EP3607116B1 - Method for electrolytically depositing a chromium or chromium alloy layer on at least one substrate - Google Patents

Method for electrolytically depositing a chromium or chromium alloy layer on at least one substrate Download PDF

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Publication number
EP3607116B1
EP3607116B1 EP18714275.7A EP18714275A EP3607116B1 EP 3607116 B1 EP3607116 B1 EP 3607116B1 EP 18714275 A EP18714275 A EP 18714275A EP 3607116 B1 EP3607116 B1 EP 3607116B1
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Prior art keywords
chromium
total
range
current density
deposition bath
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German (de)
English (en)
French (fr)
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EP3607116A1 (en
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Anke WALTER
Oleksandra YEVTUSHENKO
Franziska PAULIG
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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    • 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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • 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
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/619—Amorphous layers

Definitions

  • the present invention relates to a method for electrolytically depositing a chromium or chromium alloy layer on at least one substrate.
  • the present invention refers to functional chromium layers, also often referred to as hard chromium layers.
  • Functional chromium layers usually have a much higher average layer thickness (from at least 1 ⁇ m up to several hundreds of micro meters) compared to decorative chromium layers (typically below 1 ⁇ m) and are characterized by excellent hardness and wear resistance.
  • chromium deposition methods relying on hexavalent chromium are more and more replaced by deposition methods relying on trivalent chromium.
  • Such trivalent chromium-based methods are much more health- and environment friendly.
  • Hexavalent chromium is a serious contaminant in deposition methods relying on trivalent chromium and is typically formed at the anode from trivalent chromium ions in an undesired electrochemical reaction. It is crucial to at least suppress to the best extent possible the formation of such hexavalent chromium or even to prevent it. If hexavalent chromium accumulates in a respective deposition bath the quality of the deposited chromium layer is significantly reduced and eventually the entire deposition method comes to a halt if a critical concentration is exceeded. For example, a total amount of 1 g/L hexavalent chromium in a trivalent chromium deposition bath is in most cases sufficient to completely ruin a deposition bath and is therefore inacceptable.
  • bromide ions have been utilized as suppressors to catalyze anodic oxidation of chemical species such as a variety of organic and inorganic compounds rather than oxidation of trivalent chromium to hexavalent chromium.
  • US 4,477,315 A discloses a huge variety of reducing agents in an amount effective to maintain the concentration of hexavalent chromium ions formed in the bath at a level at which satisfactory chromium deposition is still obtained.
  • US'315 primarily refers to decorative applications.
  • WO 2015/110627 A1 refers to an electroplating bath for depositing chromium and to a process for depositing chromium on a substrate using said electroplating bath. It is furthermore disclosed that the electroplating bath is separated from the anode by a membrane, preferably by an anodic or cationic exchange membrane.
  • membranes or diaphragms also exhibits significant disadvantages. Very frequently, such membranes are highly susceptible to high currents and often show serious burnings and damages after a certain time interval of bath usage. Furthermore, a plating setup comprising such a membrane or diaphragm is typically more sophisticated to control, demands higher costs, and requires a higher degree of maintenance.
  • EP 3 106 544 A2 discloses a continuous trivalent chromium plating method and relates to a trivalent chromium solution for decorative purposes.
  • the solution contains boric acid, has a pH in the range between 3.4 and 4.0, and utilizes a specific anode to cathode ratio.
  • the applied current density is in the range from 4 A/dm 2 to 12 A/dm 2 .
  • US 2,748,069 relates to an electroplating solution of chromium, which allows obtaining very quickly a chromium coating of very good physical and mechanical properties.
  • the chromium plating solution can be used for special electrolyzing methods, such as those known as spot or plugging or penciling galvanoplasty. In such special methods the substrate is typically not immersed into a respective electroplating solution.
  • RU 2139369 C1 refers to a method of electrochemical chrome plating of metals and their alloys.
  • This objective is solved by a method for electrolytically depositing a chromium or chromium alloy layer according to claim 1.
