EP4259855A1 - Substrat plaqué noir - Google Patents

Substrat plaqué noir

Info

Publication number
EP4259855A1
EP4259855A1 EP21834800.1A EP21834800A EP4259855A1 EP 4259855 A1 EP4259855 A1 EP 4259855A1 EP 21834800 A EP21834800 A EP 21834800A EP 4259855 A1 EP4259855 A1 EP 4259855A1
Authority
EP
European Patent Office
Prior art keywords
chromium
black
layer
plating layer
less
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.)
Pending
Application number
EP21834800.1A
Other languages
German (de)
English (en)
Inventor
Berkem Özkaya
Philipp Wachter
Michael Jonat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and 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 and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Publication of EP4259855A1 publication Critical patent/EP4259855A1/fr
Pending legal-status Critical Current

Links

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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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
    • C25D21/08—Rinsing
    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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

Definitions

  • the present invention relates to a black plated substrate comprising a base-substrate and deposited thereon a layer stack, wherein the layer stack comprises a black chromium plating layer comprising on its surface a conversion layer having a depth of 30 nm or more, characterized in that the conversion layer does not comprise metallic chromium or comprises metallic chromium only up to 2 at.-%, based on the element chromium and the total number of chromium atoms in the conversion layer.
  • each chromium layer in particular dark chromium layers, are characterized by color values referenced to the L*a*b* color-space system. While the value L* defines the brightness (or sometimes also referred to as lightness), values a* and b* define the color of a respective chromium layer. While a L* value of 100 defines a diffuse white, a L* value of 0 is a deep black. Values for a* and b* can be positive and negative, wherein a* values describe the colors green (negative) and red (positive), while b* values describe the colors blue (negative) and yellow (positive). A combination of a* and b* with 0 describes a neutral grey color, turning into a deep neutral black the lower the L* value (e.g. of 50 or below).
  • L* defines the brightness (or sometimes also referred to as lightness)
  • values a* and b* define the color of a respective chromium layer. While a L* value of 100 defines a diffuse white,
  • US 2020/094526 A1 refers to a black plated resin part and method producing the same. It discloses a black chromium plating layer comprising such a surface-modified layer.
  • US’526 discloses that the thickness of the surface-modified layer correlated with the amount of agent M added (see US’526, [0078]) and current density applied (see [0079]). Furthermore, US’526 discloses a thickness of the surface-modified layer up to 37.7 nm (see Sample No. 1).
  • a black plated substrate comprising a base-substrate and deposited thereon a layer stack, wherein the layer stack comprises
  • - comprises the elements chromium, carbon, and oxygen; - comprises on its surface a conversion layer having a depth of 30 nm or more measured from the surface towards the one or more than one intermediate plating layer; and
  • the conversion layer does not comprise metallic chromium or comprises metallic chromium only up to 2 at.-%, based on the element chromium and the total number of chromium atoms in the conversion layer.
  • the black plated substrate and therefore the black chromium plating layer preferably refers to a decorative black plated substrate and a decorative black chromium plating layer, respectively.
  • the black chromium plating layer is preferably not a black hard chromium plating layer.
  • the black substrate comprises a black chromium plating layer obtained from a plating process, preferably an electrolytic plating process. This includes that the black chromium plating layer is obtained by a wet-chemical plating process. In other words, the black plated substate and the black chromium plating payer, respectively, are not obtained by physical deposition methods, e.g. vapor deposition.
  • the present invention particularly refers to such a specifically designed black plated substrate with a respective black chromium plating layer comprising a conversion layer as defined above and throughout the present text.
  • the black plated substrate of the present invention comprises a base-substrate.
  • a black plated substrate of the present invention wherein the base-substrate comprises, preferably is, a metallic or non-metallic base-substrate, preferably a non-metallic base-substrate, most preferably a plastic base-substrate.
  • the metallic basesubstrate is an iron-comprising metallic base-substrate, preferably an iron base-substrate, most preferably a cast iron base-substrate.
  • an iron-comprising metallic base-substrate comprises a brass base-substrate and/or a zinc-based die-cast basesubstrate.
  • the non-metallic base-substrate preferably the plastic base-substrate
  • the non-metallic base-substrate comprises acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene styrene - polycarbonate (ABS-PC), polypropylene (PP), polyamide (PA), polyurethane (Pll), polyepoxide (PE), polyacrylate, polyetherimide (PEI), a polyetherketone (PEK), mixtures thereof, and/or composites thereof; preferably acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene styrene - polycarbonate (ABS-PC), polyamide (PA), polyurethane (Pll), polyepoxides (PE), polyacrylate, mixtures thereof, and/or composites thereof.
