WO2020129095A1 - Bain galvanique pour fabriquer un placage à base d'alliage de palladium et de nickel résistant à la corrosion et à l'oxydation, sa préparation et son utilisation - Google Patents

Bain galvanique pour fabriquer un placage à base d'alliage de palladium et de nickel résistant à la corrosion et à l'oxydation, sa préparation et son utilisation Download PDF

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Publication number
WO2020129095A1
WO2020129095A1 PCT/IT2018/000168 IT2018000168W WO2020129095A1 WO 2020129095 A1 WO2020129095 A1 WO 2020129095A1 IT 2018000168 W IT2018000168 W IT 2018000168W WO 2020129095 A1 WO2020129095 A1 WO 2020129095A1
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WO
WIPO (PCT)
Prior art keywords
palladium
solution
nickel
effective amount
galvanic bath
Prior art date
Application number
PCT/IT2018/000168
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English (en)
Inventor
Lorenzo BERTOCCHI
Original Assignee
Top Finish 2002 S.R.L.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Top Finish 2002 S.R.L. filed Critical Top Finish 2002 S.R.L.
Priority to PCT/IT2018/000168 priority Critical patent/WO2020129095A1/fr
Publication of WO2020129095A1 publication Critical patent/WO2020129095A1/fr

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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

  • the present invention relates to a solution/a galvanic bath for making a plating of an article, wherein said plating is palladium and nickel alloy-based corrosion- and oxidation-resistant (thereinafter, defined palladium-nickel inox alloy, for convenience) .
  • the present invention relates also to the relative method for preparing said solution/galvanic bath and the use thereof.
  • the palladium and nickel-based galvanic bath has been known for a long time and in use in the field of galvanic technology in many industrial fields such as, for example, car, electronic field and so on.
  • the aim of the present invention is to provide an adequate response to the technical problem described above .
  • the object of the present invention is an aqueous solution/galvanic bath comprising or consisting of effective amounts of one palladium complex salt, one nickel complex salt and suitable additives, as described in the attached independent claim and the dependent claims thereof .
  • An additional object of the present invention is the process for preparing the solution/galvanic bath as described above, as described in the attached independent claim.
  • An additional object of the present invention is the use of the solution as described above for the corrosion- and oxidation-resistant plating of an article, as described in the attached independent claim.
  • An additional object of the present invention is also the said corrosion- and oxidation-resistant palladium and nickel inox alloy-based plating, as described in the attached independent claim.
  • An additional object of the present invention is also an article plated with said corrosion- and oxidation- resistant palladium and nickel inox alloy, as described in the attached independent claim.
  • the solution/galvanic bath of the present invention for making the corrosion- and oxidation-resistant inox palladium and nickel alloy-based plating of an article comprises :
  • Said palladium complex salt is, for example, selected from the group consisting of: dichloro-tetraamine- palladium ( Pd (NH 3) 4 CI 2) , dibromo-tetraamine-palladium (Pd (NH 3) 4 Br2) , diiodo-tetraamine-palladium ( Pd (NH3) 4I2) , tetraamine-palladium dinitrate ( Pd (NH 3) 4 ( NO 3) 2) , tetraamine-palladium dinitrite (Pd (N3 ⁇ 4) 4 ( NO 2) 2) , tetraamine-palladium disulphite (Pd (NH 3) 4 ( SO3) 2) , tetraamine-palladium disulphate (Pd (NH 3) 4 ( SO 4) 2) , dichloro- diamine-palladium (Pd (NH 3) 2 CI 2) , dibromo-dianaine-palladium ( Pd (NH 3) 2 Br2) , diiodo
  • said palladium complex salt is selected from dichloro-tetraamine-palladium or tetraamine-palladium sulphate or a mixture thereof.
  • Said at least one palladium complex salt of the present invention is present in the solution in an amount from 0,1 to 20 g/1, in terms of palladium metal in the solution; preferably, in an amount comprised from 1 to 15 g/1; more preferably, in an amount comprised from 3 to 6 g/1; even more preferably, in an amount comprised from 4 to 5 g/1.
  • the solution/galvanic bath of the present invention as per the description above further comprises:
  • Said nickel complex salt is a nickel salt complexed with ammonia.
  • said salt is selected from the group consisting of: nickel sulphate, nickel chloride, nickel nitrate, nickel phosphate, nickel carbonate, or a mixture thereof, all of them complexed with ammonia.
  • nickel complex salt is selected from: nickel sulphate, nickel chloride or a mixture thereof, all of them complexed with ammonia.
