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CN-121971710-A - Cobalt oxide-carbon co-doped hydroxyapatite artificial bone material and preparation method thereof

CN121971710ACN 121971710 ACN121971710 ACN 121971710ACN-121971710-A

Abstract

The invention discloses a cobaltosic oxide-carbon co-doped hydroxyapatite artificial bone material and a preparation method thereof, belonging to the technical field of biomedical ceramic materials. The method takes hydroxyapatite as a matrix, adopts potassium hexacyanocobaltate as a cobalt source and a carbon source precursor, and adopts sectional gradient sintering under load and inert atmosphere to generate cobaltosic oxide nano particles and a carbon phase in situ, and the artificial bone scaffold material is obtained after molding and degreasing. The cobaltosic oxide in the obtained material can refine grains, improve mechanical strength, and the in-situ carbon phase is used as a flexible toughening phase to reduce brittleness, so that the strength and toughness are synchronously improved in a cooperative manner, and meanwhile, a precursor pyrolysis gas production cooperative pore-forming structure with excellent connectivity is formed. The invention has simple process and good dispersion uniformity, and solves the problems of poor mechanical property, large brittleness, insufficient pore connectivity and the like of pure hydroxyapatite.

Inventors

  • LIAO LIANG
  • ZHAO JINMIN
  • ZHANG JIN
  • LIU XIAOHUI

Assignees

  • 广西医科大学第一附属医院

Dates

Publication Date
20260505
Application Date
20260408

Claims (7)

  1. 1. The preparation method of the cobaltosic oxide-carbon co-doped hydroxyapatite artificial bone material is characterized by comprising the following steps of: s1, preparing a composite precursor, namely dissolving potassium hexacyanocobaltate in deionized water to obtain a solution A, dispersing hydroxyapatite powder in absolute ethyl alcohol to obtain an HA suspension, dropwise adding the solution A into the HA suspension under the stirring condition, continuously stirring, centrifuging, washing and vacuum drying to obtain the composite precursor; S2, preparing composite powder by gradient sintering, namely placing the composite precursor in an inert atmosphere of nitrogen or argon for sectional gradient sintering, wherein the temperature is raised to 300-360 ℃ in the first stage, and the precursor is thermally decomposed to generate Co 3 O 4 particles and form a carbon phase in situ; S3, molding and post-treatment, namely grinding the composite powder, adding a polyvinyl alcohol binder, uniformly mixing, pressing, sintering again to remove the binder, and cooling along with a furnace to obtain the Co 3 O 4 -carbon Co-doped hydroxyapatite artificial bone scaffold material.
  2. 2. The preparation method of claim 1, wherein the dosage of potassium hexacyanocobaltate in S1 is 0.3-0.6 mmol, and deionized water is 20-35 mL; 10-12 g of hydroxyapatite powder and 50-65 mL of absolute ethyl alcohol.
  3. 3. The preparation method according to claim 1, wherein the stirring temperature in the step S1 is 25-30 ℃, the stirring speed is 300-400 r/min, and the stirring is continued for 60-90 min after the dripping.
  4. 4. The preparation method according to claim 1, wherein the vacuum drying temperature in S1 is 50-60 ℃ and the drying time is 10-12 hours.
  5. 5. The preparation method according to claim 1, wherein the first stage temperature rise rate in S2 is 2-3 ℃ per minute, the heat preservation time is 3-4 hours, the second stage temperature rise rate is 3-4 ℃ per minute, and the heat preservation time is 4-6 hours.
  6. 6. The preparation method of the polyvinyl alcohol powder according to claim 1, wherein the mass fraction of the polyvinyl alcohol binder in the S3 is 5% -8%, the pressure of compression molding is 15-20 MPa, the dwell time is 30-60S, the re-sintering temperature is 450-455 ℃, and the sintering time is 2-3 h.
  7. 7. A cobaltosic oxide-carbon co-doped hydroxyapatite artificial bone material, characterized by being prepared by the preparation method according to any one of claims 1 to 6.

