WO2019111071A1 - Bain électrolytique pour l'obtention de revêtements composites métalliques antibactériens de laiton-particules métalliques antibactériennes (zn-cu/pma's)) - Google Patents

Bain électrolytique pour l'obtention de revêtements composites métalliques antibactériens de laiton-particules métalliques antibactériennes (zn-cu/pma's)) Download PDF

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Publication number
WO2019111071A1
WO2019111071A1 PCT/IB2018/058118 IB2018058118W WO2019111071A1 WO 2019111071 A1 WO2019111071 A1 WO 2019111071A1 IB 2018058118 W IB2018058118 W IB 2018058118W WO 2019111071 A1 WO2019111071 A1 WO 2019111071A1
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Prior art keywords
copper
agnp
antibacterial
electrolytic bath
coatings
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PCT/IB2018/058118
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English (en)
Spanish (es)
Inventor
Gabriel TREJO CÓRDOVA
Claudia RÍOS ÁLVAREZ
MarÍa Yolanda REYES VIDAL
Yunny MEAS VONG
José de Jesús PÉREZ BUENO
Mónica Lizbeth RAZO NEGRETE
Montserrat SILVA ICHANTE
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Centro De Investigacion Y Desarrollo Tecnologico En Electroquimica S.C.
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Publication of WO2019111071A1 publication Critical patent/WO2019111071A1/fr

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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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • 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
    • C25D3/26—Electroplating: Baths therefor from solutions of cadmium
    • C25D3/28—Electroplating: Baths therefor from solutions of cadmium from cyanide baths
    • 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
    • C25D3/46—Electroplating: Baths therefor from solutions of silver
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys

Definitions

  • the present invention relates to Zinc (Zn) - Copper (Cu) alloy coatings, also known as Brass, which contain occluded and homogeneously dispersed antibacterial metal agents throughout the coating, more specifically with the composition of an electrolyte bath to obtain a antibacterial metallic coating of Zinc-Copper-Silver nanoparticles (Zn-Cu / AgNP's).
  • Zinc-Copper-Silver nanoparticles Zinc-Copper-Silver nanoparticles
  • Electrodeposited metal coatings include: decorative coatings for bathroom accessories, kitchen accessories, handles, jewelry, musical instruments such as saxophones and trombones, coins, all kinds of fittings such as hinges and door handles, among others, in addition to other highly glossy; with the particularity that the Zinc-Copper / Silver Nanoparticles (Zn-Cu / AgNP's) coatings developed, provide antibacterial protection, unlike conventional Zinc-Copper coatings.
  • the main objective of the present invention is to provide a non-cyanide and glycine-based alkaline electrolytic bath, which makes it possible to obtain Zn-Cu / AgNP's metal composites coatings by electrodeposition, whose Silver nanoparticles (AgNP's) are occluded and dispersed homogeneously throughout the coating thickness.
  • the second objective of the present invention is to provide Zinc-Copper / Silver Nanoparticle composite coatings (Zn-Cu / AgNP's) that prevent and inhibit the growth and / or eliminate bacteria of both types: Gram-negative such as Escherichia coli and Gram-positive as Staphybcoccus aureus, at least 90% on its surface.
  • Zn-Cu / AgNP's Zinc-Copper / Silver Nanoparticle composite coatings
  • bacteria and viruses are the main cause of the spread of infectious diseases from one person to another.
  • CONACYT Information Agency students from the University Center of Mexico carried out a study in which they cultivated samples taken from the Metro in Mexico City and observed the presence of staphylococci (bacteria that cause skin infections), Escherichia (the genus E. coli, whose symptomatology is varied, is present in the intestines); Salmonella (associated with diarrheal diseases) and enterobacteria (associated with respiratory, urinary and wound infections in immunocompromised people), among other bacteria.
  • staphylococci bacteria that cause skin infections
  • Escherichia the genus E. coli, whose symptomatology is varied, is present in the intestines
  • Salmonella associated with diarrheal diseases
  • enterobacteria associated with respiratory, urinary and wound infections in immunocompromised people
  • the aforementioned structures are generally made of a base metal, for example of steel, with some metallic coating, such as Chromium (Cr), Nickel (Ni), Zinc (Zn) or Zinc-Copper alloy (Zn-Cu).
  • Zn coatings or their alloys such as Zinc-Copper alloy or also known as brass, are the most used to protect steel surfaces, since they are more resistant to environmental corrosion than the substrate itself. steel. They also provide brightness, as well as different shades of color to the substrate, greatly improving its aesthetic appearance.
  • AgP's are used in numerous physical, biological and pharmaceutical applications, for example: in the manufacture of sportswear, washing machines, food packaging material, and importantly, in the medical field as bactericidal and therapeutic agents.
  • AgP's are also used in the manufacture of dental devices, such as bactericidal coatings in water filters and as antibacterial agents in the air, aerosols disinfectants, pillows, respirators, socks, wet wipes, detergents, soaps, shampoos, toothpastes and many other consumer products.
  • the glycine-based electrodeposition process without cyanides was used to form Zn-Cu metal composite coatings containing ocluid silver nanoparticles (AgNP's) as an antibacterial agent, dispersed homogeneously throughout the thickness of the coating.
  • the antibacterial agent in this case silver nanoparticles ( AgNP's)
  • AgNP's silver nanoparticles
  • the Zn-Cu / AgNP's metallic composite coating obtained by the electrodeposition process satisfies the high aesthetic standards required for decorative finishes including, but not limited to; shine and adhesion.
  • Gram-negative such as Escherichia coli and Gram-positive as Staphybcoccus aureus, at least 90% on its surface.
  • antibacterial agents can be added to the surface of different metals such as, for example: stainless steel sheets, chromium coatings or Zinc coatings, using the thermal spray technique, as described in patent documents W02010069104A1, US2012 / 0225312A1 and WO2012122666A1 respectively.
  • the thermal spraying process has the main disadvantage of its high cost, in addition to that some characteristics of the metal, such as gloss and adhesion, are altered by the formed antimicrobial film.
  • Thermosetting resin compositions containing antimicrobial agents have also been developed to be used as coating materials for various metals, such as: iron, aluminum, copper and stainless steel, as described in WO2013052683A2, WO2012158702A2, W02003043745A1 and W02013033802A1.
