CN108863332A

CN108863332A - A kind of three-dimensional porous calcium silicates bone bracket and preparation method thereof with micro-nano structure surface

Info

Publication number: CN108863332A
Application number: CN201810788500.4A
Authority: CN
Inventors: 冯佩; 帅词俊
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2018-07-18
Filing date: 2018-07-18
Publication date: 2018-11-23

Abstract

The invention discloses a kind of three-dimensional porous calcium silicates bone bracket and preparation method thereof with micro-nano structure surface.The three-dimensional porous calcium silicates bone bracket with micro-nano structure surface includes the CaSiO with three-dimensional porous structure₃Bone bracket and it is coated on the CaSiO₃The HAp nanometer layer with micro-nano structure of bone rack surface.The CaSiO that the present invention is prepared by selective laser sintering₃Bone bracket immerses in phosphate solution；By hydro-thermal reaction, that is, obtain the CaSiO with micro-nano structure surface₃Bone bracket.Prepared porous structure and surface micro-nano structure has scale, high specific surface area and attachment site abundant similar in the spatial channel interconnected and cell protein, can regenerate for the growth of the dependent interaction and tissue of cell and bracket and provide ideal microenvironment.Three-dimensional porous calcium silicates bone bracket prepared by the present invention with micro-nano structure surface has excellent biological property and degradation rate appropriate.

Description

A kind of three-dimensional porous calcium silicates bone bracket and its preparation with micro-nano structure surface Method

Technical field

The present invention relates to a kind of three-dimensional porous calcium silicates bone bracket and preparation method thereof with micro-nano structure surface, belongs to Bone bracket preparation technical field.

Background technique

Bone tissue engineering scaffold is not only that cell provides support, more to grow for cell and provide suitable external environment, to have Sticking, be proliferated and breaking up conducive to osteocyte, this requires brackets to possess the pore structure of analog skeleton.Selectivity swashs Light sintering technology can overcome micropore distribution in conventional stent preparation method, shape, space trend, connectivity etc. are uncontrollable to lack Point realizes the control to internal stent microcellular structure.Other than high porosity, interconnected microcellular structure, on hole wall One of an important factor for micro-nano structure surface is also influence bone tissue regeneration, micro-nano structure surface has high-specific surface area, can be Adsorbed bioactive molecule provides a variety of adsorption sites, promotes the interaction between cell tissue and bracket.

Calcium silicates (CaSiO₃) for bioceramic because of its biological degradability, bioactivity and absorbability are considered as that one kind has The timbering material of prospect.However, animal implantation experiment and external degradation experiment show that the degradability of calcium silicates ceramics material is too fast, It is difficult to the degradation rate of calcium silicates ceramics.

And hydroxyapatite (HAp), chemical formula Ca₁₀(PO₄)₆(OH)₂There is good biofacies in terms of biological characteristics Capacitive, it is consistent with human body hard tissue such as bone, tooth etc. on ingredient and structure, therefore when it is as implantation material implantation human body The growth of new bone may be guided, and close synostosis can be formed with bone tissue.The mechanical property of pure HAp ceramic material does not enable People is satisfied, such as brittleness is high, and bending strength and fracture toughness index are below artificial dense bone, thus it is negative in human body to limit it The application at the larger position of weight.

Summary of the invention

In view of the deficiencies of the prior art, it is an object of that present invention to provide a kind of three-dimensional porous silicon with micro-nano structure surface Sour calcium bone bracket and preparation method thereof.

To achieve the goals above, the present invention provides the following technical solution：

A kind of three-dimensional porous calcium silicates bone bracket with micro-nano structure surface, including with three-dimensional porous structure CaSiO₃Bone bracket and it is coated on the CaSiO₃The HAp nanometer layer with micro-nano structure of bone rack surface.

Preferred scheme, the HAp nanometer layer with a thickness of 1~8 μm.

As a further preference, the HAp nanometer layer with a thickness of 2~5 μm.

Preferred scheme, the HAp are nanometer chip architecture or nanorod structure.

