WO2015121790A2 - Procédé de placage au chrome trivalent en continu - Google Patents

Procédé de placage au chrome trivalent en continu Download PDF

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Publication number
WO2015121790A2
WO2015121790A2 PCT/IB2015/050974 IB2015050974W WO2015121790A2 WO 2015121790 A2 WO2015121790 A2 WO 2015121790A2 IB 2015050974 W IB2015050974 W IB 2015050974W WO 2015121790 A2 WO2015121790 A2 WO 2015121790A2
Authority
WO
WIPO (PCT)
Prior art keywords
bath
trivalent chromium
ions
trivalent
plating process
Prior art date
Application number
PCT/IB2015/050974
Other languages
English (en)
Spanish (es)
Other versions
WO2015121790A3 (fr
Inventor
Carlos Enrique MUÑOZ GARCIA
Sara Elisa MUÑOZ CASTAÑO
David MUÑOZ CASTAÑO
Marcela MUÑOZ CASTAÑO
Original Assignee
Muñoz Garcia Carlos Enrique
Muñoz Castaño Sara Elisa
Muñoz Castaño David
Muñoz Castaño Marcela
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 Muñoz Garcia Carlos Enrique, Muñoz Castaño Sara Elisa, Muñoz Castaño David, Muñoz Castaño Marcela filed Critical Muñoz Garcia Carlos Enrique
Priority to MX2016010449A priority Critical patent/MX2016010449A/es
Priority to RU2016135556A priority patent/RU2016135556A/ru
Priority to EP15748593.9A priority patent/EP3106544A4/fr
Priority to BR112016018584A priority patent/BR112016018584A2/pt
Priority to US15/118,460 priority patent/US20170167040A1/en
Priority to CN201580019366.6A priority patent/CN106164340A/zh
Publication of WO2015121790A2 publication Critical patent/WO2015121790A2/fr
Publication of WO2015121790A3 publication Critical patent/WO2015121790A3/fr

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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
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • 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
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • 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
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes

Definitions

  • the present invention belongs to the field of chemistry and metallurgy and is specifically related to a process for the electrolytic or electrophoretic production of electrochemical coatings with a bath from solutions of decorative trivalent chromium on a metallic or plastic substrate with trivalent chromium ions, sulfate ions, graphite anodes, hexavanlent chromium control and with false cathode purification in a continuous industrial operation.
  • Chromium is a metal of great importance for a wide variety of industrial applications.
  • the decorative and functional chrome plating process has been carried out with electrolytes from chromic acid, a process with high Cr + 6 ion contents, considered by the WHO, as a carcinogen for operators and personnel who come into contact with the companies where it is implemented, it forms ulcers in the nasal septum.
  • Hexavalent chromium causes a high environmental impact in aquifers.
  • the companies that have chromium plating from hexavalent chromium coexist with the quality problems associated with this type of processes, such as the low penetration power that leaves yellow in areas such as holes or angles, burning or milking in areas of High current density, stains or streaks.
  • the processes with the greatest potential for applicability are those of trivalent chromium (Cr + 3) that have been developing and increasingly occupying the attention of industrialists.
  • Trivalent chromium electrochemical coatings have been stigmatized over time, due to the cost, color and stability of the process; This has caused that its implementation is not very popular in large plants or in small workshops.
  • Trivalent chromium plating baths have been developed from two technologies: sulfate and chloride. Trivalent chromium baths from chloride ions have some disadvantages: the color is darker, they are more sensitive to metal contamination, there is chlorine release in the anodes causing occupational health and safety risks, in addition to corrosion to the equipment .
  • the trivalent chromium baths from sulfate ions are more noble, have a whiter color, very close to the color of the chromium from hexavalent ions, have greater tolerance to metallic and organic pollutants, do not produce detachments of harmful gases and they do not cause occupational health and safety risks.
  • Trivalent chromium plating baths from chloride ions work preferably with graphite anode. In the anode, chlorine gas formation occurs, there is no oxygen production, which causes Cr + 6 to not form.
  • the bath composition may include additives based on Br- and HCOO- ions that prevent the evolution of Cr + 3 to Cr + 6.
  • the trivalent chromium process from chloride ions mainly uses graphite anodes;
  • the trivalent chromate process based on sulfate ions also uses graphite anodes.
  • US3706639 discloses a process for the preparation of a trivalent chromium plating bath from compounds containing Cr + 6 using inorganic reducers, using graphite anodes and platinized titanium. In addition to the fact that the preparation of the bath from chromic products is very expensive, it does not treat the handling and evolution of Cr + 6 contaminate during the work of the bath.
  • US 5560815 defines the development of trivalent chromium plating baths from S0 4 "2 ions, referring to the use of anodes coated with iridium and tantalum oxide with characteristics of having a lower potential than oxygen and consequently inhibiting evolution from Cr + 3 to Cr + 6.
  • This type of anodes has shown that after a time of work in continuous industrial productions, it facilitates the formation of Cr + 6 in the bathroom, due to depletion of the iridium oxide layer, causing also restriction of the passage of the current in the anode and the defects associated with the Cr + 6 pollutant.
  • the EP0088192 patent defines a trivalent chromium bath from chloride ions, it refers to the use of graphite anodes in trivalent chromium processes from sulfate ions and how the release of oxygen in this type of anodes causes erosion of the surface and release of carbon particles that co-deposit with chromium causing defects in the coating.
  • WO2010051 1 18 refers to the use of manganese ions as an additive to inhibit the formation of Cr + 6 and increase the shelf life of insoluble anodes that are used in the chrome plating process from trivalent ions and sulfate, including lead, lead alloy, platinum titanium anodes, or metal anodes comprising surface coating with iridium oxide, ruthenium oxide or mixed iridium / tantalum oxide.
  • insoluble anodes including lead, lead alloy, platinum titanium anodes, or metal anodes comprising surface coating with iridium oxide, ruthenium oxide or mixed iridium / tantalum oxide.
  • the new invention based on trivalent chromium, does not use a sodium sultate as a catalyst, but the sodium sultate is a result of the reaction that is removed in a crystallization subprocess, iron or alloys cannot be involved in the new process because iron it is a contaminate in the bathroom that leaves black streaks in the finish and increases the possibility of corrision in the final finish; In addition it does not require changes of temaperatura and the trivalent chrome bath part can be applied to plastics or metals for decorative finishing.
  • the present invention solves the problem of contamination when hexavalent chromium is generated in an efficient and low-cost process, proposing a continuous indsutrial process and product obtained resistant to corrision, with uniform and non-contaminating finish from a bath with chromium ions trivalent, sulfate ions and gafite anodes in their own combination for continuous industrial operation.
  • difficulties of the prior art are overcome, such as the exhaustion and final collapse of the titanium electrodes coated with noble metals, the control and purification of the contaminants that affect the process has been simplified, generating a constant rejuvenation of the process, reducing risks, costs and allowing the novelty to be replicated without technological difficulties.
  • the invention proposes a chromium plating process from Cr + 3, which contains S0 4 "2 ions and preferably uses graphite anodes, obtaining a chromium coating with strong adhesion to the substrate, with mechanical, physical and chemical properties, reproducible in productions. industrial continuous
  • the product specifications in terms of color, thickness and resistance to corrosion and wear maintain its stability over time and changes in ambient temperature.
  • the composition of the bath has demonstrated stability in continuous productions 24 hours a day with the application of the appropriate controls and maintenance.
  • the bath has been noble to changes in temperature, pH, concentration of components and tolerant of different contaminants.
  • the process of the present invention mainly uses graphite anodes that have qualities such as being a good conductor of electricity, ease of machining to adapt to different conformations, good chemical and mechanical resistance, good resistance to anodic corrosion and a high surface to surface ratio. Volume providing a very good anodic area, they have a low cost compared to titanium electrodes coated with noble metals.
  • the use of graphite anodes is not limited and lead anodes and stainless steel are also used.
