EP3129543A1 - Carbonfasern mit modifizierter oberfläche sowie verfahren zur modifizierung einer carbonfaseroberfläche und verwendung der carbonfaser - Google Patents
Carbonfasern mit modifizierter oberfläche sowie verfahren zur modifizierung einer carbonfaseroberfläche und verwendung der carbonfaserInfo
- Publication number
- EP3129543A1 EP3129543A1 EP15726919.2A EP15726919A EP3129543A1 EP 3129543 A1 EP3129543 A1 EP 3129543A1 EP 15726919 A EP15726919 A EP 15726919A EP 3129543 A1 EP3129543 A1 EP 3129543A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon fiber
- coating
- siloxane
- plasma
- carbon
- 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- Withdrawn
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Definitions
- the invention relates to carbon fibers, in particular those used for carbon fiber composite plastics (CFKs).
- CFRKs carbon fiber composite plastics
- the surface of the carbon fibers in particular plays a decisive role, because the connection of the carbon fiber to the matrix and thus the stability of the fiber-reinforced material is decisively influenced by the molecular conditions of the carbon fiber surface.
- Carbon fiber to the matrix resin is still too weak even after treatment with sizing.
- the fiber-reinforced composite plastics thereby lose the required stiffness and strength.
- the known thin size is often used in preforming processes, as well as in braiding and guiding on deflection rollers rubbed off the fiber. Not a good adhesion of the matrix material to the carbon fiber will then take place during incorporation into the matrix at these locations because the graphite ⁇ similar surface that is non-polar and no "anchor points" such as the hydroxide formed by anodic oxidation and / or oxidation marks there, the treated carbon fiber, meets the matrix material
- Carbon fiber composite plastic overall, because the matrix resin adheres poorly in places of low polarity.
- the invention is a devisflä ⁇ chenmod e carbon fiber having a siloxane Umman- telung.
- the invention relates to a process for the surface modification of a carbon fiber, in which a carbon fiber with a siloxane-containing sheath is produced via a plasma coating.
- siloxane-containing coating here is a thin, to 500 ⁇ maximum ⁇ thick coating of SiO x referred to, which is amorphous, ie glassy.
- surface-modified carbon fiber refers to a carboxylic ⁇ fiber whose original graphite Similar upper ⁇ surface modified by a method, that is to implementation-with a coating material is activated.
- the modification is carried out by anodic oxidation, whereas according to the invention, the modification is carried out by plasma.
- the surface of a carbon fiber before the loading is preferably modified coating, advantageously fourth acti ⁇ plasma.
- the carbon fibers are not, or not only anodized after their production, but in a plasma at ⁇ play as activated in an atmospheric plasma.
- the plasma is wholly or partly generated with silane-containing precursors and thereby coated the carbon fiber with a glassy layer.
- AD plasma atmospheric pressure or normal pressure plasma
- Activation unlike an activated plasma coating, lasts only a few hours and does not increase the density of polar groups on the surface of the surface
- Carbon fiber This can be demonstrated by measuring the wetting ability of Owens, Wendt, Rabel and Kälble.
- the contact angle of 61 ° for the poorly wettable untreated carbon fiber surface decreases to less than 10 ° for the plasma activated carbon fiber surfaces.
- the water droplet spreads comparatively quickly and wets the surface.
- the activation of the carbon fiber surface and the coating are carried out in a single plasma treatment, in particular when the precursors for the plasma coating are activated with air.
- the surface of the carbon fiber is charged, ionized and / or radicals are formed.
- the ionized plasma gases combine with surface atoms.
- the following molecular groups are formed:
- the new surface molecules react with each other to form an amorphous siloxane layer.
- the siloxane layer can be controlled by the speed of the nozzle or by changing the process parameters such as precursor quantity, plasma power, nozzle geometry, etc.
- the layer thicknesses produced are in the nanometer range, are therefore thinner than lym, in particular they are below 500 nm, for example in the range of 10 to 300 nm, in particular 20 to 200 nm and preferably in the range of 50 to 150 nm.
- the siloxane layer formed by plasma adheres very well to the carbon fiber surface.
- An adjoining epoxy coating leads to a better adhesion of the epoxy coating on the siloxane layer than on the conventional anodically oxidized carbon fiber surface.
- amorphous SiO x layer with similar siloxane precursors eg HMDSO, TEOS, VTMS.
- ge ⁇ Switzerland is according to this method on the carbon fiber surface, an amorphous SiO x - layer, the harder, that is, for example, accelerated processing conditions in the carbon fiber-processing
- oxygen is present on the surface in functional groups such as -C-OR and -COOR
- the oxygen content at the surface increases to more than 30% through the plasma coating, preferably by using material mixtures containing more than 50%, by using highly TEOS-containing material mixtures. at.
- the concentration of acid ⁇ material in the near-surface layer of approximately 5 nm is detected by XPS photoelectron spectroscopy.
- the significantly increased concentration of polar groups leads to increased wetting and adhesion of the size, a thermoplastic matrix and / or a resin matrix.
