EP3106544A2 - Procédé de placage au chrome trivalent en continu - Google Patents

Procédé de placage au chrome trivalent en continu Download PDF

Info

Publication number
EP3106544A2
EP3106544A2 EP15748593.9A EP15748593A EP3106544A2 EP 3106544 A2 EP3106544 A2 EP 3106544A2 EP 15748593 A EP15748593 A EP 15748593A EP 3106544 A2 EP3106544 A2 EP 3106544A2
Authority
EP
European Patent Office
Prior art keywords
bath
ions
trivalent
chromium
chromate plating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15748593.9A
Other languages
German (de)
English (en)
Other versions
EP3106544A4 (fr
Inventor
Carlos Enrique MUÑOZ GARCIA
Sara Elisa MUÑOZ CASTAÑO
David MUÑOZ CASTAÑO
Marcela MUÑOZ CASTAÑO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP3106544A2 publication Critical patent/EP3106544A2/fr
Publication of EP3106544A4 publication Critical patent/EP3106544A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • 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

  • This invention belongs to the field of chemistry and metallurgy and it is specifically related to a process for the electrolytic and electrophoretic production of electrochemical coatings with a bath from trivalent decorative chromium solutions on a metal or plastic substrate with trivalent chromium ions, sulfate ions, graphite anodes, hexavalent chromium control and false cathode purifications in a continuous industrial operation.
  • Chromium is a very important metal for a large range of industry applications. Over more than 70 years chromate plating decorative and functional process of has been carried out with electrolytes from chromium acid, process with a high content of the Cr+6 ion, considered by the WHO as a carcinogen for operators and personnel entering in contact with companies where it is used which is manifested in ulcers in the nasal septum. Hexavalent chromium has a strong impact in water environment.
  • Electrochemical coatings of trivalent chromium has been stigmatized throughout the time due to their cost and the process color and stability; these has caused that its implementations is not that popular in large sites or small workshops.
  • Trivalent chromate plating baths have been developed from two technologies: sulfate and chloride.
  • Trivalent chromium baths from chloride ions have some disadvantages: a darker color, more sensitivity to metal contaminants and chlorine detachments in the anodes causing safety and occupational health risks, besides of equipment corrosion.
  • Trivalent chromium baths from sulfate ions are more noble, are whiter, close more to the chromate plating from hexavalent ions, are more tolerant to metal and organic contaminants, they do not produce detachment of noxious gases and do not cause safety and occupational health risks.
  • Trivalent chromate plating baths from chloride ions work preferably with graphite anode. Anode is produced by the formation of chlorine gas, there is no oxygen production, which causes the formation of Cr+6.
  • the bath composition may include additives from Br- and HCOO- ions which prevent the evolution of Cr+3 to Cr+6.
  • the trivalent chromate plating process from chloride ions mainly uses graphite anodes
  • the trivalent chromate plating from sulfate ions also uses graphite anodes.
  • Patent 1602404 used a tank with two compartments, in one compartment a Pb anode is immersed in a H2SO4 anolyte, which is separated by a permeable membrane, and in the other compartment is a solution with Cr+3 ions that has no contact with the anode and as consequence no oxidation of the Cr+3 to Cr+6 is produced.
  • the disadvantage of this two-compartmental systems is the cost and efficiency in a continuous industrial process.
  • Patent US3706639 describes a process for preparing a trivalent chromate plating bath from Cr+6 compounds by using inorganic reducers and platinized graphite and titanium anodes. Besides bath preparations from chromium products are expensive, they do not address the management and evolution of the contaminant Cr+6 during the bath work.
  • Patent US 5560815 defines the development of trivalent chromate plating baths from SO 4 -2 ions, describing the use of anodes coated with iridium and tantalum oxide with the characteristic of a potential lower than the oxygen and as consequence it inhibits the evolution of the Cr+3 to Cr+6.
  • This type of anodes after a work time in continuous industrial productions, have proven to make easier the formation of Cr+6 in the bath, due to the exhausting of the iridium oxide layer, causing the restriction of the current pass in the anode and defects related to the Cr+6 contaminant.
  • patent EP0088192 defines a trivalent chromate plating bath different from the chloride ions, it refers to the use of graphite anodes in the trivalent chromate plating processes from sulfate ions and how the release of oxygen in this kind of anodes causes surface erosion and carbon particles release that accumulates in the chromium producing coating defects.
  • Patent WO2010051118 refers to the use of manganese ions as additive to inhibit the formation of Cr+6 and increase the shelf-life of insoluble anodes used in the chromate plating process from trivalent and sulfate ions, including lead, lead alloy, platinized titanium anodes or metal anodes that consist of the coating of surface with iridium oxide, ruthenium oxide or mixed iridium/tantalum oxide. Although the shelf-life of this type of anodes increases, they will eventually collapse. In a continuous industrial production 24/6/360, it is difficult to determine the time when they exhaust and the Cr+6 production starts. On the other hand, concentration of Mn ion bath has to be closely controlled due to the risk of an excess that may cause a deposit with chromium changing the coating color and affecting the corrosion resistance.
  • Patent US5413646 HEAT-TREATABLE CHROMIUM refers to a bath that is part of a hexavalent chromium and an alloy of iridium to reduce it to trivalent chromium through methanol, ammonium formate and sodium sulfate as catalyzer, where the reaction is made from the contaminant hexavalent chromium that reacts in the process with platinum and graphite anodes in order to obtain functional non-uniform chromium.
  • the new invention comes from trivalent chromium, it does not use sodium sulfate as catalyzer but sodium sulfate as a result of the reaction of a crystallization sub process.
  • Iron or alloys can not be used in the new process since iron is a bath contaminant that leaves black veins in the finishing and increases the possibility of corrosion in the final finishing. Likewise, it does not need any temperature changes and the trivalent chromium batch may be applied on plastic or metal for decorative finishing.
  • the present invention solves the contamination problem when hexavalent chromium is generated in a low-cost efficient process, proposing a continuous industrial process and corrosion-resistant product with uniform finishing and non contaminant from a bath with trivalent chromium ions, sulfate ions and graphite anodes in a combination appropriate for a continuous industrial operation.
