CN105343935A - Calcium phosphate whisker frame and porous composite scaffold and their preparation methods - Google Patents

Calcium phosphate whisker frame and porous composite scaffold and their preparation methods Download PDF

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Publication number
CN105343935A
CN105343935A CN201410766951.XA CN201410766951A CN105343935A CN 105343935 A CN105343935 A CN 105343935A CN 201410766951 A CN201410766951 A CN 201410766951A CN 105343935 A CN105343935 A CN 105343935A
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China
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calcium phosphate
whisker
skeleton
described
porous
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CN201410766951.XA
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Chinese (zh)
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肖占文
叶兴江
朱向东
樊渝江
张兴栋
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四川大学
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Abstract

The invention discloses a calcium phosphate whisker frame and a porous composite scaffold and their preparation methods. The frame is made by interconnecting submicron whiskers converted from a porous wall of a macroporous calcium phosphate ceramic scaffold, composed of polycrystalline particles; the high-strength high-toughness calcium phosphate-based porous composite biological scaffold can also be obtained by filling the whisker frame formed porous wall with biological ceramic or polymer slurry. A 'whisker frame-slurry' porous wall structure similar to an architectural 'reinforcement-concrete' structure is obtained by filling the porous calcium phosphate ceramic of whisker frame structure with a slurry filler in vacuum and filling voids of the whisker frame with the slurry, and finally, heat treatment conditions for the filled macroporous scaffold are determined according to the property of the filling slurry. The calcium phosphate whisker frame-based porous composite scaffold has good mechanical properties and biological activity owing to its unique whisker frame structure and is expected to be used for repairing human weight-bearing bones.

Description

A kind of calcium phosphate whisker skeleton and porous compound support frame and preparation method thereof

Technical field

The invention belongs to field of biomedical materials, be specifically related to a kind of preparations and applicatio of high strength macropore calcium orthophosphate base biological activity compound rest.

Technical background

Desirable bone substitutes the mechanical property that implant (artificial bone) should have loose structure, good biology performance and necessity.Calcium phosphate ceramic is because having the inorganic phase composition similar with tooth to natural bone, very easily form entirety by chemical bond-linking and natural bone, and to albumen (such as attachment proteins) and somatomedin (such as BMP-2), also there is good affinity, be thus regarded as optimal artificial bone.But the low-intensity of calcium phosphate porous pottery and intrinsic fragility make it mainly be used as inserts and bioactive coating material, and can not be directly used in the reparation of knochenbruch defect and load-bearing bone defect, although some calcium phosphate porous pottery has good osteoinductive.

Whisker reinforcement is a kind of effective ways improving the mechaanical property of materials.Traditional whisker reinforcement method is dispersed in matrix continuous phase by whisker, because the low and whisker of whisker phase content is difficult to be dispersed in substrate, cause between the intensity of this composite and Whisker Content and there is an optimum (marginal value), after Whisker Content exceedes this marginal value, the increase of the intensity Whisker Content of composite declines on the contrary.Therefore, adopt the enhancing multiplying power of traditional whisker reinforcement mode to calcium phosphate porous composite not high.

Summary of the invention

For the problems referred to above, the present invention, by carrying out hydrothermal treatment consists to existing porous calcium phosphate ceramic support, makes hole wall calcium phosphate be transformed into the high whisker of degree of crystallinity, and this whisker part cross lock in growth course forms whisker skeleton.

The present invention is achieved through the following technical solutions:

A kind of calcium phosphate whisker skeleton, the main body of described skeleton is porous calcium phosphate ceramic, and the hole wall of described calcium phosphate ceramic is interconnected to constitute skeleton primarily of the whisker that submicron is thick.

Alternately, in above-mentioned calcium phosphate whisker skeleton, described whisker size is: 2 ~ 100 μm long, and 100 ~ 1000nm is thick.

Alternately, in above-mentioned calcium phosphate whisker skeleton, obtain whisker nucleation in the macropore hole wall of calcium phosphate ceramic, and with the angle of nucleating point for the angle of 50-90 ° forms to Growth In Space.

