US20010036516A1 - Modified freeform fabricated part and a method for modifying the properties of a freeform fabricated part - Google Patents

Modified freeform fabricated part and a method for modifying the properties of a freeform fabricated part Download PDF

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US20010036516A1
US20010036516A1 US09/847,136 US84713601A US2001036516A1 US 20010036516 A1 US20010036516 A1 US 20010036516A1 US 84713601 A US84713601 A US 84713601A US 2001036516 A1 US2001036516 A1 US 2001036516A1
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freeform
infiltrant
fabricated part
densified
ceramic
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US09/847,136
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Wayde Schmidt
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Priority to US10/189,955 priority patent/US6593008B2/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00Apparatus for additive manufacturing; Details thereof or accessories therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20Post-treatment, e.g. curing, coating or polishing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/4535Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension
    • C04B41/4537Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension by the sol-gel process
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/455Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application the coating or impregnating process including a chemical conversion or reaction
    • C04B41/4554Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application the coating or impregnating process including a chemical conversion or reaction the coating or impregnating material being an organic or organo-metallic precursor of an inorganic material
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30Auxiliary operations or equipment
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249924Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/249928Fiber embedded in a ceramic, glass, or carbon matrix
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/8305Miscellaneous [e.g., treated surfaces, etc.]

Definitions

  • This invention relates to freeform fabricated parts and in particular, to a method for modifying the properties of a freeform fabricated part by increasing its density.
  • Freeform fabrication originated with a process called stereolithography wherein a focussed ultra-violet laser scans the top of a bath of a photopolymerizable liquid polymer plastic material, thereby causing the top of the bath and the area just below the surface to polymerize.
  • the polymerized layer is thereafter lowered into the bath and the laser scanning process is repeated until a second polymerized layer is formed. As the second polymerized layer forms, it bonds to the first layer. This process is repeated until a plurality of superimposed layers form the desired part.
  • the shape of the part is first designed in a computer aided design system (i.e., a CAD/CAM system), which is linked to the machine performing the stereolithography process.
  • a computer aided design system i.e., a CAD/CAM system
  • Most freeform fabrication processes include a computer aided design system for coordinating the execution of the freeform fabrication process.
  • the laser beam scans the area of the bath necessary to form the freeform fabricated part (hereinafter referred to as “freeform part”) designed on the computer aided design system.
  • the ability to produce an actual part directly from a design provides many advantages.
  • One advantage includes eliminating the time traditionally used to develop the necessary tooling to manufacture the freeform part.
  • Another advantage includes reducing the amount of machining, such as grinding, milling, drilling, etc., required to complete the part because the freeform fabrication process produces a substantially readily usable final product. Minimizing the amount of hands-on machining, therefore, translates into reducing the amount of potential human error and increasing efficiency.
  • the amount of time saved in preparing for manufacturing also makes the freeform fabrication process attractive for rapid prototype development, which has been one of the main interests surrounding this technology in recent years.
  • the benefit of rapid prototyping includes the ability to manufacture various configurations in a short amount of time, thereby providing designers with actual models of their designs.
  • Another method of freeform fabrication includes a technique called Three-Dimensional Printing (3DP), which consists of depositing a powdered material (e.g., a powdered ceramic, powdered metal, powdered plastic, or combination thereof) in sequential layers, one on top of the other. After depositing each layer of powdered material, a liquid binder is selectively supplied to the layer of powdered material using a type of ink-jet printing technique in accordance with a computer model of the three-dimensional part being fabricated. Following the sequential application and binding all of the required powder layers, the unbound powder is removed, thereby resulting in the formation of the designed three-dimensional part.
  • 3DP Three-Dimensional Printing
  • a third method of freeform fabrication includes Selective Laser Sintering (SLS).
  • SLS includes a process whereby a powder dispenser deposits a layer of powdered material into a target area.
  • a laser control mechanism which typically includes a computer that houses the design, modulates and moves the laser beam to selectively sinter a layer of powder dispensed in the target area. Specifically, the control mechanism operates to selectively sinter only the powder disposed within the defined boundaries of the design.
  • the control mechanism operates the laser to selectively sinter sequential layers of powder, producing a completed part comprising a plurality of layers sintered together yielding the completed design.
  • a fourth method of freeform fabrication includes Ballistic Particle Manufacturing (BPM).
  • BPM uses an ink-jet printing apparatus wherein an ink-jet stream of liquid polymer or polymer composite material is used to create three-dimensional objects under computer control, similar to the way an ink-jet printer produces two-dimensional graphic printing.
  • the device is formed by printing successive cross-sections, one layer after another, to a target using a cold welding or rapid solidification technique, which causes bonding between the particles and the successive layers.
  • FDM Fused Deposition Modeling
  • FDM consists of building solid objects in a layering fashion from polymer/wax compositions by following the signals produced by a computer aided design system. Specifically, FDM builds structures by extruding a fine filament of plastically deformable material through a small nozzle. The computer aided design system appropriately directs the nozzle over a build surface in the x, y and z directions, thereby creating a three-dimensional object that resembles the design.
  • Another method of freeform fabrication includes a technique called Photochemical Machining, which uses intersecting laser beams to selectively harden or soften a polymer plastic block.
  • the underlying mechanism used is the photochemical cross-linking or degradation of the material.
  • U.S. Pat. No. 5,490,962 provides a detailed summary of each of the above mentioned freeform fabrication techniques and is hereby incorporated by reference.
