Titanium implant and method of constructing a hydrophilic surface thereof

Abstract

The application discloses a titanium implant and a hydrophilic surface construction method thereof, and belongs to the technical field of medical materials; the titanium implant hydrophilic surface construction method provided by the application comprises the following steps: performing carbon spraying treatment on a pretreated titanium alloy, performing laser cladding after the carbon spraying treatment, and then performing cleaning and drying. The titanium implant prepared by using the titanium implant hydrophilic surface construction method provided by the application has high hydrophilicity and high biological activity. Moreover, the titanium implant hydrophilic surface construction method provided by the application is simple and easy to implement, convenient to operate, and low in cost, and can be widely applied to actual production.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of medical materials, and particularly relates to a titanium implant and a method for constructing a hydrophilic surface thereof. BACKGROUND

[0002] Titanium and its alloys have high specific strength, good corrosion resistance and good biocompatibility, and have been widely used in the field of biomedical materials, such as surgical instruments, artificial joint replacement, oral repair and the like. However, the natural biological inertia of titanium bone implants can cause poor combination with human tissues. Therefore, the surface modification method is usually used to endow titanium alloy with biological activity, for example, a titanium implant is treated by sand blasting, acid etching and anodic oxidation to construct a micro-nano composite structure of a hydrophilic surface, and the biological activity is significantly improved.

[0003] At present, the methods for improving the biological activity of medical titanium alloy mainly include preparation of calcium phosphate coating, construction of micro-nano composite structure similar to human bone and construction of hydrophilic surface. However, the bonding force between the non-in situ grown coating and the substrate is not ideal, and the process steps such as conventional sand blasting, acid etching and hydrothermal treatment are complicated, and the yield is difficult to guarantee.

[0004] Therefore, it is necessary to develop a titanium alloy biological activity surface with simple process, convenient operation and stable performance. SUMMARY

[0005] The application aims to overcome the shortcomings of the prior art and provide a method for constructing a hydrophilic surface of a titanium implant, which is simple in process, convenient in operation and high in surface hydrophilicity.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the application is as follows: a method for constructing a hydrophilic surface of a titanium implant, which comprises the following steps: carbon spraying treatment is performed on a pretreated titanium alloy, laser cladding is performed after the carbon spraying treatment, and then cleaning and drying are performed.

[0007] In the method for constructing a hydrophilic surface of a titanium implant provided by the application, carbon spraying treatment is first performed, so that a uniform and flat carbon layer is formed on the surface of the titanium implant, and then laser cladding is performed. Under the action of laser, the titanium implant undergoes rapid melting and solidification, thereby spontaneously forming a micro-nano composite structure. Through this step, the carbon deposited on the surface of the titanium implant after the carbon spraying treatment can be partially fixed on the surface. Therefore, the surface of the titanium implant contains a suitable amount of carbon powder, thereby improving the surface hydrophilicity of the titanium implant. The coating formed by laser cladding and fixed with the carbon powder is well combined with the surface of the titanium implant substrate, so that the long-term hydrophilicity and biological activity of the titanium implant can be guaranteed. At the same time, the treatment process provided by the application can also ensure that the roughness of the titanium implant is within a suitable range.

[0008] As a preferred embodiment of the method for constructing a hydrophilic surface of a titanium implant, the time of the carbon spraying treatment is 3-9s.

[0009] As a preferred embodiment of the method for constructing a hydrophilic surface of a titanium implant, the time of the carbon spraying treatment is 5-7s.

[0010] Preferably, the time of the carbon spraying treatment is 6s.

[0011] The inventors have found that controlling the time of the carbon spraying treatment during the carbon spraying treatment can ensure that the subsequent treatment contains an appropriate range of carbon powder in the coating, thereby achieving high hydrophilicity of the surface of the titanium implant.

[0012] As a preferred embodiment of the method for constructing a hydrophilic surface of a titanium implant, the current of the carbon spraying treatment is 30-60A, and the power is 900-1800W.

[0013] As a preferred embodiment of the method for constructing a hydrophilic surface of a titanium implant, the current of the carbon spraying treatment is 40-50A, and the power is 1200-1500W.

[0014] Preferably, the current of the carbon spraying treatment is 45A, and the power is 1350W.

[0015] The inventors have found that the current and power during the carbon spraying treatment affect the uniformity and flatness of the subsequently deposited carbon spraying layer, and further affect the carbon content subsequently fixed on the surface. Under the preferred treatment current and power of the present application, the hydrophilic performance of the product is more excellent.

