CN103585677B - A kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material and its preparation method and application - Google Patents
A kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material, be characterized in taking calcium phosphate as matrix of materials phase, is that wild phase is to promote the mechanical property of material by doped hydroxyapatite (HA) micro-nano whisker.Its preparation technology synthesizes calcium phosphate substrate phase front to drive powder body material, hydroxyapatite micro-nano whisker wild phase material respectively; Again by micro-nano for the hydroxyapatite of 3 ~ 10% whisker doped and compounded in ceramic idiosome powder, carry out the making of porous ceramics idiosome, formed finally by Muffle furnace calcining and strengthen porous calcium phosphate bioactive ceramics.This biomaterial is calcium phosphate and hydroxyapatite component, the two has similar chemical composition to nature bone, the loose structure of meticulous customization makes pottery have excellent biological activity, the ceramic mechanical property of doping hydroxyapatite whisker reinforcement, this kind of porous ceramics is as osseous tissue renovating material, there is excellent biological activity and have good mechanical property concurrently, Orthopedic Clinical has broad application prospects.
Description
Technical field
The present invention relates to a kind of hydroxyapatite (HA) micro-nano whisker reinforcement calcium phosphate ceramic material and its preparation method and application, belong to field of biomedical materials.
Background technology
Biomaterial for load Bone Defect Repari requires that material has good mechanical property and biological activity concurrently simultaneously.Porous calcium phosphate ceramic (Calcium Phosphate Bioceramics, CaP), because its chemical composition is similar with body bone tissue, and there is loose structure, make it have the multiple excellent biological characteristicses such as good bone conduction, self-bone grafting, degradable absorption.The demand of growing into meet freshman bone tissue merges speed with increase bone, and bone renovating material necessarily requires to have mutually through three-dimensional porous structure, and its desirable macropore size is 100 ~ 500 μm, and porosity should be greater than 60%.But causing the strength of materials not enough due to the existence of pore structure and self fragility of pottery, the comprcssive strength of the series of calcium phosphate porous material of report is only 0.3 ~ 3.3MPa at present, limits the reparation application using it for bearing position Cranial defect.
Carry out the mechanical property of reinforcing material on basis that a large amount of correlational study is intended to guarantee ceramic active in recent years.A kind of effective way improving ceramics strength is compound/interpolation wild phase, and usual way adds to strengthen granule or whisker, and the effect of wherein adding whisker is more remarkable.It is matrix with hydroxyapatite that Chinese patent CN1935270A reports a kind of, by composite bioceramic material and technology of preparing thereof that interpolation diopside and aluminium oxide are toughened and reinforced phase, composite ceramics prepared by this technology has better fracture toughness, bending strength and comprcssive strength with pure ha ceramic phase ratio, but the calcium phosphate ceramic adding doping phase certainly will reduce the biological activity of material.
Separately studies have reported that, by adding bioactivity glass phase, series of calcium phosphate porous bio-ceramic not only effectively improves its mechanical property, also can ensure the biological activity of material simultaneously.Chinese patent 03149539.7 describes at CaO-SiO
2na is added in system
2o, CaF
2or B
2o
3synthesize a kind of bioactivity glass phase, and use the doped sintered technology preparing calcium phosphate glass sintered body of this glassy phase.Chinese patent 200610013334.8 reports a kind of CaO-P
2o
5-Na
2the preparation method of O-MgO glass reinforced porous bata-tricalcium phosphate bioceramic.United States Patent (USP) 5,675,720 to disclose component be CaO-Na
2o-SiO
2-P
2o
5the preparation method of Porous bioglass, US Patent No. 5,125971 report by adding containing SiO
2glass improves the sintering character of ceramic bases and the technology of mechanical property.Correlational study has confirmed that these contain SiO
2the pottery of glassy phase has excellent biological activity, when in the implanted body of material, form silicon-rich layer by dissolving-precipitation mechanism at material interface at humoral effect lower-glass body, attract the calcium in body fluid, phosphonium ion migrates to host interface and form amorphous calcium phosphate, so again with the OH in body fluid
-, CO
3 2-in conjunction with generation osteoid apatite, thus impel implant and host that gluing occurs to merge.But, SiO
2be different from calcium phosphate, they are not the constituent of human body hard tissue, by organism degrades and absorption, finally can not can not become a part for body bone tissue.Therefore, this kind of biomaterial can only be regarded as having bioactive implant, and they still need to be improved with the designing requirement of satisfied biomaterial of new generation, that is: " meet material biological function; and have and initiatively repair, inducing tissue regeneration, reconstruction damaged tissues " requirement.