  • the present invention exploits the porosity of a freeform fabricated part by packing the pores of a freeform part with an infiltrant that is capable of transforming to a ceramic or a ceramic-containing phase.
  • the infiltrant comprises a preceramic polymer, which is selected to bond with the freeform part such that the resulting composition improves the mechanical, thermal and other characteristics of the freeform part. Packing the pores of the freeform part, therefore, increases its density and concomitantly decreases its porosity. Particularly, increasing the density of the freeform part increases one or more or all of the following properties: mechanical strength, hardness, temperature resistance, abrasion resistance, thermal conductivity, and erosion resistance. These properties may be enhanced by carefully fabricating the freeform part such that a certain porosity is imparted, selecting particular infiltrants with various concentrations that add the desired properties to the freeform part, and repeating the infiltration process until the desired density is achieved.
  • one aspect of the present invention is a process for modifying the properties of a porous freeform part comprising the steps of depositing a porous freeform part in an infiltrant bath, drawing a vacuum on the porous freeform part and the infiltrant bath such that the infiltrant enters the pores within the freeform part, and removing the densified freeform part from the infiltrant bath.
  • the infiltrant is normally a preceramic polymer that is capable of transforming to a ceramic or a ceramic-containing phase.
  • the preceramic polymer is preferably a polymer capable of nanocrystalline ceramic phase growth such that the preceramic polymer can enter the pores within the freeform part.
  • a second embodiment of the present invention includes pressurizing the infiltrant as an alternative to or in conjunction with drawing a vacuum on the porous freeform part and the infiltrant bath such that the infiltrant enters the pores within the freeform part.
  • a third embodiment of the present invention includes heating the infiltrant while pressure is being applied.
  • a fourth embodiment of the present invention includes placing the porous freeform part in a vacuum dessicator, applying a vacuum and allowing an infiltrant to enter the vacuum dessicator such that the infiltrant enters the pores within the freeform part.
  • a fifth embodiment of the present invention includes subjecting the densified freeform part to a series of post-processing steps upon being removed from the infiltrant bath such that the infiltrant within the pores of the densified freeform part transforms to a ceramic or a ceramic-containing phase.
  • the post-processing steps may include one or more or all of the following steps: curing the infiltrant, heating the infiltrant at a rate, duration and temperature such that the infiltrant transforms to a ceramic or ceramic-containing phase within the pores of the freeform article, annealing the transformed infiltrant and cooling the freeform fabricated part and the transformed infiltrant.
  • a still further embodiment of the present invention includes a freeform fabricated part having pores therein comprising a ceramic or a ceramic-containing phase disposed within a portion of the pores with the freeform part.
  • infiltrants such as preceramic polymers, which are inorganic or organic polymers that transform to ceramic when subjected to intense heat, are capable of infiltrating the pores of a freeform part.
  • the inventor of the present invention also recognized that increasing the density of the freeform part with certain infiltrants improved the mechanical characteristics of the freeform part, which serves as a support structure for the infiltrants.
  • the present invention is a process comprising the steps of fabricating a freeform part, depositing the freeform part in an infiltrant bath, drawing a vacuum on the porous freeform part and the infiltrant bath such that the infiltrant enters the pores of the freeform, and subjecting the freeform part and infiltrant to a treating process that may include one or more post-processing steps.
  • Freeform parts for use in practicing the method of the present invention were fabricated using a three-dimensional printing technique similar to that described in U.S. Pat. Nos. 5,204,055 and 5,340,656 and 5,387,380, which are hereby incorporated by reference.
  • the freeform parts in these experiments were made using the three-dimensional printing technique
  • the present invention may be used with freeform parts made by virtually any known freeform fabrication technique such as stereolithography, selective laser sintering, fused deposition modeling, ballistic particle manufacturing, and photochemical machining. It is preferable that the freeform parts be capable of withstanding the type of post-processing steps associated with transforming an infiltrant to a ceramic or ceramic-containing phase.
  • Three different types of freeform parts were fabricated using the three-dimensional printing technique. One was a 1 ⁇ 4 inch by 1 ⁇ 4 inch by 4 inch Acrysol bonded silicon carbide (SiC) part.
  • silicon carbide powder manufactured by Washington Mills under the tradename SIKA I
  • the organic binder Acrysol WS-24 which is an acrylic colloidal dispersion manufactured by Rohm & Haas.
  • the second type of freeform part was a 1 ⁇ 4 inch by 1 ⁇ 4 inch by ⁇ fraction (1 1/2) ⁇ inch alumina part.
  • brown aluminum oxide (Al 2 O 3 ) powder manufactured by Norton Company under the product code 7131 was bonded by the same Arysol WS-24 binder.
  • the third type of freeform part was also a 1 ⁇ 4 inch by 1 ⁇ 4 inch by 1 1 ⁇ 2 inch alumina part fabricated using the same brown aluminum oxide (Al 2 O 3 ) powder manufactured by Norton Company mentioned above using the three-dimensional printing technique.
  • this third type of freeform part was fabricated using the inorganic binder, colloidal silica (SiO 2 ), manufactured by the Norton Company under the tradename Nyacol.
  • colloidal silica SiO 2
  • the three freeform-fabricated parts used in our experiments were manufactured using silicon carbide and aluminum oxide, other materials such as metal, ceramic and metal-ceramic composites could be manufactured using the three-dimensional printing technique.
