CN103585677A - HA (hydroxylapatite) micro-nano whisker reinforced calcium phosphate ceramic material and preparation method and application thereof - Google Patents
HA (hydroxylapatite) micro-nano whisker reinforced calcium phosphate ceramic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a HA (hydroxylapatite) micro-nano whisker reinforced calcium phosphate ceramic material which is characterized by using calcium phosphate as a material matrix phase and mixing hydroxyapatite (HA) micro-nano whisker as a reinforcing phase for improving material mechanical properties. The preparation process is as follows: respectively synthesizing a calcium phosphate matrix phase precursor powder material and a hydroxyapatite micro-nano whisker reinforced phase material; then doping 3 ~ 10% of the hydroxyapatite micro-nano whisker to composite into ceramic body powder for preparing a porous ceramic body, finally calcining by a muffle furnace to obtain the reinforced porous bioactive calcium phosphate ceramic. Biological materials are a calcium phosphate component and a hydroxyapatite component which have similar chemical compositions with natural bones, the ceramic has excellent bioactivity due to a finely specially made porous structure, the mechanical properties of the ceramic are reinforced by doping of the micro-nano hydroxyapatite whisker, and the porous ceramic used as a bone repair material has the excellent bioactivity and good mechanical properties and has a wide application prospect in clinical departments of orthopedics.
Description
Technical field
The present invention relates to the micro-nano whisker of a kind of hydroxyapatite (HA) and strengthen calcium phosphate ceramic material and its preparation method and application, belong to field of biomedical materials.
Background technology
Biomaterial for the reparation of load bone requires material to have 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 there is the multiple good biological characteristicses such as good bone conduction, bone induction, degradable absorption.Demand and the increase bone fusion speed of in order to meet freshman bone tissue, growing into, bone renovating material necessarily requires to have the three-dimensional porous structure of mutual perforation, and its desirable macropore is of a size of 100～500 μ m, and porosity should be greater than 60%.Yet because the fragility of the existence of pore structure and pottery self causes the strength of materials not enough, the comprcssive strength of the series of calcium phosphate porous material of report is only 0.3～3.3MPa at present, has limited and used it for the reparation application that bearing position bone is damaged.
Carried out in recent years the mechanical property that a large amount of correlational studyes are intended to guarantee reinforcing material on the active basis of pottery.A kind of effective way of improving ceramics strength is compound/interpolation wild phase, and usual way is to add to strengthen granule or whisker, and the effect of wherein adding whisker is more remarkable.Chinese patent CN1935270A has reported a kind ofly take hydroxyapatite as matrix, by adding composite bioceramic material and the technology of preparing thereof that 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, yet the calcium phosphate ceramic of interpolation 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 guarantee the biological activity of material simultaneously.Chinese patent 03149539.7 has been introduced at CaO-SiO
2in system, add Na
2o, CaF
2or B
2o
3synthetic a kind of bioactivity glass phase, and use the doped sintered technology of preparing calcium phosphate glass sintered body of this glassy phase.Chinese patent 200610013334.8 has been reported 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 has been reported 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 good biological activity, in the implanted body of material, at humoral effect lower-glass body, by dissolving-precipitation mechanism, at material interface, form silicon-rich layer, attract calcium, phosphonium ion in body fluid to migrate to host's interface formation amorphous calcium phosphate, so again with body fluid in OH
-, CO
3 2-in conjunction with generating osteoid apatite, thereby impel implant and host that gluing occurs, merge.But, SiO
2be different from calcium phosphate, they are not the constituent of human body hard tissue, can not by organism, be degraded and absorb, and finally can not become a part for body bone tissue.Therefore, this class biomaterial can only be regarded as having bioactive implant, and they still need to be improved to meet the designing requirement of biomaterial of new generation, that is: " meet material biological function; and have initiatively and repair, induced tissue regeneration, reconstruction damaged tissues " requirement.
Summary of the invention
The micro-nano whisker of a kind of HA that the object of the invention is to develop for the deficiencies in the prior art strengthens calcium phosphate ceramic material and its preparation method and application, be characterized in simulating the chemical composition of natural 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 damaged repair and reconstruction of load osseous tissue, in load osseous tissue defect as repair materials, the initial strength of timbering material is provided, the generation of induction new bone tissue rapidly, strengthens bone connection and healing function.
Object of the present invention is realized by following technical measures, and wherein said raw material umber, except specified otherwise, is mass fraction.
The substrate of the micro-nano whisker enhancing of HA 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 in hydroxyapatite, β phase tricalcium phosphate or biophasic calcium phosphate ceramic.
