[go: up one dir, main page]

EP3343164A1 - Revêtements fonctionnels, améliorant les performances de condenseur - Google Patents

Revêtements fonctionnels, améliorant les performances de condenseur Download PDF

Info

Publication number
EP3343164A1
EP3343164A1 EP17209826.1A EP17209826A EP3343164A1 EP 3343164 A1 EP3343164 A1 EP 3343164A1 EP 17209826 A EP17209826 A EP 17209826A EP 3343164 A1 EP3343164 A1 EP 3343164A1
Authority
EP
European Patent Office
Prior art keywords
coated
condenser
coating
tube
metal
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Withdrawn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
EP17209826.1A
Other languages
German (de)
English (en)
Inventor
Bong June ZHANG
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.)
NBD Nanotechnologies Inc
Original Assignee
NBD Nanotechnologies Inc
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
Priority claimed from US15/394,268 external-priority patent/US10921072B2/en
Application filed by NBD Nanotechnologies Inc filed Critical NBD Nanotechnologies Inc
Publication of EP3343164A1 publication Critical patent/EP3343164A1/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
    • F28F13/185—Heat-exchange surfaces provided with microstructures or with porous coatings
    • F28F13/187—Heat-exchange surfaces provided with microstructures or with porous coatings especially adapted for evaporator surfaces or condenser surfaces, e.g. with nucleation sites
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
    • F28F13/182—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing especially adapted for evaporator or condenser surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/40—Metallic substrate based on other transition elements
    • B05D2202/45—Metallic substrate based on other transition elements based on Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/65—Adding a layer before coating metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2260/00—Heat exchangers or heat exchange elements having special size, e.g. microstructures

