CN115814151A - Preparation method of 3D printing bone implant surface multilevel micron structure - Google Patents

Preparation method of 3D printing bone implant surface multilevel micron structure Download PDF

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CN115814151A
CN115814151A CN202211646389.8A CN202211646389A CN115814151A CN 115814151 A CN115814151 A CN 115814151A CN 202211646389 A CN202211646389 A CN 202211646389A CN 115814151 A CN115814151 A CN 115814151A
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bone implant
titanium alloy
acid
sand blasting
treatment
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赵素丽
岳术俊
许奎雪
宋宁宁
吴倩
李慧
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Beijing Chunlizhengda Medical Instruments Co Ltd
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Beijing Chunlizhengda Medical Instruments Co Ltd
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Abstract

The invention discloses a preparation method of a 3D printing bone implant surface multistage micron structure, and belongs to the technical field of artificial prostheses. The method specifically comprises the following steps of S1, preparing a 3D printing titanium alloy bone implant, S2, pre-cleaning, S3, performing sand blasting treatment, S4, performing acid etching treatment, S5, performing secondary cleaning, S6, performing alkali treatment, and S7, performing tertiary cleaning. The invention has better hydrophilicity and improves the bioactivity.

Description

Preparation method of 3D printing bone implant surface multilevel micron structure
Technical Field
The invention relates to the technical field of artificial prostheses, in particular to a preparation method of a 3D printing bone implant surface multilevel micron structure.
Background
In recent years, 3D printing and molding techniques have been studied and developed in various fields. Because the 3D printing technology has the advantages of rapid forming, personalized customization and the like, the 3D printing bone implant replaces the damaged bone tissue of the human body to become an important part in the field of biological medical treatment. However, the titanium alloy implant formed by 3D printing still has the disadvantages of the conventional formed titanium alloy implant, namely, the defects of low surface bioactivity, incapability of actively inducing osteogenesis and the like.
Disclosure of Invention
In order to solve the problems existing in the prior art, the invention provides a preparation method of a 3D printing bone implant surface multilevel micron structure. It has good hydrophilicity and improved bioactivity.
The technical solution of the present invention is achieved in that,
a preparation method of a 3D printing bone implant surface multilevel micron structure specifically comprises the following steps:
step 1, preparing a 3D printed titanium alloy bone implant, wherein the pore diameter of a trabecular bone porous structure on the titanium alloy bone implant is as follows: 500 +/-300 mu m; the silk diameter of the trabecular bone porous structure is as follows: 500 +/-200 mu m; porosity of trabecular bone porous structure: 50% -80%;
step 2, ultrasonically cleaning the titanium alloy bone implant for 10min by using analytically pure acetone, alcohol and deionized water in sequence, and then drying the titanium alloy bone implant in a drying oven;
step 3, carrying out sand blasting treatment on the surface of the dried titanium alloy bone implant;
and 4, placing the titanium alloy bone implant subjected to sand blasting into an acid etching solution for acid etching treatment, wherein the acid etching treatment temperature is 20-60 ℃, and the acid etching treatment time is 10-40 min. The acid etching solution comprises the following components of hydrochloric acid, nitric acid, hydrofluoric acid, an acid mist inhibitor and water, wherein the volume ratio of the hydrochloric acid to the nitric acid to the hydrofluoric acid to the water is (2-5): (1-4): (1-2): (4-10), the mass fraction of the acid mist inhibitor is 0.1-0.8%;
step 5, ultrasonically cleaning the titanium alloy bone implant subjected to acid etching treatment in absolute ethyl alcohol and deionized water for multiple times, wherein each time of cleaning is at least 10min;
step 6, soaking the titanium alloy bone implant which is washed for many times in the step 5 in alkali liquor for 5 to 20 hours, wherein the soaking temperature is 5 to 60 ℃, and the concentration of the alkali liquor is 1 to 10mol/L; after alkali treatment, the water contact angle is between 30 and 70 degrees;
and 7, ultrasonically cleaning the titanium alloy bone implant subjected to alkali treatment in absolute ethyl alcohol and deionized water for a plurality of times, wherein each time of cleaning is at least 10min.