Summary of the invention
The object of the invention is a kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material developed for the deficiencies in the prior art and its preparation method and application, be characterized in the chemical composition simulating nature bone, adopt the micro-nano whisker enhancement techniques of HA to promote mechanical property and the induction bone tissue restoration regeneration function of ceramic material.
Another object of the present invention is to provide the application of above-mentioned bioceramic in biomedical sector, in particular for the repair and reconstruction of load osseous tissue defect, in load osseous tissue defect as repair materials, the initial strength of timbering material is provided, the generation of rapid induction new bone tissue, strengthens bone and connects and healing function.
Object of the present invention is realized by following technical measures, and wherein said raw material number, except specified otherwise, is mass fraction.
The substrate of HA micro-nano whisker reinforcement calcium phosphate ceramic material is coordinated and is divided into calcium phosphate, and wild phase composition is the micro-nano whisker of HA, and the mass percent of each component is:
Calcium phosphate 90% ~ 97wt%,
The micro-nano whisker 10 ~ 3wt% of HA.
Described calcium phosphate is: any one in hydroxyapatite, β phase tricalcium phosphate or biophasic calcium phosphate ceramic.
The micro-nano whisker of described HA is: minute hand shape, pattern are homogeneous, length is 10 ~ 50 μm, and diameter is 0.3 ~ 2 μm, and draw ratio is the hydroxyapatite crystal whisker of 5 ~ 167.
The preparation method of HA micro-nano whisker reinforcement calcium phosphate ceramic material comprises the following steps:
1) by " wet chemistry reaction " synthetic substrate calcium phosphate phase powder body, this powder body synthesizes hydroxyapatite (HA) powder body, β phase tricalcium phosphate (β-TCP) powder body and biphasic calcium phosphate (HA/TCP) three kinds of powder body through reaction controlling; Dry and through comminution by gas stream, screen the dry powder that diameter is 80 ~ 160 μm, as the forerunner's powder preparing porous ceramics idiosome;
2) synthesize the micro-nano whisker of wild phase HA by " coating method ", take Ca: P mol ratio be 1.67: 1 soluble calcium salt and microcosmic salt be dissolved in deionized water and make it be starchiness; KNO is taken by 1: 1: 1 mol ratio
3, LiNO
3, KOH add deionized water be mixed into starchiness be used as cosolvent, then these two kinds of starchiness slurries are fully mixed, pH=4 ~ 6.8 are modulated with acid, be coated on clean titanium plate surface, be placed in the hydrothermal reaction kettle that politef is substrate, be warming up to 200 ~ 350 DEG C with the speed of 5 DEG C/min, reaction 6 ~ 12h, naturally cool to room temperature, product through washing, alcohol wash, filtration, dry to obtain the micro-nano whisker of HA;
3) adulterate, the micro-nano whisker of HA of Homogeneous phase mixing 10 ~ 3wt% is in 90% ~ 97wt% calcium phosphate powder, with the polyvinyl alcohol of 3 ~ 5wt%, with hydrogen peroxide modulation ceramic size to sposh shape, decompose hydrogen peroxide by microwave-oven-heating after stirring and produce gas with foamed ceramic slurry, 80 × 30 × 30cm(will be positioned over containing the ceramic size enriching foam long × wide × high) mould in dry obtained porous ceramics idiosome;
4) sinter, ceramic idiosome is put into Muffle furnace and sinters, with the speed of 5 DEG C/min, from room temperature to 1000 ~ 1200, a DEG C insulation 1 ~ 3h sinters, and then furnace cooling, obtains HA micro-nano whisker reinforcement calcium phosphate ceramic material;
This calcium phosphate ceramic material is multiporous biological active ceramic, its pore structure is 60% ~ 95% of ceramic overall porosity, and micropore size is 100 ~ 500 microns, and micropore is mutually three-dimensional through, hole inwall is covered with capillary micropore, and the micro-nano whisker of HA is uniformly distributed among ceramic matrix material.