Definitions

  • the present disclosure relates to the field of coatings for enhancing performance of materials surfaces. More particularly, exemplary embodiments provide chemical coating materials useful for coating condenser components.
  • Nanoscale surface modification is also of importance in macro-application.
  • condenser tubes play an important role in electrical power generation.
  • an electrical power plant such as a coal fired power plant, operates by burning fuel (i.e. coal) to heat water in a boiler.
  • the steam produced by the boiler is transferred to a power generator which, in some systems, includes a water box.
  • an external coolant such as water from an external source (e.g. river water).
  • an external source e.g. river water
  • the hot steam come in contact with condenser tubes in the water box, the steam changes phase from gas to liquid by forming a condensate on the condenser tubes.
  • the phase change from gas to liquid causes a pressure drop within the water box that compels a turbine that is connected to the water box to rotate, thus creating electricity.
  • Improved heat-transfer surfaces are provided with metal or polymer-based porous coatings to alter the mode of liquid condensation and heat transfer properties on, from and to those surfaces.
  • These polymers-based particles may have number average diameters of between 50 nm and 5 microns and may further contain additives to further modify the physical properties of the polymer-based compounds or to alter chemical properties to resist deterioration of the particles during use.
  • the surfaces of the metal particles may be in the form of thin oxides or may be coated in a manner to minimize reduction in thermal transfer properties, as thicker coatings tend to act as insulators on a condenser. Better tailoring of hydroscopic or hygroscopic surface properties of the particles is enabled.
  • a condenser system comprising at least one vapor condensing surface having metal or polymer-based compounds distributed across the surface of the vapor-condensing surface to form a porous coating on the vapor-condensing surface.
  • the particles preferably have an average size distribution within a range of ⁇ 100, ⁇ 50% or ⁇ 20% within an average size range of 50 nm to 5 ⁇ m, or within 100 nm to 3 ⁇ m.
  • the particles may provide a static water contact angle (SWCA) on the vapor-condensing surface of between 90 to 160 degrees or 100 and 160 degrees with deionized water at a temperature of 70-90°C.
  • SWCA static water contact angle
  • the disclosure provides a condenser system comprising a vapor condensing surface having metal coating and optionally a top coating comprising a perfluorinated compound or a polymer-based compound.
  • the disclosure provides a method of producing a condenser system or coated condenser tube comprising a. contacting a condenser tube with a metal coating solution to provide a metal nanoparticle coated surface (also described herein as a treated metal), and b. optionally contacting the metal nanoparticle coated surface with a top coating comprising a perfluorinated compound or a polymer-based compound.
  • the metal coating is silver.
  • the metal coating solution is an aqueous silver nitrate solution. In some embodiments, the metal coating solution is an aqueous silver nitrate solution having a concentration of less than or equal to about 0.5 mM. In some embodiments, the metal coating solution is an aqueous silver nitrate solution having a concentration of about 0.5 mM.
  • the perfluorinated compound is applied in a solution of an alcohol solvent. In some embodiments, the alcohol solvent is methanol or ethanol. In some embodiments, the perfluorinated compound is applied as a perfluorinated compound solution comprising about a 0.3 to about 1.5 wt% of the perfluorinated compound in an alcohol solvent.
  • the perfluorinated compound is a perfluoroalkyl trialkoxysilane. In some embodiments, the perfluorinated compound is a perfluorooctyl triethoxysilane. In some embodiments, the perfluorinated compound solution is about 0.5 wt% perfluorooctyl triethoxysilane in ethanol. In some embodiments, the perfluorinated compound solution is about 1 wt% perfluorooctyl triethoxysilane in ethanol.
  • Described herein are embodiments of coating materials, methods of forming the coating materials, methods of coating a substrate, surfaces (e.g., a condenser surface) coated with the coating materials, and a coated article formed by methods disclosed herein. Instead of forming a film on a surface, water forms as droplets on coated surfaces as described herein.
  • a coating of a metal substrate includes bound or embedded metal particles and at least one layer of polymer.
  • a metal substrate includes copper, zinc, nickel, iron, aluminum, and alloys thereof.
  • the metal particles can be nano particles.
  • the metal particles can be of an average size of 200 nm to 3 ⁇ m.
  • the metal substrate can be treated and then immersed in an aqueous solution comprising the metal particles (e.g., a silver solution, e.g., AgNO 3 ).
  • metal particles e.g., silver or gold
  • a polymer or combination of polymers coat a surface of the treated metal. Thereby, a polymer or a combination of polymers coats a surface that is embedded or bound with metal particles.
  • a perfluorinated compound or combination of perfluorinated compounds coat a surface of the treated metal. Thereby, a perfluorinated compound or combination of perfluorinated compounds coats a surface that is embedded or bound with metal particles.
  • the surface is an inside surface, an outside surface, or both inside and outside surfaces.
  • a copper or copper alloy substrate includes silver self-assembled nanoparticles bound to the surface and further coated with a polymer.
  • a copper or copper alloy substrate includes silver self-assembled nanoparticles bound to the surface and further coated with a perfluorinated compound.
  • a polymer should be stable to a moist environment so that a robust condensing surface is provided.
  • Polymers may vary across the spectrum of hydrophilicity and hydrophobicity and may include fluorinated polymers (e.g., perfluorinated polymers of halogenated polymers comprising at least 25% by number of the halogen atoms as fluorine), olefinic polymers, sulfonated hydrocarbon polymers, phosphonated hydrocarbon polymers, silicone polymers and the like.