  • this invention the difficulties of the previous state-of-the-art are overpassed, such as wear and final collapse of titanium electrodes covered with noble metals, the control and purification of contaminants affecting the process have been eliminated generating a continuous rejuvenation of process, reducing risks, costs and allowing replicating the novelty without technological difficulties.
  • the invention proposes a chromate plating process from Cr+3, having SO 4 ⁇ 2 ions and preferably using graphite anodes, obtaining a chromium coating with strong adherence to substate, with mechanical, physical and chemical properties reproducible in continuous industrial productions.
  • the specifications of products of color, thickness and resistance to corrosion and wearing maintains his stability in time and to temperature changes.
  • composition of the bath has proven stability in 24 hours continuous productions with the application of appropriate controls and maintenance.
  • the bath has been noble to changes of temperature, pH, components concentration and tolerant to different contaminants.
  • the process of this invention mainly uses graphite anodes that have qualities such as good conducer of electricity, mechanized facility to be adapted to different conformations, good chemical and mechanic resistance, good resistant to anodic corrosion and high relation of surface-volume providing a very good anodic area, they are cost-effective compared to titanium electrodes coated with noble metals.
  • the use of graphite anodes is not limited and also lead and stainless steel anodes are used. With the use of graphite anodes in trivalent chromate plating solutions with SO 4 ⁇ 2 ions, a better anode-cathode relation can be used as well as better current density without affecting the electrodes, compared to titanium electrodes coated with noble metal which tend to crack when subjected to high current densities.
  • graphite anodes must not have pores, since they cause penetration of the bath solution and an electrical reactions when releasing oxygen that cause an early erosion leaving too much carbon residues.
  • Graphite anode must be put in acid-resistant fabric bags as those used in the nickel plating process to avoid the pass of anode eroded particles to the solution.
  • the continuous filtration is used at a speed of 4 times to 8 times and preferably from 4 times to 6 times the bath volume per hour. This secures that carbon particles in the batch are controlled and protects the coating quality.
  • the bath relationship of anode/cathode must be 3:1 and preferable a relation of 2:1, a greater relation and a greater direct current improve the process efficiency, producing a best cathode coating area.
  • the density of current applied must be between 4dm2 to 12 A/dm2 and preferable between 5 A/dm2 to 8 A/dm2.
  • the bath prepared for the use with graphite anodes contains Cr+3 ions, the Cr+3 ions concentration in the bath is between 10g/l to 30 g/l, preferably between 15-g/l to 25 g/l.
  • the Cr 2 ( SO 4 ) 3 salt is used as the Cr+3 source.
  • the bath prepared contains organic and organic chromium complexes that are stable, forming bonds that allow the Cr+3 ion and its reduction to Cr0 in the cathode surface forming a metal sheet with mechanic, physical and chemical properties with strong adherence to the substrate and reproducible in continuous industrial production.
  • Chromium complexes of this preparation also have properties allowing an easier degradation when residual waters treatment is made, with which a reduction of the environmental impacts is assured.
  • the presence of H3BO3 in an electrolytic solution between 40-g/l to 60 g/l, preferably between 45g/l to 50 g/l increases conductivity and acts as a buffer agent and also as an inhibitor of the anode decreasing the attack and detachment of the graphite anode by the presence of B-ions which reduce the 02 overproduction.
  • the Na 2 SO 4 salt is addes as a conducer, between 30 g/l to 60 g/l, preferable between 40 g/l to 50 g/l. In the present invention this salt is added only to form the bath since during the process it produces and increases its concentration due to the different reactions of oxide-reduction.
  • the bath of the present invention also includes salts containing Na+, K+ and NH 4 + ions.
  • the chromium complex discomposes by action of the electrical current and deposits Cr0 on the cathode and releases SO 4 ⁇ 2 anion which combines with sodium ions present in the solution forming Na 2 SO 4 . Also during the mechanism of reduction from Cr+6 to Cr+3, an increase of acidity is produced by the formation of H 2 SO 4 , the control of acidity is made with NaOH, Na 2 CO 3 , neutralizing the solution with formation of Na 2 SO 4 . In this type of bath using graphite anodes, it always tends to become acid.
  • pH must be controlled between 3,4 of pH to 4,0. High pH values favor the formation of oxygen and promotes the attack of graphite anode.
  • the bath superficial tension must be between 30 dynes to 70 dynes. Adjustment is made by adding moistening agents such as octyl alcohol.
  • Process temperature must be between 40°C to 60°C, preferably between 45°C to 50°C. Due to the constant reduction from Cr+6 to Cr+3, bath is concentrating from Na 2 SO 4 , and a reduction of temperature may cause the crystallization of this salt.
  • the process of the present invention does not require purification with selective resins allowing a reduction of contaminants produced in the regeneration and a reduction of costs.
  • the use of sequestering agents as EDTA for metal purification is not recommendable in this process because if produce side effects as progressive accumulation by making strong organometallic complexes that affect coating quality and causes problems in the effluent treatment.
  • Addition of reducers is made controlling the consumption of amperes-hour and maintaining the Cr+6 between 0ppm to 40 ppm, preferably between 0ppm 20 ppm, rank in which there is no side effect in the coating quality.
  • Results have been obtained with the bath of the present invention from Cr+3 and SO 4 ⁇ 2 ions by using graphite anodes, in Hull Cell the penetrations were between 80 % to 92 % even after five trials with the same solution and photometric analysis in presence of diphenylcarbazide with results of Cr+6 between 20ppm to 30ppm, concentration that did not affect coating quality, color was white to almost the hexavalent chromium color without dark veins formation.
  • the thickness of coating obtained in decorative coatings from Cr+3, is between 0,3 ⁇ m to 2 ⁇ m, very similar to those obtained with the process of traditional Cr+6.
  • the invention is a novelty preparation of a trivalent chromium bath from SO 4 ⁇ 2 ions offering the advantage to preferably work with graphite anodes and we have solved the control of Cr+6 generation and control and elimination of the different contaminants, obtaining a chromium coating with strong adherence to the substrate with excellent mechanical, physical and chemical properties, commercially reproducible in continuous industrial productions. Product specifications of color, thickness, resistance to corrosion and wearing have been stable throughout the time.