  • Said at least one nickel complex salt of the present invention is present in the solution in an amount from 0,1 to 20 g/1, in terms of nickel metal in the solution; preferably, in an amount comprised from 0,1 to 10 g/1, preferably, in an amount comprised from 1 to 8 g/1; more preferably, in an amount comprised from 2 to 6 g/1; even more preferably, in an amount comprised from 3 to 5 g/1.
  • the solution/galvanic bath of the present invention as per the description above further comprises:
  • Said element belonging to the non-metal group is phosphorus (P), preferably in the form of one suitable corrosion- and oxidation-resistant hypophosphite salt.
  • Said element belonging to the non-metal group (P) that is the hypophosphite salt described above, is selected from the group consisting of: sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite, nickel hypophosphite, or a mixture thereof.
  • said derivative of an element belonging to the non-metal group (P) , hypophosphite, as described above, is selected from: sodium hypophosphite, potassium hypophosphite or a mixture thereof.
  • Said at least one derivative of an element belonging to the non-metal group (P) , of the present invention, as described above, is present in an amount comprised from 1 to 1000 g/1; preferably, in an amount comprised from 1 to 500 g/1; more preferably, in an amount comprised from 1 to 50 g/1; even more preferably, in an amount comprised from 20 to 40 g/1; for example, in an amount comprised from 25 to 30 g/1.
  • the solution/galvanic bath of the present invention as per the description above further comprises:
  • Said conductor salt as above is, for example, selected from the group consisting of: ammonium sulphamate, potassium sulphamate, sodium sulphamate, ammonium chloride, potassium chloride, sodium chloride, potassium sulphate, sodium sulphate, ammonium nitrate, potassium nitrate, sodium nitrate, sodium nitrite, potassium nitrite, sodium tartrate, potassium tartrate, ammonium tartrate.
  • said conductor salt as above is ammonium sulphamate .
  • Said conductor salt as above is present in the solution in an effective amount for adjusting the solution density to about 13 °Be (Baume degrees; corresponding to 1,100 g/cm 3 ); preferably, comprised from 12 °Be to 14 Be; more preferably, comprised from 12,5 °Be to 13,5 °Be; or 13 °Be.
  • Said conductor salt can optionally have also a buffer and regulator function against the pH of the solution; said value of the pH of the solution having to be substantially basic.
  • said pH value of the solution is comprised from 7 to 12; more preferably, from 8 to 9.
  • the regulation of the pH of the solution within the limits defined above is carried out by adding a sufficient quantity of ammonium hydroxide.
  • the solution/galvanic bath of the present invention as per the description above further comprises:
  • Said at least one primary brightening agent is, for example, selected from the group consisting of: organic compounds having hydroxy functional groups -OH, for example, alcohols, ethanol, butanediol, hexanediol, methanol, 2-propenol, allyl, saccharine, isobutyl alcohol, saccharose, glucose, fructose, maltose, xylitol, sorbitol, mannitol; organic compounds having the -CHO functional group, for example, formaldehyde, acetaldehyde, acrolein, butyraldehyde; organic compounds having the -CO functional group, for example, pinacolin and acetone; organic compounds having the N functional group, for example, amines, such as methylamine, triethanolamine, pyridine and bipyridine, isopropylamine, diethylamine, triethylamine, methylamine; inorganic sulphurated compounds, for example,
  • said brightening agent as above is selected from: allyl, saccharine, sodium sulphite, potassium sulphite or mixtures thereof.
  • Said at least one brightening agent is present in the solution in an amount from 1 to 100 g/1, preferably, in an amount comprised from 10 to 90 g/1; more preferably, in an amount comprised from 20 to 80 g/1; even more preferably, in an amount comprised from 30 to 70 g/1; for example, in an amount comprised from 40 to 60 g/1.
  • the solution/galvanic bath of the invention consists of an aqueous solution buffered at a substantially basic pH, comprising:
  • the pH of the aqueous solution is comprised from 7 to 12, more preferably from 8 to 9, preferably by addition of ammonium hydroxide, and the characteristics of ingredients from A) to E) are as described above.
  • the solution/galvanic bath of the invention consists of an aqueous solution buffered at a substantially basic pH, consisting of:
  • the pH of the aqueous solution is comprised from 7 to 12, more preferably from 8 to 9, preferably by addition of ammonium hydroxide, and the characteristics of ingredients from A) to E) are as described above.
