WO2023104999A1 - Composition aqueuse de décapage pour le retrait, de manière électrolytique, d'un dépôt métallique à partir d'un substrat - Google Patents

Composition aqueuse de décapage pour le retrait, de manière électrolytique, d'un dépôt métallique à partir d'un substrat Download PDF

Info

Publication number
WO2023104999A1
WO2023104999A1 PCT/EP2022/085062 EP2022085062W WO2023104999A1 WO 2023104999 A1 WO2023104999 A1 WO 2023104999A1 EP 2022085062 W EP2022085062 W EP 2022085062W WO 2023104999 A1 WO2023104999 A1 WO 2023104999A1
Authority
WO
WIPO (PCT)
Prior art keywords
mmol
salts
composition
aqueous stripping
acid
Prior art date
Application number
PCT/EP2022/085062
Other languages
English (en)
Inventor
Florence Lagorce-Broc
Original Assignee
Atotech Deutschland GmbH & Co. KG
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 Atotech Deutschland GmbH & Co. KG filed Critical Atotech Deutschland GmbH & Co. KG
Publication of WO2023104999A1 publication Critical patent/WO2023104999A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00—Electrolytic stripping of metallic layers or coatings

Definitions

  • Aqueous stripping composition for electrolytically removing a metal deposit from a substrate
  • the present invention relates to an aqueous stripping composition for electrolytically removing a metal deposit from a substrate, the composition comprising
  • the present invention furthermore relates to a respective use thereof and a respective method utilizing said aqueous stripping composition.
  • Stripping of a metal deposit is generally important in the plating industry, particularly in the electroplating industry.
  • the substrate to be plated needs to be somehow fixed in, or at least restricted to, a certain place (i.e. a fixation), e.g. on a rack or in a barrel, respectively, before it is contacted with an electroplating composition.
  • a fixation e.g. on a rack or in a barrel, respectively
  • the metal layers are not only deposited on the substrate but also, at least partly, on the respective fixation. Since the fixation is re-used, the metal layers are accumulating over time, forming an undesired and comparatively thick metal deposit. This is particularly a problem for electrical contact areas in the fixation (also often named contact tips).
  • the fixation comprises or is made of stainless-steel as a base material.
  • stripping compositions are known in the art.
  • US 6,332,970 B1 refers to electrolytic stripping solutions comprising oxoacids and/or oxoacid salts, and hydrogen peroxide for the rapid removal of electroless nickel from iron, steel, aluminum, and titanium alloys as well as other selected electrically conductive substrates.
  • EP 3 168 332 B1 refers to the use of a jig electrolytic stripper for removing palladium, comprising for example nitric acid, a further nitrogen-containing compound, and a bromide.
  • the objective of the present invention to provide a more sustainable stripping composition without compromising the stripping quality and stripping selectivity. It is particularly an objective to reduce wastewater treatment steps/efforts and most preferably to even allow at least partially a recycling of at least some ingredients, primarily of stripped metals. Furthermore, the stripping composition should be able to reduce/prevent an undesired surface roughening particularly on stainless-steel, e.g. stainless-steel contact areas.
  • an aqueous stripping composition for electrolytically removing a metal deposit from a substrate, the composition comprising
  • the aqueous stripping composition contains nitrate anions as the only nitrogen-containing species (or compound).
  • nitrogen-containing compounds such as ammonia and/or other amines are typically problematic in view of wastewater treatment due to their stable metal-complex formation.
  • stripped metals must be removed beforehand to comply with common wastewater regulations.
  • ammonia and/or other amines typically various treatment steps are included to remove them, such as precipitation, decantation, filtration, chemical oxidation, neutralization, and/or chemical reduction.
  • most aqueous stripping compositions, particularly for removing copper and nickel do require all or almost all of these treatment steps.
  • the aqueous stripping composition of the present invention generally conforms to legal regulations already after a single neutralization and precipitation step, without the need of further chemical oxidation and/or reduction. This is accomplished due to being free of nitrogen-containing compounds other than nitrate anions.
  • the aqueous stripping composition of the present invention allows a selective removal of nickel (including very noble semi-bright to less noble bright nickel), copper, chromium, palladium and alloys comprising at least one thereof without a substantial removal of stainless-steel, which is a typical base material for substrates such as e.g. for fixations.
  • nickel including very noble semi-bright to less noble bright nickel
