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CN-121971696-A - Biomedical graphene/ZTA composite ceramic material, preparation method and application

CN121971696ACN 121971696 ACN121971696 ACN 121971696ACN-121971696-A

Abstract

The invention discloses a biomedical graphene/ZTA composite ceramic material, a preparation method and application. The preparation method comprises the steps of mixing and ball milling composite ceramic powder, a binder, an auxiliary agent, an organic solvent and water to obtain mixed slurry, spraying and granulating the mixed slurry to obtain granulated powder, pressing and forming the granulated powder to obtain a biscuit, degreasing and sintering the biscuit to obtain the biomedical graphene/ZTA composite ceramic material. The biomedical graphene/ZTA composite ceramic material has the graphene content less than or equal to 0.5 percent, and is matched with SrO and Cr 2 O 3 with specific content, so that the biological safety can be ensured, the mechanical property and the biological activity of the material can be maintained or even improved, and the preparation method is efficient and controllable.

Inventors

  • WANG XINYU
  • ZHANG BOWEN
  • LUO JING
  • LI ZHI

Assignees

  • 武汉理工大学

Dates

Publication Date
20260505
Application Date
20260306

Claims (10)

  1. 1. The preparation method of the biomedical graphene/ZTA composite ceramic material is characterized by comprising the following steps of: Mixing and ball milling composite ceramic powder, a binder, an auxiliary agent, an organic solvent and water to obtain mixed slurry; Spraying and granulating the mixed slurry to obtain granulated powder; pressing and forming the granulated powder to obtain a biscuit; degreasing and sintering the biscuit to obtain a biomedical graphene/ZTA composite ceramic material; The composite ceramic powder comprises, by weight, 70% -90% of aluminum oxide, 9% -29% of yttria-stabilized zirconia, 0.5% -2% of SrO, 0.1% -1% of Cr 2 O 3 and 0.1% -0.5% of graphene.
  2. 2. The method for preparing biomedical graphene/ZTA composite ceramic material according to claim 1, wherein the alumina is α -alumina; The alumina is submicron alumina; In the yttria-stabilized zirconia, the mass fraction of the yttria is 3% -15%; The particle size D 50 of the yttria-stabilized zirconia is 50-200nm; the number of layers of the graphene is less than 10, and the sheet diameter D 50 of the graphene is 7-12 mu m.
  3. 3. The method for preparing biomedical graphene/ZTA composite ceramic material according to claim 1, wherein the binder is polyvinyl alcohol; The addition amount of the binder is 1% -1.5% of the mass of the composite ceramic powder; The auxiliary agent comprises at least one of a dispersing agent and a defoaming agent; the addition amount of the auxiliary agent is 1% -5% of the mass of the composite ceramic powder; The organic solvent is dimethylformamide; the mass ratio of the graphene to the organic solvent is (0.5-2) 100.
  4. 4. The method for preparing biomedical graphene/ZTA composite ceramic material according to claim 1, wherein mixing and ball milling composite ceramic powder, binder, auxiliary agent, organic solvent and water to obtain mixed slurry comprises: Mixing alumina, yttria-stabilized zirconia, srO, cr 2 O, a binder, an auxiliary agent and water, and regulating the pH value to 6.5-7.5 to obtain intermediate slurry; dispersing graphene into an organic solvent to obtain graphene dispersion liquid; mixing and ball milling the intermediate slurry and the graphene dispersion liquid to obtain mixed slurry, wherein, Ammonia water is adopted to adjust the pH value; the solid content of the intermediate slurry is 45% -55%; Ultrasonically dispersing graphene into an organic solvent for 0.5-2h; In the ball milling process, the ball milling medium is zirconia balls, the ball-material ratio is (2-4): 1, the rotating speed is 200-400rpm, and the ball milling time is 2-4 hours.
  5. 5. The preparation method of biomedical graphene/ZTA composite ceramic material according to claim 1, wherein in the spray granulation process, the inlet temperature is 140-160 ℃ and the outlet temperature is 80-100 ℃; The particle size of the granulated powder is less than 100 meshes.
  6. 6. The method for preparing biomedical graphene/ZTA composite ceramic material according to claim 1, wherein the compression molding process comprises sequentially subjecting granulated powder to dry compression molding and cold isostatic molding to obtain a biscuit, In the dry pressing forming process, the forming pressure is 150-250MPa, and the dwell time is 5-10 minutes; In the cold isostatic pressing process, the forming pressure is 200-300MPa, and the pressure maintaining time is 5-10 minutes.
  7. 7. The preparation method of the biomedical graphene/ZTA composite ceramic material according to claim 1, wherein the degreasing process comprises heating a biscuit to 450-600 ℃ at 10-20 ℃ per hour for 0-0.5h under a protective atmosphere; In the sintering process, microwave sintering is adopted, the microwave frequency is 2.45GHz, and the power density is 15-25W/cm 3 ; The sintering process comprises the steps of heating from room temperature to a first temperature at a first heating rate under protective atmosphere, heating from the first temperature to a second temperature at a second heating rate, preserving heat for a first time at the second temperature, and naturally cooling to obtain the biomedical graphene/ZTA composite ceramic material, wherein the first heating rate is 25-50 ℃ per minute, the first temperature is 1280-1320 ℃, the second heating rate is 10-30 ℃ per minute, the second temperature is 1480-1520 ℃, and the first time is 0.8-1.2h.
  8. 8. The method for preparing the biomedical graphene/ZTA composite ceramic material according to claim 1, further comprising grinding and polishing the biomedical graphene/ZTA composite ceramic material until the roughness reaches a target range, The target range of the roughness is Ra less than 0.01 mu m.
  9. 9. The biomedical graphene/ZTA composite ceramic material is characterized in that the biomedical graphene/ZTA composite ceramic material is obtained by the preparation method of the biomedical graphene/ZTA composite ceramic material according to any one of claims 1-8.
  10. 10. The use of the biomedical graphene/ZTA composite ceramic material according to claim 9, wherein the biomedical graphene/ZTA composite ceramic material is used for preparing an artificial joint.

