EP2440692A2 - Functionally graded coatings and claddings for corrosion and high temperature protection - Google Patents
Functionally graded coatings and claddings for corrosion and high temperature protectionInfo
- Publication number
- EP2440692A2 EP2440692A2 EP10737391A EP10737391A EP2440692A2 EP 2440692 A2 EP2440692 A2 EP 2440692A2 EP 10737391 A EP10737391 A EP 10737391A EP 10737391 A EP10737391 A EP 10737391A EP 2440692 A2 EP2440692 A2 EP 2440692A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- functionally
- coating
- ceramic
- graded coating
- graded
- 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.)
- Granted
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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
-
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31605—Next to free metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
Definitions
- Electrolytic deposition describes the deposition of metal coatings onto metal or other conductive substrates and can be used to deposit metal and ceramic materials via electrolytic and electrophoretic methods. Electrodeposition which is a low-cost method for forming a dense coating on any conductive substrate and which can be used to deposit organic primer (i.e. "E-coat” technology) and ceramic coatings.
- organic primer i.e. "E-coat” technology
- the embodiments described herein include methods and materials utilized in manufacturing functionally graded coatings or claddings for at least one of corrosion, tribological and high temperature protection of an underlying substrate.
- the technology described herein also is directed to articles which include a wear resistant, corrosion resistant and/or high temperature resistant coating including a functionally-graded matrix.
- One embodiment provides a method which will allow for the controlled growth of a functionally-graded matrix of metal and polymer or metal and ceramic on the surface of a substrate, which can corrode, or otherwise degrade, such as a metal.
- Another embodiment provides a method which includes the electrophoretic deposition of controlled ratios of ceramic pre-polymer and atomic-scale expansion agents to form a ceramic (following pyrolysis). This form of electrophoretic deposition may then be coupled with electrolytic deposition to form a hybrid structure that is functionally graded and changes in concentration from metal (electrolytically deposited) to ceramic, polymer or glass (electrophoretically deposited).
- Embodiments of the methods described here provide a high-density, corrosion and/or heat resistant material (e.g., ceramic, glass, polymer) that is deposited onto the surface of a substrate to form a functionally-graded polyme ⁇ metal, ceramic:metal, or glassrmetal coating.
- a coating of controlled density, composition, hardness, thermal conductivity, wear resistance and/or corrosion resistance, that has been grown directly onto a surface.
- the functionally-graded coating made according to the methods disclosed herein may be resistant to spallation due to mismatch in any of : coefficient of thermal expansion, hardness, ductility, toughness, elasticity or other property (together “Interface Property”), between the substrate and the ceramic, polymer, pre-ceramic polymer (with or without fillers) or glass (together “Inert Phase”) as the coating incorporates a material at the substrate interface, which more closely matches the Interface Property of the substrate.
- Interface Property coefficient of thermal expansion, hardness, ductility, toughness, elasticity or other property
- Inert Phase the coating incorporates a material at the substrate interface, which more closely matches the Interface Property of the substrate.
- coatings made according to methods described herein are resistant to wear, corrosion and/or heat due to the hard, abrasion-resistant, non-reactive and/or heat-stable nature of the Inert Phase.
- Polymer-derived ceramics that incorporate active fillers e.g., TiN, Ti disilicide, and others
- active fillers e.g., TiN, Ti disilicide, and others
- Polymer-derived ceramic composites have been demonstrated for applications, including-oxidation resistance and thermal barriers, due to their high density and low open-pore volume (e.g., the ceramic has less than 1, 5, 10, 20, 30, 40, or 50 percent voids based on volume). See, JD Torrey and RX Bordia, Journal of European Ceramic Society 28 (2008) 253-257.
- These polymer-derived ceramics can be electrophoretically deposited. Electrophoretic deposition is a two-step process.
- a first step particles suspended in a liquid are forced to move towards one of the electrodes by applying an electric field to the suspension (electrophoresis).
- a second step the particles collect at one of the electrodes and form a coherent deposit on it. Since the local composition of the deposit is directly related to the concentration and composition of the suspension at the moment of deposition, the electrophoretic process allows continuous processing of functionally graded materials. Polymer-derived ceramics is the method used in commercial production of Nicalon® and Tyranno fibers. [00011]
- the technology of this disclosure includes the use of electrochemical deposition processes to produce composition-controlled functionally-graded coating through chemical and electrochemical control of the initial suspension.