  • copper including very noble semi-bright to less noble bright nickel
  • chromium, palladium and alloys comprising at least one thereof without a substantial removal of stainless-steel, which is a typical base material for substrates such as e.g. for fixations.
  • stainless-steel which is a typical base material for substrates such as e.g. for fixations.
  • the metal deposit comprises at least one or more than one metal selected from the group consisting of copper, nickel, chromium, and palladium; alternatively the metal deposit preferably comprises one or more than one metal selected from the group consisting of copper, nickel, chromium, palladium, and tin.
  • This preferably includes alloys comprising at least one of the aforementioned metals.
  • copper and/or (preferably and) nickel are present in a higher amount than palladium, preferably individually as well as in combination.
  • copper and/or (preferably and) nickel are present in a higher amount than chromium, preferably individually as well as in combination.
  • palladium is present in the lowest amount compared to the individual amounts of copper, nickel, and chromium.
  • the aqueous stripping composition of the present invention shows a particular well balanced base material removal. This means that the removal of the base material is not entirely zero but rather very low. It was first assumed that even a very low removal is not desired. However, surprisingly it turned out that such a very low removal contributes to a desired surface smoothing. This means that undesired pits and scratches are leveled or even prevented, cavities are opened and smoothened, and a superior surface cleaning effect is obtained, which reduces contamination of a respective subsequent electroplating composition. Furthermore, an improved rinsing property was observed.
  • the aqueous stripping composition of the present invention allows an electrowinning application.
  • the stripped metals (which are anodically dissolved in the aqueous stripping composition) can be deposited on the cathode.
  • This most particularly applies to copper and palladium, most preferably to copper.
  • stripped nickel ions are also applicable to stripped nickel ions.
  • stripped metals do not need to be discarded fully but rather are preferably recycled, at least partly. Even a selective cathodic metal deposition is most preferably possible in order to separate stripped metals from each other prior to recycling.
  • a respective deposit is cathodically formed, which preferably mainly comprises copper, as copper is present in a higher amount than palladium in an utilized aqueous stripping composition.
  • the term “removing” and “removed” denotes a dissolving (i.e. a dissolution), preferably an electro-chemical dissolving and dissolution, respectively. It likewise means a stripping, preferably an electro-chemical stripping.
  • the removal primarily depends on the electrical current as a driving force accelerating and primarily pushing the dissolution.
  • it includes a transition from an insoluble state into a soluble state, most preferably by electro-chemical anodic oxidation.
  • metals of the metal form an anode connected to a rectifier while a counter electrode is used as a cathode to allow said electro-chemical dissolution.
  • the removed metals preferably form metal ions.
  • the aqueous stripping composition of the present invention comprises a solvent.
  • the solvent is electroconductive to support said anodic dissolution.
  • the aqueous stripping composition of the present invention is aqueous, i.e. it comprises water, preferably at least 55 vol.-% or more is water, based on the total volume of the aqueous stripping composition, more preferably 65 vol.-% or more, even more preferably 75 vol.-% or more, yet even more preferably 85 vol.-% or more, still more preferably 90 vol.-% or more, most preferably 95 vol.-% or more. Most preferably, water is the only solvent.
  • aqueous stripping composition of the present invention wherein the aqueous stripping composition is alkaline, acidic or neutral, preferably acidic or neutral, most preferably acidic.
  • aqueous stripping composition of the present invention wherein the aqueous stripping composition has a pH ranging from 4 to 9, preferably from 4.5 to 8.5, more preferably from 5 to 8, more preferably from 5.3 to 7.5, even more preferably from 5.5 to 7, most preferably from 5.7 to 6.5.
  • an aqueous stripping composition of the present invention wherein (i) has a concentration ranging from 10 mmol/L to 2600 mmol/L, based on the total volume of the aqueous stripping composition, preferably from 100 mmol/L to 2000 mmol/L, more preferably from 200 mmol/L to 1600 mmol/L, even more preferably from 300 mmol/L to 1400 mmol/L, yet even more preferably from 400 mmol/L to 1200 mmol/L, most preferably from 500 mmol/L to 900 mmol/L, yet most preferably from 550 mmol/L to 750 mmol/L.
