A SLM-molded titanium mesh and its surface treatment method

Abstract

The present invention discloses a SLM-molded titanium mesh and a surface treatment method thereof, belonging to the technical field of biomedical implantable metal materials; the surface treatment method provided by the present invention comprises laser remelting, pickling, anodizing treatment, and hydrophobic treatment. The surface treatment method of the SLM-molded titanium mesh provided by the present invention combines the steps of laser remelting, pickling, anodizing treatment, and hydrophobic treatment, thereby obtaining an SLM-molded titanium mesh with high strength and strong hydrophobicity, which can be easily removed after bone augmentation is completed in subsequent applications. In addition, the surface treatment method provided by the present invention is simple to operate, has low equipment requirements, and is suitable for practical use.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical implant metal materials, and in particular relates to a SLM-molded titanium mesh and a surface treatment method thereof. Background Art

[0002] Titanium-based metals have a high yield strength, can easily distribute stress to adjacent bone tissue, and have good biocompatibility, making them the most attractive bone implant materials. With the aging of the domestic population, more and more people are facing the troubles caused by tooth loss, and denture restoration is the preferred treatment for tooth loss. Denture restoration requires implants to be implanted in the alveolar bone to form a good bone bond. Mechanical damage or long-term tooth loss can lead to alveolar bone defects or atrophy, so the regeneration and reconstruction of alveolar bone defects in the implant area are the key points and difficulties of oral implants. For patients with alveolar bone defects, titanium mesh is usually used for bone augmentation surgery first. After the alveolar bone repair is stable, the titanium mesh is surgically removed and dental implants are implanted. The titanium mesh currently used commercially is a two-dimensional plane of different sizes and pore sizes. According to the degree of local alveolar bone loss of different patients, it is manually shaped during bone augmentation surgery to fit the patient's alveolar bone morphology as much as possible.

[0003] Titanium mesh manufactured using traditional techniques has a simple structure and requires doctors to bend it before use. This is prone to residual stress and is time-consuming. It increases the probability of infection and also increases the patient's pain. It is also difficult to fit the alveolar bone defect perfectly. The sharp edges produced when trimming the titanium mesh can easily cause mechanical damage to the mucosal flap, leading to soft tissue trauma and exposure of the titanium mesh. Traditional titanium mesh has poor clinical effects and cannot meet the precise requirements of bone augmentation treatment. For titanium mesh that has not been surface treated, new bone can easily grow into the titanium mesh during alveolar bone repair and fixation, making secondary removal of the titanium mesh more difficult and even causing adverse effects on the new alveolar bone. Summary of the Invention

[0004] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a SLM-molded titanium mesh with high strength and easy secondary removal after bone augmentation, and a surface treatment method thereof.

[0005] To achieve the above object, the technical solution adopted by the present invention is: a surface treatment method for SLM-molded titanium mesh, the surface treatment method comprising the following steps:

[0006] (1) Laser remelting: Pulsed laser is used to remelt the surface of the SLM-molded titanium mesh;

[0007] (2) Pickling: placing the SLM-molded titanium mesh obtained in step (1) in a pickling solution for pickling treatment;

[0008] (3) Anodizing treatment: placing the SLM-molded titanium mesh obtained in step (2) into an electrolyte for anodizing;

[0009] (4) Hydrophobic treatment: The SLM-molded titanium mesh obtained in step (3) is placed in a perfluorozinc acid aqueous solution for hydrophobic treatment, and then dried to obtain the SLM-molded titanium mesh.

[0010] The present invention provides a surface treatment method for SLM-molded titanium mesh, combining the steps of laser remelting, pickling, anodizing, and hydrophobizing. This method can produce a SLM-molded titanium mesh with high strength and strong hydrophobicity, making it easy to remove after bone augmentation in subsequent applications. Specifically, laser remelting can remove surface defects and incompletely melted titanium spheres from the SLM-molded titanium mesh, pickling can remove debris generated during the laser remelting process, anodizing can form micro-nanostructures on the surface in combination with laser remelting, and hydrophobizing can further increase the surface water contact angle of the SLM-molded titanium mesh, thereby facilitating subsequent removal.