  • FIG. 1 a cathode current efficiency (CCE) plot is depicted, wherein on the x-axis the usage of the bath is shown in Ah/L and on the y-axis the cathode current efficiency.
  • CCE cathode current efficiency
  • the term "at least one” denotes (and is exchangeable with) "one, two, three or more than three”.
  • trivalent chromium refers to chromium with the oxidation number +3.
  • trivalent chromium ions refers to Cr 3+ -ions in a free or complexed form.
  • hexavalent chromium refers to chromium with the oxidation number +6 and thereto related compounds including ions containing hexavalent chromium.
  • not comprising denotes that respective compounds are not intentionally added to the aqueous deposition bath, such as boron containing compounds, in particular boric acid is not contained in the deposition bath.
  • the aqueous deposition bath is substantially free of such compounds. This does not exclude that such compounds are dragged in as impurities of other chemicals (preferably in a total amount of less than 10 mg/L, based on the total volume of the deposition bath). However, typically the total amount of such compounds is below the detection range and therefore not critical during step (c) of the method of the present invention.
  • boron containing compounds are not desired because they are environmentally problematic. Containing boron containing compounds, waste water treatment is expensive and time consuming. Furthermore, boric acid which is known as well working buffer compound typically shows poor solubility and therefore has the tendency to form precipitates. Although such precipitates can be solubilized upon heating, a respective aqueous deposition bath cannot be utilized during this time. There is a significant risk that such precipitates facilitate an undesired surface roughness. Thus, the aqueous deposition bath utilized in the method of the present invention does not contain boron containing compounds. Surprisingly, the aqueous deposition bath utilized in the method of the present invention performs very well without boron containing compounds. As a result, such compounds are not needed.
  • hexavalent chromium is intentionally added to the aqueous deposition bath.
  • the aqueous deposition bath is free of hexavalent chromium, i.e. the total amount of it is zero mg/L.
  • hexavalent chromium is usually formed at the anode in an undesired electrochemical reaction if trivalent chromium ions are not separated from the anode or otherwise prevented from its oxidation.
  • very tiny amounts of hexavalent chromium are also contaminants of other chemical compounds utilized in the aqueous deposition bath (such contaminants are not intentionally added to the deposition bath).
  • such tiny amounts of hexavalent chromium are acceptable, for example if the total amount of such hexavalent chromium is below the lower detection limit of typical measuring methods (e.g. photometry with diphenylcarbazide; lower detection limit is typically 15 to 20 mg per liter deposition bath). If the total amount of hexavalent chromium is more than zero but 15 mg/L or below, it is considered that the respective deposition bath does not contain hexavalent chromium. Furthermore, such a total amount of hexavalent chromium apparently does not at all negatively affect the deposition method in step (c) of the method of the present invention.
  • a total amount of anodically formed hexavalent chromium exceeding the lower detection limit e.g. a total amount of 100 mg/L or even 200 mg/L
  • the amount refers to a conversion to elementary chromium with a molecular weight of 52 g/mol, which likewise includes hexavalent chromium ions.
  • the method of the present invention includes steps (a) and (b), wherein the order is (a) and subsequently (b) or vice versa.
  • step (c) is carried out after both steps, (a) and (b), have been carried out.
  • At least one substrate forming the cathode is utilized.
  • more than one substrate is utilized in the method of the present invention simultaneously, forming an overall cathode surface with the total cathodic current density of 18 A/dm 2 or more, and wherein the maximum total cathodic current density is 250 A/ dm 2 .
  • the total cathodic current density includes all cathodes (substrates) utilized in step (c) for simultaneous deposition.
  • the method of the present invention more than one anode is utilized, forming an overall anode surface with the total anodic current density of 6 A/dm 2 or more, and wherein the maximum total anodic current density is 50 A/dm 2 .
  • the total anodic current density includes all anodes utilized in step (c) for deposition.
  • the term "overalltinct surface” refers to the geometrically derived overall surface actively participating in the deposition process.
  • an anode partly covered by a shielding material exhibits a reduced active surface because the shielded surface area of the anode does not participate in the deposition process.