  • the concentration is significantly below 10 mmol/L, in many cases the metal deposit is insufficiently removed, in particular the removal of nickel and its alloys is insufficient. If the concentration is significantly exceeding 2600 mmol/L, often it was observed that the removal is excessive, including that even stainless-steel is too strongly removed. Therefore, aforementioned well-balanced individual removal is deteriorated.
  • an aqueous stripping composition of the present invention wherein (i) has a total concentration of at least 100 mmol/L, based on the total volume of the aqueous stripping composition, preferably of at least 140 mmol/L, more preferably of at least 200 mmol/L. This applies most preferably in combination with the upper concentration limits mentioned in the ranges above for (i). In a few cases, if (i) has a total concentration below 100 mmol/L an undesired stainless-steel removal was observed.
  • a preferred source of said nitrate anions is an alkaline nitrate salt, preferably sodium nitrate.
  • nitrate anions primarily interact with hydronium cations generated from anodic water hydrolysis. This leads to a local generation of nitric acid, which, on the one hand, efficiently dissolves the metal deposit, particularly copper and nickel. On the other hand, nitric acid forms a protective passivation layer on stainless-steel. Upon dissolution of the metal deposit, dissolved metal cations form soluble nitrate salts.
  • an aqueous stripping composition of the present invention wherein (ii) has a total concentration ranging from 25 mmol/L to 3000 mmol/L, based on the total volume of the aqueous stripping composition, preferably from 70 mmol/L to 2000 mmol/L, more preferably from 120 mmol/L to 1500 mmol/L, even more preferably from 230 mmol/L to 1000 mmol/L, yet even more preferably from 300 mmol/L to 900 mmol/L, most preferably from 370 mmol/L to 800 mmol/L, even most preferably from 450 mmol/L to 700 mmol/L.
  • the concentration is significantly below 25 mmol/L, in a number of cases the conductivity of the aqueous stripping composition is too low such that the dissolution of the metal deposit is too slow. Under such conditions, the dissolution typically requires very high amounts of energy and a respective method is not economic anymore. If the concentration is significantly exceeding 2500 mmol/L, it was often observed that a blocking salt layer was formed on the anode, stopping or at least diminishing the current flow and therefore deteriorating the complete stripping process.
  • the one or more than one carboxylic acid and/or salts thereof preferably serves as conductivity agent and/or complexing agent.
  • an aqueous stripping composition of the present invention wherein (i) to (iii) has a molar ratio ranging from 1 to 20, based on the total concentration of (iii), preferably from 1 .1 to 15, more preferably from 1.3 to 11 , even more preferably from 1.5 to 9, yet even more preferably from 1.6 to 7, most preferably from 1.7 to 4.
  • a ratio ranging from 1.7 to 2.8 is very preferred.
  • Very preferred is a ratio of (i) to (iii) of below 10 (but more than zero), preferably below 9. In some cases, an undesired surface roughening was observed if this ratio is significantly exceeding 10.
  • an aqueous stripping composition of the present invention wherein (ii) to (iii) has a molar ratio ranging from 1 to 8, based on the individual total concentration of (ii) and (iii), preferably from 1.3 to 6, more preferably from 1.5 to 4, even more preferably from 1.7 to 3.5, most preferably from 1.8 to 2.3.
  • the aqueous stripping composition of the present invention comprises one or more than one carboxylic acid and/or salts thereof, preferably in a total concentration and/or molar ratio as defined above.
  • the one or more than one carboxylic acid and salts thereof do not comprise nitrogen.
  • said one or more than one carboxylic acid and/or salts thereof are the only organic compounds in the aqueous stripping composition.
  • aqueous stripping composition of the present invention wherein (ii) comprises (ii-a) one or more than one C1-C4 carboxylic acid and/or salts thereof, preferably one or more than one C1-C3 carboxylic acid and/or salts thereof, most preferably one or more than one C2-C3 carboxylic acid and/or salts thereof. This preferably applies to a monocarboxylic acid.
  • carboxylic acids according to (ii-a) primarily serve as conductivity agents in the context of the present invention and preferably serve in addition as buffer agent.
  • aqueous stripping composition of the present invention wherein (ii-a) has a total (i.e. the total of all individual (ii-a)) concentration ranging from 50 mmol/L to 2000 mmol/L, based on the total volume of the aqueous stripping composition, preferably from 100 mmol/L to 1500 mmol/L, more preferably from 150 mmol/L to 1000 mmol/L, even more preferably from 200 mmol/L to 900 mmol/L, yet even more preferably from 250 mmol/L to 800 mmol/L, most preferably from 300 mmol/L to 700 mmol/L, even most preferably from 400 mmol/L to 600 mmol/L.