- LEAF Layered Electrophoretic and Faradaic Depostion
- the composition and current evolution during the deposition process affords the means to engineer step-graded and continuously graded compositions; see Figs, and reference graphs that show dependence of Ni and Si as a function of solution chemistry and current density.
- Control of current evolution and direction of the electric field also offers the possibility to orient anisotropic powders allowing intimate control of both the density AND the morphology of the Inert Phase (e.g., the content and organization of added ceramic, polymer or glass materials incorporated into an electrodeposited functionally- graded coating).
- the resulting density of ceramic can be varied through the coatings to produce a varying morphology of ceramic/metal composition.
- FIG. 1. is an illustration of a functionally graded material.
- FIG. 2. is an illustration of a pipe based on functionally graded material shown in FIG. 1.
- FIG. 3. is graph illustrating mass loss of a substrate per area over time for several materials exposed to concentrated sulfuric acid at 200 degrees C.
- FIG. 4 illustrates Active Filler Controlled Pyrolysis.
- FIG. 5 illustrates LEAF electrophoretic deposition process on a fiber mat.
- FIG. 6 illustrates the concentration of Si and nickel in deposits found by changing the current density.
- Si is the left most member of each bar graph pair and nickel the right most member of each bar graph pair measured at a specific current density
- FIG. 7 illustrates the concentration of Ni in the emulsion increases from left to right.
- Si is the left most member of each bar graph pair and nickel the right most member of each bar graph pair prepared with the noted solution concentration of nickel.
- Polymer-derived ceramics have shown promise as a novel way to process low- dimensional ceramics, including matrices, fibers and coatings. Polymer-derived ceramic composites have been demonstrated for applications including oxidation barriers, due to their high density and low open-pore volume. See, Torrey and RK Bordia, Journal of European Ceramic Society 28 (2008) 253-257.
- AACP Active Filler Controlled Pyrolysis
- polymer-derived ceramics offer many benefits over tradition ceramic processing methods including:
- the active-filler additive can be occluded into the liquid polymer prior to casting and sintering. During sintering, this additive acts as an expansion agent, resulting in a fully dense part with near zero volume loss (e.g., there are no voids present).
- Active fillers include Si, Al, Ti and other metals, which on pyrolysis form SiC, AI2O 3 or TiSi 2 , for example.
- One of the limitations of this process, as it is practiced currently, is the limited reactivity of the fillers. In many cases, due to kinetic limitations, even for the finest available powders, the filler conversion is incomplete.
- the AFCoP concept and the LEAF deposition process are combined to enable a manufacturing capability which can produce tailorable, low-cost, ultra-high-performance SiC f /SiC composites and parts.
- the Layered Electrophoretic And Faradaic (LEAF) production process employed herein enables the low-cost production of tailored ceramic matrices.
- Scheme A Scheme A Machine or Weave Preform ⁇ Place in Plating Tank
- a first portion of the LEAF process consists in depositing either direct SiC powders, pre-ceramic polymer emulsions (including active fillers) or a combination of these onto the SiC fiber.
- Electrophoretic deposition is a two-step process. In a first step, particles suspended in a liquid are forced to move towards one of the electrodes by applying an electric field to the suspension (electrophoresis). In a second step (deposition), the particles collect at one of the electrodes and form a coherent deposit on it. Since the local composition of the deposit is directly related to the concentration and composition of the suspension at the moment of deposition, the electrophoretic process allows continuous continuous processing of functionally graded materials.
- compositions described herein are prepared by the LEAF electrophoretic deposition process outlined above on fiber mat as illustrated in Figure 5.
- the LEAF process offers the ability to reliably produce composition- controlled "green” (not yet sintered) ceramic through chemical and electrochemical control of the initial suspension. By shaping the starting fiber, which serves as a mandrel, LEAF provides a means to manufacture free standing parts of complex geometry, and hybrid, strength-tailored materials.
- LEAF By controlling the composition and current evolution during deposition process, LEAF affords the means to engineer step-graded and continuously graded compositions. Control of current evolution and direction of the electric field also offers the possibility to orient anisotropic powders allowing intimate control of both the density AND the morphology of the ceramic deposit.
- Layer thickness can be controlled by, among other things, the application of current in the electrodeposition process.
- current density may be varied within the range between 0.5 and 2000 mA/cm 2 .
