CN103145438A - Preparation method of biomimetic gradient porous ceramic material - Google Patents
Preparation method of biomimetic gradient porous ceramic material Download PDFInfo
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- CN103145438A CN103145438A CN2013100462862A CN201310046286A CN103145438A CN 103145438 A CN103145438 A CN 103145438A CN 2013100462862 A CN2013100462862 A CN 2013100462862A CN 201310046286 A CN201310046286 A CN 201310046286A CN 103145438 A CN103145438 A CN 103145438A
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Abstract
The invention discloses a preparation method of a biomimetic gradient porous ceramic material. The method includes: subjecting a ceramic slurry to freezing, then conducting vacuum freeze drying, and finally performing sintering, thus obtaining the biomimetic gradient porous ceramic material. The preparation method of the biomimetic gradient porous ceramic material provided in the invention combines slip casting and repeated freeze drying technologies, and the obtained gradient porous ceramic material has porosity decreasing from inside to outside and a biomimetic structure with a sparse inside and a dense outside. While functions of the pores are ensured, the biomimetic gradient porous ceramic material has good mechanical properties, its gradient interface changes continuously, and at the same time, the gradient change range is controllable, so that the biomimetic gradient porous ceramic material has wide application prospects in the fields of biological tissue engineering, filter materials, catalyst carriers, and fuel cells, etc.
Description
Technical field
The invention belongs to technical field of ceramic material, relate to a kind of bionical gradient porous ceramics material preparation method.
Background technology
Porous ceramics is a kind of ceramic that contains than multiple hole, utilize in material pore space structure and (or) surface-area, the character of bond material itself reaches physics and the chemical properties such as needed heat, electricity, magnetic, light, thereby as the material of filtration, separation, dispersion, infiltration, heat insulation, heat exchange, sound absorption, sound insulation, absorption carrier, reaction sensing and the purposes such as biological.Based on above these characteristics, the application of porous ceramics expands to electronics, photoelectricity, biological chemistry and field of medical materials gradually from traditional filtration, thermal technology etc., but because the fragility of stupalith is larger, cause the mechanical property (such as compressive strength etc.) of porous ceramics relatively poor, become one of bottleneck of its large-scale application, become one of present problem demanding prompt solution so development has the porous ceramics of higher force performance.
There is in recent years the investigator to find, the vegeto-animal weight bearing area of nature, as the shin bone of animal and the stem of plant etc., have the gradient-structure of a kind of " close outside interior dredging ": outer porosity is lower, has crushing resistance preferably, plays protection and supporting role; Interior layer porosity is higher, possess the functional of porous ceramics, this bionical gradient-structure makes porous ceramics have higher mechanical property when having guaranteed functional (as filtration, separation, dispersion, infiltration, heat insulation etc.), so the preparation of gradient porous ceramics becomes one of study hotspot.
Chinese patent " a kind of hole gradient silicon carbide porous ceramics and preparation method thereof " (application number: 201110252396.5, publication number: 102417366A, open day: 2012-04-18) disclose a kind of hole gradient silicon carbide porous ceramics and technology of preparing thereof, take Polycarbosilane and silicon carbide powder as raw material, carbon dust is pore-forming material, prepare gradient porous ceramics by dry-pressing formed and sintering process, its gradient-structure mainly depends on diameter and the addition of carbon dust, the connectedness in hole mainly depends on the cracking of Polycarbosilane, and the scope of application is narrower.Chinese patent " a kind of method for preparing zirconia gradient porous ceramics take ice as template " (application number: 201110264529.0, publication number: 102424603A, open day: 2012-04-25) disclose a kind of method for preparing zirconia gradient porous ceramics take ice as template, take ice as the pore-forming template, obtain zircite porous ceramic through vacuum lyophilization and sintering process.Graded pore structure mainly changes along freezing direction, but its ultimate compression strength is only 8MPa, can not satisfy actual needs.the paper " Bioinspired structure of bioceramics for bone regeneration in load-bearing sites " that Faming Zhang etc. delivers (" being used for the biomimetic features biological ceramics that the weight bearing area osteanagenesis is repaired "), be selected from " Acta Biomaterialia " (" biomaterial magazine ") the 3rd volume 896-904 page in 2007, the employing polymer microsphere is pore-forming material, in the injection moulding preparation, layer porosity is higher, outer closely knit porous bio-ceramic, but its graded scope is narrower, while ectonexine place porosity is stepped, has larger unrelieved stress.