  • Such plastic base-substrates are typically used in decorative applications such as automotive parts, in particular ABS and ABS-PC
  • the black plated substrate of the present invention furthermore comprises a layer stack deposited on the base-substrate.
  • the layer stack comprises
  • the one or more than one intermediate plating layer comprises one or more than one selected from the group consisting of a nickel layer, a nickel alloy layer, a copper layer, and a copper alloy layer. Preferably, they are consecutive; forming a sequence of intermediate plating layers; being adjacent.
  • the layer stack comprises two or more than two intermediate plating layers, most preferably at least one intermediate layer comprising copper and/or a copper alloy and furthermore at least one intermediate layer comprising nickel and/or a nickel alloy.
  • a layer stack comprising more than one intermediate plating layer consecutively following on each other.
  • plating denotes a deposition utilizing and not utilizing an external electrical source. Thus, it preferably includes electroplating as well as electroless plating, e.g. electroless plating with the help of a reducing agent.
  • the one or more than one intermediate plating layer formed on the base-substrate comprises at least one micro-porous nickel-plating layer (sometimes also referred to as MPS nickel-plating layer).
  • a layer comprises non-conductive micro-particles.
  • the base-substrate is a non-metallic base-substrate, preferably a plastic base-substrate.
  • this intermediate plating layer if present, is adjacent to the black chromium plating layer.
  • the one or more than one intermediate plating layer formed on the base-substrate comprises at least one bright nickel-plating layer or at least one satin nickel-plating layer. This most preferably applies, if the base-substrate is a non-metallic base-substrate, preferably a plastic basesubstrate.
  • a black plated substrate of the present invention wherein the one or more than one intermediate plating layer formed on the base-substrate comprises at least one semi-bright nickel-plating layer. This most preferably applies, if the base-substrate is a non-metallic base-substrate, preferably a plastic base-substrate. More preferred is a black plated substrate of the present invention, wherein said semi-bright nickel-plating layer is present additionally to said bright nickel-plating layer or satin nickel-plating layer.
  • the one or more than one intermediate plating layer formed on the base-substrate comprises at least one nickel alloy plating layer, preferably adjacent (i.e. directly on) to the base-substrate. This most preferably applies, if the base-substrate is a non-metallic base-substrate, preferably a plastic base-substrate.
  • the one or more than one intermediate plating layer formed on the base-substrate comprises at least one copper plating layer, preferably adjacent (i.e. directly on) to aforementioned at least one nickel alloy plating layer. This most preferably applies, if the base-substrate is a non- metallic base-substrate, preferably a plastic base-substrate.
  • a black plated substrate of the present invention comprising
  • non-metallic base-substrate preferably a plastic base-substrate, most preferably a plastic base-substrate as aforementioned as being preferred;
  • a nickel or nickel alloy plating layer preferably an electroless nickel alloy plating layer
  • a copper plating layer preferably an electrolytic copper plating layer
  • a passivation layer and/or anti-fingerprint layer optionally, a passivation layer and/or anti-fingerprint layer.
  • features and preferred features regarding the mentioned individual layers apply likewise also the individual layers in this very preferred black plated substrate of the present invention.
  • additional layers in the layer stack e.g. an activation layer comprising palladium, is not excluded and can be also one of the one or more than one intermediate plating layer.
  • the black chromium plating layer (including the conversion layer) or the passivation layer, if present and deposited on top of the black chromium plating layer, is the outermost layer of the layer stack.
  • the optional passivation layer comprises trivalent chromium phosphate and/or (preferably or) a manganese species.
  • the optional passivation layer has no significant effect on the optical appearance of the black chromium plating layer, most particularly regarding L*, a*, and b* values of the black chromium plating layer.
  • the layer stack further comprises a black chromium plating layer formed on the one or more than one intermediate plating layer.
  • a black plated substrate of the present invention is preferred, wherein the black chromium plating layer is adjacent to the outermost intermediate plating layer.
  • the black chromium plating layer is preferably an electroplated black chromium plating layer.
  • the chromium plating layer is black. This black is preferably optically perceived as a deep dark black. Most preferably, the entire black plated substrate is perceived in this manner. Most preferred is a black plated substrate of the present invention, wherein the black chromium plating layer is obtained from a trivalent chromium electroplating bath. This means that the source of the chromium in the black chromium plating layer is chromium in its trivalent state and not from hexavalent chromium.