- Other ranges for current densities are also possible, for example, a current density may be varied within the range between: about 1 and 20 mA/cm 2 ; about 5 and 50 mA/cm 2 ; about 30 and 70 mA/cm 2 ; 0.5 and 500 mA/cm 2 ; 100 and 2000 mA/cm 2 ; greater than about 500 mA/cm 2 ; and about 15 and 40 mA/cm 2 base on the surface area of the substrate or mandrel to be coated.
- the frequency of the wave forms may be from about 0.01 Hz to about 50 Hz. In other embodiments the frequency can be from: about 0.5 to aboutlO Hz; 0.02 to about IHz or from about 2 to 20Hz; or from about 1 to about 5 Hz.
- the electrical potential employed to prepare the coatings is in the range of 5V and 5000 V. In other embodiments the electrical potential is within a range selected from 5 and 200 V; about 50 and 500 V; about 100 and 1000 V; 250 and 2500 V; 500 and 3000 V; 1,000 and 4,000 V; and 2000 and 5000 V.
- Density gradation allows for the design and development of a highly optimized SiC-fiber:SiC-matrix interface. Density gradation provides a means for balancing the optimization of the interface strength, while still maintaining a high density, and in some embodiments gas impermeable and hermetically sealed matrix. Gas impermeability is especially important in corrosion protection where a high level of gas diffusion through the coating may result in substrate attack.
- the LEAF process enables control and gradation of density such that a high density region near the substrate may protect the substrate from attack while a low density region near the surface may reduce the thermal conductivity of the coating.
- a sample composition can be controlled by controlling the voltage. Specifically, by slowly transitioning from a low voltage electrolytic deposition regime to a high voltage electrophoretic deposition regime it may be possible to create a functionally-graded material that gradually changes from metal to ceramic or polymer.
- metalxeramic functionally graded SiC composite material would significantly increase the corrosion-resistance, wear-resistance, toughness, durability and temperature stability of a ceramic-coated structure.
- the coating composition can be functionally-graded by modifying the metal concentration in the electrolyte solution during electrochemical deposition.
- This approach affords an additional means to control the composition of the functionally-graded coating, and allows for deposition to occur at relatively lower current densities and voltages, which produced a better quality in the deposited composites.
- the standard cathodic emulsion system where the emulsion particles comprise polymer, pre- ceramic polymer, ceramic or a combination thereof, can be adjusted by adding increasing amounts of nickel to the solution. This embodiment is described in Example #3.
- this disclosure provides a corrosion resistant coating, which changes in composition throughout its depth, from a high metal concentration at the interface with the substrate to which it is applied to an Inert Phase at the surface.
- the present disclosure provides a heat resistant coating, which changes in composition throughout its depth, from a high metal concentration at the interface with the substrate to which it is applied to an Inert Phase at the surface.
- Inert Phase means any polymer, ceramic, pre-ceramic polymer (with or without fillers) or glass, which can be electrophoretically deposited.
- This Inert Phase may include Al 2 O 3 , SiO 2 , TiN, BN, Fe 2 O 3 , MgO, and TiO 2 , SiC, TiO, TiN, silane polymers, polyhydriromethylsilazane and others.
- M is selected from Li, Sr, La, W, Ta, Hf, Cr, Ca, Na, Al, Ti, Zr, Cs, Ru, and Pb.
- metal means any metal, metal alloy or other composite containing a metal. These metals may comprise one or more of Ni, Zn, Fe, Cu, Au, Ag, Pd, Sn, Mn, Co, Pb, Al, Ti, Mg and Cr. In embodiments where metals are deposited, the percentage of each metal may independently be selected. Individual metals may be present at about 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20, 25, 30, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, 99, 99.9, 99.99, 99.999 or 100 percent of the electrodeposited species/composition.
- the coating can have a coating thickness that varies according to properties of the material that is to be protected by the coating, or according to the environment that the coating is subjected to.
- the coating can range from 0.2 and 250 millimeters, and in other embodiments the range can vary from 0.2 to 25 millimeters, 25 to 250 millimeters, or be greater than about 25 millimeter and less than about 250 millimeters.
- the coating thickness can range from 0.5 to 5 millimeters, 1 to 10 millimeters, 5 to 15 millimeters, 10 to 20 millimeters, and 15 to 25 millimeters.