The micro-nano whisker of described HA is: minute hand shape, pattern homogeneous, length are 10～50 μ m, and diameter is 0.3～2 μ m, the hydroxyapatite crystal whisker that draw ratio is 5～167.
The preparation method that the micro-nano whisker of HA strengthens calcium phosphate ceramic material comprises the following steps:
1), by " wet chemistry reaction " synthetic substrate calcium phosphate phase powder body, this powder body is controlled and is synthesized hydroxyapatite (HA) powder body, β phase tricalcium phosphate (β-TCP) powder body and three kinds of powder body of biphasic calcium phosphate (HA/TCP) through reaction; Dry and through comminution by gas stream, screening diameter is the dry powder of 80～160 μ m, as forerunner's powder of preparing porous ceramics idiosome;
2) by " coating method " the synthetic micro-nano whisker of wild phase HA, take Ca: the soluble calcium salt that P mol ratio is 1.67: 1 and microcosmic salt are dissolved in deionized water and make it be starchiness; By 1: 1: 1 mol ratio, take KNO
3, LiNO
3, KOH adds deionized water and is mixed into starchiness as cosolvent, then these two kinds of starchiness slurries are fully mixed, with acid, modulate pH=4～6.8, be coated on clean titanium plate surface, be placed in the hydrothermal reaction kettle that politef is substrate, with the speed of 5 ℃/min, be warming up to 200～350 ℃, react 6～12h, naturally cool to room temperature, product through washing, alcohol wash, filtration, dry to obtain the micro-nano whisker of HA;
3) doping, the micro-nano whisker of HA that evenly mixes 10～3wt% is in 90%～97wt% calcium phosphate powder, polyvinyl alcohol with 3～5wt%, with hydrogen peroxide, modulate ceramic size to sposh shape, after stirring, by microwave-oven-heating, decompose hydrogen peroxide and produce gas with foamed ceramic slurry, by containing the ceramic size that enriches foam, be positioned over 80 * 30 * 30cm(length * wide * height) mould in oven dry make porous ceramics idiosome;
4) sintering, puts into Muffle furnace sintering by ceramic idiosome, with the speed of 5 ℃/min, from room temperature, is warming up to 1000～1200 ℃ of insulation 1～3h sintering, and then furnace cooling, obtains the micro-nano whisker of HA and strengthen 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 three-dimensional perforation mutually, 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 in O; Microcosmic salt is: (NH
4)
2hPO
4, (NH
4) H
2pO
4, K
2hPO
4or NaH
2pO
4in any.
The acid that in described step 2, the regulation and control of pH adopt is nitric acid, or hydrochloric acid, or any in phosphoric acid.
The micro-nano whisker of described HA strengthens calcium phosphate ceramic material for damaged reparation and the scaffold material of bone tissue engineering of human body hard tissue.
Structural characterization and performance test:
1, the pore structure of calcium phosphate ceramic material is characterized by mercury injection apparatus test.
Result shows: the pore structure of material is for mutually connecting loose structure, and testing ceramic overall porosity is 60%～95%.
2, the microstructure of material is tested through SEM.
The results detailed in 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 three-dimensional perforation mutually, 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 and is characterized by XRD.
The results detailed in 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 is cultivated test by external mesenchymal stem cells MSCs (MSCs).
The results detailed in shown in Fig. 5 (a)～(d).
Result shows: the material after the micro-nano whisker of HA is compound has good biocompatibility, can promote differentiation, propagation and the growth of mesenchymal stem cells MSCs.
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 bone inducibility of porous calcium phosphate ceramic, induces rapidly the generation of new bone tissue, strengthens bone connection 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
The micro-nano whisker of Fig. 1 .HA strengthens preparation technology's flow chart of porous calcium phosphate ceramic biomaterial;
1, choose calcium, phosphorus proportioning; 2, the micro-nano increasing whisker of HA is synthetic; 3, calcium phosphate ceramic precursor powder is synthetic; 4, calcium phosphate ceramic powder body screening; 5, doping, the micro-nano whisker/ceramic powder of mixing HA; 6, porous ceramics part is made; 7, porous ceramics oven dry, sintering; 8, sterilizing, storage.
