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  • 专利说明
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    • 专利摘要:
    A method for electroplating antimicrobial coatings consisting of copper-silver alloys for highly and frequently bacterial contaminated surfaces in e.g. healthcare settings and food industry. The present invention describes a method for electroplating antimicrobial consisting of copper-silver alloys comprising between 50 and 65 wt% copper and correspondingly 50 to 35 wt% silver in the final deposit of a thickness up to 10 ± 0.5 μm. A highly antibacterial electroplated copper-silver (60-40) alloy coating can only be manufactured according to the method here described. Surface structure, composition and combination of solely copper and silver as metallic mixture in the final deposit are together responsible for the excellent antibacterial properties of the electroplated copper-silver alloy coating. According to the method described in the present invention, various-shaped metallic, plastic, ceramic or composite substrates can be electroplated with an antimicrobial copper-silver alloy coating.
    公开号:DK201900223A1
    申请号:DKP201900223
    申请日:2019-02-20
    公开日:2020-10-16
    发明作者:Rasmussen Jan；Ciacotich Nicole；Møller Per；Gram Lone
    申请人:Univ Danmarks Tekniske；Elplatek As Af 1995；
    IPC主号:
    专利说明:

    DK 2019 00223 A1 The present invention relates to a method for electroplating antimicrobial coatings consisting of copper-silver alloys comprising 50-65 wt.% copper and 50-35 wt.% silver in the final deposit. Antimicrobial coatings are receiving increasing interest as material solution against microbial transmission and spread in a number of applications. Among manufacturing methods, electroplating appears particularly advantageous being a consolidated technique in the coating manufacturing industry. Here, the purpose of the present invention is to provide a method for electroplating a copper-silver alloys having a copper content from 50 to 65 wt.% (and correspondingly a silver content of 50 to 35 wt..%) in the final deposited layer.
    — Obtaining copper-silver alloys in the described composition range is rather challenging with manufacturing methods other than electroplating, due to the limited solid solubility that characterizes the Ag-Cu system. By following the steps described in the present invention, this composition range in a thick (10 + 0.5 um) final deposited layer can be achieved.
    — The present invention relates to the method for manufacturing an antimicrobial electroplated copper-silver (60-40) alloy coating of proven high antibacterial efficacy. A related prior art to this invention is Ciacotich et al., An electroplated copper—silver alloy as antibacterial coating on stainless steel, Surface & Coating Technology Elsevier 2018 published by the inventors here.
    In Ciacotich et al., the antimicrobial electroplated copper-silver (60-40) alloy coating is characterized and its high antibacterial activity demonstrated. This prior art document does not disclose the description of the manufacturing method (referred as “commercially modified copper-silver bath”), which is a non-conventional electroplating process. The method described in the present invention comprises of the four steps according to claim 3 and is the only manufacturing method non disclaimed before for obtaining the highly antimicrobial copper-silver alloy coating presented in Ciacotich et al. The antimicrobial copper-silver alloy coating owes it antibacterial properties to the combination of the two metals in an alloy of the mentioned composition and the surface structure typical of an electroplated deposit. In Ciacotich at al., the antibacterial properties of the electroplated copper-silver (60-40) alloy coating have been demonstrated against S. aureus and E. coli.
    DK 2019 00223 A1 The method for producing the antimicrobial electroplated copper-silver (60-40) alloy coating and antimicrobial electroplated copper-silver alloy coatings comprising 50-65 wt.% copper and 50-35 wt.% silver according to claims 1 and 2 is provided here.
    The method comprises of four steps. a) Surface preparation (e.g. electrocleaning) b) Surface activation (e.g.
    Wood’s nickel strike, autocatalytic deposition) c) Simultaneous copper-silver alloy electroplating d) Automated brush (e.g. brass) grinding 40 a) The substrate material may be submitted to cathodic or anodic electrocleaning after the removal of organic soil and scale transferred during manufacturing processes, or a milder surface cleaning through e.g. alkaline cleaners depending on the base material. 45 b) Before the electrolytic plating, an activation step is necessary to remove residues from the electrocleaning process and surface oxide layers in order to ensure adequate adhesion in the successive step.
    Wood’s nickel process may be used if the substrate is a chromium-alloyed steel, pickling in sulfuric acid or nitric acid bright-dipping process if copper and alloys.
    In the case of non-conductive base materials, etching, 50 activation with a colloidal metal, autocatalytic deposition of copper or nickel may be performed prior to electrolytic plating. c) Simultaneous copper-silver alloy electroplating is performed in the electrolytic plating solution comprising a copper ion and silver ion containing compounds, a 55 complexing agent, a conductivity-improving additive and deionized water.
    Copper ion containing compound CuCN is selected in the composition range 0.54-0.70 M, and correspondingly the silver ion containing compound AgCN in the composition range 13-9 mM is added to achieve 50-65 wt.% metallic copper and 50-35 wt.% metallic silver in the final deposit.
