WO2011005535A1 - Composites céramique-polymère - Google Patents

Composites céramique-polymère Download PDF

Info

Publication number
WO2011005535A1
WO2011005535A1 PCT/US2010/039524 US2010039524W WO2011005535A1 WO 2011005535 A1 WO2011005535 A1 WO 2011005535A1 US 2010039524 W US2010039524 W US 2010039524W WO 2011005535 A1 WO2011005535 A1 WO 2011005535A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite
ceramic
phase
polymer
pores
Prior art date
Application number
PCT/US2010/039524
Other languages
English (en)
Inventor
Ellen M. Dubensky
Chan Han
Lameck Banda
Christian A. Steinbeck
Amy Wetzel
Gerald F. Billovits
Ari K. Kar
Steven R. Lakso
Original Assignee
Dow Global Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies, Inc. filed Critical Dow Global Technologies, Inc.
Publication of WO2011005535A1 publication Critical patent/WO2011005535A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/63—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A61L27/427—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of other specific inorganic materials not covered by A61L27/422 or A61L27/425
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/185—Mullite 3Al2O3-2SiO2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/0605—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances by sublimating
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/4853—Epoxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/282—Selecting composite materials, e.g. blades with reinforcing filaments
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/15—Ceramic or glass substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00836—Uses not provided for elsewhere in C04B2111/00 for medical or dental applications
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6586—Processes characterised by the flow of gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2225/00—Synthetic polymers, e.g. plastics; Rubber
    • F05C2225/08—Thermoplastics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/20—Oxide or non-oxide ceramics
    • F05D2300/21—Oxide ceramics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/20—Oxide or non-oxide ceramics
    • F05D2300/21—Oxide ceramics
    • F05D2300/2112—Aluminium oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the invention relates generally to structural composite ceramic-polymer compositions. More specifically, the invention relates to structural compositions comprising ceramic and polymer phases, the ceramic phase having a truss-like structure and a co- continuous polymer phase, the structural composition having enhanced properties such as increased thermal and compressive stability as well as increased strength, stiffness, and elongation.
  • Ceramic polymer composites based on porous ceramic sponge infiltrated with polymers are reported in the literature to have improved strength-elongation over ceramic or polymer alone. These materials are reported to have utility in impact and wear applications.
  • Gomez et al. "Compression Strength and Wear Resistance of Ceramic Foams - Polymer Composites," Materials Letters 60(2006) 1687-1692, reported on SiC and SiO 2 ZrO 2 , among others, ceramic foams that were filled with epoxy vinyl-ester resins to produce composite materials.
  • Gomez et al. identified a number of crystalline shapes within the foams including tetragonal, rhombohedric, hexagonal, and orthorhombic. Compression strength values were provided for SiC and SiO 2 ZrO 2 .
  • a ceramic- polymer composite comprising a ceramic phase, the ceramic phase having an interconnected network of pores, the interconnected network of pores comprising truss-like structures, and a co-continuous polymer phase integrated with the ceramic phase, wherein the polymer phase is contained within the pores of the ceramic phase.
  • porous acicular mullite was infiltrated with low-viscosity polymers to produce ceramic-polymer composites with better mechanical properties than ceramic-polymers reported in the literature.
  • Another aspect of the invention is a method of treating a subterranean formation by injecting into the formation of a fracturing fluid that comprises a proppant to be deposited into the subterranean formation.
  • the invention is a ceramic-polymer composite material with an excellent strength to weight ratio, high modulus and improved elongation over ceramics alone.
  • the composite is made with a truss-like porous ceramic structure, such as, for example, acicular mullite or alumina, and then infiltrating with polymer to fill the pores or void spaces.
  • the density of the composite of the invention ranges from about 1 g/cc to 2 g/cc.
  • Compressive strengths for the composite of the invention reach as high as about 10,000 psi, preferably about 15,000 psi, and more preferably about 20,000 psi.
  • the heat stability of the composite of the invention provides these strengths at temperatures of at least about HO 0 C, preferably 15O 0 C, and more preferably 22O 0 C.
  • One property distinguishing of the invention is the "pseudo ductility" which the composite of the invention offers.
  • the composite of the invention offers flexural strength, elongation and Young's modulus all of which distinguish the invention. Percent elongation generally depends on the polymer phase but may range to at least about 0.3%. At the same time, flexural strength ranges to at least about 50 MPa. Further, Young's modulus for the composite of the invention is at least about 20.
  • the composites of the invention also offer other properties like low coefficients of thermal expansion in all three primary axis. While all of these parameters distinguish the invention, each of them may be used individually to distinguish the invention from earlier materials and composites.
  • the properties of the composite can be altered significantly by the choice of the polymer.
  • the composite By infiltrating the ceramic with thermoplastic or elastomeric polymer, the composite may exhibit ductile-type fracture behavior.
  • a thermosetting polymer such as an epoxy, the resulting composite displays brittle fracture properties, but with higher strength and elongation.
  • Figures Ia and Ib are Scanning Electron Micrographs (SEM) of a representative ceramic phase showing truss-like and needle-like structures in accordance with the invention.
  • Figure 2 is a graphical representation of the data of Example 1 in accordance with one embodiment of the invention.
  • Figure 3 is a graphical representation of the data of Example 2 in accordance with one embodiment of the invention.
  • Figure 4 is a Scanning Electron Micrograph (SEM) of Example 3 in accordance with one embodiment of the invention.
  • Figures 5 is a graphical depictions of certain results of Example 3.
  • Figure 6 is a graphical/SEM depiction of the results of Example 6 (PROPPANT).
  • Figures 7 and 8 are SEM depictions of the composition of Example 6
  • Figure 9 is a SEM of the composition of Example 7 (PROPPANT) in accordance with one aspect of the invention.
  • the invention is a ceramic-polymer composite.
  • the composite of the invention comprises two phases.
  • the first phase is a ceramic having a continuous lattice network of voids or pores throughout that phase.
  • the second phase comprises an organic polymer composition which is substantially contained within the ceramic phase.
  • the polymer and ceramic phases are co-continuous with the polymer being located throughout the pores of the ceramic phase.
  • the ceramic phase of the composite of the invention has a level of porosity ranging from about 40 to 85% by volume.
  • the polymer phase of the invention is contained within up to about 100% by volume of the pore space of the ceramic phase.
  • the polymer phase of composite of the invention is co-continuous which means that the polymer fills about 80% by volume, preferably about 90% by volume, and more preferably about 95% by volume up to 100% by volume of the pore or void space of the ceramic phase.
  • the ceramic phase comprises a truss-like structure.
  • a truss is a three membered geometric shape most clearly identified as a triangle. The three members of a triangle each have a given length each of which is connected at their first and second respective ends to create a closed structure.