Alternately, in above-mentioned calcium phosphate whisker skeleton, described calcium phosphate whisker skeleton is the one in hydroxyapatite crystal whisker skeleton and biphasic calcium phosphate whisker skeleton.

Alternately, in above-mentioned calcium phosphate whisker skeleton, described whisker is hydroxyapatite crystal whisker, because hydroxyapatite crystal belongs to lower state, more easily obtains.

Present invention also offers the porous compound support frame that a kind of calcium phosphate whisker skeleton strengthens, comprise any one calcium phosphate whisker skeleton above-mentioned and be filled in the implant in described whisker gap.Described implant fills whisker skeleton gap, obtains " whisker skeleton-implant " hole wall structure of " reinforcing bar-mixed earth " structure in resemble construction.

Alternately, above-mentioned porous compound support frame consisting of according to mass percent: calcium phosphate whisker skeleton: 50% ~ 90%, implant: 50% ~ 10%.

Alternately, the porosity of above-mentioned porous compound support frame entirety is 50% ~ 90%.Described compound rest has the multistage intercommunicating pore structure of macropore-aperture-micro-nano hole.Macropore diameter: 200 ~ 800 microns, have aperture (50 ~ 100 microns) mutually through between macropore, macropore inwall is covered with micro-nano hole.

Alternately, in above-mentioned porous compound support frame, described implant is hydroxyapatite, bata-tricalcium phosphate, biphasic calcium phosphate, bio-vitric, polylactic acid, poly butyric, PEEK(polyether-ether-ketone), PEKK(polyether-ketone), the combination of one or more in collagen.

Present invention also offers a kind of preparation method of above-mentioned calcium phosphate whisker skeleton, it is characterized in that, comprise the following steps:

(1) porous calcium phosphate ceramic substrate holder material is immersed in aqueous solution, in airtight hydrothermal reaction kettle, carries out hydro-thermal reaction;

(2) naturally cool to room temperature, after washing, drying bracket, obtain calcium phosphate whisker skeleton.

Alternately, in the preparation method of above-mentioned calcium phosphate whisker skeleton, described in step (1), the pH value of aqueous solution is 4 ~ 10, and preferable ph is 5 ~ 8 aqueous solutions.

Alternately, in the preparation method of above-mentioned calcium phosphate whisker skeleton, the temperature of described hydro-thermal reaction is 100 ~ 200 DEG C, and the response time is 12h ~ 72h.Further, the temperature of described reaction is 120 ~ 180 DEG C.Calcium phosphate ceramic hole wall can be made under this condition to be all transformed into whisker skeleton.

Alternately, in the preparation method of above-mentioned calcium phosphate whisker skeleton, described porous calcium phosphate substrate holder is biophasic calcium phosphate ceramic (BCP) support, and the mass percent of its phase constituent composition is: hydroxyapatite (HA): bata-tricalcium phosphate (β-TCP)=1:9 ~ 4:6.

Alternately, in the preparation method of above-mentioned calcium phosphate whisker skeleton, the porosity of described porous calcium phosphate substrate holder is 50% ~ 90%.Further, described porous calcium phosphate substrate holder has the multistage intercommunicating pore structure of macropore-aperture-micro-nano hole, macropore diameter: 200 ~ 800 microns, has aperture (50 ~ 100 microns) mutually through between macropore.

Present invention also offers a kind of preparation method of above-mentioned porous compound support frame, be specially and prepare calcium phosphate whisker skeleton according to the preparation method of above-mentioned calcium phosphate whisker skeleton, then under negative pressure by the solution of implant or filled therewith in whisker skeleton gap, then carry out drying, solidification obtains porous compound support frame.Be filled with under negative pressure and be beneficial to the gap that implant gos deep into whisker, but do not affect the porosity of support entirety, do not destroy the loose structure of support entirety.Macropore calcium phosphate ceramic after hydro-thermal whiskerizing is poured into filled therewith thing by this method under vacuo, makes filled therewith whisker skeleton gap, obtains " whisker skeleton-slurry " hole wall structure of " reinforcing bar-mixed earth " structure in resemble construction.Finally, the heat-treat condition of the macropore support after to perfusion is determined according to the character of filling paste.This calcium phosphate whisker skeleton base macropore compound rest, because the whisker frame structure of its uniqueness makes it have good mechanical property and biological activity, is expected to can be used in human bearing's Bone Defect Repari.

