CN103861153B - Preparation method of carbon nanofiber composite Beta-calcium phosphate with three-dimensional net structure - Google Patents
Preparation method of carbon nanofiber composite Beta-calcium phosphate with three-dimensional net structure Download PDFInfo
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Abstract
The invention discloses a preparation method of carbon nanofiber composite Beta-calcium phosphate with a three-dimensional net structure, relating to a biomaterial preparation technology. The preparation method comprises the following steps: purifying bacterial cellulose, putting the purified bacterial cellulose into a calcium nitrate solution, stirring, slowly adding a diammonium phosphate solution, controlling the pH value of the system, aging for 12-24 hours after the reaction is finished, carrying out freeze-drying, and then heating the dried material in an atmosphere furnace, and finally cooling to obtain the composite material having a three-dimensional net structure and Beta-calcium nitrate being uniformly distributed on carbon. The preparation method is simple and feasible and convenient to operate; the carbon nanofiber functionalized by Beta-calcium nitrate is good in biocompatibility, has certain biological activity and osteoconduction and favorable biomechanical property and can be applied to the biomedical field as a bone tissue repair material.
Description
Technical field
The present invention relates to technical field of biological material, refers to a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure especially.
Background technology
Carbon fiber is the carbon fibre that organic fiber obtains after carbonization treatment, there is hot strength and the stretch modulus of superelevation, stable chemical property, high-caliber corrosion resistance, in addition, carbon fiber also have, specific heat good without creep, fatigue durability and electric conductivity between nonmetal and metal, the feature such as thermal coefficient of expansion is little, X-ray transparent is good.Along with the development of science and technology, the application of carbon fiber grows with each passing day, they also can be used on the aspects such as stationery sports goods, textile machine, medical apparatus and instruments, biological engineering, construction material, chemical machinery, haulage vehicle except being widely used in the high-tech sectors such as Aero-Space.
Carbon nano-fiber refers to the carbon fiber with nanoscale, many performance basis of carbon fiber add nano effect, carbon nano-fiber is had characteristics such as high-strength light, heat conductivity are good, high conductivity, can be expected to be applied to high-capacity electrode material, high-performance composite materials, the contour performance products of bio-medical material.Particularly, the mechanical property that carbon nano-fiber is good, chemical stability, high-specific surface area can combine with the biomaterial with hydrophilic radical and be applied to bio-medical field.Research shows, carbon nano-fiber can promote Oesteoblast growth, be lowered into fibrocellular sticking simultaneously, in order to strengthen the compatibility of carbon nano-fiber and osseous tissue, reducing embedded material because of the damage around exercise upon bone tissue, is a kind of very effective method by bioactive materials and carbon nano-fiber compound.
The natural inorganic that beta-calcium phosphate (β-TCP) is similar to people's bone is formed, there is the biocompatibility being better than other inorganic material, engage well with body bone after implanting, bone conductibility is good, beta-calcium phosphate can progressively be degraded in vivo, and the calcium of degraded generation, phosphonium ion can be absorbed by the body, and contribute to the formation of new bone.Therefore, beta-calcium phosphate is a kind of desirable osseous tissue renovating material, the existing two dimension of repair materials of current osseous tissue builds and develops into 3 D stereo structure, beta-calcium phosphate is prepared into three-dimensional stent material and contributes to the growth of osteocyte, amplification the growth microenvironment of analogue body inner tissue cell, and be conducive to the transmission of nutritional labeling.But the preparation of beta-calcium phosphate is mainly based on Powdered, machine-shaping artifact mechanical strength is not good, and fragility is comparatively large, is not easily shaped, is difficult to the reparation at osseous tissue load position.