Summary of the invention
The purpose of this invention is to provide a kind of bionical gradient porous ceramics material preparation method, solved the narrow and little problem of ultimate compression strength of the gradient scope of gradient porous ceramics of prior art preparation.
The technical solution adopted in the present invention is that bionical gradient porous ceramics material preparation method is carried out vacuum lyophilization with ceramic size through after freezing, finally by oversintering, namely obtains bionical gradient porous ceramics material.
Characteristics of the present invention also are,
Specifically implement according to following steps:
Step 1, the preparation ceramic size
Add successively dispersion agent and ceramic particle in solvent, be mixed to get ceramic size, prepare altogether n 〉=2 group ceramic size, be labeled as T
1, T
2, T
3..., T
n-1, T
n, wherein in n group slurry, the volume ratio of solvent is less than the volume ratio that n-1 organizes solvent in slurry;
Step 2, freezing
Freezing employing is repeatedly freezing, and freezing number of times is identical with the number of plies of bionical gradient porous ceramics material, and the freezing mould of freezing employing is freezing, and the sidewall of freezing mould is the tubulose lagging material, and the bottom surface is heat-conducting metal, and the common n of freezing mould 〉=2 groups is labeled as respectively M
1, M
2, M
3..., M
n-1, M
n, freezing mould M wherein
nInterior diameter be greater than freezing mould M
n-1Interior diameter; The body that freezes of each freezing rear acquisition is labeled as respectively F
1, F
2, F
3..., F
n-1, F
n
Freezing concrete steps are as follows:
The 1st time freezing: with ceramic size T
1Inject freezing mould M
1In, then with freezing mould M
1Be placed on low-temperature receiver directed freezingly, obtain by frozen ceramic size T
1The cylindric body F that freezes that forms
1
The 2nd time freezing: at first with the 1st the freezing cylindric body F that freezes that obtains
1Be placed on freezing mould M
2The center, then with ceramic size T
2Inject the cylindric body F that freezes
1With freezing mould M
2Sidewall between the gap in, standing after again with freezing mould M
2Be placed on low-temperature receiver directed freezingly, obtain by frozen ceramic size T
1With frozen ceramic size T
2The compound body F that freezes of cylindrical coaxial that forms
2
The the one n time is freezing: at first with the n-1 time freezing n-1 layer that obtains by frozen ceramic size T
1, T
2... T
n-1The compound body F that freezes of cylindrical coaxial that forms
n-1Be placed on freezing mould M
nThe center, then with ceramic size T
nInject the n-1 layer by frozen ceramic size T
1, T
2... T
n-1The compound body F that freezes of cylindrical coaxial that forms
n-1With freezing mould M
nBetween the gap in, standing after again with freezing mould M
nBe placed on low-temperature receiver directed freezingly, obtain the n layer by frozen ceramic size T
1, T
2... T
nThe compound body F that freezes of cylindrical coaxial that forms
n
Step 3, vacuum lyophilization
The compound body F that freezes of cylindrical coaxial that step 2 is obtained
nLyophilize under vacuum environment makes the compound body F that freezes of cylindrical coaxial
nIn solvent crystallization body distillation, obtain gradient porous base substrate;
Step 4, sintering
The gradient porous base substrate that step 3 is obtained namely gets bionical gradient porous ceramics material at 800～1800 ℃ of sintering.
In step 1, the volume ratio of solvent, ceramic particle and dispersion agent is 9500～5000:495～4750:5～450;
Solvent is any one in water, the trimethyl carbinol, amphene, water-t-butanol solution, the trimethyl carbinol-amphene solution; Ceramic particle is metal oxide, any one in metal nitride, hydroxyapatite, tricalcium phosphate, clay, silicon carbide, silicon carbide and trichroite or any several mixture; Dispersion agent is any one in polyacrylate, polyvinylpyrrolidone, polyvinyl butyral acetal and citric acid.
In step 2, directed freezing freezing temp is-50～50 ℃.
Ceramic size T in step 2
2-T
nTemperature be controlled at 5～80 ℃.
In step 2, time of repose is 1～10min.
The invention has the beneficial effects as follows, the bionical gradient porous ceramics material preparation of the present invention method, by injection forming and the repeatedly combination of Freeze Drying Technique, obtain porosity and reduce from inside to outside, have the interior gradient porous ceramics material of dredging outer close biomimetic features, has simultaneously a mechanical property preferably guaranteeing that porous is functional, its gradient interface changes continuously, the graded scope is controlled simultaneously, has broad application prospects in fields such as bioengineered tissue, filtering material, support of the catalyst, fuel cells.
