US20120234681A1 - Functionally graded coatings and claddings for corrosion and high temperature protection - Google Patents

Functionally graded coatings and claddings for corrosion and high temperature protection Download PDF

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US20120234681A1
US20120234681A1 US13/323,431 US201113323431A US2012234681A1 US 20120234681 A1 US20120234681 A1 US 20120234681A1 US 201113323431 A US201113323431 A US 201113323431A US 2012234681 A1 US2012234681 A1 US 2012234681A1
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functionally
ceramic
coating
metal
polymer
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Christina A. LOMASNEY
John D. Whitaker
Brian Flinn
Rajendra Kumar Bordia
Jesse A. Unger
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Modumetal Inc
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Modumetal LLC
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Priority to US14/712,626 priority patent/US20150322588A1/en
Assigned to MODUMETAL, LLC reassignment MODUMETAL, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: UNGER, JESSE
Assigned to MODUMETAL, LLC reassignment MODUMETAL, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WHITAKER, JOHN D.
Assigned to MODUMETAL, LLC reassignment MODUMETAL, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LOMASNEY, CHRISTINA A.
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    • 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

  • a process for depositing functionally graded materials and structures is described for manufacturing materials that possess the high temperature and corrosion resistant performance of ceramics and glasses, while at the same time eliminating the common mismatches encountered when these are applied to structural metal or composite substrates.
  • An example of the structure of a functionally graded coating is shown in FIG. 1 .
  • An example of the functionally graded coating structure applied to a pipe is shown in FIG. 2 .
  • 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.
  • 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 polymer:metal, ceramic:metal, or glass:metal 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.
  • 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 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, J D Torrey and R K 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).
  • 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.
  • 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.
  • This deposition process is referred to as Layered Electrophoretic and Faradaic Depostion (LEAF).
  • LEAF Layered Electrophoretic and Faradaic Depostion
  • 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 R K Bordia, Journal of European Ceramic Society 28 (2008) 253-257.
  • the Active Filler Controlled Pyrolysis (AFCoP), polymer-derived ceramics offer many benefits over tradition ceramic processing methods including:
  • volume shrinkage up to 50%, upon sintering.
  • AFCoP process is employed, as shown in FIG. 4 .
  • 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, Al2O 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. As will be shown in the processes described herein, the reactive “filler” and the polymer will mixed at molecular scale leading to highly efficient conversion of the filler to the product phase.
  • Polymer-derived ceramics and in particular, AFCoP ceramics have shown promise as a novel way to process a variety of ceramics forms, including matrices, fibers and coatings.
  • 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. See, J D Torrey and R K Bordia, Journal of European Ceramic Society 28 (2008) 253-257.
  • 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.
  • 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 FIG. 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.
  • 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 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 about 10 Hz; 0.02 to about 1 Hz or from about 2 to 20 Hz; 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.
  • 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.
  • 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:
  • the resistance of a TiSi 2 filled and an unfilled coating to degradation by 200 degree C. concentrated sulfuric acid is shown in FIG. 3 .
  • a standard of Alloy 20 and 316 stainless steel are provide for reference.
  • the filled coating showed the least loss of weight.
  • 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.
  • a standard nickel plating bath was added to the polymer emulsion in 1% increments by volume up to 10%.
  • the nickel emulsion system can be optimized through concentration alteration and current and voltage modulation to create a structural material suitable for corrosion resistant, wear resistant, heat resistant and other applications.
  • 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 100-1000V). The high voltage was held for a period of time.
  • gray masses are the SiC fibers
  • the darker gray areas are a mixed matrix of SiOC and SiC.
  • 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° F. for 2 hours.

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US20120276403A1 (en) * 2010-02-04 2012-11-01 Kazushi Nakagawa Heat sink material
US9434653B1 (en) * 2012-03-02 2016-09-06 Dynamic Material Systems, LLC Method for producing bulk ceramic components from agglomerations of partially cured gelatinous polymer ceramic precursor resin droplets
US9744694B2 (en) 2015-04-02 2017-08-29 The Boeing Company Low-cost tooling and method for manufacturing the same
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
US9944021B2 (en) 2012-03-02 2018-04-17 Dynamic Material Systems, LLC Additive manufacturing 3D printing of advanced ceramics
CN108385143A (zh) * 2018-04-11 2018-08-10 珠海市跳跃自动化科技有限公司 一种金刚线生产线及生产方法
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
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