  • fluorinated polymers e.g., perfluorinated polymers of halogenated polymers comprising at least 25% by number of the halogen atoms as fluorine
  • olefinic polymers e.g., sulfonated hydrocarbon polymers, phosphonated hydrocarbon polymers, silicone polymers and the like.
  • specific polymers identified are poly(phenylene-sulfide), polytetrafluorethylene, and the like.
  • Perfluorinated compounds may include, by way of non-limiting examples, silicone polymers, polysiloxanes, and the like.
  • a perfluorinated compound should be stable to a moist environment so that a robust condensing surface is provided.
  • Perfluorinated compounds may vary across the spectrum of hydrophilicity and hydrophobicity and may include fluorinated trialkoxysilanes, such as perfluorooctyl triethoxysilane.
  • the thickness of the coating on a surface is less than about 2 ⁇ m, about 1.9 ⁇ m, about 1.8 ⁇ m, about 1.7 ⁇ m, about 1.6 ⁇ m, about 1.5 ⁇ m, about 1.4 ⁇ m, about 1.3 ⁇ m, about 1.2 ⁇ m, about 1.1 ⁇ m, about 1 ⁇ m, about 975 nm, about 950 nm, about 925 nm, about 900 nm, about 875 nm, about 850 nm, about 825 nm, about 800 nm, about 775 nm, about 750 nm, about 725 nm, or about 700 nm.
  • DWC Properly promoted "drop-wise” condensation
  • CHTC substantially Condensation Heat Transfer Coefficient
  • FWC film-wise condensation
  • FIG. 1A representing an FWC mode, a large portion of liquid condensate with poor thermal conductivity hampers efficient heat transfer passage. Residing liquid film prevents refreshing the surface and nucleating liquid condensates.
  • DWC mode shows discrete rupture of drops/droplets on the heat transfer surface in FIG. 1b .
  • Drop-shaped condensates roll-off and merge with adjacent premature condensates during sweeping the surface.
  • DWC mode leads to a continuous cycle of condensate nucleation.
  • DWC mode increases condensate detachment frequency, which reduces the effect of thermal resistance due to condensate on the heat transfer surface.
  • a hydrophobic coating with enhanced interfacial tension induces neighboring tiny condensates to coalesce and leads to droplet-shaped condensates.
  • Research has focused on fabrication of a hydrophobic surface/coating with high Water Contact Angle (WCA), which is measured by a sessile drop.
  • WCA Water Contact Angle
  • organic coating materials with low surface energy have received considerable attention since it is assumed that hydrophobic capabilities of the coated-surface promote DWC.
  • Due to superhydrophobic WCA (> 150°) numerous droplets were shown throughout the axis of the test tubes.
  • condensates on the polymer-based coatings rarely rolled-off and resided on the surface until they reached critical radius.
  • a porous surface with hydrophobic coating escalate its WCA into superhydrophobic regime and shows rolling-off motion ( B. J. Zhang, K. J. Kim, H. K. Yoon, Bioinsp. Biomim. 7, 036011 (2012 ).
  • vapor cluster impinges onto the condensing surface. Numerous condensates fill into the condensing surface. Eventually, condensate drops experience additional drag and lead to longer retention on the surface.
  • a silver nano particle deposited coating (i) has low surface energy, (ii) reduces liquid drag, and (iii) can optimize silver nano-particles for condensation. These features promote effective DWC and lead to a substantial DWC enhancement by increasing nucleating sites and liquid condensate detachment frequency.
  • the metal particles may be any metal or metalloid that can form and maintain solid particles within the operating temperature range (about 20°C to about 280°C depending on the type of material) of vapors and liquids to which they will be subjected during use.
  • the ability to form thin, oxide coatings on the surface that will resist deep oxidation of the metal is desirable, but not essential.
  • metals/metalloids and alloys thereof such as aluminum, chromium, copper, chrome-steel, stainless steel, iron, tin, titanium, or a combination thereof can coat the inside, outside, or both the inside and outside of tubes/tubing and fins used in various condensation applications.
  • the size range of the particles may vary over an average size range of 50 nm to 5 ⁇ m, as stated above. Both smaller and larger average diameter particles and averages may be used with varying efficiencies.
  • the particles may be bound to the surface of the condenser plate by fusion of the polymeric surface of the particles to the condenser surface, a coating provided on the particles bonding the particles to the condenser plate surface (the coating must provide the surface properties to the particles that offer the benefits of the technology) or a thin adhesive layer may be present on the condenser plate to cause the particles to adhere to that surface.
  • the thickness of the coatings may be in similar ranges, although with smaller particles, multi-particle layer thickness is more desirable, while with the larger diameter size particles (e.g., 750 nm to 5 ⁇ m), mono-particle layer thicknesses can be more useful.
  • the SEM images show a thickness of the particle coatings of 1-2 ⁇ m.
  • the coating may be a monolayer or multiple-particle layer of the metal, metalloid, or alloy substrate as described herein.
  • a coating can include a polymer or material comprising a silane or thiol end group.
  • One coating that can be used is 1-dodecanethiol, which consists of saturated carbon backbone with a thiol (-SH) group. In ethanolic solution, 1-dodecanethiol does not polymerize with other particles. Once the solution is sprayed out on a metal substrate, a thiol group can interact with hydrogen binding sites on a metal substrate, and in particular metal particles (e.g., silver or gold) coated on or embedded in the substrate.
  • the coating thickness is about 750 nm to about 1 ⁇ m, about 800 nm to about 1 ⁇ m, about 825 nm to about 1 ⁇ m, about 850 nm to about 1 ⁇ m, about 875 nm to about 1 ⁇ m, about 900 nm to about 1 ⁇ m, about 925 nm to about 1 ⁇ m, about 950 nm to about 1 ⁇ m, or about 975 nm to about 1 ⁇ m. Coatings as described herein that less or equal to about 1 ⁇ m remain durable.
  • Hydrophobic coatings (1-dodecanethiol) are not exclusively polymer-based. To control surface wetting, hydroxyl group-functionalized coating (mercapto-based) can be used. For dropwise condensation application, hydrophilicity does not need to be considered since it will not help condensation.
  • hydrophobic coatings include perfloroalkyl trialkoxysilane coatings. In some embodiments, the hydrophobic coating can be a perfluorooctyl triethoxysilane coating.