  • the black chromium plating layer has a L* value of 53 or less, preferably 51 or less, more preferably 50 or less, even more preferably 49 or less, yet even more preferably 47 or less, most preferably 45 or less, yet even most preferably 43 or less. This most preferably applies likewise to the entire black plated substrate.
  • the L* value of the black chromium plating layer is ranging from 30 to 55, preferably from 32 to 53, more preferably from 34 to 51 , even more preferably from 36 to 49, most preferably from 38 to 47, even most preferably from 40 to 45. This most preferably applies likewise to the entire black plated substrate.
  • optical perception of a deep dark black with reduced or without any optical perception of another color such as yellowish, brownish, bluish, etc.
  • the deep dark black optical perception is most preferably a neutral dark black optical perception.
  • a black plated substrate of the present invention wherein the black chromium plating layer has, according to the L*a*b color system, a b* value of +7 or less, of +6 or less, more preferably of +5 or less, even more preferably of +4 or less, most preferably of +3 or less. This most preferably applies likewise to the entire black plated substrate.
  • a black plated substrate of the present invention wherein the b* value of the black chromium plating layer is ranging from -6 to +6, preferably from -5 to +5, more preferably from -4 to +4, even more preferably from -3 to +3, most preferably from -2 to +2, even most preferably from -1 to +1. This most preferably applies likewise to the entire black plated substrate.
  • a black plated substrate of the present invention wherein the black chromium plating layer has, according to the L*a*b color system, an a* value of +5 or less, of +4 or less, more preferably of +3 or less, even more preferably of +2 or less, most preferably of +1 or less. This most preferably applies likewise to the entire black plated substrate. More preferred is a black plated substrate of the present invention, wherein the a* value of the black chromium plating layer is ranging from -5 to +5, preferably from -4 to +4, more preferably from -3 to +3, most preferably from -2 to +2, even most preferably from -1 to +1. This most preferably applies likewise to the entire black plated substrate.
  • the black chromium plating layer typically comprises chromium, preferably primarily in a metallic state.
  • the black chromium plating layer comprises chromium in a total amount ranging from 20 at.-% to 70 at.-%, based on the total amount of atoms in the black chromium plating layer including the conversion layer, preferably from 25 at.-% to 63 at.-%, more preferably from 29 at.-% to 56 at.-%, even more preferably from 33 at.-% to 51 at.-%, most preferably from
  • the source of the chromium in the black chromium plating layer is preferably from chromium in its trivalent state.
  • This typically includes that complexing agents are utilized in a respective electroplating bath in order to complex the respective trivalent chromium ions.
  • this results in a certain carbon content in the black chromium plating layer compared to a chromium plating layer originating from hexavalent chromium sources.
  • the black chromium plating layer comprises carbon in a total amount ranging from 5 at.-% to 40 at.-%, based on the total amount of atoms in the black chromium plating layer including the conversion layer, preferably from 6 at.-% to 33 at.-%, more preferably from 7 at.-% to 28 at.-%, even more preferably from 8 at.-% to 24 at.-%, most preferably from 9 at.-% to 20 at.-%, even most preferably from 10 at.-% to 16 at.-%.
  • the black chromium plating layer comprises oxygen in a total amount ranging from 12 at.-% to 40 at.- %, based on the total amount of atoms in the black chromium plating layer including the conversion layer, preferably from 14 at.-% to 38 at.-%, more preferably from 16 at.-% to
  • blackening agents are typically utilized in a respective electroplating bath for depositing the black chromium plating layer.
  • organic and/or inorganic blackening agents are preferred.
  • Very preferred inorganic blackening agents comprise iron-containing compounds, preferably iron ions, most preferably iron (II) ions, cobalt-containing compounds, preferably cobalt ions, most preferably cobalt (II) ions, thiocyanic acid, and/or salts thereof.
  • Preferred organic blackening compounds comprise methionine and/or salts thereof.
  • inorganic blackening agents, most preferably said iron-containing and cobalt-containing compounds are incorporated into the black chromium plating layer.
  • the black chromium plating layer comprises iron, preferably in a total amount ranging from 5 at.-% to 23 at.-%, based on the total amount of atoms in the black chromium plating layer including the conversion layer, preferably from 6 at.-% to 21 at.-%, more preferably from 7 at.- % to 19 at.-%, even more preferably from 8 at.-% to 17 at.-%, most preferably from 9 at- % to 15 at.-%, even most preferably from 10 at.-% to 13 at.-%.
  • black chromium plating layer comprises cobalt, preferably in a total amount ranging from 5 at.-% to 23 at.-%, based on the total amount of atoms in the black chromium plating layer including the conversion layer, preferably from 6 at.-% to 21 at.-%, more preferably from 7 at.-% to 19 at.-%, even more preferably from 8 at.-% to 17 at.-%, most preferably from 9 at.-% to 15 at.-%, even most preferably from 10 at.-% to 13 at.-%.