  • the process begins with a preparation of the trivalent chromium solution with graphite anodes so that the bath starts working.
  • hexavalent chromium is produced above the pollutant limit, so hexavalent chromium reducers are added to the bath as explained below.
  • the reducers convert the excess of hexavalent chromium into trivalent chromium, releasing sodium sulfate that must be removed from the bath, and to crystallize it, a crystallization stage is performed by cooling the bath.
  • the graphite anodes should not present pores, since these cause the bath solution to penetrate and in the electrochemical reaction when oxygen is released, they erode prematurely leaving too much carbon residue.
  • the graphite anode should be placed in acid-resistant cloth bags, such as those used in the nickel plating process to prevent the passage to the solution of eroded particles of the anode.
  • acid-resistant cloth bags such as those used in the nickel plating process to prevent the passage to the solution of eroded particles of the anode.
  • continuous filtration at a speed of 4 times to 8 times and preferably 4 times to 6 times the volume of the bath per hour is used. This ensures that the carbon particles in the bath are controlled and do not harm the quality of the coating.
  • the ratio in the anode / cathode bath should be 3: 1 and preferably a ratio of 2: 1, a higher ratio and a higher direct current improve the efficiency of the process, achieving a greater cathodic area of coating.
  • the applied current density should be between 4dm2 at 12 A / dm2 and preferably between 5 A / dm2 at 8 A / dm2.
  • the bath prepared for use with graphite anodes contains Cr + 3 ions, the concentration of Cr + 3 ions in the bath is between 10g / I at 30 g / l, preferably between 15-g / la 25 g / l .
  • a salt of Cr 2 ⁇ SO) z is used as the source of Cr + 3 ions.
  • the prepared bath contains chromium complexes of organic and inorganic type that are stable, forming bonds that allow the release of the Cr + 3 ion and its reduction to CrO on the cathode surface to form a metal film with mechanical, physical and chemical properties of strong adhesion to the substrate and reproducible in continuous industrial productions.
  • the chromium complexes of this preparation also have properties that allow them to be easily degraded when the sewage treatment is carried out, which guarantees a reduction of environmental impacts.
  • the organic acid salts HCOONa I HCOONH 4 I NaCH 3 COO I NH3CH3COO have been used as a source of products that form complexes with trivalent chromium; lactate ions C 3 H 5 0 ⁇ 3 , Oxalate ions (COO) 2 ⁇ 2 , malate C 4 H 6 ⁇ 3 ⁇ 4, glycine NH 2 CH 2 COOH. These types of compounds are used individually or a mixture of these, with C + 3 to form complexes.
  • the concentration should be between 50/1 to 150 g / l, preferably between 70g / l to 120 g / l.
  • H3B03 in an electrolytic solution, between 40-g / 60 g / l, preferably between 45g / 50 g / l increases conductivity and acts as a buffering agent and also as an anode inhibitor reducing the attack and the collapse of the graphite anode by the presence of B- ions that reduce the overproduction of 02.
  • Na 2 S0 4 is added as conductive salt, between 30 g / l to 60 g / l, preferably between 40 g / l to 50 g / l.
  • this salt is added only for the formation of the bath since during the process it is being produced and increasing its concentration, due to the effect of the different oxide-reduction reactions.
  • the bath of the present invention also includes salts containing Na +, K + and (NH) 4 + ions.
  • the chromium complex decomposes by action of the electric current and deposits CrO on the cathode and releases the anion S0 4 '2 that is combined with the sodium ions that are present in solution forming Na 2 S0 4 . Also during the mechanism of reduction of Cr + 6 to Cr + 3, there is an increase in acidity by formation of H 2 S0 4 , acidity control is carried out with NaOH, Na 2 C0 3 , neutralizing the solution with formation of Na 2 S0 4 . In this type of bath using graphite anodes, there is always a tendency to become acidic.
  • the pH should be controlled between 3.4 pH to 4.0 pH. High pH values favor the formation of oxygen and promote the attack of the graphite anode.
  • the surface tension of the bath should be handled between 30 dynes to 70 dynes.
  • the adjustment is made with the addition of wetting agents such as octyl alcohol.
  • the process temperature should be between 40 ° C to 60 ° C, preferably between 45 ° C to 50 ° C. Due to the constant reduction of Cr + 6 to Cr + 3, the bath is concentrated from Na 2 S0 4 , and a temperature reduction can cause crystallization of this salt.
  • the addition of the reducers is carried out in a controlled way by consumption of amp hours, trying to keep Cr + 6 between Oppm at 40 ppm, preferably between Oppm 20 ppm, a range in which there is no adverse effect on the quality of the coating.
  • Reduction compounds for Cr + 6 are well known in the art.
  • S0 3 '2 anions mainly NaHS0 3 , Na 2 S 2 0 5 , A / a 2 S (3 ⁇ 4, ⁇ NH) 4 HS0 3 , Na 2 S 2 0 4 , and optionally sulfur compounds derived from S 2 Q ⁇ '2 , or a mixture of the above.
  • S 2 Q ⁇ '2 sulfur compounds derived from S 2 Q ⁇ '2
  • results obtained at industrial level in continuous productions demonstrate the degree of development of the present process, several hundreds of thousands of dm2 of products for export and local use, show the stability and quality of the process.
  • Results have been obtained with the bath of the present invention from Cr + 3 ions and S0 4 '2 using graphite anodes, Hull Cell penetration between 80% to 92% even after five trials with the same solution and
  • the photometric analysis in the presence of diphenylcarbazide gave Cr + 6 results between 20ppm at 30ppm, a concentration that did not affect the quality of the coating, the color was very close white to the color of the hexavalent chromium and without dark streaks.
  • the thickness of the coating obtained in decorative coatings of Cr + 3 is between 0.3 ⁇ to 2 ⁇ , very similar to those obtained with the traditional Cr + 6 process.
  • the inventors have managed to replicate the results in a continuous commercial production with a bath of 1 .500 liters of trivalent chromium plating provided by the present invention with S0 4 "2 ions working preferably with graphite anodes, controlling the production of Cr + 6 with reducers mentioned above, applying crystallization to maintain the content of Na 2 S0 4 within the working ranges without discarding the bath in whole or part of the bath since it can be infinitely reused when controlling the production of hexavalent chromium in the process.
  • the invention is a novel preparation of bath trivalent chromium from S0 4 '2 ions which offers the advantage of preferably working with graphite anodes and have provided solutions to control the generation of Cr + 6 and the control and elimination of different pollutants, obtaining a chromium coating of strong adhesion to the substrate with excellent mechanical, physical and chemical properties, commercially reproducible in continuous industrial productions.
  • the specifications of the product in terms of color, thickness and resistance to corrosion and wear have been stable over time.