  • these resin compositions include particulate materials, such as zeolites and oxides which may be unwanted materials on the surface of the articles, for example, decorative or functional articles, which have high aesthetic requirements.
  • Another process for forming antibacterial coatings is electrodeposition, as described in patent document W02009120784A2 wherein the use of electrodeposition is specified to manufacture antibacterial coatings formed by organic antibacterial agents dispersed on the surface of the coating. Also, in patent documents EP2438216A1 and EP2522377A1, use the electrodeposition process to form amorphous coatings of Cobalt (Co) with antibacterial properties.
  • Co Cobalt
  • Antibacterial metals are those that inhibit the growth of bacteria or kill them and that are preferably biocompatible.
  • Preferred biocompatible antibacterial metals include: Silver (Ag), Gold (Au), Copper (Cu), Platinum (Au), Palladium (Pd) and Iridium (Ir) (noble metals).
  • the antibacterial properties of silver nanoparticles are combined with the protective and decorative ability of Zn-Cu coatings to form Zn-Cu / AgNP's composite coatings, where the silver nanoparticles are occluded in the matrix of zinc-copper metal alloy coating, without losing its antibacterial properties, thus forming part of the coating instead of a surface film; In this way, decorative metallic antibacterial coatings are formed.
  • the combination of the antibacterial properties of silver particles (AgNP's) with the protective and decorative capacity of the Zn-Cu coatings, allows the possibility of a number of new applications for Zn-Cu / AgNP's composites, for example, in the biomedical field, in food processing, among others.
  • an electrolytic bath for electrodeposite r a metallic composition Nickel-Phosphorus-antibacterial metal nanoparticles (Ni-P- MANP ' s), comprising salts such as sulfamates of the N 2+ ion to be deposited, a pH buffering agent, a phosphorus containing acid and furthermore containing nanoparticles of an antibacterial metal (MANP ' s).
  • Ni-P- MANP ' s Nickel-Phosphorus-antibacterial metal nanoparticles
  • an acid electrolytic bath for electrodepositing a Zinc-nanoparticle metal composites antibacterial (Zn-MANP ' s), comprising salts such as Zn2 + ion chlorides to deposit, a pH buffer, an acid that contains Boron, surfactants and also contains nanoparticles of an antibacterial metal (MANP ' s).
  • Zn-MANP ' s Zinc-nanoparticle metal composites antibacterial
  • the problem that is solved by the present invention refers to achieve the homogeneous dispersion of antibacterial silver metal nanoparticles in alkaline copper-zinc electrolytic baths without glycine-based cyanides, in such a way that coatings are obtained that meet the aesthetic and functional standards of brass coatings.
  • the present invention consists of an alkaline electrolytic bath without cyanides and glycine-based, to electrodeposite a Zinc-Copper-antibacterial Silver nanoparticles (Zn-Cu / AgNP's) metal composition, comprising salts such as Zn2 + ion chlorides and Cu2 + ion deposit, a buffering agent, also contains silver nanoparticles (AgNP's), with an average size between 10 and 100 nanometers (nm), the occlusion of the AgNP's in the metal matrix of the coating gives antibacterial properties to the metallic composite coating.
  • Zn-Cu / AgNP's Zinc-Copper-antibacterial Silver nanoparticles
  • It also contains a cationic type surfactant that keeps the AgNP's stable in the suspension, In addition, it transfers a positive surface charge to the AgNP's, which facilitates its occlusion in the metal matrix of the composite during the electrodeposition of the metal ion.
  • the composite coatings obtained from the electrolytic bath have the capacity to prevent, inhibit and / or eliminate bacteria of both types: Gram-negative such as Escherichia co / i and Gram-positive as Staphylococcus aureus, at least 90% on its surface.
  • the present invention consists of an electrolytic bath that allows to obtain by electrodeposition metallic composite coatings of Zn-Cu / AgNP's, was developed on the basis of the following considerations: the salts of the metal ions to be deposited that can be chlorides, have the function of provide the Zn2 + and Cu2 + ions. Likewise, the occlusion of the Silver nanoparticles (AgNP's) in the metal matrix of the coating provides antibacterial characteristics.
  • CTAB Hexadecyltrimethylammonium bromide
  • Composite coatings obtained from the electrolytic bath have a content between 10.0 and 60.0 mg / cm3 of AgNP's in the metallic matrix, a Zinc content between 0.5 and 2.0 g / cm3 and a Copper content between 8.0 and 12.0 g / cm3 , depending on the electrodeposition conditions.
  • the Zn-Cu / AgNP's coatings inhibit the growth of the bacterium Escherichia coii between 40 and 100% and for the bacterium Staphylococcus aureus, between 50.0 and 95.0% depending on the contact time between the bacteria and the surface of the Zn-Cu coating with Silver nanoparticles (AgNP's), as well as the concentration of AgNP's in the Zn-Cu coating.
  • AgNP's Silver nanoparticles
  • an electrolytic bath containing:
  • Zn2 + ions in a concentration between 50 and 300 g / L, with 82 g / L being the preferred concentration.
