Silver-containing fluorhydroxyapatite coating, and preparation method and application of coating

Abstract

The invention provides a silver-containing fluorhydroxyapatite coating, and a preparation method and an application of the coating. A molecular formula of the coating is as shown below: AgxCa10-x(PO4)6(OH)2-yFy, wherein x is greater than 0 and less than or equal to 10; and y is greater than 0 and less than 2. The coating is applied to a medical magnesium metal surface. The method comprises the steps that a component containing a silver ion is added to an electrodeposition solution; the coating is electrodeposited on the magnesium metal surface; and nitrate solution soaking is performed, so that the stability of the coating is further improved and the uniformity of silver content is ensured. According to the coating, the method and the application, the stability of silver-containing fluorhydroxyapatite is adjusted by adjusting F content and hydroxyl content, so that a degradation cycle and a rate of the silver-containing fluorhydroxyapatite are adjusted and controlled, and the coating is applicable to different application positions and requirements; and the surface has certain porosity, so that bone ingrowth is facilitated, and a binding force of an implant is increased. The coating has effects of controlling bacteria of an implantation position and reducing a postoperative infection rate.

Description

technical field

[0001] The invention relates to a surface modification coating of a biomedical magnesium metal material, in particular to an Ag-containing fluorohydroxyapatite which can be used for a biomedical absorbable magnesium metal implant device and has antibacterial function, and a preparation method thereof . Background technique

[0002] Magnesium metal materials have attracted extensive attention due to their good biocompatibility, high comprehensive mechanical properties, and the characteristics of being degradable and absorbable by the human body. In order to solve the problem that the degradation rate of magnesium metal is too fast, many literatures have reported that the degradation rate is controlled after the coating is prepared through surface modification treatment. Among various surface modification methods, surface modification of hydroxyapatite is one of the most promising methods, because hydroxyapatite can not only effectively slow down the degradati...

Examples

Embodiment 1

[0039] Electrodeposition of Ag-containing FHA coating on the surface of high-purity magnesium screws.

[0040] The first step is to prepare the electrodeposition solution so that its ion concentration is: 0.04mol / L Ca 2+ , 0.02mol / L of H 2 PO 4 - , 2×10 -3 mol / L of fluoride ion F - and 6×10 -4 mol / L AgNO 3 , the pH was adjusted to 4.4.

[0041] In the second step, at a current density of 4mA / cm 2 1. Electrodeposit high-purity magnesium bone screws for 30 minutes at a temperature of 60°C.

[0042] In the third step, the coated bone nail obtained by electrodeposition was soaked in 0.05 mol / L AgNO3 aqueous solution for 20 minutes, and the Ag-containing fluorohydroxyapatite coating was finally obtained.

[0043] figure 2 It is a photograph of the microstructure of Ag-containing FHA taken by a scanning electron microscope. It can be seen that its structure is composed of rod-like or needle-like crystals, forming a coating structure with a certain surface porosity.

[00...

Embodiment 2

[0049] Ag-containing FHA coating was prepared on the surface of AZ31 magnesium alloy bone plate.

[0050] The first step is to prepare the electrodeposition solution, the concentration is: 0.03mol / L Ca 2+ , 0.01mol / L of H 2 PO 4 - , 1×10 -3 mol / L of fluoride ion F - and 5×10 -4 mol / L AgNO 3 , pH adjusted to 4.0.

[0051] In the second step, at a current density of 0.3mA / cm 2 , Electrodeposition for 20 minutes at a temperature of 50°C.

[0052] In the third step, soak the AZ31 bone plate obtained by electrodeposition in 1×10 -4 mol / L AgNO3 aqueous solution, the immersion time is 1 minute, and the Ag-containing fluorohydroxyapatite coating is finally obtained.

[0053] After testing its chemical composition, the molecular formula of the coating is Ag 2 Ca 8 (PO 4 ) 6 (OH) 1.99 f 0.01 , porosity 10%, thickness 2 microns. And after XRD diffraction analysis, the main peak (the first strong peak) of XRD diffraction has a diffraction angle (2θ angle) greater than 25°...

Embodiment 3

[0056] Preparation of Ag-containing FHA coating on ZK60 alloy processed spinal intervertebral fusion cage.

[0057] The first step is to prepare the electrodeposition solution, the concentration is: 0.05mol / L Ca 2+ , 0.03mol / L of H 2 PO 4 - , 3×10 -3 mol / L of fluoride ion F - and 8×10 -4 mol / L AgNO 3 , pH adjusted to 5.0.

[0058] In the second step, at a current density of 6mA / cm 2 , Electrodeposition for 40 minutes at a temperature of 70°C.