Further, the sand blasting treatment in the step 3 is specifically as follows:
adopting a mixed sand blasting medium, wherein the mixed sand blasting medium comprises white corundum, titanium dioxide, rutile sand and aluminum oxide, and the white corundum, the titanium dioxide, the rutile sand and the aluminum oxide are all 20-100 meshes; the sand blasting pressure is 2-8 bar, and the sand blasting time is 20-120 s.
Compared with the prior art, the invention has the following beneficial effects:
1. the material is 3D printing titanium alloy, and the problems that the existing sand blasting and acid etching process is not suitable for the 3D printing material and a multi-stage microporous structure cannot be prepared on the surface of the 3D printing material can be solved.
2. The surface microporous structure prepared by the invention mainly improves the surface roughness, has better hydrophilicity, and is beneficial to the attachment, proliferation and growth of osteoblasts.
3. The spraying material adopted by the sand blasting treatment in the invention is a mixture of different types and different particle sizes, a deeper multistage pit structure can be formed on the surface of the material, and the effects of cell adhesion, proliferation and osteoblast differentiation are better.
4. The acid etching treatment in the invention adds the acid mist inhibitor, which can solve the problem that a large amount of volatile acid etching liquid in the prior art damages the environment and operators.
5. According to the method, a deeper hole structure can be prepared on the surface of the 3D printing material through acid etching treatment, so that the specific surface area is further increased, and the roughness is increased.
6. The alkali treatment in the invention can improve the surface hydrophobicity of the implant, so that the implant has better hydrophilicity and improves the bioactivity.
Drawings
Fig. 1 is a scanning electron microscope image of a titanium alloy bone implant according to example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of a titanium alloy bone implant according to example 2 of the present invention.
Fig. 3 is a scanning electron microscope image of a titanium alloy bone implant according to example 3 of the present invention.
Fig. 4 is a scanning electron microscope image of a titanium alloy bone implant according to example 4 of the present invention.
Fig. 5 is a scanning electron microscope image of a titanium alloy bone implant according to example 1 of the present invention before sandblasting and acid etching.
Fig. 6 is a scanning electron microscope image of the titanium alloy bone implant subjected to sand blasting and acid etching in example 1 of the present invention.
Fig. 7 is a graph comparing the water contact angles after the blast etching of examples 1 to 4 of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A preparation method of a 3D printing bone implant surface multilevel micron structure specifically comprises the following steps:
step 1, preparing a 3D printed titanium alloy bone implant, wherein the pore diameter of a trabecular bone porous structure on the titanium alloy bone implant is as follows: 500 +/-300 mu m; the silk diameter of the trabecular bone porous structure is as follows: 500 +/-200 mu m; porosity of trabecular bone porous structure: 50% -80%;
step 2, ultrasonically cleaning the titanium alloy bone implant for 10min by using analytically pure acetone, alcohol and deionized water in sequence, and then drying the titanium alloy bone implant in a drying oven;
step 3, carrying out sand blasting treatment on the surface of the dried titanium alloy bone implant;
and 4, placing the titanium alloy bone implant subjected to sand blasting into an acid etching solution for acid etching treatment, wherein the acid etching treatment temperature is 20-60 ℃, and the acid etching treatment time is 10-40 min. The acid etching solution comprises the following components of hydrochloric acid, nitric acid, hydrofluoric acid, an acid mist inhibitor and water, wherein the volume ratio of the hydrochloric acid to the nitric acid to the hydrofluoric acid to the water is (2-5): (1-4): (1-2): (4-10), the mass fraction of the acid mist inhibitor is 0.1-0.8%;
step 5, ultrasonically cleaning the titanium alloy bone implant subjected to acid etching treatment in absolute ethyl alcohol and deionized water for multiple times, wherein each time of cleaning is at least 10min;
step 6, soaking the titanium alloy bone implant which is washed for many times in the step 5 in alkali liquor for 5 to 20 hours, wherein the soaking temperature is 5 to 60 ℃, and the concentration of the alkali liquor is 1 to 10mol/L; after alkali treatment, the water contact angle is between 30 and 70 degrees;
and 7, ultrasonically cleaning the titanium alloy bone implant subjected to alkali treatment in absolute ethyl alcohol and deionized water for a plurality of times, wherein each time of cleaning is at least 10min.
Further, the sand blasting treatment in the step 3 is specifically as follows:
adopting a mixed sand blasting medium, wherein the mixed sand blasting medium comprises white corundum, titanium dioxide, rutile sand and alumina, and the white corundum, the titanium dioxide, the rutile sand and the alumina are all 20-100 meshes; the sand blasting pressure is 2-8 bar, and the sand blasting time is 20-120 s.