  • Organic blackening agents are typically incorporated into the black chromium plating layer by their sulfur atoms.
  • a black plated substrate of the present invention wherein the black chromium plating layer comprises sulfur, preferably in a total amount ranging from 0.1 at.-% to 10 at.-%, based on the total amount of atoms in the black chromium plating layer including the conversion layer, preferably from 0.3 at.-% to 9 at.-%, more preferably from 0.5 at.-% to 8 at.-%, even more preferably from 0.7 at.-% to 7 at.-%, most preferably from 1 at.-% to 6 at.-%, even most preferably from 1.3 at.-% to 5 at.-%.
  • the black chromium plating layer comprises nitrogen, preferably in a total amount ranging from 0.1 at.- % to 10 at.-%, based on the total amount of atoms in the black chromium plating layer including the conversion layer, preferably from 0.5 at.-% to 9 at.-%, more preferably from
  • the black chromium plating layer comprises on its surface a conversion layer.
  • the conversion layer has a depth (or thickness) of at least 30 nm. This is considered to be a useful minimum depth (or thickness) to provide a minimum of a desired wear and abrasion resistance, respectively, to maintain a comparatively long optical lifetime of the black plated substrate.
  • the conversion layer has a depth ranging from 30 nm to 90 nm, preferably from 32 nm to 85, more preferably from 35 nm to 80 nm, even more preferably from 38 nm to 70 nm, yet even more preferably from 41 nm to 66 nm, most preferably from 44 nm to 62 nm, even most preferably from 48 nm to 60 nm.
  • the black chromium plating layer excluding the conversion layer, preferably has a higher thickness than the depth (or thickness) of the conversion layer.
  • the black chromium plating layer, excluding the conversion layer is at least twice the thickness of the conversion layer, preferably at least 3 times, more preferably at least 4 to 5 times, even more preferably at least 6 to 7 times, most preferably at least 8 to 9 times, even most preferably at least 10 times.
  • depth or thickness of the conversion layer is determined according to B. R. Strohmeier, Surface and Interface Analysis, Volume 15, page 51 to 56, (1990).
  • the black chromium plating layer has a total thickness of 130 nm or more, including said conversion layer, preferably 160 nm or more, more preferably 190 nm or more, even more preferably 220 nm or more, yet even more preferably 250 nm or more, most preferably 275 nm or more, even most preferably 300 nm or more.
  • the black chromium plating layer has a total thickness ranging from 100 nm to 1000 nm, preferably from 130 nm to 900, more preferably from 160 nm to 800 nm, even more preferably from 190 nm to 700 nm, yet even more preferably from 220 nm to 600 nm, most preferably from 250 nm to 500 nm, even most preferably from 275 nm to 400 nm.
  • Such a total thickness typically provides excellent color stabilities over a typical lifetime of a respective black plated substrate, even if it is regularly touched and/or cleansed by wiping from time to time.
  • the conversion layer does not comprise metallic chromium or comprises metallic chromium only up to 1.7 at.-%, based on the element chromium and the total number of chromium atoms in the conversion layer; preferably does not comprise metallic chromium or comprises metallic chromium only up to 1.5 at.-%; more preferably does not comprise metallic chromium or comprises metallic chromium only up to 1.2 at.-%, even more preferably does not comprise metallic chromium or comprises metallic chromium only up to 1 at.-%, yet even more preferably does not comprise metallic chromium or comprises metallic chromium only up to 0.8 at.-%, most preferably does not comprise metallic chromium or comprises metallic chromium only up to 0.5 at.-%, yet most preferably does not comprise metallic chromium or comprises metallic chromium only up to 0.3 at.-%.
  • the conversion layer furthermore comprises chromium hydroxide and chromium oxide.
  • chromium is only present in the form of metallic chromium up to a maximum of 2 at.-% (including zero at.-%), chromium hydroxide and chromium oxide.
  • the conversion layer consists thereof, based on chromium species in the conversion layer.
  • the conversion layer comprises chromium in the form of chromium hydroxide, preferably in a total amount ranging from 40 at.-% to 75 at.-%, based on the element chromium and the total number of chromium atoms in the conversion layer, preferably from 46 at.-% to 70 at.- %, more preferably from 50 at.-% to 66 at.-%, most preferably from 54 at.-% to 62 at.-%.
  • the conversion layer comprises chromium in the form of chromium oxide, preferably in a total amount ranging from 25 at.-% to 55 at.-%, based on the element chromium and the total number of chromium atoms in the conversion layer, preferably from 29 at.-% to 51 at.-%, more preferably from 32 at.-% to 48 at.-%, most preferably from 35 at.-% to 45 at.-%.
  • the conversion layer comprises chromium oxide and chromium hydroxide, wherein the chromium hydroxide has a higher total amount than the chromium oxide. Own experiments have shown that this is as well a very preferred characteristic of the black plated substrate according to the invention (see examples below).