Soluble calcium salt in described step 2 is: CaCl
2, or Ca (NO
3)
24H
2o or (CH
3cOO)
2caH
2any one in O; Microcosmic salt is: (NH
4)
2hPO
4, (NH
4) H
2pO
4, K
2hPO
4or NaH
2pO
4in any one.
The acid that in described step 2, the regulation and control of pH adopt is nitric acid, or hydrochloric acid, or any one in phosphoric acid.
Described HA micro-nano whisker reinforcement calcium phosphate ceramic material is used for reparation and the scaffold material of bone tissue engineering of human body hard tissue defect.
Structural characterization and performance test:
1, the pore structure of calcium phosphate ceramic material is tested by mercury injection apparatus and is characterized.
Result shows: the pore structure of material is mutual through loose structure, and testing ceramic overall porosity is 60% ~ 95%.
2, the microstructure of material is tested through SEM.
Shown in Fig. 2 (a) ~ (d).
Result shows: the microstructure of material is loose structure, and its micropore size is 100 ~ 500 microns, and micropore is mutually three-dimensional through, and hole inwall is covered with capillary micropore, and the micro-nano whisker of HA is uniformly distributed among ceramic matrix material.
3, the micro-nano whisker phase constituent of HA is identified by XRD and is characterized.
Shown in Fig. 3 (a) ~ (b).
Result shows: the micro-nano whisker of wild phase of material is the incomplete hydroxyapatite crystal whisker of crystallization.
4, material mechanical performance is through dynamic mechanical test (Dynamic mechanical analysis, DMA).
Shown in Fig. 4.
Result shows: after the micro-nano whisker composite strengthening of HA, the maximum compressive strength of material is significantly enhanced, and its numerical value is enhanced to 1.5 ~ 8.0MPa by 0.5 ~ 2.5MPa of pure phosphoric acid calcium ceramic material.
5, the biological characteristics of material cultivates test by external mesenchymal stem cells MSCs (MSCs).
Shown in Fig. 5 (a) ~ (d).
Result shows: the material after HA micro-nano whisker compound has good biocompatibility, can promote the differentiation of mesenchymal stem cells MSCs, propagation and growth.
Tool of the present invention has the following advantages,
1, the present invention is through the enhancing ceramic material of the micro-nano whisker doping of HA, and the maximum compressive strength of material is enhanced to 1.5 ~ 8.0MPa by 0.5 ~ 2.5MPa of pure phosphoric acid calcium ceramic material.
2, the present invention can keep the good biological activity of material, guarantees the self-bone grafting ability of porous calcium phosphate ceramic, rapidly the generation of induction new bone tissue, strengthens bone and connects and healing function;
3, preparation technology of the present invention is simple, and production efficiency is high, and cost is lower, is conducive to suitability for industrialized production.
Accompanying drawing explanation
Preparation technology's flow chart of Fig. 1 .HA micro-nano whisker reinforcement porous calcium phosphate ceramic biomaterial;
1, calcium, phosphorus proportioning is chosen; 2, the micro-nano increasing whisker synthesis of HA; 3, calcium phosphate ceramic precursor powder synthesis; 4, calcium phosphate ceramic powder body screening; 5, adulterate, mix the micro-nano whisker/ceramic powder of HA; 6, porous ceramics part makes; 7, porous ceramics is dried, is sintered; 8, sterilizing, storage.