  • aqueous stripping composition of the present invention wherein (ii) comprises (ii-b) one or more than one C5-C14 carboxylic acid and/or salts thereof, preferably one or more than one C6-C10 carboxylic acid and/or salts thereof, more preferably one or more than one C6-C9 carboxylic acid and/or salts thereof, most preferably one or more than one C6-C8 carboxylic acid and/or salts thereof, yet most preferably one or more than one C6-C7 carboxylic acid and/or salts thereof.
  • This preferably applies to a hydroxycarboxylic acid.
  • a monocarboxylic acid, a dicarboxylic acid, and/or a tricarboxylic acid most preferably to a monocarboxylic acid.
  • a tricarboxylic acid, preferably a hydroxy-tricarboxylic acid, most preferably citric acid, and/or salts thereof are preferred.
  • (ii-b) is present in addition to (ii-a), which is in most cases significantly improving the efficiency of the aqueous stripping composition.
  • carboxylic acids according to (ii-b) primarily serve as complexing agents in the context of the present invention.
  • aqueous stripping composition of the present invention wherein (ii-b) has a total (i.e. the total of all individual (ii-b)) concentration ranging from 1 mmol/L to 1000 mmol/L, based on the total volume of the aqueous stripping composition, preferably from 10 mmol/L to 500 mmol/L, more preferably from 20 mmol/L to 250 mmol/L, even more preferably from 30 mmol/L to 150 mmol/L, yet even more preferably from 35 mmol/L to 120 mmol/L, most preferably from 40 mmol/L to 90 mmol/L, even most preferably from 45 mmol/L to 75 mmol/L.
  • aqueous stripping composition of the present invention wherein (ii) comprises only monocarboxylic acids and/or salts thereof. In some rare cases it is preferred that (ii-b) comprises only tricarboxylic acids and/or salts thereof.
  • an aqueous stripping composition of the present invention wherein (ii) comprises formic acid, acetic acid, and/or salts thereof, preferably acetic acid and/or salts thereof.
  • (ii) comprises at least one hydroxy carboxylic acid and/or salts thereof.
  • aqueous stripping composition of the present invention wherein (ii) comprises citric acid, gluconic acid, heptagluconic acid, and/or salts thereof, most preferably gluconic acid and/or salts thereof.
  • aqueous stripping composition of the present invention wherein (ii) comprises
  • a first mono-carboxylic acid and/or salts thereof preferably a C1-C4 monocarboxylic acid and/or salts thereof, more preferably formic acid, acetic acid, and/or salts thereof, most preferably acetic acid and/or salts thereof, and additionally
  • a second mono-carboxylic acid and/or salts thereof preferably a C5-C14 mono-carboxylic acid and/or salts thereof, more preferably a C5-C14 hy- droxy-monocarboxylic acid and/or salts thereof, most preferably gluconic acid, heptagluconic acid, and/or salts thereof.
  • aqueous stripping composition of the present invention comprises (iii) one or more than one kind of halogen anions.
  • the one or more than one kind of halogen anions primarily support removal of oxides, particularly of nickel oxides. This supports the removal of the metal deposit.
  • aqueous stripping composition of the present invention wherein (iii) comprises fluoride, chloride, bromide and/or iodide, preferably chloride, bromide, and/or iodide, more preferably chloride and/or bromide, most preferably bromide.
  • (iii) comprises only chloride and/or bromide, most preferably only bromide.
  • bromide is the only kind of halogen anions in the aqueous stripping composition.
  • an aqueous stripping composition of the present invention wherein (iii) has a total concentration ranging from 1 mmol/L to 1250 mmol/L, based on the total volume of the aqueous stripping composition, preferably from 40 mmol/L to 1000 mmol/L, more preferably from 80 mmol/L to 880 mmol/L, even more preferably from 120 mmol/L to 760 mmol/L, yet even more preferably from 160 mmol/L to 640 mmol/L, most preferably from 200 mmol/L to 520 mmol/L, yet most preferably from 280 mmol/L to 400 mmol/L. This most preferably applies to bromide.
  • an aqueous stripping composition of the present invention wherein (iii) has a total concentration of at least 100 mmol/L, based on the total volume of the aqueous stripping composition, preferably of at least 180 mmol/L. This applies most preferably to the upper concentration limits mentioned in the ranges above for (iii).
  • the concentration is significantly below 1 mmol/L, in many cases the removal of the metal deposit is retarded, particularly for nickel. If the concentration is significantly exceeding 1250 mmol/L, it was surprisingly observed that the well-balanced base material removal (i.e. the surface smoothening) of stainless-steel is too low, particularly if bromide is involved.
  • the aqueous stripping composition (i) is the only nitrogen-con- taining species.
  • the aqueous stripping composition of the present invention is preferably substantially free of, preferably does not comprise, ammonium ions.