Preferred scheme, the CaSiO of the three-dimensional porous structure₃Bone bracket is prepared by selective laser sintering.

In technical solution of the present invention, CaSiO is obtained using Selective Laser Sintering₃Bone bracket, selective laser are burnt Knot technology can overcome uncontrollable disadvantages such as micropore distribution in conventional stent preparation method, shape, space trend, connectivity, Realize the control to internal stent microcellular structure.

Preferred scheme, the CaSiO₃The HAp nanometer layer with micro-nano structure of bone rack surface is by CaSiO₃Bone bracket Utilize hydro-thermal reaction in-situ preparation in the liquid phase.

The present invention utilizes CaSiO₃The degradable formation silicon-rich layer of bone bracket adsorbs calcium ion and phosphate anion deposition, from And in the hydroxyapatite of rack surface inducing bioactivity (HAp) feature, by hydro-thermal reaction, quick in situ is formed in liquid phase HAp nanometer layer be coated on CaSiO₃It is uniform controllable to be formed by the HAp crystal grain with nanostructure for bone rack surface.

A kind of preparation method of the three-dimensional porous calcium silicates bone bracket with micro-nano structure surface, will pass through selective laser It is sintered the CaSiO of preparation₃Bone bracket immerses in phosphate solution；By hydro-thermal reaction, that is, obtaining has micro-nano structure surface CaSiO₃Bone bracket.

Preferred scheme, the phosphate are selected from sodium phosphate or sodium dihydrogen phosphate.

Inventors have found that phosphatic type is to the very big influence of HAp nanostructure is formed by, in sodium radio-phosphate,P-32 solution In, it is formed by as nano bar-shape HAp, the generation nano-sheet HAp in sodium dihydrogen phosphate, and it is molten in other phosphate The controllable nanostructure of rule can not be induced in liquid.

Preferred scheme, in the phosphate solution, phosphatic concentration is 0.15~0.25mol/L.

Inventors have found that phosphatic concentration has a certain impact to material tool, concentration is lower than obtained when 0.15mol/L HAp particle size distribution range is wide, and particle diameter distribution is uneven, and after concentration is higher than 0.25mol/L, the growth of HAp crystal grain does not almost have It changes.

Preferred scheme, the CaSiO₃The solid-liquid mass volume ratio of bone bracket and phosphate solution is

1:70~100 (g：ml).Solid-liquid mass volume ratio when too low HAp particle size distribution range obtained it is wide, partial size It is unevenly distributed.

Preferred scheme, the temperature of the hydro-thermal reaction are 180~200 DEG C.

Inventors have found that the temperature of hydro-thermal reaction has a certain impact to the pattern tool of the HAp nanometer layer of micro-nano structure, instead It answers temperature too low, is unfavorable for structure cell development and the particle growth of HAp crystal, the crystal property for generating HAp is inadequate, and reaction temperature When excessively high, HAp crystal undue growth, mechanical properties decrease.

Preferred scheme, time of the hydro-thermal reaction is 3~for 24 hours.

As a further preference, the time of the hydro-thermal reaction be 6~for 24 hours.

As it is further preferably, the time of the hydro-thermal reaction is 16~for 24 hours.

Preferred scheme, with CaSiO₃Biological ceramic powder is raw material, prepares CaSiO by selective laser sintering₃Bone branch Frame, the CaSiO₃The partial size of biological ceramic powder is 0.5~2 μm, purity >=99%.

As a further preference, the CaSiO₃First through being dried, the temperature of the drying is biological ceramic powder 60~80 DEG C, the dry time is 6~12h.

The technological parameter of preferred scheme, the selective laser sintering is：Laser power is 10~15W, scanning speed For 1.5~2.5mm/s, sweep span is 1.0~3.0mm, and spot diameter is 0.3~1mm.

In the present invention, it prepares by the way that selective laser sintering is controllable with three-dimensional porous calcium silicates skeleton, it can be with Overcome uncontrollable disadvantage such as the distribution of gained bone bracket micropore, shape, space trend, connectivity in the prior art.