Fig. 2. (a) is that the HA micro-nano enhancing whisker SEM that " coating method " synthesizes schemes
Fig. 2. the porous ceramics mixed powder SEM that (b) strengthens whisker for the 10%HA that adulterates in embodiment 5 schemes
Fig. 2. (c) for embodiment 1 adulterate 5%HA strengthen whisker ceramic post sintering after SEM figure
Fig. 2. (d) is HA enhancing whisker porous biophasic calcium phosphate ceramic SEM shape appearance figure in embodiment 4
Fig. 3. (a) HA micro-nano whisker phase constituent qualification XRD figure for synthesizing in the present invention
Fig. 3. (b) is HA crystal standard XRD pattern
Fig. 4 .HA micro-nano whisker reinforcement porous calcium phosphate ceramic Measurement of Material Mechanical Performance figure
Fig. 5. (a) is material mesenchymal stem cells MSCs (MSCs) the In vitro culture laser co-focusing figure of 1 day
Fig. 5. (b) is material mesenchymal stem cells MSCs (MSCs) the In vitro culture laser co-focusing figure of 3 days
Fig. 5. (c) is material mesenchymal stem cells MSCs (MSCs) the In vitro culture laser co-focusing figure of 7 days
Fig. 5. (d) is material mesenchymal stem cells MSCs (MSCs) the In vitro culture laser co-focusing figure of 14 days
Detailed description of the invention
By the following examples the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make improvement and the adjustment of some non-intrinsically safes to the present invention according to the content of the invention described above.
Embodiment 1:
1) by " wet chemistry reaction " synthetic substrate phase β phase tricalcium phosphate (β-TCP) powder body, dry and through comminution by gas stream, screen the dry powder that diameter is 80 ~ 160 μm, as the forerunner's powder preparing porous ceramics idiosome;
2) synthesize the micro-nano whisker of wild phase HA by " coating method ", take the Ca (NO that Ca: P mol ratio is 1.67: 1
3)
24H
2o and (NH
4)
2hPO
4be dissolved in deionized water and make it be starchiness; KNO is taken by 1: 1: 1 mol ratio
3, LiNO
3, KOH add deionized water be mixed into starchiness be used as cosolvent, then these two kinds of starchiness slurries are fully mixed, pH=6.5 is modulated with hydrochloric acid, be coated on clean titanium plate surface, be placed in the hydrothermal reaction kettle that politef is substrate, be warming up to 350 DEG C with the speed of 5 DEG C/min, reaction 10h, naturally cool to room temperature, product through washing, alcohol wash, filtration, dry to obtain the micro-nano whisker of HA;
3) adulterate, the micro-nano whisker of HA of Homogeneous phase mixing 5% is in 95% calcium phosphate powder, with the polyvinyl alcohol of 5wt%, with hydrogen peroxide modulation ceramic size to sposh shape, decompose hydrogen peroxide by microwave-oven-heating after stirring and produce gas with foamed ceramic slurry, 80 × 30 × 30cm(will be positioned over containing the ceramic size enriching foam long × wide × high) mould in dry obtained porous ceramics idiosome;
4) sinter, ceramic idiosome is put into Muffle furnace sinter, with the speed of 5 DEG C/min from room temperature to 1200 DEG C insulation 3h sintering, then furnace cooling, obtain HA micro-nano whisker reinforcement calcium phosphate ceramic material, subsequently the enhancing porous ceramics of gained is cut into product specification size.