Fig. 2. (a) be the micro-nano enhancing whisker of " coating method " synthetic HA SEM figure
Fig. 2. (b) for the 10%HA that adulterates in embodiment 5, strengthen the porous ceramics mixed powder SEM figure of whisker
Fig. 2. be (c) that embodiment 1 doping 5%HA strengthens SEM figure after the ceramic post sintering of whisker
Fig. 2. be (d) that in embodiment 4, HA strengthens whisker porous biophasic calcium phosphate ceramic SEM shape appearance figure
Fig. 3. (a) for the micro-nano whisker phase constituent of HA synthetic in the present invention is identified XRD figure
Fig. 3. (b) be HA crystal standard x RD collection of illustrative plates
The micro-nano whisker of Fig. 4 .HA strengthens porous calcium phosphate ceramic Measurement of Material Mechanical Performance figure
Fig. 5. (a) be material mesenchymal stem cells MSCs (MSCs) the In vitro culture laser co-focusing figure of 1 day
Fig. 5. (b) be material mesenchymal stem cells MSCs (MSCs) the In vitro culture laser co-focusing figure of 3 days
Fig. 5. (c) be material mesenchymal stem cells MSCs (MSCs) the In vitro culture laser co-focusing figure of 7 days
Fig. 5. (d) be material mesenchymal stem cells MSCs (MSCs) the In vitro culture laser co-focusing figure of 14 days
The specific embodiment
By the following examples the present invention is specifically described; be necessary to be pointed out that at this 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 according to the content of the invention described above improvement and the adjustment of some non-intrinsically safes to the present invention.
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, screening diameter is the dry powder of 80～160 μ m, as forerunner's powder of preparing porous ceramics idiosome;
2) by " coating method " the synthetic micro-nano whisker of wild phase HA, take Ca: the Ca (NO that P mol ratio is 1.67: 1
3)
24H
2o and (NH
4)
2hPO
4being dissolved in deionized water makes it be starchiness; By 1: 1: 1 mol ratio, take KNO
3, LiNO
3, KOH adds deionized water and is mixed into starchiness as cosolvent, then these two kinds of starchiness slurries are fully mixed, with hydrochloric acid, modulate pH=6.5, be coated on clean titanium plate surface, be placed in the hydrothermal reaction kettle that politef is substrate, with the speed of 5 ℃/min, be warming up to 350 ℃, reaction 10h, naturally cool to room temperature, product through washing, alcohol wash, filtration, dry to obtain the micro-nano whisker of HA;
3) doping, evenly the micro-nano whisker of HA of mixing 5% is in 95% calcium phosphate powder, polyvinyl alcohol with 5wt%, with hydrogen peroxide, modulate ceramic size to sposh shape, after stirring, by microwave-oven-heating, decompose hydrogen peroxide and produce gas with foamed ceramic slurry, by containing the ceramic size that enriches foam, be positioned over 80 * 30 * 30cm(length * wide * height) mould in oven dry make porous ceramics idiosome;
4) sintering, ceramic idiosome is put into Muffle furnace sintering, with the speed of 5 ℃/min, from room temperature, be warming up to 1200 ℃ of insulation 3h sintering, then furnace cooling, obtain the micro-nano whisker of HA and strengthen calcium phosphate ceramic material, subsequently the enhancing porous ceramics of gained is cut into product specification size.
The overall porosity that the micro-nano whisker of the porous HA of gained strengthens calcium phosphate ceramic material is 85%, macropore diameter is 400 μ m, its scanning electron microscope picture is as shown in Fig. 2-(c), from SEM figure, can see, diameter be about the micro-nano whisker of HA of 500nm mixed admix in TCP ceramic substrate mutually in, thereby strengthened ceramic intensity.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 HA that do not adulterate promotes 1.89 times.
Embodiment 2:
Take biphasic calcium phosphate powder body (HA/TCP) as ceramic substrate phase constituent 95%, and the micro-nano whisker of HA that mass percent is 5% is that wild phase is prepared porous calcium phosphate bioactive ceramics product.Its product preparation process and step are identical with embodiment 1, and it is biphasic calcium phosphate material by " wet chemistry reaction " synthesizing ceramic powder that difference is in step 1.After the micro-nano whisker of HA of gained strengthens, 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 HA of not adulterating promotes 1.86 times, than the high 1.08MPa of enhancing porous ceramics maximum compressive strength in embodiment 1, this is because better the biphasic calcium phosphate matrix of materials of mechanical property has been contributed extra mechanical strength mutually.