- the overall thickness of the functionally-graded coating can vary greatly as, for example, between 2 micron and 6.5 millimeters or more. In some embodiments the overall thickness of the functionally-graded coating can also be between 2 nanometers and 10,000 nanometers, 4 nanometers and 400 nanometers, 50 nanometers and 500 nanometers, 100 nanometers and 1,000 nanometers, 1 micron to 10 microns, 5 microns to 50 microns, 20 microns to 200 microns, 200 microns to 2 millimeters (mm), 400 microns to 4 mm, 200 microns to 5 mm, 1 mm to 6.5 mm, 5 mm to 12.5 mm, 10 mm to 20 mm, 15 mm to 30 mm.
- the functionally graded coatings described herein are suitable for coating a variety of substrates that are susceptible to wear and corrosion.
- the substrates are particularly suited for coating substrates made of materials that can corrode and wear such as iron, steel, aluminum, nickel, cobalt, iron, manganese, copper, titanium, alloys thereof, reinforced composites and the like.
- the functionally graded coatings described herein may be employed to protect against numerous types of corrosion, including, but not limited to corrosion caused by oxidation, reduction, stress (stress corrosion), dissolution, dezincification, acid, base, sulfidation and the like.
- the functionally graded coatings described herein may be employed to protect against thermal degradation.
- the coatings will have a lower thermal conductivity than the substrates (e.g., metal surfaces) to which they are applied.
- the coatings described herein may be employed to protect against numerous types of corrosion, including, but not limited to corrosion caused by oxidation, reduction, stress (stress corrosion), dissolution, dezincification, acid, base, sulfidation and the like.
- the coatings are resistant to the action of strong mineral acid, such as sulfuric, nitric, and hydrochloric acids.
- Example 1 Preparation of a functionally graded coating comprising a Inert
- Phase and a metal formed utilizing a combination of electrolytic (faradaic) and electrophoretic deposition includes the following steps:
- a low-content of a metal binder e.g., nickel in this Example
- a metal binder e.g., nickel in this Example
- the concentration of nickel in deposits can be controlled by changing the current density employed.
- Example 4 Nickel, a siloxane-based pre-ceramic polymer particles and ceramic SiC particles are added to an organic electrolyte Note that in this case, the polymer is not deposited as an emulsion, but rather directly as a lacquer. A cathode and an anode were connected to a power supply.
- the substrate was connected to the cathode and inert anodes were connected to the anode.
- a potential was applied across the anodes and cathode, which potential ramped from a low voltage (around 5-100V) to a high voltage (about 100- 1000 V).
- the high voltage was held for a period of time.
- gray masses are the SiC fibers
- SiOC is present due to the heat treatment in an environment in which oxygen was present.
- the white areas are where the nickel was able to infiltrate into the cracks and reinforce the structure of the material.
- Fiber break analysis was performed on a selection of samples that contained the functionally graded metal:SiC structure to determine the toughness and fracture characteristics of various SiC bundles.
- the toughness of the fiber matrix can be determined through the visual inspection of fiber pull-out during fracture. This is observed in SEM images of the fracture surface of a dipped coated ceramic bundle cross-linked at 500 0 F for 2 hours.
