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CN-118320171-B - Medical nano hydroxyapatite coating porous tantalum implantation material and preparation method thereof

CN118320171BCN 118320171 BCN118320171 BCN 118320171BCN-118320171-B

Abstract

The invention discloses a medical nano hydroxyapatite coating porous tantalum implantation material and a preparation method thereof, wherein the preparation method comprises the steps of etching a graphite carbon skeleton by adopting an HCl solution, washing and drying to obtain a porous carbon skeleton, placing the porous carbon skeleton into a vapor deposition reaction chamber, introducing treatment gas and reducing gas into the reaction chamber to perform vapor deposition to deposit a tantalum coating on the surface of the porous carbon skeleton to obtain a porous tantalum metal bracket, dissolving a calcium source, a phosphorus source and sodium chloride in deionized water to obtain a mixed solution, regulating the pH value to be 4.3 to obtain an electrolyte, taking the tantalum metal porous bracket as a working electrode, and carrying out electrochemical deposition in the electrolyte by adopting a pulse current mode to deposit a nano hydroxyapatite coating on the surface of the tantalum metal porous bracket, wherein the treatment gas comprises a tantalum source and a carrier gas, and the elasticity modulus is less than 30Gpa.

Inventors

  • XIE HUI
  • ZHOU KE
  • WANG XINYI
  • XU LONGHUI
  • LI YADA
  • YUAN BO

Assignees

  • 大连大学附属中山医院

Dates

Publication Date
20260505
Application Date
20240416

Claims (7)

  1. 1. The preparation method of the medical nano hydroxyapatite coating porous tantalum implant material is characterized by comprising the following steps of: S1, etching a graphite carbon skeleton by adopting an HCl solution, washing and drying to obtain a porous carbon skeleton, and placing the porous carbon skeleton into a vapor deposition reaction chamber; s2, introducing a processing gas and a reducing gas into a vapor deposition reaction chamber to perform vapor deposition so as to deposit a tantalum coating on the surface of the porous carbon skeleton, thereby obtaining a porous tantalum metal bracket; s3, dissolving a calcium source, a phosphorus source and sodium chloride in deionized water to obtain a mixed solution; S4, adjusting the pH value of the mixed solution to 4.3 by adopting a pH regulator to obtain an electrolyte; S5, taking the porous tantalum metal stent as a working electrode, taking graphite as a counter electrode, performing electrochemical deposition in the electrolyte by adopting a pulse current mode to deposit a nano hydroxyapatite coating on the surface of the porous tantalum metal stent, and washing and drying to obtain the medical nano hydroxyapatite coating porous tantalum implant material; in the step S3, the concentration of the calcium source in the mixed liquor is 2.5mmol/L, the concentration of the phosphorus source in the mixed liquor is 1.5mmol/L and the concentration of the sodium chloride in the mixed liquor is 0.1mol/L; in the step S5, in the electrochemical deposition, the pulse current is 0.075mA, the period is 17S, the cathode pulse on time is 16S, the anode pulse on time is 1S, the electrochemical deposition time is 30min, and the electrochemical deposition temperature is 85 ℃; The medical nano hydroxyapatite coating porous tantalum implantation material comprises a porous carbon skeleton and a composite coating; The composite coating comprises a tantalum coating which is deposited on the porous carbon skeleton in a vapor phase and a nano hydroxyapatite coating which is deposited on the tantalum coating in an electrochemical mode, wherein the weight ratio of the tantalum coating in the composite coating is 70% -80%; the thickness of the nano hydroxyapatite coating is 4.5 mu m; The porosity of the medical nano hydroxyapatite coating porous tantalum implant material is 75% -85%, the elastic modulus is less than 30Gpa, and the compressive strength is 30-45 MPa; The porosity of the nano hydroxyapatite coating is 75% -85%, and the pore diameter is 400-600 mu m.
  2. 2. The method for preparing the medical nano-hydroxyapatite coating porous tantalum implant material according to claim 1, wherein in the step S1, the concentration of the HCl solution is 10%, and the etching time is 10-20 min.
  3. 3. The preparation method of the medical nano hydroxyapatite coating porous tantalum implant material according to claim 1 is characterized by comprising the steps of simultaneously introducing a treatment gas and a reducing gas into a vapor deposition reaction chamber, reacting for 4-6 hours under the conditions of 900-1500 ℃ and 10-15 Pa vacuum, placing a tantalum source into a source tank, heating to 120-250 ℃, introducing a tantalum metal compound in the source tank into the reaction chamber by taking 300 ℃ inert gas as carrier gas, wherein the flow rate of the treatment gas is 80-100 ml/min, the flow rate of the reducing gas is 100-150 ml/min, and the inert gas comprises one or two of argon and helium.
  4. 4. The method for preparing a medical nano-hydroxyapatite coated porous tantalum implant material according to claim 1, wherein in the step S2, the tantalum source comprises one or two of tantalum pentachloride and tantalum fluoride, the particle size of the tantalum source is 400 meshes, and the reducing gas is hydrogen.
  5. 5. The method for preparing the medical nano-hydroxyapatite coated porous tantalum implant material according to claim 1, wherein the step S2 further comprises the steps of adjusting the size of the porous tantalum metal stent to phi 10mm multiplied by 1.5mm, and sequentially performing ultrasonic cleaning for 20min by adopting acetone, absolute ethyl alcohol and deionized water.
  6. 6. The method for preparing a medical nano-hydroxyapatite coated porous tantalum implant material according to claim 1, wherein in the step S3, the calcium source comprises one or two of calcium nitrate and calcium phosphate; in step S4, the pH adjuster is 10% hydrochloric acid.
  7. 7. The method for preparing a medical nano-hydroxyapatite coated porous tantalum implant material according to claim 1, wherein the porosity of the porous carbon skeleton is more than 70%, and the pore diameter is 210-600 μm; the thickness of the tantalum coating is 40-60 mu m.

