CN108546107A - A kind of gradient porous calcium polyphosphate ceramic material and preparation method thereof - Google Patents
A kind of gradient porous calcium polyphosphate ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of gradient porous calcium polyphosphate ceramic materials and preparation method thereof.The present invention is using calcium dihydrogen phosphate as raw material, calcium polyphosphate presoma is prepared for using the method that washing and drying is sintered, by the way that the pore-foaming agent of calcium polyphosphate precursor powder obtained and different proportion to be uniformly mixed, it is pressed, dries and is sintered and gradient porous calcium polyphosphate ceramic material is made.The presence of compacted zone and aperture transition zone improves the whole compression strength of ceramics in gradient porous calcium polyphosphate ceramic material, but also there are micropore and macropore and deposits and be more conducive to growing into for new bone.
Description
Technical field
The invention belongs to bioceramic material technical fields, and in particular to a kind of gradient porous calcium polyphosphate ceramic material and
Preparation method.
Background technology
Bio-medical material is for its disease damage tissue, organ or increasing is diagnosed, treated, repaired or replaced to organism
Quality of life and the service life of the mankind, but current population are helped to improve into the novel High-tech Material bio-medical material of its function
Aging serious and wound increases, and people are particularly suitable for bio-medical material the need of the biomaterial of bone tissue engineer
Ask more and more, its research and development have become one of emphasis of medical research.
Calcium orthophosphate base biomaterial has similar ingredient with the mineral in bone, and has preferable biodegradation
Property, bioactivity and osteoconductive can be prepared into high-strength functional branch similar with bone structure by molding, sintering process
Frame, being implanted into the calcium phosphorus product after material degradation can be used as raw material to be absorbed for new bone remoulding by osteoblast.Therefore, with hydroxyl
Apatite (HA), the calcium phosphate ceramic material that bata-tricalcium phosphate (β-TCP) is representative become the research of bio-medical material
Hot spot.
As one kind in calcium phosphate ceramic, calcium polyphosphate (CPP) has good bioactivity and cytotoxic, tool
There is controllable biological degradability, while as bone holder material, CPP has ideal mechanical performance, with bon e formation very strongization
It learns and combines；Under the action of circulatory mediator, Partial digestion can occur for CPP, and chain rupture of degrading, the energy released can guarantee that cell is lived
Property need, catabolite has phosphate, soluble calcium salt and free calcium, and phosphonium ion, these products are conducive to the life of cell
It is long, while being absorbed and utilized by tissue, new tissue is grown, and the inflammatory reaction of host's surrounding tissue will not be caused, without thin
Cellular toxicity, to preferably generate bone conduction effect.Therefore calcium polyphosphate becomes a kind of novel of domestic and foreign scholars' primary study
Bone tissue engineer repair materials.However since the temperature range of the degree of polymerization, crystal transfer to CPP is at present there is also disagreement,
Mainly use the system of " melting → wire drawing → water quenching → drying → ethyl alcohol wet-milling → forming and sintering " to the preparation of CPP both at home and abroad at present
Standby technique is easy to pollute material, causes purity that medical rank is not achieved；Simultaneously in preparation process, polymerisation and
Crystal transfer temperature is also difficult to control, and is caused to fail to obtain ideal material property, is limited CPP materials in clinical research and answer
With the development of aspect.It is therefore desirable to more be goed deep into systematic research to calcium polyphosphate biological ceramic.
Invention content
In view of the above shortcomings of the prior art, inventor passes through long-term technology and practical exploration, is with calcium dihydrogen phosphate
Raw material is prepared for calcium polyphosphate presoma using the method for washing and drying-sintering, by by calcium polyphosphate precursor obtained
The pore-foaming agent of end and different proportion is uniformly mixed, and is pressed, dries and is sintered and gradient porous calcium polyphosphate pottery is made
Ceramic material.The presence of compacted zone and aperture transition zone improves the whole pressure resistance of ceramics in gradient porous calcium polyphosphate ceramic material
Degree, but also there are micropore and macropore and deposit and be more conducive to growing into for new bone.
To achieve the above object, the present invention adopts the following technical scheme that：
The first aspect of the invention provides a kind of gradient porous calcium polyphosphate ceramic material, the ceramic material packet
Including compacted zone (zone of calcifying cartilage) and weaker zone (subchondral bone), the weaker zone includes aperture transition zone and macroporous layer, wherein
Aperture transition zone is fitted closely with compacted zone and macroporous layer respectively as middle layer, and compacted zone, aperture transition zone and macroporous layer
Pore size be distributed at gradient with porosity, the ceramic material is made of calcium polyphosphate,
Further, the calcium polyphosphate is β type calcium polyphosphates；
Further, the dense layer thickness is 200-700 μm, and further preferred thickness is 300-600 μm, pore size
It is 1-10 μm；
Aperture transition region thickness in the weaker zone is 800-2000 μm, and further preferred thickness is 1000-1500 μm,
Pore size is 100-200 μm；
Macropore layer thickness in the weaker zone is 3-7mm, and further preferred thickness is 5-6mm, pore size 200-
600μm；
The gradient porous calcium polyphosphate ceramics porosity is controlled in 59-65%.It is caused needed for Optimal gradient porous structure
The mass fraction of hole agent is:Compacted zone/aperture transition zone/macroporous layer is 0/30/35, porosity 64-65%.
The second aspect of the invention provides the preparation method of above-mentioned ceramic material, including：
S1. with calcium dihydrogen phosphate raw material, heat up calcining after washing and drying, and natural cooling obtains poly- phosphorus after keeping the temperature a period of time
Sour calcium presoma；
S2. after binder ball milling, drying screening are added into calcium polyphosphate presoma made from step S1., from different grains
Diameter pore-foaming agent mixes, and is laid in mold layer by layer by the sequence of pore-foaming agent grain size from big to small, by compression moulding, drying and burning
It ties and gradient porous calcium polyphosphate ceramic material is made.
Further, in the step S1., calcination condition is：3~8 DEG C/min of heating rate (preferably 5 DEG C/min),
400~600 DEG C of calcination temperature (preferably 500 DEG C)；1~10h of soaking time (preferably 10h)；
Further, in the step S2., binder is polyvinyl alcohol, and the polyvinyl alcohol mass fraction is 4~6%
(preferably 5%)；
Further, in the step S2., pore-foaming agent is stearic acid, and the stearic acid grain size is 50~120 mesh, described
Stearic acid mass fraction is 10~50%；
Further, the step S2. specific methods are：
By the calcium polyphosphate presoma that polyvinyl alcohol has been added be 25%, 30% or 35% with mass fraction and grain size is
The stearic acid mixing of 50-80 mesh tiles 3-7mm (preferably 5-6mm) as macroporous layer in a mold；Polyvinyl alcohol will be added
The stearic acid that calcium polyphosphate presoma is 20%, 25% or 30% with mass fraction and grain size is 80-120 mesh mixes in a mold
800-2000 μm of tiling (preferably 1000-1500 μm) is used as weaker zone；The calcium polyphosphate presoma that polyvinyl alcohol is added is existed
Last layer is tiled in mold as compacted zone, control thickness is 200-700 μm (preferably 300-600 μm)；And then it is done
Molded, the dry-pressing formed condition is：1Mpa pressurizes 1min；
Sintering condition is：3~5 DEG C/min of heating rate (preferably 4 DEG C/min) is 350~450 DEG C to temperature and (is preferably
400℃)；1.5~2.5h of soaking time (preferably 2h)；To exclude stearic acid；
Then continue to keep heating rate 3~8 DEG C/min (preferably 5 DEG C/min) to temperature be 800~900 DEG C (preferably
It it is 850 DEG C)；0.05~5h of soaking time (preferably 1.5h)；After natural cooling to obtain the final product.