[0016] As a preferred embodiment of the method for constructing a hydrophilic surface of a titanium implant, the carbon spraying treatment is performed under vacuum conditions.

[0017] As a preferred embodiment of the method for constructing a hydrophilic surface of a titanium implant, the diameter of the carbon rope used in the carbon spraying treatment is 0.8-2.5mm, and the density is 1.2-2.5g / m 3 .

[0018] The inventors have found that when the carbon rope used is within the diameter and density range given in the present application, the hydrophilicity of the product is excellent.

[0019] As a preferred embodiment of the method for constructing a hydrophilic surface of a titanium implant, in the laser cladding, the laser processing speed is 20-60mm / s, the power is 30-110%, and the frequency is 35-45KHz.

[0020] In a preferred embodiment of the method for constructing a hydrophilic surface for titanium implants according to the present invention, the laser cladding process has a laser processing speed of 40-50 mm / s, a power of 60-80%, and a frequency of 35-45 kHz.

[0021] Preferably, in the laser cladding process, the laser processing speed is 45 mm / s, the power is 70%, and the frequency is 40 kHz.

[0022] The inventors discovered that the processing speed, power, and frequency in laser cladding all affect the amount of carbon powder fixed on the final surface of the product, thus affecting the hydrophilicity of the product surface. Specifically, excessively high processing speeds cause rapid splashing of carbon powder on the surface, resulting in unnecessary carbon powder loss and reducing the amount of carbon powder subsequently fixed; excessively low processing speeds lead to low efficiency. The power affects the thickness of the remelting, thus ultimately affecting the amount of carbon powder fixed on the surface; the frequency also has a certain impact on the amount of fixed carbon powder. When the selected laser cladding parameters are within the range given in this invention, it can ensure that the product has excellent hydrophilicity.

[0023] In a preferred embodiment of the method for constructing a hydrophilic surface for titanium implants according to the present invention, the pretreatment involves grinding the titanium alloy, immersing it in ethanol for ultrasonic cleaning, and then drying it.

[0024] Preferably, the polishing is done with 600-3000 grit silicon carbide sandpaper.

[0025] The inventors discovered that polishing with sandpaper of a suitable grit size can help with the adhesion and deposition of carbon in subsequent carbon spraying and the fixation of carbon in laser cladding.

[0026] Preferably, the ultrasonic cleaning is performed at 20-30°C for 8-12 minutes.

[0027] In a preferred embodiment of the method for constructing a hydrophilic surface for titanium implants according to the present invention, the cleaning is performed by ultrasonic cleaning in deionized water for 8-12 minutes.

[0028] In addition, the present invention also provides a titanium implant, which is constructed using the hydrophilic surface construction method described in the present invention.

[0029] The titanium implant prepared by the method of the present invention has a micro-nano composite structure on its surface and contains an appropriate amount of fixed carbon powder. It has excellent overall hydrophilicity, high bioactivity, and roughness within a suitable range.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] This application provides a method for constructing a hydrophilic surface for titanium implants. First, carbon spraying is performed to form a uniform and smooth carbon layer on the surface of the titanium implant. Then, laser cladding is performed. Under the action of the laser, the titanium implant undergoes rapid melting and solidification, spontaneously forming a micro-nano composite structure. This application also specifies the specific parameters for the carbon spraying and laser cladding processes, thereby achieving high hydrophilicity and high bioactivity in the titanium implant, while maintaining a suitable roughness. Furthermore, the method for constructing a hydrophilic surface for titanium implants provided by this invention is simple, easy to operate, and low in cost, making it widely applicable to actual production. Attached Figure Description

[0032] Figure 1 The image shows the surface microstructure (50 μm) of the product prepared in Example 1.

[0033] Figure 2 The image shows the surface microstructure (5 μm) of the product prepared in Example 1.

[0034] Figure 3 The image shows the surface microstructure (300 nm) of the product prepared in Example 1.

[0035] Figure 4 The image shows the surface energy spectrum of the product prepared in Example 1. Detailed Implementation

[0036] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0037] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field.

[0038] Example 1

[0039] This invention provides a titanium implant with a hydrophilic surface, wherein the method for constructing the hydrophilic surface of the titanium implant includes the following steps:

[0040] (1) Pretreatment: The surface of the titanium alloy was polished with 2000-grit silicon carbide sandpaper. The polished titanium alloy was then immersed in ethanol and ultrasonically cleaned at room temperature (25°C) for 10 minutes before drying to obtain the pretreated titanium alloy.