  • the preparation of the solution/galvanic bath of the present invention is carried out (into a suitable mixer commonly used in the field, made from glass, steel or plastic; or also directly into the vessel intended for containing the galvanic bath of the invention and making the plating of the desired article) by simply mixing at room temperature and under stirring, in water at pH comprised from 7 to 12 (obtained by adding the needed amount of ammonium hydroxide) the ingredients as described in points A-E, added in the order as described above or also in any order, maintaining everything under stirring for the time needed for obtaining the desired final solution .
  • the solution for plating a number of test samples (in this case, one or more brass lattens 10 x 7,5 cm) with the palladium-nickel inox alloy is directly prepared into the vessel of the galvanic bath (made from glass, 2 liters) by mixing the elements as described above for making a buffered solution at a pH comprised from 7 to 12, with the use of ammonium hydroxide, containing from 50 to 300 g/1 of one conductor salt (ammonium sulphamate) , from 1 to 20 g/1 in terms of palladium metal (from dichloro- tetraamine-palladium) , from 0,1 and 10 g/1 in in terms of nickel metal (from nickel sulphate complexed with ammonia) , from 1 to 1000 g/1 of a derivative of an element (P) belonging to the non-metal group, making it corrosion- resistant (sodium hypophosphite, for example, 28 g/1) , and from 1 to 100 g/1 of a bright
  • the temperature of the subsequent process of deposition/plating of the palladium-nickel inox alloy of the present invention is comprised from 20°C to 35°C; the cathodic current density (in this case formed by a net of rare-earth mixed oxides) is varied from 0,5 A/dm 2 to 10 A/dm 2 .
  • the resistance of the deposit to the oxidizing agents may vary.
  • the preferable current density for having a deposit with great resistance without losing brightness and the lack of aesthetic defects proved to be approximately, preferably, 3 A/dm 2 , once identified, on a case by case basis, the optimum mix of the amount of the element of the bath.
  • the thickness of palladium and nickel in the alloy proved to be variable depending on the amount of the metals in the solution, on pH, on current density used and on deposition time.
  • a palladium-nickel inox alloy in accordance with the present invention has been obtained containing 0,6 palladium microns and 0,10 nickel microns.
  • the obtained alloy can be made up of 80% palladium and 20% nickel, to 50% palladium and 50% nickel.
  • Plated brass lattens obtained as described above, have been subsequently tested as follows in order to check the corrosion- and oxidation-resistance thereof.
  • a brass latten deposited with the palladium/nickel inox alloy is subjected to 10' with a current density of 3 A/dm 2 to a rubbing of concentrated HN03 (at 98%) along the deposited surface for a time of approximately 30''.
  • the deposit is not subjected to corrosion along the whole rubbing from high current densities to low current densities for the observation time.
  • a brass latten deposited with the palladium-nickel alloy is subjected to 10' with a current density of 3 A/dm 2 to the salt spray test (in accordance with NSS ISO 9227:2017) for 96 h at a pH of the saline solution between 6,5 and 7,2 and at a temperature of 35°C with RH of 50% and 1 Bar of pressure. No defects were visible after this time .
  • a brass latten deposited with the palladium-nickel alloy is subjected to 10' with a current density of 3 A/dm 2 to test the corrosion test with thioacetamide (in accordance with the TAA UNI EN ISO 4538: 1998). After the time set by standards, no evident aesthetic defect was found.
  • the solution of plating/galvanic bath of the present invention can be directly used onto any type of substrate, such as, for example, plastic, metal or other materials, such as a composite material which has to be coated by a corrosion- and oxidation-resistant plating (for example, usable in conventional industrial fields, but also, preferably, in the field of fashion accessories) , or as final layer for having a very good layer onto previous platings, corrosion- and oxidation-resistant, without losing a bright layer and lacking aesthetic/functional defects .
  • a corrosion- and oxidation-resistant plating for example, usable in conventional industrial fields, but also, preferably, in the field of fashion accessories
  • a further object of the present invention is an article plated with the palladium-nickel inox alloy of the present invention, obtained by using onto said article the solution/galvanic bath of the present invention described above.
  • another object of the present invention is an article plated with the palladium-nickel inox alloy of the present invention, obtained by depositing onto said article the solution/galvanic bath of the present invention described above.