  • the truss-like structure of the invention is an interconnected porous structure composed of needles and platelets where the pore size is defined as the space between the needles and platelets.
  • Figures Ia and Ib show an exemplary truss-like structure comprising needles and platelets.
  • the truss-like structure of the ceramic phase is a three dimensional network of triangles, the triangles being interconnected through shared joints and lengths. Since a triangle will not change shape when the lengths of the sides are fixed, it is the simplest geometric shape and inherently resistant to stress when placed under load.
  • the composite of the invention comprises from about 15 vol.-% up to about 60 vol.-%, preferably up to about 50 vol.-%, and more preferably up to about 40 vol.-% ceramic.
  • the truss-like structure comprises at least about 40% by volume, preferably at least about 60% by volume, and more preferably about 80% by volume of the ceramic phase.
  • the composite of the invention exhibits properties which may vary in accordance with the materials used in the ceramic and polymer phases.
  • the composite of the invention provides a unique combination of strength and ductility when placed under stress.
  • the composite of the invention provides a higher resistance to fracture when subjected to tensile stresses or compressive stresses.
  • the composite of the invention provides fracture strain which exceeds that of ceramic structures.
  • the composite of the invention provides a compressive strength of at least about 10,000 psi, preferably at least about 15,000 psi, and more preferably at least about 20,000 psi. Further, the density of the composite of the invention may be varied in great measure ranging from at least about 1 gm/cm 3 , preferably at least about 1.2 gm/cm 3 up to about 1.9 gm/cm 3 , preferably 2 gm/cm 3 .
  • the composite of the invention also provides heightened heat stability. In this context, heat stability may generally be considered compressive strength at higher temperatures. To this end, the composite of the invention provides the compressive strengths indicated above at temperatures of up to at least about 110 0 C.
  • the composite of the invention comprises a ceramic phase.
  • the ceramic phase of the composite provides stiffness or rigidity and resistance to compressive forces which may strain the composite in use.
  • the ceramic phase comprises a lattice or network of truss-like structures which facilitate this function.
  • any ceramic may be used which provides a continuous porous network framed by three dimensional truss-like structures. Ceramics known to form truss-like structures in situ, or during the reaction to form the porous body, are alumina and mullite.
  • One preferred ceramic, mullite, preferably acicular mullite (ACM) grains, may be chemically bound together to create a porous structure. It is desirable that the mullite grains comprise at least 90 percent of the mullite composition. Preferably the mullite grains comprise at least about 95 percent, more preferably at least 98 percent, even more preferably at least 99 percent by volume of the ceramic phase.
  • the mullite composition (in addition to the mullite grains), almost invariably contains a glassy phase comprised of silica, alumina and metal impurities in the form of oxides. The glassy phase is generally situated at the mullite grain surfaces and at intersecting grain surfaces.
  • the bulk Al/Si stoichiometry of the mullite composition may be any suitable ratio, such as 4 Al/Si to 2.5 Al/Si.
  • Bulk stoichiometry means the overall ratio of Al to Si in the total body, (that is not each individual grain).
  • Acicular mullite grains are grains that have an aspect ratio, defined as the length of the grain divided by the width, of greater than about 2 to about 50.
  • the acicular mullite grains present in the mullite composition have an average aspect ratio of at least about 5.
  • the average aspect ratio is at least about 10, more preferably at least about 15, even more preferably at least about 20 and most preferably at least about 40.
  • mullite composition Essentially all of the grains of the mullite composition are chemically bound to other mullite grains of the body. Chemically bound, generally, is when the grains are sintered or fused together. The fusing and sintering occurs at the grain interfaces, and is generally comprised of a glassy (i.e., disordered) amorphous oxide phase of Si, Al or a mixture thereof. As described above, the glassy phase may also contain other metal oxide impurities.
  • a glassy (i.e., disordered) amorphous oxide phase of Si, Al or a mixture thereof As described above, the glassy phase may also contain other metal oxide impurities.
  • the microstructure may be determined by suitable techniques such as microscopy on a polished section.
  • the average mullite grain size may be determined from a scanning electron micrograph (SEM) of a polished section of the ceramic body, wherein the average grain size may be determined by the intercept method described by Underwood in Quantitative Stereology, Addison Wesley, Reading, Mass. (1970).
  • the mullite precursors may contain impurities of magnesium and/or iron.
  • the mullite composition has a glassy phase at the surface of the mullite grains which may have iron and magnesium incorporated therein.
  • the magnesium and iron may essentially be incorporated into the glassy phase when, at most, trace amounts of crystalline precipitates of Mg and/or Fe maybe detected by X-ray diffraction or electron diffraction.
  • crystalline Mg and/or Fe crystalline precipitates are undetectable by electron diffraction.
  • the mullite composition is substantially free of fluorine.
  • the heat-treatment of this invention also causes the fluorine content to be reduced, while accomplishing the incorporation of the Mg and Fe into the glass.
  • mullite compositions contains 2 to 3 percent by weight of fluorine.
  • the mullite compositions, where the Mg and Fe are incorporated into the glass phase have an amount of fluorine of at most about 0.75 percent by weight of the composition.
  • the amount of fluorine is less than about 0.5 percent, more preferably less than about 0.25 percent, even more preferably less than about 0.1 percent and most preferably at most a trace amount by weight in the mullite composition.
  • precursor compounds containing Al, Si and oxygen are mixed to form a mixture capable of forming mullite.
  • Precursor compounds that may be used are described in U.S. Pat. Nos. 5,194,154; 5,198,007; 5,173,349; 4,911,902; 5,252,272; 4,948,766 and 4,910,172, all of which are incorporated herein by reference.
  • mullite bodies including porous mullite bodies are known to those of skill in the art including those disclosed in U.S. Patent Nos. 7,425,297; 6,596,665; and 7,381,680, all of which are incorporated herein by reference.
  • the acicular mullite which may be used in accordance with the invention may be synthesized from naturally occurring fibers or fibers synthesized from granulated materials.
  • mullite is granulated through any known process including spray drying. The granules are then heat reacted at a temperature ranging from about 500 0 C to 1000 0 C in an SiF 4 environment. Needles form through this processing. Once needles or platelets are formed, the formed product is then heated up to about 1400 0 C for up to about six hours to form the porous truss-like network characteristic of the ceramic phase of the invention.
  • mullite is formulated from a mixture, the mixture is generally comprised of clay (that is, hydrated aluminum silicate) and compounds such as, alumina, silica, aluminum trifluoride, fluorotopaz and zeolites.
  • the precursor compounds are selected from the group consisting of clay, silica, alumina and mixtures thereof.
  • the mixture is comprised of clay and alumina.
  • the mixture may be made by any suitable method such as those known in the art. Examples include ball milling, ribbon blending, vertical screw mixing, V-blending and attrition milling.
  • the mixture may be prepared dry (that is, in the absence of a liquid medium) or wet.
  • the mixture is then shaped into a porous body by any suitable method, such as those known in the art.