[0041] (2) Carburizing treatment: The pretreated titanium alloy was placed in a sputtering carburizer and carburized under vacuum conditions; the carburizing treatment time was 6 seconds, and the carbon rope used in the carburizing treatment was a special carbon rope for the sputtering carburizer with a diameter of 1.5 mm and a density of 2.0 g / m³. 3 The current during carbon spraying is 45A and the power is 1350W.

[0042] (3) Laser cladding: The carbon-sprayed titanium alloy is transferred to the laser equipment and laser cladding is performed according to the preset program; the laser processing speed is 45mm / s, the power is 70%, and the frequency is 40KHz.

[0043] (4) Post-processing: The titanium alloy after laser cladding is ultrasonically cleaned in deionized water for 10 minutes, and then placed in an oven to dry, to obtain the titanium implant after surface hydrophilic construction.

[0044] Example 2

[0045] This invention provides a titanium implant with a hydrophilic surface, wherein the method for constructing the hydrophilic surface of the titanium implant includes the following steps:

[0046] (1) Pretreatment: The surface of the titanium alloy was polished with 600-mesh silicon carbide sandpaper. The polished titanium alloy was then immersed in ethanol and ultrasonically cleaned at room temperature (25°C) for 8 minutes and then dried to obtain the pretreated titanium alloy.

[0047] (2) Carburizing treatment: The pretreated titanium alloy was placed in a sputtering carburizer and carburized under vacuum conditions; the carburizing treatment time was 5 seconds, and the carbon rope used in the carburizing treatment was a special carbon rope for the sputtering carburizer with a diameter of 1 mm and a density of 1.2 g / m³. 3 The current during carbon spraying is 50A and the power is 1500W.

[0048] (3) Laser cladding: The carbon-sprayed titanium alloy is transferred to a laser device and laser cladding is performed according to a preset program; the laser processing speed is 50 mm / s, the power is 60%, and the frequency is 45 kHz.

[0049] (4) Post-processing: The laser-clad titanium alloy was ultrasonically cleaned in deionized water for 8 minutes, and then dried in an oven to obtain the titanium implant after surface hydrophilic construction.

[0050] Example 3

[0051] This invention provides a titanium implant with a hydrophilic surface, wherein the method for constructing the hydrophilic surface of the titanium implant includes the following steps:

[0052] (1) Pretreatment: The surface of the titanium alloy was polished with 3000-grit silicon carbide sandpaper. The polished titanium alloy was then immersed in ethanol and ultrasonically cleaned at room temperature (25°C) for 12 minutes before drying to obtain the pretreated titanium alloy.

[0053] (2) Carbide spraying treatment: The pretreated titanium alloy was placed in a sputtering carbide evaporator for carbide spraying under vacuum conditions; the carbide spraying treatment time was 7 seconds, and the carbon rope used in the carbide spraying treatment was a special carbon rope for the sputtering carbide evaporator with a diameter of 2.5 mm and a density of 2.5 g / m³. 3 The current during carbon spraying is 40A and the power is 1200W.

[0054] (3) Laser cladding: The carbon-sprayed titanium alloy is transferred to a laser device and laser cladding is performed according to a preset program; the laser processing speed is 40 mm / s, the power is 80%, and the frequency is 35 kHz.

[0055] (4) Post-processing: The titanium alloy after laser cladding is ultrasonically cleaned in deionized water for 12 minutes, and then dried in an oven to obtain the titanium implant after surface hydrophilic construction.

[0056] Example 4

[0057] This invention provides a titanium implant with a hydrophilic surface constructed. The only difference between the method for constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the carbon spraying treatment time is 3 seconds.

[0058] Example 5

[0059] This invention provides a titanium implant with a hydrophilic surface constructed. The only difference between the method for constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the carbon spraying treatment time is 9 seconds.

[0060] Example 6

[0061] This invention provides a titanium implant with a hydrophilic surface constructed. The only difference between the method for constructing the hydrophilic surface of the titanium implant and that in Example 1 is that the current in the carbon spraying process is 30A and the power is 900W.

[0062] Example 7

[0063] This invention provides a titanium implant with a hydrophilic surface constructed. The only difference between the method for constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the current in the carbon spraying process is 60A and the power is 1800W.

[0064] Example 8

[0065] This invention provides a titanium implant with a hydrophilic surface constructed. The only difference between the method for constructing the hydrophilic surface of the titanium implant and that in Example 1 is that the laser processing speed is 20 mm / s and the power is 110% in the laser cladding process.