  • the Zn2 + ions are added to the electrolytic solution from a soluble salt of Zinc Chloride (ZnCl2) that is commercially available.
  • Cu2 + ions in a concentration between 5 and 50 g / L, with 17 g / L being the preferred concentration.
  • the Cu2 + ions are added to the electrolytic solution from a soluble salt of Copper Chloride dihydrate (CuCI2-2H20) which is commercially available.
  • Glycine which acts as a complexing agent, is found in concentrations of 50 to 500 g / L, with the preferred concentration being 300 g / L.
  • the final pH is adjusted to 10.0, preferably using potassium hydroxide.
  • the electrolytic bath is controlled at a temperature between 21 and 35 ° C; obtaining particularly satisfactory results at 25 ° C.
  • An inorganic antibacterial agent non-toxic and biocompatible with the environment during all the time of use. The antibacterial agent used does not affect the aesthetic finish of the electrodeposited metal coating.
  • antibacterial agents contemplated for use in the formulation of the present invention include antibacterial metals such as: Silver or Copper particles, with size between 10 and 100 nanometers, at a concentration in the solution between 0.1 and 10 g / L; where the most suitable concentration depends on the current density applied for the formation of the coating.
  • antibacterial metals such as: Silver or Copper particles, with size between 10 and 100 nanometers, at a concentration in the solution between 0.1 and 10 g / L; where the most suitable concentration depends on the current density applied for the formation of the coating.
  • the occlusion in the metallic matrix of the antibacterial agent nanoparticles gives the coating the antibacterial characteristic.
  • Silver or Copper particles are commercially available.
  • a cationic surfactant agent whose main function is to form a stable suspension with the particles of the antibacterial metal; in addition, being a cationic surfactant, it confers a positive charge on the particles, which facilitates that these particles are attracted electrostatically to the cathode surface during the electrodeposition process, and favors the occlusion of the particles in the metallic matrix, producing homogeneous coatings in composition.
  • the surfactant agent used does not affect the aesthetic finish of the electrodeposited metal composite coating.
  • the surfactant agent considered is of cationic type: Hexadecyltrimethylammonium bromide (CTAB for its acronym in English). The concentration is between 0.04 and 10.0 g / L, with 4 g / L being the preferred concentration.
  • the chemical effect was achieved that allows to stabilize the suspension of silver particles in the electrolytic bath, in order to obtain soft, glossy composites, homogeneous chemical composition, and antibacterial activity.
  • the electrolytic bath can be operated in a range of current densities from 0.01 to 0.07 A / cm2.
  • the optimum current density for the operation of the bath depends on the concentration used of AgNP's.
  • the duration of the electrodeposition may vary depending on the composition of the bath, the current density used and the desired thickness of the coating.
  • the metal substrate to be coated can be cathodically electrified using a power source and graphite anodes.
  • the bath and method of the present invention is characterized by its versatility, stability, simple control and is particularly adaptable for the production of antibacterial metal composites (Zn-Cu / AgNP's) in hanging, regardless of the geometry of the parts to be coated.
  • Example 1 For the purpose of illustrating in the present invention the composition of the electrolytic bath for electrodepositing Zn-Cu / AgNP's metal composites, the following examples are shown. The examples are proposed to illustrate the method and are not the limiting conditions of the invention. Example 1.
  • the pH of the electrolyte is adjusted to 10 using a 5% by volume solution of Potassium Hydroxide (KOH).
  • the electrolytic suspension was controlled at a temperature of 25 ° C; A plate of AISI 1018 steel was used as cathode and a graphite plate as an anode.
  • the coatings obtained were adherent and glossy.
  • concentration of silver in the coatings was determined using the analysis technique known as inductively coupled plasma spectroscopy "ICP" (Inductively Coupled Plasma) and the results obtained are shown in Table 2.
  • microbiological analysis was carried out in accordance with the international standard JIS Z 2801 / ISO
  • Table 2 shows the results obtained in Colony Forming Units (CFU mL-1) for Staphylococcus aureus Escherichia coli.
  • the present invention proposes the composition of an electrolytic bath using the electrodeposition process can be applied on electrified metal substrates to obtain a composite metal coating Zn-Cu / AgNP's homogeneous composition throughout the thickness of the coating and with capacity to prevent or inhibit the growth and / or eliminate bacteria of both types: Gram-negative such as Escherichia coli and Gram-positive as Staphybcoccus aureus, at least 90% on its surface.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