Description of drawings
Fig. 1 is the cross-sectional morphology figure of the two-layer bionical gradient porous ceramics material of the embodiment of the present invention 1 preparation;
Fig. 2 is the two-layer bionical gradient porous ceramics material gradient cross-sectional morphology figure at the interface of the embodiment of the present invention 1 preparation;
Fig. 3 is the vertical section shape appearance figure of the two-layer bionical gradient porous ceramics material of the embodiment of the present invention 1 preparation.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
The bionical gradient porous ceramics material preparation of the present invention method is carried out vacuum lyophilization with ceramic size through after freezing, finally by oversintering, namely obtains bionical gradient porous ceramics material.
Specifically implement according to following steps:
Step 1, the preparation ceramic size
Add successively dispersion agent and ceramic particle in solvent, be mixed to get ceramic size, prepare altogether n 〉=2 group ceramic size, be labeled as T
1, T
2, T
3..., T
n-1, T
n, wherein in n group slurry, the volume ratio of solvent is less than the volume ratio that n-1 organizes solvent in slurry, and wherein the volume ratio of solvent, ceramic particle and dispersion agent is 9500～5000:495～4750:5～450; Solvent is any one in water, the trimethyl carbinol, amphene, water-t-butanol solution, the trimethyl carbinol-amphene solution; Ceramic particle is metal oxide, any one in metal nitride, hydroxyapatite, tricalcium phosphate, clay, silicon carbide, silicon carbide and trichroite or any several mixture; Dispersion agent is any one in polyacrylate, polyvinylpyrrolidone, polyvinyl butyral acetal and citric acid;
Step 2, freezing
Freezing employing is repeatedly freezing, and freezing number of times is identical with the number of plies of biomimetic porous stupalith, and the freezing mould of freezing employing is freezing, and the sidewall of freezing mould is the tubulose lagging material, and the bottom surface is heat-conducting metal, and the common n of freezing mould 〉=2 groups is labeled as respectively M
1, M
2, M
3..., M
n-1, M
n, freezing mould M wherein
nInterior diameter be greater than freezing mould M
n-1Interior diameter; The n of each freezing rear acquisition 〉=2 groups freezes body and is labeled as respectively F1, F
2, F
3..., F
n-1, F
n
Freezing concrete steps are as follows:
The 1st time freezing: with ceramic size T
1Inject freezing mould M
1In, then with freezing mould M
1Be placed on low-temperature receiver directed freezingly, freezing temp is-50～50 ℃, obtains by frozen ceramic size T
1The cylindric body F that freezes that forms
1
The 2nd time freezing: at first with the 1st the freezing cylindric body F that freezes that obtains
1Be placed on freezing mould M
2The center, then with the ceramic size T of 5～80 ℃
2Inject the cylindric body F that freezes
1With freezing mould M
2Sidewall between the gap in, after standing 1～10min again with freezing mould M
2Be placed on low-temperature receiver directed freezingly, freezing temp is-50～50 ℃, obtains by frozen ceramic size T
1With frozen ceramic size T
2The compound body F that freezes of cylindrical coaxial that forms
2
The the one n time is freezing: at first with the n-1 time freezing n-1 layer that obtains by frozen ceramic size T
1, T
2... T
n-1The compound body F that freezes of cylindrical coaxial that forms
n-1Be placed on freezing mould M
nThe center, then with the ceramic size T of 5～80 ℃
nInject the n-1 layer by frozen ceramic size T
1, T
2... T
n-1The compound body F that freezes of cylindrical coaxial that forms
n-1With freezing mould M
nBetween the gap in, after standing 1～10min again with freezing mould M
nBe placed on low-temperature receiver directed freezingly, freezing temp is-50～50 ℃, obtains the n layer by frozen ceramic size T
1, T
2... T
nThe compound body F that freezes of cylindrical coaxial that forms
n
Step 3, vacuum lyophilization
The compound body F that freezes of cylindrical coaxial that step 2 is obtained
nLyophilize under vacuum environment makes the compound body F that freezes of cylindrical coaxial
nIn solvent crystallization body distillation, obtain gradient porous base substrate;
Step 4, sintering
The gradient porous base substrate that step 3 is obtained namely gets bionical gradient porous ceramics material at 800～1800 ℃ of sintering.