A kind of preparation method of the three-dimensional porous calcium silicates bone bracket with micro-nano structure surface of the present invention, including following master Want step：

(1) according to the bone supporting structure at bone defect position, threedimensional model is designed.

(2) by CaSiO₃Biological ceramic powder dry 6~12h at 60~80 DEG C, it is quick to be then placed in laser for powder It is sintered layer by layer in formation system according to threedimensional model, after the completion of sintering, removes unsintered powder using compressed air, obtain Obtain three-dimensional porous CaSiO₃Bone bracket, main technologic parameters are：Laser power is 10~15W, and scanning speed is 1.5~2.5mm/ S, sweep span are 1.0~3.0mm, and spot diameter is 0.3~1mm.

(3) by three-dimensional porous CaSiO₃Bone bracket cleaned after in 50~80 DEG C of dry 6~12h, then will it is dry after Three-dimensional porous CaSiO₃Bone bracket is with 1：The solid-to-liquid ratio of 70~100g/mL is placed in 0.15~0.25mol/L phosphate solution, Reaction 3~for 24 hours is subsequently placed in hydrothermal reaction kettle at 180 DEG C~200 DEG C, i.e., in CaSiO₃Bone rack surface forms HAp and receives Rice layer；The CaSiO handled through hydro-thermal reaction₃Bone bracket is washed with distilled water at 3~6 times, 50~80 DEG C dry 6 after taking out~ 12h obtains the three-dimensional porous calcium silicates bone bracket with micro-nano structure surface.

The principle of the present invention and advantage：

The present invention utilizes calcium silicates bioceramic (CaSiO₃) degradable formation silicon-rich layer, adsorb calcium ion and phosphate radical from Son deposition, so that the principle of hydroxyapatite (HAp) formation in rack surface inducing bioactivity, utilizes the high temperature of hydro-thermal high Pressure, can promote calcium silicates ceramic surface and reaction media rapidly carries out ion exchange release calcium ion and provides calcium source, and prop up Frame surface forms elecrtonegativity silanol group and provides nucleation point for calcium phosphorus precipitation, so that quick in situ is generated by nanometer on entire bracket The micro-nano structure that structural hydroxyl apatite is constituted, and received by the conditional regulatory of control reaction media chemical composition and hydro-thermal reaction The structure of rice hydroxyapatite, thus the specific micrometer structure surface needed for obtaining.

The present invention preferably goes out two kinds of phosphate of sodium phosphate or sodium dihydrogen phosphate, under both solution systems and hydro-thermal The control down regulation of reaction condition induces the grain structure of generated HAp, to obtain the HAp nanometer of particular nanostructure Layer.

The present invention, which first uses selective laser sintering to obtain, has three-dimensional porous calcium silicates bone bracket, is then based on bionics Principle, by crystal growth, in three-dimensional porous CaSiO₃Bracket hole wall surface growth in situ nano HA p forms similar natural bone Interstitial space structure.The three-dimensional porous CaSiO with micro-nano structure surface of the method preparation according to the present invention₃Bone bracket A three-dimensional macro micro-structure and big specific surface area and many same comparable adsorption sites of cell protein size are provided, is thin The adherency and growth that born of the same parents' group is woven on bracket provide ideal interface environments.It is measured through MG-63 cell culture, prepared tool There is the porous support of micro-nano structure surface that can effectively facilitate adherency, extension, proliferation and the differentiation of cell, in Bone Defect Repari and bone tissue Regeneration field has important application value.

The present invention is realized using selective laser sintering technique to CaSiO₃The controllable preparation of bone internal stent porous structure； The present invention efficiently controls bracket hole wall surface HAp in hydro-thermal reaction treatment process, by control reaction media and reaction time Forming core growth, to obtain controllable micro-nano structure surface.

Preparation method of the invention is simple, and technique is controllable, and the biology of bracket is effectively raised using surface micro-nano structure Activity simultaneously slows down degradation rate.