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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)
  • Automation & Control Theory (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

La présente invention appartient au domaine de la chimie et de la métallurgie et est reliée spécifiquement à un procédé de production électrolytique ou électrophorétique de revêtements électrochimiques avec un bain, à partir de solutions de chrome trivalent décoratif sur un substrat métallique ou plastique avec des ions de chrome trivalent, des ions sulfate, des anodes en graphite, avec un contrôle du chrome hexavalent et la purification de fausse cathode dans une opération industrielle en continu.
PCT/IB2015/050974 2014-02-11 2015-02-09 Procédé de placage au chrome trivalent en continu WO2015121790A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
MX2016010449A MX2016010449A (es) 2014-02-11 2015-02-09 Proceso de cromado trivalente continuo.
RU2016135556A RU2016135556A (ru) 2014-02-11 2015-02-09 Способ непрерывного нанесения покрытия из трехвалентного хрома
EP15748593.9A EP3106544A4 (fr) 2014-02-11 2015-02-09 Procédé de placage au chrome trivalent en continu
BR112016018584A BR112016018584A2 (pt) 2014-02-11 2015-02-09 processo de banho continuo de cromo trivalente
US15/118,460 US20170167040A1 (en) 2014-02-11 2015-02-09 Continuous trivalent chromium plating method
CN201580019366.6A CN106164340A (zh) 2014-02-11 2015-02-09 三价铬酸盐电镀的连续方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CO14-28206 2014-02-11
CO14028206A CO7190036A1 (es) 2014-02-11 2014-02-11 Proceso de cromado trivalente continuo

Publications (2)

Publication Number Publication Date
WO2015121790A2 true WO2015121790A2 (fr) 2015-08-20
WO2015121790A3 WO2015121790A3 (fr) 2016-01-21

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PCT/IB2015/050974 WO2015121790A2 (fr) 2014-02-11 2015-02-09 Procédé de placage au chrome trivalent en continu

Country Status (8)

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US (1) US20170167040A1 (fr)
EP (1) EP3106544A4 (fr)
CN (1) CN106164340A (fr)
BR (1) BR112016018584A2 (fr)
CO (1) CO7190036A1 (fr)
MX (1) MX2016010449A (fr)
RU (1) RU2016135556A (fr)
WO (1) WO2015121790A2 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3607116B1 (fr) 2017-04-04 2022-12-21 Atotech Deutschland GmbH & Co. KG Procédé de dépôt électrolytique d'une couche de chrome ou d'alliage de chrome sur au moins un substrat
AT520829B1 (de) * 2018-10-19 2019-08-15 Andritz Ag Maschf Verfahren zum Verchromen von Metallbändern
WO2020189802A1 (fr) * 2019-03-15 2020-09-24 유한회사 한국신기술 Antioxydan, comprenant un composite à groupe cyano-carboxyle exempt de constituant soufré, pour empêcher l'oxydation d'ions chrome trivalents en ions chrome divalents, et solution d'électrodéposition de chrome trivalent le comprenant
CN110760900A (zh) * 2019-11-29 2020-02-07 扬州大学 一种六价铬废水还原作电镀铬源的方法及其电镀方法
RU2734986C1 (ru) * 2020-03-23 2020-10-27 Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д. И. Менделеева" (РХТУ им. Д. И. Менделеева) Способ электрохимического нанесения хромовых покрытий из саморегулирующегося электролита на основе соединений трехвалентного хрома
CN113774438A (zh) * 2021-08-24 2021-12-10 上原汽车铭牌（惠州）有限公司 汽车标识生产用三价铬电镀液配方及三价铬电镀工艺

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Also Published As

Publication number Publication date
EP3106544A4 (fr) 2017-08-09
MX2016010449A (es) 2017-06-19
CN106164340A (zh) 2016-11-23
BR112016018584A2 (pt) 2019-08-20
RU2016135556A (ru) 2018-03-15
EP3106544A2 (fr) 2016-12-21
CO7190036A1 (es) 2015-02-19
US20170167040A1 (en) 2017-06-15
RU2016135556A3 (fr) 2018-10-29
WO2015121790A3 (fr) 2016-01-21

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