  • a porous anode usually exhibits a larger surface compared to the geometrically derived surface of the same anode.
  • the term refers to the geometrically derived surface actively participating in the deposition process in order to determine the total anodic and cathodic current density.
  • the total cathodic current density is higher than the anodic current density, preferably the total cathodic current density is at least twice the total anodic current density.
  • the total anodic current density is higher than the total cathodic current density, in particular if the at least one substrate has an extraordinarily large surface.
  • the electrical current is a direct current (DC), more preferably a direct current without interruptions during step (c).
  • the direct current is preferably not pulsed (non-pulsed DC). Furthermore, the direct current preferably does not include reverse pulses.
  • the present invention is mainly based on the finding that a deposition method for a functional chromium or chromium alloy layer can be effectively stabilized by carefully setting the total anodic current density to 6 A/dm 2 or more, wherein the maximum total anodic current density is 50 A/dm 2 .
  • a total anodic current density significantly below 6 A/dm 2 e.g. 5 A/dm 2 or 5.5 A/dm 2 is for practical reasons not desired because the positive effect is not noticeable. As a result, no substantial stabilization effect is obtained and undesired amounts of hexavalent chromium are formed.
  • aqueous deposition bath has a pH in the range from 4.1 to 7.0.
  • highly acidic deposition baths (as mostly used for decorative purposes) did not provide satisfying results or could not be used at all if utilized in step (c) of the method of the present invention, even if the defined current densities were applied.
  • the method of the present invention is an improved and more stabilized method.
  • This improved method is more simplified compared to methods known from the art and furthermore results in excellent functional chromium or chromium alloy layers with excellent wear resistance and hardness.
  • the at least one substrate obtained after step (c) exhibits a Vickers Hardness of at least 700 HV (0.05) (determined with 50 g "load").
  • the wear resistance is comparatively good as the wear resistance obtained from hexavalent chromium based deposition methods.
  • the upper limit of the total anodic current density is 50 A/dm 2 .
  • the total anodic current density is not exceeding 30 A/dm 2 .
  • a method of the present invention is preferred, wherein the total anodic current density is in the range from 8 A/dm 2 (preferably 9 A/dm 2 ) to 30 A/dm 2 , preferably in the range from 8 A/dm 2 (preferably 9 A/dm 2 ) to 28 A/dm 2 , most preferably in the range from 8 A/dm 2 (preferably 9 A/dm 2 ) to 22 A/dm 2 .
  • a higher total anodic current density is preferred, preferably a maximum total anodic current density of 40 A/dm 2 or 50 A/dm 2 .
  • the total anodic current density is not exceeding 40 A/dm 2 and 50 A/dm 2 , respectively.
  • maximum anodic current densities might be necessary if substrates with sophisticated geometries are subjected to the method of the present invention; in particular if the substrate comprises an inside surface and an outside surface and both surfaces are simultaneously to be deposited in step (c) of the method of the present invention. In such cases the at least one substrate typically has an extraordinarily large surface.
  • the total cathodic current density is in the range from 20 A/dm 2 to 50 A/dm 2 , preferably in the range from 35 A/dm 2 to 50 A/dm 2 .
  • the maximum total cathodic current density is not in particular limited. According to the invention, the maximum total cathodic current density is 250 A/dm 2 , preferably 200 A/dm 2 . Preferred examples include 180 A/dm 2 , 150 A/dm 2 , 100 A/dm 2 , and 80 A/dm 2 . However, in exceptional cases, not being according to the present invention, the maximum total cathodic current density might exceed even 250 A/dm 2 .
  • Such a high maximum total cathodic current density usually requires high currents, which are possible because no means for separation (such as a membrane or a diaphragm) are used in the method of the present invention. In many cases, such separation means would suffer severe damage if exposed to such high currents. Comparatively high cathodic current densities are desired in order to obtain high deposition rates.
  • a method of the present invention is preferred, wherein the ratio of the total anodic current density to the total cathodic current density is in the range from 1:2 to 1:8, preferably in the range from 1:2 to 1:6, more preferably in the range from 1:3 to 1:6, even more preferably in the range from 1:3 to 1:5.
