WO2023217411A2 - Utilisation d'acides sulfoniques dans des électrolytes secs pour éliminer des revêtements déposés par évaporation sous vide et/ou par pulvérisation thermique sur des surfaces métalliques - Google Patents

Utilisation d'acides sulfoniques dans des électrolytes secs pour éliminer des revêtements déposés par évaporation sous vide et/ou par pulvérisation thermique sur des surfaces métalliques Download PDF

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Publication number
WO2023217411A2
WO2023217411A2 PCT/EP2023/025205 EP2023025205W WO2023217411A2 WO 2023217411 A2 WO2023217411 A2 WO 2023217411A2 EP 2023025205 W EP2023025205 W EP 2023025205W WO 2023217411 A2 WO2023217411 A2 WO 2023217411A2
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WO
WIPO (PCT)
Prior art keywords
dry
electrolytes
conductive liquid
dry electrolytes
sulfonic acids
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Application number
PCT/EP2023/025205
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English (en)
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WO2023217411A3 (fr
Inventor
Olivier Mikael Daniel Marcel MESSE
Simon Andreas KRESSER
Original Assignee
Oerlikon Surface Solutions Ag, Pfäffikon
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Publication date
Application filed by Oerlikon Surface Solutions Ag, Pfäffikon filed Critical Oerlikon Surface Solutions Ag, Pfäffikon
Publication of WO2023217411A2 publication Critical patent/WO2023217411A2/fr
Publication of WO2023217411A3 publication Critical patent/WO2023217411A3/fr

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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

