CN102058907B - Hydroxyapatite/silk fibroin composite material and preparation method thereof - Google Patents
Hydroxyapatite/silk fibroin composite material and preparation method thereof Download PDFInfo
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- CN102058907B CN102058907B CN 201010618923 CN201010618923A CN102058907B CN 102058907 B CN102058907 B CN 102058907B CN 201010618923 CN201010618923 CN 201010618923 CN 201010618923 A CN201010618923 A CN 201010618923A CN 102058907 B CN102058907 B CN 102058907B
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- wollastonite
- fibroin albumen
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Abstract
The invention discloses a composite bionic bone material and a preparation method thereof, and in particular relates to a hydroxyapatite/silk fibroin composite bionic material and a preparation method thereof, belonging to the technical field of medical materials. The composite material comprises the following components in percent by mass: 40-60 percent of hydroxyapatite, 10-30 percent of wollastonite and 25-35 percent of silk fibroin. On the basis of tight matching and higher biological property of the hydroxyapatite/silk fibroin material, the wollastonite with better biological property and mechanical behavior is introduced, the mechanical behavior of the composite material is greatly improved without influencing the biological property, the three materials are compounded to obtain a bone tissue coloboma repairing material perfectly combining the mechanical behavior with the bioactivity and compatibility, and the bone tissue coloboma repairing material has better practicability and application prospect.
Description
Technical field
The present invention relates to a kind of composite bionic bone material and preparation method thereof, relate in particular to compound biomimetic material of a kind of hydroxyapatite and fibroin albumen and preparation method thereof, belong to the medical material field that learns a skill.
Background technology
Bone injury and bone are damaged to be common clinically disease, and the bone of damage can be repaired with endogenous bone or external source bone.Endogenous bone repairing effect is fine, but its quantity is very limited, and need second operation, and adopt external source bone repairing effect to can not show a candle to endogenous bone, there is immunological rejection in present external source bone reparation means, difficult degradation may have potential pathogen and other side reactions etc., and therefore there is urgent needs domestic and foreign market to hard, soft tissue repair material.The biomaterial that is used for the bone reparation at present is divided into following four kinds: medical metal material, medical bio pottery, medical macromolecular materials, medical composite material.And in the medical bio pottery, the bionic bone matrix material namely imitates the material that natural bone material design has bionic structure and function bionics has become the research focus, this kind material can be degraded in vivo, avirulence and other untoward reaction, and can promote the generation of new bone, for the bone reparation provides a kind of brand-new approach.
The human body bone mainly is made up of nanometer hydroxyapatite and type i collagen, and last century, the middle nineteen thirties scientists went out hydroxyapatite with regard to synthetic, it is a kind of artificial bone of biology performance excellence, but the hydroxyapatite fragility of one-component is big, toughness is relatively poor, mechanical property is not enough, degraded slowly and easily from implanting the some migration, this has all limited its use as human material implantation body.Replace the bionical bone of the hydroxylapatite mineralized preparation of type i collagen induced nano to be widely studied with fibroin albumen at present, and obtained the higher hydroxyapatite/fibroin albumen composite material of biological activity, though the method by mineralising merges fibroin albumen and apatite more closely, improved mechanical property to a certain extent, but its mechanical strength is still not enough, is difficult to satisfy clinical requirement.And mostly used bone cement is the composite of apatite and wollastonite, wollastonite has very high biological activity and the compatibility, and in simulated body fluid, the speed that hydroxyapatite forms on the calcium silicates surface is greater than the speed in other biological glass and the formation of glass-ceramic surface, so apatite-wollastonite glass ceramics has certain bone conductibility and degradability, and good biocompatibility and activity are arranged, this type of material is through high-temperature calcination, be complete crystalline structure, though intensity is bigger, degradability and toughness are relatively poor.Above-mentioned two kinds of materials mechanical property and biology performance in conjunction with aspect also have obvious deficiency, far can not satisfy clinical needs.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of have good biological activity and the compatibility, mechanical strength is higher, can satisfy hydroxyapatite-wollastonite/fibroin albumen composite bionic material of human loaded bone requirement and preparation method thereof.
Technical scheme of the present invention provides a kind of hydroxyapatite/fibroin albumen composite material, and by mass percentage, its component comprises wollastonite powder body 10%～30%, fibroin albumen 25%～35%, hydroxyapatite 40%～60%.