In sum, beta-calcium phosphate and carbon nano-fiber compound are prepared into biocompatibility, biological activity that the composite with three-dimensional net structure effectively can improve carbon nano-fiber, and strengthen the mechanical property of beta-calcium phosphate, be expected to become a kind of desirable osseous tissue renovating material.The main method preparing carbon nano-fiber at present has chemical vapour deposition, polymer blending melt spinning method and method of electrostatic spinning.These methods prepare the very complicated equipment that nanofiber often needs, and set loaded down with trivial details preparation parameter, and the nanofiber of preparation only has one dimension or two-dimensional structure, cannot form the complicated nanofiber with three-dimensional network.Bacterial cellulose is a kind of natural biopolymer, has hyperfine network structure, is combined into the thick fibre bundle of 40 ~ 60 nanometers by the fento of diameter 3 ~ 4 nanometer, and is intertwined to form flourishing hyperfine network structure.The characteristic of the high-purity of Bacterial cellulose, high-crystallinity, high polymerization degree and numberator height orientation, makes it have the primary condition becoming carbon nano-fiber presoma.
This patent adopts liquid-phase precipitation method to utilize bacterial cellulose three-dimensional network to prepare nano tricalcium phosphate powder body, through the Bacterial cellulose of special handling as the presoma of carbon nano-fiber, through high-temperature heating treatment, the carbon fiber finally obtaining having three-dimensional net structure is uniformly distributed the composite of beta-calcium phosphate.Improve the biocompatibility of carbon nano-fiber, biological activity, and strengthen the mechanical property of beta-calcium phosphate.Preparation is simple in the present invention, easy to operate, obtain by the carbon nano-fiber of beta-calcium phosphate functionalization, and there is good space three-dimensional network structure, good biocompatibility, have certain biological activity and bone conductibility, biomechanical property well can be used as osseous tissue renovating material and is applied to bio-medical field.
Summary of the invention
The object of this invention is to provide a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure.Relate to a kind of biomaterial technology of preparing.Preparation is simple in the present invention, easy to operate, obtain by the carbon nano-fiber material of beta-calcium phosphate functionalization and there is good space three-dimensional network structure, improve the biocompatibility of carbon nano-fiber, biological activity, and enhance the mechanical property of beta-calcium phosphate, bio-medical field can be applied to as a kind of high-strength osseous tissue renovating material with bone conductibility.
The invention discloses a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure, comprise: Bacterial cellulose purification process is put into calcium nitrate solution and stirred, slowly add ammonium dibasic phosphate solution and hierarchy of control pH value, ageing 12 ~ 24h after completion of the reaction, lyophilization, then dried material is put into atmosphere furnace heating, after cooling, obtain the composite of uniform load beta-calcium phosphate on a kind of carbon fiber with three-dimensional net structure.
As preferred technical scheme:
Wherein, a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as above, described purification process refers to, Bacterial cellulose through the sodium hydrate aqueous solution high temperature steaming 0.5 ~ 1h of 5 ~ 10wt%, and by washed with de-ionized water to neutral.In the Bacterial cellulose raw material of bacterial fermentation, have a large amount of antibacterial Remained mass, material is formed local defect by these residues in heating (carbonization, graphitization) process, has a strong impact on mechanical property and the three-dimensional net structure of the carbon nano-fiber obtained.Sodium hydroxide solution steaming and decocting thoroughly can be removed tropina and be sticked to the residual media on cellulose membrane, ensures the cellulose high-purity of bacteria cellulose material.Sodium hydroxide solution process simultaneously can effectively activate oh groups a large amount of on Bacterial cellulose nanofiber, contributes to calcium ion uniform deposition on Bacterial cellulose nanofiber time prepared by tricalcium phosphate powder body liquid phase.
A kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as above, described calcium nitrate solution refers to the calcium nitrate aqueous solution of 0.6 ~ 1mol/L, described ammonium dibasic phosphate solution refers to the ammonium dibasic phosphate aqueous solution of 0.4 ~ 0.6mol/L, and in system, the rate of charge of calcium ion and phosphate anion is 1:1.5.Lime nitrate and diammonium phosphate react and can generate flocculence amorphous state tricalcium phosphate and precipitate, and in course of reaction, first calcium ion interacts with the hydroxyl on Bacterial cellulose nanofiber, is evenly distributed on nanofiber by electrostatic force; Then react with diammonium phosphate gradually and generate nanometer amorphous tricalcium phosphate granule under the template action of nanofiber network.
A kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as above, described slowly adding refers to that ammonium dibasic phosphate solution drips with the speed of 1 ~ 5ml/min, and described hierarchy of control pH value refers to that the pH value with ammonia controls system in whole course of reaction is 9.7 ~ 10.3.
Have a preparation method for the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as above, described lyophilization refers to the freezing 12 ~ 24h at-20 DEG C ~-80 DEG C of the Bacterial cellulose after by purification process, then vacuum drying 24 ~ 48h.Lyophilization object is three-dimensional network microstructure when maintaining Bacterial cellulose hygrometric state.
A kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as above; described heating is that material is under vacuum, argon or nitrogen protection; by room temperature to 850 DEG C ~ 1100 DEG C; wherein 100 ~ 300 DEG C of interval heating rates are 1 ~ 3 DEG C/min; 300 ~ 500 DEG C of interval heating rates are 3 ~ 5 DEG C/min; 500 ~ 800 DEG C of interval heating rates are 5 ~ 7 DEG C/min, and 800 DEG C ~ 1100 DEG C interval heating rates are 10 DEG C/min, and are incubated 1 ~ 2h.In this patent, calefactive interzone is divided into four sections of controls, 100 ~ 300 DEG C of intervals are mainly Bacterial cellulose and lose physical absorption water, hydrogen bonded water and intermolecular hydrogen bonding, intramolecular hydrogen bond fracture decomposition; Simultaneously to the amorphous state tricalcium phosphate particle high-temperature calcination processing being deposited in Bacterial cellulose nanofiber surface, make tricalcium phosphate granule by amorphous state to crystalline state.300 ~ 500 DEG C of intervals are mainly the fracture of Bacterial cellulose carbochain and decompose, and generate a small amount of volatilization gas.These two calefactive interzones are keys of material carbonisation, and in Bacterial cellulose carbonisation, quality can significantly reduce, and volume can along with contraction.In the meantime in order to maintain the original three-dimensional net structure of Bacterial cellulose, strictly must control the heating rate of carbonisation, preventing the too fast network structure that causes of heating rate from subsiding.500 ~ 800 DEG C of interval Bacterial cellulose carbonizations complete; Tricalcium phosphate starts to be changed to beta-calcium phosphate by apatite.800 DEG C ~ 1100 DEG C intervals, the bacteria cellulose fibre after carbonization carries out graphitization; Tricalcium phosphate becomes beta-calcium phosphate completely mutually, and makes lattice structure be tending towards complete through insulation.
Have a preparation method for the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as above, described cooling refers to that the material after terminating that heats up slowly cools to room temperature in atmosphere furnace.
A kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as above, described composite refers to that the carbon nano-fiber diameter with three-dimensional network space structure is about 10 ~ 30nm, fiber is evenly distributed with beta-calcium phosphate crystal.
Another object of the present invention is to provide a kind of carbon nano-fiber compound beta-calcium phosphate with three-dimensional net structure, it is characterized in that: comprise Bacterial cellulose and beta-calcium phosphate.