Alternately, in the preparation method of above-mentioned porous compound support frame, the concrete mode of described drying, solidification can be selected flexibly according to the kind of implant and performance characteristics.Such as, the mode of heat drying or sintering can be adopted to carry out drying and solidification for inorganic fillers such as pottery, bio-vitrics, corresponding organic material can adopt the modes such as crosslinked or heat cure.

Alternately, in the preparation method of above-mentioned porous compound support frame, filling described above, drying and curing schedule can be repeated in order to improve loading.

Alternately, in the preparation method of above-mentioned porous compound support frame, described filling, dry, curing schedule is specially: calcium phosphate whisker skeleton is placed in Dewar bottle, after startup vacuum pump makes Dewar bottle be in negative pressure state 5-10 minute, it is the calcium phosphate slurry (hydroxyapatite of 10 ~ 100mg/ml by the concentration of preparation, bata-tricalcium phosphate or biphasic calcium phosphate nano pulp) be added drop-wise in Dewar bottle until slurry submergence calcium phosphate whisker skeleton by constant pressure funnel, continue aerofluxus after 5-10 minute, take out calcium phosphate whisker skeleton, and be placed in high temperature sintering furnace, just described calcium orthophosphate base whisker skeleton compound rest is obtained calcine 2h at 1100 DEG C after.

Present invention also offers the application of a kind of above-mentioned calcium phosphate whisker skeleton or its porous compound support frame, use it for the impairment renovation material making large scale knochenbruch impairment renovation material or load-bearing bone.

All features disclosed in this description, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.

Beneficial effect of the present invention:

The hole wall of calcium phosphate macropore pottery is first transformed into whisker skeleton by hydro-thermal method by the present invention, and then fill whisker skeleton by implant, thus obtain with whisker skeleton for continuous phase, implant is the porous compound support frame of decentralized photo.This based on the Biocomposite material of calcium phosphate whisker skeleton, because Whisker Content is high, and the formation framework entirety that is connected to each other between whisker, thus drastically increase the intensity of composite; Meanwhile, the package action of filling relative whisker too increases the fracture toughness of composite.Therefore, the present invention's preparation is expected to for human body large scale knochenbruch defect repair with the biological activity compound rest that calcium phosphate whisker skeleton is substrate.

Whisker skeleton of the present invention strengthens method compared with existing whisker reinforcement method, there are the difference of essence and unique advantage: the whisker in whisker skeletal composite is not independent dispersion, but be self-assembled into the framing structure of mutual interconnection, as continuous phase entirety, there is fixing contour structures and independently weight capacity; Because whisker nucleation is in calcium phosphate macropore hole wall, and to form to Growth In Space for the angle of 50-90 ° with the angle of nucleating point, therefore, there is certain gap and can not reunite between the whisker of this growth in situ, thus whisker distribution is very even; Whisker mass fraction high (~ 50%-90%) causes composite to have very high intensity.And traditional metal whisker reinforced composite, not only whisker mass fraction little (2-20%), and whisker is randomly dispersed within substrate can not individualism, even if the whisker in substrate occurs to reunite and all whiskers also can not be caused to be connected to each other to a whisker grid or skeleton is overall.In fact, in existing metal whisker reinforced composite, when Whisker Content is too high, because of the whisker skewness that whisker agglomeration causes, thus causes Stress non-homogeneity to distribute, finally cause the increase of the intensity Whisker Content of composite and significantly reduce.As can be seen here, whisker skeletal composite of the present invention, has Whisker Content high, whisker is evenly distributed, all whiskers are interconnected to constitute can the stable framework of individualism, and exist mutually even without filling, this whisker frame structure also has certain weight capacity.