The third aspect of the invention provides application of the above-mentioned ceramic material as degradable implant material.
Further, the application include the ceramic material as degradable implant material in artificial bone defect healing
In application.
Beneficial effects of the present invention：
The application is prepared for calcium polyphosphate presoma using calcium dihydrogen phosphate as raw material, using the method for washing and drying-sintering,
By the way that the pore-foaming agent of calcium polyphosphate precursor powder obtained and different proportion is uniformly mixed, be pressed, dry and
It is sintered and gradient porous calcium polyphosphate ceramic material is made.Compacted zone and aperture transition in gradient porous calcium polyphosphate ceramic material
The presence of layer improves the whole compression strength of ceramics, but also there are micropore and macropore and deposits and be more conducive to growing into for new bone.
Experiment proves that, no matter CPP materials are degraded in Tris buffer solutions or in SBF simulated body fluids, different crystal forms CPP simultaneously
The degradation rate of material is different, and degradation rate is all γ-CPP>γ+β-CPP>β-CPP；The CPP degree of polymerization is smaller simultaneously, degradation speed
Rate is faster.Material sintering temperature is lower, and material degradation must be faster；Soaking time is longer, and non-crystalline areas forms more, degradation rate
It is faster.The application the studies above is to prepare new degradable implant material to lay a good foundation.
Description of the drawings
Fig. 1 is the DSC-TGA curve graphs of calcium dihydrogen phosphate, wherein 10 DEG C/min of heating rate；
Fig. 2 is the infrared spectrum comparison diagram of calcium dihydrogen phosphate and calcium polyphosphate imitation frosted glass powder；
Fig. 3 is the Raman collection of illustrative plates of calcium polyphosphate；
Fig. 4 is the XRD spectra that calcium polyphosphate keeps the temperature that 1.5h is sintered powder at different temperatures；Wherein Fig. 4 (a) is polyphosphoric acid
Calcium keeps the temperature the XRD spectra of 1.5h sintering powder at 500 DEG C, 600 DEG C, 625 DEG C, 650 DEG C, 700 DEG C；Fig. 4 (b) is calcium polyphosphate
The XRD spectra of 1.5h sintering powder is kept the temperature at 800 DEG C, 900 DEG C, 930 DEG C, 950 DEG C, 960 DEG C；
Fig. 5 is the NMR spectra that 850 DEG C are warming up to after keeping the temperature different time respectively at 500 DEG C；Wherein Fig. 5 (a) is heat preservation
1h；Fig. 5 (b) is heat preservation 5h；Fig. 5 (c) is heat preservation 10h；
Fig. 6 is that three kinds of calcium polyphosphates made from 1h, 5h, 10h are kept the temperature at a temperature of 500 DEG C31The solid NMR collection of illustrative plates office of P
Portion's enlarged drawing；
Fig. 7 is the β-CPPXRD collection of illustrative plates that different polymerization degree made from 1h, 5h, 10h is kept the temperature at a temperature of 500 DEG C；
Fig. 8 is the SEM figures that three kinds of calcium polyphosphates made from 1h, 5h, 10h are kept the temperature at a temperature of 500 DEG C；
Fig. 9 is the compression strength variation diagram that three kinds of calcium polyphosphates made from 1h, 5h, 10h are kept the temperature at a temperature of 500 DEG C；
Figure 10 is the XRD diagram of calcium polyphosphate material made from (0,500,625,650,700 DEG C) under different calcination temperatures；
Figure 11 is that the SEM of different crystal forms calcium polyphosphate ceramic material schemes, and wherein Figure 11 (a) is γ-CPP；Figure 11 (b) is γ
+β-CPP；Figure 11 (c) is β-CPP；
Figure 12 is the compression strength of different crystal forms calcium polyphosphate ceramic material, and wherein Figure 12 (a) is γ-CPP；Figure 12 (b)
For γ+β-CPP；Figure 12 (c) is β-CPP；
Figure 13 is the XRD diagram of different soaking time calcium polyphosphate materials at 850 DEG C, wherein Figure 13 (a) is 5min；Figure
13 (b) is 1.5h, and Figure 13 (c) is 3h；
Figure 14 is in embodiment 1 at 850 DEG C, and the SEM of different soaking time calcium polyphosphate materials schemes, wherein Figure 14 (a)
For 5min；Figure 14 (b) is 1.5h, and Figure 14 (c) is 3h；
Figure 15 is the compression strength figure that three kinds of calcium polyphosphates made from 5min, 1.5h, 3h are kept the temperature at 850 DEG C；
Figure 16 is the compression strength variation diagram of different-grain diameter calcium polyphosphate；
Figure 17 is the infrared spectrum for adding pore-foaming agent (a) and being not added with pore-foaming agent (b)；
Figure 18 is the relational graph of calcium polyphosphate ceramic material porosity and compressive strength；
Figure 19 is the SEM shape appearance figures of gradient porous calcium polyphosphate ceramics；Wherein, (a) be compacted zone, (b, c) its weaker zone,
(a1) be fine and close layer segment pattern；(a2) it is (a1) amplified pattern；(b1) amplify for the aperture transition zone of loose layer segment
Pattern；(c1) be loose layer segment macroporous layer amplify pattern；
Figure 20 is the relationship of gradient porous calcium polyphosphate ceramic material porosity and compressive strength；
Figure 21 is weight-loss curve of the different crystal forms CPP materials in Tris buffer solutions；
Figure 22 is weight-loss curve of the different polymerization degree β-CPP materials in Tris buffer solutions；
Surface topography SEM before and after Figure 23 different crystal forms CPP ceramic materials impregnate 28 days in Tris buffer solutions schemes；Its
In,
Before degradation：(a):γ-CPP；(b):γ+β-CPP；(c):β-CPP
After degradation：(a1):γ-CPP；(b1):γ+β-CPP；(c1):β-CPP
Figure 24 is the surface topography SEM figures that different polymerization degree CPP ceramic materials are degraded front and back in Tris buffer solutions；Its
In,
Before degradation：(a)1h-850；(b)5h-850；(c)10h-850
After degradation：(a1)1h-850；(b1)5h-850；(c1)10h-850；
Figure 25 is the change curve of different crystal forms CPP materials compression strength in degradation process in SBF simulated body fluids；
Figure 26 is the weight-loss curve that different different polymerization degree CPP ceramic materials impregnate 28 days in SBF simulated body fluids；
Figure 27 is different crystal forms and the degree of polymerization CPP ceramic materials pH variation diagrams in SBF simulated body fluids；
Figure 28 is the surface topography SEM figures after different crystal forms CPP ceramic materials are degraded in SBF simulated body fluids；Wherein,
Figure A1A2A3 is γ-CPP；Figure B1B2B3 is γ+β-CPP；Figure C1C2C3 is β-CPP；
Figure 29 is the surface topography SEM before and after gradient porous CPP ceramic materials (β-CPP) are degraded in SBF simulated body fluids
Figure；Wherein,
Before degradation：(a)(a1)；After degradation：(b)(b1)；
Figure 30 is the surface topography before and after different polymerization degree CPP ceramic materials (β-CPP) are degraded in SBF simulated body fluids
SEM schemes；
Wherein, before degradation：(a)1h；(b)5h；(c)10h；After degradation：(a1) 500 DEG C of heat preservation 1h；(b1) 500 DEG C of heat preservation 5h；
(c1) 500 DEG C of heat preservation 10h；
Figure 31 is infared spectrum after different crystal forms CPP ceramic materials are degraded 28 days in SBF simulated body fluids；
Figure 32 is the change curve of different polymerization degree CPP materials compression strength in degradation process in SBF simulated body fluids；
Figure 33 is the change curve of different crystal forms CPP materials compression strength in degradation process in SBF.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
Explanation is further explained to the present invention by the following examples, but is not construed as limiting the invention.