[0011] As a preferred embodiment of the surface treatment method described in the present invention, the preparation process of the SLM-molded titanium mesh without surface treatment includes the following steps: using an oral scanner to perform an oral scan of the patient's alveolar bone loss area to obtain corresponding data, and establishing a personalized titanium mesh model through CAD design software; then importing the personalized designed titanium mesh three-dimensional model into the selective laser melting molding equipment, using titanium powder as raw material, scanning layer by layer to obtain the SLM-molded titanium mesh without surface treatment.

[0012] The unsurface-treated SLM-molded titanium mesh prepared by the above method can fit the patient's alveolar bone defect well, providing a basis for subsequent precise treatment.

[0013] As a preferred embodiment of the surface treatment method of the present invention, in steps (1) to (3), after each step, the obtained SLM-molded titanium mesh is sequentially placed in acetone, 95% ethanol, and deionized water for ultrasonic cleaning and drying.

[0014] As a preferred embodiment of the surface treatment method of the present invention, in step (1), the remelting temperature is 5-10°C, and the parameters of the pulse laser are: speed of 1 mm / s, power of 9000-15000%, and frequency of 70 kHz.

[0015] As a preferred embodiment of the surface treatment method of the present invention, in step (2), the pickling solution is a mixture of nitric acid, hydrofluoric acid and deionized water, and the mass ratio of nitric acid, hydrofluoric acid and deionized water in the pickling solution is nitric acid: hydrofluoric acid: deionized water = (2.3-3.0): (0.1-0.6): (6-8).

[0016] As a preferred embodiment of the surface treatment method of the present invention, in the step (2), the pickling temperature is 40-80° C., and the pickling time is 5-15 seconds.

[0017] As a preferred embodiment of the surface treatment method of the present invention, in step (3), the electrolyte is a hydrofluoric acid aqueous solution with a mass percentage of 0.25-1%.

[0018] As a preferred embodiment of the surface treatment method of the present invention, in step (3), the parameters of the anodic oxidation are: the distance between the anode and the cathode is 3-6 cm, the anode is a titanium mesh, the cathode is a copper plate, the voltage is 20-50 V, and the oxidation time is 0.5-2 h.

[0019] As a preferred embodiment of the surface treatment method of the present invention, in step (4), the molar concentration of the perfluorozincic acid aqueous solution is (0.005-0.015) mol / L, the hydrophobicization temperature is 22-28°C, and the hydrophobicization treatment time is 50-70 min.

[0020] As a preferred embodiment of the surface treatment method of the present invention, in step (4), the anodized titanium mesh is placed in a perfluorozinc acid aqueous solution for hydrophobic treatment, and the drying step after the treatment is repeated three times. After the third drying, the SLM-molded titanium mesh is obtained.

[0021] The inventors have found that when the preferred parameters of each step are within the above range, the hardness of the SLM-molded titanium mesh obtained after surface treatment is more significantly improved and the hydrophobicity improvement effect is also better.

[0022] In addition, the present invention also provides an SLM-molded titanium mesh, which is prepared using the preparation method of the present invention.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The surface treatment method for SLM-formed titanium mesh provided by the present invention combines laser remelting, pickling, anodizing, and hydrophobicity treatment to produce a strong, highly hydrophobic SLM-formed titanium mesh. This allows for easy removal after bone augmentation in subsequent applications. Furthermore, the surface treatment method provided by the present invention is simple to operate and requires minimal equipment, making it suitable for practical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a macroscopic morphology of the SLM-formed titanium mesh without surface treatment in Example 1 of the present invention;

[0026] Figure 2This is a microscopic morphology image (50X) of the SLM-molded titanium mesh without surface treatment in Example 1 of the present invention;

