CN108096639A - A kind of gradient porous material - Google Patents

A kind of gradient porous material Download PDF

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Publication number
CN108096639A
CN108096639A CN201611041788.6A CN201611041788A CN108096639A CN 108096639 A CN108096639 A CN 108096639A CN 201611041788 A CN201611041788 A CN 201611041788A CN 108096639 A CN108096639 A CN 108096639A
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gradient
porous material
hole
porous
aperture
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叶雷
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Chongqing Runze Pharmaceutical Co Ltd
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Chongqing Runze Pharmaceutical Co Ltd
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Priority to CN201611041788.6A priority Critical patent/CN108096639A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/06Titanium or titanium alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/20Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2068Other inorganic materials, e.g. ceramics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1103Making porous workpieces or articles with particular physical characteristics
    • B22F3/1109Inhomogenous pore distribution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1121Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10Shaped 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/636Polysaccharides or derivatives thereof
    • C04B35/6365Cellulose or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06Porous 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
    • C04B38/063Preparing or treating the raw materials individually or as batches
    • C04B38/0635Compounding ingredients
    • C04B38/0645Burnable, meltable, sublimable materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

A kind of gradient porous material, wherein the gradient of porous material is classified according to the pore size of the gradient porous material body mesoporous, the gradient porous material is using the porous material of minimal gradient grade as raw material, the porous material that the hole of aperture bigger is formed is made, the hole for forming each gradient grade porous material of gradient porous material is mutually communicated.The gradient porous material of this kind of structure, the porous materials of different gradient grades have identical minimum level porous material structural unit, substantially reduce the effect of the interface that connects between different gradients, ensure that the realization of the performance of gradient porous material.

Description

A kind of gradient porous material
Technical field
The present invention relates to porous materials, and in particular to a kind of gradient porous material.
Background technology
Important component of the gradient porous material as function-graded material, in people's daily life, production and national defence It has been more and more widely used in cause, such as biomaterial, heat-insulating material, porous electrode, piezoelectric material, catalysis Device, sound-absorbing material, combustion chamber and filter etc., for example, when gradient porous material is applied to catalysis or filter condition, gradient pore knot The sieves of structure is more convenient for hole flushing, catalytic efficiency higher.According to the chemical composition of material, it is more that gradient porous material can be divided into gradient Mesoporous metal, gradient porous ceramics, gradient porous polymer and composite material.It is often each gradient due to the needs of function Porous material occupy certain space, have between the porous material of other gradients and connect interface to distinguish graded.
Patent CN 104212990A describe a kind of preparation method of gradient porous titanium, will according to order from fine to coarse The sized spherical titanium powder of different-grain diameter is sequentially placed in graphite jig, is applied to the pressure on titanium valve as 5-20MPa, and vacuum degree≤ 3Pa is warming up to 500-650 DEG C with the heating rate of 50-200 DEG C/min, is sintered 20 minutes, that is, obtains and be with pore size The porous titanium material of graded, available for preparing filtering product.
Patent CN 10488616A describe a kind of method that macropore metal surface prepares micropore metal layer.Its detailed process For hydroxide slurry brush is carried out plug-hole in the surface of macropore metallic matrix using spread coating, blocked up after dry with sand paper to above-mentioned The metal base surface in hole is polished, cleans, dried step by step;The metal powder for preparing micropore metal layer is mixed into system with organic additive It is standby to form green body, the high temperature sintering under inertia or reducing atmosphere into suspension, and coated on metal base surface;Finally useization It learns reagent and obtains high gradient pore structure porous metals with being cleaned by ultrasonic the removal in vivo remaining inorganic material of base.
A kind of nano-artificial bone stents of transverse gradients pore structure of patent CN 102429745B and preparation method thereof introduction There is the nano-artificial bone stent of the transverse gradients pore structure as nature bone.Preparation method is to be dissolved in hydroxyapatite Hydroxyapatite colloidal sols are made in salt solvent, then polycaprolactone is slowly dissolve into hydroxyapatite colloidal sols, then exist Heating removal solvent at a temperature of higher, is finally cast to the nanometer people that transverse gradients pore structure is made in special mold layer by layer Work bone stent.
In above-mentioned many gradient porous materials, the porous material of different gradients is mutually incoherent, connects between different gradients Interface, which is led to the problem of, more to be protruded, and resistance is larger when flowing through interface such as working media, and the chemical reaction of interface both ends is different, prepares It is easily cracked in interface in the process, interface both ends porous material binding ability is bad etc..
The content of the invention:
The object of the present invention is to provide a kind of gradient porous materials for the effect of the interface that connects between reduction gradients at different levels.