Landscapes

  • 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)
EP15748593.9A 2014-02-11 2015-02-09 Procédé de placage au chrome trivalent en continu Withdrawn EP3106544A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CO14028206A CO7190036A1 (es) 2014-02-11 2014-02-11 Proceso de cromado trivalente continuo
PCT/IB2015/050974 WO2015121790A2 (fr) 2014-02-11 2015-02-09 Procédé de placage au chrome trivalent en continu

Publications (2)

Publication Number Publication Date
EP3106544A2 true EP3106544A2 (fr) 2016-12-21
EP3106544A4 EP3106544A4 (fr) 2017-08-09

Family

ID=53191871

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15748593.9A Withdrawn EP3106544A4 (fr) 2014-02-11 2015-02-09 Procédé de placage au chrome trivalent en continu

Country Status (8)

Country Link
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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018185154A1 (fr) 2017-04-04 2018-10-11 Atotech Deutschland Gmbh Procédé de dépôt électrolytique d'une couche de chrome ou d'alliage de chrome sur au moins un substrat
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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT520829B1 (de) * 2018-10-19 2019-08-15 Andritz Ag Maschf Verfahren zum Verchromen von Metallbändern
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
CN120006288A (zh) * 2025-02-13 2025-05-16 东莞煜森精密端子有限公司 一种提高连接器端子硬度的电镀镀铬工艺