    Complexing agent KCN is correspondingly added 60 in the composition range 1.78-2.31 M, as complexant for the metal ions and as surplus (free cyanide) to increase the conductivity and the diffusion overpotential of silver.
    In aqueous solution copper cyanide CuCN dissolves and forms cyanocuprate ions Cu(CN)2~, Cu(CN): , Cu(CN)4 in excess of cyanide.
    Depending on the pH of 1
    DK 2019 00223 A1 the solution some species may predominate and (1), (2), (3), (4) and (5) describe the 65 equilibrium reactions.
    CuCN=Cu" + CN- (1) CuCN + CN= Cu(CN)" (2) Cu” + 2CN" = CuUCN)" 3) CuUCN) + CN-'= Cu(CN: (4) 70 Cu(CN);2+ CN" =Cu(CN)s (5) Similarly, the formation of silver cyanide species (6), (7) is considered. Ag+ + 2CN" = Ag(CN)2~ (6) Ag(CN)” + CN" =Ag(CN): (7) The ratio between CuCN, AgCN and KCN is calculated according to the 75 cyanocuprate ions and silver cyanide complexes that are formed at pH 14 in the here described electrolytic plating solution. KCN is preferred over NaCN due to its superior conductivity. KOH is the only introduced additive in order to increase the bath conductivity, no other plating additive (e.g. levelling agents or brighteners) are required.
    80 The simultaneous copper-silver electroplating is conducted with a current density of 4-8 A/dm for 2 minutes at 50-70 °C. It is essential that no electrolyte agitation is performed during plating in order to get the desired composition in the deposit, due to the different mechanisms of deposition of the two metals (current- and diffusion- controlled).
    85 Silver or stainless steel anodes may be used, and the composition of the electrolytic plating solution may be monitored and periodically filtered to remove possible presence of impurities.
    As an example, the antimicrobial electroplated copper-silver (60-40) alloy coating is obtained with an electrolytic plating solution consisting of 0.65 M CuCN, 0.01 M 90 AgCN, 2.15 M KCN, 0.69 M KOH in deionized water. Simultaneous electroplating is 2
    DK 2019 00223 A1 conducted using silver anodes with a current density of 6 A/dm for 2 minutes at 60 °C.
    Alternatively, the simultaneous electrodeposition of copper and silver can also be carried out using a pyrophosphate-based electrolytic process.
    The composition of the 95 pyrophosphate-based plating bath is 0.5-1.5 M Cu2P207, 12-35 mM AgsO7P2, 1.8-5.4 M K4P207, 0.9-2.3 M K2HPO4, 0.2-0.7 M KNO: in deionized water.
    Concentrated solutions of copper and silver complexes may be prepared separately in excess of potassium pyrophosphate.
    Concentrated NHs is used to control the pH between 7-8 and the temperature of the plating bath may be 20-40 °C.
    A current 100 density of 1-4 A/dm is applied.
    Electroplating may be performed using constant current, pulse and pulse-reverse plating.
    As an example, an antimicrobial electroplated copper-silver alloy coating with a composition of 65 wt.% copper and 35 wt.% silver is obtained with 0.7 M Cu2P207, 18 mM Ag407P2, 2.7 M K4P207 1.2 M K2HPO4, 0.4 M KNOs3 in deionized water. 105 Simultaneous electroplating is conducted using silver anodes with a current density of 2 A/dm for 10 minutes at 32 °C. d) After the electrolytic plating, the item is submitted to automatic brush grinding using e.g. brass or nylon brushes in order to confer it superior finishing and allow 110 subsequent plating without any other step than regular rising.
    Approx. one cycle is sufficient to get the desired finishing, and the item can be directly recoated in the copper-silver electrolytic bath.
    This process may be repeated four times in order to get a thick final electroplated deposit. 115 A scheme of the automated electroplating production line for the process described in this invention is reported in fig. 1. In fig 1. the plating tanks for surface preparation, activation, simultaneous copper-silver electroplating as described above are alternated with water tanks for rinsing.
    At the end of the automated electroplating production line for the process described in this 3
    DK 2019 00223 A1 120 invention, grinding brushes are mounted inside the assigned tank. Rack plating is assumed in the presented setup. According to claim 4, A final electroplated deposit of a thickness ranging from 2 to 10 +
    0.5 um depending on the number of repeated steps c) and d) according to claim 1 and 3.