Embodiment 1
Pore-foaming agent additive amount is the preparation of 0/20/25 gradient porous calcium polyphosphate ceramic material:
The preparation and optimization of calcium polyphosphate ceramic powders：
The preparation of 1 calcium polyphosphate ceramic powders
Calcium dihydrogen phosphate raw material is taken, with deionized water washing, stirring, drying, is subsequently poured into clean crucible (because of calcining
Temperature is not high, can be held with unglazed pottery, and crucible is placed in batch-type furnace, and the top of crucible will add protection to arrange
It applies, prevents kiln from falling dirty).500 DEG C are raised to the speed of 4 DEG C/min, keeps the temperature several hours.After kiln cooling, raw material is taken
Go out, is ground.Feedstock portions can be bonded on sidewall of crucible at this time, take middle section, and the calcium polyphosphate of different polymerization degree is made
Ceramic powders presoma.
Mixing is carried out to the right middle suitable polyvinyl alcohol adhesive of addition of presoma of the calcium polyphosphate powder of preparation to pour into
Ball milling is carried out in ball grinder.This experiment uses the ball and tank of zirconium oxide.Ball milling uses planetary ball mill, 230r/m, 30min.
The slurry that ball milling finishes is put into baking oven under the conditions of 55 DEG C to dry.Powder is ground sieve into suitable grain after drying
Degree.The pore-foaming agent of calcium polyphosphate precursor powder obtained and different proportion is uniformly mixed, dry method compression moulding is carried out.Pressure
For 1Mpa, pressurize 1min.The green body that will be suppressed, is put into batch-type furnace and is sintered.It is given birth to 400 DEG C with the rate of 4 DEG C/min
2h is kept the temperature, certain temperature is risen to the rate of 5 DEG C/min, appropriate time is kept the temperature, waits for stove natural cooling.
Pore-foaming agent arrangement of gradients method is will to be mixed with the aggregate of different-grain diameter pore-foaming agent by pore-foaming agent grain size from big to small suitable
Gradient porous calcium polyphosphate ceramics are made by compression moulding, drying and sintering for sequence being laid in mold in layer.
The optimization of 2 calcium polyphosphate powder processes：
The TG curves of 2.1 calcium dihydrogen phosphates
Fig. 1 is the DSC-TGA figures of calcium dihydrogen phosphate.It can be seen from the figure that with the raising of temperature, calcium dihydrogen phosphate warp
Multiple weightless process is gone through, DSC curve shows the heat content variation in these places, shows nearby to have occurred at 147 DEG C and 269 DEG C
Decomposition reaction, and significant weightlessness is shown in TG curves, the former loses the crystallization water by calcium dihydrogen phosphate and causes, and the latter may
It is that polycondensation reaction occurs to cause.There is weightless processes different twice in this stage in TG curves, 237.01-278.41 DEG C it
Between weightlessness it is more apparent, apparent weightlessness is not shown between 500~800 DEG C.It can be seen that the polycondensation of calcium dihydrogen phosphate
With the characteristic gradually polymerizeing, a polycondensation nearby occurs at 269 DEG C first and along with significant weightless process, shows this
One stage calcium dihydrogen phosphate is quickly generated dimer or oligomer；Oligomer continues the high polymerization of polymerization generation at 500-800 DEG C
The product of degree, but this stage there is no along with significant weightlessness, especially sent out almost without weightlessness at 500~600 DEG C
It is raw, show that polymerisation tends to balance, further increasing temperature, then polymerisation continues, and the baseline of DSC curve is at 800 DEG C
It nearby tends to balance and shows that reaction system tends to balance, continuing heating, then side reaction aggravation causes the degree of polymerization to reduce.To sum up, it uses
The method of fractional steps carries out polymerization and is more advantageous to the degree of polymerization for improving calcium polyphosphate.In conjunction with above discussion, calcium dihydrogen phosphate can be speculated
Polycondensation process reaction is as follows：
Entire reaction is solid state polycondensation, and from reaction equation it can be seen that product generates, water is more, and the degree of polymerization is got over
It is high.The structure of polymer is generated, it is both related with the degree of functionality of various monomers itself for participating in reaction, also have with their proportioning
It closes.When the polymerisation of C-stage occurs, it is understood that there may be the product anhydrous dihydro calcium phosphate and B-stage intramolecular dehydration in A stages
The calcium pyrophosphate of generation.If in B-stage intramolecular dehydration does not occur completely for anhydrous dihydro calcium phosphate generates calcium pyrophosphate, C ranks
There are two kinds of monomers in section polymerisation, the CPP of generation is branched or reticular structure when occurring, but in this experiment from TG figures B ranks
The weight-loss ratio 8.182% of section, it can be seen that anhydrous CPP has had occurred intramolecular dehydration in B-stage substantially and generated coke completely
Calcium phosphate as the monomer of C-stage polymerisation, therefore can tentatively judge that the CPP that this experiment reaction generates polymerize for chain
Object.