  • organic and inorganic binders other than Arysol WS-24 and colloidal silica could be used in the three-dimensional printing process.
  • the original density of the three types of parts was about thirty percent (30%) to about thirty seven percent (37%). In other words, sixty three percent (63%) to about seventy percent (70%) of the three-dimensional fabricated freeform part was porous. Therefore, it may also be preferable to subject the freeform part to post-processing methods, such as mild sintering or annealing, but doing so only improves the density to about thirty eight percent (38%) to about thirty-nine (39%).
  • the density of a freeform part is increased by depositing the freeform part into an infiltrant bath consisting of a preceramic polymer (i.e., ceramic precursor), which can be an organic or inorganic polymer but is generally in the form of an inorganic polymer.
  • a preceramic polymer i.e., ceramic precursor
  • Any preceramic polymer capable of transforming to a ceramic or a ceramic-containing phase having nanocrystalline structures therein may be used as an infiltrant.
  • the preceramic polymers used in all of the following examples were in the form of a liquid or a sol-gel, the preceramic polymer could be in a number of other forms, such as an organic solvent based solution or a liquid dispersion containing solid particles.
  • the freeform parts were deposited in the following preceramic polymers: alumina sol-gel, silicon oxycarbide (SiOC), poly(methylvinylsilane) (PMVS), perhydridopolysilazane (PHPS), polysilazane, and poly(aluminosilazane).
  • preceramic polymers that could be used as infiltrants include polysilane, polycarbosilazane, poly(borosilazane), polysiloxane and polycarbosilane, and other molecularly mixed polymers that are capable of producing nanocrystalline ceramics or metals or mixtures hereof.
  • Various polysilanes, polysilazanes, silicon oxycarbide (SiOC), polycarbosilazane, polysiloxane, perhydridopolysilazane and polycarbosilanes are commercially available.
  • the alumina sol-gel used in Example 1 was prepared using a known process.
  • the silicon oxycarbide (SiOC) used in Example 2 is produced by Allied Signal under the tradename Blackglas.
  • the BlackglasTM silicon oxycarbide (SiOC) actually consists of a monomer solution, BlackglasTM 489A, and a catalyst, BlackglasTM 489C, which are combined before the freeform-fabricated part is deposited into such a bath.
  • the perhydridopolysilazane used in Example 4 is sold by Tonen, and the polysilazane used in Examples 5 is distributed by UBE under the tradename Tyranno Coat.
  • a poly(methylvinylsilane), a poly(aluminosilazane) or a poly(borosilazane) may not be manufactured on a commercial scale, it is known how to manufacture such preceramic polymers.
  • a reactive endblocked poly(methylvinylsilane) as described in a Final Technical Report entitled Novel Precursor Approaches for CMC Derived by Polymer Pyrolysis dated Feb. 15, 1994 prepared under Government Contract No.
  • infiltrants may have destroyed a portion of the inter-particle bonds formed during the three-dimensional printing process, such as dissolution of the bond between an organic based binder and the three-dimensional printed part, the density of the resulting composition surpassed the density of the original freeform part.
  • the density of the freeform part increased to about fifty percent (50%) to about sixty percent (60%).
  • the density of the freeform part infiltrated with the alumina sol-gel increased to about forty percent (40%) to about forty-five (45%).
  • the infiltration process of the present invention therefore, decreased the porosity and increased the density of the freeform part.
  • the density of each freeform part is further increased and its porosity further decreased upon repeating the process until the desired density and porosity are achieved.
  • An alternate process for modifying the properties of a porous freeform-fabricated part comprises the further step of pressurizing the infiltrant after drawing a vacuum on infiltrant and freeform part. This pressurizing step increases the potential of packing the pores in the freeform part with the infiltrant.
  • Another alternate process comprises the steps of depositing an individual freeform part in a vacuum dessicator containing an infiltrant and pressurizing the infiltrant rather than drawing a vacuum. Regardless of whether a vacuum is drawn on the infiltrant and freeform part, it may also be beneficial to heat the infiltrant as pressure is being applied in order to initiate curing of the infiltrant within the pores of the freeform part.
  • Still another alternate process for modifying the properties of a porous freeform part comprises placing the freeform part in an empty vacuum dessicator, drawing a vacuum on the freeform part and then introducing an infiltrant into the vacuum dessicator such that the infiltrant enters the pores within the freeform part.

Abstract

The present invention is a process for modifying the properties of a porous freeform fabricated part by increasing its density and reducing its porosity. The porosity and density of a freeform fabricated part are altered by packing the pores in a freeform part with an infiltrant, such as a preceramic polymer. The process includes drawing a vacuum on or pressurizing the freeform part while it is in an infiltrant bath, thereby forcing the infiltrant into the pores of the freeform part. After removing the densified freeform part from the infiltrant bath, the freeform part is subjected to a treating process, such that the infiltrant within the pores transforms to a ceramic or ceramic-containing phase to thereby increasing the density of the freeform part.