  • suitable method such as those known in the art. Examples include extrusion, spray drying, tumbling, tape casting, isostatic pressing, uniaxial pressing or other means of making articles known to those of skill in the art.
  • the next step of the process is the heating of the porous green shape under an atmosphere having fluorine and a temperature sufficient to form the mullite composition.
  • Fluorine may be provided in the gaseous atmosphere from sources such as SiF 4 , AlF 3 ,
  • the source of fluorine is from SiF 4 .
  • This gas preferably is a gas containing SiF 4 .
  • the porous body is preferably heated to a temperature and for a time sufficient to convert the precursor compounds in the porous body to fiuorotopaz and sufficient to form the mullite composition.
  • the temperature may be from 500°C. to 1000°C.
  • the temperature is at least 550°C, more preferably at least 65O 0 C. and most preferably at least
  • 700°C. to preferably at most 850°C, more preferably at most 800°C.
  • the time required at the heat treatment temperature is a function of the heat treatment atmosphere and the temperature selected. For example, a heat treatment in wet air
  • ambient air dry air or nitrogen (air having a relative humidity from 20 percent to 80 percent at room temperature) desirably is heated to 1400°C. for up to about 6 hours.
  • the ceramic phase of the composite may also be comprised of alumina.
  • Alumina platelets may be formed when pure alumina is reacted in a SiF 4 environment.
  • the shaped aluminum particles are porous and comprise an interconnected network of truss structures.
  • the three-dimensional network of alumina platelets has voids which may be filled with a polymer phase to create a composite.
  • the alumina platelets may be made into shaped porous bodies using any number of methods known to those of skill in the art including those disclosed in
  • the alumina bodies once formed into a composite with polymer, may be relied upon to provide a compressive strength of at least about 10,000 psi, preferably at least about 15, 000 psi, more preferably at least about 20,000 psi.
  • the alumina platelets when used as an element of the composite of the invention provides a heat stability of at least about HO 0 C, preferably about 150 0 C, and more preferably about 220 0 C.
  • the alumina also provides a porous network having a porosity of at least about 60% by volume porosity, preferably about 65% by volume, and more preferably at least about 70% by volume porosity.
  • the porous network within the alumina may be as great at 80%-volume, preferably 75%-volume, and more preferably about 74%-volume.
  • the platelets of alumina are fused together or interlocked in diameter to create a three dimensional network.
  • the platelets have a size ranging from about 5 ⁇ m to about 20 ⁇ m in diameter and from about 0.3 ⁇ m to about 1 ⁇ m in thickness.
  • Characterization of the alumina platelets useful in the invention may be found in Shaklee et al., Growth ofa- AI 2 O 3 Platelets in the HF- ⁇ y-AI 2 O 3 System, J. Am. Ceram. Soc, 77(11), 2977-84 (1994), which is incorporated herein by reference.
  • An alternative method may be to form the porous network ex situ from pre-existing needles or platelets.
  • the needles or platelets are again heated to a level where sintering takes place creating a porous network.
  • This process may be used with any ceramic that forms needles and plates to form truss-like structures.
  • Useful ceramics such as, for example, binary, tertiary, quaternary ceramics including oxides of aluminum, antimony, arsenic, beryllium, bismuth, boron, calcium, copper, iron, gallium, germanium, indium, lanthanum, lead, magnesium, molybdenum, neodynium, nickel, niobium, phosphorous, silicon, strontium, tantalum, tellurium, titanium, tungsten, vanadium, yttrium, zirconium, and zinc; silicates of aluminium; nitrides of aluminium, boron, gallium and gallium aluminium, and silicon; barium titanate, lead titanate, lead lanthanum zirconate titanate, lead magnesium niobate, lead zirconate, lead zinc niobate; lithium niobate, lithium tantalate; bismuth calcium strontium copper oxide, cobalt ferrite, lanthanum nickel ferrite,
  • wollastonite among other ceramics. These compounds may be processed in the same manner as the mullite granules to produce acicular fines, needles or platelets. In turn, these numbers may be processed into a three-dimensional porous network comprising truss-like structures and ceramic phase of the invention.
  • Wollastonite is generally as calcium inosilicate (CaSiO 3 ). Small impurities in the form of iron, magnesium and manganese may take the place of silicon in the compound. Wollastonite may be processed in the same manner as mullite and alumina noting that it has a common melting point of about 154O 0 C. [0052] Generally, once processed, the wollastonite will form a ceramic lattice with truss- like structures. The general pore size will range from about 3 ⁇ m to 30 ⁇ m with the pore content in the three dimensional ceramic phase ranging from about 40 to 88 percent by volume, and preferably about 60 to 85 percent by volume.
  • the composite of the invention also comprises a polymer phase which is formed within the voids of the interconnected porous network of the ceramic phase.
  • the polymer phase of the invention functions to provide further ductility to the composite.
  • the polymer phase comprises a co-continuous matrix filling up to 100 vol.-% of the pores of the ceramic.
  • the polymer phase may also be used in adjusting the density of the composite.
  • the density of the composite may be adjusted according to the application and in accordance with the invention. Useful densities include those of at least 1 gm/cm 3 , and preferably 1.3 gm/cm 3 .
  • Higher ranges include densities up to about 2 gm/cm 3 and preferably up to about 1.8 gm/cm 3 .
  • the overall density of the composite may be effectively lowered.
  • the combination of ceramic and polymer provides a strength which enhances the activity of the composite in the intended environments of use.
  • any number of polymer systems may be used in accordance with the invention.
  • Basic families of polymers include thermoplastic and thermosetting polymers as well as combinations thereof.
  • Thermosetting compositions may be used to enhance the mechanical properties of the composite such as hardness and impact resistance. Any variety of curable thermoset compositions which are capable of being crosslinked or cured through heat may be used within the composition of the invention.
  • Thermosetting compositions useful in the composition of the invention include epoxies, polyurethanes, curable polyesters, hybrid thermosets, and curable acrylics as well as polyolefins, and alkyl, aryl and aromatic hydrocarbon resins, among a large number of other compositions.
  • bismaleimides such as the partial reaction product of the bismaleimide of methyl dianiline.
  • thermosetting compositions which are useful with the invention include silicones, phenolics, polyamids, and polysulfides, among others.
  • Preferred thermosetting compositions which are useful with the invention include curable and unsaturated polyester resins such as, for example, maleate resins formed by the reaction of various polyols and maleic anhydride.
  • Orthophthalic resins may be used the present invention and can be formed by reaction of phthalic anhydride and maleic anhydride or fumaric acid and as the dibasic acids.
  • Isophthalic resins are also useful with the invention and may be formed by preparing isophthalic acid and maleic anhydride or fumaric acid.
  • composition of the invention may also use bis-phenol fumarates which may be prepared by the reaction of propyloxylated or ethoxylated bis-phenol A with fumaric acid.
  • Chlorendic polyester resins may also be used in the composition of the invention. Generally, chlorendic polyester resins are prepared by reacting chlorendic anhydride with maleic anhydride or fumaric acid. Vinyl esters may also be used in the invention as well as dicyclopentadiene resins.