Accompanying drawing explanation

Fig. 1 is preparation technology's flow chart of the present invention.

Fig. 2 is scanning electron microscope (SEM) photo of sample segment in embodiment 1.

Fig. 3 is scanning electron microscope (SEM) photo of sample segment in embodiment 3.

detailed description of the invention:

Again foregoing of the present invention is described in further detail by the following examples.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following example.Not departing from any amendment made within the spirit and principles in the present invention, and the equivalent replacement made according to ordinary skill knowledge and customary means or improvement, all should be included in protection scope of the present invention.

embodiment 1:

The preparation of the high strength macropore calcium phosphate bioactive ceramics bracket of hydroxyapatite crystal whisker skeleton Composite Double calcium phosphate phase granule:

(1) customize macroporous biphasic calcium phosphate (BCP, HA/ β-TCP=2:8) ceramics bracket.50 ~ 100 μm, through hole aperture between macroporous biphasic calcium phosphate ceramic brace aperture rate 70% ± 2%, macropore diameter 200 ~ 500 μm, macropore: biphasic calcium phosphate (BCP) powder Wet Method Reaction prepared is dried, hydrogen peroxide foaming is adopted to prepare porous ceramics idiosome subsequently, pottery idiosome is after 1100 DEG C of sintering 2h, cut into the cylindric block being of a size of Φ 5 × 10mm, obtain BCP macropore support, its section microstructure is as shown in Fig. 2 (a).

(2) the BCP macropore support of (1) middle preparation being immersed in pH is in the acid solution of 6.0, is jointly placed in autoclave, hydrothermal treatment consists 15h at temperature is 180 DEG C.After reactor natural cooling, HA whisker skeleton is obtained after taking out bulk drying, its macro morphology has no obvious difference when not doing hydrothermal treatment consists, still present loose structure, and microscopic appearance there occurs obvious change, the section microstructure of gained HA whisker skeleton is as shown in Fig. 2 (b), and gained HA whisker is about 40 ~ 80 μm, diameter is 500 ~ 1000nm about, is the angle of 50-90 ° with macropore hole wall.

(3) being propped up by the HA whisker skeleton of (2) middle preparation is placed in Dewar bottle, be decompressed to≤10Pa time, drip BCP nano pulp that the concentration prepared is 30mg/ml until slurry floods whisker skeleton, after pressurize 15min by constant pressure funnel, supersonic oscillations 5min again, recovers normal pressure.Repeat above step once, obtain compound rest idiosome.

(4) the compound rest idiosome high temperature sintering of preparation in is (3) incubated 2h to 1100 DEG C, after naturally cooling to room temperature, obtains high strength macropore HA whisker skeleton base calcium phosphate ceramic compound rest.Implant fill in hole wall whisker gap in, gained compound rest still has multistage intercommunicating pore structure, and porosity is still 70% ± 2%.

The section structure of this HA whisker skeleton base calcium phosphate ceramic compound rest is as shown in Fig. 2 (c), and its hole wall structure high magnification map is as shown in Fig. 2 (d).Adopt dynamic test system, respectively Mechanics Performance Testing is carried out to the compound rest (sample number into spectrum is C1) obtained after the whisker skeleton (sample number into spectrum is B1) obtained after the calcium phosphate porous support of prepared by foaming same batch (porosity 70% ± 2%) (sample number into spectrum is A1), hydrothermal treatment consists and filling BCP.Compress as shown in table 1 with three-point bend test result: whisker skeleton itself (B1) and the BCP(A1 do not dealt with) compared with, comprcssive strength and modulus of compressibility all improve about 1 times; HA whisker skeleton base calcium phosphate ceramic compound rest (C1) is compared with the same batch of calcium phosphate porous support (A1) do not strengthened, and comprcssive strength about improves 2.3 times, and modulus of compressibility about improves 2.6 times, visible, and the reinforced effects of whisker skeleton is very remarkable.Three-point bend test result shows, with the BCP(A1 do not dealt with) compared with, the bending strength of whisker skeleton (B1) itself and fracture strength improve 1 times and 4.3 times respectively; Whisker skeleton base calcium phosphate ceramic compound rest (C1) then improves 4.6 times and 5.6 times.This shows whisker skeleton, and not only reinforced effects is remarkable, and its toughening effect is also very remarkable.This has important function to the reliability of the carrying mechanics improving calcium phosphate ceramic support.