Compared with prior art, the invention has the beneficial effects as follows:
This patent adopts liquid-phase precipitation method to utilize bacterial cellulose three-dimensional network to prepare nano tricalcium phosphate powder body, through the Bacterial cellulose of special handling as the presoma of carbon nano-fiber, through high-temperature heating treatment, the carbon fiber finally obtaining having three-dimensional net structure is uniformly distributed the composite of beta-calcium phosphate.In preparation process, maintain the original three-dimensional network space structure of Bacterial cellulose to greatest extent, fibers carbonization process, graphitization processing and calcium phosphate are calcined and are carried out simultaneously; Control fast, efficiently to prepare the controlled beta-calcium phosphate/Carbon Nanofibers/Epoxy Resin Composite Materials of crystalline phase by rational temperature.Improve the biocompatibility of carbon nano-fiber, biological activity, and enhance the mechanical property of beta-calcium phosphate.Preparation is simple in the present invention, easy to operate, obtain by the carbon nano-fiber of beta-calcium phosphate functionalization and there is good space three-dimensional network structure, good biocompatibility, there are certain biological activity and bone conductibility, biomechanical property is good, can be used as osseous tissue renovating material and is applied to bio-medical field.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1:
Bacterial cellulose is placed in the sodium hydrate aqueous solution high temperature steaming 1h of 10wt%, and by washed with de-ionized water to neutral.The calcium nitrate aqueous solution that 0.6mol/L put into by material after purification process stirs, slowly be added dropwise to 0.4mol/L ammonium dibasic phosphate aqueous solution with the speed of 5ml/min and the pH value controlling system in whole course of reaction with ammonia is 10.3, the rate of charge of calcium ion and phosphate anion is 1:1.5.Ageing 24h after completion of the reaction.
Reacted material is freezing 24h at-80 DEG C, then vacuum drying 24h.Then material is put into atmosphere furnace and be heated to 850 DEG C by room temperature under nitrogen protection; wherein 100 ~ 300 DEG C of interval heating rates are 1 DEG C/min; 300 ~ 500 DEG C of interval heating rates are 3 DEG C/min; 500 ~ 800 DEG C of interval heating rates are 5 DEG C/min; 800 DEG C ~ 850 DEG C interval heating rates are 10 DEG C/min, and are incubated 2h.Heat up and terminate rear material and in atmosphere furnace, slowly cool to the carbon nano-fiber diameter that room temperature obtains having three-dimensional network space structure be about 10nm, fiber is evenly distributed with beta-calcium phosphate crystal.
Embodiment 2:
Bacterial cellulose is placed in the sodium hydrate aqueous solution high temperature steaming 1h of 5wt%, and by washed with de-ionized water to neutral.The calcium nitrate aqueous solution that 0.75mol/L put into by material after purification process stirs, slowly be added dropwise to 0.5mol/L ammonium dibasic phosphate aqueous solution with the speed of 2ml/min and the pH value controlling system in whole course of reaction with ammonia is 10.0, the rate of charge of calcium ion and phosphate anion is 1:1.5.Ageing 18h after completion of the reaction.
Reacted material is freezing 24h at-20 DEG C, then vacuum drying 24h.Then material is put into atmosphere furnace and be heated to 900 DEG C by room temperature under vacuo, wherein 100 ~ 300 DEG C of interval heating rates are 2 DEG C/min, 300 ~ 500 DEG C of interval heating rates are 4 DEG C/min, 500 ~ 800 DEG C of interval heating rates are 6 DEG C/min, 800 DEG C ~ 900 DEG C interval heating rates are 10 DEG C/min, and are incubated 2h.Heat up and terminate rear material and in atmosphere furnace, slowly cool to the carbon nano-fiber diameter that room temperature obtains having three-dimensional network space structure be about 30nm, fiber is evenly distributed with beta-calcium phosphate crystal.
Embodiment 3:
Bacterial cellulose is placed in the sodium hydrate aqueous solution high temperature steaming 0.6h of 6wt%, and by washed with de-ionized water to neutral.The calcium nitrate aqueous solution that 0.9mol/L put into by material after purification process stirs, slowly be added dropwise to 0.6mol/L ammonium dibasic phosphate aqueous solution with the speed of 3ml/min and the pH value controlling system in whole course of reaction with ammonia is 10.1, the rate of charge of calcium ion and phosphate anion is 1:1.5.Ageing 16h after completion of the reaction.
