposition of a broad range of alloy compositions (see Examples 13, 14 and 15).
- the iodide addition appears effective over the typical pH range of about 7-9 normally employed in commercial plating baths.
- the connector terminal acts as a solid cathode electrode to which the palladium-nickel alloy is to be electroplated.
- An adsorbed monolayer of the added iodide ion forms an effective "bridge" for the palladium ion in the bath, probably the Pd(NH3)4++ ion, to transfer charges to the electrode.
- the iodide ion does not offer an effective "bridge” to the nickel ion species. This "ligand-bridging" effect has been described in the literature.
- such a "bridge” eases the transfer of charge to or from the target ion (in this case, the palladium ion) by both adsorbing on the electrode and also inserting itself into the coordinating sphere of the target ion.
- Adsorption of the iodide ion will be facilitated if the cathode is at a potential more positive than its point of zero charge (PZC). At more positive potentials than the PZC, the electrode surface has a net positive charge; at a more negative potentials than the PZC, it has a net negative charge.
- PZC point of zero charge
- the optimum concentration of iodide in the bulk solution may differ under differing conditions of plating, mass transfer, etc.
- the palladium-nickel alloy coating thicknesses were 60 ⁇ in. which is sufficient to permit accurate composition analysis using an Energy-Dispersive X-ray Analysis (EDXA) technique with an accelerating voltage for exciting electrons of 20 kV.
- EDXA Energy-Dispersive X-ray Analysis
- the plating process composition and plating conditions were as follows: Bath Chemistry Pd concentration: 20 g/l from salts cited in Table I Ni concentration: 10 g/l as nickel ammine sulfate Sodium vinyl sulfonate: 2.8 g/l Ammonium sulfate: 50 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH.
- Plating Conditions Temperature: 48°C pH: 8.5 (adjusted by addition of NH4OH or HCl) Speed of disk rotation: 500 rpm Disks were plated with palladium-nickel alloy coatings at current densities ranging from 25 to 200 amp/sq.ft.
- Palladium-nickel alloy coatings were electrodeposited on disks at current densities ranging from 25 to 200 asf using the bath chemistry and plating conditions set forth below: Bath Chemistry Pd concentration: 17.0 g/l as palladous tetrammine dichloride Ni concentration: 11.0 g/l as nickel ammine chloride Sodium vinyl sulfonate: 2.8 g/l Ammonium sulfate: 50 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH. Plating Conditions Temperature: 48°C pH: 8.0 Speed of rotation: 500 rpm Results for coating composition analyses as a function of current density appear in Table III. The process had a ⁇ Wt% Pd (100-25) parameter of 21.4. Table III Current Density (asf) Pd-Ni Alloy Composition Wt% Pd Wt% Ni 25 47.3 52.7 50 54.9 45.1 75 62.5 37.5 100 68.7 31.3 200 77.0 23.0
- Palladium-nickel alloy coatings were electrodeposited on disks at current densities ranging from 25 to 200 asf using the bath chemistries and plating conditions set forth below: Bath Chemistry Pd concentration: 15.0 g/l as palladous tetrammine dichloride Ni concentration: 7.5 g/l as nickel chloride "Pyridinium salt": 0.6 g/l Ammonium chloride: 30 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH. Plating Conditions Temperature: 48°C pH: 8.5 Speed of rotation: 500 rpm Results for coating composition analyses as a function of current density appear in Table IV. The process had a ⁇ Wt% Pd (100-25) of 16.9. Table IV Current Density (asf) Pd-Ni Alloy Composition Wt% Pd Wt% Ni 25 64.5 35.5 50 72.1 27.9 75 77.4 22.6 100 81.4 18.6 200 84.2 15.8
- This example illustrates the beneficial effect of iodide ion addition to a palladium-nickel alloy plating bath significantly improving the constancy of alloy composition.
- Palladium-nickel alloy coatings were electrodeposited on disks at current densities ranging from 25 to 200 asf from plating baths containing 15 and 50 ppm of iodide ions, and from 10 to 200 asf from a plating bath containing 25 ppm iodide.
- the basic bath chemistry and plating conditions were as follows: Bath Chemistry Pd concentration: 20 g/l palladous tetrammine dichloride Ni concentration: 10 g/l as nickel ammine sulfate Ammonium sulfate: 50 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH. Plating Conditions Temperature: 48°C pH: 8.5 Speed of rotation: 500 rpm Coating composition analyses as a function of current density and iodide ion concentration level appear in Table V. The plating bath containing 15 ppm iodide had a ⁇ Wt% Pd (100-25) of 2.
- This example illustrates the beneficial effect of iodide ion addition to a palladium-nickel alloy plating bath containing sodium vinyl sulfonate in significantly improving the constancy of alloy composition.