    125 — According to claim 3, after step d) of the processing method the electroplated deposit has a thickness of 2+ 0.5 um. If steps c) and d) are repeated four times the thickness of the final electroplated deposit is 10+0.5 um. According to claim 5, the present invention relates to a method for manufacturing antimicrobial surfaces on a various-shaped metallic, plastic, ceramic or composite 130 substrates to be applied on highly and frequently bacterial contaminated surfaces such as furniture items, instruments or part of, equipment or part of in e.g. healthcare settings and food industry. According to claim 1, 2 and 3, various-shaped metallic, plastic, ceramic or composite base materials can be the substrates for the electroplated antimicrobial copper-silver 135 alloys coatings consisting of 50-65 wt.% copper and 50-35 wt.% silver. In the case of non-conductive base materials, surface preparation and autocatalytic deposition of copper or nickel may be performed prior to electrolytic plating. The electroplated antimicrobial copper-silver alloys coatings obtained according to the method described in claim 3 contain only metallic copper and silver, and there is no 140 — presence of nickel in the deposit, well-known responsible for allergic contact dermatitis. This is a high-priority requirement in the case of antimicrobial applications that foresee contact with skin. The electroplated antimicrobial copper-silver alloys coatings obtained according to the method described in the present invention are characterized by a pleasant warm ruddy silver color, therefore meeting also potential high demand on 145 aesthetic requirements as well as visual appearance. The electroplated antimicrobial copper-silver alloys coatings are thus suitable to be applied on highly and frequently bacterial contaminated furniture items, instruments or parts thereof, equipment or parts thereof in e.g. healthcare settings and food industry.
    4
    DK 2019 00223 A1 According to claim 2, the antimicrobial copper-silver alloy coatings obtained according 150 tothe method described in the present invention are homogeneous metallic mixtures of 50-65 wt.% copper and respectively 50-35 wt.% silver with a characteristic surface morphology and finishing. Composition and surface characteristics are unitedly responsible for the high antibacterial activity of the antimicrobial copper-silver (60-40) alloy coating as demonstrated previously in Ciacotich et al.
    155 — The antimicrobial copper-silver alloy coatings obtained according to the method described in the present invention can be subjected to routine cleaning procedures and sterilization, although not strictly necessary.
    The lifetime of the antimicrobial copper-silver alloy coatings obtained according to the method described in the present invention may be adjusted depending on the desired 160 thickness and the intended application.
    The same item may be multiply recoated and re-installed in the light of a regenerative design approach. Alternatively, exhausted copper-silver alloy coatings may be stripped by using persulfate-based chemistry, and copper and silver oxide particles may be recovered and reclaimed by filtering or electrolytic methods.
    165 — According to claim 5, the antimicrobial copper-silver alloy coatings obtained according to the method described in the present invention may be applied on instruments and equipment including but not limited to parts thereof in e.g. food industry that are difficult (if not impossible) to clean efficiently due to design demands.
    According to claim 5, the antimicrobial copper-silver alloy coatings obtained according 170 tothe method described in the present invention may be applied to e.g. basic hospital equipment and furniture, including but not limited to life support equipment, bed rails, tables, doorknobs and handles, and medical devices and accessories such as stethoscopes, IV drip tubes, syringes, etc.
    175
    权利要求:
    Claims (5)
    [1] 1. The present invention relates to a method for electroplating antimicrobial coatings consisting of copper-silver alloys comprising 50-65 wt% copper and 50-35 wt% silver in the final deposit.
    [2] 2. The present invention relates to the method for manufacturing an antimicrobial electroplated copper-silver (60-40) alloy coating of proven high antibacterial efficacy.
    [3] 3. The method for producing antimicrobial coatings according to claim 1, comprising the steps of: a) Surface preparation b) Surface activation c) Simultaneous copper-silver alloy electroplating d) Brush grinding wherein the copper-silver electrolytic plating solution comprises a copper ion and silver ion containing compounds, a complexing agent and a conductivity- improving additive, and the electroplating is conducted with a current density of 4-8 A/dm without electrolyte agitation.
    [4] 4. A final electroplated copper-silver alloy deposit of a thickness ranging from 2 to 10 + 0.5 um depending on the number of repeated steps c) and d) according to claim 1 and 3.
    [5] 5. The present invention relates to a method for manufacturing antimicrobial surfaces on a various-shaped metallic, plastic, ceramic or composite substrates to be applied on highly and frequently bacterial contaminated surfaces such as furniture items, instruments or part of, equipments or part of in e.g. healthcare settings and food industry.
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    同族专利:
    公开号 | 公开日
    DK180529B1|2021-06-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2020-10-16| PAT| Application published|Effective date: 20200821 |
    2021-06-10| PME| Patent granted|Effective date: 20210610 |
    优先权:
    申请号 | 申请日 | 专利标题
    DKPA201900223A|DK180529B1|2019-02-20|2019-02-20|A method for electroplating antimicrobial coatings consisting of copper-silver alloys for highly and frequently bacterial contaminated surfaces in healthcare settings and food industry.|DKPA201900223A| DK180529B1|2019-02-20|2019-02-20|A method for electroplating antimicrobial coatings consisting of copper-silver alloys for highly and frequently bacterial contaminated surfaces in healthcare settings and food industry.|
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