Description

    CROSS REFERENCES TO RELATED APPLICATIONS
  • This application is a continuation-in-part (CIP) of U.S. patent application, Ser. No. 09/220,922, entitled “Method for Reducing the Porosity of a Freeform Fabricated Part”, which was filed Dec. 24, 1998.[0001]
  • TECHNICAL FIELD
  • This invention relates to freeform fabricated parts and in particular, to a method for modifying the properties of a freeform fabricated part by increasing its density. [0002]
  • BACKGROUND ART
  • As a result of the demand for ways to improve manufacturing efficiency and the need for rapid prototype development, freeform fabrication has become a popular method for manufacturing parts. Freeform fabrication originated with a process called stereolithography wherein a focussed ultra-violet laser scans the top of a bath of a photopolymerizable liquid polymer plastic material, thereby causing the top of the bath and the area just below the surface to polymerize. The polymerized layer is thereafter lowered into the bath and the laser scanning process is repeated until a second polymerized layer is formed. As the second polymerized layer forms, it bonds to the first layer. This process is repeated until a plurality of superimposed layers form the desired part. The shape of the part is first designed in a computer aided design system (i.e., a CAD/CAM system), which is linked to the machine performing the stereolithography process. Most freeform fabrication processes include a computer aided design system for coordinating the execution of the freeform fabrication process. In the case of stereolithography, the laser beam scans the area of the bath necessary to form the freeform fabricated part (hereinafter referred to as “freeform part”) designed on the computer aided design system. [0003]
  • The ability to produce an actual part directly from a design provides many advantages. One advantage includes eliminating the time traditionally used to develop the necessary tooling to manufacture the freeform part. Another advantage includes reducing the amount of machining, such as grinding, milling, drilling, etc., required to complete the part because the freeform fabrication process produces a substantially readily usable final product. Minimizing the amount of hands-on machining, therefore, translates into reducing the amount of potential human error and increasing efficiency. The amount of time saved in preparing for manufacturing also makes the freeform fabrication process attractive for rapid prototype development, which has been one of the main interests surrounding this technology in recent years. The benefit of rapid prototyping includes the ability to manufacture various configurations in a short amount of time, thereby providing designers with actual models of their designs. [0004]
  • Another method of freeform fabrication includes a technique called Three-Dimensional Printing (3DP), which consists of depositing a powdered material (e.g., a powdered ceramic, powdered metal, powdered plastic, or combination thereof) in sequential layers, one on top of the other. After depositing each layer of powdered material, a liquid binder is selectively supplied to the layer of powdered material using a type of ink-jet printing technique in accordance with a computer model of the three-dimensional part being fabricated. Following the sequential application and binding all of the required powder layers, the unbound powder is removed, thereby resulting in the formation of the designed three-dimensional part. [0005]
  • A third method of freeform fabrication includes Selective Laser Sintering (SLS). SLS includes a process whereby a powder dispenser deposits a layer of powdered material into a target area. A laser control mechanism, which typically includes a computer that houses the design, modulates and moves the laser beam to selectively sinter a layer of powder dispensed in the target area. Specifically, the control mechanism operates to selectively sinter only the powder disposed within the defined boundaries of the design. The control mechanism operates the laser to selectively sinter sequential layers of powder, producing a completed part comprising a plurality of layers sintered together yielding the completed design. [0006]
  • A fourth method of freeform fabrication includes Ballistic Particle Manufacturing (BPM). BPM uses an ink-jet printing apparatus wherein an ink-jet stream of liquid polymer or polymer composite material is used to create three-dimensional objects under computer control, similar to the way an ink-jet printer produces two-dimensional graphic printing. The device is formed by printing successive cross-sections, one layer after another, to a target using a cold welding or rapid solidification technique, which causes bonding between the particles and the successive layers. [0007]
  • An additional freeform fabrication technique, includes Fused Deposition Modeling (FDM). FDM consists of building solid objects in a layering fashion from polymer/wax compositions by following the signals produced by a computer aided design system. Specifically, FDM builds structures by extruding a fine filament of plastically deformable material through a small nozzle. The computer aided design system appropriately directs the nozzle over a build surface in the x, y and z directions, thereby creating a three-dimensional object that resembles the design. [0008]
  • Another method of freeform fabrication includes a technique called Photochemical Machining, which uses intersecting laser beams to selectively harden or soften a polymer plastic block. The underlying mechanism used is the photochemical cross-linking or degradation of the material. U.S. Pat. No. 5,490,962 provides a detailed summary of each of the above mentioned freeform fabrication techniques and is hereby incorporated by reference. [0009]
  • The methods described above, however, often result in the fabrication of a porous freeform part, thereby creating undesirable mechanical properties for the freeform part. A freeform part having inadequate strength, unsatisfactory hardness, low temperature tolerance, low abrasion resistance, rough surface finish, poor bonding of individual layers or poor bonding of powder particles within the layers presents a significant limitation to the types of applications in which freeform parts can be utilized. Therefore, what is needed is a means for increasing the mechanical, thermal or other physical properties of freeform parts. [0010]
  • DISCLOSURE OF INVENTION