The object of the invention is achieved through the following technical solutions:
The gradient of a kind of gradient porous material, wherein porous material is according in the gradient porous material body in classification shape The pore size classification in hole, which is using the porous material of minimal gradient grade as raw material, makes aperture more The porous material that big hole is formed, the hole for forming each gradient grade porous material of gradient porous material are mutually communicated, this The gradient porous material of kind structure, material body have integral structure, and gradient porous materials at different levels all have minimal gradient The respective attributes of grade porous material, and the interface that connects between gradient at different levels by minimum level porous material due to can mutually be passed through Logical, the poor performance alienation for the integral material that interfacial structure is brought reduces, and the effect of the interface that connects between gradients at different levels is substantially reduced.
Furtherly, the gradient porous material, two neighboring gradient grade porous materials connect interfacial area more than two For neighboring gradient grade porous material using plane as the area at the interface that connects, this kind of structure causes two adjacent porous materials of gradient grade Material intermeshes, and degree is high, and the series that interface problem is brought influences smaller.The gradient porous material of this structure, due to whole material The integration of material, the porous material different properties of different gradient grades, but also have same possessed by minimal gradient grade porous material One attribute, to embody the superiority of entire gradient porous material performance.
Gradient porous material provided by the present invention, design structure is ingenious, reasonable, entire gradient porous material minimum level Base material material is identical, and various adverse effects caused by can eliminating the interface problem between gradient porous material difference gradient become A kind of real meaning without interface integral structure material.
Furtherly, the aperture in the hole of the gradient grade porous material of the aperture minimum of the gradient porous material 10 μm with Under, the gradient porous material of this structure is particularly useful for making the implant containing cortex bone or for filtering 10 μm or more of grain Material.
Furtherly, the gradient porous material, the gradient grade of the aperture maximum of the gradient porous material are porous The aperture in the maximum level-one hole of material is 100-1500 μm, and the gradient porous material of this structure is particularly useful for making containing spongiosa The implant of bone.
Furtherly, the gradient porous material, wherein a gradient grade porous material is three-level Porous materials, according to aperture Size be classified, first order hole aperture is maximum, and third level hole aperture is minimum, second level hole aperture first order hole aperture with Between the aperture of third level hole, second level hole is distributed on first order vestibule wall, third level hole is distributed on the vestibule wall of the second level, then Furtherly, the aperture in first order hole is 100-1500 μm, and below 10 μm, the aperture in second level hole is in the aperture in third level hole 10 -100μm.The gradient porous material of this structure particularly useful for making simultaneously the implant containing cancellous bone and cortex bone, three Grade hole regeneration effect is more preferably.
Beneficial effects of the present invention:
Gradient porous material provided by the invention, can reduce in existing various gradient porous materials between different functionally gradient material (FGM)s due to Connect the series of problems of interface zone.It by gradient porous material by integrally realizing integral structure, more specifically, leads to It crosses using the porous material of minimal gradient grade as raw material, forms gradient porous material making the hole of aperture bigger so that each Gradient grade porous material is respectively provided with identical minimum structural unit, becomes really integrated porous material, so as to greatly reduce Effect of the interface, ensure that the realization of the various performances of gradient porous material.
Gradient porous material provided by the invention, smart structural design, rationally, particularly to being classified with pore size Gradient porous material integral structure, for being used as medical embedded material, particularly bone implant material, such as cortex bone, pine Matter bone integration implantation material, cortex bone, spongiosa osseointegration intensity are high, and the gradient porous material of this structure is more advantageous to bone again It is raw;After being implanted into human body, Bone Ingrowth better off.
Description of the drawings
Below in conjunction with attached drawing, the present invention is further elaborated with embodiment.
Fig. 1 is 1 structure diagram of the embodiment of the present invention.
Fig. 2 is 2 structure diagram of embodiment.
Specific embodiment
Below in conjunction with the accompanying drawings to the present invention specific embodiment explain, embodiment based on the technical solution of the present invention, Detailed embodiment and specific operating process are given, but protection scope of the present invention is not limited only to following embodiment party Formula.
Gradient porous material with two-stage as shown in Figure 1,1 is first gradient grade porous material(Namely minimal gradient Grade porous material), 1-1 is the hole of first gradient grade porous material, and 2 be the second gradient grade porous material(Namely greatest gradient grade Porous material), 2-1 is the macropore of the second gradient grade porous material, and 2-2 is the aperture of the second gradient grade porous material.
