Magnesium alloy implant composite material and preparation method and application thereof

Abstract

The invention discloses a magnesium alloy implant composite material and a preparation method and application thereof. The magnesium alloy implant composite material is prepared by the following steps of: by taking a model manufactured from magnesium alloy powder through 3D printing as a magnesium alloy implant substrate, forming a micro-arc oxidation layer on the surface of the magnesium alloy implant substrate through a micro-arc oxidation method; then forming a hydroxyapatite layer or a hydroxyfluorapatite layer on the surface of the micro-arc oxidation layer by means of an electrochemical deposition method; and finally, immersing the surface of the hydroxyapatite layer or the hydroxyfluorapatite layer to form a polylactic acid layer. According to the material provided by the invention, individual development of the magnesium alloy implant material is realized from data acquisition of an original damaged bone structure to preparation of a final multi-coating composite material, so that the high quality magnesium alloy implant composite material is obtained. A polarizing test shows that the anti-corrosive property of the material can be enhanced by four orders of magnitudes, and osteoblast cultivation shows that the magnesium alloy composite material has a better osteocyte promoting ability.

Description

[0001] (1) Technical field

[0002] The invention relates to a magnesium alloy multilayer biocomposite material with good biocompatibility and a preparation method thereof, that is, by scanning the damaged bone structure of the human body with multilayer spiral CT, and then processing and repairing the original data, and then by 3D printing, micro-arc oxidation, electrochemical deposition and other methods to prepare implant composite materials with magnesium alloy / micro-arc oxidation film layer / hydroxyapatite (or fluorohydroxyapatite) / polylactic acid biopolymer layer structure.

[0003] (2) Background technology

[0004] At present, in the field of clinical application, medical metal materials mainly include stainless steel, cobalt-based alloys, and titanium alloys. However, these types of materials have some disadvantages. For example, 316L stainless steel sometimes produces crevice corrosion, friction Corrosion and fatigue corrosion cracking and other issues. Titanium alloy...

Examples

Embodiment 1

[0039] 1. Preparation of magnesium alloy implant matrix

[0040] (1) CT scanning of the patient's bone structure (GE LightSpeed ​​16-slice spiral CT) to collect damaged bone structure data and save the data in DICOM format;

[0041] (2) Input the obtained CT scan data into Materialize three-dimensional modeling software (MaterialiseMagics20), perform threshold division, and then use the region growing method to remove the noise of the imported image, remove redundant data, and segment the damaged bone structure region;

[0042] (3) Obtain the three-dimensional structural data of the damaged bone structure through the calculation of the Materialize three-dimensional modeling software, and then input the obtained three-dimensional data into the UG software (NX9.0) to obtain a digital three-dimensional model of the bone defect, and carry out the repair design of the bone defect;

[0043] (4) Use computer-aided software (CAD) (AutoCAD2010) to design the bone defect module accordin...

Embodiment 2

[0063] Steps (1)~(5) are identical with the conditions in Example 1;

[0064] Step (6) changes the composition of the micro-arc oxidation treatment liquid in the embodiment 1 step (6) into: 8g / L Na 2 SiO 3 , 10g / LNa 3 PO 4 , 8g / L NaOH, 3g / L KF, 3g / L Na 2 CO 3 , 1g / L KOH, 50mL / L absolute ethanol, the solvent is deionized water, and the pH value is natural. The control parameters of the micro-arc oxidation were changed to: the frequency is 550Hz, the micro-arc time is 15min, the duty cycle is 15%, and the current density is 15A / cm 2 , and other conditions remain unchanged; the magnesium alloy implant matrix / micro-arc oxidation film layer is obtained.

[0065] Step (7) changes the composition of the electrochemical deposition solution in the embodiment 1 step (7) to: 0.042mol / L Ca(NO 3 ) 2 , 0.5mol / L NaNO 3 , 0.025mol / L NH 4 h 2 PO 4 , 30mL / L absolute ethanol, 30mL / L hydrogen peroxide, 0.004mol / L alkylphenol polyoxyethylene ether OP-21, 0.1mol / L trisodium citrate, 0.0...

Embodiment 3

[0069] Steps (1)~(5) are identical with the conditions in Example 1;

[0070] Step (6) changes the composition of the micro-arc oxidation treatment liquid in the embodiment 1 step (6) into: 12g / L Na 2 SiO 3 , 12g / L Na 3 PO 4 , 10g / L NaOH, 7g / L KF, 8g / L Na 2 CO 3 , 5g / L KOH, 100mL / L absolute ethanol, the solvent is deionized water, and the pH value is natural. The control parameters of micro-arc oxidation are changed to: frequency is 650Hz, micro-arc time is 30min, duty cycle is 30%, current density is 20A / cm 2 , and other conditions remain unchanged; the magnesium alloy implant matrix / micro-arc oxidation film layer is obtained.