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  • 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)

Abstract

La présente invention concerne une solution/un bain galvanique pour fabriquer un placage d'un article, ledit placage étant à base d'alliage de palladium et de nickel et résistant à la corrosion et à l'oxydation. Le bain est constitué d'une solution aqueuse tamponnée à un pH sensiblement basique, comprenant : A) une quantité efficace d'au moins un sel complexe de palladium soluble dans l'eau ; B) une quantité efficace d'au moins un sel complexe de nickel soluble dans l'eau ; C) une quantité efficace d'au moins un dérivé résistant à la corrosion et à l'oxydation d'un élément appartenant au groupe des non-métaux ; D) une quantité efficace d'un sel conducteur ; E) une quantité efficace d'au moins un agent de blanchiment primaire. La présente invention concerne en outre le procédé associé de préparation de ladite solution/dudit bain galvanique et d'utilisation de ceux-ci.
PCT/IT2018/000168 2018-12-20 2018-12-20 Bain galvanique pour fabriquer un placage à base d'alliage de palladium et de nickel résistant à la corrosion et à l'oxydation, sa préparation et son utilisation WO2020129095A1 (fr)

Priority Applications (1)

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PCT/IT2018/000168 WO2020129095A1 (fr) 2018-12-20 2018-12-20 Bain galvanique pour fabriquer un placage à base d'alliage de palladium et de nickel résistant à la corrosion et à l'oxydation, sa préparation et son utilisation

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PCT/IT2018/000168 WO2020129095A1 (fr) 2018-12-20 2018-12-20 Bain galvanique pour fabriquer un placage à base d'alliage de palladium et de nickel résistant à la corrosion et à l'oxydation, sa préparation et son utilisation

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112479906A (zh) * 2020-12-12 2021-03-12 弘健制药(上海)有限公司 一种葡甲胺生产工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416740A (en) * 1981-03-06 1983-11-22 Langbein-Pfanhauser Werke Ag Method and bath for the electrodeposition of palladium/nickel alloys
US4430172A (en) * 1981-09-11 1984-02-07 Langbein-Pfanhauser Werke Ag Method of increasing corrosion resistance in galvanically deposited palladium/nickel coatings
JP2010031312A (ja) * 2008-07-28 2010-02-12 Ne Chemcat Corp パターンめっき皮膜、及びその形成方法
CN104561943A (zh) * 2014-12-27 2015-04-29 广东致卓精密金属科技有限公司 用于线路板的化学镀镍钯合金工艺
CN104928659A (zh) * 2014-11-28 2015-09-23 广东致卓精密金属科技有限公司 一种化学镀镍钯合金镀液及工艺

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416740A (en) * 1981-03-06 1983-11-22 Langbein-Pfanhauser Werke Ag Method and bath for the electrodeposition of palladium/nickel alloys
US4430172A (en) * 1981-09-11 1984-02-07 Langbein-Pfanhauser Werke Ag Method of increasing corrosion resistance in galvanically deposited palladium/nickel coatings
JP2010031312A (ja) * 2008-07-28 2010-02-12 Ne Chemcat Corp パターンめっき皮膜、及びその形成方法
CN104928659A (zh) * 2014-11-28 2015-09-23 广东致卓精密金属科技有限公司 一种化学镀镍钯合金镀液及工艺
CN104561943A (zh) * 2014-12-27 2015-04-29 广东致卓精密金属科技有限公司 用于线路板的化学镀镍钯合金工艺

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112479906A (zh) * 2020-12-12 2021-03-12 弘健制药(上海)有限公司 一种葡甲胺生产工艺

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