The following are more specific examples:
example 1
(1) Preparing a 3D printed titanium alloy bone implant, wherein the pore size of the trabecular bone porous structure is: 500 +/-300 mu m; the silk diameter of the trabecular bone porous structure is as follows: 500 +/-200 mu m; porosity of trabecular bone porous structure: 50 to 80 percent.
(2) Pre-cleaning: and (3) taking the 3D printed titanium alloy bone implant, ultrasonically cleaning the implant for 10min by using analytically pure acetone, alcohol and deionized water in sequence, drying the implant in a drying oven, and storing the implant for later use.
(3) Sand blasting treatment: and carrying out sand blasting treatment on the surface of the cleaned 3D printed titanium alloy bone implant, wherein the sand blasting treatment adopts mixed sand blasting media with different types and different particle sizes, the mixed sand blasting media comprise a mixture of 20-40 meshes of white corundum, titanium dioxide, rutile sand and alumina, the sand blasting pressure is 4bar, and the sand blasting time is 20s.
(4) Acid etching treatment: and (3) placing the bone implant subjected to sand blasting into an acid etching solution for acid etching treatment, wherein the acid etching treatment temperature is 45 ℃, and the acid etching treatment time is 20min. The acid etching solution comprises the components of hydrochloric acid, nitric acid, hydrofluoric acid, an acid mist inhibitor and water, wherein the volume ratio of the hydrochloric acid to the nitric acid to the hydrofluoric acid to the water is 2:1:1:8, the mass fraction of the acid mist inhibitor is 0.2 percent.
(5) Secondary cleaning: and ultrasonically cleaning the 3D printed bone implant prosthesis subjected to acid etching treatment in absolute ethyl alcohol and deionized water for multiple times, wherein each cleaning is at least 10min.
(6) Alkali treatment: and soaking the cleaned 3D printed bone implant prosthesis in a sodium hydroxide solution for 10 hours, wherein the soaking temperature is 55 ℃, and the concentration of an alkali liquor is 6mol/L. After alkali treatment, the water contact angle is between 30 and 70 degrees, which is a better contact angle range for promoting cell adhesion and can accelerate cell adherence.
(7) And (3) washing for three times: ultrasonically cleaning the 3D printed bone implant prosthesis subjected to alkali treatment in absolute ethyl alcohol and deionized water respectively for multiple times, wherein each cleaning is at least 10min.
A scanning electron micrograph of the titanium alloy bone implant of example 1 is shown in fig. 1.
Referring to fig. 5 and 6, scanning electron micrographs before and after blasting.
Example 2
(1) Preparing a 3D printed titanium alloy bone implant, wherein the pore size of the trabecular bone porous structure is: 500 +/-300 mu m; the silk diameter of the trabecular bone porous structure is as follows: 500 +/-200 mu m; porosity of trabecular bone porous structure: 50 to 80 percent.
(2) Pre-cleaning: and (3) taking the 3D printed titanium alloy bone implant, ultrasonically cleaning the implant for 10min by using analytically pure acetone, alcohol and deionized water in sequence, drying the implant in a drying oven, and storing the implant for later use.
(3) Sand blasting treatment: and carrying out sand blasting treatment on the surface of the cleaned 3D printed titanium alloy bone implant, wherein the sand blasting treatment adopts mixed sand blasting media with different types and different particle sizes, the mixed sand blasting media comprise a mixture of 40-60 meshes of white corundum, titanium dioxide, rutile sand and alumina, the sand blasting pressure is 4bar, and the sand blasting time is 30s.
(4) Acid etching treatment: and (3) placing the bone implant subjected to sand blasting into an acid etching solution for acid etching treatment, wherein the acid etching treatment temperature is 45 ℃, and the acid etching treatment time is 25min. The components of the acid etching solution are hydrochloric acid, nitric acid, hydrofluoric acid, an acid mist inhibitor and water, wherein the volume ratio of the hydrochloric acid to the nitric acid to the hydrofluoric acid to the water is 2:2:1:8, the mass fraction of the acid mist inhibitor is 0.2 percent.