[0027] Figure 3 This is a surface morphology image (2000X) after pickling and cleaning in Example 1 of the present invention;

[0028] Figure 4 This is the surface morphology image (9000X) after anodizing and cleaning in Example 1 of the present invention. DETAILED DESCRIPTION

[0029] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0030] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0031] Example 1

[0032] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, which specifically includes the following steps:

[0033] (1) Construction of SLM-molded titanium mesh without surface treatment: The oral cavity of patient 1 with alveolar bone loss was scanned using an oral scanner to obtain the corresponding data, and a personalized titanium mesh model was established using CAD design software. The personalized titanium mesh 3D model was then imported into the selective laser melting molding equipment, and titanium powder was used as the raw material. The SLM-molded titanium mesh without surface treatment was scanned layer by layer. The macroscopic morphology of the obtained SLM-molded titanium mesh without surface treatment is shown in FIG. Figure 1 As shown, the microscopic morphology is Figure 2 (Magnification 50 times) shown;

[0034] (2) Laser remelting and cleaning: The surface of the SLM-molded titanium mesh obtained in step (1) was remelted using a pulsed laser at 8°C, wherein the pulsed laser parameters were: speed 1 mm / s, power 12000%, and frequency 70 kHz; after laser remelting, the SLM-molded titanium mesh was ultrasonically cleaned in acetone, 95% ethanol, and deionized water for 10 min, respectively, and then taken out and dried;

[0035] (3) Pickling and cleaning: The SLM-molded titanium mesh obtained in step (2) was placed in a pickling solution (nitric acid: hydrofluoric acid: deionized water = 2.7:0.4:6.9) at a temperature of 40°C for 10 seconds, and then the SLM-molded titanium mesh was placed in acetone, 95% ethanol, and deionized water for ultrasonic cleaning for 10 minutes respectively, and then taken out and dried; the surface morphology of the SLM-molded titanium mesh after pickling and cleaning was as follows: Figure 3(Magnification 2000 times) shown;

[0036] (4) Anodizing and cleaning: The SLM-molded titanium mesh obtained in step (3) was placed as an anode and a copper plate as a cathode in an electrolyte (the electrolyte was a hydrofluoric acid aqueous solution with a mass percentage of 0.25%), with a distance of 3 cm between the two electrodes. A DC regulated power supply was used to provide a voltage of 20 V for pulse anodizing for 2 h at room temperature. The SLM-molded titanium mesh was then placed in acetone, 95% ethanol, and deionized water for ultrasonic cleaning for 10 min, respectively, and then taken out and dried. The surface morphology of the anodized and cleaned titanium mesh was as follows: Figure 4 (Magnification 9000 times) shown;

[0037] (5) Hydrophobic treatment: The SLM-molded titanium mesh obtained in step (4) was immersed in a 0.01 mol / L, 25°C perfluorozinc acid aqueous solution for 1 h, then taken out and dried. The cycle was repeated 3 times to obtain the SLM-molded titanium mesh.

[0038] Example 2

[0039] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, which specifically includes the following steps:

[0040] (1) Construction of SLM-molded titanium mesh without surface treatment: An oral scanner was used to scan the alveolar bone loss area of ​​patient 2 to obtain the corresponding data, and a personalized titanium mesh model was established using CAD design software; the personalized titanium mesh 3D model was then imported into the selective laser melting molding equipment, and titanium powder was used as the raw material, and the SLM-molded titanium mesh without surface treatment was obtained by scanning layer by layer;

[0041] (2) Laser remelting and cleaning: The surface of the SLM-molded titanium mesh obtained in step (1) was remelted using a pulsed laser at 5°C, wherein the pulsed laser parameters were: speed 1 mm / s, power 9000%, and frequency 70 kHz; after laser remelting, the SLM-molded titanium mesh was ultrasonically cleaned in acetone, 95% ethanol, and deionized water for 10 min, respectively, and then taken out and dried;

[0042] (3) Pickling and cleaning: The SLM-molded titanium mesh obtained in step (2) was placed in a pickling solution at a temperature of 60°C (nitric acid: hydrofluoric acid: deionized water = 2.7:0.4:6.9 in the pickling solution) for 5 seconds. The SLM-molded titanium mesh was then ultrasonically cleaned in acetone, 95% ethanol, and deionized water for 10 minutes each, and then taken out and dried.