Gradient porous material with three-level as shown in Figure 2,3 be first gradient grade porous material(Namely minimal gradient Grade porous material), 3-1 is the hole of first gradient grade porous material, and 4 be the second gradient grade porous material(Namely Middle-gradient grade Porous material), 4-1 is the macropore of the second gradient grade porous material, and 4-2 is the aperture of the second gradient grade porous material, and 5 be the Three gradient grade porous materials(Namely greatest gradient grade porous material), 5-1 is the macropore of 3rd gradient grade porous material, and 5-2 is The aperture of 3rd gradient grade porous material.
The embodiment of the present invention is given in detail below:
Embodiment 1
The gradient of a kind of gradient porous material, wherein porous material is according in the gradient porous material body in classification shape The pore size classification in hole, which is using the porous material of minimal gradient grade as raw material, then makes aperture The porous material that the hole of bigger is formed, the hole for forming each gradient grade porous material of gradient porous material are mutually communicated, And two neighboring gradient grade porous materials connect more than two neighboring gradient grade porous materials of interfacial area with flat in this example Area of the face as the plane at the interface that connects.
In this example, referring specifically to Fig. 1, the gradient porous material of the present embodiment is porous tantalum, is divided into two gradient grades, the One gradient grade porous material 1 is the porous tantalum in 1-9 μm of aperture, and hole 1-1 is mutually communicated, and the second gradient grade porous material 2 is Two-stage hole tantalum, macropore 2-1 apertures are 1200-1500 μm, and hole is mutually communicated, the cavity wall material and first gradient of macropore 2-1 Grade porous material 1 is identical, i.e., is made of porous tantalum be mutually communicated, 1-9 μm of aperture, aperture 2-2 and hole 1-1 size distribution phases Together, macropore 2-1 and aperture 2-2 are mutually communicated, and macropore 2-1 and hole 1-1 is also what is be mutually communicated, aperture 2-1 and hole 1-1 It is perforation.
The preparation method of this kind of porous tantalum is as follows:
(1)The tantalum powder that grain size is 2 ± 0.1 μm is taken, grain size is 3-15 μm of polymethyl methacrylate, and 4-7 μm of diameter is 40 μm long Polyurethane fiber, according to volume ratio tantalum powder:Polymethyl methacrylate powder:Polyurethane fiber is 7:2:1 mixing, is stirred repeatedly It is made uniformly to mix, mixed powder is put into sintered-carbide die, applies 10MPa pressure and flattens, it is porous to prepare first gradient grade The green compact of material.
(2)The tantalum powder that grain size is 2 ± 0.1 μm is taken, grain size is 3-15 μm of polymethyl methacrylate, and 4-7 μm of diameter is long 40 μm of polyurethane fiber, grain size is 1400-1750 μm of urea, according to volume ratio tantalum powder:Polymethyl methacrylate powder:It is poly- Urethane fiber:Urea is 21:6:3:110 mixing, repeatedly stirring make it uniformly be put into containing first gradient grade porous material green compact Mold, apply 500MPa pressure compactions, pressurize 20s forms the second gradient grade hole and the incorporated life in first gradient grade hole Base.
(3)Green compact are put into vacuum drying oven, start cryopumping:With FF-160/620 types molecular pump+mechanical pump vacuum body System, which vacuumizes, reaches 10-4Pa rises to 300 DEG C from room temperature with the rate of 1 DEG C/min, keeps the temperature 90min, then equally to heat speed Degree rises to 400 DEG C, keeps the temperature 60min, then rises to 500 DEG C with similary firing rate, keeps the temperature 60min, then similary firing rate liter To 600 DEG C, 40min is kept the temperature, then carries out high temperature sintering:1200 DEG C are risen to from room temperature with the rate of 8 DEG C/min, heat preservation Then 30min rises to 1600 DEG C with the rate of 10 DEG C/min, keep the temperature 40min, 2300 DEG C are risen to the rate of 40 DEG C/min, 140min is kept the temperature, then 1400 DEG C are cooled to the rate of 10 DEG C/min, 30min is kept the temperature, is cooled to the rate of 10 DEG C/min 1150 DEG C, 60min is kept the temperature, is cooled to 750 DEG C with the rate of 10 DEG C/min, then furnace cooling.
(4)Sample is put into vacuum annealing furnace, vacuum degree is made to reach 10-4Pa, with the rate of 120 DEG C/min from room temperature 1250 DEG C are risen to, keeps the temperature 280min, then 1000 DEG C are cooled to the rate of 5 DEG C/min, 200min is kept the temperature, with 10 DEG C/min's Rate is cooled to 700 DEG C, keeps the temperature 160min, is cooled to room temperature with the rate of 16 DEG C/min, finally carries out conventional post processing and is made Gradient porous tantalum, referring to Fig. 1.