(5) Secondary cleaning: and ultrasonically cleaning the 3D printed bone implant prosthesis subjected to acid etching treatment in absolute ethyl alcohol and deionized water for multiple times, wherein each cleaning is at least 10min.
(6) Alkali treatment: and soaking the cleaned 3D printed bone implant prosthesis in alkali liquor for 8 hours, wherein the soaking temperature is 60 ℃, and the concentration of the alkali liquor is 8mol/L. After alkali treatment, the water contact angle is between 30 and 70 degrees, which is a better contact angle range for promoting cell adhesion and can accelerate cell adherence.
(7) And (3) washing for three times: ultrasonically cleaning the 3D printed bone implant prosthesis subjected to alkali treatment in absolute ethyl alcohol and deionized water respectively for multiple times, wherein each cleaning is at least 10min.
A scanning electron micrograph of the titanium alloy bone implant of example 2 is shown in fig. 2.
Example 3
(1) Preparing a 3D printed titanium alloy bone implant, wherein the pore size of the trabecular bone porous structure is: 500 +/-300 mu m; the silk diameter of the trabecular bone porous structure is: 500 +/-200 mu m; porosity of trabecular bone porous structure: 50 to 80 percent.
(2) Pre-cleaning: and (3) taking the 3D printed titanium alloy bone implant, ultrasonically cleaning the implant for 10min by using analytically pure acetone, alcohol and deionized water in sequence, drying the implant in a drying oven, and storing the implant for later use.
(3) Sand blasting treatment: and carrying out sand blasting treatment on the surface of the cleaned 3D printed titanium alloy bone implant, wherein the sand blasting treatment adopts mixed sand blasting media with different types and different particle sizes, the mixed sand blasting media comprise a mixture of 60-80 meshes of white corundum, titanium dioxide, rutile sand and alumina, the sand blasting pressure is 3bar, and the sand blasting time is 25s.
(4) Acid etching treatment: and (3) placing the bone implant subjected to sand blasting into an acid etching solution for acid etching treatment, wherein the acid etching treatment temperature is 50 ℃, and the acid etching treatment time is 30min. The components of the acid etching solution are hydrochloric acid, nitric acid, hydrofluoric acid, an acid mist inhibitor and water, wherein the volume ratio of the hydrochloric acid to the nitric acid to the hydrofluoric acid to the water is 1:2:1:6, the mass fraction of the acid mist inhibitor is 0.15%.
(5) Secondary cleaning: and ultrasonically cleaning the 3D printed bone implant prosthesis subjected to acid etching treatment in absolute ethyl alcohol and deionized water for multiple times, wherein each cleaning is at least 10min.
(6) Alkali treatment: and soaking the cleaned 3D printed bone implant prosthesis in alkali liquor for 10 hours, wherein the soaking temperature is 55 ℃, and the concentration of the alkali liquor is 10mol/L. After alkali treatment, the water contact angle is between 30 and 70 degrees, which is a better contact angle range for promoting cell adhesion and can accelerate cell adherence.
(7) And (3) washing for three times: ultrasonically cleaning the 3D printed bone implant prosthesis subjected to alkali treatment in absolute ethyl alcohol and deionized water respectively for multiple times, wherein each cleaning is at least 10min.
A scanning electron micrograph of the titanium alloy bone implant of example 3 is shown in fig. 3.
Example 4
(1) Preparing a 3D printed titanium alloy bone implant, wherein the pore size of the trabecular bone porous structure is: 500 +/-300 mu m; the silk diameter of the trabecular bone porous structure is as follows: 500 +/-200 mu m; porosity of trabecular bone porous structure: 50 to 80 percent.
(2) Pre-cleaning: and (3) taking the 3D printed titanium alloy bone implant, ultrasonically cleaning the implant for 10min by using analytically pure acetone, alcohol and deionized water in sequence, drying the implant in a drying oven, and storing the implant for later use.
(3) Sand blasting treatment: and carrying out sand blasting treatment on the surface of the cleaned 3D printed titanium alloy bone implant, wherein the sand blasting treatment adopts mixed sand blasting media with different types and different particle sizes, the mixed sand blasting media comprise a mixture of 20-40 meshes of white corundum, titanium dioxide, rutile sand and alumina, the sand blasting pressure is 3bar, and the sand blasting time is 20s.