[0043] (4) Anodizing and cleaning: The SLM-molded titanium mesh obtained in step (3) was placed as an anode and a copper plate as a cathode in an electrolyte (the electrolyte was a hydrofluoric acid aqueous solution with a mass percentage of 0.4%), with a distance of 4 cm between the two electrodes. A DC regulated power supply was used to provide a voltage of 30 V for 1.5 h of pulse anodizing at room temperature. The SLM-molded titanium mesh was then placed in acetone, 95% ethanol, and deionized water for ultrasonic cleaning for 10 min each, and then taken out and dried.

[0044] (5) Hydrophobic treatment: The SLM-molded titanium mesh obtained in step (4) was immersed in a 0.01 mol / L, 25°C perfluorozinc acid aqueous solution for 1 h, then taken out and dried. The cycle was repeated 3 times to obtain the SLM-molded titanium mesh.

[0045] Example 3

[0046] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, which specifically includes the following steps:

[0047] (1) Construction of SLM-molded titanium mesh without surface treatment: The patient's 3 alveolar bone loss site was scanned using an oral scanner to obtain the corresponding data, and a personalized titanium mesh model was established using CAD design software; the personalized titanium mesh 3D model was then imported into a selective laser melting molding device, and titanium powder was used as the raw material, and the SLM-molded titanium mesh without surface treatment was obtained by scanning layer by layer;

[0048] (2) Laser remelting and cleaning: The surface of the SLM-molded titanium mesh obtained in step (1) was remelted using a pulsed laser at 10°C, wherein the pulsed laser parameters were: speed 1 mm / s, power 15000%, and frequency 70 kHz; after laser remelting, the SLM-molded titanium mesh was ultrasonically cleaned in acetone, 95% ethanol, and deionized water for 10 min, respectively, and then taken out and dried;

[0049] (3) Pickling and cleaning: The SLM-molded titanium mesh obtained in step (2) was placed in a pickling solution at a temperature of 60°C (nitric acid: hydrofluoric acid: deionized water = 2.7:0.4:6.9 in the pickling solution) for 15 seconds. The SLM-molded titanium mesh was then placed in acetone, 95% ethanol, and deionized water for ultrasonic cleaning for 10 minutes each, and then taken out and dried.

[0050] (4) Anodizing and cleaning: The SLM-molded titanium mesh obtained in step (3) was placed as an anode and a copper plate as a cathode in an electrolyte (the electrolyte was a hydrofluoric acid aqueous solution with a mass percentage of 0.5%), with a distance of 5 cm between the two electrodes. A DC regulated power supply was used to provide a voltage of 40 V for pulse anodizing for 1 h at room temperature. The SLM-molded titanium mesh was then placed in acetone, 95% ethanol, and deionized water for ultrasonic cleaning for 10 min, respectively, and then taken out and dried.

[0051] (5) Hydrophobic treatment: The SLM-molded titanium mesh obtained in step (4) was immersed in a 0.01 mol / L, 25°C perfluorozinc acid aqueous solution for 1 h, then taken out and dried. The cycle was repeated 3 times to obtain the SLM-molded titanium mesh.

[0052] Example 4

[0053] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, which specifically includes the following steps:

[0054] (1) Construction of SLM-molded titanium mesh without surface treatment: The patient's four alveolar bone loss sites were scanned using an oral scanner to obtain the corresponding data, and a personalized titanium mesh model was established using CAD design software. The personalized titanium mesh 3D model was then imported into a selective laser melting molding device, and titanium powder was used as the raw material. The SLM-molded titanium mesh without surface treatment was scanned layer by layer.