[0066] Example 9

[0067] This invention provides a titanium implant with a hydrophilic surface constructed. The only difference between the method for constructing the hydrophilic surface of the titanium implant and that in Example 1 is that the laser processing speed is 60 mm / s and the power is 30% in the laser cladding process.

[0068] Comparative Example 1

[0069] This invention provides a titanium implant with a hydrophilic surface constructed, the method for constructing the hydrophilic surface of the titanium implant comprising the following steps:

[0070] (1) Pretreatment: The surface of the titanium alloy was polished with 2000-grit silicon carbide sandpaper. The polished titanium alloy was then immersed in ethanol and ultrasonically cleaned at room temperature (25°C) for 10 minutes before drying to obtain the pretreated titanium alloy.

[0071] (2) Laser cladding: The pretreated titanium alloy is transferred to a laser device and laser cladding is performed according to a preset program; the laser processing speed is 45 mm / s, the power is 70%, and the frequency is 40 kHz.

[0072] (3) Carburizing treatment: The laser-clad titanium alloy was placed in a sputtering carburizer for carburizing under vacuum conditions; the carburizing time was 6 seconds, and the carbon rope used in the carburizing treatment was a special carbon rope for the sputtering carburizer with a diameter of 1.5 mm and a density of 2.0 g / m³. 3 The current during carbon spraying is 45A and the power is 1350W.

[0073] (4) Post-treatment: The carbon-sprayed titanium alloy was ultrasonically cleaned in deionized water for 10 minutes, and then dried in an oven to obtain the titanium implant after surface hydrophilic construction.

[0074] Comparative Example 2

[0075] This invention provides a titanium implant with a hydrophilic surface constructed, the method for constructing the hydrophilic surface of the titanium implant comprising the following steps:

[0076] (1) Pretreatment: The surface of the titanium alloy was polished with 2000-grit silicon carbide sandpaper. The polished titanium alloy was then immersed in ethanol and ultrasonically cleaned at room temperature (25°C) for 10 minutes before drying to obtain the pretreated titanium alloy.

[0077] (2) Carburizing treatment: The pretreated titanium alloy was placed in a sputtering carburizer and carburized under vacuum conditions; the carburizing treatment time was 6 seconds, and the carbon rope used in the carburizing treatment was a special carbon rope for the sputtering carburizer with a diameter of 1.5 mm and a density of 2.0 g / m³. 3 The current during carbon spraying is 45A and the power is 1350W.

[0078] (3) Post-treatment: The carbon-sprayed titanium alloy was ultrasonically cleaned in deionized water for 10 minutes, and then dried in an oven to obtain the titanium implant after surface hydrophilic construction.

[0079] Comparative Example 3

[0080] This invention provides a titanium implant with a hydrophilic surface constructed, the method for constructing the hydrophilic surface of the titanium implant comprising the following steps:

[0081] (1) Pretreatment: The surface of the titanium alloy was polished with 2000-grit silicon carbide sandpaper. The polished titanium alloy was then immersed in ethanol and ultrasonically cleaned at room temperature (25°C) for 10 minutes before drying to obtain the pretreated titanium alloy.

[0082] (2) Laser cladding: The pretreated titanium alloy is transferred to a laser device and laser cladding is performed according to a preset program; the laser processing speed is 45 mm / s, the power is 70%, and the frequency is 40 kHz.

[0083] (3) Post-processing: The titanium alloy after laser cladding is ultrasonically cleaned in deionized water for 10 minutes, and then placed in an oven to dry, to obtain the titanium implant after surface hydrophilic construction.

[0084] Comparative Example 4

[0085] The present invention provides a titanium implant with a hydrophilic surface constructed, the only difference between the method of constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the carbon spraying treatment time is 2 seconds.

[0086] Comparative Example 5

[0087] The present invention provides a titanium implant with a hydrophilic surface constructed, the only difference between the method of constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the carbon spraying treatment time is 10s.

[0088] Comparative Example 6

[0089] The present invention provides a titanium implant with a hydrophilic surface constructed in a comparative example. The only difference between the method for constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the current in the carbon spraying treatment is 20A and the power is 600W.

[0090] Comparative Example 7

[0091] The present invention provides a titanium implant with a hydrophilic surface constructed in a comparative example. The only difference between the method for constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the current in the carbon spraying treatment is 70A and the power is 2100W.

[0092] Comparative Example 8

[0093] The present invention provides a titanium implant with a hydrophilic surface construction method. The only difference between the method of constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the laser processing speed is 70 mm / s in the laser cladding process.

