Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D21/00—Processes for servicing or operating cells for electrolytic coating
  • C25D21/04—Removal of gases or vapours ; Gas or pressure control
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D21/00—Processes for servicing or operating cells for electrolytic coating
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/003—Electroplating using gases, e.g. pressure influence
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/04—Electroplating with moving electrodes
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/10—Electroplating with more than one layer of the same or of different metals
  • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/18—Electroplating using modulated, pulsed or reversing current
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/60—Electroplating characterised by the structure or texture of the layers
  • C25D5/623—Porosity of the layers
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/60—Electroplating characterised by the structure or texture of the layers
  • C25D5/625—Discontinuous layers, e.g. microcracked layers
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D7/00—Electroplating characterised by the article coated
  • C25D7/10—Bearings

Definitions

• the present invention concerns a method for deposition of a hard chrome layer on a substrate surface.
• the present invention concerns a method for deposition of hard chrome layers at high rates of deposition.
• Hard chrome layers are widespread as coatings on technical parts. Thus, for example, it is known how to provide valve bodies, bushings, brake pistons or axle hubs with hard chrome layers.
• the deposited chrome layer serves, on the one hand, as corrosion protection for the substrate surface located underneath, and on the other hand also as a protective layer against friction and wear, since the deposited hard chrome layers have great hardness.
• the substrate surfaces being coated after a suitable pretreatment to prepare the surface are brought into contact with an electrolyte having at least the metal (chromium) being deposited, while a deposition voltage is applied between the cathodically contacted substrate surface and an anode.
• a deposition voltage is applied between the cathodically contacted substrate surface and an anode.
• the layers so deposited can have tensile or compressive internal stresses. Compressive internal stresses can lead to microcracks in the deposited layers, which means that the layers are not continuously closed, but rather possess a network of microcracks.
• Tensile internal stresses can lead to deep cracks in the deposited layers, into which moisture or corrosive substances can migrate and thus lead to corrosion effects in the substrate surface underneath the chrome layer, ultimately resulting in damaging of the chrome layer, even a flaking off.
• the coated substrate surfaces undergo subsequent machining according to the prior art, e.g., by grinding or honing, in order to do away with the internal tensile stresses occurring in the layers.
• the machining can also lead to a damaging of the deposited chrome layers, which ultimately reduces their property as a corrosion protection layer drastically.
• chromium in itself is a relatively non-noble metal in chemical respect, thanks to the formation of a thin oxide layer on the surface and the concomitant very positive potential chromium layers act to protect against corrosion and exhibit corrosion protection properties comparable to noble metals such as gold, silver or platinum in regard to their corrosion and tarnish protection.
• the network of cracks occurring in galvanically deposited chrome layers due to internal compressive stresses does not have merely negative influence on the corrosion protection property of the deposited layer, but instead leads positively to improved properties of the so coated moving parts, since lubricants for reducing the frictional resistance between moving parts can become embedded in the microcracks, and thus they have a depot effect for the lubricants.
• This capability of the layers is known as oil carrying capacity and it is absolutely desirable for such mechanical parts. For example, this is important in the case of piston rings, to maintain the fire stability.
• GB 1 551 340 A discloses the depositing of a hard chrome layer on a substrate surface at a temperature of 60° C. and a current density set at 80 A/dm 2 in a low-pressure chamber with chromium deposition electrolytes flowing through it.
• U.S. Pat. No. 2,706,175 A discloses a device for coating the insides of hollow cylinders, wherein a chrome layer is deposited under low pressure.
• EP 1 191 129 A discloses a method for depositing a hard chrome layer under low pressure, wherein electrolyte and substrate move with a velocity of 0.4 m/sec relative to each other.
• US 2001/054557 A1 discloses a method for the galvanic deposition of hard chrome layers, in which the chrome layer is likewise deposited under low pressure at a current density of 30 to 40 A/dm 2 and a pulse frequency of 5 to 700 Hz.
• EP 0 024 946 A discloses a method for depositing of hard chrome layers at low pressure with a current density in the range of 200 A/dm 2 and the addition of a relative motion between electrolyte and substrate being coated.