  • aqueous stripping composition of the present invention wherein the aqueous stripping composition is substantially free of, preferably does not comprise, sulfuric acid, preferably is substantially free of, preferably does not comprise, sulfate anions.
  • aqueous stripping composition of the present invention wherein the aqueous stripping composition is substantially free of, preferably does not comprise, phosphoric acid, preferably is substantially free of, preferably does not comprise, phosphate anions.
  • the present invention furthermore relates to a use of an aqueous stripping composition as defined above, preferably as defined above as being preferred, for electrolytically removing partly or fully a metal deposit comprising palladium, copper, nickel, chromium, and/or alloys comprising at least one thereof from a substrate, wherein the substrate is different from the metal deposit.
  • the metal deposit comprises palladium, copper, nickel, chromium, tin, and/or alloys comprising at least one thereof.
  • aqueous stripping composition of the present invention including features defined as being particularly preferred, preferably applies likewise to the use according to the present invention.
  • the present invention furthermore relates to a method for removing partly or fully a metal deposit from a substrate, the method comprising the steps
  • aqueous stripping composition of the present invention including features defined as being particularly preferred, preferably applies likewise to the method of the present invention.
  • the metal deposit comprises palladium, copper, nickel, chromium, tin, and/or alloys comprising at least one thereof.
  • the substrate comprises iron, preferably is a stainless-steel substrate.
  • the substrate is a fixation, preferably a rack, most preferably a fixation and rack, respectively, for holding substrates to be plated in a wet-chemical plating process.
  • the aqueous stripping composition of the present invention as well as the method of the present invention may not be limited to such specific substrates.
  • the aqueous stripping composition of the present invention shows a particular well balanced base material removal. As a result thereof, a desired surface smoothing is obtained as well as maintained.
  • Preferred is a method of the present invention, wherein the substrate has a surface roughness R a ranging from 0.5 pm to 1.5 pm, preferably ranging from 0.7 pm to 1.3 pm, most preferably from 0.9 pm to 1.1 pm. More preferred is a method of the present invention, wherein said roughness R a is maintained after step (d) is repeatedly carried out.
  • the present invention allows an electrowinning application. This is a huge advantage over conventional stripping compositions and allows a very sustainable application because removed (i.e. stripped) metals can be recycled.
  • At least one of palladium, copper, nickel, and chromium alternatively at least one of palladium, copper, nickel, chromium, and tin
  • the metal deposit comprises at least copper and during step (d) copper is simultaneously deposited onto the at least one cathode.
  • the term “simultaneously” denotes while step (d) is carried out and takes place.
  • step (d) More preferred is a method of the present invention, wherein during step (d) more than one of palladium, copper, nickel, and chromium (alternatively more than one of palladium, copper, nickel, chromium, and tin) from the metal deposit are selectively and individually deposited onto more than one cathode.
  • This is a very preferred selective electrowinning application. Own experiments indicate that on the basis of selective and individual cathodic current densities palladium, copper, nickel, and chromium (being removed in step (d) from the metal deposit) are individually deposited onto the respective cathode. While removed nickel preferably requires a comparatively high current density (i.e.
  • palladium preferably requires a comparatively low cathodic current density (i.e. a cathode with a comparatively large surface area).
  • removed copper requires a cathodic current density between the cathodic current density defined for palladium and nickel.
  • step (d) more than one of palladium, copper, nickel, and chromium (alternatively more than one of palladium, copper, nickel, chromium, and tin) from the metal deposit are jointly deposited onto one cathode.
  • the at least one cathode comprises iron, lead, carbon, titanium, platinum, copper, nickel, mixtures, and/or oxides thereof. This preferably refers to the at least one cathode without a deposited metal thereon, i.e. in its blank condition.
  • the at least one cathode comprises a steel cathode, a lead cathode, a graphite cathode, a titanium cathode, a platinum cathode, a copper cathode, a nickel cathode, and/or a mixed metal oxide (MMO) cathode.
  • the at least one cathode comprises a steel cathode, a lead cathode, a graphite cathode, a titanium cathode, a platinum cathode, a copper cathode, a nickel cathode, and/or a mixed metal oxide (MMO) cathode.