[0055] (2) Laser remelting and cleaning: The surface of the SLM-molded titanium mesh obtained in step (1) was remelted using a pulsed laser at 10°C, wherein the pulsed laser parameters were: speed 1 mm / s, power 10000%, and frequency 70 kHz; after laser remelting, the SLM-molded titanium mesh was ultrasonically cleaned in acetone, 95% ethanol, and deionized water for 10 min, respectively, and then taken out and dried;

[0056] (3) Pickling and cleaning: The SLM-molded titanium mesh obtained in step (2) was placed in a pickling solution at a temperature of 80°C (nitric acid: hydrofluoric acid: deionized water = 2.7:0.4:6.9 in the pickling solution) for 10 seconds. The SLM-molded titanium mesh was then placed in acetone, 95% ethanol, and deionized water for ultrasonic cleaning for 10 minutes each, and then taken out and dried.

[0057] (4) Anodizing and cleaning: The SLM-molded titanium mesh obtained in step (3) was placed as an anode and a copper plate as a cathode in an electrolyte (the electrolyte was a hydrofluoric acid aqueous solution with a mass percentage of 1%), with a distance of 6 cm between the two electrodes. A DC regulated power supply was used to provide a voltage of 50 V for 0.5 h of pulse anodizing at room temperature. The SLM-molded titanium mesh was then placed in acetone, 95% ethanol, and deionized water for ultrasonic cleaning for 10 min each, and then taken out and dried.

[0058] (5) Hydrophobic treatment: The SLM-molded titanium mesh obtained in step (4) was immersed in a 0.01 mol / L, 25°C perfluorozinc acid aqueous solution for 1 h, then taken out and dried. The cycle was repeated 3 times to obtain the SLM-molded titanium mesh.

[0059] Example 5

[0060] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof. The only difference between the embodiment 1 and the embodiment 1 is that in step (2), the parameters of the pulsed laser are: speed of 2 mm / s, power of 6000%, and frequency of 50 kHz.

[0061] Example 6

[0062] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof. The only difference between the embodiment 1 and the embodiment 1 is that in step (3), the ratio of nitric acid: hydrofluoric acid: deionized water in the pickling solution is 0.5:3:6.

[0063] Example 7

[0064] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, the only difference between which and Example 1 is that in step (3), the pickling temperature is 100°C.

[0065] Example 8

[0066] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, the only difference between which and embodiment 1 is that in step (4), the electrolyte is a hydrofluoric acid aqueous solution with a mass percentage of 0.05%.

[0067] Example 9

[0068] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, the only difference between which and embodiment 1 is that in step (4), the electrolyte is a hydrofluoric acid aqueous solution with a mass percentage of 2%.

[0069] Example 10

[0070] The embodiment of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof. The only difference between the embodiment 1 and the embodiment 1 is that in step (5), the SLM-molded titanium mesh obtained in step (4) is immersed in a 0.05 mol / L, 25° C. perfluorozinc acid aqueous solution for 1 hour.

[0071] Comparative Example 1

[0072] The comparative example of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, the only difference between which and Example 1 is that step (5) of hydrophobic treatment is omitted.

[0073] Comparative Example 2

[0074] The comparative example of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, the only difference between which and Example 1 is that step (4) of anodizing and cleaning is omitted.

[0075] Comparative Example 3

[0076] The comparative example of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, the only difference between which and Example 1 is that step (3) of pickling and cleaning is omitted.

[0077] Comparative Example 4

[0078] The comparative example of the present invention provides an SLM-molded titanium mesh and a surface treatment method thereof, the only difference between which and Example 1 is that step (2) of laser remelting and cleaning is omitted.