- the invention proposes for the first time a thin but hard plasma coating with amorphous, ie vitreous, siloxane on a carbon fiber. This gives the carbon fiber a surface that can be worked like a glass fiber surface.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102014212241.4A DE102014212241A1 (de) | 2014-06-25 | 2014-06-25 | Carbonfasern mit modifizierter Oberfläche sowie Verfahren zur Modifizierung einer Carbonfaseroberfläche und Verwendung der Carbonfaser |
PCT/EP2015/061743 WO2015197299A1 (de) | 2014-06-25 | 2015-05-27 | Carbonfasern mit modifizierter oberfläche sowie verfahren zur modifizierung einer carbonfaseroberfläche und verwendung der carbonfaser |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3129543A1 true EP3129543A1 (de) | 2017-02-15 |
Family
ID=53284230
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15726919.2A Withdrawn EP3129543A1 (de) | 2014-06-25 | 2015-05-27 | Carbonfasern mit modifizierter oberfläche sowie verfahren zur modifizierung einer carbonfaseroberfläche und verwendung der carbonfaser |
Country Status (5)
Country | Link |
---|---|
US (1) | US20170130393A1 (de) |
EP (1) | EP3129543A1 (de) |
JP (1) | JP2017524835A (de) |
DE (1) | DE102014212241A1 (de) |
WO (1) | WO2015197299A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107936273A (zh) * | 2017-11-29 | 2018-04-20 | 西华大学 | 一种碳纤维增强树脂基的高性能轻量化复合材料及其制备方法 |
DE102018113587B8 (de) | 2018-06-07 | 2024-02-29 | Reinhard Koch | Faserprofile zum Einsatz als Bewehrung in Betonbauten für hohe brandschutztechnische Anforderungen und Verfahren zu ihrer Herstellung |
CN113338027A (zh) * | 2021-05-12 | 2021-09-03 | 北京化工大学 | 一种碳纤维的表面处理方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5599624A (en) * | 1995-07-03 | 1997-02-04 | General Electric Company | Amorphous silicon oxycarbide coated silicon carbide or carbon fibers |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1320908A (en) * | 1969-08-26 | 1973-06-20 | English Electric Co Ltd | Coated carbon fibres |
JPS59106572A (ja) * | 1982-12-06 | 1984-06-20 | 信越化学工業株式会社 | 炭素繊維の表面処理方法 |
DE3706218A1 (de) * | 1987-02-26 | 1988-09-08 | Werner Prof Dr Weisweiler | Vorrichtung und verfahren zur kontinuierlichen beschichtung der einzelnen fasern eines faserbuendels mit oberflaechenschuetzenden und haftvermittelnden carbid- oder plasmapolymer-filmen |
US4961971A (en) * | 1988-12-19 | 1990-10-09 | United Technologies Corporation | Method of making oxidatively stable water soluble amorphous hydrated metal oxide sized fibers |
JPH06173118A (ja) * | 1992-12-02 | 1994-06-21 | Osaka Gas Co Ltd | 酸化珪素により被覆された炭素繊維の製造方法 |
US5358747A (en) * | 1992-12-28 | 1994-10-25 | Aluminum Company Of America | Siloxane coating process for carbon or graphite substrates |
DK0833850T3 (da) * | 1995-06-22 | 2000-09-11 | Jasha Jacob I Kleiman | Overflademodifikation af polymerer og carbonbaserede materialer |
JPH1171146A (ja) * | 1997-06-16 | 1999-03-16 | Dai Ichi Kogyo Seiyaku Co Ltd | コンクリート用起泡剤 |
FR2801908B1 (fr) * | 1999-12-06 | 2002-03-01 | Snecma | Procede pour l'obtention de tissu en fibres de carbone par carbonisation en continu d'un tissu en fibres cellulosiques |
JP4261956B2 (ja) * | 2003-03-31 | 2009-05-13 | ニチアス株式会社 | 導電性樹脂および導電性樹脂用組成物、およびそれらの製造方法 |
US8227051B1 (en) * | 2004-06-24 | 2012-07-24 | UT-Battle, LLC | Apparatus and method for carbon fiber surface treatment |
JP5166689B2 (ja) * | 2005-10-17 | 2013-03-21 | 昭和電工株式会社 | シリカ被覆炭素繊維の製造方法 |
JP2007254906A (ja) * | 2006-03-22 | 2007-10-04 | Shinshu Univ | シリカ被覆炭素繊維およびその製造方法 |
US8951632B2 (en) * | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
GB2467366A (en) * | 2009-02-03 | 2010-08-04 | Rolls Royce Plc | Fibre-reinforced Composite Materials with Glass Coated Carbon Fibres |
US20100224129A1 (en) * | 2009-03-03 | 2010-09-09 | Lockheed Martin Corporation | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
DE102012214784B4 (de) * | 2012-08-20 | 2015-07-23 | Schunk Kohlenstofftechnik Gmbh | Anlage zur chemischen Gasphasenabscheidung mit Kohlenstofffaser-Filamenten sowie Verfahren zur Herstellung der Kohlenstofffaser-Filamente |
-
2014