The overall porosity of the porous HA micro-nano whisker reinforcement calcium phosphate ceramic material of gained is 85%, macropore diameter is 400 μm, its scanning electron microscopic picture is as shown in Fig. 2-(c), can see from SEM figure, diameter be about the micro-nano whisker of HA of 500nm mixed admix in TCP ceramic substrate mutually in, thus enhance the intensity of pottery.Adopting dynamic mechanical test to record its maximum compressive strength is 2.27MPa, and the pure β calcium phosphate ceramics 1.20MPa of the micro-nano whisker of the HA that do not adulterate promotes 1.89 times.
Embodiment 2:
With biphasic calcium phosphate powder body (HA/TCP) for ceramic substrate phase constituent 95%, mass percent be 5% the micro-nano whisker of HA be that wild phase prepares porous calcium phosphate bioactive ceramics product.Its product preparation process and step identical with embodiment 1, it is biphasic calcium phosphate material that difference to be in step 1 by " wet chemistry reaction " synthesizing ceramic powder.After the micro-nano whisker reinforcement of HA of gained, the maximum compressive strength of ceramic material is 3.35MPa, the pure biophasic calcium phosphate ceramic material 1.80MPa of the micro-nano whisker of the HA that do not adulterate promotes 1.86 times, than the enhancing porous ceramics maximum compressive strength height 1.08MPa in embodiment 1, this is because better the biphasic calcium phosphate matrix of materials of mechanical property contribute to extra mechanical strength mutually.
Embodiment 3:
With pure ha powder body (HA) for ceramic substrate phase constituent 95%, mass percent be 5% the micro-nano whisker of HA be that wild phase prepares porous calcium phosphate bioactive ceramics product.Its product preparation process and step identical with embodiment 1, it is hydroxyapatite that difference to be in step 1 by " wet chemistry reaction " synthesizing ceramic powder.After the micro-nano whisker reinforcement of HA of gained, the maximum compressive strength of ceramic material is 4.31MPa, the pure biophasic calcium phosphate ceramic material lift 1.96 times of the micro-nano whisker of the HA that do not adulterate, than the enhancing porous ceramics maximum compressive strength height 2.04MPa in embodiment 1, this is because in series of calcium phosphate pottery, same holes structure is with under identical sintering process conditions, and the intensity sequence of different phosphoric acid calcium ceramic material is: HA > BCP > TCP.
Embodiment 4:
Other condition and technique with embodiment 1, namely choose β phase tricalcium phosphate (β-TCP) for the micro-nano whisker of ceramic substrate phase constituent 97%, HA be wild phase doped and compounded.Difference is the micro-nano whisker reinforcement of HA of doping different quality mark.This example adopts the maximum compressive strength of the porous calcium phosphate bioactive ceramics product obtained by the micro-nano whisker compound of HA of 3% to be 2.02MPa, only than the pure β phase calcium phosphate ceramics strength enhancing 0.82MPa of the micro-nano whisker of the HA that do not adulterate.This result illustrate, the micro-nano whisker of HA is significant for the improvement of ceramics strength, different doping ratios to the reinforced effects of pottery by different.
Embodiment 5:
Other condition and technique are with embodiment 1, and difference is the micro-nano whisker reinforcement of the more a high proportion of HA of doping.The present embodiment adds the micro-nano whisker of HA of 10% in the β phase tricalcium phosphate (β-TCP) of 90%, the maximum compressive strength of obtained porous calcium phosphate bioactive ceramics product is 3.75MPa, the pure β phase calcium phosphate ceramics strength enhancing 2.55MPa of the micro-nano whisker of the HA that do not adulterate, promotes 1.48MPa further than the product strength of gained in embodiment 1.This result explanation, the promotion of the micro-nano whisker of HA to ceramics strength plays main contribution function, bridge joint, crack deflection can be relied on the material after whisker compound and extract effect to absorb energy, eliminate crack tip concentrated stress, thus the toughness of reinforcing material and intensity, thus effectively improve the mechanical property of material.