The Mechanical test results of each sample in table 1 embodiment 1

embodiment 2:

Identical with embodiment 1 step, difference is that the porosity of the porous BCP ceramics bracket that this example uses is 76% ± 3%.Result show, implant fill in hole wall whisker gap in, gained compound rest still has multistage intercommunicating pore structure, and porosity is still about 76%.Mechanical test test result is as shown in table 2: whisker skeleton itself (B2) and the BCP(A2 do not dealt with) compared with, comprcssive strength improves about 82%, and modulus of compressibility improves about 1 times; HA whisker skeleton base calcium phosphate ceramic compound rest (C2) is compared with the same batch of calcium phosphate porous support (A2) do not strengthened, and comprcssive strength about improves 3.1 times, and modulus of compressibility about improves 3.9 times, and the reinforced effects of whisker skeleton is also very remarkable.

The Mechanical test results of each sample in table 2 embodiment 2

Sample number into spectrum A2 B2 C2 Comprcssive strength/MPa 2.3±0.4 4.2±0.3 9.5±0.7 Modulus of compressibility/MPa 221±25 437±48 875±67

embodiment 3:

Fill calcium phosphate whisker skeleton with collagen protein, prepare macropore calcium phosphate whisker skeleton-collagen protein compound rest.The porosity of the porous BCP ceramics bracket that this example uses is 76% ± 3%, calcium phosphate whisker skeleton preparation method is with embodiment 2, difference is, replaces the BCP nano pulp vacuum filling HA whisker skeleton support in embodiment 1 with the collagen solution that concentration is 5mg/ml.The whisker skeleton of perfusion collagen protein is immersed in the glutaraldehyde water solution of 0.5%, collagen protein is occurred crosslinked, obtain macropore calcium phosphate whisker skeleton-collagen protein compound rest, its microstructure as shown in Figure 3, implant fill in hole wall whisker gap in, gained compound rest still has multistage intercommunicating pore structure, and porosity is still about 76%.Mechanical test results shows: HA whisker skeleton base collagen composite support (C3) is compared with the same batch of calcium phosphate porous support (A2) do not strengthened, comprcssive strength improves about 82%, reach 4.2 ± 0.2MPa, modulus of compressibility improves about 1 times, reaches 450 ± 67MPa.

embodiment 4

Changing the biphasic calcium phosphate in described step (1) into HA/ β-TCP respectively is in embodiment 1 1:9, 1:5, 3:5 and 4:6, all successfully obtain calcium phosphate whisker skeleton, and in the gap of described whisker, fill different implant (hydroxyapatite, bata-tricalcium phosphate, biphasic calcium phosphate, bio-vitric, polylactic acid, poly butyric, PEEK(polyether-ether-ketone), PEKK(polyether-ketone), at least one in collagen), obtain a series of compound rest, mechanical experimental results shows, adopt described calcium phosphate whisker skeleton can increase substantially the mechanical property of timbering material, and gained compound rest remains macro porosity led and multistage intercommunicating pore structure, there is good biological activity, be expected to for large scale knochenbruch defect repair.

Alternately, common porous ceramics preparation method, as the hydrogen peroxide foaming that microsphere occupy-place method or foam slip casting method etc. can replace the present invention to use, obtained porosity is 50% ~ 90%, macropore diameter: 200 ~ 800 microns, small aperture: a series of porous ceramicss of 50 ~ 100 microns, the porous calcium phosphate ceramic of preparation also can be obtained described calcium phosphate whisker skeleton through hydrothermal treatment consists, also can obtain after filling and there is good mechanical strength and bioactive compound rest, by weighing to the sample of filling front and back, obtaining described implant shared mass percent in compound rest is 10% ~ 50%.