  • thermosetting compositions useful in the present invention include the reaction product of orthotolyl biguanide known as casmine and commercially available from SBS Chemicals Inc. and the diglycidyl ether made from bis-phenol A- epichlorohydrin; triglycidyl isocyanurate thermosetting compositions; bis-phenol A- epichlorohydrin diglycidyl ether cured with phenolic crosslinking agents; aliphatic urethane thermosetting compositions such as an unblocked isophorone diisocyanate-E-caprolactam available from Ruco Polymer Corporation under the commercial name NI 2 which may be used with Ruco HBF which is a hydroxyl terminated polyester resin also available from Ruco Polymer Corporation; BTDA thermosetting compositions which are generally the reaction product of 3,3,4,4-benzophenone tetracarboxylic dianhydride and a bis-phenol A- epichlorohydrin diglycidyl ether; hybrid thermosetting compositions which are the
  • Curing agents known to those of skill in the art and which are also useful in the thermoset compositions of the present invention include melamines such as dialkyl melamines; amides such as dicyandiamide, adipamide, and isophthalyl diamide; ureas such as ethylene thiourea or guanylurea; azides such as thiosemicarbiazide, or adipyldihydrazide, and aminophthalyldihylzide dihydrazide; azoles such as guanazole, or 3 amino- 1,2,4 triazole; and anilines such as dialkylanalines like dimethyl aniline or diethyl aniline.
  • melamines such as dialkyl melamines
  • amides such as dicyandiamide, adipamide, and isophthalyl diamide
  • ureas such as ethylene thiourea or guanylurea
  • azides such as thiose
  • the viscosity and cure properties of the invention are such to facilitate permeation os the polymer into the ceramic particle.
  • Exemplary viscosities range from about 100 cP to 12,000 cP at 25 0 C.
  • High temperature stability of the polymer also assists in providing thermal stability to the composite of the invention.
  • the thermosetting polymer once crosslinked, provides heat tolerance up to at least about 100 0 C, preferably at least about 15O 0 C, and more preferably at least about 22O 0 C.
  • Thermoplastic polymers may also be used in the composition of the invention to increase the flexibility and ductility of the work piece.
  • useful thermoplastics include vinyl polymers, polyesters, polyamides, polyimides, polyamide-imides, polyethers, block polyamides-polyethers, block polyesterspolyethers, polycarbonates, polysulfones, poly bisimidazoles, polybisoxazoles, poly bisthiazoles, and polyphenyl polymers.
  • thermoplastics include nylons, polyacetals, polyester elastomers, polyurethanes, polyphenyl- aniline sulfides, poly-propylenes, polyether ether ketones, as well as elastomeric thermoplastics including butyl rubber, ethylene vinyl acetate copolymers, as well as SOS, SBS and SIS block copolymers and the like.
  • polycarbonates, and polyolefins such as polypropylene, as well as polyimides.
  • Vinyl polymers useful in the composition of the invention include polyethylene, polypropylene; rubbery polymers and copolymers prepared from monomers including ethylene, propylene, styrene, acrylonitrile, butadiene, isoprene, and others, acrylic acid, methacrylic acid, methylacrylate, methylmethacrylate, vinyl acetate, hydroxyl methacrylate, hydroxyl ethylacrylate, as well as other known vinyl monomers.
  • thermoplastic saturated polyesters made from di- or tri- carboxylic acid in combination with di- or tri- hydroxyl compounds.
  • the composition of the invention may be used as a proppant or propping agent.
  • Propping agents or proppants are pumped into the formation under pressure sufficient to crack the rock formation and create conductive channels from deep within the reservoir to the wellbore and out to the surface.
  • Proppants such as sand, resin-coated sand, and high-strength ceramics are typically denser (specific gravity 2.5-3.7) and heavier than the carrier fluid used for transport. This can lead to settling and inhomogenous fracturing.
  • the fluid is either viscosified and/or pumped at very high rates (> 100 barrels per minute).
  • Viscosified or gelled fracture fluids tend to leave polymer and surfactant residues within the fractures, significantly reducing permeability, and conductivity, and thereby impeding the flow of oil or natural gas through the fracture.
  • these gels are needed to suspend and transport the dense proppants, and keep them from settling out prematurely, before they can be placed in the newly created fracture.
  • the density of the proppant can be matched to the carrier fluid as well.
  • the composite proppant particle of the inventor comprises co-continuous ceramic and polymer phases, the ceramic phase having an interconnected network of pores, the interconnected network comprising truss-like structures.
  • the truss-like structures have one or more triangular shapes, and the polymer phase is integrated within the ceramic phases, wherein the polymer phase is contained within the pores of said ceramic phase.
  • the first phase is mullite ceramic having an interconnected network of pores.
  • the interconnected network of pores has a truss-like structure comprising one or more triangular shapes.
  • the triangular shapes have members selected from the group consisting of a needle, a plate, and mixtures thereof.
  • the polymer phase comprises a polymer integrated with the ceramic phase to provide a co-continuous matrix.
  • the polymer phase is contained within the pores of the ceramic phase.
  • the co-continuous ceramic-polymer composite has a density ranging from about 1.3 to 1.9 gm/cm 3 , a compressive strength of at least about 10,000 psi and does not fail catastrophically like ceramics.
  • Compressive strength of single proppant beads can be measured by placing a proppant particle between the platens of a compression test machine, applying load at a constant rate, and recording the particle deformation.
  • Compressive strength, at any amount of deformation can be calculated by dividing the load by the cross-sectional area of the bead. Percent strain is calculated as the amount of deformation divided by the original bead diameter.
  • Resistance to fracturing can be determined by observing whether or not the bead fractures into two or more smaller particles during the compression test. Generally, a proppant that does not fracture into two or more particles can have percent strain of 20% to 60% or higher.
  • the proppant of the invention also provides increased heat stability.
  • heat stability may generally be considered compressive strength at higher temperatures.
  • the proppant composition of the invention provides the compressive strengths indicated above at temperatures of up to at least about 110° C or more.
  • the proppant may take the form of any number of shapes including small spheres (a characteristic size being 100 ⁇ m-2mm) with a reduced density compared to purely ceramic particles, exhibiting the high thermal and mechanical stability required for hydraulic fracturing. As such the material is highly suitable as a light-weight proppant, outperforming current proppants in terms of temperature and pressure stability.
  • the proppant of the invention also provides effective density matching to the stimulation fluid.
  • the composite is made by starting with a porous ceramic structure, for example a truss-like material such as acicular mullite (ACM) or alumina and then infiltrating with an organic polymer, prepolymer or monomer to fill the pores of void spaces.
  • ACM acicular mullite
  • the properties of the composite can be altered significantly by the choice of the polymer and ceramic components.
  • One property distinguishing of the invention is the "pseudo ductility" which the composite of the invention offers.
  • the composite of the invention offers compressive strength, percent strain and Young's modulus all of which distinguish the invention.
  • Percent strain generally depends on the polymer phase but may range from least about 20% to 60% or higher.
  • compressive strength of the proppant ranges from at least about 10,000 psi, preferably at least about 15,000 psi, to more preferably 20,000 psi or higher.
  • Young's modulus for the composite of the invention is at least about 20GPa.
  • the composites of the invention also offer other properties like low coefficients of thermal expansion in all three primary axis.
  • the proppant compositions of this invention may also be resistant to tensile stresses. While all of these parameters distinguish the invention, each of them may be used individually to distinguish the invention from earlier materials and composites.