The bionical gradient porous ceramics material preparation of the present invention method, by injection forming and the repeatedly combination of Freeze Drying Technique, obtain porosity and reduce from inside to outside, have the interior gradient porous ceramics material of dredging outer close biomimetic features, has simultaneously a mechanical property preferably guaranteeing that porous is functional, its gradient interface changes continuously, the graded scope is controlled simultaneously, has broad application prospects in fields such as bioengineered tissue, filtering material, support of the catalyst, fuel cells.
Embodiment 1
2 layers of bionical gradient porous ceramics material need freezing 2 times.
Add successively 3ml sodium polyacrylate and 27ml hydroxylapatite ceramic particle in 70ml water, obtain ceramic size T after closing evenly
1, add successively 4.5ml sodium polyacrylate and 40.5ml hydroxylapatite ceramic particle in 55ml water, obtain ceramic size T after mixing
2
With ceramic size T
1Injecting internal diameter is the freezing mould M of 10mm
1In, then freezing mould being placed on that to carry out the 1st orientation on low-temperature receiver freezing, freezing temp is-30 ℃, obtains by frozen ceramic size T
1The cylindric body F that freezes that forms
1With the 1st the freezing cylindric body F that freezes that obtains
1Being placed on interior diameter is the freezing mould M of 15mm
2The center is with the ceramic size T of 30 ℃
2Inject the cylindric body F that freezes
1With freezing mould M
2Between the gap in, standing 10min is then with freezing mould M
2Be placed on low-temperature receiver directed freezingly, freezing temp is-30 ℃, obtains the compound body F that freezes of cylindrical coaxial
2
In vacuum environment to the compound body F that freezes of cylindrical coaxial
2Carry out lyophilize, make the compound body F that freezes of cylindrical coaxial
2In water crystallization body distillation, obtain gradient porous base substrate, this gradient porous base substrate is comprised of HA ceramic particle and sodium polyacrylate;
Gradient porous base substrate at 1250 ℃ of sintering, is namely got 2 layers of bionical gradient porous ceramics material.
Embodiment 2
2 layers of bionical gradient porous ceramics material need freezing 2 times.
Add successively 0.05ml citric acid and 4.95mlAl in 95ml water-t-butanol solution
2O
3Ceramic particle obtains ceramic size T after mixing
1Add successively 0.5ml citric acid and 19.5mlAl in 80ml water-t-butanol solution
2O
3Ceramic particle obtains ceramic size T after mixing
2
With ceramic size T
1Injecting internal diameter is the freezing mould M of 12mm
1In, then freezing mould being placed on that to carry out the 1st orientation on low-temperature receiver freezing, freezing temp is-50 ℃, obtains by frozen ceramic size T
1The cylindric body F that freezes that forms
1With the 1st the freezing cylindric body F that freezes that obtains
1Being placed on interior diameter is the freezing mould M of 18mm
2The center is with the ceramic size T of 5 ℃
2Inject the cylindric body F that freezes
1With freezing mould M
2Between the gap in, standing 5min is then with freezing mould M
2Be placed on low-temperature receiver directed freezingly, freezing temp be-50 ℃, the compound body Fx that freezes of acquisition cylindrical coaxial;
In vacuum environment to the compound body F that freezes of cylindrical coaxial
2Carry out lyophilize, make the compound body F that freezes of cylindrical coaxial
2In the distillation of water-trimethyl carbinol mixing solutions xln, obtain gradient porous base substrate, this gradient porous base substrate is by Al
2O
3Ceramic particle and citric acid form;
Gradient porous base substrate at 1800 ℃ of sintering, is namely got 2 layers of bionical gradient porous ceramics material.
Embodiment 3
3 layers of bionical gradient porous ceramics material need freezing 3 times.