Embodiment 3:
Take pure ha powder body (HA) as ceramic substrate phase constituent 95%, and the micro-nano whisker of HA that mass percent is 5% is that wild phase is prepared porous calcium phosphate bioactive ceramics product.Its product preparation process and step are identical with embodiment 1, and it is hydroxyapatite by " wet chemistry reaction " synthesizing ceramic powder that difference is in step 1.After the micro-nano whisker of HA of gained strengthens, the maximum compressive strength of ceramic material is 4.31MPa, do not adulterate 1.96 times of the pure biophasic calcium phosphate ceramic material lift of the micro-nano whisker of HA, than the high 2.04MPa of enhancing porous ceramics maximum compressive strength in embodiment 1, this is because in series of calcium phosphate pottery, under same holes structure and identical sintering process conditions, the sequence of the intensity of different phosphoric acid calcium ceramic materials is: HA > BCP > TCP.
Embodiment 4:
Other condition and technique are with embodiment 1, and choosing β phase tricalcium phosphate (β-TCP) is ceramic substrate phase constituent 97%, and the micro-nano whisker of HA is wild phase doped and compounded.Difference be the to adulterate micro-nano whisker of HA of different quality mark strengthens.The maximum compressive strength of the compound prepared porous calcium phosphate bioactive ceramics product of the micro-nano whisker of HA of this example employing 3% is 2.02MPa, only than the pure β phase calcium phosphate ceramics strength enhancing 0.82MPa of the micro-nano whisker of HA that do not adulterate.This presentation of results, the micro-nano whisker of HA is significant for the improvement of ceramics strength, different doping ratios to ceramic reinforced effects by different.
Embodiment 5:
Other condition and technique are with embodiment 1, and difference is that the micro-nano whisker of the more a high proportion of HA of doping strengthens.In the β phase tricalcium phosphate (β-TCP) of the micro-nano whisker to 90% of HA of the present embodiment interpolation 10%, the maximum compressive strength of prepared porous calcium phosphate bioactive ceramics product is 3.75MPa, the do not adulterate pure β phase calcium phosphate ceramics strength enhancing 2.55MPa of the micro-nano whisker of HA, further promotes 1.48MPa than the product strength of gained in embodiment 1.This presentation of results, the micro-nano whisker of HA plays main contribution function to the promotion of ceramics strength, material after compound with whisker can rely on bridge joint, crack deflection and extract effect and absorb energy, eliminate crack tip concentrated stress, thereby the toughness of reinforcing material and intensity, thereby effectively improve the mechanical property of material.
Embodiment 6:
Other condition and technique are with embodiment 1, and difference has been to change the pore structure of porous ceramics.After the micro-nano whisker of HA of the present embodiment interpolation 5%, by hydrogen peroxide foam process, control and obtain thering is the more pottery of low porosity than the product in embodiment 1, the whole porosity of its product is about 60%%, macropore diameter is 300 μ m, the maximum compressive strength of Mechanics Performance Testing material, for being promoted to 4.85MPa, further promotes 2.58MPa than the product strength of embodiment 1.This explanation, the substrate of pottery is still significant with respect to ceramic intensity, and the intensity of substrate phase material itself and structure are by the final mechanical property participating in after contribution Material cladding.
Embodiment 7:
Other condition and technique are with embodiment 1, and difference has been to change the pore structure of porous ceramics.The present embodiment adds 5% the micro-nano whisker of HA, controls that the porous ceramics overall porosity obtaining is 90%, macropore diameter is 350 μ m by hydrogen peroxide foam process, 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 has been to change the sintering process parameter of porous ceramics.Originally be implemented in and in step 4, adopt the speed of 5 ℃/min to be warming up to 1200 ℃ of insulation 1h sintering from room temperature, 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 has been to change the sintering process parameter of porous ceramics.Originally be implemented in and in step 4, adopt the speed of 5 ℃/min to be warming up to 1000 ℃ of insulation 3h sintering from room temperature, 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 has been to change the sintering process parameter of porous ceramics.Originally be implemented in and in step 4, adopt the speed of 5 ℃/min to be warming up to 1100 ℃ of insulation 2h sintering from room temperature, then furnace cooling obtains product, and the maximum compressive strength of this product Mechanics Performance Testing material is 3.85MPa.
Application example 1:
Take biphasic calcium phosphate powder body (HA/TCP) as ceramic substrate phase constituent, and the micro-nano whisker of HA that mass percent is 8% is that wild phase is prepared porous calcium phosphate bioactive ceramics product.The whole porosity of product is 85%, macropore diameter is that 400 μ m, material maximum compressive strength are 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 ceramic inner hole wall growth, cell proliferation is obvious, on material hole wall, differentiation is extended, connect into gradually network-like structure, cell overall growth in order, illustrates that this kind of material has good biocompatibility and biological activity.