(4) Acid etching treatment: and (3) placing the bone implant subjected to sand blasting into an acid etching solution for acid etching treatment, wherein the acid etching treatment temperature is 50 ℃, and the acid etching treatment time is 20min. The acid etching solution comprises the components of hydrochloric acid, nitric acid, hydrofluoric acid, an acid mist inhibitor and water, wherein the volume ratio of the hydrochloric acid to the nitric acid to the hydrofluoric acid to the water is 2:2:2:10, the mass fraction of the acid mist inhibitor is 0.2 percent.
(5) Secondary cleaning: and ultrasonically cleaning the 3D printed bone implant prosthesis subjected to acid etching treatment in absolute ethyl alcohol and deionized water for multiple times, wherein each cleaning is at least 10min.
(6) Alkali treatment: and soaking the cleaned 3D printed bone implant prosthesis in alkali liquor for 15 hours, wherein the soaking temperature is 60 ℃, and the concentration of the alkali liquor is 6mol/L. After alkali treatment, the water contact angle is between 30 and 70 degrees, which is a better contact angle range for promoting cell adhesion and can accelerate cell adherence.
(7) And (3) washing for three times: ultrasonically cleaning the 3D printed bone implant prosthesis subjected to alkali treatment in absolute ethyl alcohol and deionized water respectively for multiple times, wherein each cleaning is at least 10min.
A scanning electron micrograph of the titanium alloy bone implant of example 4 is shown in fig. 4.
A comparison of the water contact angles after the blast etching of examples 1 to 4 is shown in fig. 7.
The above description is only an embodiment of the present invention, but the present invention is not limited to the embodiment. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit and principle of the invention, and the equivalents or substitutions are included in the scope defined by the claims of the present application.

Claims (2)

1. A preparation method of a 3D printing bone implant surface multilevel micron structure is characterized by comprising the following steps:
step 1, preparing a 3D printed titanium alloy bone implant, wherein the pore diameter of a trabecular bone porous structure on the titanium alloy bone implant is as follows: 500 +/-300 mu m; the silk diameter of the trabecular bone porous structure is as follows: 500 +/-200 mu m; porosity of trabecular bone porous structure: 50% -80%;
step 2, ultrasonically cleaning the titanium alloy bone implant for 10min by using analytically pure acetone, alcohol and deionized water in sequence, and then drying the titanium alloy bone implant in a drying oven;
step 3, carrying out sand blasting treatment on the surface of the dried titanium alloy bone implant;
and 4, placing the titanium alloy bone implant subjected to sand blasting into an acid etching solution for acid etching treatment, wherein the acid etching treatment temperature is 20-60 ℃, and the acid etching treatment time is 10-40 min. The acid etching solution comprises the following components of hydrochloric acid, nitric acid, hydrofluoric acid, an acid mist inhibitor and water, wherein the volume ratio of the hydrochloric acid to the nitric acid to the hydrofluoric acid to the water is (2-5): (1-4): (1-2): (4-10), wherein the mass fraction of the acid mist inhibitor is 0.1-0.8%;
step 5, ultrasonically cleaning the titanium alloy bone implant subjected to acid etching treatment in absolute ethyl alcohol and deionized water for multiple times, wherein each time of cleaning is at least 10min;
step 6, soaking the titanium alloy bone implant which is washed for many times in the step 5 in alkali liquor for 5 to 20 hours, wherein the soaking temperature is 5 to 60 ℃, and the concentration of the alkali liquor is 1 to 10mol/L; after alkali treatment, the water contact angle is between 30 and 70 degrees;
and 7, ultrasonically cleaning the titanium alloy bone implant subjected to alkali treatment in absolute ethyl alcohol and deionized water for a plurality of times, wherein each time of cleaning is at least 10min.
2. The method for preparing the 3D printing bone implant surface multilevel micron structure according to the claim 1, wherein the sand blasting treatment in the step 3 is as follows:
adopting a mixed sand blasting medium, wherein the mixed sand blasting medium comprises white corundum, titanium dioxide, rutile sand and alumina, and the white corundum, the titanium dioxide, the rutile sand and the alumina are all 20-100 meshes; the sand blasting pressure is 2-8 bar, and the sand blasting time is 20-120 s.
CN202211646389.8A 2022-12-21 2022-12-21 Preparation method of 3D printing bone implant surface multilevel micron structure Pending CN115814151A (en)

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