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)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18605709P | 2009-06-11 | 2009-06-11 | |
PCT/US2010/001677 WO2010144145A2 (en) | 2009-06-11 | 2010-06-11 | Functionally graded coatings and claddings for corrosion and high temperature protection |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2440692A2 true EP2440692A2 (en) | 2012-04-18 |
EP2440692B1 EP2440692B1 (en) | 2017-05-10 |
Family
ID=43063528
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10737391.2A Active EP2440692B1 (en) | 2009-06-11 | 2010-06-11 | Functionally graded coatings and claddings for corrosion and high temperature protection |
Country Status (5)
Country | Link |
---|---|
US (2) | US20120234681A1 (en) |
EP (1) | EP2440692B1 (en) |
CA (2) | CA2764968C (en) |
ES (1) | ES2636742T3 (en) |
WO (1) | WO2010144145A2 (en) |
Families Citing this family (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2381015B1 (en) | 2005-08-12 | 2019-01-16 | Modumetal, Inc. | Compositionally modulated composite materials |
CA2730252C (en) | 2008-07-07 | 2018-06-12 | Modumetal Llc | Low stress property modulated materials and methods of their preparation |
BR122013014461B1 (en) | 2009-06-08 | 2020-10-20 | Modumetal, Inc | corrosion resistant multilayer coating on a substrate and electroplating method for producing a multilayer coating |
JP5006993B2 (en) * | 2010-02-04 | 2012-08-22 | 日本精機宝石工業株式会社 | Heat dissipation material |
US9764987B2 (en) | 2012-03-02 | 2017-09-19 | Dynamic Material Systems, LLC | Composite ceramics and ceramic particles and method for producing ceramic particles and bulk ceramic particles |
US8961840B1 (en) * | 2012-03-02 | 2015-02-24 | Dynamic Material Systems, LLC | Method for producing bulk ceramic components from agglomerations of partially cured gelatinous polymer ceramic precursor resin droplets |
US10399907B2 (en) | 2012-03-02 | 2019-09-03 | Dynamic Material Systems, LLC | Ceramic composite structures and processing technologies |
US9944021B2 (en) | 2012-03-02 | 2018-04-17 | Dynamic Material Systems, LLC | Additive manufacturing 3D printing of advanced ceramics |
CN105143521B (en) | 2013-03-15 | 2020-07-10 | 莫杜美拓有限公司 | Method and apparatus for continuous application of nanolaminate metal coatings |
CN105189826B (en) | 2013-03-15 | 2019-07-16 | 莫杜美拓有限公司 | Pass through the composition and nanometer layer pressing gold of the electro-deposition of the product of addition manufacturing process preparation |
WO2014146114A1 (en) | 2013-03-15 | 2014-09-18 | Modumetal, Inc. | Nanolaminate coatings |
CN108486622B (en) | 2013-03-15 | 2020-10-30 | 莫杜美拓有限公司 | Nickel-chromium nanolaminate coating with high hardness |
GB201308473D0 (en) * | 2013-05-10 | 2013-06-19 | Authentix Inc | Plating of articles |
EP3071652B1 (en) | 2013-11-19 | 2017-12-13 | BASF Coatings GmbH | Aqueous coating composition for dipcoating electrically conductive substrates containing aluminium oxide |
WO2015074680A1 (en) | 2013-11-19 | 2015-05-28 | Basf Coatings Gmbh | Aqueous coating composition for the dip-paint coating of electrically conductive substrates containing magnesium oxide |
AR102068A1 (en) | 2014-09-18 | 2017-02-01 | Modumetal Inc | METHODS OF PREPARATION OF ITEMS BY ELECTRODEPOSITION AND ADDITIVE MANUFACTURING PROCESSES |
EP3194642A4 (en) | 2014-09-18 | 2018-07-04 | Modumetal, Inc. | A method and apparatus for continuously applying nanolaminate metal coatings |
US9744694B2 (en) | 2015-04-02 | 2017-08-29 | The Boeing Company | Low-cost tooling and method for manufacturing the same |
CN104975326B (en) * | 2015-07-06 | 2017-10-24 | 常州大学 | A kind of preparation method of surface electro-deposition nano rare earth modified cobalt base composite cladding |
CN105332010B (en) * | 2015-11-18 | 2017-05-10 | 常州大学 | Preparation method of pulse electrodeposition Co/Y2O3 nanometer composite plating layer |
US10060042B2 (en) | 2016-04-04 | 2018-08-28 | The Boeing Company | Tooling having a durable metallic surface over an additively formed polymer base and method of forming such tooling |
US11365488B2 (en) | 2016-09-08 | 2022-06-21 | Modumetal, Inc. | Processes for providing laminated coatings on workpieces, and articles made therefrom |
US20190360116A1 (en) | 2016-09-14 | 2019-11-28 | Modumetal, Inc. | System for reliable, high throughput, complex electric field generation, and method for producing coatings therefrom |
US12076965B2 (en) | 2016-11-02 | 2024-09-03 | Modumetal, Inc. | Topology optimized high interface packing structures |
WO2018175975A1 (en) | 2017-03-24 | 2018-09-27 | Modumetal, Inc. | Lift plungers with electrodeposited coatings, and systems and methods for producing the same |
CA3060619A1 (en) | 2017-04-21 | 2018-10-25 | Modumetal, Inc. | Tubular articles with electrodeposited coatings, and systems and methods for producing the same |