- Palladium-nickel coatings were electrodeposited on disks at current densities ranging from 25 to 100 asf from plating baths containing 0, 6, 15, 25, 50 and 100 ppm of iodide ion.
- the basic bath chemistry and plating conditions were as follows: Bath Chemistry Pd concentration: 20 g/l palladous tetrammine dichloride Ni concentration: 10 g/l as nickel ammine sulfate Sodium vinyl sulfonate: 2.8 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH.
- This example illustrates the beneficial effect of iodide ion addition to a palladium-nickel alloy plating bath containing a quaternized pyridine in improving the constancy of alloy composition.
- Palladium-nickel coatings were electrodeposited on disks at current densities ranging from 25 to 100 asf from plating baths containing 0, 23, 100 and 300 ppm of iodide ion.
- the basic bath chemistry and plating conditions were as follows: Bath Chemistry Pd concentration: 15.0 g/l palladous tetrammine dichloride Ni concentration: 7.5 g/l as nickel chloride "Pyridinium salt": 0.6 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH.
- This example illustrates the beneficial effect of palladium salt purification in improving the constancy of composition of electrodeposited palladium-nickel alloys.
- Part of a shipment of a lot of commercially available palladous tetrammine dichloride salts was purified by one recrystallization cycle as described above.
- Palladium-nickel alloy coatings were electrodeposited on disks at current densities ranging from 25 to 100 asf from a bath formulated with the as-received palladium salt and a bath of identical basic chemistry formulated with the purified palladium salts under the same plating conditions.
- the basic bath chemistry and plating conditions were identical to those for Example 1.
- the iodide ion concentrations for the baths were ⁇ 1 ppm.
- the process formulated with the as-received palladium salt had a stability parameter of 18.7 whereas that formulated with the purified salt had a stability parameter of 14.5.
- This example illustrates the beneficial effect of iodide ion addition and palladium salt purification on the constancy of the composition of electrodeposited palladium-nickel alloys.
- a sample of palladous tetrammine chloride salt was purified through one recrystallization cycle as described earlier.
- Palladium-nickel alloys were plated on disks at current densities ranging from 25 to 100 asf using a bath chemistry and plating conditions set forth below: Bath Chemistry Pd concentration: 20 g/l Ni concentration: 10 g/l as nickel ammine sulfate Sodium vinyl sulfonate: 2.8 g/l Iodide ion: 31 ppm Ammonium sulfate: 50 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH. Plating Conditions Temperature: 48°C pH: 8.5 Speed of rotation: 500 rpm The ⁇ Wt% Pd (100-25) for the process was 4.2.
- This example illustrates the beneficial effect of iodide ion addition and palladium salt purification on the constancy of the composition of electrodeposited palladium-nickel alloys.
- a sample of palladous tetrammine chloride salt was purified through two recrystallization cycles as described earlier.
- Palladium-nickel alloys were plated on disks at current densities ranging from 25 to 100 asf using a bath chemistry and plating conditions set forth below: Bath Chemistry Pd concentration: 20 g/l Ni concentration: 10 g/l as nickel ammine sulfate Sodium vinyl sulfonate: 2.8 g/l Iodide ion: 35 ppm Ammonium sulfate: 50 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH. Plating Conditions Temperature: 48°C pH: 8.5 Speed of rotation: 500 rpm The ⁇ Wt% Pd (100-25) for the process was 0.4.
- Palladium-nickel alloy coatings were electrodeposited on disks at current densities ranging from 25 to 100 asf under identical operating conditions from baths that were formulated with three different types of nickel salts, an ammine sulfate, a sulfate, and a chloride.
- the palladium salt, other basic process chemistry parameters, and plating conditions were identical to those for Example 8.
- the constancy of palladium alloy composition for the three different types of nickel salt appear in Table VIII.
- Table VIII Nickel Salt Type ⁇ Wt% Pd (100-25) Ammine sulfate 4.2 Sulfate 2.8 Chloride 2.3
- Palladium-nickel alloy coatings were electrodeposited on disks at current densities ranging from 25 to 100 asf under identical operating conditions from baths that were formulated with two different types of conductive salts.
- the palladium salt, other basic process chemistry parameters, and plating conditions were identical to those for Example 8.
- the constancy of palladium alloy composition for the two different types of conductive salts appear in Table IX.
- Table IX Conductive Salt Type ⁇ Wt% Pd (100-25) Ammonium sulfate 4.2 Ammonium Chloride 0.8
- This example illustrates the effectiveness of iodide ion additions in achieving constancy of palladium-nickel alloy composition as a function of current density for a range of agitation levels.