Description

Biomedical graphene/ZTA composite ceramic material, preparation method and application Technical Field The invention relates to the technical field of biomedical materials, in particular to a biomedical graphene/ZTA composite ceramic material, a preparation method and application. Background The artificial joint replacement material needs to meet the requirements of high strength, high wear resistance and good biocompatibility. Although the traditional Zirconia Toughened Alumina (ZTA) ceramic has certain biological inertia and moderate toughness, the bending strength (generally less than or equal to 500 MPa) and the fracture toughness (less than or equal to 5 MPa) of the traditional Zirconia Toughened Alumina (ZTA) ceramicM 1/2) and limited tribological properties, and are difficult to meet long-term use requirements under dynamic physiological loads. In the prior art, methods for improving ceramic performance by adding nano reinforcing phases have been widely studied, but challenges still remain in achieving uniform dispersion of reinforcing phases, optimizing interface bonding, and regulating biocompatibility. Graphene is used as a two-dimensional nano material, and has excellent mechanical strength and self-lubricating property, but in the prior art, graphene is easy to agglomerate in a ceramic matrix, and the influence rules of different graphene addition amounts on the mechanical properties and biocompatibility of the material are not clear, so that the application of the graphene in the biomedical field is limited. In order to improve toughness of ZTA ceramics, high content of graphene (more than or equal to 1 wt%) is generally adopted for reinforcement. However, when the graphene content is too high (> 0.5 wt%) excessive Reactive Oxygen Species (ROS) are released on the surface of the material, so that cytotoxicity is remarkably increased, the standard of the ISO 10993 biomedical material cannot be met, in the traditional sintering process, graphene is easy to react with Al 2O3 at high temperature to generate a brittle Al 4C3 phase, the two-dimensional structure of the graphene is damaged, a crack source is formed at a crystal boundary, in addition, although the osteogenesis activity can be improved by adding SrO, the crystal boundary is weakened, and the mechanical property is reduced by more than 30%. Therefore, how to realize high mechanical properties and bioactivity on the premise of ensuring biological safety (low graphene content) is a technical problem to be solved in the field. Disclosure of Invention The invention aims to overcome the technical defects, and provides a biomedical graphene/ZTA composite ceramic material, a preparation method and application thereof, and the technical problem that zirconia toughened alumina ceramic in the prior art cannot achieve both high mechanical properties and high bioactivity on the premise of ensuring biosafety is solved. In a first aspect, the invention provides a preparation method of biomedical graphene/ZTA composite ceramic material, comprising the following steps: Mixing and ball milling composite ceramic powder, a binder, an auxiliary agent, an organic solvent and water to obtain mixed slurry; spraying and granulating the mixed slurry to obtain granulated powder; Compacting and forming the granulated powder to obtain a biscuit; Degreasing and sintering the biscuit to obtain a biomedical graphene/ZTA composite ceramic material; The composite ceramic powder comprises, by weight, 70% -90% of alumina, 9% -29% of yttria-stabilized zirconia, 0.5% -2% of SrO, 0.1% -1% of Cr 2O3 and 0.1% -0.5% of graphene. In a second aspect, the invention provides a biomedical graphene/ZTA composite ceramic material, which is obtained by the preparation method of the biomedical graphene/ZTA composite ceramic material provided by the first aspect of the invention. In a third aspect, the invention provides an application of biomedical graphene/ZTA composite ceramic material, and the biomedical graphene/ZTA composite ceramic material is applied to preparation of an artificial joint. Compared with the prior art, the invention has the beneficial effects that: the biomedical graphene/ZTA composite ceramic material has the graphene content less than or equal to 0.5 percent, can ensure biological safety, can maintain and even improve the mechanical property and biological activity of the material by matching with the bioactive material (SrO) and Cr 2O3 with specific content, can solve the performance bottleneck of the existing ZTA ceramic in artificial joint application, and has high efficiency and controllability. Drawings FIG. 1 is an XRD pattern of different biomedical graphene/ZTA composite ceramic materials of examples 1-3 and comparative example 1 of the present invention; FIG. 2 is a Raman spectrum of different biomedical graphene/ZTA composite ceramic materials and graphene in examples 1-3 of the present invention; FIG. 3 is an SEM image of granulated powder according to