CN108385143A (en) * | 2018-04-11 | 2018-08-10 | 珠海市跳跃自动化科技有限公司 | A kind of diamond wire production line and production method |
US11519093B2 (en) | 2018-04-27 | 2022-12-06 | Modumetal, Inc. | Apparatuses, systems, and methods for producing a plurality of articles with nanolaminated coatings using rotation |
CN110129864B (en) * | 2019-05-30 | 2020-04-28 | 中国石油大学(华东) | Reduced graphene oxide-nickel-based gradient coating and preparation method thereof |
US11969796B2 (en) * | 2020-01-03 | 2024-04-30 | The Boeing Company | Tuned multilayered material systems and methods for manufacturing |
CN111825479B (en) * | 2020-07-24 | 2022-08-05 | 江西宁新新材料股份有限公司 | Method for preparing graphite high-temperature-resistant composite coating through electrochemistry-impregnation cooperation |
CN114656275B (en) * | 2022-03-11 | 2023-08-04 | 西北工业大学 | SiC preparation by vacuum impregnation combined with reaction melt infiltration f Method for preparing/Si-Y-B-C composite material |
CN114759419B (en) * | 2022-03-17 | 2024-01-09 | 江苏海洋大学 | Preparation method of copper-aluminum gradient alloy transition joint for submarine cable welding |
CN114657615B (en) * | 2022-03-25 | 2023-11-14 | 重庆理工大学 | Wear-resistant nickel coating with gradient nano structure and preparation method thereof |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5660704A (en) * | 1994-02-21 | 1997-08-26 | Yamaha Hatsudoki Kabushiki Kaisha | Plating method and plating system for non-homogenous composite plating coating |
US5865976A (en) * | 1994-10-07 | 1999-02-02 | Toyoda Gosei Co., Inc. | Plating method |
JPH08311696A (en) * | 1995-05-18 | 1996-11-26 | Brother Ind Ltd | Formation of composite plated film having gradient composition |
US6607844B1 (en) * | 1999-03-15 | 2003-08-19 | Kobe Steel, Ltd. | Zn-Mg electroplated metal sheet and fabrication process therefor |
DE10301135B4 (en) * | 2003-01-14 | 2006-08-31 | AHC-Oberflächentechnik GmbH & Co. OHG | Object with a wear protection layer |
US20050112399A1 (en) * | 2003-11-21 | 2005-05-26 | Gray Dennis M. | Erosion resistant coatings and methods thereof |
US9005420B2 (en) * | 2007-12-20 | 2015-04-14 | Integran Technologies Inc. | Variable property electrodepositing of metallic structures |
-
2010
- 2010-06-11 CA CA2764968A patent/CA2764968C/en active Active
- 2010-06-11 ES ES10737391.2T patent/ES2636742T3/en active Active
- 2010-06-11 EP EP10737391.2A patent/EP2440692B1/en active Active
- 2010-06-11 WO PCT/US2010/001677 patent/WO2010144145A2/en active Application Filing
- 2010-06-11 CA CA2991617A patent/CA2991617C/en active Active
-
2011
- 2011-12-12 US US13/323,431 patent/US20120234681A1/en not_active Abandoned
-
2015
- 2015-05-14 US US14/712,626 patent/US20150322588A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO2010144145A2 * |
Also Published As
Publication number | Publication date |
---|---|
CA2991617C (en) | 2019-05-14 |
WO2010144145A3 (en) | 2013-01-17 |
CA2991617A1 (en) | 2010-12-16 |
WO2010144145A9 (en) | 2013-03-07 |
CA2764968A1 (en) | 2010-12-16 |
US20120234681A1 (en) | 2012-09-20 |
ES2636742T3 (en) | 2017-10-09 |
US20150322588A1 (en) | 2015-11-12 |
EP2440692B1 (en) | 2017-05-10 |
WO2010144145A2 (en) | 2010-12-16 |
CA2764968C (en) | 2018-03-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2440692B1 (en) | Functionally graded coatings and claddings for corrosion and high temperature protection | |
Li et al. | Preparation of Ni-W/SiC nanocomposite coatings by electrochemical deposition | |
Susan et al. | Electrodeposited NiAl particle composite coatings | |
Xue et al. | Fabrication of NiCo coating by electrochemical deposition with high super-hydrophobic properties for corrosion protection | |
Sabzi et al. | The effect of pulse-reverse electroplating bath temperature on the wear/corrosion response of Ni-Co/tungsten carbide nanocomposite coating during layer deposition | |
CN102575367B (en) | Plating or coating method for producing metal-ceramic coating on a substrate | |
Qu et al. | Fabrication of Ni–CeO2 nanocomposite by electrodeposition | |
Li et al. | Influence of alumina nanoparticles on microstructure and properties of Ni-B composite coating | |
Zhou et al. | Electrodeposition and corrosion resistance of Ni–P–TiN composite coating on AZ91D magnesium alloy | |
US6410086B1 (en) | Method for forming high performance surface coatings and compositions of same | |
Safavi et al. | Incorporation of Y2O3 nanoparticles and glycerol as an appropriate approach for corrosion resistance improvement of Ni-Fe alloy coatings | |
Hashemi et al. | Effect of SiC nanoparticles on microstructure and wear behavior of Cu-Ni-W nanocrystalline coating | |
WO2012145750A2 (en) | Electroplated lubricant-hard-ductile nanocomposite coatings and their applications | |