- Palladium-nickel alloys were plated on disks rotated at speeds of 100 and of 500 rpm using a bath chemistry and plating conditions set forth below: Bath Chemistry Pd concentration: 20 g/l as palladous diammine dichloride Ni concentration: 10 g/l as nickel ammine sulfate Sodium vinyl sulfonate: 2.8 g/l Iodide ion conc.: 31 ppm Ammonium sulfate: 50 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH.
- This example illustrates the beneficial effects of iodide ion addition in improving the constancy of the composition of palladium-nickel alloys electrodeposited from a bath having palladium-to-nickel molar concentration ration of 0.86.
- Palladium-nickel alloys were plated on disks at current densities ranging from 25 to 100 asf using a bath chemistry and plating conditions set forth below: Bath Chemistry Pd concentration: 17.0 g/l as palladous diammine dichloride Ni concentration: 11.0 g/l as nickel ammine sulfate Sodium vinyl sulfonate: 2.8 g/l Ammonium sulfate: 50 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH.
- This example illustrates the beneficial effects of iodide ion addition in improving the constancy of the composition of palladium-nickel alloys electrodeposited from a bath having palladium-to-nickel molar concentration ratio of 0.55.
- Palladium-nickel alloys were plated on disks at current densities ranging from 25 to 100 asf using a bath chemistry and plating conditions set forth below: Bath Chemistry Pd concentration: 15.6 g/l as palladous diammine dichloride Ni concentration: 15.4 g/l as nickel ammine sulfate Sodium vinyl sulfonate: 2.8 g/l Ammonium sulfate: 50 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH.
- This example illustrates the beneficial effects of iodide ion addition in improving the constancy of the composition of palladium-nickel alloys electrodeposited from a bath having a low palladium-to-nickel molar concentration ratio of 0.24.
- Palladium-nickel alloys were plated on disks at current densities ranging from 25 to 100 asf using a bath chemistry and plating conditions set forth below: Bath Chemistry Pd concentration: 7.4 g/l as palladous diammine dichloride Ni concentration: 17.0 g/l as nickel ammine sulfate Sodium vinyl sulfonate: 2.8 g/l Iodide ion conc.: 11 ppm Ammonium sulfate: 50 g/l Ammonium hydroxide: Quantity sufficient to achieve desired pH.
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)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/880,872 US4743346A (en) | 1986-07-01 | 1986-07-01 | Electroplating bath and process for maintaining plated alloy composition stable |
AT88301636T ATE89337T1 (de) | 1988-02-25 | 1988-02-25 | Elektroplattierungsbad und verfahren zum stabilhalten der zusammensetzung der plattierten legierung. |
DE88301636T DE3881022T2 (de) | 1988-02-25 | 1988-02-25 | Elektroplattierungsbad und Verfahren zum Stabilhalten der Zusammensetzung der plattierten Legierung. |
EP88301636A EP0329877B1 (fr) | 1988-02-25 | 1988-02-25 | Bain de dépôt électrolytique et procédé pour maintenir stable la composition de l'alliage déposé |
HK97101977A HK1000382A1 (en) | 1988-02-25 | 1997-10-21 | Electroplating bath and process for maintaining plated alloy composition stable |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP88301636A EP0329877B1 (fr) | 1988-02-25 | 1988-02-25 | Bain de dépôt électrolytique et procédé pour maintenir stable la composition de l'alliage déposé |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0329877A1 true EP0329877A1 (fr) | 1989-08-30 |
EP0329877B1 EP0329877B1 (fr) | 1993-05-12 |
Family
ID=8199970
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88301636A Expired - Lifetime EP0329877B1 (fr) | 1986-07-01 | 1988-02-25 | Bain de dépôt électrolytique et procédé pour maintenir stable la composition de l'alliage déposé |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0329877B1 (fr) |
AT (1) | ATE89337T1 (fr) |
DE (1) | DE3881022T2 (fr) |
HK (1) | HK1000382A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0335683A2 (fr) * | 1988-04-01 | 1989-10-04 | E.I. Du Pont De Nemours And Company | Revêtements d'un alliage électroplaqué ayant une composition d'alliage stable |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3206383A (en) * | 1964-03-26 | 1965-09-14 | Kappel Mario | Electrolyte for use in the galvanic deposition of bright leveling nickel coatings |
US3467584A (en) * | 1966-10-24 | 1969-09-16 | Ernest H Lyons Jr | Plating platinum metals on chromium |
US4358352A (en) * | 1981-06-22 | 1982-11-09 | Mpd Technology Corporation | Electrodeposition of platinum from a cis-diamminedihaloplatinum (II) electrolyte |
US4463060A (en) * | 1983-11-15 | 1984-07-31 | E. I. Du Pont De Nemours And Company | Solderable palladium-nickel coatings and method of making said coatings |
-
1988