  • The present invention exploits the porosity of a freeform fabricated part by packing the pores of a freeform part with an infiltrant that is capable of transforming to a ceramic or a ceramic-containing phase. The infiltrant comprises a preceramic polymer, which is selected to bond with the freeform part such that the resulting composition improves the mechanical, thermal and other characteristics of the freeform part. Packing the pores of the freeform part, therefore, increases its density and concomitantly decreases its porosity. Particularly, increasing the density of the freeform part increases one or more or all of the following properties: mechanical strength, hardness, temperature resistance, abrasion resistance, thermal conductivity, and erosion resistance. These properties may be enhanced by carefully fabricating the freeform part such that a certain porosity is imparted, selecting particular infiltrants with various concentrations that add the desired properties to the freeform part, and repeating the infiltration process until the desired density is achieved. [0011]
  • Accordingly, one aspect of the present invention is a process for modifying the properties of a porous freeform part comprising the steps of depositing a porous freeform part in an infiltrant bath, drawing a vacuum on the porous freeform part and the infiltrant bath such that the infiltrant enters the pores within the freeform part, and removing the densified freeform part from the infiltrant bath. The infiltrant is normally a preceramic polymer that is capable of transforming to a ceramic or a ceramic-containing phase. Furthermore, the preceramic polymer is preferably a polymer capable of nanocrystalline ceramic phase growth such that the preceramic polymer can enter the pores within the freeform part. Upon being removed from the infiltrant bath the density of the freeform part increases because the previously empty pores now contain infiltrant, and the infiltrant within the pores of the freeform part transforms to a ceramic or a ceramic-containing phase. Subjecting the freeform part to multiple infiltration processes further decreases the porosity of the freeform part and concomitantly increases its density. A second embodiment of the present invention includes pressurizing the infiltrant as an alternative to or in conjunction with drawing a vacuum on the porous freeform part and the infiltrant bath such that the infiltrant enters the pores within the freeform part. [0012]
  • A third embodiment of the present invention includes heating the infiltrant while pressure is being applied. [0013]
  • A fourth embodiment of the present invention includes placing the porous freeform part in a vacuum dessicator, applying a vacuum and allowing an infiltrant to enter the vacuum dessicator such that the infiltrant enters the pores within the freeform part. [0014]
  • A fifth embodiment of the present invention includes subjecting the densified freeform part to a series of post-processing steps upon being removed from the infiltrant bath such that the infiltrant within the pores of the densified freeform part transforms to a ceramic or a ceramic-containing phase. The post-processing steps may include one or more or all of the following steps: curing the infiltrant, heating the infiltrant at a rate, duration and temperature such that the infiltrant transforms to a ceramic or ceramic-containing phase within the pores of the freeform article, annealing the transformed infiltrant and cooling the freeform fabricated part and the transformed infiltrant. [0015]
  • A still further embodiment of the present invention includes a freeform fabricated part having pores therein comprising a ceramic or a ceramic-containing phase disposed within a portion of the pores with the freeform part. [0016]
  • The foregoing features and advantages of the present invention will become more apparent in light of the following detailed description of exemplary embodiments thereof as illustrated in the accompanying drawings.[0017]
  • BEST MODE FOR CARRYING OUT THE INVENTION
  • Through conducting a series of experiments, the inventor of the present invention recognized that infiltrants such as preceramic polymers, which are inorganic or organic polymers that transform to ceramic when subjected to intense heat, are capable of infiltrating the pores of a freeform part. The inventor of the present invention also recognized that increasing the density of the freeform part with certain infiltrants improved the mechanical characteristics of the freeform part, which serves as a support structure for the infiltrants. Therefore, the present invention is a process comprising the steps of fabricating a freeform part, depositing the freeform part in an infiltrant bath, drawing a vacuum on the porous freeform part and the infiltrant bath such that the infiltrant enters the pores of the freeform, and subjecting the freeform part and infiltrant to a treating process that may include one or more post-processing steps. Freeform parts for use in practicing the method of the present invention were fabricated using a three-dimensional printing technique similar to that described in U.S. Pat. Nos. 5,204,055 and 5,340,656 and 5,387,380, which are hereby incorporated by reference. Although the freeform parts in these experiments were made using the three-dimensional printing technique, the present invention may be used with freeform parts made by virtually any known freeform fabrication technique such as stereolithography, selective laser sintering, fused deposition modeling, ballistic particle manufacturing, and photochemical machining. It is preferable that the freeform parts be capable of withstanding the type of post-processing steps associated with transforming an infiltrant to a ceramic or ceramic-containing phase. Three different types of freeform parts were fabricated using the three-dimensional printing technique. One was a ¼ inch by ¼ inch by 4 inch Acrysol bonded silicon carbide (SiC) part. Specifically, silicon carbide powder, manufactured by Washington Mills under the tradename SIKA I, was bonded by the organic binder Acrysol WS-24, which is an acrylic colloidal dispersion manufactured by Rohm & Haas. The second type of freeform part was a ¼ inch by ¼ inch by {fraction (1 1/2)} inch alumina part. In that instance, brown aluminum oxide (Al[0018] 2O3) powder manufactured by Norton Company under the product code 7131 was bonded by the same Arysol WS-24 binder. The third type of freeform part was also a ¼ inch by ¼ inch by 1 ½ inch alumina part fabricated using the same brown aluminum oxide (Al2O3) powder manufactured by Norton Company mentioned above using the three-dimensional printing technique. However, this third type of freeform part was fabricated using the inorganic binder, colloidal silica (SiO2), manufactured by the Norton Company under the tradename Nyacol. Although the three freeform-fabricated parts used in our experiments were manufactured using silicon carbide and aluminum oxide, other materials such as metal, ceramic and metal-ceramic composites could be manufactured using the three-dimensional printing technique. Additionally, organic and inorganic binders other than Arysol WS-24 and colloidal silica could be used in the three-dimensional printing process.