The gradient porous tantalum can be used for preparing comprising cortex bone, the implant of cancellous bone, for filling bone defects position.
Embodiment 2:
The gradient of a kind of gradient porous material, wherein porous material is according in the gradient porous material body in classification shape The pore size classification in hole, which is using the porous material of minimal gradient grade as raw material, then makes aperture The porous material that the hole of bigger is formed, the hole for forming each gradient grade porous material of gradient porous material are mutually communicated, And two neighboring gradient grade porous materials connect more than two neighboring gradient grade porous materials of interfacial area with flat in this example Area of the face as the plane at the interface that connects.
In this example, for concrete structure referring to Fig. 2, the gradient porous material of the present embodiment is Al2O3, it is divided into 3 gradient grades, First gradient grade porous material 3(Namely minimal gradient grade porous material), for the porous Al in 20-40 μm of aperture2O3, hole 3-1 is phase It mutually penetrates through, the second gradient grade porous material 4 is two-stage hole Al2O3, macropore 4-1 apertures are 100-200 μm, the cavity wall of macropore 4-1 It is identical with first gradient grade porous material 3, i.e., by the porous Al in 20-40 μm of aperture that is being mutually communicated2O3It forms, 3rd gradient grade Porous material 5 is two-stage hole Al2O3, macropore 5-1 apertures are 400-500 μm, cavity wall and the porous material of first gradient grade of macropore 5-1 Expect that 3 is identical, i.e., by the porous Al in 20-40 μm of aperture that is being mutually communicated2O3It forms.
This kind of porous Al2O3Preparation method it is as follows:
(1)Take the Al that grain size is 5 ± 1 μm2O3Powder, grain size is 30-50 μm of methylcellulose powder, according to volume ratio Al2O3Powder: Methylcellulose powder is 1:1 mixing, repeatedly stirring make it uniformly mix, and mixed powder is put into sintered-carbide die, applies 10MPa Pressure flattens, and prepares the green compact of first gradient grade porous material 3.
(2)Take the Al that grain size is 5 ± 1 μm2O3Powder, grain size are 30-50 μm of methylcellulose powder, and grain size is 160-300 μm Urea, according to volume ratio Al2O3Powder:Methylcellulose powder:Urea is 2:2:1 mixing, repeatedly stirring make it uniformly be put into and contain Have a mold of the green compact of first gradient grade porous material 3, apply 10MPa pressure and flatten, formed first gradient grade porous material 3 with Second gradient grade porous material, 4 incorporated green compact.
(3)Take the Al that grain size is 5 ± 1 μm2O3Powder, grain size are 30-50 μm of methylcellulose powder, and grain size is 500-600 μm Urea, according to volume ratio Al2O3Powder:Methylcellulose powder:Urea is 3:3:4 mixing, repeatedly stirring make it uniformly be put into and contain There is the mold of 4 incorporated green compact of first gradient grade porous material 3 and the second gradient grade porous material, apply 400MPa pressure Compacting, pressurize 20s form 3rd gradient grade porous material 5, the second gradient grade porous material 4 and first gradient grade porous material 3 Incorporated green compact.
(4)Green compact are put into vacuum drying oven, 1200 DEG C is risen to according to the rate of 2 DEG C/min, keeps the temperature 180min, then press 600 DEG C are cooled to according to 10 DEG C/min, then furnace cooling is to get to the gradient porous Al of three-level2O3
This kind of porous Al2O3Available for filtering material, filter medium is smooth by interface between gradient, makes filtering by gradient Efficiency significantly improves, and improves the service life of filtering material.
Embodiment 3
The gradient porous material of the present embodiment is POROUS TITANIUM, and structure is similar to Example 1, and difference is porous for first gradient grade Titanium is the POROUS TITANIUM of aperture 700-900nm, and the second gradient grade POROUS TITANIUM is three-level hole titanium, and first order hole aperture is 400-600 μ M, cavity wall are formed by aperture by 40-70 μm of second level POROUS TITANIUM, and the cavity wall of second level POROUS TITANIUM is by aperture 700-900nm's Third level POROUS TITANIUM is formed, and third level POROUS TITANIUM is identical material with first gradient grade POROUS TITANIUM.
The preparation method of this kind of POROUS TITANIUM is as follows:
(1)Material prepares
It for the titanium valve of 200-300nm is raw material to use grain size, and grain size is that the urea of 800nm-1000nm is made as minimum level-one hole Hole agent, by the use of the starch that grain size is 800-1000nm as adhesive, by titanium valve:Urea:Starch:Distilled water by volume 4:1:1: 12 are configured to slurry, and ultrasonic disperse 30 minutes, then drying is powdery.