[0059] In the third step, the coated intervertebral fusion cage obtained by electrodeposition was soaked in 2mol / L AgNO3 aqueous solution for 60 minutes, and the Ag-containing fluorohydroxyapatite coating was finally obtained.

[0060] After testing its chemical composition, the molecular formula of the coating is Ag 8 Ca 2 (PO 4 ) 6 (OH) 0.2 f 1.8 , porosity 70%, thickness 2 microns. And after XRD diffraction analysis, the main peak (the first strong peak) of XRD diffraction has a diffraction angle (2θ angle) greater th...

technical field

[0001] The invention relates to a surface modification coating of a biomedical magnesium metal material, in particular to an Ag-containing fluorohydroxyapatite which can be used for a biomedical absorbable magnesium metal implant device and has antibacterial function, and a preparation method thereof . Background technique

[0002] Magnesium metal materials have attracted extensive attention due to their good biocompatibility, high comprehensive mechanical properties, and the characteristics of being degradable and absorbable by the human body. In order to solve the problem that the degradation rate of magnesium metal is too fast, many literatures have reported that the degradation rate is controlled after the coating is prepared through surface modification treatment. Among various surface modification methods, surface modification of hydroxyapatite is one of the most promising methods, because hydroxyapatite can not only effectively slow down the degradati...

Examples

Embodiment 1

[0039] Electrodeposition of Ag-containing FHA coating on the surface of high-purity magnesium screws.

[0040] The first step is to prepare the electrodeposition solution so that its ion concentration is: 0.04mol / L Ca 2+ , 0.02mol / L of H 2 PO 4 - , 2×10 -3 mol / L of fluoride ion F - and 6×10 -4 mol / L AgNO 3 , the pH was adjusted to 4.4.

[0041] In the second step, at a current density of 4mA / cm 2 1. Electrodeposit high-purity magnesium bone screws for 30 minutes at a temperature of 60°C.

[0042] In the third step, the coated bone nail obtained by electrodeposition was soaked in 0.05 mol / L AgNO3 aqueous solution for 20 minutes, and the Ag-containing fluorohydroxyapatite coating was finally obtained.

[0043] figure 2 It is a photograph of the microstructure of Ag-containing FHA taken by a scanning electron microscope. It can be seen that its structure is composed of rod-like or needle-like crystals, forming a coating structure with a certain surface porosity.

[00...

Embodiment 2

[0049] Ag-containing FHA coating was prepared on the surface of AZ31 magnesium alloy bone plate.

[0050] The first step is to prepare the electrodeposition solution, the concentration is: 0.03mol / L Ca 2+ , 0.01mol / L of H 2 PO 4 - , 1×10 -3 mol / L of fluoride ion F - and 5×10 -4 mol / L AgNO 3 , pH adjusted to 4.0.

[0051] In the second step, at a current density of 0.3mA / cm 2 , Electrodeposition for 20 minutes at a temperature of 50°C.

[0052] In the third step, soak the AZ31 bone plate obtained by electrodeposition in 1×10 -4 mol / L AgNO3 aqueous solution, the immersion time is 1 minute, and the Ag-containing fluorohydroxyapatite coating is finally obtained.

[0053] After testing its chemical composition, the molecular formula of the coating is Ag 2 Ca 8 (PO 4 ) 6 (OH) 1.99 f 0.01 , porosity 10%, thickness 2 microns. And after XRD diffraction analysis, the main peak (the first strong peak) of XRD diffraction has a diffraction angle (2θ angle) greater than 25°...

Embodiment 3

[0056] Preparation of Ag-containing FHA coating on ZK60 alloy processed spinal intervertebral fusion cage.

[0057] The first step is to prepare the electrodeposition solution, the concentration is: 0.05mol / L Ca 2+ , 0.03mol / L of H 2 PO 4 - , 3×10 -3 mol / L of fluoride ion F - and 8×10 -4 mol / L AgNO 3 , pH adjusted to 5.0.

[0058] In the second step, at a current density of 6mA / cm 2 , Electrodeposition for 40 minutes at a temperature of 70°C.

[0059] In the third step, the coated intervertebral fusion cage obtained by electrodeposition was soaked in 2mol / L AgNO3 aqueous solution for 60 minutes, and the Ag-containing fluorohydroxyapatite coating was finally obtained.

[0060] After testing its chemical composition, the molecular formula of the coating is Ag 8 Ca 2 (PO 4 ) 6 (OH) 0.2 f 1.8 , porosity 70%, thickness 2 microns. And after XRD diffraction analysis, the main peak (the first strong peak) of XRD diffraction has a diffraction angle (2θ angle) greater th...

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