  • The original density of the three types of parts was about thirty percent (30%) to about thirty seven percent (37%). In other words, sixty three percent (63%) to about seventy percent (70%) of the three-dimensional fabricated freeform part was porous. Therefore, it may also be preferable to subject the freeform part to post-processing methods, such as mild sintering or annealing, but doing so only improves the density to about thirty eight percent (38%) to about thirty-nine (39%). In the method of the present invention, the density of a freeform part is increased by depositing the freeform part into an infiltrant bath consisting of a preceramic polymer (i.e., ceramic precursor), which can be an organic or inorganic polymer but is generally in the form of an inorganic polymer. Any preceramic polymer capable of transforming to a ceramic or a ceramic-containing phase having nanocrystalline structures therein may be used as an infiltrant. Although the preceramic polymers used in all of the following examples were in the form of a liquid or a sol-gel, the preceramic polymer could be in a number of other forms, such as an organic solvent based solution or a liquid dispersion containing solid particles. In the latter case, the liquid provides a medium to deliver particles into the pores of a fabricated freeform part. [0019]
    TABLE 1
    Variable No. 1 No. 2 No. 3 No. 4 No. 5 No. 6
    Infil- Alumina Black- poly (met Perhydri Tyranno Polyalu-
    trant sol-gel glas ™ hylvinyl dopolysi Coat ™ minosila
    silicon silane) lazane Polysila zane
    oxycar- (PMVS) (PHPS) zane (PAS)
    bide
    Vacuum 5 × 10−3 5 × 10−3 5 × 10−3 5 × 10−3 5 × 10−3 5 × 10−3
    Pressure torr torr torr torr torr torr
    Vacuum 5 to 60 5 to 60 5 to 60 5 to 60 5 to 60 5 to 60
    Time min min min min min min
    Composi- Air or Nitrogen Argon Air, Nitrogen Nitrogen
    tion of oxygen or argon Nitrogen or argon
    Curing or argon
    Atmos-
    phere
    Curing 110° C. 85° C. 150 to 100° C. 110° C. 80 to
    Tempera- 250° C. 200° C.
    ture
    Curing 2 hours 5 to 12 1 to 3 1 to 3 1 to 3 1 to 3
    Time hours hours hours hours hours
    Composi- Air or Nitrogen Argon Air or Nitrogen Nitrogen
    tion of oxygen or argon Nitrogen or argon
    Convert- or argon
    ing
    Atmos-
    phere
    Initial 110° C. 100° C. 250° C. 150° C. 150° C. 150° C.
    Convert-
    ing
    Tempera-
    ture
    Rate of 2 to 10 2 to 10 2 to 10 2 to 10 2 to 10 2 to 10
    Increas- ° C./min ° C./min ° C./min ° C./min ° C./min ° C./min
    ing
    Convert-
    ing
    Tempera-
    ture
    Final 1000° C. 1000° C. 1000° C. 1000° C. 1000° C. 1000° C.
    Convert-
    ing
    Tempera-
    ture
    Composi- Air or Nitrogen Argon Air, Nitrogen Nitrogen
    tion of oxygen or argon Nitrogen or argon
    Anneal- or argon
    ing
    Atmos-
    phere
    Anneal- 1000 to 1000 to 1000 to 1000 to 1000 to 1000 to
    ing 1600° C. 1600° C. 1800° C. 1800° C. 1800° C. 1800° C.
    Tempera-
    ture
    Anneal- 1 to 8 1 to 8 1 to 8 1 to 8 1 to 8 1 to 8
    ing Time hours hours hours hours hours hours
    Rate of 10° C./min 10° C./min 10° C./min 10° C./min 10° C./min 10° C./min
    Cooling
  • Referring to Table 1, the freeform parts were deposited in the following preceramic polymers: alumina sol-gel, silicon oxycarbide (SiOC), poly(methylvinylsilane) (PMVS), perhydridopolysilazane (PHPS), polysilazane, and poly(aluminosilazane). Other potential preceramic polymers that could be used as infiltrants include polysilane, polycarbosilazane, poly(borosilazane), polysiloxane and polycarbosilane, and other molecularly mixed polymers that are capable of producing nanocrystalline ceramics or metals or mixtures hereof. Various polysilanes, polysilazanes, silicon oxycarbide (SiOC), polycarbosilazane, polysiloxane, perhydridopolysilazane and polycarbosilanes are commercially available. The alumina sol-gel used in Example 1 was prepared using a known process. The silicon oxycarbide (SiOC) used in Example 2 is produced by Allied Signal under the tradename Blackglas. The Blackglas™ silicon oxycarbide (SiOC) actually consists of a monomer solution, Blackglas™ 489A, and a catalyst, Blackglas™ 489C, which are combined before the freeform-fabricated part is deposited into such a bath. The perhydridopolysilazane used in Example 4 is sold by Tonen, and the polysilazane used in Examples 5 is distributed by UBE under the tradename Tyranno Coat. Although a poly(methylvinylsilane), a poly(aluminosilazane) or a poly(borosilazane) may not be manufactured on a commercial scale, it is known how to manufacture such preceramic polymers. Particularly, when using a poly(methylvinylsilane), it is preferred to use a reactive endblocked poly(methylvinylsilane) as described in a Final Technical Report entitled Novel Precursor Approaches for CMC Derived by Polymer Pyrolysis dated Feb. 15, 1994 prepared under Government Contract No. F49620-91-C-0017 and/or a Final Technical Report entitled A Study of the Critical Factors Controlling the Synthesis of Ceramic Matrix Composites from Preceramic Polymers prepared under Government Contract No. F49620-87-C-0093, which are both hereby incorporated by reference. Also, [0020]
    TABLE 2
    Coupon Part Resulting
    Material Infiltrant Composition
    Al2O3 Alumina sol-gel Al2O3/Al2O3
    Al2O3 Blackglas ™ SiOC/Al2O3