  • the ratio of the total anodic current density to the total cathodic current density is in the range from 1:2 to 1:8, preferably in the range from 1:2 to 1:6, more preferably in the range from 1:3 to 1:6, even more preferably in the range from 1:3 to 1:5.
  • a very significant suppression of formed hexavalent chromium is obtained.
  • the aqueous deposition bath is provided (providing also includes its manufacturing).
  • a preferred source of the trivalent chromium ions is basic or acidic chromium (III) sulfate or chromium (III) chloride.
  • a well-known basic chromium sulfate is Chrometan.
  • other available trivalent chromium salts can be used.
  • the aqueous deposition bath utilized in the method of the present invention contains sulfate ions, preferably in a total amount in the range from 50 g/L to 250 g/L, based on the total volume of the deposition bath.
  • the method of the present invention in particular supports chemical suppressors such as bromide ions.
  • a method of the present invention is preferred, wherein the deposition bath comprises bromide ions, preferably in a total amount of at least 0.06 mol/L, based on the total volume of the deposition bath, preferably at least 0.1 mol/L, more preferably at least 0.15 mol/L.
  • Bromide ions are still an effective means to chemically suppress the formation of anodic hexavalent chromium.
  • formation of anodic hexavalent chromium is impressively and surprisingly additionally suppressed.
  • the aqueous deposition bath preferably contains at least one further compound selected from the group consisting of organic complexing compounds and ammonium ions.
  • organic complexing compounds are carboxylic organic acids and salts thereof, preferably aliphatic mono carboxylic organic acids and salts thereof. More preferably the aforementioned organic complexing compounds (and its preferred variants) have 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms.
  • Complexing compounds primarily form complexes with the trivalent chromium ions in the aqueous deposition bath to increase bath stability.
  • the molar ratio of the trivalent chromium ions to the organic complexing compounds is in the range from 1:0.5 to 1:10.
  • the pH of the deposition bath is crucial.
  • the above or below mentioned pH-values are referenced to 20°C.
  • Preferred is a method of the present invention, wherein the deposition bath has a pH in the range from 4.5 to 6.5, preferably in the range from 5.0 to 6.0, most preferably in the range from 5.3 to 5.9. If the pH is too acidic or significantly beyond pH 7.0, no satisfying functional chromium or chromium alloy layer is obtained. Furthermore, precipitation easily occurs if the pH is too acidic. As a result, the aqueous deposition bath can be optimally handled if the pH is at least 5.0, preferably at least 5.3. An optimal chromium or chromium alloy layer is obtained if the maximum pH is 6.0 and 5.9, respectively.
  • the aqueous deposition bath is sensitive to a number of metal cations which are undesired.
  • the deposition bath contains copper ions, zinc ions, nickel ions, and iron ions, each independently in a total amount of 0 mg/L to 40 mg/L, based on the total volume of the deposition bath, preferably each independently in a total amount of 0 mg/L to 20 mg/L, most preferably each independently in a total amount of 0 mg/L to 10 mg/L.
  • This preferably also includes compounds comprising said metal cations.
  • none of the above mentioned metal cations are present at all, i.e. they are present each independently in a total amount of zero mg/L.
  • chromium is the only side group element.
  • the deposition bath does not comprise glycine, aluminium ions, and tin ions.
  • the deposition bath does not comprise glycine, aluminium ions, and tin ions. This ensures a functional chromium and chromium alloy layer, respectively, with the desired attributes as outlined throughout the text. Own experiments have shown that in a number of cases aluminium and tin ions, in particular aluminium ions, significantly disturb and even inhibit the deposition in step (c).
  • aqueous deposition bath does not contain sulfur containing compounds with a sulfur atom having an oxidation number below +6. It is assumed that the absence of said sulfur containing compounds results in an amorphous chromium layer and chromium alloy layer, respectively.