Add successively 1.5ml polyvinyl butyral acetal and 28.5ml ZrO in the 70ml amphene
2Ceramic particle obtains ceramic size T after mixing
1Add successively 2ml polyvinyl butyral acetal and 38ml ZrO in the 60ml amphene
2Ceramic particle obtains ZrO after mixing
2Ceramic size T
2Add successively 2.5ml polyvinyl butyral acetal and 47.5ml ZrO in the 50ml amphene
2Ceramic particle obtains ceramic size T after mixing
3
With ceramic size T
1Injecting internal diameter is the freezing mould M of 5mm
1In, then freezing mould being placed on that to carry out the 1st orientation on low-temperature receiver freezing, freezing temp is 50 ℃, obtains by frozen ceramic size T
1The cylindric body F that freezes that forms
1With the 1st the freezing cylindric body F that freezes that obtains
1Being placed on interior diameter is the freezing mould M of 10mm
2The center is with the ceramic size T of 80 ℃
2Inject cylindric body F1 and the freezing mould M of freezing
2Between the gap in, standing 1min is then with freezing mould M
2Be placed on low-temperature receiver directed freezingly, freezing temp is 50 ℃, obtains the compound body F that freezes of cylindrical coaxial
2With the 2nd the freezing compound body F that freezes of cylindrical coaxial that obtains
2Being placed on interior diameter is the freezing mould M of 15mm
3The center is with the ceramic size T of 80 ℃
3Inject the compound body F that freezes of cylindrical coaxial
2With freezing mould M
3Between the gap in, standing 1min is then with freezing mould M
3Be placed on low-temperature receiver directed freezingly, freezing temp is 50 ℃, obtains the compound body F that freezes of cylindrical coaxial
3
In vacuum environment to the compound body F that freezes of cylindrical coaxial
3Carry out lyophilize, make the compound body F that freezes of cylindrical coaxial
3In amphene xln distillation, obtain gradient porous base substrate, this gradient porous base substrate is by ZrO
2Ceramic particle and polyvinyl butyral acetal form;
Gradient porous base substrate at 1350 ℃ of sintering, is namely got 3 layers of bionical gradient porous ceramics material.
Embodiment 4
4 layers of bionical gradient porous ceramics material need freezing 4 times.
Add successively 0.6ml polyvinylpyrrolidone and 19.4ml TiO in the 80ml trimethyl carbinol
2Ceramic particle obtains ceramic size T after mixing
1Add successively 1.6ml polyvinylpyrrolidone and 28.4ml TiO in the 70ml trimethyl carbinol
2Ceramic particle obtains ceramic size T after mixing
2Add successively 2.1ml polyvinylpyrrolidone and 37.9ml TiO in the 60ml trimethyl carbinol
2Ceramic particle obtains ceramic size T after mixing
3Add successively 2.5ml polyvinylpyrrolidone and 47.5ml TiO in the 50ml trimethyl carbinol
2Ceramic particle obtains ceramic size T after mixing
4
With ceramic size T
1Injecting internal diameter is the freezing mould M of 5mm
1In, then freezing mould being placed on that to carry out the 1st orientation on low-temperature receiver freezing, freezing temp is 10 ℃, obtains by cylindric frozen ceramic size T
1The cylindric body F that freezes that forms
1With the 1st the freezing cylindric body F that freezes that obtains
1Being placed on interior diameter is the freezing mould M of 10mm
2The center is with the ceramic size T of 30 ℃
2Inject the cylindric body F that freezes
1With freezing mould M
2Between the gap in, standing 7min is then with freezing mould M
2Be placed on low-temperature receiver directed freezingly, freezing temp is 10 ℃, obtains the compound body F that freezes of cylindrical coaxial
2With the compound body F that freezes of cylindrical coaxial
2Being placed on interior diameter is the freezing mould M of 15mm
3The center is with the ceramic size T of 30 ℃
3Inject the compound body F that freezes of cylindrical coaxial
2With freezing mould M
3Between the gap in, standing 7min is then with freezing mould M
3Be placed on low-temperature receiver directed freezingly, freezing temp is 10 ℃, obtains the compound body F that freezes of cylindrical coaxial
3With the compound body F that freezes of cylindrical coaxial
3Being placed on interior diameter is the freezing mould M of 20mm
4The center is with the ceramic size T of 30 ℃
4Inject the compound body F that freezes of cylindrical coaxial
3With freezing mould M
4Between the gap in, standing 7min is then with freezing mould M
4Be placed on low-temperature receiver directed freezingly, freezing temp is 10 ℃, obtains the compound body F that freezes of cylindrical coaxial
4
In vacuum environment to the compound body F that freezes of cylindrical coaxial
4Carry out lyophilize, make cylindrical coaxial complex body F
4In trimethyl carbinol xln distillation, obtain gradient porous base substrate, this gradient porous base substrate is by TiO
2Ceramic particle and polyvinylpyrrolidone form;
Gradient porous base substrate at 800 ℃ of sintering, is namely got 4 layers of bionical gradient porous ceramics material.