Detailed description of the invention

The bracket of Fig. 1 is the whole shape appearance figure of the porous support without hydro-thermal reaction processing in comparative example 1.

Fig. 2 be bracket micro-nano structure surface shape appearance figure, wherein Fig. 2 (a) be it is laser sintered after without hydro-thermal reaction processing Porous scaffold surface shape appearance figure, Fig. 2 (b) be embodiment 1 in gained porous scaffold surface shape appearance figure, Fig. 2 (c) be embodiment 2 The surface topography map of middle gained porous support

Fig. 3 is the micro-nano structure surface and cross-section morphology figure that embodiment 1 obtains, wherein Fig. 3 (a), and Fig. 3 (b) is to amplify not With the micro-nano structure surface of multiple, Fig. 3 (c) is micro-nano structure section.

Fig. 4 is the micro-nano structure surface and cross-section morphology figure that embodiment 2 obtains, wherein Fig. 4 (a), and Fig. 4 (b) is to amplify not With the micro-nano structure surface of multiple, Fig. 4 (c) is micro-nano structure section.

Fig. 5 is that micro-nano structure obtained by different time hydro-thermal reaction shows shape appearance figure.Wherein Fig. 5 (a1) is with Na₃PO₄It is water-soluble Micro-nano structure surface pattern of the liquid as the resulting porous support of material liquid hydro-thermal process 6h；Fig. 5 (b1) is with Na₃PO₄Aqueous solution Micro-nano structure surface pattern as the resulting porous support of material liquid hydro-thermal process 16h；Fig. 5 (c1) for the institute of embodiment 1 much The micro-nano structure surface pattern of hole bracket；Fig. 5 (d1) is with NaH₂PO₄Aqueous solution is resulting more as material liquid hydro-thermal process 6h The micro-nano structure surface pattern of hole bracket, Fig. 5 (e1) are with NaH₂PO₄Aqueous solution is resulting more as material liquid hydro-thermal process 16h The micro-nano structure surface pattern of hole bracket, Fig. 5 (f1) are the micro-nano structure surface pattern of 2 gained porous support of embodiment.

Fig. 6 is 1 porous scaffold surface shape appearance figure of comparative example, wherein Fig. 6 (a), and Fig. 6 (b) is the micro-nano for amplifying different multiples Body structure surface, Fig. 6 (c) are micro-nano structure section.

Fig. 7 is adherency, proliferation and differentiation situation map of the cell on bracket.

Fig. 8 is adherency, proliferation and differentiation situation map of the cell on bracket.

Specific embodiment

Embodiments of the present invention are further described combined with specific embodiments below, but the content of the present invention not office It is limited to this.

Embodiment 1

1) porous structure and individuation configuration design are carried out to compound rest using SolidWorks Three-dimensional Design Software, it will Designed three-dimensional data model imports computer and carries out hierarchy slicing processing, obtains each layer of section profile information.

2) weighing particle size respectively using electronic balance is 1 μm, and the calcium silicates powder 50g that fusing point is 1540 DEG C is in electric heating Dry in air dry oven, main technologic parameters are：Drying temperature is 80 DEG C, soaking time 12h.

3) mixed-powder after drying is placed in selective laser sintering system and is sintered experiment, computer is according to boundary Facial contour information is selectively sintered dusty material progress layer by layer, after the completion of sintering, is removed using compressed air un-sintered Powder, the 3D solid of artificial bone needed for being formed, main technologic parameters are：Main technologic parameters are：Laser power is 12W, Scanning speed is 2.0mm/s, sweep span 2.0mm, spot diameter 0.8mm.

4) cleaning 3 times is carried out to above-mentioned bracket with dehydrated alcohol and distilled water, with 80 DEG C of dry 12h in drying box.

By the bracket after drying with 1：The solid-to-liquid ratio of 85g/mL is placed in 0.2M Na3PO4 aqueous solution, is subsequently placed in 100mL Hydrothermal reaction kettle in heated 24 hours at 180 DEG C, rack surface generate nano bar-shape HAp.