    Silicon oxycarbide
    Al2O3 poly (methylvinyl- SiC (+C)/Al2O3
    silane) (PMVS)
    Al2O3 Perhydridopolysila- SiO2 (with air)/
    zane Si3N4 (+Si)/Al2O3
    (PHPS)
    Al2O3 UBE Si3N4 (+Si)/Al2O3
    Tyranno Coat ™
    Polysilazane
    Al2O3 Polyaluminosilazane SiC/AlN/Si3N4 /Al2O3
    (PAS)
    SiC Alumina sol-gel Al2O3/SiC
    SiC Blackglas ™ SiOC/SiC
    Silicon oxycarbide
    SiC Poly(methylvinyl- SiC (+C)/SiC
    silane) (PMVS)
    SiC Perhydridopolysila- SiO2 (with air)/
    zane Si3N4 (+Si) /SiC
    (PHPS)
    SiC UBE Tyranno Coat ™ Si3N4 (+Si) /SiC
    Polysilazane
    SiC Polyaluminosilazane SiC/AlN/Si3N4 /SiC
    (PAS)
  • Although certain infiltrants may have destroyed a portion of the inter-particle bonds formed during the three-dimensional printing process, such as dissolution of the bond between an organic based binder and the three-dimensional printed part, the density of the resulting composition surpassed the density of the original freeform part. Specifically, upon undergoing the infiltration process described herein and infiltrating the freeform part with Blackglas™ silicon oxycarbide (SiOC), poly(methylvinylsilane) (PMVS) Perhydridopolysilazane (PHPS), Tyranno Coat™ Polysilazane, and Polyaluminosilazane (PAS), the density of the freeform part increased to about fifty percent (50%) to about sixty percent (60%). The density of the freeform part infiltrated with the alumina sol-gel increased to about forty percent (40%) to about forty-five (45%). [0021]
  • The infiltration process of the present invention, therefore, decreased the porosity and increased the density of the freeform part. The density of each freeform part is further increased and its porosity further decreased upon repeating the process until the desired density and porosity are achieved. It is beneficial to practicing the process of the present invention to first engineer the porosity of the freeform part to receive the infiltrants. Specifically, by fabricating freeform articles having an adaptable porosity, varying the type of infiltrant, controlling the concentration of the infiltrant and subjecting the freeform part to various and multiple infiltration processes, one can manipulate the porosity and mechanical characteristics of a freeform article such that a freeform part having desired properties of hardness, strength and density is produced. [0022]
  • An alternate process for modifying the properties of a porous freeform-fabricated part comprises the further step of pressurizing the infiltrant after drawing a vacuum on infiltrant and freeform part. This pressurizing step increases the potential of packing the pores in the freeform part with the infiltrant. [0023]
  • Another alternate process comprises the steps of depositing an individual freeform part in a vacuum dessicator containing an infiltrant and pressurizing the infiltrant rather than drawing a vacuum. Regardless of whether a vacuum is drawn on the infiltrant and freeform part, it may also be beneficial to heat the infiltrant as pressure is being applied in order to initiate curing of the infiltrant within the pores of the freeform part. [0024]
  • Still another alternate process for modifying the properties of a porous freeform part comprises placing the freeform part in an empty vacuum dessicator, drawing a vacuum on the freeform part and then introducing an infiltrant into the vacuum dessicator such that the infiltrant enters the pores within the freeform part. [0025]
  • Although the invention has been described and illustrated with respect to the exemplary embodiments thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions and additions may be made without departing from the spirit and scope of the invention. [0026]

Claims (37)

What is claimed is:
1. A process for modifying one or more properties of a porous freeform fabricated part, comprising the steps of:
(a) depositing a porous freeform fabricated part in a bath comprising an infiltrant;
(b) infiltrating the porous freeform fabricated part such that the infiltrant enters at least a portion of the pores resulting in a densified freeform-fabricated part; and
(c) removing the densified freeform fabricated part from the bath.
2. The process of
claim 1
wherein the step of infiltrating the porous freeform fabricated part comprises drawing a vacuum on the porous freeform fabricated part and the infiltrant such that the infiltrant enters at least a portion of the pores, resulting in a densified freeform fabricated part.
3. The process of
claim 2
where the vacuum is drawn on the porous freeform fabricated part for from about five minutes to about sixty minutes.
4. The process of
claim 2
wherein the pressure of the vacuum drawn on the porous freeform part is from about 100 torr to about 5×10−3 torr.
5. The process of
claim 2
further comprising the step of pressurizing the infiltrant.
6. The process of
claim 5
further comprising the step of heating the infiltrant while pressurizing the infiltrant.
7. The process of
claim 1
wherein the step of infiltrating the porous freeform fabricated part comprises pressurizing the infiltrant such that the infiltrant enters at least a portion of the pores, resulting in a densified freeform fabricated part.
8. The process of
claim 7
further comprising the step of heating the infiltrant while pressurizing the infiltrant.