  • MMO mixed metal oxide
  • a preferred steel cathode comprises a stainless-steel cathode.
  • a preferred titanium cathode comprises a platinized titanium cathode.
  • the at least one cathode comprises copper, preferably is copper.
  • the at least one copper cathode is furthermore deposited with comparatively pure metallic copper such that a homogeneous cathode body with additional copper is obtained.
  • Such a cathode body is of high value and can be easily recycled.
  • the at least one cathode comprises iron, preferably comprises (most preferably is) stainless-steel.
  • step (d) the aqueous stripping composition has a temperature ranging from 20°C to 80°C, preferably ranging from 21 °C to 65°C, more preferably ranging from 22°C to 55°C, even more preferably ranging from 23°C to 45°C, most preferably ranging from 24°C to 36°C.
  • step (d) the metal deposit is partly or fully removed with a rate ranging from 0.1 pm/min to 30 pm/min, preferably ranging from 1 pm/min to 26 pm/min, more preferably ranging from 3 pm/min to 22 pm/min, even more preferably ranging from 5 pm/min to 18 pm/min, yet even more preferably ranging from 7 pm/min to 15 pm/min, most preferably ranging from 11 pm/min to 13 pm/min.
  • a rate ranging from 0.1 pm/min to 30 pm/min, preferably ranging from 1 pm/min to 26 pm/min, more preferably ranging from 3 pm/min to 22 pm/min, even more preferably ranging from 5 pm/min to 18 pm/min, yet even more preferably ranging from 7 pm/min to 15 pm/min, most preferably ranging from 11 pm/min to 13 pm/min.
  • this most preferably applies to copper and nickel in the metal deposit.
  • step (d) the electrical current has a current density ranging from 10 A/dm 2 to 100 A/dm 2 , preferably ranging from 20 A/dm 2 to 90 A/dm 2 , more preferably ranging from 30 A/dm 2 to 80 A/dm 2 , even more preferably ranging from 40 A/dm 2 to 70 A/dm 2 , most preferably ranging from 45 A/dm 2 to 60 A/dm 2 , even most preferably ranging from 47 A/dm 2 to 53 A/dm 2 .
  • step (d) is a method of the present invention, wherein in step (d) the contacting is carried out by immersing the substrate into the aqueous stripping composition.
  • step (d) the contacting is preferably carried out for a time period ranging from 10 seconds to 120 minutes, preferably ranging from 30 seconds to 100 minutes, more preferably ranging from 1 minute to 80 minutes, even more preferably ranging from 1.5 minutes to 60 minutes, most preferably ranging from 2 minutes to 45 minutes.
  • the time period depends on the total thickness of the metal deposit, its composition, and the applied conditions. In some cases, a very preferred time period is ranging from 30 seconds to 30 minutes, preferably from 60 seconds to 20 minutes.
  • Aqueous stripping compositions The following examples “E1” to “E6” (according to the invention) were prepared by dissolving the respective compounds in water. Further details are summarized in Table 1; concentrations are given in mmol/L if not stated otherwise. When required, a pH correction has been carried out using sodium hydroxide.
  • E2 Due to a lower total amount of (i) and (iii), E2 exhibits an increased electrical resistance compared to the other compositions. Although this is slightly less preferred, E2 provides still very acceptable results (see below).
  • Stripping compositions according to examples E1 to E6 were tested at a temperature ranging from 25°C to 35°C for electrolytically stripping metal deposits.
  • the anodic current density was about 50 A/dm 2 .
  • the tested metal deposits were subjected to the respective aqueous stripping compositions for about 2 minutes, except for stainless-steel, which was so mildly attacked that exposure of about 10 minutes were applied.
  • the tested metal deposits typically in form of a respective panel or wire thereof, and the respective stripping rates are summarized in Table 2.
  • the striping rates were determined based on weight loss.
  • the surface roughness of a stainless-steel substrate was determined before subjecting it to the respective aqueous stripping compositions and was characterized with S a of about 1 pm. After above mentioned 10 minutes the measurement was repeated with the result that for all examples the S a was again about 1 , in case of E3 even 0.8 pm and of E6 0.9 pm.
  • S a denotes, as an absolute value, the difference in height of each point compared to the arithmetical mean of the surface and is commonly used to evaluate surface roughness. This is a key pre-requisite for the surface smoothing effect obtained by the present invention. As a result, an initial surface roughness of a respective stain- less-steel substrate can be maintained.
  • Nickel-phosphorous ranging from 2 pm/min to 15 pm/min depending on phosphorous content in the alloy (high phosphorous leads to a decreased stripping rate)
  • Tin (galvanic layer, acidic) 4 pm/min up to 25 pm/min