La présente invention concerne l'utilisation d'un bain électrolytique pour déposer par électrolyse des revêtements composites métalliques de zinc-cuivre-nanoparticules de métaux à pouvoir antibactérien, qui empêche la croissance de bactéries telles qu'Escherichia coli et Staphylococcus aureus, au moins sur 90% de leur surface. Le procédé de formulation d'un bain électrolytique permettant d'obtenir des revêtements antibactériens comprend les étapes consistant à : a) à ajouter, des naniparticules d'argent à pouvoir antibactérien en suspension dans un tensioactif cationique, dans un bain électrolytique à base de glycine et contenant des sels de Zn2+ dissous, des sels de Cu2+ dissous, b) à réaliser l'électrodéposition du revêtement composite métallique zinc-cuivre/nanoparticules d'argent. L'occlusion de nanoparticules de métaux à pouvoir antibactérien dans la matrice du revêtement lui confère des caractéristiques antibactériennes.
PCT/IB2018/058118 2017-12-04 2018-10-18 Bain électrolytique pour l'obtention de revêtements composites métalliques antibactériens de laiton-particules métalliques antibactériennes (zn-cu/pma's)) WO2019111071A1 (fr)

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MXMX/A/2017/015645 2017-12-04
MX2017015645A MX2017015645A (es) 2017-12-04 2017-12-04 Baño electrolitico para obtener recubrimientos compositos metalicos antibacteriales de laton-particulas metalicas antibacteriales (zn-cu/pma´s).

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6251249B1 (en) * 1996-09-20 2001-06-26 Atofina Chemicals, Inc. Precious metal deposition composition and process
MX2015005364A (es) * 2015-04-23 2016-10-24 Centro De Investigación Y Desarrollo Tecnológico En Electroquímica S C Baño electrolítico para obtener recubrimientos compositos metálicos antibacteriales zinc-partículas metálicas antibacteriales (zn/pma).

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6251249B1 (en) * 1996-09-20 2001-06-26 Atofina Chemicals, Inc. Precious metal deposition composition and process
MX2015005364A (es) * 2015-04-23 2016-10-24 Centro De Investigación Y Desarrollo Tecnológico En Electroquímica S C Baño electrolítico para obtener recubrimientos compositos metálicos antibacteriales zinc-partículas metálicas antibacteriales (zn/pma).

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Title
BALLESTEROS, J. ET AL.: "Desarrollo de un proceso libre de cianuros para la electrodeposici6n de peliculas de cobre-zinc con aplicaciones en la production de hidr6geno y lat6n comercial", CIENCIA UANL, November 2015 (2015-11-01), XP055616952, Retrieved from the Internet <URL:http://cienciauanl.uanl.mx/?p=5144> [retrieved on 20190204] *
BALLESTEROS, J. ET AL.: "Study of the electrochemical co-reducction of Cu2 + and Zn2+ ions from alkaline no cianured solution containing glycine", JOURNAL OF ELECTROANALYTICAL CHEMISTRY, vol. 727, 2014, pages 104 - 112, XP029008393 *
BALLESTEROS, J.: "Desarrollo de un bano alcalino libre de cianuros para el electrodepósito de latón a base de glicina", TESIS PARA OBTENER EL GRADE DE DOCTOR EN ELECTROQUIMICA, May 2011 (2011-05-01), XP055616955, Retrieved from the Internet <URL:https://cideteq.repositorioinstitucional.mx/jspui/bitstream/1021/94/1/Desarrollo%20de%20un%20ba%C3%B1o%20alcalino%20libre%20de%20cianuros%20para%20el%20%20electrodep%C3%B3sitode%20lat%C3%B3n%20a%20base%20de%20glicina..pdf> [retrieved on 20190204] *
RASHWAN, S.: "Electrodeposition of Zn-Cu coatings from alkaline sulphate bath containing glycine", TRANSACTIONS OF THE IMF, vol. 85, no. 4, 2007, pages 217 - 224, XP001507672, doi:10.1179/174591907X216440 *
REYES-VIDAL, Y. ET AL.: "Electrodeposition, characterization, and antibacterial activity of zinc/silver particle composite coating s", CIENCIA DE LA SUPERFICIE APLICADA, vol. 342, 1 July 2015 (2015-07-01), pages 34 - 41, XP055323901, Retrieved from the Internet <URL:https://doi.org/10.1016/j.apsusc.2015.03.037> doi:10.1016/j.apsusc.2015.03.037 *

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