• U.S. Pat. No. 5,277,785 discloses a method and a device for depositing of hard chrome layers by means of a brush deposition.
• the invention is directed to a method for galvanic depositing of a hard chrome (i.e., chromium-based) layer on a substrate surface, having the steps of making contact between the substrate surface being coated and a chromium-containing electrolyte suitable for galvanic deposition; and applying a voltage between the substrate surface being coated and a counterelectrode for the galvanic deposition of a hard chrome layer on the substrate surface; wherein the deposition occurs in a container essentially gas-tight to the surroundings, and at least during the applying of the voltage a low pressure is established in the container essentially gas-tight to the surroundings and wherein substrate surface and chrome-containing electrolyte are moved with a velocity of 0.1 m/s to 5 m/s, preferably >1 m/s to 5 m/s relative to each other.
• a hard chrome i.e., chromium-based
• the pressure difference to be established lies in a range of 10 mbar to 800 mbar, preferably 20 mbar to 200 mbar.
• a second hard chrome layer is deposited on a first deposited hard chrome layer, wherein for the depositing of the first hard chrome layer a pulsed current is applied between substrate surface and counterelectrode, and for the depositing of the second hard chrome layer a direct current is applied to the first hard chrome layer.
• a first hard chrome layer is deposited, having no internal stresses and being free of microcracks thanks to the pulsed current applied.
• a second hard chrome layer is deposited on the already deposited first hard chrome layer free of cracks and internal stresses, the second layer having internal tensile stress and the mechanically desirable microcracks.
• the resulting compound layer structure has excellent corrosion resistance and furthermore excellent mechanical properties as running or sliding surfaces, thanks to the microcracks occurring in the upper chrome layer.
• the pulsed current can be applied with a pulse frequency of 5 Hz to 5000 Hz, preferably 50 Hz to 1000 Hz.
• a current density between 25 A/dm 2 and 1000 A/dm 2 , preferably 50 A/dm to 500 A/dm 2 is adjusted for this.
• a direct current can be adjusted with a current density in the range between 25 A/dm 2 and 1000 A/dm 2 , likewise with a preferred range between 50 A/dm 2 and 500 A/dm 2 .
• the substrate surface being coated makes contact with the chromium-containing electrolyte at a temperature between 30° C. and 85° C., and the electrolyte can have a pH value in the range of ⁇ pH 3, preferably ⁇ pH 1.
• the chromium-containing electrolyte can have a conductivity K of 200 mS/cm to 550 mS/cm (at 20° C.).
• the method can be carried out with only one electrolyte in a single coating cell.
• a relative motion can be produced at least temporarily between the electrolyte and the substrate surface being coated.
• the relative motion can lie in a range between 0.1 m/s and 5.0 m/s.
• the substrate surfaces can be moved or the electrolyte can be appropriately delivered.
• Stirring devices or pumps are suitable for the delivery of the electrolyte.
• Relative motion between electrolyte and substrate surface so produced encourages a detachment of the forming hydrogen bubbles, in addition to the low pressure applied.
• the substrate surface being coated makes contact with the electrolyte in a cell, in which the chromium-containing electrolyte flows in from below and can flow away across a spillway, and a sufficient flow velocity is adjusted to sustain the detachment of the resulting hydrogen bubbles.
• a coating reactor is especially suitable, having the shape of a cylinder and being outfitted with a cylindrical inner anode of platinum-coated metal, such as platinum-coated titanium, niobium or tantalum.
• platinum-coated metal such as platinum-coated titanium, niobium or tantalum.
• At the top and bottom of the coating reactor there can be supports for the structural part being chrome plated.
• a coating reactor of this kind is particularly suitable for the coating of cylindrical parts. At least one of the two supports serves to supply current to the part being coated and is accordingly configured as an electrical contact.
• an electrolyte is suctioned from a reservoir tank through the reactor to the top part of the reactor and from there back to the reservoir tank.
• the electrolyte can be degasified by means of suitable devices.
• the gas mixture separated in this way is taken to the outside via a drop separator.
• a separate degasification tank can be provided.