  • a method of the present invention is preferred, wherein the layer deposited in step (c) is amorphous, determined by x-ray diffraction. This applies to the chromium or chromium alloy layer obtained during step (c) of the method of the present invention and prior to any further post-deposition surface treatment that might affect the atomic structure of the deposited layer, changing it from amorphous to crystalline or partly crystalline. It is furthermore assumed that such sulfur containing compounds negatively affect the hardness of the functional chromium or functional chromium alloy layer deposited in step (c).
  • the method of the present invention is preferably designed for industrial application and large scale use. This means that typically a plurality of substrates is immersed in the deposition bath in one single deposition scenario. Furthermore, the bath is usually in active use over several weeks and months, which includes a reuse of the deposition bath after step (c) for a subsequent deposition scenario. In order to ensure a long bath life time, improved method stability, as obtained with the method of the present invention, is much beneficial.
  • a method of the present invention is preferred, wherein the method is repeated with the aqueous deposition bath obtained after step (c) and another substrate.
  • the method of the present invention is preferably a continuous method.
  • aqueous deposition bath provided in step (a) is repeatedly utilized in the method of the present invention, preferably for a usage of at least 70 Ah per liter aqueous deposition bath, preferably at least 100 Ah per liter, more preferably at least 200 Ah per liter, most preferably at least 300 Ah per liter.
  • step (b) of the present invention the at least one substrate and the at least one anode is provided.
  • the at least one substrate is a metal or metal alloy substrate, preferably a metal or metal alloy substrate independently comprising one or more than one metal selected from the group consisting of copper, iron, nickel, and aluminium, more preferably a metal or metal alloy substrate comprising iron.
  • the at least one substrate is a steel substrate, which is a metal alloy substrate comprising iron.
  • a steel substrate with a wear resistant functional chromium or chromium alloy layer is needed. This can in particular be achieved by the method of the present invention.
  • the substrate is preferably a coated substrate, more preferably a coated metal substrate (for preferred metal substrates see the text above).
  • the coating is preferably a metal or metal alloy layer, preferably a nickel or nickel alloy layer, most preferably a semibright nickel layer.
  • a steel substrate coated with a nickel or nickel alloy layer is preferred.
  • preferably other coatings are alternatively or additionally present. In many cases such a coating significantly increases corrosion resistance compared to a metal substrate without such a coating.
  • the substrates are not susceptible to corrosion due to a corrosion inert environment (e.g. in an oil bath). In such a case a coating, preferably a nickel or nickel alloy layer, is not necessarily needed.
  • the at least one anode is independently selected from the group consisting of graphite anodes and mixed metal oxide anodes (MMO), preferably independently selected from the group consisting of graphite anodes and anodes of mixed metal oxide on titanium.
  • MMO mixed metal oxide anodes
  • the at least one anode does not contain any lead or chromium.
  • step (c) of the method of the present invention the deposition of the chromium or chromium alloy layer takes place.
  • a method of the present invention is preferred, wherein the layer deposited in step (c) is a chromium alloy layer.
  • Preferred alloying elements are carbon and oxygen. Carbon is typically present because of organic compounds usually present in the aqueous deposition bath.
  • the chromium alloy layer does not comprise one, more than one or all elements selected from the group consisting of sulfur, nickel, copper, aluminium, tin and iron. More preferably, the only alloying elements are carbon and/or oxygen, most preferably carbon and oxygen.
  • the chromium alloy layer contains 90 weight percent chromium or more, based on the total weight of the alloy layer, more preferably 95 weight percent or more.
  • the deposition bath in step (c) has a temperature in the range from 20°C to 90°C, preferably in the range from 30°C to 70°C, more preferably in the range from 40°C to 60°C, most preferably in the range from 45°C to 60°C. If the temperature significantly exceeds 90°C, an undesired vaporization occurs, which negatively affects the concentration of the bath components (even up to the danger of precipitation). Furthermore, the formation of hexavalent chromium is significantly less suppressed. If the temperature is significantly below 20°C the deposition is insufficient.
  • a temperature of at least 40°C preferably a temperature in the range from 40°C to 90°C, more preferably in the range from 40°C to 70°C, even more preferably in the range from 40°C to 60°C.