A kind of method for preparing hydroxyapatite/fibroin albumen composite material comprises the steps:
(1) compound concentration is the Ca (NO of 0.5～1.0 mol/L
3)
2Solution and concentration are the Na of 0.5～1.0 mol/L
2SiO
3Solution; Be that 0.3%～1.0% poly-vinyl alcohol solution joins Ca (NO as dispersant with mass fraction
3)
2In the solution, under stirring condition, drip Na
2SiO
3Solution, with resulting precipitate deionized water, absolute ethanol washing, drying obtains the wollastonite powder body after the calcining;
(2) with Ca (NO
3)
24H
2O fusion under 80～140 ℃ temperature conditions is dissolved in fibroin albumen Ca (NO again
3)
2In the solution, form SF-Ca (NO
3)
2Solution;
With Na
3PO
412H
2O is mixed with the Na that concentration is 0.4～1.0 mol/L
3PO
4Solution;
The wollastonite powder body is scattered in the deionized water to form mass fraction be 1%～5% suspension;
Be under 35～40 ℃ the stirring condition, in suspension, to drip SF-Ca (NO simultaneously in temperature
3)
2Solution and Na
3PO
4Solution, 9～11, the dropping time is 30～60 minutes, preserving heat after reaction ends mineralising 48～72 hours with NaOH solution control pH value of reaction system;
(3) precipitate is carried out sucking filtration, be washed with distilled water to neutrality earlier, use absolute ethanol washing again 3～5 times, in dried under 60～80 ℃ the temperature conditions after 24～48 hours, grind, sieve, obtain hydroxyapatite-wollastonite/fibroin albumen composite granule; In the composite granule, by mass percentage, the wollastonite powder body is 10%～30%, and fibroin albumen is 25%～35%, by Ca (NO
3)
24H
2O and Na
3PO
412H
2Hydroxyapatite after O is synthetic is 40%～60%;
(4) with above-mentioned composite granule cold isostatic compaction, obtain hydroxyapatite-wollastonite/fibroin albumen composite bionic material.
Wollastonite particle diameter of the present invention is 20～100nm.
The present invention introduces the wollastonite powder body in hydroxyapatite/fibroin albumen, except the deposition that is conducive to hydroxyapatite, also help in graft and to constitute the wollastonite toughness reinforcing net that interweaves; Simultaneously, compound biological activity and the biocompatibility that can controlled material of hydroxyapatite and wollastonite, namely when not influencing the material biology performance, make this composite mechanical property be improved significantly.
Compared with prior art, hydroxyapatite-wollastonite of the present invention/fibroin albumen composite bionic material, be on the basis of the tight fusion of fibroin-hydroxyapatite material and higher biological property, the wollastonite that introducing has good biological performance and mechanical property can improve its mechanical property by a relatively large margin, the compound osseous tissue impairment renovation material that is expected to obtain a kind of mechanical property and biological activity and compatibility perfect adaptation of these three kinds of materials has better practicability and application prospect.
Description of drawings
Fig. 1 is preparation technology's flow chart of a kind of hydroxyapatite/fibroin albumen composite granule of providing of the embodiment of the invention;
Fig. 2 is a kind of hydroxyapatite/fibroin albumen composite bionic material SEM that sample surfaces contrasts before and after simulated body fluid soak test figure that the embodiment of the invention provides;
Fig. 3 is a kind of hydroxyapatite/fibroin albumen composite bionic material SEM that sample surfaces contrasts before and after simulated body fluid soak test figure that another embodiment of the present invention provides;
Fig. 4 is that hydroxyapatite/fibroin albumen composite bionic material that different embodiments of the invention provide is composed in the XRD figure that the sample simulated body fluid soaks rear surface product contrast.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described.
Embodiment one: referring to accompanying drawing 1, present embodiment provides a kind of hydroxyapatite-wollastonite/fibroin albumen composite bionic preparation methods, and its step is as follows:
1, compound concentration is 0.5mol/LCa (NO respectively
3)
2Solution and Na
2SiO
3Solution, mass fraction are that 0.5% poly-vinyl alcohol solution joins Ca (NO as dispersant
3)
2In the solution, drip Na while stirring
2SiO
3Solution.After treating that it fully reacts, with resulting precipitate with deionized water, absolute ethanol washing, obtain the wollastonite powder body behind the drying and calcining.
2, be respectively 30%, 20%, 50% amount meter according to fibroin albumen, wollastonite, hydroxyapatite mass percent in the composite granule, preparation 10g composite granule need take by weighing fibroin fiber and the 2g wollastonite powder body that the silkworm silk after 3g comes unstuck obtains respectively, and the needed 11.76g Ca of the hydroxyapatite of synthetic 5g (NO
3)
24H
2O and 11.36g Na
3PO
412H
2O; Na
3PO
412H
2O adds the Na that the 50ml deionized water is mixed with 0.60mol/L
3PO
4Solution, and Ca (NO
3)
24H
2O directly is dissolved in Ca (NO with the 3g fibroin fiber that weighs up then then 90 ℃ of direct fusions
3)
2In the solution, form SF-Ca (NO
3)
2Solution; Simultaneously the 2g wollastonite powder body that weighs up is scattered in the 100ml deionized water that to form mass fraction be 2% suspension, drips SF-Ca (NO simultaneously on 37 ℃ of following stirred suspension limits
3)
2Solution and Na
3PO
4Solution is controlled pH value of reaction system 10 with NaOH solution, preserving heat after reaction ends mineralising 72 hours.