9. The process of
claim 8
wherein the bath is pressurized for from about five minutes to about sixty minutes.
10. The process of
claim 9
wherein the step of pressurizing the bath occurs at a pressure of about 100 torr to about 5×10−3 torr.
11. The process of
claim 1
further comprising the steps of removing the densified freeform fabricated part from the bath and treating the densified freeform fabricated part such that the infiltrant within the pores of the densified freeform fabricated part transform to a ceramic or a ceramic-containing phase.
12. The process of
claim 11
wherein the treating step comprises curing the infiltrant within the densified freeform part.
13. The process of
claim 12
wherein curing the infiltrant occurs by either chemical curing or radiation curing.
14. The process of
claim 13
wherein radiation curing occurs through thermal curing.
15. The process of
claim 14
wherein thermal curing occurs by subjecting the infiltrant within the densified freeform part to a temperature ranging from about 80° C. to about 250° C.
16. The process of
claim 12
wherein the treating step further comprises heating the infiltrant within the densified freeform fabricated part such that the infiltrant transforms to a ceramic or ceramic containing phase.
17. The process of
claim 16
wherein the infiltrant is heated at a rate of about two degrees Celsius per minute to about ten degrees Celsius per minute.
18. The process of
claim 16
wherein the infiltrant is heated to a temperature ranging from about one hundred degrees Celsius to about one thousand two hundred degrees Celsius.
19. The process of
claim 16
wherein the infiltrant is heated in an atmosphere containing a gas selected from the group consisting essentially of air, argon and nitrogen.
20. The process of
claim 16
wherein the treating step further comprises annealing the ceramic or ceramic containing phase.
21. The process of
claim 20
wherein the step of annealing the infiltrant in the freeform fabricated part includes heating the freeform fabricated part and the infiltrant at a temperature of about 1000 degrees Celsius to about 1800 degrees Celsius for about one hour to about eight hours.
22. The process of
claim 20
wherein the treating step further comprises cooling the densified freeform fabricated part.
23. The process of
claim 22
wherein the step of cooling the infiltrant and densified freeform fabricated part comprises cooling the infiltrant and freeform fabricated part at a rate of about two degrees Celsius per minute to about ten degrees Celsius per minute.
24. The process of
claim 1
wherein the porous freeform fabricated part is fabricated by a method from the group consisting essentially of three-dimensional printing, stereolithography, selective laser sintering, fused deposition modeling, ballistic particle manufacturing, and photochemical machining.
25. The process of
claim 1
wherein the porous freeform fabricated part is made of metal, ceramic or a mixture thereof.
26. The process of
claim 1
wherein the porous freeform fabricated part is fabricated by a three dimensional printing process that bonds together the particles of silicon carbide powder using polymer emulsion as a binder.
27. The process of
claim 1
wherein the porous freeform fabricated part is fabricated by a three dimensional printing process that bonds together the particles of aluminum oxide powder using a binder from the group consisting essentially of colloidal silica and polymer emulsion.
28. The process of
claim 1
wherein the infiltrant is in the form of a solution selected from the group consisting essentially of a liquid, a liquid containing solid particles and an organic solvent based solution.
29. The process of
claim 1
wherein the infiltrant comprises a precursor selected from the group consisting of alumina sol-gel, polysilane, polysilazane, silicon oxycarbide (SiOC), poly(methylvinylsilane), poly(aluminosilazane), perhydridopolysilazane, poly(borosilazane), polycarbosilazane, poly(siloxane), poly(carbosilane) and mixtures thereof.
30. The process of
claim 29
wherein the infiltrant further comprises a powder selected from the group consisting essentially of metal, ceramic or ceramic metal.
31. A process for modifying one or more properties of a porous freeform fabricated part, comprising the steps of:
(a) placing a porous freeform-fabricated part in a vacuum dessicator;
(b) drawing a vacuum on the porous freeform fabricated part; and
(c) introducing an infiltrant into the vacuum dessicator such that the infiltrant enters the pores within the porous freeform part.
32. The process of
claim 31
further comprising the step of treating the densified freeform part such that the infiltrant within the densified freeform part transforms to a ceramic or ceramic-containing phase.
33. A densified freeform-fabricated part produced by the process of:
(a) depositing a porous freeform fabricated part into a bath comprising an infiltrant;
(b) infiltrating the porous freeform fabricated part such that the infiltrant enters at least a portion of the pores resulting in a densified freeform fabricated part; and
(c) removing the densified freeform fabricated part from the bath.
34. The densified freeform-fabricated part of
claim 33
further comprising the step of treating the densified freeform fabricated part such that the infiltrant within the densified freeform part transforms to a ceramic or a ceramic-containing phase.
35. A densified freeform fabricated part, comprising:
(a) a freeform fabricated part having pores therein; and
(b) a ceramic or a ceramic containing-phase within a portion of said pores.
36. The freeform-fabricated part of
claim 35
wherein the freeform fabricated part is either a metal, ceramic or a mixture thereof.
37. The freeform fabricated part of
claim 35
wherein the ceramic or ceramic containing phase originated from a precursor selected from the group consisting essentially of alumina sol-gel, polysilane, polysilazane, silicon oxycarbide (SiOC), poly(methylvinylsilane), poly(aluminosilazane), perhydridopolysilazane, poly(borosilazane), polycarbosilazane, poly(siloxane), poly(carbosilane) and mixtures thereof.
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