Description

Cobalt oxide-carbon co-doped hydroxyapatite artificial bone material and preparation method thereof Technical Field The invention belongs to the technical field of biomedical ceramic material preparation, and in particular relates to a cobaltosic oxide-carbon co-doped hydroxyapatite artificial bone material and a preparation method thereof. Background The chemical composition of the Hydroxyapatite (HA) ceramic is highly matched with the crystal structure and the inorganic components of human bone tissue, HAs excellent biocompatibility, bone conductivity and biodegradability, and is the most widely applied artificial bone material in the current clinical bone defect repair. The pure hydroxyapatite ceramic HAs two major core defects, namely, the pure hydroxyapatite ceramic HAs weak mechanical properties, HAs low bending strength and compression strength, HAs high brittleness and poor toughness, cannot meet the mechanical bearing requirements of non-load-bearing to light-load parts of human bodies, is easy to crack and collapse after implantation, directly influences the bone repair effect, HAs the defects of pore structure, HAs low porosity and poor pore connectivity, is mostly isolated and closed, can not provide a three-dimensional growth space for adhesion, proliferation and differentiation of osteoblasts, is difficult to realize high-efficiency transmission of nutrient substances and smooth discharge of metabolic wastes, and finally HAs low osseointegration efficiency. In the prior art, although the osteoinductive activity of HA can be improved to a certain extent by single ion doping (such as Sr 2+、Mg2+、Zn2+), the effect of improving the mechanical property is extremely limited, the problems of uneven pore size, disordered distribution, greatly reduced material density and the like are easily caused by simply adopting pore-forming agents for pore-forming, the mechanical strength is further weakened, the brittleness of the material can be reduced by a small extent by the exogenous doping of carbon materials (such as graphene, carbon nano tubes and activated carbon), the mechanical toughness is improved, but the interfacial compatibility of the carbon materials and an HA matrix is poor, agglomeration is extremely easy to occur, uniform dispersion cannot be realized, the interfacial binding force is weak, defects are easily caused, and the osteoinductive activity and the structural stability cannot be considered by single carbon doping, so that the comprehensive performance requirement of clinical bone repair is difficult to be met. In recent years, the metal oxide HAs excellent modification potential in the biomedical material field, wherein the cobaltosic oxide HAs good biocompatibility and interface bonding capability, can effectively promote osteoblast adhesion and proliferation, can refine HA grains, optimize a microstructure of the material and improve the mechanical strength of the material, and meanwhile, in-situ carbon doping can form a flexible interface phase in an HA matrix, fill gaps among the grains, relieve stress concentration among the grains, effectively reduce inherent brittleness of HA ceramic, enhance matrix binding force and mechanical toughness, greatly improve bending resistance and compression resistance of the material from a structural level, and can synergistically optimize pore connectivity. Disclosure of Invention Aiming at the problems of high brittleness, low mechanical strength, poor porosity and connectivity and poor osseointegration efficiency of the existing pure hydroxyapatite artificial bone material, the invention provides the tricobalt tetraoxide-carbon Co-doped hydroxyapatite artificial bone material and the preparation method thereof, through an in-situ carbon doping technology, cobalt oxide metal oxide and carbon are uniformly dispersed in an HA matrix, and through the synergistic modification effect of cobaltosic oxide (Co 3O4) and carbon, the microstructure and pore morphology of the material are optimized, the brittleness of the material is reduced, the mechanical bearing performance and toughness are improved, a three-dimensional communicated porous structure is constructed, and the bone conduction and bone induction activity are enhanced. In order to achieve the above purpose, the present invention provides the following technical solutions: a cobaltosic oxide-carbon co-doped hydroxyapatite artificial bone material: The artificial bone material takes Hydroxyapatite (HA) as a matrix, co 3O4 metal oxide and a carbon phase are introduced in situ, the carbon phase is derived from pyrolysis of cobalt-based Prussian blue precursor and is uniformly distributed in gaps of HA crystal grains, the carbon phase is taken as a flexible reinforcing phase, so that HA crack expansion can be effectively blocked, stress concentration among crystal grains is relieved, ceramic brittleness is greatly reduced, the material presents a three-dimensional multistage communicated pore st