3, will react the precipitation that produces and carry out sucking filtration, and be washed with distilled water to neutrality earlier, and use absolute ethanol washing again 3 times, the powder body of 60 ℃ of dryings after 24 hours grinds, sieves, and namely gets hydroxyapatite-wollastonite/fibroin albumen composite granule.
4, pour above-mentioned composite granule into the mold cold isostatic compaction, do not need sintering namely to get hydroxyapatite-wollastonite/fibroin albumen composite bionic material.
After measured, the main performance of the hydroxyapatite-wollastonite that makes/fibroin albumen composite bionic material: comprcssive strength reaches 85 MPa, and the hardness Barcol value reaches 48, can reach the mechanical property requirements of load osseous tissue as an alternative.
Referring to accompanying drawing 2, it is the composite bionic material SEM that sample surfaces contrasts before and after simulated body fluid (37 ℃) the soak test figure that present embodiment provides; Among the figure, (a) be the sample before soaking, (b) be the sample of immersion after 7 days, can be found by the contrast of SEM collection of illustrative plates, layer of substance that immersion back material surface is newly-generated, the apatite of confirming as weak crystallization through the XRD test (referring to the figure in the accompanying drawing 4 a), shows that the material of providing for oneself has certain biological activity.
Embodiment two: present embodiment provides a kind of hydroxyapatite-wollastonite/fibroin albumen composite bionic preparation methods, and its step is as follows:
1, compound concentration is 0.5mol/LCa (NO respectively
3)
2Solution and Na
2SiO
3Solution, mass fraction are that 0.5% poly-vinyl alcohol solution joins Ca (NO as dispersant
3)
2In the solution, drip Na while stirring
2SiO
3Solution.After treating that it fully reacts, with resulting precipitate with deionized water, absolute ethanol washing, obtain the wollastonite powder body behind the drying and calcining.
2, be respectively 30%, 30%, 40% amount meter according to fibroin albumen, wollastonite, hydroxyapatite mass percent in the composite granule, preparation 10g composite granule need take by weighing fibroin fiber and the 3g wollastonite powder body that obtains after 3g silkworm silk comes unstuck respectively, and the needed 9.41g Ca of the hydroxyapatite of synthetic 4g (NO
3)
24H
2O and 9.09g Na
3PO
412H
2O; Na
3PO
412H
2O adds the Na that the 50ml deionized water is mixed with 0.48mol/L
3PO
4Solution, and Ca (NO
3)
24H
2O directly is dissolved in Ca (NO with the 3g fibroin fiber that weighs up then then 110 ℃ of direct fusions
3)
2In the solution, form SF-Ca (NO
3)
2Solution; Simultaneously the 3g wollastonite powder body that weighs up is scattered in the 100ml deionized water that to form mass fraction be 3% suspension, drips SF-Ca (NO simultaneously on 37 ℃ of following stirred suspension limits
3)
2Solution and Na
3PO
4Solution adds NaOH solution control pH value of reaction system 11, preserving heat after reaction ends mineralising 60 hours.
3, will react the precipitation that produces and carry out sucking filtration, and be washed with distilled water to neutrality earlier, and use absolute ethanol washing again 3 times, the powder body of 70 ℃ of dryings after 48 hours grinds, sieves, and namely gets hydroxyapatite-wollastonite/fibroin albumen composite granule.
4, pour above-mentioned composite granule into the mold cold isostatic compaction, do not need sintering namely to get hydroxyapatite-wollastonite/fibroin albumen composite bionic material.
After measured, the main performance of the hydroxyapatite-wollastonite that makes/fibroin albumen composite bionic material: comprcssive strength reaches 90 MPa, and the hardness Barcol value reaches 52, can reach the mechanical property requirements of load osseous tissue as an alternative.
Referring to accompanying drawing 3, it is a kind of composite bionic material SEM that sample surfaces contrasts before and after simulated body fluid (37 ℃) soak test figure that present embodiment provides; Among the figure, (a) be the sample before soaking, (b) be the sample of immersion after 14 days; SEM collection of illustrative plates by the sample surfaces contrast can be found, layer of substance that immersion back material surface is newly-generated, and the apatite (referring to the figure b in the accompanying drawing 4) of crystallization shows that the material that provides has certain biological activity a little less than the XRD test is confirmed as.