  • An aspect of the disclosure includes a method of forming the coated material.
  • a metal substrate is contacted with a metal particle solution.
  • the contacting is substrate immersion in a liquid metal solution.
  • the metal substrate is copper or a copper alloy.
  • the metal particle solution is a silver solution.
  • the silver solution is silver nitrate.
  • the silver nitrate solution is about 1 to about 100 mM, about 10 to about 100 mM, about 20 to about 100 mM, about 25 to about 100 mM, about 30 to about 100 mM, about 40 to about 100 mM, about 50 to about 100 mM, about 60 to about 100 mM, about 70 to about 100 mM, about 75 to about 100 mM, about 1 to about 50 mM, about 1 to about 75 mM, or about 10 to about 50 mM.
  • the silver nitrate solution is less than 1 mM. In some particularly preferred embodiments, the silver nitrate solution is less than 0.5 mM. In one particularly preferred embodiment, the silver nitrate solution is about a 0.5 mM aqueous silver nitrate solution.
  • the nanoparticles in a silver solution can be about 200 nm to about 3 ⁇ m.
  • silver nanoparticles deposited on, coated on, or embedded within a substrate service can be about 200 nm to about 3 ⁇ m, 300 nm to about 3 ⁇ m, 400 nm to about 3 ⁇ m, 500 nm to about 3 ⁇ m, 600 nm to about 3 ⁇ m, 700 nm to about 3 ⁇ m, 800 nm to about 3 ⁇ m, 900 nm to about 3 ⁇ m, 1 ⁇ m to about 3 ⁇ m, 2 ⁇ m to about 3 ⁇ m, about 200 nm to about 2 ⁇ m, 300 nm to about 2 ⁇ m, 400 nm to about 2 ⁇ m, 500 nm to about 2 ⁇ m, 600 nm to about 2 ⁇ m, 700 nm to about 2 ⁇ m, 800 nm to about 2 ⁇ m, 900 nm to about 2 ⁇ m, 1 ⁇ m to
  • silver particles are embedded in the surface of the substrate.
  • the silver particles both cluster on the surface of the substrate and are embedded in the surface of the substrate.
  • the silver particles provide a binding platform for a coating (e.g., coating comprising a silane or thiol end group).
  • areas of silver on and/or embedded in the surface of the substrate are heavily hydroxylized and can covalently bond to a self-assembled monolayer.
  • the self-assembled monolayer is a hydrocarbon or fluorocarbon.
  • the hydrocarbon or fluorocarbon is silane-based or contains a thiol end group.
  • coated surfaces of the prior art for example Gu, C. et al., Micro/Nanobinary Structure of Silver Films on Copper Alloys with Stable Water-Repellent Property under Dynamic Conditions, Langmuir, 2009, 25(20, 1299-12307 , coated surfaces that are prepared at concentrations of 1 mM or higher and using longer dip times for the surface coating (25 min to 45 min), show superhydrophobicity at atmospheric pressure, but the surface also contains hierarchical structures. Without being bound by theory, it is believed that the hierarchical structures of surfaces produced under such conditions create air cavities in the surface that, when exposed to condenser system conditions, will cause water to impregnate the substructures within the hierarchical structures to fill the air cavities. It is believed that this process will prevent heat transfer by creating a thermal resistance, and thus retard the condensation process.
  • the dip time of the manufacturing process is less than about one minute per dip cycle. In some embodiments, the dip time of the manufacturing process is less than about 30 seconds per dip cycle. In some embodiments, the dip time of the manufacturing process is less than about 20 seconds per dip cycle. In some embodiments, the dip time of the manufacturing process is less than about 15 seconds per dip cycle. In some embodiments, the dip time of the manufacturing process is less than about 10 seconds per dip cycle.
  • the dip time of the manufacturing process is less than about 5 seconds per dip cycle. It will be appreciated that such short dip times per dip cycle can be repeated from 1 to 100 times depending on the application.
  • the coating process is conducted in about 3 to about 50 dip cycles. In some embodiments, the coating process is conducted in about 3 to about 25 dip cycles. In some embodiments, the coating process is conducted in about 3 to about 10 dip cycles. In some embodiments, the coating process is conducted in about 10 to about 40 dip cycles. It will be appreciated that depending on the application, the number of dip cycles can be any chosen value between 1 and about 100 dip cycles.
  • the self-assembled monolayer is 1-dodecanethiol.
  • a copper or copper alloy substrate comprises silver particles clustered on or embedded in at least one surface, and further comprising a self-assembled monolayer of 1-dodecanethiol.
  • the coated surface provides a water contact angle of about 90° to about 115°, about 95° to about 115°, about 100° to about 115°, about 105° to about 115°, about 90° to about 110°, about 95° to about 110°, about 100° to about 110°, about 101° to about 110°, about 102° to about 110°, about 103° to about 110°, about 104° to about 110°, about 105° to about 110°, about 106° to about 110°, about 107° to about 110°, about 108° to about 110°, or about 109° to about 110°.
  • a surface coated as described herein comprises a condensate detachment frequency of about 0.5 Hz to about 2.0 Hz, 0.5 Hz to about 1.9 Hz, 0.5 Hz to about 1.8 Hz, 0.5 Hz to about 1.7 Hz, 0.5 Hz to about 1.6 Hz, 0.5 Hz to about 1.5 Hz, about 0.5 Hz to about 1.4 Hz, about 0.5 Hz to about 1.3 Hz, about 0.5 Hz to about 1.2 Hz, about 0.5 Hz to about 1.1 Hz, 0.6 Hz to about 1.5 Hz, about 0.6 Hz to about 1.4 Hz, about 0.6 Hz to about 1.3 Hz, about 0.6 Hz to about 1.2 Hz, about 0.6 Hz to about 1.1 Hz, 0.7 Hz to about 1.5 Hz, about 0.7 Hz to about 1.4 Hz, about 0.7 Hz to about 1.3 Hz, about 0.7 Hz to about 1.2 Hz, about 0.7 Hz to about 1.5 Hz, about 0.7 Hz
  • Condensation is the change of the physical state of matter from a gaseous phase into a liquid phase, and is the reverse of vaporization.
  • Condensers are used in a variety of technical fields. They may be used for capturing specific vapors, and especially water vapor, from the air, condensing steam in power generation systems, such as nuclear reactors and coal burning generators.
  • the condensation systems may be powered or passive.
  • air well or aerial well generators which are structures or devices that collect water by promoting the condensation of moisture from air. Designs for air wells are many and varied, but the simplest designs are completely passive, require no external energy source and have few, if any, moving parts.