Application example 2:
Take β phase tricalcium phosphate (β-TCP) as ceramic substrate phase constituent, and the micro-nano whisker of HA that mass percent is 10% is that wild phase is prepared porous calcium phosphate bioactive ceramics product.The whole porosity of product is 85%, macropore diameter is that 400 μ m, material maximum compressive strength are 3.06MPa.This kind strengthens porous calcium phosphate biological active ceramic material Marrow Mesenchymal Stem Cells In Vitro (MSCs) 14 days, result shows that MSCs is attached at ceramic inner hole wall growth, 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 overall growth in order, illustrates that this kind of material has good biocompatibility and biological activity.
Application example 3:
Take hydroxy apatite powder (HA) as ceramic substrate phase constituent, and the micro-nano whisker of HA that mass percent is 3% is that wild phase is prepared porous calcium phosphate bioactive ceramics product.The whole porosity of product is 85%, macropore diameter is that 400 μ m, material maximum compressive strength are 3.46MPa.This kind strengthens porous calcium phosphate biological active ceramic material Marrow Mesenchymal Stem Cells In Vitro (MSCs) 14 days, result shows that MSCs is attached at ceramic inner hole wall growth, cell proliferation is obvious, on material hole wall, differentiation is extended, connect into space three-dimensional network-like structure, cell overall growth in order, illustrates that this kind of material has good biocompatibility and biological activity.
Claims (7)
1. the micro-nano whisker of HA strengthens a calcium phosphate ceramic material, and the substrate that it is characterized in that this 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.
2. the micro-nano whisker of HA strengthens calcium phosphate ceramic material as claimed in claim 1, it is characterized in that calcium phosphate is: any in hydroxyapatite, β phase tricalcium phosphate or biphasic calcium phosphate.
3. the micro-nano whisker of HA strengthens calcium phosphate ceramic material as claimed in claim 1, it is characterized in that the micro-nano whisker of HA is: minute hand shape, pattern homogeneous, length are 10～50 μ m, and diameter is 0.3～2 μ m, the hydroxyapatite crystal whisker that draw ratio is 5～167.
4. as described in one of claim 1～3, the micro-nano whisker of HA strengthens the preparation method of calcium phosphate ceramic material, it is characterized in that the method comprises the following steps:
1), by " wet chemistry reaction " synthetic substrate calcium phosphate phase powder body, this powder body is controlled and is synthesized hydroxy apatite powder, β phase tricalcium phosphate powder body and three kinds of powder body of biphasic calcium phosphate through reaction; Dry and through comminution by gas stream, screening diameter is the dry powder of 80～160 μ m, as forerunner's powder of preparing porous ceramics idiosome;
2) by " coating method " the synthetic micro-nano whisker of wild phase HA, take Ca: the soluble calcium salt that P mol ratio is 1.67: 1 and microcosmic salt are dissolved in deionized water and make it be starchiness; By 1: 1: 1 mol ratio, take KNO
3, LiNO
3, KOH adds deionized water and is mixed into starchiness as cosolvent, then these two kinds of starchiness slurries are fully mixed, with acid, modulate pH=4～6.8, be coated on clean titanium plate surface, be placed in the hydrothermal reaction kettle that politef is substrate, with the speed of 5 ℃/min, be warming up to 200～350 ℃, react 6～12h, naturally cool to room temperature, product through washing, alcohol wash, filtration, dry to obtain the micro-nano whisker of HA;
3) doping, the micro-nano whisker of HA that evenly mixes 10～3wt% is in 90%～97wt% calcium phosphate powder, polyvinyl alcohol with 3～5 wt%, with hydrogen peroxide, modulate ceramic size to sposh shape, after stirring, by microwave-oven-heating, decompose hydrogen peroxide and produce gas with foamed ceramic slurry, by containing the ceramic size that enriches foam, be positioned over 80 * 30 * 30 cm(length * wide * height) mould in oven dry make porous ceramics idiosome;
4) sintering, puts into Muffle furnace sintering by ceramic idiosome, with the speed of 5 ℃/min, from room temperature, is warming up to 1000～1200 ℃ of insulation 1～3h sintering, and then furnace cooling, obtains the micro-nano whisker of HA and strengthen calcium phosphate ceramic material; This calcium phosphate ceramic material has multiporous biological active ceramic, its pore structure is 60%～95% of ceramic overall porosity, and micropore size is 100～500 microns, and micropore is three-dimensional perforation mutually, hole inwall is covered with capillary micropore, and the micro-nano whisker of HA is uniformly distributed among ceramic matrix material.