  • the present invention relates to a process for removing a coating from workpieces such as for example coated tools and in particular coated cutting tools. Processes for removing coatings are used for stripping coatings from worn or improperly coated workpieces and thus preparing them for recoating.
  • coat-stripping facilities are used for example that include a tank for containing a liquid electrolyte, wherein inside the tank a counter-electrode can be connected to one pole of a power supply device is provided.
  • the workpieces have to be individually contacted in such a way that they are connected as anodes and the counter-electrode as cathode to a power supply.
  • the tank is filled with the electrolyte and the workpiece is immersed in the electrolyte.
  • a predetermined constant voltage is applied that causes the workpiece's coating to be removed.
  • the counter-electrode surface must be formed and positioned in such a way that the current flow is distributed as evenly as possible over the workpiece's surface areas whose coating is to be removed, in order to achieve a uniform removal of the coating and to avoid corrosion of the base body bearing the coating.
  • a further factor that influences the coating removal process is the conductivity of the layer or layers to be removed.
  • One problem that can occur when removing in particular non-conducting layers is the damage to the surface of the base body such that the latter, after the coating removal according to the state of the art, is scarred with statistically distributed indentations.
  • EP3795722 exclusively relates to polishing. Accordingly the objective of EP3795722 is to develop an improved method to smooth and polish metals through ion transport by means of free solid bodies.
  • a dry electrolyte comprises a set of porous particles with the capacity to retain a given amount of liquid and a given amount of electrically conductive liquid
  • EP3795722 specifically refers to dry electrolytes that comprise porous particles with the capacity to retain a given amount of liquid, and a given amount of electrically conductive liquid that contains at least one sulfonic acid.
  • the electrically conductive liquid comprises at least one sulfonic acid.
  • the sulfonic acids are composed with a general formula RSOsH, where R can be any organic substituent, either alkyl aromatic, another functional group or a halogen atom. This is the general structure of a sulfonic acid.
  • the sulfonic acids used are those having a high solubility in water or another chosen dissolvent.
  • those sulfonic acids that form soluble salts with the related metals can be used, but without limiting purposes, the sulfonic acids such as the methanesulfonic acid CH3SO3H, the trifluorosulfonic acid CF3SO3H, the fluorosulfonic acid FSO3H, the chlorosulfonic acid CISO3H, the para-toluenesulfcnic acid -CHsCe ⁇ SOsH and the sulfamic acid NH2SO3H, all of them thereafter represented
  • the sulfonic acids can be used pure in the event that they are liquid at the working temperature or in solution.
  • the optimal concentration of sulfonic acid shall be empirically determined as it depends on the sulfonic acid chosen, the dissolvent and also the parameters of the part to be treated, such as the type of metal, the full surface and the shape.
  • the preferred options of solvent are water or a polar solvent due to conductivity and solubility reasons.
  • the water is the chosen dissolvent.
  • Concentrations of sulfonic acid in the conductive liquid from 1 to 70 % demonstrated to be active in this process.
  • concentrations from 2 to 40 %. These concentrations refer to the final concentration of the electrically conductive liquid in the dry electrolyte, regardless of how the dry electrolytes are prepared.
  • the sulfonic acids are strong acids, and their handling in liquids or in solutions, as for their use in the classic electropolishing, carried many handling risks. In liquid state or in solution, these sulfonic acids can produce an unwanted attack on the metal surfaces. Therefore, after using sulfonic acids in the classic electropolishing, often a further neutralizing step is required.
  • the sulfonic acids with an organic waste such as, for example, without limiting purposes, methanesulfonic acid, trifluorosulfonic acid and para-toluenesulfonic acid, are much less polar than the inorganic acids. Therefore, the reduced localized polarity of these sulfonic acids facilitates their movement through the apolar resin. Namely, the smaller sulfonic acid that contains an organic waste, the methanesulfonic acid, will benefit of this effect while not sustaining steric hindrances.
  • the complexing agents having more than one functional group are known as chelating agents.
  • the effects of capturing and transferring metal ions would be even higher by the use of chelating agents, such as the citric acid, EDTA or phosphonates.
  • the said agents would have a high affinity due to the metal ions formed on the surface and would help to carry the said ions to the particles.
  • the complexing chelating agent is a polyether.
  • Polyether is defined as a compound including more than one ether group (C-O-C) in its structure, without prejudice that it can include in turn other functional groups such as esters, acids, amino, amide, etc.
  • the polyether is a linear alkyl polyether.
  • the polyethers are specifically included to crown ethers and to alkylpolyethers.
  • the alkylpolyethers can have different shapes, such as linear, star-shaped, branched or comb-shaped.
  • the linear alkylpolyethers provide best results in the process, as they are more active at the moment of forming metal complexes.
  • polyethyleneglycol or PE is standing out, also called poly(oxy-1 ,2-ethinhediyl), poly (ethylene oxide), polyoxyethylene, polyethylene oxide and brands such as Carbowax or Macrogol;
  • polypropyleneglycol or PPG is also standing out the polypropyleneglycol or PPG.
  • R can be any radical or functional group, preferably H or CH3.
  • R can be any radical or functional group, preferably H or CH3.
  • the molecular weights of 200 to 500 Da are the preferred.
  • PEG 300 is the most preferred.
  • the given amount of electrically conductive liquid to impregnate the porous particles has to be sufficiently high to allow a measurable electric conductivity through the dry electrolyte. In addition, this amount has to be below the saturation point of the porous particle, in order there is no observable free liquid, being thus a "dry" electrolyte.
  • the amount of conductive liquid is close to but below the saturation point of the porous particle. This amount must be empirically determined because it depends on the sulfonic acid used, the type of resin, the temperature, the dissolvent and the concentration.
  • AMBERLITE 252RFH with a water retention capacity from 52 to 58 % the optimal amount of a conductive liquid that consists in 32 % of methanesulfonic acid in water is ranging from 35 to 50 % with respect to the resin absolutely dry weight.
  • the material of the porous particles used is preferably based on a sulfonate polymer, which means that it has active sulfonic acid groups RSO3H or RSO3 - joined.
  • the porous particles sulfonate polymer is based in a styrenecopolymer and divinylbenzene.
  • the porous particles can be ion exchange resins, such as for example but without any limiting purpose, AMBERLITE 252RFH having an ion exchange capacity of 1.7 eq/l, a density of 1.24 g/ml, a diameter ranging from 0.6 to 0.8 mm, and a water retention capacity ranging from 52 to 58 %.
  • a dry electrolyte was prepared mixing and homogenizing 1.5 kg of ion exchange resin AMBERLITE 252RFH with 550 ml of a solution of methanesulfonic acid to 4 % of water.
  • This dry electrolyte is used to polish a part of iron alloy with the following composition expressed in % C (0.17-0.23) Si (0.40) Mn (0.65-0.95) V (0.025) S (0.050) Cr (0.35-0.70) Ni (0.40-0.70) Mo (0.15-0.55) Cu (0.35) Al (0.050) with a surface area of 5 cm2 .
  • the counter-electrode was a network of iridium on titanium.
  • the current used was a positive wave of an electric current of 50 Hz at 20 V, that provided an intensity of 0.1 A.
  • the part had a downwards/upwards movement at around 4 Hz and the dry electrolyte container was submitted to a vibration. After 5 minutes of this proceeding, the metal surface had acquired spectacular properties.
  • a dry electrolyte was prepared mixing and homogenizing 5.3 kg of ion exchange resin AMBERLITE 252RFH with 1950 ml of a methanesulfonic acid solution at 32 % in water. This dry electrolyte is used to polish a part of iron alloy having the same composition as before with a surface area of 36 cm2 .
  • the counter-electrode was a network of iridium on titanium. The current used was a positive wave of an electric current of 50 Hz at 30 V. The part had an upwards/downwards movement at around 4 Hz and the dry electrolyte container was submitted to a vibration. After 10 minutes of this process, the metal surface had acquired spectacular properties.
  • a solution was prepared with 550 mL of methane sulfonic acid 70 %, 160 mL PEG and 3000 mL of deionized water. This solution is mixed and homogenized with 6.7 kg of ion exchange resin AMBERLITE 252RFH to produce a dry electrolyte.
  • This dry electrolyte was used to polish a part of carbon steel of 36 cm2.
  • the counter-electrode used was a network of iridium on titanium.
  • the current used was a positive wave of an electric current of 50 Hz at 30 V.
  • the part had a downwards/upwards movement ca. 4 Hz and the dry electrolyte container was submitted to vibration. After 5 minutes of this process the metal surface had acquired spectacular properties.
  • the object of this invention refers to the method to strip vapor deposited coatings fand/or thermally sprayed coatings from a metallic surface of a substrate.
  • the core of the invention is the use of ion transport that uses free solid bodies that contain sulfonic acids as electrolytes. All the aspects as described above related to EP3795722 can be applied to the stripping process according to the present invention.
  • sulfonic acids in free solid bodies or particles as described above are used to remove vapor deposited and/or thermally sprayed coatings from metal surfaces through ions transport. This can be used in the same way as described above for polishing.
  • the vapor deposited coatings could be for example physical vapor deposited (PVD) coatings and/or chemical vapor deposited (CVD) coatings.
  • a CrAIN-based coating (brand name "FORMERA") which had been cathodic arc deposited onto an iron alloy.
  • the thickness of the coating was about 5um.
  • a dry electrolyte was prepared mixing and homogenizing 1.5 kg of ion exchange resin AMBERLITE 252RFH with 550 ml of a solution of methanesulfonic acid to 4 % of water. This dry electrolyte is used to strip the iron alloy substrate.
  • the counter-electrode was a network of iridium on titanium. The current used was a positive wave of an electric current of 50 Hz at 20 V, that provided an intensity of 0.1 A.
  • FIG. 1 shows in addition that the surface of the substrate is slightly roughened, which proposes that this process is different to a polishing process.
  • AICrN-based coating brand name "ALNOVA" which had been cathodic arc deposited onto an carbon steel.
  • the thickness of the coating was again about 5pm.
  • a solution was prepared with 550 mL of methane sulfonic acid 70 %, 160 ml PEG and 3000 mL of deionized water. This solution is mixed and homogenized with 6.7 kg of ion exchange resin AMBERLITE 252RFH to produce a dry electrolyte.
  • This dry electrolyte was used to strip the carbon steel substrate.
  • the counter-electrode used was a network of iridium on titanium.
  • the current used was a positive wave of an electric current of 50 Hz at 30 V.
  • the part had a downwards/upwards movement ca. 4 Hz and the dry electrolyte container was submitted to vibration. After 30 minutes of this process the coating was completely removed as can be seen in figure 2.
  • the present invention relates to the use of dry electrolytes to strip vapor or thermal spray deposition coated metal surfaces through ion transport, characterized in that the conductive liquid of the dry electrolyte comprises at least a sulfonic acid.
  • the porous particles of the dry electrolyte can comprise sulfonate polymer.
  • the porous particles of the dry electrolyte can comprise ions exchange resins of polystyrene- divinylbenzene.
  • the conductive liquid of the dry electrolyte can comprise methane-sulfonic acid.
  • the concentration of sulfonic acid in relation to the solvent can ranging from 1 to 70 %.
  • the conductive liquid of the dry electrolyte can comprises a complexing agent.
  • the complexing agent can comprise a polyether.
  • the polyether can be a linear alkyl.
  • the polyether can comprise or be polyethyleneglycol.
  • the polyethyleneglycol can have a molecular weight ranging from 200 to 500 Da.
  • the polyether can be polypropyleneglycol.
  • the conductive liquid of the dry electrolyte can be a chelating agent.