  • vanes, blades, coils, tubes, fins, or other condenser surfaces may be metals, alloys, composites, ceramic, metal oxides and the like as known in the art. Such vanes, blades, tubes, fins, coils, or other condenser surfaces may be coated with a coating as described herein.
  • Coated surfaces as disclosed herein increase energy efficiency of heat transfer materials (e.g., condenser based systems).
  • embodiments of coated surfaces can increase the heat coefficient by changing how water interacts with materials (e.g., a condenser surface). Instead of forming a film on a surface, water forms as droplets on coated surfaces as described herein (e.g., condenser coils). The droplets roll off coated surfaces as described herein faster, thereby allowing new water droplets to form on the surface. Thereby the cycle of droplet formation and collection occurs more quickly. Thus, heat can be removed more efficiently.
  • the heat coefficient of coated surfaces is 100 to 150% greater than uncoated surfaces.
  • the overall heat transfer coefficient (UA) of coated surfaces as described herein, such as coated copper alloy condenser tubes is from about 5% to about 40% greater than uncoated tubes. In some embodiments, the overall heat transfer coefficient (UA) of coated surfaces as described herein, such as coated copper alloy condenser tubes, is from about 10% to about 30% greater than uncoated tubes. In some embodiments, the overall heat transfer coefficient (UA) of coated surfaces as described herein, such as coated copper alloy condenser tubes, is from about 15% to about 25% greater than uncoated tubes. In some embodiments, the overall heat transfer coefficient (UA) of coated surfaces as described herein, such as coated copper alloy condenser tubes, is from about 15% to about 22% greater than uncoated tubes.
  • the disclosed coating can also coat condenser fins, such as those used in air conditioning units.
  • condenser fins can be located on an outdoor portion of an air conditioner near a compressor.
  • Air conditioner fins can be a part of the condenser that assists heat in moving away from the air conditioner so that the heat disperses more quickly.
  • Condensers with at least one vapor condensing surface coated as disclosed herein can be included in air conditioning units for multiple applications, such as industrial air conditioners, consumer (e.g., home) air conditioners, automotive air conditioners, aircraft air conditioners, etc.
  • the water comes off of a coated fin and collected at the bottom and not blown out of the air conditioner.
  • condenser systems include at least one coated vapor condensing surface as discussed herein, wherein the surface has a total surface energy of less than about 20 mJ/m 2 to about 40 mJ/m 2 , 25 mJ/m 2 to about 40 mJ/m 2 , 26 mJ/m 2 to about 40 mJ/m 2 , 27 mJ/m 2 to about 40 mJ/m 2 , 28 mJ/m 2 to about 40 mJ/m 2 , 29 mJ/m 2 to about 40 mJ/m 2 , 30 mJ/m 2 to about 40 mJ/m 2 , about 20 mJ/m 2 to about 35 mJ/m 2 , about 25 mJ/m 2 to about 35 mJ/m 2 , about 26 mJ/m 2 to about 35 mJ/m 2 , about 27 mJ/m 2 to about 35 mJ/m 2 , about 28 mJ/m 2 to about 35 m
  • condenser systems include at least one coated vapor condensing surface as discussed herein, wherein the surface has a total surface energy of less than about 40 mJ/m 2 , about 39 mJ/m 2 , about 38 mJ/m 2 , about 37 mJ/m 2 , about 36 mJ/m 2 , about 35 mJ/m 2 , about 34 mJ/m 2 , about 33 mJ/m 2 , about 32 mJ/m 2 , about 31 mJ/m 2 , about 30 mJ/m 2 , about 29 mJ/m 2 , or about 28 mJ/m 2 .
  • ⁇ h is a surface energy component due to a hydrogen bonding and dipole-dipole interactions
  • ⁇ d is a dispersion component of surface energy.
  • ⁇ h 137.5 + 256.1 cos ⁇ H 2 O ⁇ 118.6 cos ⁇ CH 2 I 2 44.92 2
  • ⁇ d 139.9 + 181.4 cos ⁇ CH 2 I 2 ⁇ 41.5 cos ⁇ H 2 O 44.92 2 .
  • the nanoparticle coating on a surface with a total energy as described above is self-assembled.
  • a condenser component e.g., a fin, a coil, etc.
  • the polymer coating is a hydrocarbon or fluorocarbon polymer.
  • the coating is 1-dodecanethiol.
  • Condenser systems having at least one coated vapor condensing surface as discussed herein have various applications. Such condenser systems can be utilized in dehumidification, desalination, electric power plants, refrigeration, water generation, and chemical separation processes.
  • water desalination systems typically comprise a) an evaporator for evaporating saline to produce water vapor and b) a condenser for condensing the water vapor.
  • a water desalination system comprises tubes (e.g., stainless steel) arranged either horizontally or vertically in a condenser-evaporator chamber. The energy to evaporate the water can be obtained from film or drop-wise condensation of desorbed water vapor.
  • a water desalination system can include a condenser system comprising at least one vapor condensing surface coated according to the disclosure herein.
  • water desalination includes vapor compression where feed water can be preheated (e.g., in a heat exchanger) outside tubes of a condenser-evaporator. After heating (e.g., boiling), the vapor release is compressed and directed to condense inside the tubes of the condenser-evaporator.
  • feed water can be preheated (e.g., in a heat exchanger) outside tubes of a condenser-evaporator. After heating (e.g., boiling), the vapor release is compressed and directed to condense inside the tubes of the condenser-evaporator.
  • Such tubes can be according to the disclosure herein.
  • Condenser systems as disclosed herein can also be utilized in steam power generation (e.g., air-steam, pure steam, etc.).
  • a condenser system as disclosed herein in a steam powered turbine can include an exhaust gas inlet part that introduces turbine exhaust gases containing steam and non-condensable gases.
  • a geothermal steam turbine comprises a condenser system as disclosed herein.
  • a condensing system as disclosed herein can be connected to a steam jet ejector for condensing geothermal steam into geothermal water including substantially no non-condensed gas by directly contacting the steam to the condensate from the main condenser.
  • a low pressure condensing steam turbine includes a condenser system as disclosed herein.
  • the condenser converts exhaust back to water and thereby condensation of the steam and the change of the steam from a vapor to water creates a partial vacuum that pulls the exhaust through the last stages of the low pressure turbine.