2.2 infrared spectrums and Raman analysis
Fig. 2 is the infrared spectrum comparison diagram of calcium dihydrogen phosphate and CPP imitation frosted glass powder.Figure it is seen that calcium dihydrogen phosphate
After pyroreaction, the corresponding 3467cm of-OH stretching vibrations-1Peak disappears substantially, this can be with preliminary judgement, calcium dihydrogen phosphate
Have occurred that polycondensation reaction.And it can see by Fig. 3, in about 1278cm-1There is the asymmetric of O-P=O functional groups to stretch
Contracting vibration peak, in about 1173cm-1And 713cm-1There is the stretching vibration peak of straight chain P-O-P functional groups in place, this shows phosphoric acid
Calcium dihydrogen is after high temperature polymerization, and product has linear chain structure, and preliminary proof product is calcium polyphosphate.
2.3XRD material phase analysis
This experiment is prepared for calcium polyphosphate powder under condition of different temperatures, and carries out XRD analysis to it respectively.Powder X-ray
Ray diffraction results are the powerfuls for mutually carrying out qualitative analysis to substance.When X-ray passes through crystal, each crystal
Matter has respective unique diffraction spectrogram, feature that can use the crystal boundary spacing d of each reflecting surface and the relative intensity of reflected ray
To characterize.Fig. 4 (a), (b) be calcium polyphosphate imitation frosted glass respectively 500 DEG C, 600 DEG C, 625 DEG C, 650 DEG C, 700 DEG C, 800 DEG C, 900
DEG C, 930 DEG C, 950 DEG C, at 960 DEG C heat preservation 1.5h sintering powder XRD spectra.It can be seen that before 600 DEG C from Fig. 4 (a)
Mainly with γ-Ca (PO3)2Crystalline phase exists, and occurs β-Ca (PO at 625 DEG C3)2Crystalline phase, 700 DEG C -950 DEG C, mainly with β -
Ca(PO3)2Crystalline phase exists, and β-Ca (PO3)2Existing temperature range is wider, is easy to control.
3. influence of the different polymerization degree to calcium polyphosphate ceramic material property
Fig. 5 is calcium polyphosphate31P-NMR collection of illustrative plates.Part collection of illustrative plates is only listed in Fig. 6, and chemical shift has been indicated in figure
Ownership.As shown in figure 5, Q0It is represented at this time without shared oxygen atom, with such for the chemical shift of phosphorus atoms in orthophosphoric acid, 0
Push away Q1For the chemical shift of end of the chain phosphorus atoms, Q2For the chemical shift of phosphorus atoms in linear chain structure.As shown in fig. 6, most collection of illustrative plates are several
All without Q0Chemical shift, show that calcium dihydrogen phosphate reacts completely.It can be calculated by the peak area of these chemical shifts
The degree of polymerization of calcium polyphosphate:PD=(Q0+Q1+Q2)/(Q0+0.5Q1).At 500 DEG C, heat preservation 1h (a), 5h (b), 10h (c) rise respectively
Temperature is about 20,25,28 by calculating to the degree of polymerization after 850 DEG C.But from Fig. 7, it can be seen that there is no apparent for three collection of illustrative plates
Difference, and it is β-CPP that crystal form, which does not change all, and only a little variation occurs for the intensity of three strongest peak.It can be seen by Fig. 8
The calcium polyphosphate ceramic material surfaces pattern for going out 3 kinds of different polymerization degrees has no very big difference, and 10h systems are kept the temperature at a temperature of 500 DEG C
Calcium polyphosphate SEM figures show its crystal grain distribution more it is thin more evenly.Fig. 9 is the CPP powder of different polymerization degree material
After sintering, the comparison of the surveyed compression strength of solid material is made, it can be seen from the figure that the material resistance to compression of the different degree of polymerization
Intensity is also different, and with the increase of the degree of polymerization, compression strength increases.
4. influence of the different crystal forms to calcium polyphosphate ceramic material property
As shown in Figure 10, with the raising of temperature, the phase structure generated by calcium dihydrogen phosphate reaction changes, and 625
DEG C or less mainly with γ-CPP exist, temperature raising gradually form β-CPP.Figure 11 can be seen that the raising with temperature, different
The calcium polyphosphate ceramic material surfaces pattern of crystal form has changed a lot.It is gradually become and is completely embedded and flexible by sheet
's.Figure 12 is it is found that the different influence to compression strength of crystal form is very big, γ-CPP<γ+β-CPP<β-CPP.
5. influence of the different soaking times to calcium polyphosphate ceramic material property
Figure 13 is the XRD diagram of different soaking time CPP materials at 850 DEG C, and soaking time is respectively (a) 5min (b)
1.5h and (c) 3h.Comparing three to scheme to can be seen that the increase with soaking time, the peak of highest peak position is more and more stronger,
5min and 1.5h basic indifferences in XRD peak shapes；It can be seen that in conjunction with material surface pattern under Figure 14 difference soaking times
Connected when 5min, between crystal grain and crystal grain it is not close, when being completely embedded between crystal grain and crystal grain when 1.5h, but keeping the temperature 3h, crystal grain
Between there is thicker non-crystalline areas, cause material crystalline not perfect, to influence the performance of material.Integrated comparative can obtain
Go out, heat preservation 1.5h is best.As can be seen from Figure 15, the compression strength of ceramic material increases with the extension of soaking time
Add.In analysis in front as can be seen that with soaking time increase, variation be particle crystallization degree of perfection.Ceramics
The incompressible intensity of material may be related to the degree of perfection of crystallization, and crystallization is more perfect, and the internal stress of the internal particle of holder is got over
It is small, externally just show preferable mechanical property；Conversely, the mechanical property of holder is with regard to less better.But keep the temperature 3h when, crystal grain it
Between there is thicker non-crystalline areas, cause material crystalline not perfect, to influence the performance of material.
6. the selection of imitation frosted glass grain size
As can be seen from Figure 16, the compression strength of the ceramic material prepared using ball-milled powder will be far above other two grains
Holder prepared by diameter range.It is different caused that this is mainly due to the tightness degrees of particle internal combustion.It is shone in conjunction with the SEM in figure
Piece can significantly find out gap there are many internal stents by the imitation frosted glass preparation of 80-100 mesh grain sizes, and the combination between particle is not
It is good.Under the effect of external force, this combination, which is susceptible to, collapses, and causes supporting structure to destroy, it is very low to show compression strength.By
Holder prepared by the imitation frosted glass of 200-300 mesh grain sizes wants a little better.And the surface area of ball-milled powder is big, particle is easy tight with particle
Contiguity is touched, and closely fusion provides possibility on surface between particle, to show higher mechanical strength.
7. the selection of pore-foaming agent
Using sodium bicarbonate (foaming), three kinds of methods such as ammonium hydrogen carbonate+stearic acid (foaming agent+pore-foaming agent) and stearic acid
It is studied.The aperture of requirement according to the growth of cell to aperture of porous material, ceramic material should be controlled at 100-500 μm
It is more suitable for growing into for bone.The stearic acid of final choice 50-80 mesh and 80-120 mesh uses dry-pressing formed side as pore-foaming agent
Formula.