  • a black plated substrate of the present invention is preferred, wherein the black chromium plating layer comprises particles, preferably nano particles.
  • Preferred particles comprise one or more than one chemical element selected from the group consisting of silicon, aluminum, and carbon, preferably silicon and aluminum, most preferably aluminum.
  • the particles have a particle size of less than 1000 nm, preferably of less than 500 nm, more preferably at least 90% of the particles have a particle size of less than 500 nm, most preferably at least 90% of the particles have a particle size of less than 150 nm.
  • the particles have an average particle diameter D50 of 100 nm or less, preferably of 80 nm or less, more preferably of 60 nm or less, even more preferably of 50 nm or less, most preferably of 40 nm or less, very most preferably of 30 nm or less, even most preferably of 25 nm or less, based on volume.
  • the particles comprise aluminum oxide, preferably are aluminum oxide particles.
  • ABS plaques were used which prior to deposition of the black chromium plating layer were pre-treated as follows:
  • ABS plaques were cleaned with Uniclean® 151 (product of Atotech) for 5 minutes at 50°C.
  • the cleaned substrates were subjected to a chromo-sulfuric acid etch for about 10 minutes at about 70°C.
  • the etched substrates were activated with the help of colloidal palladium.
  • the activated substrates were subjected to an electroless nickel plating step (10 minutes, 40°C), followed by a 10 vol.-% sulfuric acid dipping step and an electroless copper plating step.
  • the copper plated substrates were furthermore subjected to an electrolytic copper plating step (25°C, 50 minutes, 4 A/dm 2 ).
  • the electrolytically copper plated substrates were subjected to a semi- bright nickel plating step (55°C, 15 minutes, 4 A/dm 2 ), followed by a bright nickel plating step (55°C, 25 minutes, 4 A/dm 2 ).
  • a sixth step bright nickel plated substrates were subjected to a micro-porous nickel layer plating step (55°C, 4 minutes, 3 A/dm 2 ).
  • aqueous (i.e. only solvent was water) trivalent chromium electroplating bath was used for depositing a black chromium plating layer: ca. 20 g/L to 25 g/L Cr 3+ ions (provided as basic chromium sulfate), ca. 30 g/L to 45 g/L Formic acid, ca. 60 g/L Boric acid, Tbl. 1 Potassium thiocyanate,
  • the electroplating baths further comprised small amounts (up to 4 g/L) of saccharin and between 5 g/L and 50 g/L of a S-containing diol.
  • the pH value was adjusted to 3.2.
  • electroplating was carried out for about 3 minutes and with a current density of about 10 A/dm 2 .
  • the temperature of the respective electroplating bath was about 35°C. Agitation was achieved via air agitation. As a result, homogeneously distributed black chromium plating layers were deposited.
  • the substrates plated with the black chromium plating layer were subjected to a passivation composition comprising permanganate.
  • the substrates were immersed into hot water (80°C) in a rinse step for 10 minutes. This was applied to example E and CE1 , wherein for example CE2 no such immersion was carried out.
  • L*a*b* values according to the L*a*b* color-space system, were determined (Konica Minolta CM-700 D spectrophotometer; CIE standard illuminator D65 and 10° standard observer). Calibration of the spectrophotometer was done with black and white standards.
  • E refers to examples according to the invention, wherein “CE” refers to comparative examples.
  • Table 1 shows that a decreasing overall content of methionine and potassium thiocyanate (from 435 mmol/L for E to 251 mmol/L for CE2) results in a correspondingly decreasing layer thickness of the conversion layer (from 55 nm for E to 25 nm of CE2).
  • Comparative example CE2 was not subjected to the immersion into hot water at 80°C, wherein comparative example CE1 was. As seen from Table 1 , it is mainly the combined total amount of methionine and potassium thiocyanate seemingly having a significant effect on the conversion layer thickness.
  • example E according to the invention shows a higher relative total amount of chromium hydroxide than chromium oxide.
  • the black chromium plating layer of example E subjected to intensive cleaning, was protected longer against undesired abrasion and therefore dark color stability was better than for the black chromium plating layers of comparative examples CE1 and CE2. It was observed that a brighter black color appeared under the conversion layer if the conversion layer was at least almost removed from the black chromium plating layer.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention se rapporte à un substrat plaqué noir comprenant un substrat de base sur lequel est déposé un empilement de couches, l'empilement de couches comprenant une couche de placage de chrome noir comprenant sur sa surface une couche de conversion présentant une profondeur de 30 nm ou plus, caractérisé en ce que la couche de conversion ne comprend pas de chrome métallique ou comprend du chrome métallique uniquement jusqu'à 2 % atomique sur la base de l'élément chrome et du nombre total d'atomes de chrome dans la couche de conversion.
EP21834800.1A 2020-12-11 2021-12-10 Substrat plaqué noir Pending EP4259855A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP20213572 2020-12-11
EP20213575 2020-12-11
PCT/EP2021/085219 WO2022123023A1 (fr) 2020-12-11 2021-12-10 Substrat plaqué noir