Embodiment 6:
Other condition and technique are with embodiment 1, and difference is the pore structure changing porous ceramics.After the present embodiment adds the micro-nano whisker of HA of 5%, control to obtain the pottery than the product in embodiment 1 with more low porosity by hydrogen peroxide foam process, its Total Product porosity is about 60%%, macropore diameter is 300 μm, the maximum compressive strength of Mechanics Performance Testing material, for being promoted to 4.85MPa, promotes 2.58MPa further than the product strength of embodiment 1.This illustrates, the substrate of pottery is still significant relative to the intensity of pottery, the final mechanical property that the intensity of host phase material itself and structure will participate in after contribution Material cladding.
Embodiment 7:
Other condition and technique are with embodiment 1, and difference is the pore structure changing porous ceramics.The present embodiment adds the micro-nano whisker of HA of 5%, and the porous ceramics overall porosity controlling to obtain by hydrogen peroxide foam process is 90%, macropore diameter is 350 μm, and the maximum compressive strength of Mechanics Performance Testing material is 3.89MPa.
Embodiment 8:
Other condition and technique are with embodiment 1, and difference is the sintering process parameter changing porous ceramics.This enforcement adopts the speed of 5 DEG C/min from room temperature to 1200 DEG C insulation 1h sintering in step 4, and then furnace cooling obtains product, and the maximum compressive strength of this product Mechanics Performance Testing material is 3.98MPa.
Embodiment 9:
Other condition and technique are with embodiment 1, and difference is the sintering process parameter changing porous ceramics.This enforcement adopts the speed of 5 DEG C/min from room temperature to 1000 DEG C insulation 3h sintering in step 4, and then furnace cooling obtains product, and the maximum compressive strength of this product Mechanics Performance Testing material is 3.70MPa.
Embodiment 10:
Other condition and technique are with embodiment 1, and difference is the sintering process parameter changing porous ceramics.This enforcement adopts the speed of 5 DEG C/min from room temperature to 1100 DEG C insulation 2h sintering in step 4, and then furnace cooling obtains product, and the maximum compressive strength of this product Mechanics Performance Testing material is 3.85MPa.
Application example 1:
With biphasic calcium phosphate powder body (HA/TCP) for ceramic substrate phase constituent, mass percent be 8% the micro-nano whisker of HA be that wild phase prepares porous calcium phosphate bioactive ceramics product.Total Product porosity is 85%, macropore diameter is 400 μm, material maximum compressive strength is 3.96MPa.This kind strengthens porous calcium phosphate biological active ceramic material Marrow Mesenchymal Stem Cells In Vitro (MSCs) 7 days, result as shown in Figure 5, MSCs is attached at the growth of ceramic inner hole wall, cell proliferation is obvious, on material hole wall, differentiation is extended, connect into network-like structure gradually, cell population upgrowth situation is good, illustrates that this kind of material has good biocompatibility and biological activity.
Application example 2:
With β phase tricalcium phosphate (β-TCP) for ceramic substrate phase constituent, mass percent be 10% the micro-nano whisker of HA be that wild phase prepares porous calcium phosphate bioactive ceramics product.Total Product porosity is 85%, macropore diameter is 400 μm, material maximum compressive strength is 3.06MPa.This kind strengthens porous calcium phosphate biological active ceramic material Marrow Mesenchymal Stem Cells In Vitro (MSCs) 14 days, result display MSCs is attached at the growth of ceramic inner hole wall, cell proliferation is more obvious compared with the product in application example 1, cell breaks up extension on material hole wall, connect into space three-dimensional network-like structure, cell population upgrowth situation is good, illustrates that this kind of material has good biocompatibility and biological activity.