It is found in being compared from Figure 17 additions with the infrared spectrum for being not added with pore-foaming agent, has no significant change, illustrate pore-foaming agent
It does not remain.
8. the selection of particle size
As artificial synthesized engineering material of bone tissue, porous structure has very important effect the growth of bone, hole
The size of gap should meet the space needed for osteon and bone cell growth.In vivo and in vitro shows that the osteoblast of the mankind can be with
Macropore is diffused by internal interface channel, and is proliferated wherein.Requirement of the growth of cell to aperture of porous material is as follows：
The inside interface channel minimum diameter of osteocyte infiltration is 20 μm, most beneficial for the inside interface channel diameter of osteoblast infiltration
Be greater than 40 μm, when the aperture of porous material be 5-40 μm, allow generally for fibr tissue to grow into；Aperture is 4-100 μm, is allowed non-
The osteoid tissue of mineralising is grown into；Can be that growing into for bone tissue provides ideal place when aperture reaches 150 μm or more.Pore size
It is the basic demand of osteoacusis more than 200 μm, 200-500 μm most beneficial for new bone growth.Thus, it will be seen that 50-60 mesh causes
Aperture obtained by the agent of hole is between 200-400 μm.
9. the screening of mechanical strength
As seen from Figure 18, pure calcium polyphosphate ceramics are not fine and close, there are micropores, and with the addition of pore-foaming agent,
Porosity increases therewith；Pore-foaming agent is added excessively, and ceramic compression strength can be caused lower, loose.When the amount that quality agent is added reaches
To after 50%, hardness is too low, is unfavorable for applying.10%, 20% pore-foaming agent dosage (porosity of formation is 55%) left and right is added,
The intensity of material drastically declines, and it by majority is closed pore that reason, which may be hole in material, and it is trepanning to be changed into most of.It is made
Material porosity is 65%, and the intensity of material is 4Mpa or so, can tentatively meet the requirement of loose bone alternate material.
The preparation of 0/20/25 gradient porous calcium polyphosphate ceramic material:The calcium polyphosphate forerunner of polyvinyl alcohol will be added
The stearic acid that body is 25% with mass fraction and grain size is 50-80 mesh mixes the 3-7mm that tiles in a mold (preferably 5-6mm) and makees
For macroporous layer；By the calcium polyphosphate presoma that polyvinyl alcohol is added and mass fraction is 20% and grain size is 80-120 mesh tristearin
Acid mixing tiles 800-2000 μm (preferably 1000-1500 μm) as weaker zone in a mold；The poly- of polyvinyl alcohol will be added
Calcium phosphate presoma tiles last layer as compacted zone in a mold, and control thickness is 200-700 μm of (preferably 300-600 μ
m)；And then carrying out dry-pressing formed, the dry-pressing formed condition is：1Mpa pressurizes 1min；
Sintering condition is：3~5 DEG C/min of heating rate (preferably 4 DEG C/min) is 350~450 DEG C to temperature and (is preferably
400℃)；1.5~2.5h of soaking time (preferably 2h)；To exclude stearic acid；
Then continue to keep heating rate 3~8 DEG C/min (preferably 5 DEG C/min) to temperature be 800~900 DEG C (preferably
It it is 850 DEG C)；0.05~5h of soaking time (preferably 1.5h)；After natural cooling to obtain the final product.
In conjunction with Figure 19, the gradient porous calcium polyphosphate ceramic material outermost layer that the application is prepared is without addition pore
The compacted zone of agent, centre are the aperture transition zone of the weaker zone of addition different proportion 80-120 mesh pore-foaming agents, and bottom is addition
The macroporous layer of the stearic weaker zone of different proportion 50-80 mesh pore-foaming agents.
Prepared gradient porous calcium polyphosphate ceramics are β type calcium polyphosphates, and dense layer thickness is 200-700 μm, into one
It is 300-600 μm to walk preferred thickness, and pore size is 10 μm；Aperture transition region thickness in weaker zone is 800-2000 μm, into
One step preferred thickness is 1000-1500 μm, and pore size is 100-200 μm；Macropore layer thickness in weaker zone is 3-7mm, into
One step preferred thickness is 5-6mm, and pore size is 200-600 μm.In conjunction with Figure 20, porosity 59-61%, compression strength 9-
10MPa is satisfied by the needs of articular cartilage reparation.
To sum up,
1) the application obtains the calcium polyphosphate material of different polymerization degree by the improvement to calcium polyphosphate powder process
Presoma, and calcium polyphosphate powder precursor is sintered at different temperatures, prepare γ-CPP, γ+β-CPP and
The CPP of three kinds of different crystal forms of β-CPP.And then further define the temperature existence range of the CPP materials of different crystal forms.500-625℃
For γ-CPP；625-700 DEG C is γ+β-CPP, and 700-950 DEG C is β-CPP；
2) different polymerization degree is analyzed, the influence of the CPP ceramics of different crystal forms to material compression strength finds sintering temperature
Higher crystal form, its corresponding compression strength is bigger, and for the size of the degree of polymerization also on compression strength by influencing, the degree of polymerization is bigger, resists
Compressive Strength reduces after accordingly increasing；And the relationship of porous ceramics hole rate and compression strength is further inquired into, porosity is got over
Height, compression strength reduce therewith, find when porosity reaches 65% or so, and compression strength keeps 4MPa or more.
3) it by the optimization to preparation process, finds the structure of gradient, under the premise of ensureing porosity, suitable can change
The mechanical property of kind ceramic material finds that gradient porous calcium polyphosphate ceramics porosity under 0/20/25 proportioning is 62-65%,
Compression strength is 6.2-6.5MPa, is satisfied by the needs of articular cartilage reparation.And it in conjunction with Figure 29, is impregnated in SBF simulated body fluids
After 28 days, it is found that the appearance of many granular class precipitation of hydroxyapatite objects, gradient porous calcium polyphosphate ceramics have fine
Biology performance.Because the presence of compacted zone and aperture transition zone improves the whole compression strength of ceramics but also there are micropores
With macropore and deposit and be more conducive to growing into for new bone.Both it had improved porous ceramic film material intensity and has also retained higher porosity,
The stephanoporate calcium polyphosphate ceramics for optimizing single layer, have prepared that bone subchondral bone structure is similar, mechanical property is good and biology
The good gradient porous CPP materials of energy.