Referring to accompanying drawing 4, it is that the composite bionic material that the embodiment of the invention one and two provides is composed in the XRD figure that sample simulated body fluid (37 ℃) soaks rear surface product contrast; Among the figure, (a) result of material after simulated body fluid soaks 7 days who provides for embodiment one, (b) result of material after simulated body fluid soaks 14 days who provides for embodiment two, layer of substance that immersion back material surface is newly-generated, detect the apatite of confirming as weak crystallization through XRD, Fig. 4 shows that material provided by the present invention has certain biological activity.
Claims (2)
1. a method for preparing hydroxyapatite-wollastonite/fibroin albumen composite material is characterized in that comprising the steps:
(1) compound concentration is the Ca (NO of 0.5～1.0 mol/L
3)
2Solution and concentration are the Na of 0.5～1.0 mol/L
2SiO
3Solution; Be that 0.3%～1.0% poly-vinyl alcohol solution joins Ca (NO as dispersant with mass fraction
3)
2In the solution, under stirring condition, drip Na
2SiO
3Solution, with resulting precipitate deionized water, absolute ethanol washing, drying obtains the wollastonite powder body after the calcining;
(2) with Ca (NO
3)
24H
2O fusion under 80～140 ℃ temperature conditions is dissolved in fibroin albumen Ca (NO again
3)
2In the solution, form SF-Ca (NO
3)
2Solution;
With Na
3PO
412H
2O is mixed with the Na that concentration is 0.4～1.0 mol/L
3PO
4Solution;
The wollastonite powder body is scattered in the deionized water to form mass fraction be 1%～5% suspension;
Be under 35～40 ℃ the stirring condition, in suspension, to drip SF-Ca (NO simultaneously in temperature
3)
2Solution and Na
3PO
4Solution, 9～11, the dropping time is 30～60 minutes, preserving heat after reaction ends mineralising 48～72 hours with NaOH solution control pH value of reaction system;
(3) precipitate is carried out sucking filtration, be washed with distilled water to neutrality earlier, use absolute ethanol washing again 3～5 times, in dried under 60～80 ℃ the temperature conditions after 24～48 hours, grind, sieve, obtain hydroxyapatite-wollastonite/fibroin albumen composite granule; In the composite granule, by mass percentage, the wollastonite powder body is 10%～30%, and fibroin albumen is 25%～35%, by Ca (NO
3)
24H
2O and Na
3PO
412H
2Hydroxyapatite after O is synthetic is 40%～60%;
(4) with above-mentioned composite granule cold isostatic compaction, obtain hydroxyapatite-wollastonite/fibroin albumen composite material.
2. a kind of method for preparing hydroxyapatite-wollastonite/fibroin albumen composite material according to claim 1, it is characterized in that: described wollastonite particle diameter is 20～100nm.
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|---|---|---|---|
| CN 201010618923 CN102058907B (en) | 2010-12-31 | 2010-12-31 | Hydroxyapatite/silk fibroin composite material and preparation method thereof |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104043149A (en) * | 2014-06-20 | 2014-09-17 | 苏州大学 | Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof |
| CN106620861A (en) * | 2016-12-09 | 2017-05-10 | 宁波芸生纺织品科技有限公司 | Silk fibroin/strontium carbonate composite material and preparation method thereof |
| CN107137774A (en) * | 2017-06-06 | 2017-09-08 | 上海理工大学 | A kind of fibroin albumen with three-dimensional structure/hydroxyapatite compound rest and preparation method thereof |
| CN107715172A (en) * | 2017-11-08 | 2018-02-23 | 江苏华友装饰工程有限公司 | Preparation method of bone bionic composite material |
| CN111569149B (en) * | 2020-06-05 | 2022-06-17 | 武汉亚洲生物材料有限公司 | Co-assembled artificial periosteum and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502672A (en) * | 2009-03-19 | 2009-08-12 | 浙江大学 | Method for preparing hydroxyapatite/silk fibroin compound porous stand material |
| CN101897994A (en) * | 2010-07-23 | 2010-12-01 | 山东大学 | Biological composite scaffold for repairing bone defect and preparation method thereof |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502672A (en) * | 2009-03-19 | 2009-08-12 | 浙江大学 | Method for preparing hydroxyapatite/silk fibroin compound porous stand material |
| CN101897994A (en) * | 2010-07-23 | 2010-12-01 | 山东大学 | Biological composite scaffold for repairing bone defect and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Fabrication and characterization of bioactive silk fibroin/wollastonite composite scaffolds;Hailin Zhu et al;《Materials Science and Engineering C》;20090917;第30卷(第1期);132–140 * |
| Hailin Zhu et al.Fabrication and characterization of bioactive silk fibroin/wollastonite composite scaffolds.《Materials Science and Engineering C》.2009,第30卷(第1期),132–140. |
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