In the present embodiment, solvent is the trimethyl carbinol, also can be the trimethyl carbinol-amphene; In the present embodiment, ceramic particle is TiO
2, also can be other metal oxides, any one in metal nitride, hydroxyapatite, tricalcium phosphate, clay, silicon carbide, silicon carbide and trichroite or any several mixture.
The inventive method recently controls by the volume of controlling from inside to outside solvent in every layer of ceramic size the scope that the gradient porous ceramics porosity gradient changes, and controls the hole shape of gradient porous ceramics by the kind of solvent.Take the bionical gradient porous ceramics material of embodiment 1 preparation as example, Fig. 1 is the cross-sectional morphology figure of the two-layer bionical gradient porous ceramics material of the embodiment of the present invention 1 preparation, as can see from Figure 1, the hole of bionical gradient porous ceramics material is stratiform, and the porosity gradient scope is 35～46%.
The inventive method is by controlling ceramic size T
nTemperature at 5～80 ℃, inject the compound body F that freezes of cylindrical coaxial
n-1With freezing mould M
nBetween the gap in, directed freezing again after standing 1～10min, allow the gradient interface place that partial melting-recrystallize occurs, make porosity gradient at the interface change continuously.Take the bionical gradient porous ceramics material of embodiment 1 preparation as example, Fig. 2 is the two-layer bionical gradient porous ceramics material gradient cross-sectional morphology figure at the interface of the embodiment of the present invention 1 preparation, as can see from Figure 2, the gradient interface continuous transition of outer and interior interlayer does not have obvious boundary.
The inventive method adopts directed freezing, and solvent is all along freezing direction crystallization, and the final gradient porous ceramics material that obtains has the clear opening along freezing direction.Take the bionical gradient porous ceramics material of embodiment 1 preparation as example, Fig. 3 is the vertical section shape appearance figure of the two-layer bionical gradient porous ceramics material of the embodiment of the present invention 1 preparation, as can see from Figure 3, the duct of gradient porous ceramics all is arranged in parallel along freezing direction.
Interface conditions, porosity gradient scope and the mechanical property of the bionical gradient porous ceramics material of the embodiment of the present invention 1,2,3 and 4 preparations are as shown in table 1.
Interface conditions, porosity gradient scope and the mechanical property of the bionical gradient porous ceramics material of table 1 embodiment of the present invention 1,2,3 and 4 preparations
As can be seen from Table 1, by controlling ceramic size T
nTemperature at 5～80 ℃, directed freezing again after standing 1～10min after injecting, allow the gradient interface place that partial melting-recrystallize occurs, make embodiment 1,2, each layer gradient interface all changes continuously in 3,4; Simultaneously, by controlling from inside to outside the volume ratio of solvent in every layer of ceramic size, can realize that the porous ceramics porosity changes within the specific limits in gradient; In addition, because the outer porosity of bionical gradient porous ceramics is little, have higher compressive strength, can play and support and provide protection.
Claims (7)
1. bionical gradient porous ceramics material preparation method, is characterized in that, ceramic size is carried out vacuum lyophilization through after freezing, finally by oversintering, namely obtains bionical gradient porous ceramics material.