  • a temperature of at least 45°C preferably a temperature in the range from 45°C to 90°C, more preferably in the range from 45°C to 70°C, even more preferably in the range from 45°C to 60°C.
  • the aqueous deposition bath is preferably continually agitated, preferably by stirring.
  • step (c) the chromium or chromium alloy layer is deposited with a deposition rate in the range from 0.3 ⁇ m/min to 1.2 ⁇ m/min, based on a total cathodic current density of 40 A/dm 2 .
  • the deposition rate is to be evaluated and referenced, respectively, at a total cathodic reference current density of 40 A/dm 2 .
  • the method of the present invention needs to be carried out at only 40 A/dm 2 in order to obtain a deposition rate in the above mentioned range.
  • other deposition rates need to be referenced to 40 A/dm 2 .
  • deposition rates typically result in economically acceptable deposition times in combination with the demanded quality of the chromium or chromium alloy layer.
  • the average layer thickness of the chromium or chromium alloy layer deposited in step (c) is 1.0 ⁇ m or more, preferably 2 ⁇ m or more, more preferably 4 ⁇ m or more, even more preferably 5 ⁇ m or more, most preferably the average layer thickness is in the range from 5 ⁇ m to 200 ⁇ m, preferably 5 ⁇ m to 150 ⁇ m.
  • These are typical layer thicknesses for functional chromium or chromium alloy layers. Such thicknesses are needed to provide the needed wear resistance, which is typically demanded.
  • the lower limit preferably and specifically includes 6 ⁇ m, 8 ⁇ m, 10 ⁇ m, 15 ⁇ m or 20 ⁇ m.
  • the chromium or chromium alloy layer is directly deposited onto a steel substrate.
  • each sample containing a typical amount of 10 g/L to 30 g/L trivalent chromium ions, 50 g/L to 250 g/L sulfate ions, at least one organic complexing compound, ammonium ions, and bromide ions. No boron containing compounds have been used.
  • a functional chromium layer was successively deposited on several test plating specimens (10 cm steel rods coated with a nickel layer), and only trivalent chromium ions, the at least one organic complexing compound, and a hydroxide have been replenished in intervals according to their consumption and/or drag out during the respective scenario (no further compounds have been replenished).
  • the average chromium layer thickness was at least 10 ⁇ m.
  • CCE cathodic current efficiency
  • Fig. 1 confirms that the cathodic current efficiency in scenarios B, C, and D remains comparatively constant, wherein in scenario A the cathodic current efficiency dramatically dropped to an extent that this deposition bath sample was not any more usable.
  • total anodic and cathodic current densities as defined in the method of the present invention effectively suppress anodically formed hexavalent chromium.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
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EP18714275.7A 2017-04-04 2018-04-04 Method for electrolytically depositing a chromium or chromium alloy layer on at least one substrate Active EP3607116B1 (en)

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PCT/EP2018/058591 WO2018185154A1 (en) 2017-04-04 2018-04-04 Method for electrolytically depositing a chromium or chromium alloy layer on at least one substrate

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FI129158B (en) 2019-03-15 2021-08-13 Savroc Ltd Articles comprising a chromium-based coating on a substrate
JP2023507017A (ja) 2019-12-18 2023-02-20 アトテック ドイチェランド ゲーエムベーハー ウント コ カーゲー 基材上にクロムコーティングを堆積させるための電気めっき組成物及び方法
US20220389607A1 (en) * 2019-12-18 2022-12-08 Atotech Deutschland GmbH & Co. KG Method for reducing the concentration of iron ions in a trivalent chromium eletroplating bath

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LT3607116T (lt) 2023-06-12
EP4170071A1 (en) 2023-04-26
WO2018185154A1 (en) 2018-10-11
ES2940623T3 (es) 2023-05-09
PL3607116T3 (pl) 2023-08-07
EP3607116A1 (en) 2020-02-12
CN110446802A (zh) 2019-11-12
FI3607116T3 (fi) 2023-03-30
CN115961315A (zh) 2023-04-14
CN110446802B (zh) 2023-02-28

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