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

La présente invention concerne une composition aqueuse de décapage pour le retrait, de manière électrolytique, d'un dépôt métallique à partir d'un substrat, la composition comprenant (i) des anions nitrate, (ii) un ou plus d'un acide carboxylique et/ou des sels de celui-ci, et (iii) un ou plus d'un type d'anions halogènes. Selon l'invention, dans la composition aqueuse de décapage, (i) est la seule espèce contenant de l'azote. La présente invention concerne en outre une utilisation respective de celle-ci et un procédé respectif utilisant ladite composition aqueuse de décapage.
PCT/EP2022/085062 2021-12-08 2022-12-08 Composition aqueuse de décapage pour le retrait, de manière électrolytique, d'un dépôt métallique à partir d'un substrat WO2023104999A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21213202 2021-12-08
EP21213202.1 2021-12-08

Publications (1)

Publication Number Publication Date
WO2023104999A1 true WO2023104999A1 (fr) 2023-06-15

Family

ID=78824752

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2022/085062 WO2023104999A1 (fr) 2021-12-08 2022-12-08 Composition aqueuse de décapage pour le retrait, de manière électrolytique, d'un dépôt métallique à partir d'un substrat

Country Status (2)

Country Link
TW (1) TW202336294A (fr)
WO (1) WO2023104999A1 (fr)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619390A (en) * 1969-02-21 1971-11-09 Horst Dillenberg Aqueous electrolytic stripping bath to remove metal coatings from bases of steel
US3819494A (en) * 1973-03-29 1974-06-25 Fountain Plating Co Inc Method of removing braze
US4233124A (en) * 1979-10-29 1980-11-11 Oxy Metal Industries Corporation Electrolytic stripping bath and process
US4400248A (en) * 1982-03-08 1983-08-23 Occidental Chemical Corporation Electrolytic stripping process
US6332970B1 (en) 1999-10-22 2001-12-25 Barry W. Coffey Electrolytic method of and compositions for stripping electroless nickel
CN101935864A (zh) * 2010-09-21 2011-01-05 上海理工大学 一种镁及镁合金镍镀层的阳极退除液及其镀层的退除方法
US20120205250A1 (en) * 2011-02-14 2012-08-16 Samsung Electro-Mechanics Co., Ltd. Electrolytic copper plating solution composition
CN105336993A (zh) * 2014-06-30 2016-02-17 苏州宝时得电动工具有限公司 电解液和电池
EP3168332B1 (fr) 2015-03-13 2019-03-13 Okuno Chemical Industries Co., Ltd. Agent de décapage électrolytique pour enlever du palladium d'un gabarit
CN106400069B (zh) * 2016-09-12 2019-06-07 国家电网公司 一种铜或铜合金电网接地装置在酸性土壤中的防腐蚀方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619390A (en) * 1969-02-21 1971-11-09 Horst Dillenberg Aqueous electrolytic stripping bath to remove metal coatings from bases of steel
US3819494A (en) * 1973-03-29 1974-06-25 Fountain Plating Co Inc Method of removing braze
US4233124A (en) * 1979-10-29 1980-11-11 Oxy Metal Industries Corporation Electrolytic stripping bath and process
US4400248A (en) * 1982-03-08 1983-08-23 Occidental Chemical Corporation Electrolytic stripping process