Embodiment 2
The preparation of 0/25/30 gradient porous calcium polyphosphate ceramic material:
Calcium polyphosphate powder prepares and optimization：Described in embodiment 1
It is prepared by gradient porous ceramics：It is 30% and grain by the calcium polyphosphate presoma that polyvinyl alcohol has been added and mass fraction
Diameter is that the stearic acid mixing of 50-80 mesh tiles 3-7mm (preferably 5-6mm) as macroporous layer in a mold；Polyethylene will be added
The stearic acid that calcium polyphosphate presoma and the mass fraction of alcohol are 25% and grain size is 80-120 mesh mixes to tile in a mold
800-2000 μm (preferably 1000-1500 μm) is used as weaker zone；The calcium polyphosphate presoma of polyvinyl alcohol will be added in mold
For middle last layer of tiling as compacted zone, control thickness is 200-700 μm (preferably 300-600 μm)；And then carry out dry-pressing at
Type, the dry-pressing formed condition are：1Mpa pressurizes 1min；
Sintering condition is：3~5 DEG C/min of heating rate (preferably 4 DEG C/min) is 350~450 DEG C to temperature and (is preferably
400℃)；1.5~2.5h of soaking time (preferably 2h)；To exclude stearic acid；
Then continue to keep heating rate 3~8 DEG C/min (preferably 5 DEG C/min) to temperature be 800~900 DEG C (preferably
It it is 850 DEG C)；0.05~5h of soaking time (preferably 1.5h)；After natural cooling to obtain the final product.
In conjunction with Figure 19, the gradient porous calcium polyphosphate ceramic material outermost layer that the application is prepared is without addition pore
The compacted zone of agent, centre are the aperture transition zone of the weaker zone of addition different proportion 80-120 mesh pore-foaming agents, and bottom is addition
The macroporous layer of the stearic weaker zone of different proportion 50-80 mesh pore-foaming agents.
By the optimization to preparation process, prepared 0/25/30 gradient porous calcium polyphosphate ceramics are ensureing porosity
Under the premise of, the suitable mechanical property for improving ceramic material of energy, dense layer thickness is 200-700 μm, further preferred thickness
It it is 300-600 μm, pore size is 10 μm；Aperture transition region thickness in weaker zone is 800-2000 μm, further preferably thick
Degree is 1000-1500 μm, and pore size is 100-200 μm；Macropore layer thickness in weaker zone is 3-7mm, further preferably thick
Degree is 5-6mm, and pore size is 200-600 μm.In conjunction with Figure 20, porosity 60-61%, compression strength 6.6-6.8MPa,
It is satisfied by the needs of articular cartilage reparation.Because the presence of compacted zone and aperture transition zone improves the whole compression strength of ceramics
And it there is also micropore and macropore and deposits and is more conducive to growing into for new bone.Both improved porous ceramic film material intensity also retain compared with
High porosity optimizes the stephanoporate calcium polyphosphate ceramics of single layer, has prepared that bone subchondral bone structure is similar, mechanical property is good
And the gradient porous CPP materials that biology performance is good.
Embodiment 3
The preparation of 0/30/30 gradient porous calcium polyphosphate ceramic material:
Calcium polyphosphate powder prepares and optimization：Described in embodiment 1
It is prepared by gradient porous ceramics：It is 30% and grain by the calcium polyphosphate presoma that polyvinyl alcohol has been added and mass fraction
Diameter is that the stearic acid mixing of 50-80 mesh tiles 3-7mm (preferably 5-6mm) as macroporous layer in a mold；Polyethylene will be added
The stearic acid that calcium polyphosphate presoma and the mass fraction of alcohol are 30% and grain size is 80-120 mesh mixes to tile in a mold
800-2000 μm (preferably 1000-1500 μm) is used as weaker zone；The calcium polyphosphate presoma of polyvinyl alcohol will be added in mold
For middle last layer of tiling as compacted zone, control thickness is 200-700 μm (preferably 300-600 μm)；And then carry out dry-pressing at
Type, the dry-pressing formed condition are：1Mpa pressurizes 1min；
Sintering condition is：3~5 DEG C/min of heating rate (preferably 4 DEG C/min) is 350~450 DEG C to temperature and (is preferably
400℃)；1.5~2.5h of soaking time (preferably 2h)；To exclude stearic acid；
Then continue to keep heating rate 3~8 DEG C/min (preferably 5 DEG C/min) to temperature be 800~900 DEG C (preferably
It it is 850 DEG C)；0.05~5h of soaking time (preferably 1.5h)；After natural cooling to obtain the final product.
In conjunction with Figure 19, the gradient porous calcium polyphosphate ceramic material outermost layer that the application is prepared is without addition pore
The compacted zone of agent, centre are the aperture transition zone of the weaker zone of addition different proportion 80-120 mesh pore-foaming agents, and bottom is addition
The macroporous layer of the stearic weaker zone of different proportion 50-80 mesh pore-foaming agents.
By the optimization to preparation process, prepared 0/30/30 gradient porous calcium polyphosphate ceramics are ensureing porosity
Under the premise of, the suitable mechanical property for improving ceramic material of energy, dense layer thickness is 200-700 μm, further preferred thickness
It it is 300-600 μm, pore size is 10 μm；Aperture transition region thickness in weaker zone is 800-2000 μm, further preferably thick
Degree is 1000-1500 μm, and pore size is 100-200 μm；Macropore layer thickness in weaker zone is 3-7mm, further preferably thick
Degree is 5-6mm, and pore size is 200-600 μm.In conjunction with Figure 20, porosity 62-65%, compression strength 6.2-6.5MPa,
It is satisfied by the needs of articular cartilage reparation.Because the presence of compacted zone and aperture transition zone improves the whole compression strength of ceramics
And it there is also micropore and macropore and deposits and is more conducive to growing into for new bone.Both improved porous ceramic film material intensity also retain compared with
High porosity optimizes the stephanoporate calcium polyphosphate ceramics of single layer, has prepared that bone subchondral bone structure is similar, mechanical property is good
And the gradient porous CPP materials that biology performance is good.
Embodiment 4
The preparation of 0/30/35 gradient porous calcium polyphosphate ceramic material:
Calcium polyphosphate powder prepares and optimization：Described in embodiment 1
It is prepared by gradient porous ceramics：It is 30% and grain by the calcium polyphosphate presoma that polyvinyl alcohol has been added and mass fraction
Diameter is that the stearic acid mixing of 50-80 mesh tiles 3-7mm (preferably 5-6mm) as macroporous layer in a mold；Polyethylene will be added
The stearic acid that calcium polyphosphate presoma and the mass fraction of alcohol are 35% and grain size is 80-120 mesh mixes to tile in a mold
800-2000 μm (preferably 1000-1500 μm) is used as weaker zone；The calcium polyphosphate presoma of polyvinyl alcohol will be added in mold
For middle last layer of tiling as compacted zone, control thickness is 200-700 μm (preferably 300-600 μm)；And then carry out dry-pressing at
Type, the dry-pressing formed condition are：1Mpa pressurizes 1min；
Sintering condition is：3~5 DEG C/min of heating rate (preferably 4 DEG C/min) is 350~450 DEG C to temperature and (is preferably
400℃)；1.5~2.5h of soaking time (preferably 2h)；To exclude stearic acid；
Then continue to keep heating rate 3~8 DEG C/min (preferably 5 DEG C/min) to temperature be 800~900 DEG C (preferably
It it is 850 DEG C)；0.05~5h of soaking time (preferably 1.5h)；After natural cooling to obtain the final product.