  • a condenser system as disclosed herein can be used in a multitude of steam power generators.
  • the condenser system as described herein can be a water box as conventionally known in the art of power generation systems.
  • the condenser system as described herein can be a water box comprising a plurality of condenser tubes having one or more vapor condensing surfaces comprising a metal coating, as described herein, and optionally a top coating comprising a perfluorinated compound or a polymer-based compound, as described herein.
  • the number of condenser tubes varies from 10,000 to 100,000 in the water box.
  • the condenser tubes in a water box can be arranged in a plurality of tube sets.
  • the plurality of tube sets can be arranged at a variety of depths within the water box, such that the condenser tubes are exposed to a varying range of heat, from steam to cooled water, and a varying range of volume, from heated vapor to full emersion, depending on the location of the tube sets within the water box. It has been surprisingly discovered that the vapor condensing surfaces as described herein can provide enhanced heat transfer and more efficient condensation on condenser tubes located in a preferred environment within a water box, as described herein.
  • a condenser component is formed by contacting a liquid metal solution to at least one surface of the condenser component.
  • the condenser component is a tube, coil, fin, or vane.
  • the liquid metal solution is a silver solution.
  • the silver solution is silver nitrate, as described herein.
  • the contacting is immersion in the metal solution.
  • the contacting is spraying at least one surface of the condenser component with a metal solution.
  • the method further comprises depositing a self-assembled monolayer of a polymer on the treated condenser component (also referred to herein as a metal nanoparticle coated surface or a treated metal).
  • the polymer can be a hydrocarbon polymer or a fluorocarbon polymer.
  • the self-assembled monolayer can be 1-dodecanethiol.
  • the method further comprises depositing a coating of a perfluoroalkyl trialkoxysilane on the treated condenser component (also referred to herein as a metal nanoparticle coated surface or a treated metal).
  • the perfluoroalkyl trialkoxysilane can be perfluorooctyl triethoxysilane.
  • a further embodiment includes a method of forming a condenser system as disclosed herein.
  • at least one vapor condensing surface is etched.
  • the surface is initially cleaned with deionized water and then dried with compressed air. Once dry, the surface is submerged into an acid solution for 5 minutes.
  • the acid solution comprises a 1:1 mixture (by weight) of 70 wt% nitric acid and 1 M sulfuric acid.
  • Coated copper alloy tubes were produced according to methods disclosed herein and tested for surface properties.
  • Silver nano-particle deposition Copper alloy 122 tubes with an outside diameter of 15.9 mm and a thickness of 0.813 mm were primary surface-treated by using emery sand paper (#320) and subsequently by wire wool. The tubes were thoroughly rinsed with deionized water and ethanol. To prepare aqueous silver nitrate stock solution, silver nitrate (99.9% metal basis, Alfa Aesar) was dissolved in DI water at different concentrations (0.1-100 mM). Silver self-assembled nano particles were introduced via a wet chemistry process. Scalability of silver nano particle was governed by a self-assembly process, which was proportional to concentration of silver nitrate and immersion time. Silver self-assembled nano particles (SANPs) were examined by Field Emission-Scanning Electron Microscopy (FE-SEM) and Energy Dispersion X-ray (EDX).
  • FE-SEM Field Emission-Scanning Electron Microscopy
  • EDX Energy Dispersion X
  • WCA Water Contact Angle
  • the test setup consisted of three main parts: a test section, a cooling loop, and a boiler.
  • the test section is composed of a condensing chamber housing three condensing tubes, view ports, valves with plumbing, and measuring instruments.
  • the cooling loop consisted of a chiller/circulator (Affinity, RWE-012K) and the outlet temperature of which can be maintained within ⁇ 1°C of the present value.
  • the boiler generated steam by a submerged heating coil. Hot compressed water controlled by the heater (Advantage Engineering, Sentra SK-1035 HE) was flowing inside of the heating coil of the boiler to generate steam.
  • the inlet and outlet of the coolant temperatures were measured by resistance temperature detectors (RTDs, OMEGA, class A, ⁇ 0.35°C), and the chamber and steam temperature were measured by T-type thermocouples ( ⁇ 0.5°C).
  • the pressure of the chamber and boiler were measured by pressure transducers (AST, AST4300, 0 - 345 kPa, ⁇ 0.5%).
  • the coolant flow rate was measured by a rotameter (Blue & White, F-440, 0- 5 GPM, ⁇ 4% of full scale).
  • the condensing chamber was fully evacuated until the water could boil at vacuum pressure. Non-condensable gases can be expelled to atmosphere. Once the system reached a steady state condition, relevant heat transfer data were acquired. Pressure and coolant inlet temperature were controlled at 97.8 - 67.5 kPa and 50 - 90°C during data acquisition.
  • EDX mapping was executed in FIG. 4 .
  • the majority of elements consists of fluorine, sulfur, copper, and silver.
  • silver and nitrate were ionized. Individual ions interacted with copper and eventually crystallize into silver: Cu (s) + 2Ag + (aq) + 2NO 3 - (aq) ⁇ 2Ag (s) + Cu(NO 3 ) 2(aq) .
  • WCA measurements Surface wetting is closely related to surface roughness and surface energy. Scalability of SANPs influences surface wetting, which was visualized by Static Water Contact Angle (SWCA) in FIG. 5 .
  • the reference surface plain copper surface
  • SWCA Static Water Contact Angle
  • the reference surface plain copper surface
  • the SWCA decreased. It is assumed that enhanced wetting phenomena was caused by hydrophilic SANP surface profiles and led to the Wenzel effect.
  • scalable nano- and micro-bumps on the substrate can lead to surface wetting transition from a Wenzel (wetting) surface to a Cassie-Baxter (less wetting) surface due to hydrophobic coating.
  • a hydrophobic coating prevents liquid impingement into surface profiles and entraps noncondensible gas into surface roughness.