CZ2002572A3 (en) | Protective polyfunctional mixed coating based on light alloys and process for producing thereof | |
Chaudhari et al. | Structure and properties of electro Co-Deposited Ni-Fe/ZrO2 nanocomposites from ethylene glycol bath | |
Fayomi et al. | Anti-corrosion properties and structural characteristics of fabricated ternary coatings | |
Li et al. | Preparation of Ni-W nanocrystalline composite films reinforced by embedded zirconia ceramic nanoparticles | |
JPH03173798A (en) | Formation of high temperature gas corrosion layer deposited electrically | |
Zuo et al. | Effect of activators on the properties of nickel coated diamond composite powders | |
JP3973039B2 (en) | Composite plated product and method for producing the same | |
ThippaReddy et al. | Electrodeposited nickel composite coating containing in-situ nickel impregnated alumina particles | |
Liang et al. | Electrodeposition and characterization of Ni/Ti3Si (Al) C2 composite coatings | |
Li et al. | Effect of bath ZrO2 concentration on the properties of Ni-Co/ZrO2 coatings obtained by electrodeposition | |
CN114277421A (en) | Ti-Mo-B ternary boride coating and preparation method thereof | |
Ledwig et al. | Microstructure and corrosion resistance of composite nc-TiO2/Ni coating on 316L steel |
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: 20120102 |
|
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 SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
R17D | Deferred search report published (corrected) |
Effective date: 20130117 |
|
17Q | First examination report despatched |
Effective date: 20150605 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: UNGER, JESSE, A. Inventor name: LOMASNEY, CHRISTINA Inventor name: WHITAKER, JOHN, D. Inventor name: FLINN, BRIAN Inventor name: BORDIA, RAJENDRA, KUMAR |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C25D 5/50 20060101ALI20160504BHEP Ipc: C25D 5/18 20060101AFI20160504BHEP Ipc: C25D 15/02 20060101ALI20160504BHEP Ipc: C25D 21/12 20060101ALI20160504BHEP Ipc: C25D 5/20 20060101ALI20160504BHEP Ipc: C25D 21/14 20060101ALI20160504BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20160620 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: FLINN, BRIAN Inventor name: UNGER, JESSE, A. Inventor name: LOMASNEY, CHRISTINA Inventor name: WHITAKER, JOHN D. Inventor name: BORDIA, RAJENDRA, KUMAR |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20161117 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 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 SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 892423 Country of ref document: AT Kind code of ref document: T Effective date: 20170515 Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602010042239 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: PATENTANWAELTE SCHAAD, BALASS, MENZL AND PARTN, CH |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20170510 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2636742 Country of ref document: ES Kind code of ref document: T3 Effective date: 20171009 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 892423 Country of ref document: AT Kind code of ref document: T Effective date: 20170510 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170811 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170810 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170910 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170810 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602010042239 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
26N | No opposition filed |
Effective date: 20180213 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170611 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170611 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20170630 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170611 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20100611 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170510 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170510 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602010042239 Country of ref document: DE Representative=s name: HOFFMANN - EITLE PATENT- UND RECHTSANWAELTE PA, DE |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230403 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230626 Year of fee payment: 14 Ref country code: DE Payment date: 20230626 Year of fee payment: 14 Ref country code: CZ Payment date: 20230525 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230620 Year of fee payment: 14 Ref country code: GB Payment date: 20230627 Year of fee payment: 14 Ref country code: ES Payment date: 20230703 Year of fee payment: 14 Ref country code: CH Payment date: 20230702 Year of fee payment: 14 |