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2112691A (en) * 1936-01-30 1938-03-29 Pyrene Mfg Co Electroplating anode unit
NL75772C (fr) * 1948-03-20
US3111464A (en) * 1961-09-29 1963-11-19 Battelle Development Corp Electrodeposition of chromium and chromium alloys
US3729392A (en) * 1971-02-19 1973-04-24 Du Pont Plating of titanium with chromium
US4167460A (en) * 1978-04-03 1979-09-11 Oxy Metal Industries Corporation Trivalent chromium plating bath composition and process
US4439285A (en) * 1980-11-10 1984-03-27 Omi International Corporation Trivalent chromium electrolyte and process employing neodymium reducing agent
US4392922A (en) * 1980-11-10 1983-07-12 Occidental Chemical Corporation Trivalent chromium electrolyte and process employing vanadium reducing agent
CA1244376A (fr) * 1983-05-12 1988-11-08 Thaddeus W. Tomaszewski Electrolyte de chrome trivalent et mode d'utilisation
US7052592B2 (en) * 2004-06-24 2006-05-30 Gueguine Yedigarian Chromium plating method
US20080169199A1 (en) * 2007-01-17 2008-07-17 Chang Gung University Trivalent chromium electroplating solution and an electroplating process with the solution
JP2009074168A (ja) * 2007-08-30 2009-04-09 Nissan Motor Co Ltd クロムめっき部品およびその製造方法
CN201172698Y (zh) * 2008-02-18 2008-12-31 佛山市昭信金属制品有限公司 一种硫酸型三价铬镀液防治金属离子杂质污染装置
US7780840B2 (en) * 2008-10-30 2010-08-24 Trevor Pearson Process for plating chromium from a trivalent chromium plating bath
CN101665960A (zh) * 2009-09-04 2010-03-10 厦门大学 一种硫酸盐三价铬电镀液与制备方法
JP5732721B2 (ja) * 2010-01-08 2015-06-10 上村工業株式会社 クロムめっき方法
CN102443825B (zh) * 2011-12-07 2014-03-26 湖北振华化学股份有限公司 一种高浓度硫酸铬——氟化铵三价铬电镀液及其制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018185154A1 (fr) 2017-04-04 2018-10-11 Atotech Deutschland Gmbh Procédé de dépôt électrolytique d'une couche de chrome ou d'alliage de chrome sur au moins un substrat
EP4170071A1 (fr) 2017-04-04 2023-04-26 Atotech Deutschland GmbH & Co. KG Procédé de dépôt électrolytique d'une couche de chrome ou d'alliage de chrome sur au moins un substrat
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

Also Published As

Publication number Publication date
WO2015121790A3 (fr) 2016-01-21
MX2016010449A (es) 2017-06-19
US20170167040A1 (en) 2017-06-15
WO2015121790A2 (fr) 2015-08-20
RU2016135556A3 (fr) 2018-10-29
CO7190036A1 (es) 2015-02-19
CN106164340A (zh) 2016-11-23
BR112016018584A2 (pt) 2019-08-20
EP3106544A4 (fr) 2017-08-09
RU2016135556A (ru) 2018-03-15

Similar Documents

Publication Publication Date Title
EP3106544A2 (fr) Procédé de placage au chrome trivalent en continu
Smart et al. A novel trivalent chromium electroplating bath
US20010054557A1 (en) Electroplating of metals using pulsed reverse current for control of hydrogen evolution
KR100650961B1 (ko) 무질산 용액을 사용한 전해 산세척 방법
EP3253906B1 (fr) Électrolyte pour placage électrolytique
JP4419905B2 (ja) 電解リン酸塩化成処理方法
WO2011111391A1 (fr) Procédé de passivation d'un acier inoxydable
TWI457472B (zh) 從鉻電極電解溶解鉻
Carrillo-Abad et al. pH effect on zinc recovery from the spent pickling baths of hot dip galvanizing industries
CN102719876A (zh) 一种镀镍溶液的净化处理方法
US7833404B2 (en) Electrolytic phosphate chemical treatment method
US4127450A (en) Method for pretreating surfaces of steel parts for electroplating with organic or inorganic coatings
US5628893A (en) Halogen tin composition and electrolytic plating process
US2241585A (en) Process for removing metallic coatings from metallic parts
JP5822235B2 (ja) 酸化態窒素の除去方法
DE1931123B2 (de) Verfahren zum entfernen von cyaniden aus cyanidhaltigen waessrigen alkalischen elektrolyten durch elektrolytische oxydation des cyanids
JP5908372B2 (ja) 電気分解用電極
JP7279993B2 (ja) 酸化態窒素の処理方法
Zakiyya et al. Potentiodynamic study of the effects of nickel on the electrodeposition of zinc from chloride media
JPH0461079B2 (fr)
JP5218742B2 (ja) ３価クロムめっき浴の金属不純物除去方法
KR20140017323A (ko) 내식성 향상을 위한 오스테나이트계 스테인리스 냉연강판의 고속 산세 프로세스
JPH0437160B2 (fr)
PL224014B1 (pl) Sposób regeneracji kąpieli trawiącej w procesie usuwania powłoki miedzi z podłoża stalowego
JPH028795B2 (fr)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160912

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20170711

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 21/12 20060101ALI20170704BHEP

Ipc: C25D 21/18 20060101ALI20170704BHEP

Ipc: C25D 3/06 20060101AFI20170704BHEP

Ipc: C25D 21/14 20060101ALI20170704BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20190903