  • Dodecanethiol consists of a hydrophobic carbon backbone, which lowers surface energy and leads to hydrophobicity. Dodecanethiol (1 w/w) was dissolved in ethanol and was spray-coated several times.
  • a hydrophobic coating dramatically increased SWCA ( ⁇ 100°). This result implies that a hydrophobic coating prevents liquid from impinging into surface roughness.
  • a hydrophobic coating leads to a surface wetting transition from a Wenzel surface to a Cassie-Baxter surface by entrapping gas. Most surfaces showed SWCA of 100°.
  • This phenomenon was assumed to be related to surface profiles as shown in FIG 3 . Density of micro bumps at given surface area increased with silver conc entration. However, aspect ratio of micro bumps is not significantly enhanced until exposure time increases. To improve SWCA of structured-surfaces, aspect ratio of the substructure was assumed to be the key ( B. J. Zhang, K. J. Kim, H. K. Yoon, Bioinsp. Biomim. 7, 036011 (2012 ); C. Y. Lee, B. J. Zhang, J. Y. Park, K. J. Kim, Int. J. Heat Mass Transfer 55, 2151 (2012 )).
  • FIG. 7 the SWCA of various surfaces (a plain copper surface and self-assembled monolayer of copper) are shown for comparison.
  • a wide range of SWCA 77°-157°
  • SWCAs were almost halved (33°-75°) compared to water ( FIGS. 7D-F . Obtained results of SWCA measurements are summarized in Table 2.
  • Test tubes (inner and outer diameters were 14.3 and 15.9 mm, respectively) were cleaned with acid solution (HCl:HNO 3 ) to remove any organic residues. After acid cleaning, the tubes were thoroughly rinsed several times with distilled-water. A test tube was chemically treated with 10 mM Ag solution and 2 wt % ethanolic dodecanethiol was sprayed three times (Comparator Example 2). As shown in FIG. 8 , the temperature of subcool ( T sub ) of the external condensation heat transfer tests results were plotted with respect to heat flux and the Condensation Heat Transfer Coefficient (CHTC).
  • HCl:HNO 3 acid solution
  • CHTC Condensation Heat Transfer Coefficient
  • test results of the SANP-deposited condenser were compared to that of a plain copper tube and Self-assembled Monolayer (SAM) of copper.
  • the CHTC of the SANP-deposited condenser was approximately 2 to 2.5 times (100-150%) higher than non-surface treated ( FIG. 8B ).
  • SAM-coated condenser CHTC was approximately 25% less than non-surface treated.
  • FIG. 14 shows the condensation test results for Inventive Example 2 tubes compared to control (uncoated) tubes.
  • Tubes coated with 0.5 mM AgNO 3 generated about 20-25 percent heat transfer enhancement at 1.1 kPa.
  • the coated tubes prepared with 1.0 mM AgNO 3 showed about 35 percent at 10.0-14.0 kPa.
  • the surface prepared according to the invention advantageously provided similar heat transfer performance as Inventive Example 1 surface, but at 1/10 of the pressure.
  • Such enhanced performance at lower pressure provides a surface suitable for condenser systems in such an application as a water box in a power plant.
  • FIG. 9A shows a snapshot from the video-recording for a plain surface. Once initial condensate nucleates in the top part of tube, the condensate immediately begins to coalesce with adjacent ones and forms liquid patches. On the bottom of the tube, dangling condensates with a diameter up to 10 mm and height up to 9 mm were observed. After drop/droplet detachment, very thin residues remained on the surface. A dangling drop and thin liquid layer can play a role in thermal resistances. As heat flux increases, complete FWC appeared along the axial length of the tube.
  • FIG. 9B A SAM-coated surface had a different condensation pattern compared to that of a plain surface ( FIG. 9B ).
  • a hydrophobic coating provided nucleation site improvement.
  • numerous condensates nucleated and coalesced with neighboring condensates. Due to enhanced surface tension on the droplet rim, a sweeping mode was prevented and droplets grew horizontally. The residing droplet retarded the nucleation of condensates and deteriorated heat transfer performance. Similar phenomena were observed on the bottom of the tube. To note, a larger droplet dangling on the surface turned into a liquid patch, which induced FWC.
  • Still-frame of the SANP-deposited surface in FIG. 9C shows DWC mode throughout the horizontal tube. Significant rolling-off motion refreshed the entire surface and triggered immediate nucleation of tiny condensates. The average diameter of detaching condensates was estimated to be approximately 3 mm. The SWCA was not a critical factor in determining DWC mode. As shown in FIG. 7B-C , the SAM copper oxide was 50% enhanced WCA compared to the SANP. Once the cavity of the superhydrophobic surface becomes wet, additional driving force and/or energy are required. During condensation test, most of superhydrophobic surface showed strong WCA hysteresis, which restricted rolling-off motion and condensate detachment.
  • the growth period of the condensates was video-recorded and was normalized using the characteristic length ( l 0 ), velocity ( u 0 ), and time ( t 0 ) defined as (] Y. Nam, E. Aktinol, V. K. Dhir, Y. S. Ju, Int. J.
  • FIG. 13A depicts the contour of liquid condensate distributions of the silver-coated surface, which were taken at specified time periods.
  • FIG. 13A shows that discrete liquid condensates coalesced rolling off along the horizontal tube. Once the liquid droplet began to roll off, the mean base radius was approximately 2 mm. As the liquid droplet moved along the tube surface, its mean base radius increased to about 3 mm. Growing liquid condensate swiveled around and removed premature liquid condensates ( ⁇ 1 mm) before reaching the critical radius to have enough momentum to roll off. The time frames of FIG. 13A-D show the renewal area. Instantaneously, micro-sized liquid condensates nucleated over the condensing surface, as shown in FIG. 13B .
  • the histogram shown below the contour map in FIG. 13 represents the amount of condensate droplet population.
  • FIG. 13E droplets were distributed widely since large condensates were swept already.
  • FIG. 13B liquid droplets grew homogeneously, and the population histogram localized within a few microns regime ( FIG. 13F ).
  • FIG. 13G the localized histogram peak diminished ( FIG. 13G ).
  • the histograms shifted and were broadly distributed on a wide range of droplet radii.
  • FIG. 13H by immediately merging adjacent liquids, population peaks decreased significantly and histograms populated widely (200 - 2,000 ⁇ m).