  • the composition of the invention may also be used in any application that requires the use of small (100 ⁇ m-2mm) particles exhibiting a density similar to water and high thermal and mechanical stability.
  • the invention may be useful in geothermal energy generation as geothermal wells also often require stimulation and many of the same problems and needs as oil and gas wells are encountered.
  • the invention may also be useful in oilfield gravel pack (for sand/formation fines control), and cementing and drilling fluid applications (as density modifiers, lubricants or to improve the mechanical properties of cement).
  • Other possible areas of application for the composition of the invention include abrasion or lubrication fluids.
  • This invention uses a truss-like ceramic, which has ceramic needles or plates that are randomly oriented and which have connected joints, making a very strong material compared to sponge-like porous ceramics.
  • the truss-like structure is capable of withstanding higher loads.
  • the void spaces are also continuous and open enough to be easily infiltrated with low- viscosity polymers.
  • the resulting polymer/ceramic composites are much stronger than those made from sponge-like ceramics.
  • the ceramic truss/polymer composition of the invention provides a unique combination of compressive strength and percent strain when placed under stress.
  • the proppant of the invention also provides increased heat stability.
  • heat stability may generally be considered compressive strength at higher temperatures.
  • the proppant composition of the invention provides the compressive strengths indicated above at temperatures of up to at least about 110° C.
  • the proppant may comprise any number of particle shapes and sizes.
  • the proppant particle may have a size of at least about 10 ⁇ m, preferably about 50 ⁇ m, and more preferably about 100 ⁇ m up to about 5mm, preferably up to about 3mm, and more preferably up to about 2mm in its greatest dimension.
  • the proppant particle may also comprise a regular or irregular shape. Regular shapes include pyramidal, spherical, core and cubic among others.
  • the acicular mullite which is useful in forming the proppants of the invention may be synthesized from a mixture of naturally occurring or synthetic materials containing Al 2 O 3 and SiO 2 .
  • Al 2 O 3 and SiO 2 are mixed and granulated through any known process, including spary drying.
  • the temperature at which the topaz converts to mullite needles may be from 900 0 C to 1250°C.
  • the temperature is at least 1000°C, more preferably at least 1050 0 C and the most preferably at least HOO 0 C to preferably 1350°C, more preferably at most 1250 0 C.
  • the combination of ceramic and polymer phases provides a strength which enhances the activity of the proppant in subterranean environments.
  • Preferred single particle (bead) compressive strengths are at least 10,000 psi or greater, preferably 15,000 psi or greater, and more preferably, 20,000 psi or greater for the composition of the invention.
  • Heat stability is also provided by the composition of the invention. Generally, the heat stability of the composition of the invention is up to at least about HO 0 C, preferably, at least about 15O 0 C and more preferably, at least about 22O 0 C.
  • any number of polymer systems may be used in accordance with the invention.
  • Thermo plastic polymers especially semicrystalline polymers with melting temperatures above 200 0 C are suitable for proppant.
  • Preferred families of polymers include thermosetting polymers.
  • Any variety of curable thermoset compositions which are capable of being crosslinked or cured through heat may be used within the proppant of the invention.
  • Thermosetting compositions useful in the composition of the invention include epoxies, polyurethanes, curable polyesters, hybrid thermosets, and curable acrylics among a large number of other compositions.
  • Also useful in the composition of the invention are bismaleimides such as the partial reaction product of the bismaleimide of methyl dianiline.
  • the composite of the invention may be formulated by any means known to those of skill in the art.
  • the polymer phase may be wicked into the pores of the ceramic phase through capillary action.
  • any number of other means may be used to formulate the composite of the invention through the use of vacuum or pressurized infusion of the polymer throughout the ceramic. Heating means may also be used to fix and cure the polymer within the ceramic phase.
  • the component parts of the uncured thermoset such as an epoxy
  • the composition of the invention may be delivered to the environment of use by any suspending agent, and in any concentration, known to those of skill in the art.
  • the properties and performance of the composite of the invention may be varied considerably.
  • the composite of the invention may be used in any application where high strength, high impact resistance materials are desirable. Areas of application include containment such as containers for materials that ware volatile, ignitable or explosive, containers useful in preventing contamination either of the contained object or the external environment, and containers for transport, packaging and the like among other applications.
  • the composite of the invention may also be used in the electronics and semiconductor industries in applications such as wafer fabrication technologies including the manufacture of semiconductor components, memory, diodes, sensors, and microprocessors among other components.
  • the composite of the invention may also be used in the fabrication of any number of other solid state electronic devices.
  • the composite of the invention may be used to make any number of articles or work pieces.
  • Representative applications include those in the medical field such as use in the manufacture of any number of medical devices, surgical tools, and diagnostic articles and tools, among other devices.
  • the composite of the invention may also be used in any number of medical applications requiring splinting, bone replacement, grafting and the like among other applications.
  • the composite of the invention may also be used to form the component parts or overall structure of any vehicle such as a plane, train, auto, or cycle where the substrate can be used to replace metal parts of other parts and materials which are heavier, denser, or of less desirable strength.
  • the composite of the invention may also be useful in applications such as home, office and industry in the manufacture of furniture items, tools, housewares, building components (e.g., doors, walls, partitions, etc.), and the like.
  • the mullite-epoxy composite was prepared by infiltrating an epoxy-curing agent mixture into the acicular mullite ribbons.
  • the epoxy mixture consisted of 100 parts DER 383 and 32 parts Jeffamine D-230 which were combined and stirred in a beaker.
  • the epoxy mixture was poured slowly onto the porous acicular mullite samples. After the samples were fully saturated, the excess epoxy was wiped off using paper towel. The samples were then placed in an air over for curing according to the following schedule: 80°C for two hours, then 125 0 C for 3 hours.
  • Example 1 The dry mixture (clay+alumina+iron+talc) described in Example 1 was dry pressed into - 0.5 inch in diameter and 0.5 in length pellets. These pellets were calcined and mullitized in the same manner as described in Example 1. Resultant porous acicular mullite pellets were also infiltrated with the mixture of the epoxy resin and the curing agent described in Example 1. Properties measured using these samples were density and compressive strength. Compression testing was done on the Instron 8562 using a displacement rate of 0.01 inches/minute. The load displacement curves are shown in Figure 3 for ACM-epoxy and porous ACM. The properties measured for the ACM/epoxy samples of Example 2 are summarized in table 1.
  • Cylicrical acicular mullite samples were prepared by extrusion. 50.7 grams of clays, 46.4 grams of kappa alumina, 2.6 grams of talc and 0.3 grams of iron oxide powders were dry mixed. To this dry mixture of inorganic materials, 42 grams of water and 7 grams of A4M Methocel were added, producing an extrudable paste. This paste was extruded into 0.5" diameter rods, and it was cut to 0.75" length pellets. After drying, these pellet samples were calcined at 1065°C for 2 hours in air. Calcined pellets were converted initially to fluorotopaz at 700°C in a SiF 4 environment and then to mullite at 410/150 mm Hg SiF 4 partial pressure.
  • a cylindrical acicular mullite sample which had been infiltrated with epoxy and polymerized, was ground down to a cube of dimensions 5.0 mm x 5.0 mm.
  • the expansion of this sample in one direction (call this direction x) while heating from 30 0 C to 200°C at a rate of 5°C/min was measured using a Thermomechanical Analyzer (TA Instruments TMA Q400). After cooling back to ambient temperature, the cube was rotated such that a different pair of cube faces (call this direction y) was sandwiched between the base and the analyzer probe. Expansion of the cube in the z direction while heating from 30°C to 200°C at a rate of 5°C/min was measured as above.
  • Cylindrical wollastonite samples were prepared by extrusion. 100 grams of wollastonite, Nyglos 4 W, Lot 090918Pl 4, from Nyco, was mixed with 80 grams of water, 25 grams of Al 5LV Methocel and 2 grams of Oleic Acid were added, producing an extrudable paste using a mortar and pestal. This paste was extruded into 0.5" diameter rods, and it was cute to 0.75" length pellets. After drying, these pellet samples were heat treated at HOO 0 C allowing them to reach temperature at a ramp rate of 6°C/min and held at temperature for 12 hours in the air. The porosity of the wollastonite ribbon was approximately 60% by volume. The porous ACM samples were infiltrated with an anhydride cured cycloaliphatic epoxy using an imidazole based catalyst. The samples were infused with resin similar to a vaccum assisted resin transfer molding method.
  • Cylindrical zinc oxide samples were prepared by extrusion. 100 grams of zinc oxide polypods, Pana-Tetra, WZ-0501, from Panasonic, was mixed with 80 grams of water, 25 grams of Al 5LV Methocel and 2 grams of Oleic Acid were added, producing an extrudable paste using a mortar and pestal. This paste was extruded into 0.5: diameter rods, and it was cute to 0.75" length pellets. After drying, these pallet samples were heat treated at HOO 0 C allowing them to reach temperature at a ramp rate of 6°C/min and held at temperature for 12 hours in air. The porosity of the wollastonite ribbon was approximately 60% by volume. The porous ACM samples were infiltrated with an anhydride cured cycloaliphatic epoxy using an imidazole based catalyst. The samples were infused with resin similar to a vaccum assisted resin transfer molding method.
  • the porosity of the acicular mullite (ACM) granules produced by this technique was approximately 60% by volume.
  • the ACM-epoxy composite was prepared by infiltrating a formulated epoxy-curing agent mixture into the ACM granules.
  • the formulated epoxy mixture consisted of 100 parts DER 383 and 32 parts Jeffamine D-230 which were combined and stirred in a beaker. The epoxy mixture was poured slowly onto the porous acicular mullite granules. After the ACM granules were fully saturated, the excess epoxy resin was wiped off using paper towel.
  • the ACM/epoxy granules were then placed in an air oven and cured according to the following schedule: 80 0 C for two hours, then 125°C for 3 hours. The samples were then removed from the oven and allowed to cool to room temperature. [0094] The density of the granules was measured as 1.8 g/cm 3 . The granules were compressed using a MlOOOEC compression testing machine. The maximum load was recorded and maximum pressure was approximated by dividing the maximum load by the starting maximum cross-sectional area of the granule. Results are shown in Figure 6. The ACM/epoxy composite granules were able to withstand compressive loads in excess of 100 Ib, and indicate compressive strength greater than 25,000 psi can be achieved.
  • Example 2 shows evidence of a proppant made by first forming a porous ceramic truss structure in-situ (ACM) and then infiltrating with a thermosetting polymer (epoxy) to create a co-continuous ceramic-polymer proppant that is lightweight and can withstand a compressive load of 22,000 psi at 50% strain without spalling.
  • 400 g of the screened powder was calcined at 1065 0 C for 2 hours in air. After cooling to room temperature, 120 g of graphite (Asbury grade A625) was added to the calcined powder and mixed in a jar. The graphite was added to keep the spray dried particles from fusing together during the conversion to mullite.
  • the clay was converted initially to fluorotopaz at 750 0 C in an SiF 4 environment with SiF4 pressure of 50mmHg, and then to mullite at 350/350 mm Hg SiF 4 partial pressure. In order to remove residual SiF4 from the mullitized particles, they were heat treated at 1400 0 C for 6 hours. The graphite burned off during the 1400 0 C heat treat.
  • the particles were then re-screened to -20/+30 mesh.
  • the porosity of the acicular mullite particles was approximately 60% by volume.
  • the bulk density of the porous ACM granules was about 0.5 g/cm3. Scanning electron micrographs of the ACM particles are shown in Figures 7 and 8.
  • the mullite-epoxy composite was prepared by heating a metal bowl containing mullite particles to about 170C in an air oven for about 1 hour, removing the bowl and pouring in an epoxy mixture consisting of 100 parts DER 383 and 32 parts Jeffamine D-230. The epoxy and mullite were mixed for about 3 minutes. The epoxy-infused mullite particles were then transferred to a baking dish and were cured in an oven at 170 C for 3 hours. The cured particles were placed in a jar and shaken in order to de-agglomerate the particles. Single beads of ACM-epoxy were tested in compression using a loading rate of 2.4 mm/min.
  • the compressive strength of the single ACM-epoxy particles was about 15,000 psi at 20% strain and 22,000 psi at 50% strain. The particles were still intact after compressive testing and did not spall or fracture into pieces. The compressive strength was calculated as load/area assuming constant volume of the particle, and the percent strain was calculated as displacement/original particle diameter.
  • Example 7 shows evidence of a proppant formed by making a ceramic-truss ex-situ using a Wollastonite fibrous material, followed by infiltration with a thermosetting polymer, epoxy.
  • the resulting composite proppant shows compressive strength of about 15,000 psi at 50% strain, and it does not spall or fracture into many pieces as a result of compressive testing.
  • 80 grams wallastonite clay (RRimglos I) was mixed with 55 grams of ammonium stabilized colloidial silica (LUDOX AS-40, Dupont), and 20 grams of a methyl cellulose (Methocel Al 5: The Dow Chemical Company) was added to bind the mixture during extrusion and assist in creating additional porosity.
  • the sized powder was impregnated with epoxy resin described in Example 6.
  • the size of the wollastonite/epoxy composite particles ranged from about 0.5 mm to 1.0 mm in diameter.
  • Single particles of the Wollastonite/epoxy particles were tested in compression as described in Example 6.
  • the compressive strength of the single Wollastonite-epoxy particles was about 8,000 psi at 20% strain and about 15,000 psi at 50% strain. The single particles did not fracture into pieces during testing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur un composite ayant des phases céramique et polymère co-continues, la phase céramique ayant un réseau interconnecté de pores et un réseau interconnecté de structures de type treillis, les structures de type treillis ayant une ou plusieurs formes triangulaires, et la céramique étant choisie dans le groupe de la mullite aciculaire, l'alumine et leurs mélanges, la phase polymère étant intégrée à l'intérieur de la phase céramique, la phase polymère étant contenue à l'intérieur des pores de la phase céramique, la phase polymère étant choisie dans le groupe d'un thermoplastique, d'un thermodurci et leurs mélanges.
PCT/US2010/039524 2009-06-22 2010-06-22 Composites céramique-polymère WO2011005535A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US21923709P 2009-06-22 2009-06-22
US21924609P 2009-06-22 2009-06-22
US61/219,237 2009-06-22
US61/219,246 2009-06-22

Publications (1)

Publication Number Publication Date
WO2011005535A1 true WO2011005535A1 (fr) 2011-01-13

Family

ID=42676818

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/039524 WO2011005535A1 (fr) 2009-06-22 2010-06-22 Composites céramique-polymère

Country Status (1)

Country Link
WO (1) WO2011005535A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755340A (zh) * 2014-01-23 2014-04-30 佳木斯大学 一种钛酸铋钾压电陶瓷/自然铜复合材料及其制备方法
WO2018022447A1 (fr) 2016-07-27 2018-02-01 Corning Incorporated Composite de céramique et de polymère, ses procédés de fabrication et ses utilisations
WO2018118475A1 (fr) 2016-12-19 2018-06-28 Corning Incorporated Feuilles inorganiques autoportantes, articles, et procédés de fabrication des articles
CN109568677A (zh) * 2018-11-30 2019-04-05 杨桂红 一种用于辅助骨折后固定的纤维泥的制备方法
CN111295933A (zh) * 2017-10-27 2020-06-16 康宁股份有限公司 聚合物和多孔无机复合制品及其方法
CN113754412A (zh) * 2021-09-15 2021-12-07 北京理工大学 一种高强吸能陶瓷-聚合物复合结构的制备方法及其产品
US20220056240A1 (en) * 2018-12-03 2022-02-24 Loughborough University Composite material
CN115894071A (zh) * 2022-12-22 2023-04-04 中国科学技术大学 各向异性导热的轻质高强陶瓷基复合材料及其制备方法

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4227111A (en) * 1979-03-28 1980-10-07 The United States Of America As Represented By The Secretary Of The Navy Flexible piezoelectric composite transducers
DE3210984A1 (de) * 1982-03-25 1983-09-29 Schott Glaswerke, 6500 Mainz Kunststoff-silicat-verbundwerkstoff
EP0261067A2 (fr) * 1986-09-16 1988-03-23 Lanxide Technology Company, Lp. Procédé de fabrication d'articles en matière ceramique avec un composant consistant en un polymère
EP0268120A1 (fr) * 1986-11-03 1988-05-25 Asulab S.A. Matériau composite
US4910172A (en) 1989-02-08 1990-03-20 The United States Of America As Represented By The Secretary Of The Navy Preparation of mullite whiskers from AlF3, SiO2, and Al2 O3 powders
US4911902A (en) 1987-07-06 1990-03-27 The United States Of America As Represented By The Secretary Of The Navy Mullite whisker preparation
US4948766A (en) 1988-08-05 1990-08-14 The United States Of America As Represented By The Secretary Of The Navy Rigid mullite=whisker felt and method of preparation
US5173349A (en) 1989-07-28 1992-12-22 Engelhard Corporation Thermal shock and creep resistant mullite articles prepared from topaz and process of manufacture
US5194154A (en) 1991-12-05 1993-03-16 The Dow Chemical Company Structure for filter or heat exchanger, composed of a fused single crystal acicular ceramic
US5198007A (en) 1991-12-05 1993-03-30 The Dow Chemical Company Filter including a porous discriminating layer on a fused single crystal acicular ceramic support, and method for making the same
US5252272A (en) 1989-07-28 1993-10-12 Engelhard Corporation Thermal shock and creep resistant porous mullite articles prepared from topaz and process for manufacture
JPH08119771A (ja) * 1994-10-27 1996-05-14 Kanebo Ltd 圧電複合材料
US6596665B2 (en) 1999-08-27 2003-07-22 Dow Global Technologies Inc. Mullite bodies and methods of forming mullite bodies
US6605293B1 (en) * 1999-05-20 2003-08-12 Trustees Of Boston University Polymer re-inforced anatomically accurate bioactive protheses
US20070016437A1 (en) 2005-03-29 2007-01-18 Laura Elmufdi Product pricing system and method for providing multi-dimensional pricing capability for rates, adjustments and fees
US7381680B2 (en) 2004-04-21 2008-06-03 Dow Global Technologies Inc. Method for increasing the strength of porous ceramic bodies and bodies made therefrom
US20080202750A1 (en) * 2006-07-12 2008-08-28 Georgia-Pacific Chemicals Llc Proppant materials and methods
US7425297B2 (en) 2002-03-25 2008-09-16 Dow Global Technologies Inc. Method of forming mullite bodies