Reacted material is freezing 12h at-30 DEG C, then vacuum drying 48h.Then material is put into atmosphere furnace and be heated to 1000 DEG C by room temperature under vacuo, wherein 100 ~ 300 DEG C of interval heating rates are 3 DEG C/min, 300 ~ 500 DEG C of interval heating rates are 5 DEG C/min, 500 ~ 800 DEG C of interval heating rates are 7 DEG C/min, 800 DEG C ~ 1000 DEG C interval heating rates are 10 DEG C/min, and are incubated 1h.Heat up and terminate rear material and in atmosphere furnace, slowly cool to the carbon nano-fiber diameter that room temperature obtains having three-dimensional network space structure be about 20nm, fiber is evenly distributed with beta-calcium phosphate crystal.
Embodiment 4:
Bacterial cellulose is placed in the sodium hydrate aqueous solution high temperature steaming 0.8h of 7wt%, and by washed with de-ionized water to neutral.The calcium nitrate aqueous solution that 0.75mol/L put into by material after purification process stirs, slowly be added dropwise to 0.5mol/L ammonium dibasic phosphate aqueous solution with the speed of 4ml/min and the pH value controlling system in whole course of reaction with ammonia is 9.7, the rate of charge of calcium ion and phosphate anion is 1:1.5.Ageing 12h after completion of the reaction.
Reacted material is freezing 24h at-40 DEG C, then vacuum drying 24h.Then material is put into atmosphere furnace and be heated to 1100 DEG C by room temperature under nitrogen protection; wherein 100 ~ 300 DEG C of interval heating rates are 1 DEG C/min; 300 ~ 500 DEG C of interval heating rates are 5 DEG C/min; 500 ~ 800 DEG C of interval heating rates are 6 DEG C/min; 800 DEG C ~ 1100 DEG C interval heating rates are 10 DEG C/min, and are incubated 1h.Heat up and terminate rear material and in atmosphere furnace, slowly cool to the carbon nano-fiber diameter that room temperature obtains having three-dimensional network space structure be about 10nm, fiber is evenly distributed with beta-calcium phosphate crystal.
Embodiment 5:
Bacterial cellulose is placed in the sodium hydrate aqueous solution high temperature steaming 0.5h of 10wt%, and by washed with de-ionized water to neutral.The calcium nitrate aqueous solution that 0.6mol/L put into by material after purification process stirs, slowly be added dropwise to 0.4mol/L ammonium dibasic phosphate aqueous solution with the speed of 5ml/min and the pH value controlling system in whole course of reaction with ammonia is 9.8, the rate of charge of calcium ion and phosphate anion is 1:1.5.Ageing 24h after completion of the reaction.
Reacted material is freezing 12h at-80 DEG C, then vacuum drying 48h.Then material is put into atmosphere furnace and be heated to 1050 DEG C by room temperature under nitrogen protection; wherein 100 ~ 300 DEG C of interval heating rates are 3 DEG C/min; 300 ~ 500 DEG C of interval heating rates are 3 DEG C/min; 500 ~ 800 DEG C of interval heating rates are 7 DEG C/min; 800 DEG C ~ 1050 DEG C interval heating rates are 10 DEG C/min, and are incubated 2h.Heat up and terminate rear material and in atmosphere furnace, slowly cool to the carbon nano-fiber diameter that room temperature obtains having three-dimensional network space structure be about 10nm, fiber is evenly distributed with beta-calcium phosphate crystal.