In conjunction with Figure 19, the gradient porous calcium polyphosphate ceramic material outermost layer that the application is prepared is without addition pore
The compacted zone of agent, centre are the aperture transition zone of the weaker zone of addition different proportion 80-120 mesh pore-foaming agents, and bottom is addition
The macroporous layer of the stearic weaker zone of different proportion 50-80 mesh pore-foaming agents.
By the optimization to preparation process, prepared 0/30/35 gradient porous calcium polyphosphate ceramics are ensureing porosity
Under the premise of, the suitable mechanical property for improving ceramic material of energy, dense layer thickness is 200-700 μm, further preferred thickness
It it is 300-600 μm, pore size is 10 μm；Aperture transition region thickness in weaker zone is 800-2000 μm, further preferably thick
Degree is 1000-1500 μm, and pore size is 100-200 μm；Macropore layer thickness in weaker zone is 3-7mm, further preferably thick
Degree is 5-6mm, and pore size is 200-600 μm.In conjunction with Figure 20, porosity 64-65%, compression strength 6.1-6.5MPa,
It is satisfied by the needs of articular cartilage reparation.Because the presence of compacted zone and aperture transition zone improves the whole compression strength of ceramics
And it there is also micropore and macropore and deposits and is more conducive to growing into for new bone.Both improved porous ceramic film material intensity also retain compared with
High porosity optimizes the stephanoporate calcium polyphosphate ceramics of single layer, has prepared that bone subchondral bone structure is similar, mechanical property is good
And the gradient porous CPP materials that biology performance is good.
Embodiment 5
Performance test
1. calcium polyphosphate ceramic material prepared by embodiment 1 is placed into impregnate 28 days in Tris-HCl solution and tests its drop
Solve characteristic.
To eliminate the influence of the factors such as porosity, the experiment of this group is carried out using CPP ceramic blocks, is prepared for 550 DEG C of (γ-altogether
CPP), 625 DEG C (γ+β-CPP), three kinds of CPP being prepared at a temperature of 850 DEG C (β-CPP) carry out Tris degradation experiments.By Figure 21
As can be seen that influence of the crystal form to the CPP rates degraded is significant.Material is can be seen that from slope of a curve variation
Degradation rate with degradation time increase from large to small, be then similar to constant speed degradation, γ-CPP>γ+β-CPP>β-CPP.
γ types CPP ratio β type CPP degradation rates are nearly 26 times fast；γ+β type mixing CPP ratio β type CPP degradation rates also accelerate many close
16 times.
It can be seen that by weightlessness-time curve of Figure 22 different polymerization degree β-CPP materials in Tris buffer solutions：
The degree of polymerization of CPP is smaller, and degradation rate is faster.
Figure 23 is the surface topography before and after different crystal forms CPP ceramic materials are degraded in Tris buffer solutions.As can be seen that
For different crystal forms timbering material after degradation, slight change has occurred in surface, i.e., surface have more small gaps and
Hole shows that localized degradation has occurred in material.In terms of the degree that pattern changes, γ-CPP>γ+β-CPP>β-CPP.Difference polymerization
Degree CPP ceramic materials degrade front and back surface topography it is also seen that (Figure 24), different polymerization degree CPP in Tris buffer solutions
Ceramics have more small gaps and hole on surface, show that localized degradation has occurred in material.
2. calcium polyphosphate ceramic material prepared by embodiment 1 is placed into impregnate 28 days in SBF simulated body fluids and tests its drop
Solve characteristic.
By Figure 25,26 it is found that compared with impregnating 28 days degradation rates in Tris buffer solutions, in SBF simulated body fluids,
Not only different crystal forms also have the degradation of the CPP ceramic materials of different polymerization degree to have apparent quickening.
From Figure 27 different crystal forms CPP ceramic materials in SBF simulated body fluids pH variation in it is found that impregnate a few days ago, pH exists
Decline, then stablizes between 6.6-6.9, it is smaller than the pH value in tris, accelerate the degradation of calcium polyphosphate.Degradation rate becomes
There is relationship with pH variations soon, because calcium polyphosphate hydrolyzes, the calcium dihydrogen phosphate that can become acid is dissolved in solution.
For different crystal forms CPP materials after degradation, significant change all has occurred in surface microstructure, i.e., all goes out on surface
Deposit is showed.What the surfaces γ+β-CPP were formed is a lamellar deposit, and what is formed on the surfaces β-CPP is one layer of granular deposition
Object (surface topography after porous CPP ceramic materials degradation is more obvious).Different polymerization degree CPP ceramic materials are buffered in SBF
In solution degrade after surface topography show, at 500 DEG C keep the temperature 10h after 850 DEG C keep the temperature 1.5h under the conditions of ceramic material surfaces
Deposit is relatively some more.
Figure 28 shows that different crystal forms CPP materials are after degradation, and significant change all has occurred in surface microstructure, i.e.,
All there is deposit on surface.What the surfaces γ+β-CPP were formed is a lamellar deposit, and what is formed on the surfaces β-CPP is one
The granular deposit of layer (surface topography after the porous CPP ceramic materials degradations of Figure 29 is more obvious).See from Figure 30, it is different
Surface topography after degree of polymerization CPP ceramic materials are degraded in SBF buffer solutions is shown, 850 DEG C of guarantors after 10h are kept the temperature at 500 DEG C
Ceramic material surfaces deposit under the conditions of warm 1.5h is relatively some more.
From Figure 31 different crystal forms CPP ceramic materials degrade in SBF simulated body fluids after in infared spectrum it can be found that three kinds
The CPP ceramic materials of different crystal forms are in 570cm-1,640cm-1, 1099cm-1There are P-O functional groups in place, in 1425cm-1Place goes out
The vibration peak of C-O is showed.And in 3430cm-1And 1640cm-1There are O-H stretching vibration peaks in place.Speculate that the substance is carbon containing
The hydroxyapatite of acid group.The formation of the biologically active layer of hydroxyapatite surface containing carbonate is whether material has life
The active key factor of object.
Figure 32 is compression strength change curve caused by different polymerization degree CPP materials are degraded in SBF simulated body fluids.Such as figure
Display：The compression strength of three kinds of different polymerization degree CPP materials all reduces with the increase of degradation time, and at degradation initial stage
Reduce most fast；By degradation in 14 days, the reduction degree of the compression strength of three kinds of timbering materials was simultaneously different, is computed
Know, the ceramic material that 1h is kept the temperature at 850 DEG C has lost the 70.57% of initial strength, and 5h is kept the temperature at 850 DEG C and has lost initial strength
65.51%, at 850 DEG C keep the temperature 10h have lost the 61.90% of initial strength.The loss of timbering material intensity is because of material
The quantity of the degradation micro gap and hole that cause it internal increase, this just increases material internal microdefect, and mechanics is strong
Degree necessarily reduces.