- 1988-02-25 DE DE88301636T patent/DE3881022T2/de not_active Expired - Fee Related
- 1988-02-25 EP EP88301636A patent/EP0329877B1/fr not_active Expired - Lifetime
- 1988-02-25 AT AT88301636T patent/ATE89337T1/de not_active IP Right Cessation
-
1997
- 1997-10-21 HK HK97101977A patent/HK1000382A1/xx not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3206383A (en) * | 1964-03-26 | 1965-09-14 | Kappel Mario | Electrolyte for use in the galvanic deposition of bright leveling nickel coatings |
US3467584A (en) * | 1966-10-24 | 1969-09-16 | Ernest H Lyons Jr | Plating platinum metals on chromium |
US4358352A (en) * | 1981-06-22 | 1982-11-09 | Mpd Technology Corporation | Electrodeposition of platinum from a cis-diamminedihaloplatinum (II) electrolyte |
US4463060A (en) * | 1983-11-15 | 1984-07-31 | E. I. Du Pont De Nemours And Company | Solderable palladium-nickel coatings and method of making said coatings |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0335683A2 (fr) * | 1988-04-01 | 1989-10-04 | E.I. Du Pont De Nemours And Company | Revêtements d'un alliage électroplaqué ayant une composition d'alliage stable |
EP0335683A3 (en) * | 1988-04-01 | 1990-01-17 | E.I. Du Pont De Nemours And Company | Electroplated alloy coatings having stable alloy composition |
Also Published As
Publication number | Publication date |
---|---|
ATE89337T1 (de) | 1993-05-15 |
DE3881022T2 (de) | 1993-10-07 |
EP0329877B1 (fr) | 1993-05-12 |
DE3881022D1 (de) | 1993-06-17 |
HK1000382A1 (en) | 1998-03-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4849303A (en) | Alloy coatings for electrical contacts | |
EP0512724B1 (fr) | Bain acide pour le dépôt d'une couche intermédiaire de palladium | |
EP0146152B1 (fr) | Revêtements de palladium-nickel soudables | |
EP0921212A1 (fr) | Composition pour l'électroplacage d' alliages de palladium et procédé utilisant cette composition | |
JPH02221392A (ja) | パラジウム合金めっき方法 | |
EP2458036B1 (fr) | Bain d'électrodéposition d'or | |
EP0405340A1 (fr) | Traitement de surface noircissant pour surfaces contenant du zinc | |
US4743346A (en) | Electroplating bath and process for maintaining plated alloy composition stable | |
EP0304315B1 (fr) | Bain de déposition électrolytique d'un alliage or-cuivre-zinc | |
Horkans et al. | Alloying of a less noble metal in electrodeposited Cu through underpotential deposition | |
EP0335683B1 (fr) | Revêtements d'un alliage électroplaqué ayant une composition d'alliage stable | |
JPS6250560B2 (fr) | ||
EP0329877B1 (fr) | Bain de dépôt électrolytique et procédé pour maintenir stable la composition de l'alliage déposé | |
EP0059452B1 (fr) | Procédé de dépôt électrolytique de palladium et d'alliages de palladium | |
US4564426A (en) | Process for the deposition of palladium-nickel alloy | |
US4846941A (en) | Electroplating bath and process for maintaining plated alloy composition stable | |
US4552628A (en) | Palladium electroplating and bath thereof | |
AU602558B2 (en) | Electroplating bath and process for maintaining plating alloy composition stable | |
KR950014641B1 (ko) | 팔라듐-니켈 합금의 도금을 위한 전기도금조 및 도금 방법 | |
EP1323849B1 (fr) | Bain d'électroplacage de nickel | |
JP3437980B2 (ja) | 無電解パラジウム−ニッケルめっき浴およびこれを用いるめっき方法ならびにこの方法により得られるめっき製品 | |
US4238300A (en) | Gold electroplating process | |
US4436595A (en) | Electroplating bath and method | |
Takei | A consideration of the electrodeposition of metals | |
JPH05222568A (ja) | メッキ液組成物 |
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 |
|
17P | Request for examination filed |
Effective date: 19881217 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
17Q | First examination report despatched |
Effective date: 19910601 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 19930512 Ref country code: NL Effective date: 19930512 Ref country code: AT Effective date: 19930512 Ref country code: CH Effective date: 19930512 Ref country code: LI Effective date: 19930512 Ref country code: SE Effective date: 19930512 Ref country code: BE Effective date: 19930512 |
|
REF | Corresponds to: |
Ref document number: 89337 Country of ref document: AT Date of ref document: 19930515 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3881022 Country of ref document: DE Date of ref document: 19930617 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19940228 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030106 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20030204 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20030228 Year of fee payment: 16 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040225 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040901 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040225 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041029 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |