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WO2000030998A1 - Composites ceramiques poreux - Google Patents

Composites ceramiques poreux Download PDF

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Publication number
WO2000030998A1
WO2000030998A1 PCT/US1999/027378 US9927378W WO0030998A1 WO 2000030998 A1 WO2000030998 A1 WO 2000030998A1 US 9927378 W US9927378 W US 9927378W WO 0030998 A1 WO0030998 A1 WO 0030998A1
Authority
WO
WIPO (PCT)
Prior art keywords
porous ceramic
average
fibers
ceramic
volume
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1999/027378
Other languages
English (en)
Inventor
Melissa Crimp
Michelle Hignite
Ping Zhang
Loic M. Dejardin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Michigan State University MSU
Original Assignee
Michigan State University MSU
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 Michigan State University MSU filed Critical Michigan State University MSU
Priority to AU19162/00A priority Critical patent/AU1916200A/en
Publication of WO2000030998A1 publication Critical patent/WO2000030998A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • 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
    • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
    • 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

Definitions

  • the present invention relates generally to ceramic compositions and, more particularly, to highly porous ceramics made from such compositions which have improved compressive strength and toughness.
  • the invention also relates to the methods of manufacturing the highly porous ceramics of the present invention.
  • porous ceramics Due to their chemical inertness and stability at high temperatures, the desire for porous ceramics has increased dramatically in recent years. A relatively recent trend in the porous ceramic art has been its attempted use in bone substitution processes. The porous ceramics used in bone
  • HA hydroxyapatite
  • Hydroxyapatite is known to have superior biocompatibility, that is, it is
  • micropores in the macropore structure wall. This may promote cellular adhesion and differentiation. Interconnected micropores are also important in allowing the flow of body fluid (nutritional supply) between the
  • macropores to promote the growth of the bone in the macropores of an implant.
  • porous ceramics are considered to be useful for bone substitution applications, a perceived problem with using porous
  • HA hydroxyapatite
  • the present invention relates in part to structurally reinforced porous HA ceramic compositions. Reinforcing porous HA ceramics with short and/or continuous fibers will increase the strength and toughness, to
  • tricalcium phosphate TCP sintered form of HA
  • biocompatible reinforcements and/or fiber migration To minimize the potential for reaction, it is necessary to choose a material with superior biocompatibility and the ability to chemically bond to the matrix.
  • porous ceramics have included impregnating polymeric sponges having interconnected macropores with a ceramic slurry
  • the polymeric sponge method is work intensive and requires binders, to provide adequate
  • Binders such as aluminum orthophosphate, sodium silicate or magnesium orthoborate can leave behind residual phosphates which are susceptible to chemical attack. Residual binders, as well as anti-foaming agents and rheological agents which are useful for improving wetability, can
  • Another known method involving the process of forming HA ceramics includes manufacturing porous HA sheets by a tape casting technique with a gas forming agent such as CaCO 3 . While the resulting ceramic had a relatively high porosity, i.e., up to about 62%, the pore diameter was limited
  • porous HA ceramics Another known process of producing porous HA ceramics is via a lost wax process which uses a negative wax replica of a porous skeletal microstructure, filled with a ceramic slurry. The wax burns off during firing,
  • pores of the skeleton and for the case of in vivo use are biocompatible. Uniformity in the distribution of reinforcing fibers is also considered to pose
  • the present invention is thus directed to porous ceramic composites
  • porous ceramics composites of the present invention are generally made according to the following method in which an electrolyte solution such as 10 '3 M KNO 3 electrolyte including approximately 30% by volume of concentrated H 2 O 2 is originally provided. Added to this electrolyte solution, preferably with constant mixing is a particulate material selected from the group consisting essentially
  • reinforcing fibers selected from the group consisting essentially
  • AI 2 O 3 and hydroxyapatite fibers are optionally added to the composition in an amount of up to about 8.0 percent by volume of the solid portion of the composite.
  • the fibers, whether short or continuous, are added directly to the composite under constant mixing at ambient temperatures until
  • a creamy suspension (slurry) is obtained.
  • the creamy suspension is then introduced into molds having the desired shape and covered with a porous foil which serves to assist in regulating the pore size and uniformity of pore distribution while simultaneously allowing the evolving gas to escape.
  • the composition is then placed in a drying furnace to obtain the porous "green structure". With heating, the hydrogen peroxide breaks down into water and free oxygen. The free oxygen bubbles up through the sample creating the interconnected porous structure in its wake.
  • the dried samples are cooled in air at room
  • the resulting porous ceramic can be milled to form granules of a desired size and shape, thus allowing the granules to be used for a variety of applications.
  • macropores of between 200 and 400 ⁇ m are generally considered to be necessary to allow
  • the fiber reinforced porous HA Since ceramics having an open porosity in the above mentioned range are thought to have a structure closely related to cancellous bone which is subsequently converted to cortical bone through a progressive deposition of new bone lamellae by a series of osteons, the fiber reinforced porous HA
  • ceramics of the present invention are believed to be ideal candidates for biocompatible implants.
  • Micropores in the macropore structure wall increases the adsorption areas and may provide a favorable surface for cellular adhesion and
  • Interconnected micropores are also important in allowing the flow of body fluid (nutritional supply) between the macropores to promote the growth of the bone in the macropores.
  • Microstructural evaluation of these composites shows interconnected microporosity.
  • Figure 1a is a stereomicrograph showing the microstructure of an
  • Figure 1 b is a stereomicrograph showing the microstructure of an AI 2 O 3(f) /HA composite
  • Figure 1c is a stereomicrograph showing the microstructure of an
  • Figure 2 is a stereomicrograph of a AI 2 O 3(f) /HA composite depicting the microporous structure
  • Figure 3 is a graph plotting pore diameter as a function of HA powder volume percent
  • Figure 4 is a graph plotting pore diameter as a function of fiber volume percent
  • Figure 5 is a graph plotting percent porosity as a function of fiber volume percent
  • Figure 6 is a graph plotting pore diameter as a function of H 2 O 2 content in AI 2 O 3(f) /HA composites.
  • Figure 7 is an energy spectrum of an AI 2 O 3(f) /HA composite from energy dispersive spectroscopy.
  • One aspect of the present invention generally relates to a method for fabricating a porous ceramic composite.
  • the method includes as a first step
  • the electrolyte solution is generally selected from the group consisting essentially of NaCI,
  • the electrolyte concentrations range from 10 '7 M to 4.0 M, depending on
  • an electrolyte such as 10 "3 M KNO 3 including a 30% concentration of H 2 O 2 is useful for ceramic composites comprised of hydroxyapatite particles and hydroxyapatite fibers.
  • 0.154 M NaCI is useful for interactions between titanium and hydroxyapatite.
  • the next step of the method involves adding between about 20.0 volume percent to about 35.0 volume percent of a relatively fine particulate material b) selected from the group consisting essentially of alumina powder, hydroxyapatite powder or mixtures thereof to the solution a) while stirring the same.
  • alumina powder will have an average particle size of between about 50 nanometers (nm) to about 100 micrometers ⁇ m), with a range of 0.2 ⁇ m to 0.6 ⁇ m being preferred.
  • Alumina powders (AI 2 O 3 ) such as those marketed by Sumitomo Chemical Co. Ltd. under the trade designation AKP-30 and AKP-50 have been found to be particularly useful.
  • the hydroxyapatite powders preferably will have an average particle size of between about 0.1 ⁇ m to about 100 ⁇ m, with a range of 6 ⁇ m to about 14 ⁇ m being preferred. Hydroxyapatite particles such as those offered commercially by Hitemco iv idical Appliances, Inc. have been found to be particularly useful.
  • a fiber component c) may be added to the solution before sintering. While any suitable biocompatible fiber may be employed, fibers selected from the group consisting essentially of alumina fibers, hydroxyapatite fibers or mixtures thereof are preferred. The total amount of
  • the fibers added will be an amount sufficient to form a relatively pasty slurry. In this regard, it has been found up to about 8.0% by volume of the solid portion of the fibers are suitable, with a range of 4.0% volume to 5.0% by volume being preferred.
  • the alumina fibers if employed, may be continuous or may be chopped to an average length of less than about 10 mm. More preferably, the short alumina fibers will have an average length of between about 0.5 mm to about 7.0 mm, with a range of between about 1.0 mm to about 3.0 mm being most preferred.
  • the alumina fibers will also preferably have an average diameter of less than 1.0 mm.
  • the alumina fibers will have an average diameter of between about 5.0 ⁇ m to about 300 ⁇ m with a range of between about 10 ⁇ m to about 14 ⁇ m being most preferred.
  • Such fibers are available from the 3M Corporation under the trade designation NEXTEL AI 2 O 3 fibers.
  • the hydroxyapatite fibers may be in the form of the continuous fibers or may be chopped such that they will have an average length of less than 10 mm. More preferably, the short hydroxyapatite fibers will have an average length of between about 0.5 mm to about 7.0 mm, with
  • the hydroxyapatite fibers will also have an average diameter of less than 1.0
  • the hydroxyapatite fibers will have an average diameter of between about 5.0 ⁇ m to about 300 ⁇ m, with a range of 150 ⁇ m
  • the hydroxyapatite fibers can be made by a simple extrusion method
  • the method includes first, dissolving polyethylene glycol (PEG) in 200 proof ethanol while heating. Hydroxyapatite powder is added at a ratio of 1 part PEG to 3 parts hydroxyapatite powder
  • the slurry is stirred until enough ethanol has evaporated off to provide the desired viscosity.
  • the mixture is then placed into a 3 cc syringe fitted with a 25 gage needle to extrude the fibers out.
  • the fibers are dried at room temperature in air for 24 hours followed by sintering in air at 1350° C for two hours.
  • the foil allows evolving gases to escape while acting to maintain a constant slurry volume and controlling the pore size and uniformity of pore distribution. Absent the foil, the slurry tends to foam out and retract, resulting in a non-uniform ceramic product having uncontrolled pore size and an uneven pore distribution.
  • the composition is placed in a drying furnace to drive off moisture, thus forming a ceramic shell.
  • the shell
  • cooling times and time and temperatures required for sintering the ceramics is material, shape and volume dependent.
  • porous ceramic particularly the non-fiber reinforced porous ceramics, can be any porous ceramic, particularly the non-fiber reinforced porous ceramics.
  • the granules can be used for a number of different applications including but not limited to bone fillers, i.e. filling holes left by bone cysts, bone screws, etc.
  • bone fillers i.e. filling holes left by bone cysts, bone screws, etc.
  • the granules have an average size of between about 1.0 mm to about 2.0 mm.
  • porous compositions employing alumina particulate and/or alumina fibers can be employed to form molten metal filters, fuel sessions and catalyst supports by way of non-limiting example.
  • ceramic compositions employing alumina particulate and alumina fibers may be used for bone
  • slurry samples were prepared as shown in Table 1 below and were placed into cylindrical shaped castings having a depth of 2.5 cm and a diameter of 2.5 cm. The samples were dried for 3.0 hours at 120° C in air and thereafter allowed to cool to room
  • AI 2 O 3(f) /AI 2 O 3 compositions and for 2.0 hours at 1375° C for AI 2 O 3(f) /HA and HA (f) /HA compositions, wherein (f) is indicative of a fiber component.
  • Table 1 is a listing of "typical" values of reactant components and their corresponding results (i e , micro/macro-porosity, density, etc).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Ceramic Engineering (AREA)
  • Dermatology (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne des compositions céramiques et des céramiques poreuses formées à partir de ces compositions. Les céramiques poreuses à porosité élevée peuvent être concassées pour donner des granules de taille et de forme prédéterminées pouvant être utilisées dans différentes applications, notamment dans des applications biomédicales. On peut renforcer par fibres les céramiques fortement poreuses de manière à leur conférer une rigidité et une résistance à la compression bien plus élevées en comparaison à celles des autres compositions céramiques, notamment à celles utilisées dans des applications biomédicales.
PCT/US1999/027378 1998-11-20 1999-11-18 Composites ceramiques poreux Ceased WO2000030998A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU19162/00A AU1916200A (en) 1998-11-20 1999-11-18 Porous ceramic composites

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US19738798A 1998-11-20 1998-11-20
US09/197,387 1998-11-20

Publications (1)

Publication Number Publication Date
WO2000030998A1 true WO2000030998A1 (fr) 2000-06-02

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AU (1) AU1916200A (fr)
WO (1) WO2000030998A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005016192A3 (fr) * 2003-08-12 2005-04-21 Univ Bath Materiau substitut osseux
US7910124B2 (en) 2004-02-06 2011-03-22 Georgia Tech Research Corporation Load bearing biocompatible device
US8002830B2 (en) 2004-02-06 2011-08-23 Georgia Tech Research Corporation Surface directed cellular attachment
CN102512706A (zh) * 2011-12-16 2012-06-27 天津大学 多聚磷酸钙/硫酸钙复相生物陶瓷材料及其制备方法
US8288452B2 (en) * 2003-05-15 2012-10-16 Lo Wei J Synthetic bone graft biomaterial
CN103599561A (zh) * 2013-11-07 2014-02-26 同济大学 一种镁合金/羟基磷灰石复合材料的制备方法
CN104310438A (zh) * 2014-10-10 2015-01-28 山东诺贝丰化学有限公司 一种连续式复分解法生产硝酸钾的系统及方法
CN104310439A (zh) * 2014-10-10 2015-01-28 山东诺贝丰化学有限公司 一种硝酸钾联产氯化铵生产中废水循环利用系统及方法
CN104310442A (zh) * 2014-10-10 2015-01-28 山东诺贝丰化学有限公司 一种复分解法硝酸钾生产中氯化铵强制循环连续三效浓缩、真空结晶系统及工艺
CN104561627A (zh) * 2014-12-17 2015-04-29 辽宁工业大学 一种梯度羟基磷灰石/镁复合材料的制备方法
US9155543B2 (en) 2011-05-26 2015-10-13 Cartiva, Inc. Tapered joint implant and related tools
US9907663B2 (en) 2015-03-31 2018-03-06 Cartiva, Inc. Hydrogel implants with porous materials and methods
CN109336560A (zh) * 2018-10-04 2019-02-15 南京航空航天大学溧水仿生产业研究院有限公司 多孔贝壳陶瓷基复合材料及其制备方法
US10350072B2 (en) 2012-05-24 2019-07-16 Cartiva, Inc. Tooling for creating tapered opening in tissue and related methods
US10758374B2 (en) 2015-03-31 2020-09-01 Cartiva, Inc. Carpometacarpal (CMC) implants and methods
CN116553907A (zh) * 2023-05-10 2023-08-08 中国科学技术大学 一种跨尺度仿哈弗管结构的多孔陶瓷材料及其制备方法、金属模具

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112694320B (zh) * 2020-12-28 2023-03-10 山东鲁阳节能材料股份有限公司 陶瓷纤维无机板及其制备方法

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US4629464A (en) * 1984-09-25 1986-12-16 Tdk Corporation Porous hydroxyapatite material for artificial bone substitute
US4861733A (en) * 1987-02-13 1989-08-29 Interpore International Calcium phosphate bone substitute materials
US5030611A (en) * 1987-10-22 1991-07-09 Asahi Kogaku Kogyo K.K. Porous ceramics material

Patent Citations (4)

* Cited by examiner, † Cited by third party
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US3929971A (en) * 1973-03-30 1975-12-30 Research Corp Porous biomaterials and method of making same
US4629464A (en) * 1984-09-25 1986-12-16 Tdk Corporation Porous hydroxyapatite material for artificial bone substitute
US4861733A (en) * 1987-02-13 1989-08-29 Interpore International Calcium phosphate bone substitute materials
US5030611A (en) * 1987-10-22 1991-07-09 Asahi Kogaku Kogyo K.K. Porous ceramics material

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8288452B2 (en) * 2003-05-15 2012-10-16 Lo Wei J Synthetic bone graft biomaterial
US8101268B2 (en) 2003-08-12 2012-01-24 University Of Bath Bone substitute material
EP2206525A3 (fr) * 2003-08-12 2010-11-17 University Of Bath Matériau de substitution osseuse
WO2005016192A3 (fr) * 2003-08-12 2005-04-21 Univ Bath Materiau substitut osseux
US8002830B2 (en) 2004-02-06 2011-08-23 Georgia Tech Research Corporation Surface directed cellular attachment
US8486436B2 (en) 2004-02-06 2013-07-16 Georgia Tech Research Corporation Articular joint implant
US8895073B2 (en) 2004-02-06 2014-11-25 Georgia Tech Research Corporation Hydrogel implant with superficial pores
US7910124B2 (en) 2004-02-06 2011-03-22 Georgia Tech Research Corporation Load bearing biocompatible device
US10376368B2 (en) 2011-05-26 2019-08-13 Cartiva, Inc. Devices and methods for creating wedge-shaped recesses
US11944545B2 (en) 2011-05-26 2024-04-02 Cartiva, Inc. Implant introducer
US11278411B2 (en) 2011-05-26 2022-03-22 Cartiva, Inc. Devices and methods for creating wedge-shaped recesses
US9526632B2 (en) 2011-05-26 2016-12-27 Cartiva, Inc. Methods of repairing a joint using a wedge-shaped implant
US9155543B2 (en) 2011-05-26 2015-10-13 Cartiva, Inc. Tapered joint implant and related tools
CN102512706A (zh) * 2011-12-16 2012-06-27 天津大学 多聚磷酸钙/硫酸钙复相生物陶瓷材料及其制备方法
US10350072B2 (en) 2012-05-24 2019-07-16 Cartiva, Inc. Tooling for creating tapered opening in tissue and related methods
CN103599561B (zh) * 2013-11-07 2015-08-19 同济大学 一种镁合金/羟基磷灰石复合材料的制备方法
CN103599561A (zh) * 2013-11-07 2014-02-26 同济大学 一种镁合金/羟基磷灰石复合材料的制备方法
CN104310442A (zh) * 2014-10-10 2015-01-28 山东诺贝丰化学有限公司 一种复分解法硝酸钾生产中氯化铵强制循环连续三效浓缩、真空结晶系统及工艺
CN104310439A (zh) * 2014-10-10 2015-01-28 山东诺贝丰化学有限公司 一种硝酸钾联产氯化铵生产中废水循环利用系统及方法
CN104310438A (zh) * 2014-10-10 2015-01-28 山东诺贝丰化学有限公司 一种连续式复分解法生产硝酸钾的系统及方法
CN104561627B (zh) * 2014-12-17 2016-08-17 辽宁工业大学 一种梯度羟基磷灰石/镁复合材料的制备方法
CN104561627A (zh) * 2014-12-17 2015-04-29 辽宁工业大学 一种梯度羟基磷灰石/镁复合材料的制备方法
US10758374B2 (en) 2015-03-31 2020-09-01 Cartiva, Inc. Carpometacarpal (CMC) implants and methods
US10973644B2 (en) 2015-03-31 2021-04-13 Cartiva, Inc. Hydrogel implants with porous materials and methods
US9907663B2 (en) 2015-03-31 2018-03-06 Cartiva, Inc. Hydrogel implants with porous materials and methods
US11717411B2 (en) 2015-03-31 2023-08-08 Cartiva, Inc. Hydrogel implants with porous materials and methods
US11839552B2 (en) 2015-03-31 2023-12-12 Cartiva, Inc. Carpometacarpal (CMC) implants and methods
US10952858B2 (en) 2015-04-14 2021-03-23 Cartiva, Inc. Tooling for creating tapered opening in tissue and related methods
US11020231B2 (en) 2015-04-14 2021-06-01 Cartiva, Inc. Tooling for creating tapered opening in tissue and related methods
US11701231B2 (en) 2015-04-14 2023-07-18 Cartiva, Inc. Tooling for creating tapered opening in tissue and related methods
CN109336560A (zh) * 2018-10-04 2019-02-15 南京航空航天大学溧水仿生产业研究院有限公司 多孔贝壳陶瓷基复合材料及其制备方法
CN116553907A (zh) * 2023-05-10 2023-08-08 中国科学技术大学 一种跨尺度仿哈弗管结构的多孔陶瓷材料及其制备方法、金属模具

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