5) it is cooled to room temperature taking-up bracket after hydro-thermal process and is washed with distilled water at 4 times, 80 DEG C dry 12h, is had The porous support of nano bar-shape body structure surface.

The surface topography map of the obtained porous support of the present embodiment, as shown in Fig. 2 (b).

Micro-nano structure surface and cross-section morphology obtained are as shown in Figure 3：Wherein Fig. 3 (a), Fig. 3 (b) are different times of amplification Several micro-nano structure surfaces, Fig. 3 (c) are micro-nano structure section.From figure 3, it can be seen that bracket is complete by the HAp of nano bar-shape Covering, these HAp nanometer rods average diameters are 50nm, average length is 1.5 μm, and the average thickness of nanometer layer is 2 μm.It can see The particle size of HAp is micro-nano out, and being formed by surface is micro-nano structure surface.

6) it is found through MG-63 cell culture experiments, as shown in Figure 7, Figure 8, compared to the compound rest of non-hydrothermal treatment, Na₃PO₄Bracket cell adherence in solution after hydro-thermal process it is more, sprawl wider, cell activity improves 0.5-1 times, ALP activity is also more significant, presents better cell adherence, extension, proliferation and differentiation performance.

7) it is found through PBS Soak Test, the scaffold degradation rate in the present embodiment 1 with nano bar-shape body structure surface is three Week degradation 13%.

8) it is found through Mechanics Performance Testing, the compressive strength of the bracket in the present embodiment 1 is 20.94Mpa, fracture toughness is 1.23MPa·m^1/2, show good mechanical property.

Embodiment 2

3) mixed-powder after drying is placed in selective laser sintering system and is sintered experiment, computer is according to boundary Facial contour information is selectively sintered dusty material progress layer by layer, after the completion of sintering, is removed using compressed air un-sintered Powder, the 3D solid of artificial bone needed for being formed, main technologic parameters are：Laser power is 12W, scanning speed 2.0mm/ S, sweep span 2.0mm, spot diameter 0.8mm.

By the bracket after drying with 1：The solid-to-liquid ratio of 85g/mL is placed in 0.2M NaH2PO4 aqueous solution, is subsequently placed in It is heated 24 hours at 180 DEG C in the hydrothermal reaction kettle of 100mL, generates the HAp of nano-sheet in rack surface.

In the present embodiment 2 shown in the surface topography map of obtained porous support such as Fig. 2 (c).

Micro-nano structure surface and cross-section morphology obtained are as shown in Figure 4：Wherein Fig. 4 (a), Fig. 4 (b) are different times of amplification Several micro-nano structure surfaces, Fig. 4 (c) are micro-nano structure section.From figure 3, it can be seen that bracket is by nano-sheet in embodiment 2 HAp be completely covered, up to 20 μm, the thickness of nanometer layer is about 5 μm for HAp nanometer sheet thickness 100nm, 3 μm of width, length.Due to The particle size that this HAP is is micro-nano, so the surface formed is micro-nano structure surface.

6) it is found as shown in Figure 7, Figure 8 through MG-63 cell culture experiments, compared to the compound rest of non-hydrothermal treatment, NaH₂Bracket cell adherence in PO4 solution after hydro-thermal process it is more, sprawl wider, cell activity improves 0.5-1 times, ALP activity is also more significant, presents better cell adherence, extension, proliferation and differentiation performance.

7) it is found through PBS Soak Test, scaffold degradation rate three weeks in the present embodiment 2 with flaky nanometer structure surface Degradation 11%.

8) it is found through Mechanics Performance Testing, the compressive strength of the bracket in the present embodiment 2 is 21.11Mpa, fracture toughness is 1.21MPa·m^1/2, show good mechanical property.

Embodiment 3

By the bracket after drying with 1：The solid-to-liquid ratio of 85g/mL is placed in 0.2M Na3PO4 aqueous solution, is subsequently placed in 100mL Hydrothermal reaction kettle in heated 16 hours at 180 DEG C, rack surface generate nano bar-shape HAp.