(2)It will(1)The powder of middle preparation, the ethyl cellulose that grain size is 50-80 μm by volume 1:After 2 uniform mixing uniformly It fills in the polyester form of the three-dimensional perforation that rib is 500 μm -700 μm a diameter of, aperture is 500 μm -800 μm and then in closed die on ground Tool is pressed into dense green, pressure 400MPa, which is the green compact of the three-level hole titanium of the second gradient grade.
(3)It will(1)The powder of middle preparation is layered on(2)It is compacted on one surface of green body of preparation, pressing pressure 400MPa, institute The powder of paving forms first gradient grade POROUS TITANIUM, and the three-level hole titanium of first gradient grade POROUS TITANIUM and the second gradient grade is formed after compacting Incorporated green compact.
(4)By green compact vacuum-sintering;Sintered green body obtains required according to the conventional subsequent heat treatment of tantalum material technique progress The gradient porous titanium of two-stage.
This kind of POROUS TITANIUM can be used for preparing while the implant containing cancellous bone and cortex bone, first gradient grade POROUS TITANIUM are used as Cortex bone, the second gradient grade POROUS TITANIUM are used as cancellous bone.
Embodiment 4
The gradient porous material of the present embodiment is gradient porous titanium, and structure is similar to Example 3, and difference is first gradient grade POROUS TITANIUM is the POROUS TITANIUM in 1-9 μm of aperture, and the second gradient grade porous material is three-level hole titanium, and first order hole aperture is 1300- 1500 μm, cavity wall is formed by aperture by 70-100 μm of second level POROUS TITANIUM, and the cavity wall of second level POROUS TITANIUM is by 1-9 μm of aperture Third level POROUS TITANIUM form, third level POROUS TITANIUM and first gradient grade POROUS TITANIUM are identical material.Preparation method and embodiment 3 Similar, POROUS TITANIUM pore size is adjusted by adjusting pore creating material particle size.
This kind of POROUS TITANIUM can be used for preparing the implant containing cancellous bone and cortex bone simultaneously.
Embodiment 5
The gradient porous material of the present embodiment is gradient porous titanium, and structure is similar to Example 3, and difference is first gradient grade POROUS TITANIUM is the POROUS TITANIUM of aperture 400-600nm, and the second gradient grade porous material is three-level hole titanium, and first order hole aperture is 100- 350 μm, cavity wall is formed by aperture by 10-30 μm of second level POROUS TITANIUM, and the cavity wall of second level POROUS TITANIUM is by aperture 400- The third level POROUS TITANIUM of 600nm is formed, and third level POROUS TITANIUM is identical material with first gradient grade POROUS TITANIUM.Preparation method and reality It is similar to apply example 3, POROUS TITANIUM pore size is adjusted by adjusting pore creating material particle size.
This kind of POROUS TITANIUM can be used for preparing the implant containing cancellous bone and cortex bone simultaneously.

Claims (6)

1. the gradient of a kind of gradient porous material, wherein porous material is according to the gradient porous material body in classification shape In the pore size in hole that is surrounded by cavity wall be classified, it is characterised in that:The gradient porous material is with minimal gradient grade Porous material is made the porous material that the hole of aperture bigger formed by raw material, and each gradient grade for forming gradient porous material is more The hole of Porous materials is mutually communicated.
2. gradient porous material as described in claim 1, it is characterised in that:Two neighboring gradient grade porous materials connect interface Area is more than two neighboring gradient grade porous materials using plane as the area of the plane at the interface that connects.
3. gradient porous material as claimed in claim 1 or 2, it is characterised in that:The minimal gradient of the gradient porous material The aperture in the hole of grade porous material is below 10 μm.
4. the gradient porous material as described in claims 1 to 3 any claim, it is characterised in that:The gradient porous material The aperture in the maximum level-one hole of the greatest gradient grade porous material of material is 100-1500 μm.
5. gradient porous material as described in claim 1, it is characterised in that:A wherein gradient grade porous material is three-level hole material Material, is classified according to the size in aperture, and first order hole aperture is maximum, and third level hole aperture is minimum, and second level hole aperture is the Between level-one hole aperture and third level hole aperture, second level hole is distributed on first order vestibule wall, is distributed on the vestibule wall of the second level There is third level hole.
6. gradient porous material as claimed in claim 5, it is characterised in that:The aperture in first order hole is 100-1500 μm, the Below 10 μm, the aperture in second level hole is 10-100 μm in the aperture in three-level hole.
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