US6332970B1 (en) 1999-10-22 2001-12-25 Barry W. Coffey Electrolytic method of and compositions for stripping electroless nickel
CN101935864A (zh) * 2010-09-21 2011-01-05 上海理工大学 一种镁及镁合金镍镀层的阳极退除液及其镀层的退除方法
US20120205250A1 (en) * 2011-02-14 2012-08-16 Samsung Electro-Mechanics Co., Ltd. Electrolytic copper plating solution composition
CN105336993A (zh) * 2014-06-30 2016-02-17 苏州宝时得电动工具有限公司 电解液和电池
EP3168332B1 (fr) 2015-03-13 2019-03-13 Okuno Chemical Industries Co., Ltd. Agent de décapage électrolytique pour enlever du palladium d'un gabarit
CN106400069B (zh) * 2016-09-12 2019-06-07 国家电网公司 一种铜或铜合金电网接地装置在酸性土壤中的防腐蚀方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PARTENHEIMER WALTER ET AL: "The aerobic oxidation of bromide to dibromine catalyzed by homogeneous oxidation catalysts and initiated by nitrate in acetic acid", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL., vol. 387, 1 June 2014 (2014-06-01), NL, pages 130 - 137, XP055929978, ISSN: 1381-1169, DOI: 10.1016/j.molcata.2014.02.026 *

Also Published As

Publication number Publication date
TW202336294A (zh) 2023-09-16

Similar Documents

Publication Publication Date Title
EP0075784B1 (fr) Procédé de dépôt électrolytique direct d'or sur de l'acier inoxydable
WO2018146292A1 (fr) Procédé de passivation électrolytique d'une couche la plus extérieure de chrome ou d'alliage de chrome afin d'accroître sa résistance à la corrosion
US20110253556A1 (en) Solution system for electrolytically removing titanium carbide coating and method for same
US4404074A (en) Electrolytic stripping bath and process
US3989606A (en) Metal plating on aluminum
JP5937086B2 (ja) 高アルカリ性めっき浴を用いた無電解金属析出法
JP5247142B2 (ja) 銀めっき方法
EP3431633B1 (fr) Compositions et procédés d'électrodéposition de nickel écologiques
US3627654A (en) Electrolytic process for cleaning high-carbon steels
US3684666A (en) Copper electroplating in a citric acid bath
CN113463148A (zh) 一种在钛或钛合金基材表面电镀金的方法
WO2016147709A1 (fr) Agent de décapage électrolytique pour un gabarit
US20160108254A1 (en) Zinc immersion coating solutions, double-zincate method, method of forming a metal plating film, and semiconductor device
US3065154A (en) Method of plating chromium and the like to titanium, its alloys, and the like
WO2023104999A1 (fr) Composition aqueuse de décapage pour le retrait, de manière électrolytique, d'un dépôt métallique à partir d'un substrat
GB2117406A (en) Electrolytic stripping
JP3426800B2 (ja) アルミニウム合金材料のめっき前処理方法
US2436244A (en) Metalworking and strippingplating process
CN114016100A (zh) Mems探针表面超硬耐磨电镀涂层的制备方法
CN111485262A (zh) 铟电镀组合物和在镍上电镀铟的方法
US2871172A (en) Electro-plating of metals
JP6517501B2 (ja) ストライク銅めっき液およびストライク銅めっき方法
US1729607A (en) Process for electrodeposition of metal
JPH06346300A (ja) チタン材のめっきのための前処理方法およびチタン材の めっき方法
JP5218742B2 (ja) ３価クロムめっき浴の金属不純物除去方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22834587

Country of ref document: EP

Kind code of ref document: A1