As shown in figure 33：The compression strength of three kinds of different crystal forms CPP materials all reduces with the increase of degradation time, and
And reduce most fast at degradation initial stage；By degradation in 14 days, the reduction degree of the compression strength of three kinds of different crystal forms CPP materials
And it is different, the low temperature crystal form of CPP is more degradable than high temperature crystal form, γ-CPP on day 3 when with regard to partly losing mechanical strength,
Therefore, the mechanical strength of low temperature crystal form loses faster.
To sum up, 1) the application research finds no matter CPP materials drop in Tris buffer solutions or in SBF simulated body fluids
The degradation rate of solution, different crystal forms CPP materials is different, and degradation rate is all γ-CPP>γ+β-CPP>β-CPP；CPP is poly- simultaneously
Right smaller, degradation rate is faster.Material sintering temperature is lower, and material degradation must be faster；Soaking time is longer, non-crystalline areas shape
Cheng Yue is more, and degradation rate is faster；
2) influence of the material morphology to degradation rate, as a result porous surface timbering material be more advantageous to material and be put into degradation；
3) surface topography and intensity are all changed in degradation process.After degrading 28 days in Tris buffer solutions, sample
The micro gap and hole on product surface increase, and after degrading 28 days in SBF simulated body fluids, sample surfaces generated sheet and
Graininess deposit；Meanwhile loss of strength amount size is followed successively by, 1h-850 has lost 70.57%, the 5h-850 damages of initial strength
65.51%, the 10h-850 for having lost initial strength has lost the 61.90% of initial strength；And γ type CPP and γ+β mixed types CPP
Mechanical strength is almost lost after 14 days；
4) material composition variation before and after degradation is studied, using IR to the sample surfaces after degrading 28 days in SBF
Deposit be detected, find in the deposit contain carbonate and hydroxyl, be similar to document report the hydroxyl containing carbonate
Base apatite.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for the skill of this field
For art personnel, the application can have various modifications and variations.Within the spirit and principles of this application, any made by repair
Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of gradient porous calcium polyphosphate ceramic material, which is characterized in that the ceramic material includes compacted zone (cartilaginous calcification
Area) and weaker zone (subchondral bone), the weaker zone includes aperture transition zone and macroporous layer, and wherein aperture transition zone is as intermediate
Layer is fitted closely with compacted zone and macroporous layer respectively, and the pore size and porosity of compacted zone, aperture transition zone and macroporous layer
It is distributed at gradient, the ceramic material is made of calcium polyphosphate.
2. a kind of ceramic material as described in claim 1, which is characterized in that the calcium polyphosphate is β type calcium polyphosphates.
3. a kind of ceramic material as described in claim 1, which is characterized in that
The dense layer thickness is 200-700 μm, and preferred thickness is 300-600 μm, and pore size is 1-10 μm；
Aperture transition region thickness in the weaker zone is 800-2000 μm, and preferred thickness is 1000-1500 μm, and pore size is
100-200μm；
Macropore layer thickness in the weaker zone is 3-7mm, and preferred thickness 5-6mm, pore size is 200-600 μm；
Preferably, the gradient porous calcium polyphosphate ceramics porosity is controlled in 59-65%；Needed for Optimal gradient porous structure
The mass fraction of pore-foaming agent is:Compacted zone/aperture transition zone/macroporous layer is 0/30/35, porosity 64-65%.
4. the preparation method of ceramic material as described in claim any one of 1-3, which is characterized in that specific method is：
After binder ball milling, drying screening are added in calcium polyphosphate presoma obtained, mix, press with different-grain diameter pore-foaming agent
The sequence of pore-foaming agent grain size from big to small is laid in mold layer by layer, and gradient porous poly- phosphorus is made by compression moulding, sintering
Sour calcium ceramic material.
5. preparation method as claimed in claim 4, which is characterized in that the calcium polyphosphate presoma and quality of binder will be added
The pore-foaming agent mixing that score is 25%, 30% or 35% tiles 3-7mm (preferably 5-6mm) as macroporous layer in a mold；It will
The calcium polyphosphate presoma of addition binder is mixed with the pore-foaming agent that mass fraction is 20%, 25% or 30% to tile in a mold
800-2000 μm (preferably 1000-1500 μm) is used as aperture transition zone；The calcium polyphosphate presoma of binder will be added in mould
Last layer is tiled in tool as compacted zone, control thickness is 200-700 μm (preferably 300-600 μm).
6. preparation method as claimed in claim 4, which is characterized in that sintering condition is：3~5 DEG C/min of heating rate is (preferably
For 4 DEG C/min) to temperature be 350~450 DEG C (preferably 400 DEG C)；1.5~2.5h of soaking time (preferably 2h)；To exclude
Stearic acid；Then continue 3~8 DEG C/min of holding heating rate (preferably 5 DEG C/min) (is preferably for 800~900 DEG C to temperature
850℃)；0.05~5h of soaking time (preferably 1.5h)；After natural cooling to obtain the final product.
7. preparation method as claimed in claim 5, which is characterized in that binder is polyvinyl alcohol, preferred polyvinyl alcohol matter
Amount score is 4~6% (further preferred 5%).
8. preparation method as claimed in claim 5, which is characterized in that pore-foaming agent is stearic acid, the stearic acid grain size difference
For 50~80 mesh of macroporous layer, 80~120 mesh of aperture transition zone.
9. stating any one of ceramic material or claim the 4-8 preparation method described in claim any one of 1-3 to be prepared
Application of the ceramic material as degradable implant material.
10. application as claimed in claim 9, which is characterized in that the application includes the ceramic material as degradable implantation
Application of the body material in artificial bone defect healing.
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| CN114988910A (en) * | 2022-05-19 | 2022-09-02 | 山东大学 | 3D printing method of gradient functional foamed ceramic bone scaffold |
| CN115337460A (en) * | 2022-06-30 | 2022-11-15 | 山东大学 | Calcium polyphosphate/silicon dioxide composite ceramic material and preparation method and application thereof |
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| CN104645408A (en) * | 2015-03-09 | 2015-05-27 | 吉林大学 | Method for preparing gradient beta phase tricalcium phosphate bone substitute material |
| CN105439626A (en) * | 2015-11-30 | 2016-03-30 | 四川大学 | Preparation method of porous calcium phosphate ceramic |
| CN106946586A (en) * | 2016-01-06 | 2017-07-14 | 深圳兰度生物材料有限公司 | Porous bioceramic scaffold and preparation method thereof |
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| CN103113129A (en) * | 2013-01-31 | 2013-05-22 | 华南理工大学 | Preparation method and application of hierarchical porous bioactive ceramic |
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