[0071] Step (7) changes the composition of the electrochemical deposition solution in the embodiment 1 step (7) to: 0.042mol / L Ca(NO 3 ) 2 , 0.5mol / L NaNO 3 , 0.025mol / L NH 4 h 2 PO 4 , 50mL / L absolute ethanol, 50mL / L hydrogen peroxide, 0.006mol / L alkylphenol polyoxyethylene ether OP-21, 0.2mol / L trisodium citrate, 0.0008mol / L NaF, the sol...

[0001] (1) Technical field

[0002] The invention relates to a magnesium alloy multilayer biocomposite material with good biocompatibility and a preparation method thereof, that is, by scanning the damaged bone structure of the human body with multilayer spiral CT, and then processing and repairing the original data, and then by 3D printing, micro-arc oxidation, electrochemical deposition and other methods to prepare implant composite materials with magnesium alloy / micro-arc oxidation film layer / hydroxyapatite (or fluorohydroxyapatite) / polylactic acid biopolymer layer structure.

[0003] (2) Background technology

[0004] At present, in the field of clinical application, medical metal materials mainly include stainless steel, cobalt-based alloys, and titanium alloys. However, these types of materials have some disadvantages. For example, 316L stainless steel sometimes produces crevice corrosion, friction Corrosion and fatigue corrosion cracking and other issues. Titanium alloy...

Examples

Embodiment 1

[0039] 1. Preparation of magnesium alloy implant matrix

[0040] (1) CT scanning of the patient's bone structure (GE LightSpeed ​​16-slice spiral CT) to collect damaged bone structure data and save the data in DICOM format;

[0041] (2) Input the obtained CT scan data into Materialize three-dimensional modeling software (MaterialiseMagics20), perform threshold division, and then use the region growing method to remove the noise of the imported image, remove redundant data, and segment the damaged bone structure region;

[0042] (3) Obtain the three-dimensional structural data of the damaged bone structure through the calculation of the Materialize three-dimensional modeling software, and then input the obtained three-dimensional data into the UG software (NX9.0) to obtain a digital three-dimensional model of the bone defect, and carry out the repair design of the bone defect;

[0043] (4) Use computer-aided software (CAD) (AutoCAD2010) to design the bone defect module accordin...

Embodiment 2

[0063] Steps (1)~(5) are identical with the conditions in Example 1;

[0064] Step (6) changes the composition of the micro-arc oxidation treatment liquid in the embodiment 1 step (6) into: 8g / L Na 2 SiO 3 , 10g / LNa 3 PO 4 , 8g / L NaOH, 3g / L KF, 3g / L Na 2 CO 3 , 1g / L KOH, 50mL / L absolute ethanol, the solvent is deionized water, and the pH value is natural. The control parameters of the micro-arc oxidation were changed to: the frequency is 550Hz, the micro-arc time is 15min, the duty cycle is 15%, and the current density is 15A / cm 2 , and other conditions remain unchanged; the magnesium alloy implant matrix / micro-arc oxidation film layer is obtained.

[0065] Step (7) changes the composition of the electrochemical deposition solution in the embodiment 1 step (7) to: 0.042mol / L Ca(NO 3 ) 2 , 0.5mol / L NaNO 3 , 0.025mol / L NH 4 h 2 PO 4 , 30mL / L absolute ethanol, 30mL / L hydrogen peroxide, 0.004mol / L alkylphenol polyoxyethylene ether OP-21, 0.1mol / L trisodium citrate, 0.0...

Embodiment 3

[0069] Steps (1)~(5) are identical with the conditions in Example 1;

[0070] Step (6) changes the composition of the micro-arc oxidation treatment liquid in the embodiment 1 step (6) into: 12g / L Na 2 SiO 3 , 12g / L Na 3 PO 4 , 10g / L NaOH, 7g / L KF, 8g / L Na 2 CO 3 , 5g / L KOH, 100mL / L absolute ethanol, the solvent is deionized water, and the pH value is natural. The control parameters of micro-arc oxidation are changed to: frequency is 650Hz, micro-arc time is 30min, duty cycle is 30%, current density is 20A / cm 2 , and other conditions remain unchanged; the magnesium alloy implant matrix / micro-arc oxidation film layer is obtained.

[0071] Step (7) changes the composition of the electrochemical deposition solution in the embodiment 1 step (7) to: 0.042mol / L Ca(NO 3 ) 2 , 0.5mol / L NaNO 3 , 0.025mol / L NH 4 h 2 PO 4 , 50mL / L absolute ethanol, 50mL / L hydrogen peroxide, 0.006mol / L alkylphenol polyoxyethylene ether OP-21, 0.2mol / L trisodium citrate, 0.0008mol / L NaF, the sol...

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