- 2014-06-25 DE DE102014212241.4A patent/DE102014212241A1/de not_active Withdrawn
-
2015
- 2015-05-27 WO PCT/EP2015/061743 patent/WO2015197299A1/de active Application Filing
- 2015-05-27 JP JP2016575228A patent/JP2017524835A/ja active Pending
- 2015-05-27 EP EP15726919.2A patent/EP3129543A1/de not_active Withdrawn
- 2015-05-27 US US15/321,937 patent/US20170130393A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5599624A (en) * | 1995-07-03 | 1997-02-04 | General Electric Company | Amorphous silicon oxycarbide coated silicon carbide or carbon fibers |
Also Published As
Publication number | Publication date |
---|---|
DE102014212241A1 (de) | 2015-12-31 |
JP2017524835A (ja) | 2017-08-31 |
US20170130393A1 (en) | 2017-05-11 |
WO2015197299A1 (de) | 2015-12-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE3908418C2 (de) | Verfahren zum Innenbeschichten von Kunststoff-Behältern und Vorrichtung zum Beschichten | |
DE102013219331B3 (de) | Plasmapolymerer Festkörper, insbesondere plasmapolymere Schicht, sowie deren Verwendung | |
WO2015197299A1 (de) | Carbonfasern mit modifizierter oberfläche sowie verfahren zur modifizierung einer carbonfaseroberfläche und verwendung der carbonfaser | |
WO2014068041A1 (de) | Schichtstruktur auf polymerbasis mit oleophob-hydrophober oberfläche sowie elektrische maschine mit einer solchen | |
EP2279280A2 (de) | Verfahren zum beschichten eines faserverbundbauteils für ein luft- oder raumfahrzeug und durch ein derartiges verfahren hergestelltes faserverbundbauteil | |
EP1674255A1 (de) | Textile Verbunde aus Fluorpolymeren | |
DE102007010071A1 (de) | Schichtverbund umfassend eine Lack- und eine Trennschicht sowie Lack-Träger-Anordnung zur Übertragung von Lack | |
DE19543133C2 (de) | Verfahren zur Erzeugung stark hydrophober Polymerschichten mittels Plasmapolymerisation | |
DE102013226215A1 (de) | Verfahren zur Hydrophobierung und/oder Oleophobierung eines Werkstoffs sowie hydrophobiertes und/oder oleophobiertes Bauteil | |
EP0412242A1 (de) | Optische Faser | |
EP3200931B1 (de) | Verbund aus substrat, plasmapolymerer schicht, mischschicht und deckschicht | |
EP2742513B1 (de) | Beschichtung mit hoher koronabeständigkeit, sowie herstellungsverfahren dazu | |
EP2707152B1 (de) | Trägerfunktionsschichtanordnung | |
EP3259396B1 (de) | Verfahren zur verbesserung der haftung zwischen einem verstärkungselement und einem elastomeren matrixmaterial | |
DE102005041330A1 (de) | Silikonelastomere und deren Oberflächenmodifikationen mittels Plasmaverfahren zwecks Beschichtung | |
EP1302503A2 (de) | Verfahren zum Beschichten eines Formkörpers aus polymerem Material | |
EP1223188B1 (de) | Verfahren zur Herstellung von pulverlackierten Kunststoffprofilen | |
EP1920850B1 (de) | Verfahren zum Schutz von patinierten Oberflächen von Kupferprodukten sowie patiniertes Kupferprodukt | |
DE102020204778A1 (de) | Verfahren zur Herstellung einer Isolationsbeschichtung für einen elektrische Leiter, der Graphen und/oder Kohlenstoffnanoröhren umfasst | |
EP3259122B1 (de) | Verfahren zur herstellung eines reifens | |
DE4206747A1 (de) | Kunststoffhohlkoerper mit herabgesetzter durchlaessigkeit | |
WO2016142316A1 (de) | Nanopartikel enthaltendes fibersizing von kohlefasern | |
DE102015215483A1 (de) | Plasmabeschichtungsverfahren für Kohlenstofffasern, Vorrichtung dazu und plasmabeschichtete Kohlenstofffasern | |
EP2754504B1 (de) | Hydrophobiertes Kraftfahrzeugbauteil für Pistenpflegefahrzeuge und Pistenpflegefahrzeug mit einem hydrophobierten Kraftfahrzeugbauteil | |
DE102021117567A1 (de) | Verfahren zur selektiven Beschichtung von Mehrkomponenten-Kunststoffverbunden und Bauteile aus selektiv beschichteten Mehrkomponenten-Kunststoffverbunden |
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: 20161110 |
|
AK | Designated contracting states |
Kind code of ref document: A1 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 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SIEMENS AKTIENGESELLSCHAFT |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20180221 |
|
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: 20190226 |