Alternately, prepare in calcium phosphate whisker skeleton step in above-mentioned hydro-thermal method, adopt the salpeter solution of pH=4 or 5 respectively, pH is about the deionized water of 7, the sodium hydrate aqueous solution of pH=8 or 10 has all successfully prepared calcium phosphate whisker skeleton as the medium of hydro-thermal reaction, the size range of gained whisker is 2 ~ 100 μm long, and 100 ~ 1000nm is thick.

In addition, also investigate reaction temperature and time respectively according to the method for hydro-thermal reaction described in embodiment 1, result shows: at 100 ~ 200 DEG C, react 12h ~ 72h can successfully prepare calcium phosphate whisker skeleton, preferably at 120 ~ 180 DEG C, reacts 12h.

The foregoing is only the preferred embodiments of the present invention, is only illustrative for the purpose of the present invention, and nonrestrictive; Those of ordinary skill in the art understand, in the spirit and scope that the claims in the present invention limit, carry out many changes to it, amendment, and even equivalence is changed, but all will fall into protection scope of the present invention.

Claims (10)

1. a calcium phosphate whisker skeleton, is characterized in that, the main body of described skeleton is porous calcium phosphate ceramic, and the hole wall of described calcium phosphate ceramic is interconnected to constitute skeleton primarily of the whisker that submicron is thick.
2. calcium phosphate whisker skeleton according to claim 1, is characterized in that, described whisker size is: 2 ~ 100 μm long, and 100 ~ 1000nm is thick.
3. macropore calcium phosphate whisker skeleton according to claim 1, is characterized in that, described calcium phosphate whisker skeleton is the one in hydroxyapatite crystal whisker skeleton and biphasic calcium phosphate whisker skeleton.
4. a porous compound support frame for calcium phosphate whisker skeleton enhancing, is characterized in that, the implant comprising the calcium phosphate whisker skeleton in claim 1-3 described in any one and be filled in described whisker skeleton gap.
5. porous compound support frame according to claim 4, is characterized in that, consisting of according to mass percent: calcium phosphate whisker skeleton: 50% ~ 90%, implant: 50% ~ 10%.
6. porous compound support frame according to claim 4, it is characterized in that, described implant is the combination of one or more in hydroxyapatite, bata-tricalcium phosphate, biphasic calcium phosphate, bio-vitric, polylactic acid, poly butyric, PEEK, PEKK, collagen.
7. a preparation method for calcium phosphate whisker skeleton as claimed in claim 1, is characterized in that, comprise the following steps:
(1) porous calcium phosphate ceramic substrate holder material is immersed in aqueous solution, in airtight hydrothermal reaction kettle, carries out hydro-thermal reaction;
(2) naturally cool to room temperature, after washing, drying bracket, obtain calcium phosphate whisker skeleton.
8. preparation method according to claim 7, is characterized in that, described in described step (1), the pH value of aqueous solution is 4 ~ 10, and the temperature of described hydro-thermal reaction is 100 ~ 200 DEG C, and the response time is 12h ~ 72h.
9. preparation method according to claim 7, it is characterized in that, described porous calcium phosphate substrate holder is biophasic calcium phosphate ceramic (BCP) support, and the mass percent of its phase constituent composition is: hydroxyapatite (HA): bata-tricalcium phosphate (β-TCP)=1:9 ~ 4:6.
10. the preparation method of a porous compound support frame as claimed in claim 4, it is characterized in that, calcium phosphate whisker skeleton is prepared according to method described in claim 7, then under condition of negative pressure by the solution of implant or filled therewith in whisker skeleton gap, then carry out drying, solidification obtains porous compound support frame.
CN201410766951.XA 2014-12-15 2014-12-15 Calcium phosphate whisker frame and porous composite scaffold and their preparation methods CN105343935A (en)

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