[0079] Effect Examples

[0080] Effect Examples of the Present Invention The surface hardness and surface water contact angle of the SLM-molded titanium mesh obtained in Examples 1-10 and Comparative Examples 1-4 were tested, wherein the surface hardness was tested using a Burrows optical hardness tester, and the surface water contact angle was tested using a contact angle tester. The surface hardness improvement rate = (hardness of the SLM-molded titanium mesh - hardness of the untreated SLM-molded titanium mesh) / hardness of the untreated SLM-molded titanium mesh * 100%, and the surface water contact angle improvement rate = (water contact angle of the SLM-molded titanium mesh - water contact angle of the untreated SLM-molded titanium mesh) / hardness of the untreated SLM-molded titanium mesh * 100%. The test results and calculation results are shown in Table 1;

[0081] Table 1

[0082]

[0083]

[0084] As can be seen from Table 1, when the preparation method of the present invention is adopted, the hardness of the SLM molded titanium mesh obtained is significantly enhanced compared to that before surface treatment, with an enhancement rate of more than 30.77%, and the hydrophobicity of the SLM molded titanium mesh is also significantly improved, and the surface water contact angle obtained is increased by more than 65.10%; especially when the parameters of each step are further preferred within the scope of the present invention (Examples 1-4), the hardness improvement effect and the improvement effect on the hydrophobicity of the obtained product are more significant, the hardness enhancement rate is more than 38.97%, and the surface water contact angle is increased by more than 89.54%.

[0085] It can be seen from Example 1 and Comparative Examples 1-4 that each step in the method provided by the present invention is indispensable. If any one of the steps is missing, the hydrophobicity of the titanium mesh surface will be poor and the hardness improvement will not be significant.

[0086] Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A surface treatment method for SLM-molded titanium mesh, characterized in that: The surface treatment method comprises the following steps: (1) Laser remelting: Pulsed laser is used to remelt the surface of the SLM-molded titanium mesh; (2) Pickling: placing the SLM-molded titanium mesh obtained in step (1) in a pickling solution for pickling treatment; (3) Anodizing treatment: placing the SLM-molded titanium mesh obtained in step (2) into an electrolyte for anodizing; (4) Hydrophobic treatment: placing the SLM-molded titanium mesh obtained in step (3) in a perfluorooctanoic acid aqueous solution for hydrophobic treatment, and drying after the treatment to obtain the SLM-molded titanium mesh; In step (1), the parameters of the pulsed laser are: speed 1 mm / s, power 90-150 W, and frequency 70 kHz; In step (2), the pickling solution is a mixture of nitric acid, hydrofluoric acid and deionized water, and the mass ratio of nitric acid, hydrofluoric acid and deionized water in the pickling solution is nitric acid: hydrofluoric acid: deionized water = (2.3-3.0): (0.1-0.6): (6-8); the pickling temperature is 40-80°C, and the pickling time is 5-15s; In the step (3), the electrolyte is a hydrofluoric acid aqueous solution with a mass percentage of 0.25-1%; In the step (4), the molar concentration of the perfluorooctanoic acid aqueous solution is (0.005-0.015) mol / L.

2. The surface treatment method according to claim 1, characterized in that In steps (1) to (3), after each step, the obtained SLM-molded titanium mesh is placed in acetone, 95% ethanol, and deionized water in turn for ultrasonic cleaning and drying.

3. The surface treatment method according to claim 1, wherein: In the step (1), the temperature of the remelting treatment is 5-10°C.

4. The surface treatment method according to claim 1, characterized in that In step (3), the parameters of the anodic oxidation are: the distance between the anode and the cathode is 3-6 cm, the cathode is a copper plate, the voltage is 20-50 V, and the oxidation time is 0.5-2 h.

5. The surface treatment method according to claim 1, characterized in that: In the step (4), the temperature of the hydrophobic treatment is 22-28° C., and the time of the hydrophobic treatment is 50-70 minutes.

6. An SLM-molded titanium mesh, characterized in that: The SLM-molded titanium mesh is prepared by the surface treatment method according to any one of claims 1 to 5.

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