Description

Medical nano hydroxyapatite coating porous tantalum implantation material and preparation method thereof Technical Field The invention relates to the technical field of medical materials, in particular to a medical nano hydroxyapatite coating porous tantalum implant material and a preparation method thereof. Background Large bone defects, i.e., defects greater than the critical dimension (CSD), lack self-regenerating ability and often require surgical intervention. Among the various modern therapies, autogenous bone grafting has proven to be very effective in repairing bone defects, but autografts suffer from complications at the donor site and limited supply. Synthetic bone replacement materials are commonly used in the form of porous scaffold structures, providing an effective alternative for repairing bone defects. Among many medical materials, tantalum metal (Ta) is widely used in the fields of surgical sutures, bone fixing materials, bone implant materials, vascular stent coatings, image contrast agents, and the like, because of having good biocompatibility and excellent physicochemical and biological properties. In 1994, kaplan utilized Chemical Vapor Deposition (CVD) technology to deposit Ta on a carbon matrix, successfully obtained a porous tantalum stent similar to cancellous bone, remarkably improved mechanical properties, and effectively improved adhesion, proliferation and mineralization capabilities of osteoblasts due to good infiltration performance and high surface energy. Meanwhile, the porous tantalum material has smaller elastic modulus and higher friction coefficient, so that the stress shielding effect can be effectively avoided, and the loss of edge bones is reduced to the greatest extent. Although the porous tantalum stent has a certain clinical treatment effect, researchers still consider that the porous tantalum implant does not have enough osseointegration capability, which affects the initial stability and long-term repair effect after implantation. Disclosure of Invention The invention aims to overcome the defects in the prior art, and provides a medical nano hydroxyapatite coating porous tantalum implant material which can be similar to the mechanical properties of human bones and can be used as a permanent implant material for being applied to human bone defects and loaded bones or non-loaded parts, and a preparation method thereof, wherein a tantalum coating is uniformly deposited on the surface of a graphite carbon skeleton by a chemical vapor deposition method, then a nano hydroxyapatite coating is prepared on the surface of the tantalum coating by an electrochemical deposition method, and the prepared medical nano hydroxyapatite coating porous tantalum implant material has high porosity of more than 70% and elastic modulus of less than 30Gpa. In order to achieve the above purpose, the technical scheme of the invention is as follows: the preparation method of the medical nano hydroxyapatite coating porous tantalum implant material comprises the following steps: S1, etching a graphite carbon skeleton by adopting an HCl solution, washing and drying to obtain a porous carbon skeleton, and placing the porous carbon skeleton into a vapor deposition reaction chamber; s2, introducing a processing gas and a reducing gas into a vapor deposition reaction chamber to perform vapor deposition so as to deposit a tantalum coating on the surface of the porous carbon skeleton, thereby obtaining a porous tantalum metal bracket; s3, dissolving a calcium source, a phosphorus source and sodium chloride in deionized water to obtain a mixed solution; S4, adjusting the pH value of the mixed solution to 4.3 by adopting a pH regulator to obtain an electrolyte; And S5, taking the tantalum metal porous support as a working electrode, taking graphite as a counter electrode, performing electrochemical deposition in the electrolyte by adopting a pulse current mode to deposit a nano hydroxyapatite coating on the surface of the tantalum metal porous support, and washing and drying to obtain the medical nano hydroxyapatite coating porous tantalum implant material. The invention also discloses a medical nano-hydroxyapatite coating porous tantalum implantation material prepared by the preparation method, which comprises a porous carbon skeleton and a composite coating, wherein the composite coating comprises a tantalum coating deposited on the porous carbon skeleton in a vapor phase and a nano-hydroxyapatite coating deposited on the tantalum coating in an electrochemical mode, and the weight ratio of the tantalum coating in the composite coating is 70% -80%. The implementation of the embodiment of the invention has the following beneficial effects: (1) The medical nano hydroxyapatite coating porous tantalum implant material has high aperture ratio and communication porosity, uniform pores, a mutually communicated porous structure and less dead space of the pores, is similar to human cancellous bone, and can pro