• Devices for temperature control of the electrolyte can be provided in the reservoir tank, such as heating and/or cooling systems.
• the reservoir tank can be connected via dispensing pumps to other reservoir tanks, which contain compositions to supplement the electrolyte located in the reservoir tank, insofar as a further dispensing of the electrolyte is needed.
• the electrolyte heated by the applied deposition voltage can be taken across an evaporator unit, where water is removed from the electrolyte while cooling it at the same time.
• such a reactor configured according to the invention is outfitted with at least one movable end face, facilitating the bringing up and taking away of the part being coated. Furthermore, the usual handling systems and seals can be provided for an automation of the process.
• the part being coated in the reactor can be rinsed with rinse water or steam, or at least prerinsed.
• the supply of electrolyte to the reactor can be interrupted and replaced by rinse water or steam.
• the final rinsing can occur in a second reactor, which is basically identical in design to the first reactor, but does not have any anode or current supply.
• a workpiece being chrome plated (piston rod of steel type CK 45) was brought into contact in a reactor configured according to the invention with an electrolyte for deposition of a hard chrome layer, having 370 g/l of chromic acid and 5.3 g/l of sulfuric acid, the electrolyte flowing into the respective reactor from the bottom and it was taken away across a spillway at the top of the reactor.
• the relative velocity established in this way between the substrate surface of the workpiece being coated and the electrolyte was 4 m/s.
• the electrolyte had a temperature of 70° C.
• a pressure of 50 mbar was established inside the reactor.
• a hard chrome layer was then deposited by adjusting a current density of 235 A/dm 2 in the space of 300 seconds. The substrate was then rinsed.
• the obtained chrome layer had a layer thickness of 11 ⁇ m, it had around 40 cracks per cm, and it had a corrosion resistance in the neutral salt spray test of less than 100 h.
• a workpiece being chrome plated was brought into contact with an electrolyte in a reactor configured according to the invention, as in example 1.
• the electrolyte contained 370 g/l of chromic acid, 5.3 g/l of sulfuric acid, and 6 g/l of methane sulfonic acid.
• the deposition conditions corresponded to example 1.
• a shiny chrome layer with a layer thickness of 11 ⁇ m was obtained, which had around 250 cracks/cm and a corrosion resistance in the neutral salt spray test of less than 100 h.
• a workpiece being chrome plated was brought into contact with the electrolyte per example 2 under the conditions mentioned in example 2, wherein a pulsed current with a current density during the pulse of 235 A/dm 2 , a frequency of 1000 Hz and an On time of 50% was applied for 400 seconds.
• a shiny, crack-free chrome layer with a layer thickness of 11 ⁇ m was obtained, which had 0 cracks/cm and a corrosion resistance in the neutral salt spray test of more than 500 h.
• a workpiece being chrome plated was coated under the deposition conditions per example 3, at first applying a pulsed current with a current density of 235 A/dm 2 during the pulse, a frequency of 1000 Hz and an On time of 50% for 400 seconds and then applying a direct current in the same electrolyte with a current density of 235 A/dm 2 for 100 seconds, other conditions being equal.
• the obtained shiny chrome layer had a layer thickness of 17 ⁇ m and around 25 cracks/cm, with a corrosion resistance in the neutral salt spray test of more than 500 h.

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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 Methods And Accessories (AREA)

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• 2008
  • 2008-10-22 EP EP08018462.5A patent/EP2180088B2/fr active Active
  • 2008-10-22 PL PL08018462T patent/PL2180088T5/pl unknown
  • 2008-10-22 ES ES08018462T patent/ES2363566T5/es active Active
• 2009
  • 2009-10-22 JP JP2011533333A patent/JP5739341B2/ja active Active
  • 2009-10-22 US US13/125,622 patent/US20110198226A1/en not_active Abandoned
  • 2009-10-22 WO PCT/US2009/061683 patent/WO2010048404A1/fr active Application Filing
  • 2009-10-22 BR BRPI0920600-0A patent/BRPI0920600B1/pt active IP Right Grant
  • 2009-10-22 CN CN200980151479.6A patent/CN102257184B/zh active Active
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