Application example 3:
With hydroxy apatite powder (HA) for ceramic substrate phase constituent, mass percent be 3% the micro-nano whisker of HA be that wild phase prepares porous calcium phosphate bioactive ceramics product.Total Product porosity is 85%, macropore diameter is 400 μm, material maximum compressive strength is 3.46MPa.This kind strengthens porous calcium phosphate biological active ceramic material Marrow Mesenchymal Stem Cells In Vitro (MSCs) 14 days, result display MSCs is attached at the growth of ceramic inner hole wall, cell proliferation is obvious, on material hole wall, differentiation is extended, connect into space three-dimensional network-like structure, cell population upgrowth situation is good, illustrates that this kind of material has good biocompatibility and biological activity.
Claims (3)
1. a HA micro-nano whisker reinforcement calcium phosphate ceramic material, the substrate of this ceramic material is coordinated and is divided into calcium phosphate, wild phase composition is the micro-nano whisker of HA, the mass percent of the two is: calcium phosphate: 90% ~ 97wt%, the micro-nano whisker of HA: 10 ~ 3wt%, is characterized in that the preparation method of this material comprises the following steps:
1) by " wet chemistry reaction " synthetic substrate calcium phosphate phase powder body, this powder body synthesizes hydroxyapatite (HA) powder body, β phase tricalcium phosphate (β-TCP) powder body and biphasic calcium phosphate (HA/TCP) three kinds of powder body through reaction controlling; Dry and through comminution by gas stream, screen the dry powder that diameter is 80 ~ 160 μm, as the forerunner's powder preparing porous ceramics idiosome;
2) synthesize the micro-nano whisker of wild phase HA by " coating method ", take Ca: P mol ratio be 1.67: 1 soluble calcium salt and microcosmic salt be dissolved in deionized water and make it be starchiness; KNO is taken by 1: 1: 1 mol ratio
3, LiNO
3, KOH add deionized water be mixed into starchiness be used as cosolvent, then these two kinds of starchiness slurries are fully mixed, pH=4 ~ 6.8 are modulated with acid, be coated on clean titanium plate surface, be placed in the hydrothermal reaction kettle that politef is substrate, be warming up to 200 ~ 350 DEG C with the speed of 5 DEG C/min, reaction 6 ~ 12h, naturally cool to room temperature, product through washing, alcohol wash, filtration, dry to obtain the micro-nano whisker of HA;
3) adulterate, the micro-nano whisker of HA of Homogeneous phase mixing 10 ~ 3wt% is in 90% ~ 97wt% calcium phosphate powder, with the polyvinyl alcohol of 3 ~ 5wt%, with hydrogen peroxide modulation ceramic size to sposh shape, decompose hydrogen peroxide by microwave-oven-heating after stirring and produce gas with foamed ceramic slurry, dry obtained porous ceramics idiosome by the mould being positioned over 80 × 30 × 30cm (long × wide × high) containing the ceramic size enriching foam;
4) sinter, ceramic idiosome is put into Muffle furnace and sinters, with the speed of 5 DEG C/min, from room temperature to 1000 ~ 1200, a DEG C insulation 1 ~ 3h sinters, and then furnace cooling, obtains HA micro-nano whisker reinforcement calcium phosphate ceramic material; This calcium phosphate ceramic material has loose structure, and its pore structure is porosity 60% ~ 95%, and micropore size is 100 ~ 500 microns, and micropore is mutually three-dimensional through, and hole inwall is covered with capillary micropore, and the micro-nano whisker of HA is uniformly distributed among ceramic matrix material.
2. the preparation method of HA micro-nano whisker reinforcement calcium phosphate ceramic material as claimed in claim 1, is characterized in that the soluble calcium salt in described step 2 is: CaCl
2, or Ca (NO
3)
24H
2o or (CH
3cOO)
2caH
2any one in O; Its microcosmic salt is: (NH
4)
2hPO
4, (NH
4) H
2pO
4, K
2hPO
4or NaH
2pO
4in any one.
3. the preparation method of HA micro-nano whisker reinforcement calcium phosphate ceramic material as claimed in claim 1, is characterized in that the acid that the regulation and control of pH in step 2 adopt is nitric acid, or hydrochloric acid, or any one in phosphoric acid.
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