Publications (1)

Publication Number Publication Date
EP4259855A1 true EP4259855A1 (fr) 2023-10-18

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EP21834800.1A Pending EP4259855A1 (fr) 2020-12-11 2021-12-10 Substrat plaqué noir
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CN117488300B (zh) * 2024-01-02 2024-03-29 仪征亚新科双环活塞环有限公司 一种具有硬质镀层的活塞环及其制备方法

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US8273235B2 (en) * 2010-11-05 2012-09-25 Roshan V Chapaneri Dark colored chromium based electrodeposits
PL2886683T3 (pl) * 2011-05-03 2020-06-15 Atotech Deutschland Gmbh Kąpiel galwaniczna i sposób wytwarzania warstw z ciemnego chromu
KR20150123794A (ko) * 2013-01-10 2015-11-04 코벤트야 인크. 3가 크롬 도금욕 효율 유지 장치 및 방법
EP3299497A1 (fr) * 2016-09-27 2018-03-28 ATOTECH Deutschland GmbH Procédé de traitement d'une surface de chromium
JP6927061B2 (ja) * 2018-01-19 2021-08-25 豊田合成株式会社 めっき構造体の製造方法
JP6973242B2 (ja) * 2018-03-30 2021-11-24 豊田合成株式会社 電気めっき浴、めっき製品の製造方法、及びめっき製品
US11198944B2 (en) 2018-09-26 2021-12-14 Toyoda Gosei Co., Ltd. Black plated resin part and method for producing the same
JP7030739B2 (ja) * 2019-03-28 2022-03-07 豊田合成株式会社 黒色めっき樹脂部品及びその製造方法

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JP3242417U (ja) 2023-06-15
EP4259854A1 (fr) 2023-10-18
TW202231930A (zh) 2022-08-16
US20240011178A1 (en) 2024-01-11
JP2023553966A (ja) 2023-12-26
JP7467758B2 (ja) 2024-04-15
CN115803479A (zh) 2023-03-14
US20230193496A1 (en) 2023-06-22
JP2023531317A (ja) 2023-07-21
WO2022123019A1 (fr) 2022-06-16
WO2022123023A1 (fr) 2022-06-16

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