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4227111A (en) * 1979-03-28 1980-10-07 The United States Of America As Represented By The Secretary Of The Navy Flexible piezoelectric composite transducers
DE3210984A1 (de) * 1982-03-25 1983-09-29 Schott Glaswerke, 6500 Mainz Kunststoff-silicat-verbundwerkstoff
EP0261067A2 (fr) * 1986-09-16 1988-03-23 Lanxide Technology Company, Lp. Procédé de fabrication d'articles en matière ceramique avec un composant consistant en un polymère
EP0268120A1 (fr) * 1986-11-03 1988-05-25 Asulab S.A. Matériau composite
US4911902A (en) 1987-07-06 1990-03-27 The United States Of America As Represented By The Secretary Of The Navy Mullite whisker preparation
US4948766A (en) 1988-08-05 1990-08-14 The United States Of America As Represented By The Secretary Of The Navy Rigid mullite=whisker felt and method of preparation
US4910172A (en) 1989-02-08 1990-03-20 The United States Of America As Represented By The Secretary Of The Navy Preparation of mullite whiskers from AlF3, SiO2, and Al2 O3 powders
US5252272A (en) 1989-07-28 1993-10-12 Engelhard Corporation Thermal shock and creep resistant porous mullite articles prepared from topaz and process for manufacture
US5173349A (en) 1989-07-28 1992-12-22 Engelhard Corporation Thermal shock and creep resistant mullite articles prepared from topaz and process of manufacture
US5194154A (en) 1991-12-05 1993-03-16 The Dow Chemical Company Structure for filter or heat exchanger, composed of a fused single crystal acicular ceramic
US5198007A (en) 1991-12-05 1993-03-30 The Dow Chemical Company Filter including a porous discriminating layer on a fused single crystal acicular ceramic support, and method for making the same
JPH08119771A (ja) * 1994-10-27 1996-05-14 Kanebo Ltd 圧電複合材料
US6605293B1 (en) * 1999-05-20 2003-08-12 Trustees Of Boston University Polymer re-inforced anatomically accurate bioactive protheses
US6596665B2 (en) 1999-08-27 2003-07-22 Dow Global Technologies Inc. Mullite bodies and methods of forming mullite bodies
US7425297B2 (en) 2002-03-25 2008-09-16 Dow Global Technologies Inc. Method of forming mullite bodies
US7381680B2 (en) 2004-04-21 2008-06-03 Dow Global Technologies Inc. Method for increasing the strength of porous ceramic bodies and bodies made therefrom
US20070016437A1 (en) 2005-03-29 2007-01-18 Laura Elmufdi Product pricing system and method for providing multi-dimensional pricing capability for rates, adjustments and fees
US20080202750A1 (en) * 2006-07-12 2008-08-28 Georgia-Pacific Chemicals Llc Proppant materials and methods

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
GOMEZ ET AL.: "Compression Strength and Wear Resistance of Ceramic Foams - Polymer Composites", MATERIALS LETTERS, vol. 60, 2006, pages 1687 - 1692
KOMLEV V S ET AL: "STRENGTH ENHANCEMENT OF POROUS HYDROXYAPATITE CERAMICS BY POLYMER IMPREGNATION", JOURNAL OF MATERIALS SCIENCE LETTERS, CHAPMAN AND HALL LTD. LONDON, GB LNKD- DOI:10.1023/A:1025300617681, vol. 22, no. 17, 1 September 2003 (2003-09-01), pages 1215 - 1217, XP001199972, ISSN: 0261-8028 *
KONOPKA ET AL.: "Microstructure and Properties of Novel Ceramic - Polymer Composites", MATERIALS LETTERS, vol. 58, 2004, pages 3857 - 3862
SALIB S ET AL: "PROPERTY-POROSITY RELATIONSHIPS FOR POLYMER-IMPREGNATED SUPERCONDUCTING CERAMIC COMPOSITE", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, BLACKWELL PUBLISHING, MALDEN, MA, US LNKD- DOI:10.1111/J.1151-2916.1990.TB07595.X, vol. 73, no. 8, 1 August 1990 (1990-08-01), pages 2323 - 2329, XP000159713, ISSN: 0002-7820 *
SHAKLEE ET AL.: "Growth of a- AI203 Platelets in the HF-yy-AI203 System", J. AM. CERAM. SOC., vol. 77, no. 11, 1994, pages 2977 - 84

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755340A (zh) * 2014-01-23 2014-04-30 佳木斯大学 一种钛酸铋钾压电陶瓷/自然铜复合材料及其制备方法
WO2018022447A1 (fr) 2016-07-27 2018-02-01 Corning Incorporated Composite de céramique et de polymère, ses procédés de fabrication et ses utilisations
CN109563004A (zh) * 2016-07-27 2019-04-02 康宁股份有限公司 陶瓷和聚合物复合物、其制造方法及其用途
US10568205B2 (en) 2016-07-27 2020-02-18 Corning Incorporated Ceramic and polymer composite, and uses thereof
US11490510B2 (en) 2016-07-27 2022-11-01 Corning Incorporated Ceramic and polymer composite, methods of making, and uses thereof
WO2018118475A1 (fr) 2016-12-19 2018-06-28 Corning Incorporated Feuilles inorganiques autoportantes, articles, et procédés de fabrication des articles
CN111295933A (zh) * 2017-10-27 2020-06-16 康宁股份有限公司 聚合物和多孔无机复合制品及其方法
CN109568677A (zh) * 2018-11-30 2019-04-05 杨桂红 一种用于辅助骨折后固定的纤维泥的制备方法
US20220056240A1 (en) * 2018-12-03 2022-02-24 Loughborough University Composite material
CN113754412A (zh) * 2021-09-15 2021-12-07 北京理工大学 一种高强吸能陶瓷-聚合物复合结构的制备方法及其产品
CN115894071A (zh) * 2022-12-22 2023-04-04 中国科学技术大学 各向异性导热的轻质高强陶瓷基复合材料及其制备方法

Similar Documents

Publication Publication Date Title
WO2011005535A1 (fr) Composites céramique-polymère
US9796915B2 (en) Light weight proppant with improved strength and methods of making same
Chung Composite materials: functional materials for modern technologies
JP6546262B2 (ja) 高炉ハース部補修材
RU2605977C2 (ru) Синтетические расклинивающие наполнители и монодисперсные расклинивающие наполнители и способы их изготовления
CN100579934C (zh) 在侵蚀性介质中使用的基于β-SiC的模制件的生产方法
US8283271B2 (en) High strength proppants
WO2011081545A1 (fr) Agent de soutènement de fracture hydraulique contenant des fibres inorganiques
KR100595011B1 (ko) 다공성 세라믹스 발열체 및 그 제조방법
KR20150114468A (ko) 질화알루미늄 분말
JP6869229B2 (ja) 耐火物用骨材、その製造方法、及びそれを用いた耐火物
Sittiakkaranon Thermal shock resistance of mullite-cordierite ceramics from kaolin, talc and alumina raw materials
EP2526076A2 (fr) Corps en nitrure de silicium dense à haute resistance, à module de weibull élevé et à grande ténacité à la rupture
JP2002255650A (ja) 高破壊靭性ＳｉＣ繊維強化型ＳｉＣ複合材料の製造方法
CN114853443A (zh) 一种修补料用塑性结合剂及其制备方法
Sá Ribeiro et al. Lateritic soil geopolymer composites for ceramics and engineering construction applications
Roper et al. Properties of granite powder reinforced potassium geopolymer
JP2003040685A (ja) 酸化物繊維系複合材料、及びその製造方法
JP4527300B2 (ja) 高密度ＳｉＣ繊維強化型ＳｉＣ複合材料の製造方法
CN100526778C (zh) 软磁铁氧体烧结氮窑推板
Oliveira et al. Structural and mechanical characterisation of MgO-, CaO-and BaO-doped aluminosilicate ceramics
JP2002255648A (ja) 高強度ＳｉＣ繊維／ＳｉＣ複合材料の製造方法
Steinau et al. Functionally graded ceramics derived from preceramic polymers
KR102558563B1 (ko) 시멘트 평판 및 이의 제조 방법
JP4381760B2 (ja) 可撓性セラミックス製品及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10730932

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10730932

Country of ref document: EP

Kind code of ref document: A1