2. according to claim 1 how bionical gradient porous ceramics material preparation method, is characterized in that, specifically implements according to following steps:
Step 1, the preparation ceramic size
Add successively dispersion agent and ceramic particle in solvent, be mixed to get ceramic size, prepare altogether n 〉=2 group ceramic size, be labeled as T
1, T
2, T
3..., T
n-1, T
n, wherein in n group slurry, the volume ratio of solvent is less than the volume ratio that n-1 organizes solvent in slurry;
Step 2, freezing
Freezing employing is repeatedly freezing, and freezing number of times is identical with the number of plies of bionical gradient porous ceramics material; The freezing mould of freezing employing is freezing, and the sidewall of freezing mould is the tubulose lagging material, and the bottom surface is heat-conducting metal, and the common n of freezing mould 〉=2 groups is labeled as respectively M
1, M
2, M
3..., M
n-1, M
n, freezing mould M wherein
nInterior diameter be greater than freezing mould M
n-1Interior diameter; The body that freezes of each freezing rear acquisition is labeled as respectively F1, F
2, F
3..., F
n-1, F
n
Freezing concrete steps are as follows:
The 1st time freezing: with ceramic size T
1Inject freezing mould M
1In, then with freezing mould M
1Be placed on low-temperature receiver directed freezingly, obtain by frozen ceramic size T
1The cylindric body F that freezes that forms
1
The 2nd time freezing: at first with the 1st the freezing cylindric body F that freezes that obtains
1Be placed on freezing mould M
2The center, then with ceramic size T
2Be infused in the cylindric body F that freezes
1With freezing mould M
2Sidewall between the gap in, standing after again with freezing mould M
2Be placed on low-temperature receiver directed freezingly, obtain by frozen ceramic size T
1With frozen ceramic size T
2The cylindrical coaxial complex body that forms freezes F
2
The the one n time is freezing: at first with the n-1 time freezing n-1 layer that obtains by frozen ceramic size T
1, T
2... T
n-1The compound body F that freezes of cylindrical coaxial that forms
n-1Be placed on freezing mould M
nThe center, then with ceramic size T
nInject the n-1 layer by frozen ceramic size T
1, T
2... T
n-1The compound body F that freezes of cylindrical coaxial that forms
n-1With freezing mould M
nBetween the gap in, standing after again with freezing mould M
nBe placed on low-temperature receiver directed freezingly, obtain the n layer by frozen ceramic size T
1, T
2... T
nThe compound body F that freezes of cylindrical coaxial that forms
n
Step 3, vacuum lyophilization
The compound body F that freezes of cylindrical coaxial that step 2 is obtained
nLyophilize under vacuum environment makes the compound body F that freezes of cylindrical coaxial
nIn solvent crystallization body distillation, obtain gradient porous base substrate;
Step 4, sintering
The gradient porous base substrate that step 3 is obtained namely gets bionical gradient porous ceramics material at 800～1800 ℃ of sintering.
3. bionical gradient porous ceramics material preparation method according to claim 2, is characterized in that, in described step 1, the volume ratio of solvent, ceramic particle and dispersion agent is 9500～5000:495～4750:5～450.
4. according to claim 2 or 3 described bionical gradient porous ceramics material preparation methods, is characterized in that, described solvent is any one in water, the trimethyl carbinol, amphene, water-t-butanol solution, the trimethyl carbinol-amphene solution; Described ceramic particle is metal oxide, any one in metal nitride, hydroxyapatite, tricalcium phosphate, clay, silicon carbide, silicon carbide and trichroite or any several mixture; Described dispersion agent is any one in polyacrylate, polyvinylpyrrolidone, polyvinyl butyral acetal and citric acid.
5. according to claim 2 or 3 described bionical gradient porous ceramics material preparation methods, is characterized in that, in described step 2, directed freezing freezing temp is-50～50 ℃.
6. bionical gradient porous ceramics material preparation method according to claim 5, is characterized in that, in described step 2, the temperature of ceramic size T2-Tn is controlled at 5～80 ℃.
7. bionical gradient porous ceramics material preparation method according to claim 6, is characterized in that, in described step 2, time of repose is 1～10min.
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| CN103641509A (en) * | 2013-12-09 | 2014-03-19 | 中国建筑材料科学研究总院 | Porous carbon preform for reactive sintering, as well as preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285815A (en) * | 2011-06-07 | 2011-12-21 | 西安理工大学 | Method for preparing double-pore type porous ceramic |
| CN102826855A (en) * | 2012-06-21 | 2012-12-19 | 清华大学 | Preparation method of porous ceramic pipe with gradient through hole structure |
-
2013
- 2013-02-05 CN CN201310046286.2A patent/CN103145438B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285815A (en) * | 2011-06-07 | 2011-12-21 | 西安理工大学 | Method for preparing double-pore type porous ceramic |
| CN102826855A (en) * | 2012-06-21 | 2012-12-19 | 清华大学 | Preparation method of porous ceramic pipe with gradient through hole structure |
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| CN110732672B (en) * | 2019-12-11 | 2022-05-03 | 中南大学 | Gradient metal-based porous material and preparation method and application thereof |
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| CN116589299A (en) * | 2023-05-05 | 2023-08-15 | 哈尔滨工业大学 | Porous silicon carbide ceramic framework with bionic annual ring structure, preparation method thereof and application thereof in high-performance composite phase change material |
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| CN117550833A (en) * | 2024-01-11 | 2024-02-13 | 瑞声光电科技(常州)有限公司 | Sound-absorbing block material and preparation method and application thereof |
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