Bracket is completely covered by the HAp of nano bar-shape, these HAp nanometer diameter 52nm, draw ratio 13, it can be seen that HAp Particle size be micro-nano, be formed by surface be micro-nano structure surface.

6) it is found through PBS Soak Test, scaffold degradation rate three weeks in the present embodiment 3 with nano bar-shape body structure surface Degradation 13.8%.

7) it is found through Mechanics Performance Testing, the compressive strength of the bracket in the present embodiment 3 is 20.78Mpa, fracture toughness is 1.20MPa·m^1/2, show good mechanical property.

Embodiment 4

The embodiment mainly studies influence of the different hydro-thermal times to micro-nano structure pattern, the other conditions in the present embodiment It is identical as in embodiment 1 or embodiment 2, the time of hydro-thermal reaction is only respectively set as 6h and 16h.Gained porous support Micro-nano structure surface pattern SEM figure is as shown in figure 5, wherein Fig. 5 (a1) is with Na₃PO₄Aqueous solution is as material liquid hydro-thermal process 6h The micro-nano structure surface pattern of resulting porous support, as can be seen from Figure in Na₃PO₄In solution after hydro-thermal process 6h, bracket table Face generates the nano bar-shape HAp of diameter about 20-70nm, and the average diameter of these HAp nanometer rods is 43nm.

Wherein Fig. 5 (b1) is using Na3PO4 aqueous solution as the micro-nano of the resulting porous support of material liquid hydro-thermal process 16h Body structure surface pattern, the extension reaction time significantly stretches to 16h, these nano bar-shapes HAp along long axis direction as can be seen from Figure It is long, and there was only slight increase (diameter 52nm, draw ratio 13) in diametrical direction size.

Wherein Fig. 5 (d1) is using NaH2PO4 aqueous solution as the micro-nano of the resulting porous support of material liquid hydro-thermal process 6h Body structure surface pattern, generates the HAp of a large amount of irregular nanometer thin sheet as can be seen from Figure on rack surface, they put down Equal diameter has reached 0.76 μm.

Wherein Fig. 5 (e1) is using NaH2PO4 aqueous solution as the micro-nano of the resulting porous support of material liquid hydro-thermal process 16h Body structure surface pattern, these laminar HAp further growths become width up to 1.3 μm of length-width ratios up to 5 as can be seen from Figure Flaky nanometer structure.

Comparative example 1

4) cleaning 3 times is carried out to above-mentioned bracket with dehydrated alcohol and distilled water, with 80 DEG C of dry 12h in drying box.Branch Frame surface and cross-section morphology are illustrated in fig. 6 shown below, wherein Fig. 6 (a), and Fig. 6 (b) is the surface topography for amplifying different multiples, Fig. 6 (c) For structure section.

5) it tests and finds through immersion in vitro, bracket fast degradation in PBS solution.

6) through the discovery of MG-63 cell culture experiments as shown in Figure 7, Figure 8, cell can rack surface normally adhere to Proliferation.

7) it is found through Mechanics Performance Testing, the compressive strength of the bracket in this comparative example 1 is 20.62Mpa, fracture toughness is 1.16MPa·m^1/2。

Comparative example 2

Other conditions are same as Example 1, only Na₃PO₄The concentration of aqueous solution is 0.1mol/L, finds obtained HAp Grain particle size distribution is wide, and particle diameter distribution is uneven.

It is found through MG-63 cell culture experiments, relative to embodiment 1, the much less of cell adherence, cell in comparative example 2 Activity improves the bracket for being only slightly higher than non-hydrothermal treatment.

It is found through PBS Soak Test, scaffold degradation rate three weeks in this comparative example 2 with nano bar-shape body structure surface drop Solution 15.2%.