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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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Secondary Cells (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

La présente invention concerne l'utilisation d'électrolytes secs pour dénuder des surfaces métalliques revêtues par dépôt en phase vapeur ou par pulvérisation thermique par transport d'ions, caractérisée en ce que le liquide conducteur de l'électrolyte sec comprend au moins un acide sulfonique.
PCT/EP2023/025205 2022-05-09 2023-05-03 Utilisation d'acides sulfoniques dans des électrolytes secs pour éliminer des revêtements déposés par évaporation sous vide et/ou par pulvérisation thermique sur des surfaces métalliques WO2023217411A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102022001617.6 2022-05-09
DE102022001617 2022-05-09

Publications (2)

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WO2023217411A2 true WO2023217411A2 (fr) 2023-11-16
WO2023217411A3 WO2023217411A3 (fr) 2024-03-14

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008028311A1 (fr) 2006-09-05 2008-03-13 Oerlikon Trading Ag, Trübbach Installation d'enlèvement de couche et procédé pour son utilisation
US9512539B2 (en) 2010-09-24 2016-12-06 Oerlikon Surface Solutions Ag, Pfaffikon Process for removing a coating from workpieces
EP3795722A1 (fr) 2018-11-12 2021-03-24 Drylyte, S.L. Utilisation d'acides sulfoniques dans des électrolytes secs pour polir des surfaces métalliques par l'intermédiaire du transport d'ions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6300304B2 (ja) * 2013-12-19 2018-03-28 学校法人関東学院 電解エッチング方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008028311A1 (fr) 2006-09-05 2008-03-13 Oerlikon Trading Ag, Trübbach Installation d'enlèvement de couche et procédé pour son utilisation
US9512539B2 (en) 2010-09-24 2016-12-06 Oerlikon Surface Solutions Ag, Pfaffikon Process for removing a coating from workpieces
EP3795722A1 (fr) 2018-11-12 2021-03-24 Drylyte, S.L. Utilisation d'acides sulfoniques dans des électrolytes secs pour polir des surfaces métalliques par l'intermédiaire du transport d'ions

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