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP17209826.1A 2016-12-29 2017-12-21 Revêtements fonctionnels, améliorant les performances de condenseur Withdrawn EP3343164A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US15/394,268 US10921072B2 (en) 2013-05-02 2016-12-29 Functional coatings enhancing condenser performance

Publications (1)

Publication Number Publication Date
EP3343164A1 true EP3343164A1 (fr) 2018-07-04

Family

ID=60971894

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17209826.1A Withdrawn EP3343164A1 (fr) 2016-12-29 2017-12-21 Revêtements fonctionnels, améliorant les performances de condenseur

Country Status (1)

Country Link
EP (1) EP3343164A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112095098A (zh) * 2020-09-22 2020-12-18 湖北大学 具有规则凸起阵列、滑移表面的材料应用于水雾收集的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100143741A1 (en) * 2006-09-20 2010-06-10 The Queen's University Of Belfast Method of coating a metallic article with a surface of tailored wettability
WO2014064450A1 (fr) * 2012-10-25 2014-05-01 Oxford Nanosystems Élément échangeur de chaleur à revêtement de surface de transfert de chaleur

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100143741A1 (en) * 2006-09-20 2010-06-10 The Queen's University Of Belfast Method of coating a metallic article with a surface of tailored wettability
WO2014064450A1 (fr) * 2012-10-25 2014-05-01 Oxford Nanosystems Élément échangeur de chaleur à revêtement de surface de transfert de chaleur

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
A. K. DAS; H. P. KILTY, MARTO, ASME J. HEAT TRANSFER, vol. 7, 2000, pages 109
B. J. ZHANG; K. J. KIM; H. K. YOON, BIOINSP. BIOMIM., vol. 7, 2012, pages 036011
BONG JUNE ZHANG ET AL: "Dropwise steam condensation on various hydrophobic surfaces: Polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), and self-assembled micro/nano silver (SAMS)", INTERNATIONAL JOURNAL OF HEAT AND MASS TRANSFER., vol. 89, 3 June 2015 (2015-06-03), GB, pages 353 - 358, XP055467638, ISSN: 0017-9310, DOI: 10.1016/j.ijheatmasstransfer.2015.05.060 *
C. Y. LEE; B. J. ZHANG; J. Y. PARK; K. J. KIM, INT. J. HEAT MASS TRANSFER, vol. 55, 2012, pages 2151
CHANGDONG GU ET AL: "Micro/Nanobinary Structure of Silver Films on Copper Alloys with Stable Water-Repellent Property under Dynamic Conditions", LANGMUIR, vol. 25, no. 20, 20 October 2009 (2009-10-20), US, pages 12299 - 12307, XP055467647, ISSN: 0743-7463, DOI: 10.1021/la902936u *
D. K. OWEN; R. C. WENDT, APPL. POLYMER SCI., vol. 13, 1967, pages 1741
F. C. WANG; F. YANG; Y. P. ZHAO, APPL. PHYS. LETT., vol. 98, 2011, pages 053112
GU, C. ET AL.: "Micro/Nanobinary Structure of Silver Films on Copper Alloys with Stable Water-Repellent Property under Dynamic Conditions", LANGMUIR, vol. 25, no. 20, 2009, pages 1299 - 12307
Q. BAOJIN; Z. LI; X. HONG; S. YAN, EXP. THERM. FLUID SCI., vol. 35, 2011, pages 211
Y. NAM; E. AKTINOL; V. K. DHIR; Y. S. JU, INT. J. HEAT MASS TRANSFER, vol. 54, 2011, pages 1572
ZHANG, B.J. ET AL.: "Dropwise steam condensation on various hydrophobic surfaces: Polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE) and self-assembled micro/nano silver (SAMS", INT. J. HEAT AND MASS TRANS., vol. 89, 2015, pages 353 - 358

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112095098A (zh) * 2020-09-22 2020-12-18 湖北大学 具有规则凸起阵列、滑移表面的材料应用于水雾收集的方法
CN112095098B (zh) * 2020-09-22 2021-12-17 湖北大学 具有规则凸起阵列、滑移表面的材料应用于水雾收集的方法

Similar Documents

Publication Publication Date Title
US10525504B2 (en) Functional coatings enhancing condenser performance
US10921072B2 (en) Functional coatings enhancing condenser performance
Attinger et al. Surface engineering for phase change heat transfer: A review
Sarkar et al. Superhydrophobic coatings with reduced ice adhesion
US11293704B2 (en) Droplet ejecting coatings
Ali et al. Techniques for the fabrication of super-hydrophobic surfaces and their heat transfer applications
US20180161836A1 (en) Articles and methods for modifying condensation on surfaces
US20130251942A1 (en) Hydrophobic Materials Incorporating Rare Earth Elements and Methods of Manufacture
CN110998217B (zh) 带有微结构化涂层的热交换元件及其制造方法
Zhu et al. Heat transfer enhancement on tube surfaces with biphilic nanomorphology
Ho et al. Opportunities in nano-engineered surface designs for enhanced condensation heat and mass transfer
WO2013141877A1 (fr) Matériaux hydrophobes incorporant des éléments des terres rares et leurs procédés de fabrication
EP3343164A1 (fr) Revêtements fonctionnels, améliorant les performances de condenseur
Talesh Bahrami et al. Dropwise condensation heat transfer enhancement on surfaces micro/nano structured by a two-step electrodeposition process
EP1242650B1 (fr) Revetement d'oxyde metallique oleophile hydrophile a motif et methode de fabrication
Olceroglu et al. Biotemplated superhydrophobic surfaces for enhanced dropwise condensation
Qin et al. A novel composite coating mesh film for oil-water separation
Brockway et al. A nanoporous, ultrahydrophobic aluminum-coating process with exceptional dropwise condensation and shedding properties
Kuzma-Kichta et al. Studying the wetting of a surface with combined structure
Zhao et al. Micro/nano-texture design for improving tribological properties of DLC-IL composite films
Barthwal et al. Fabrication of a superamphiphilic SS-400 oil separator surface using a Ag-doped ZnO nanorod coating
Ye et al. Review on Anti-Frost Technology Based on Microchannel Heat Exchanger
Attinger et al. How to Engineer Surfaces to Control and Optimize Boiling, Condensation and Frost Formation?
Aili et al. Characteristics of jumping droplet-enhanced condensation on nanostructured micromesh surface
Schmiesing Characterizing the Condensation Heat Transfer Performance of Uniform and Patterned Silica Nanospring-Coated Tubes

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: 20171221

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

17Q First examination report despatched

Effective date: 20190308

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20191128

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: 20200603