It is found through Mechanics Performance Testing, the compressive strength of the bracket in this comparative example 2 is 20.71Mpa, fracture toughness is 1.19MPa·m^1/2。

Comparative example 3

Other conditions are same as Example 2, only by the bracket after drying with 1：The solid-to-liquid ratio of 85g/mL is placed in 0.2M It in NaH2PO4 aqueous solution, is subsequently placed in the hydrothermal reaction kettle of 100mL and is heated 24 hours at 220 DEG C, generated in rack surface The HAp of nano-sheet.

Up to 76 μm, the thickness of nanometer layer is about for the formed HAp nanometer sheet thickness 750nm of comparative example 3,8.2 μm of width, length 8.6μm.It was found that HAP rapid growth of crystal, mechanical property declines instead when excessively high due to reaction temperature.

It is found through MG-63 cell culture experiments, relative to embodiment 2, the much less of cell adherence, cell in comparative example 3 Activity improves the bracket for being only slightly higher than non-hydrothermal treatment.

It is found through PBS Soak Test, scaffold degradation rate three weeks in this comparative example 3 with nano bar-shape body structure surface drop Solution 8.4%.

It is found through Mechanics Performance Testing, the compressive strength of the bracket in this comparative example 3 is 20.19Mpa, fracture toughness is 1.14MPa·m^1/2。

Claims

1. a kind of three-dimensional porous calcium silicates bone bracket with micro-nano structure surface, it is characterised in that：Including with three-dimensional porous The CaSiO of structure₃Bone bracket and it is coated on the CaSiO₃The HAp nanometer layer with micro-nano structure of bone rack surface.

2. a kind of three-dimensional porous calcium silicates bone bracket with micro-nano structure surface according to claim 1, feature exist In：

The HAp nanometer layer with a thickness of 1~8 μm.

3. a kind of three-dimensional porous calcium silicates bone bracket with micro-nano structure surface according to claim 1, feature exist In：

The HAp is nanometer chip architecture or nanorod structure.

4. preparing a kind of three-dimensional porous calcium silicates bone branch with micro-nano structure surface as claimed in any one of claims 1-3 The method of frame, it is characterised in that：The CaSiO that will be prepared by selective laser sintering₃Bone bracket immerses in phosphate solution；It is logical Hydro-thermal reaction is crossed, that is, obtains the CaSiO with micro-nano structure surface₃Bone bracket.

5. a kind of preparation side of three-dimensional porous calcium silicates bone bracket with micro-nano structure surface according to claim 4 Method, it is characterised in that：

The phosphate is selected from sodium phosphate or sodium dihydrogen phosphate.

6. a kind of preparation side of three-dimensional porous calcium silicates bone bracket with micro-nano structure surface according to claim 4 Method, it is characterised in that：

In the phosphate solution, phosphatic concentration is 0.15~0.25mol/L.

7. a kind of preparation side of three-dimensional porous calcium silicates bone bracket with micro-nano structure surface according to claim 4 Method, it is characterised in that：

The CaSiO₃The solid-liquid mass volume ratio of bone bracket and phosphate solution is 1:70~100 (g：ml).

8. a kind of preparation side of three-dimensional porous calcium silicates bone bracket with micro-nano structure surface according to claim 4 Method, it is characterised in that：

The temperature of the hydro-thermal reaction is 180~200 DEG C, time of the hydro-thermal reaction is 3~for 24 hours.

9. a kind of preparation side of three-dimensional porous calcium silicates bone bracket with micro-nano structure surface according to claim 4 Method, it is characterised in that：

With CaSiO₃Biological ceramic powder is raw material, prepares CaSiO by selective laser sintering₃Bone bracket, the CaSiO₃It is raw The partial size of object ceramic powders is 0.5~2 μm, purity >=99%.

10. a kind of preparation of the three-dimensional porous calcium silicates bone bracket with micro-nano structure surface according to claim 4 or 9 Method, it is characterised in that：

The technological parameter of the selective laser sintering is：Laser power is 10~15W, and scanning speed is 1.5~2.5mm/s, Sweep span is 1.0~3.0mm, and spot diameter is 0.3~1mm.