5. the micro-nano whisker of HA strengthens the preparation method of calcium phosphate ceramic material as claimed in claim 4, it 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 in O; Its microcosmic salt is: (NH
4)
2hPO
4, (NH
4) H
2pO
4, K
2hPO
4or NaH
2pO
4in any.
6. the micro-nano whisker of HA as claimed in claim 4 strengthens the preparation method of calcium phosphate ceramic material, it 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 in phosphoric acid.
7. the micro-nano whisker of HA strengthens the purposes of calcium phosphate ceramic material as claimed in claim 1, it is characterized in that this bioceramic is for the damaged reparation of human body hard tissue and scaffold material of bone tissue engineering.
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| CN105288740A (en) * | 2015-11-23 | 2016-02-03 | 上海交通大学 | Method for preparation of controlled pore size biphasic calcium phosphate composite ceramic scaffold |
| CN106730024A (en) * | 2017-01-09 | 2017-05-31 | 中国人民解放军第二军医大学第二附属医院 | Hydroxyapatite crystal whisker strengthens biodegradable block copolymer calcium silicates composite bone repairing material |
| CN106880875A (en) * | 2017-01-09 | 2017-06-23 | 中国人民解放军第二军医大学第二附属医院 | Hydroxyapatite crystal whisker strengthens the preparation method of biodegradable block copolymer calcium silicates composite bone repairing material |
| CN107176832A (en) * | 2017-03-30 | 2017-09-19 | 苏州鼎安科技有限公司 | Biphasic calcium phosphate composite granule of high temperature solid state reaction synthesis and preparation method thereof |
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| CN113024119A (en) * | 2021-03-26 | 2021-06-25 | 昆明理工大学 | Glass ceramic material and preparation method thereof |
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| CN104973878A (en) * | 2015-06-01 | 2015-10-14 | 安徽省益民工贸集团有限公司 | Hydroxyapatite whisker reinforced glass ceramic dish and preparation method thereof |
| CN105288740A (en) * | 2015-11-23 | 2016-02-03 | 上海交通大学 | Method for preparation of controlled pore size biphasic calcium phosphate composite ceramic scaffold |
| CN106730024A (en) * | 2017-01-09 | 2017-05-31 | 中国人民解放军第二军医大学第二附属医院 | Hydroxyapatite crystal whisker strengthens biodegradable block copolymer calcium silicates composite bone repairing material |
| CN106880875A (en) * | 2017-01-09 | 2017-06-23 | 中国人民解放军第二军医大学第二附属医院 | Hydroxyapatite crystal whisker strengthens the preparation method of biodegradable block copolymer calcium silicates composite bone repairing material |
| CN107176832B (en) * | 2017-03-30 | 2020-02-07 | 苏州鼎安科技有限公司 | Preparation method of biphase calcium phosphate composite powder synthesized by high-temperature solid-phase reaction |
| CN107176832A (en) * | 2017-03-30 | 2017-09-19 | 苏州鼎安科技有限公司 | Biphasic calcium phosphate composite granule of high temperature solid state reaction synthesis and preparation method thereof |
| CN108689699A (en) * | 2018-06-14 | 2018-10-23 | 长沙鹏登生物陶瓷有限公司 | A kind of high-flexibility artificial bone joint ceramic composite and preparation method |
| CN109133907A (en) * | 2018-08-16 | 2019-01-04 | 迈海新型材料科技（固安）有限公司 | A kind of artificial bone and preparation method thereof comprising hydroxyapatite crystal whisker and biphase calcium phosphor |
| CN109260525A (en) * | 2018-09-12 | 2019-01-25 | 四川大学 | Controllable bone tissue engineering scaffold of a kind of degradation based on 3D printing and preparation method thereof |
| CN109793939A (en) * | 2019-03-19 | 2019-05-24 | 西南交通大学 | A kind of high-specific surface area calcium phosphate ceramic porous support and preparation method thereof |
| CN114080376A (en) * | 2019-07-26 | 2022-02-22 | 华沙整形外科股份有限公司 | Calcium phosphate particles and process for preparing same |
| US11498880B2 (en) | 2019-07-26 | 2022-11-15 | Warsaw Orthopedic, Inc. | Calcium phosphate granules and methods of making them |
| CN113024119A (en) * | 2021-03-26 | 2021-06-25 | 昆明理工大学 | Glass ceramic material and preparation method thereof |
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