Embodiment 6:
The carbon nano-fiber compound beta-calcium phosphate of the three-dimensional net structure prepared by embodiment 1-5 is processed into that thickness is 3mm, diameter is the disk of 4mm, through the ethanol of 75% (v/v) and ultraviolet radiation to after carrying out sterilization treatment, be placed in 96 orifice plates, soak 4h with DMEM culture fluid, after removing culture fluid, in every hole, plant 5 × 10
4individual Human osteoblast-like cell MG-63 cell, be placed in 37 DEG C, saturated humidity, 5%CO
2incubator in hatch 8h, supplemented medium after cell attachment, proceed cultivate, every day changes fresh medium.What another use one group was normally cultivated compares, and cultivates under the same terms.Cultivate after 1,3 and 5 day, remove culture fluid, fix 1h, then carry out processed with gradient concentration ethanol with after phosphate buffer drip washing with 2.5% (v/v) glutaraldehyde, room temperature in vacuo dry two days or lyophilizing, for electron microscopic observation.Cultivate the cell proliferative conditions (mtt assay measures OD value at 570nm) of 1,3 and 5 day in table 1.As shown in Table 1, MG-63 cell well-grown on the material, in cultivation after the 3rd day, proliferate is more obvious, this shows the carbon nano-fiber compound beta-calcium phosphate energy sustenticular cell growth of three-dimensional net structure of the present invention and promotes cell proliferation, there are good biocompatibility and biological activity, can be used as osseous tissue renovating material and be applied to bio-medical field.
The cell proliferation experiment (n=8) of table 1 carbon nano-fiber compound beta-calcium phosphate
| Cultivated days | Matched group | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| 1 | 0.13±0.02 | 0.15±0.03 | 0.14±0.04 | 0.15±0.02 | 0.14±0.01 | 0.16±0.03 |
| 3 | 0.20±0.02 | 0.28±0.05* | 0.29±0.06* | 0.27±0.01* | 0.30±0.02* | 0.31±0.04* |
| 5 | 0.28±0.05 | 0.57±0.10** | 0.60±0.07** | 0.55±0.11** | 0.56±0.09** | 0.59±0.10** |
(note: * P<0.05, * * P<0.01, compares with matched group.）
Embodiment 7
According to GB1040-79 respectively by beta-calcium phosphate crystal grain (matched group 1), and the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure that embodiment 1-5 obtains makes bending strength test sample and hot strength test sample.By Instron1341 Material Testing Machine, bending property test and hot strength test are carried out to sample.
The testing environment of bending property test is: loading velocity 10mm/ minute, room temperature: 25 DEG C, humidity: 65%.Computing formula is: σ
f=3pL/2bh
2, wherein σ
ffor bending strength (MPa); P is breaking load (N); L is the span (mm) of sample; B is specimen width (mm); H is sample thickness (mm).Concrete test result is in table 2.
The testing environment of hot strength test is: loading velocity 10mm/ minute, room temperature: 25 DEG C, humidity: 75%.Computing formula is: σ t=p/ah, and wherein σ t is hot strength (MPa); P is breaking load (N); A is the intermediate width (mm) of sample; H is sample thickness (mm).Concrete test result is in table 2.
Can find out according to table 2 data, the bending strength of the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure of the present invention and hot strength are obtained for and significantly improve, and show that this material has good biomechanical property.
The bending strength of table 2 carbon nano-fiber compound beta-calcium phosphate and hot strength test (n=6)
| Index | Matched group 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Bending strength/MPa | 122±2 | 163±5* | 168±4* | 166±8* | 170±7* | 167±4* |
| Hot strength/MPa | 35±4 | 56±4* | 57±3* | 61±5* | 55±2* | 59±6* |
(note: * P<0.05, compares with matched group 1.）
Embodiment 8
Matched group 1: animal bone defect without reparative experiment, at 10 week age, SD(Sprague Dawley) inside the distal femur of male rat, in the Cranial defect (diameter 3mm, dark 2mm) that manually causes, do not insert any material, directly sew up.
Reference examples 2: animal bone defect repair is tested, at 10 week age, SD(Sprague Dawley) inside the distal femur of male rat, Cranial defect (the diameter 3mm that manually causes, dark 2mm) in, the beta-calcium phosphate artificial bone (ACPC) onesize with Cranial defect is inserted in Cranial defect district, sews up.
Embodiment 1-5 group: animal bone defect repair is tested, at 10 week age, SD(Sprague Dawley) inside the distal femur of male rat, Cranial defect (the diameter 3mm that manually causes, dark 2mm) in, the carbon nano-fiber compound beta-calcium phosphate of the three-dimensional net structure that the embodiment 1-5 onesize with Cranial defect is obtained is inserted in Cranial defect district, sews up.
By matched group 1,2 and embodiment 1-5 group rat in postoperative 15,30 and 90 days, the kinetic measurement that the image of application small animal living body research micro-CT carries out area of new bone bone amount and area of new bone bone density is compared (the results are shown in Table 3), and histopathology is cut into slices the observation analysis of (H.E dyeing).Pathological section result shows, and compared with matched group 1-2, the rat of embodiment 1-5 group 90 days after surgery, namely reverts to normal bone form, cortical bone surface smoothing, eburnation.
Bone defect healing experiment (n=3) of table 3 carbon nano-fiber compound beta-calcium phosphate
(note: * P<0.05, * * P<0.01, compares with matched group 1; # P<0.05, ## P<0.01, compares with matched group 2.）
Claims (8)
1. one kind has the preparation method of the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure, it is characterized in that: Bacterial cellulose purification process is put into calcium nitrate solution and stirred, slowly add ammonium dibasic phosphate solution and hierarchy of control pH value, ageing 12 ~ 24h after completion of the reaction, lyophilization, then dried material is put into atmosphere furnace heating, after cooling, obtain the composite a kind of carbon nano-fiber with three-dimensional net structure being uniformly distributed beta-calcium phosphate.
2. a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as claimed in claim 1, it is characterized in that: described purification process refers to, Bacterial cellulose through the sodium hydrate aqueous solution high temperature steaming 0.5 ~ 1h of 5 ~ 10wt%, and by washed with de-ionized water to neutral.
3. a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as claimed in claim 1, it is characterized in that: described calcium nitrate solution refers to the calcium nitrate aqueous solution of 0.6 ~ 1mol/L, described ammonium dibasic phosphate solution refers to the ammonium dibasic phosphate aqueous solution of 0.4 ~ 0.6mol/L, and in system, the rate of charge of calcium ion and phosphate anion is 1:1.5.
4. a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as claimed in claim 1, it is characterized in that: described slowly adding refers to that ammonium dibasic phosphate solution drips with the speed of 1 ~ 5ml/min, described hierarchy of control pH value refers to that the pH value with ammonia controls system in whole course of reaction is 9.7 ~ 10.3.
5. a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as claimed in claim 1, it is characterized in that: described lyophilization refers to the freezing 12 ~ 24h at-20 DEG C ~-80 DEG C of the Bacterial cellulose after by ripening, then vacuum drying 24 ~ 48h.
6. a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as claimed in claim 1; it is characterized in that: described heating is that material is under vacuum, argon or nitrogen protection; by room temperature to 850 DEG C ~ 1100 DEG C; wherein 100 ~ 300 DEG C of interval heating rates are 1 ~ 3 DEG C/min; 300 ~ 500 DEG C of interval heating rates are 3 ~ 5 DEG C/min; 500 ~ 800 DEG C of interval heating rates are 5 ~ 7 DEG C/min; 800 DEG C ~ 1100 DEG C interval heating rates are 10 DEG C/min, and are incubated 1 ~ 2h.
7. a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as claimed in claim 1, is characterized in that: described cooling refers to that the material after terminating that heats up slowly cools to room temperature in atmosphere furnace.
8. a kind of preparation method with the carbon nano-fiber compound beta-calcium phosphate of three-dimensional net structure as claimed in claim 1, it is characterized in that: described composite refers to that the carbon nano-fiber diameter with three-dimensional network space structure is 10 ~ 30nm, fiber is evenly distributed with beta-calcium phosphate crystal.
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