[0094] Comparative Example 9

[0095] The present invention provides a titanium implant with a hydrophilic surface constructed, the only difference between the method of constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the power in the laser cladding is 20%.

[0096] Comparative Example 10

[0097] The present invention provides a titanium implant with a hydrophilic surface constructed, the only difference between the method of constructing the hydrophilic surface of the titanium implant and that of Example 1 is that the power is 120% in the laser cladding.

[0098] Comparative Example 11

[0099] The present invention provides a titanium implant after surface hydrophilic construction. The only difference between the method of constructing the hydrophilic surface of the titanium implant and Example 1 is that the silicon carbide sandpaper used for polishing in the pretreatment is 200 mesh.

[0100] Comparative Example 12

[0101] This invention provides a titanium implant with a hydrophilic surface constructed as a comparative example. The only difference between the method for constructing the hydrophilic surface of the titanium implant and Example 1 is that the diameter of the carbon cord is 3 mm and the density is 3.5 g / m³. 3 .

[0102] Comparative Example 13

[0103] This invention provides a titanium implant with a hydrophilic surface constructed as a comparative example. The only difference between the method for constructing the hydrophilic surface of the titanium implant and Example 1 is that the diameter of the carbon cord is 0.5 mm and the density is 0.8 g / m³. 3 .

[0104] Example of effect

[0105] The present invention provides examples to verify the hydrophilicity and roughness data of the titanium implants prepared after surface hydrophilic construction in the embodiments and comparative examples. The hydrophilicity test method is to use the seated drop method on a contact angle meter to test the static water contact angle. Take 3 μL of deionized water and drop it onto the surface of the titanium implant sample after surface hydrophilic construction, and measure the corresponding water contact angle. The smaller the water contact angle value, the better the hydrophilicity. The roughness test method is to use a surface roughness measuring instrument to characterize the roughness value of the sample surface. Both the water contact angle and the roughness value are measured three times and the average value is taken. The data obtained are shown in Table 1.

[0106] Table 1

[0107]

[0108] As can be seen from Table 1, when the hydrophilic surface construction method of the present invention is used, the obtained product has excellent hydrophilic properties and a suitable roughness range, wherein the water contact angle is below 23.1° and the roughness value is between 60.1 and 68.8 μm; in addition, the surface micromorphology of the product prepared in Example 1 is as follows: Figures 1-3 As shown, where Figure 1 The caliber bar is 50 μm. Figure 2 The caliber bar is 5μm. Figure 3 The metric bar is 200 nm, from Figures 1-3 It can be clearly seen that carbon spraying and laser cladding can form a micro-nano composite structure on the surface of titanium materials, exhibiting a "micro-papillary" morphology at the nanoscale, which is beneficial for forming a hydrophilic surface; at the same time, the surface energy spectrum of the product prepared in Example 1 is as follows. Figure 4 As shown, from Figure 4 As can be seen, carbon elements are fixed on the surface of the surface-treated titanium material (the attached image is in black and white, but the original image displayed on the scanning electron microscope shows that carbon elements fixed on the surface of the titanium material are shown in red). This amorphous carbon plays a crucial role in improving the surface hydrophilicity.

[0109] As can be seen from Examples 1 and Comparative Examples 1-3, when the processing sequence of the present invention is not adopted or a certain processing procedure of the present invention is missing, the hydrophilicity of the obtained product decreases significantly. Compared with Example 1, the water contact angle data of Comparative Examples 1-3 increases by 411.9-518.5%. As can be seen from Examples 1, Examples 4-5, and Comparative Examples 4-5, the carbon spraying time in the carbon spraying process affects the hydrophilicity of the product. When the carbon spraying time is outside the range given in the present invention, the hydrophilicity of the obtained product decreases significantly. Compared with Example 1, the water contact angle of the product in Comparative Examples 4-5 increases by 311.9-503.7%. As can be seen from Examples 1, Examples 6-9, and Comparative Examples 6-10, the selection of parameters in the carbon spraying and laser cladding processes also has a significant impact on the hydrophilicity of the product. Compared with Example 1, when the parameters are outside the range of the present invention, the water contact angle of the product in Comparative Examples 6-10 increases by more than 102.2%. As can be seen from Example 1 and Comparative Example 11, the polishing of the titanium alloy surface during pretreatment also has a certain impact on hydrophilicity. As can be seen from Example 1 and Comparative Examples 12-13, the selection of carbon density and diameter during carbon spraying also affects the overall performance of the product.

[0110] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not 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 modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for constructing a hydrophilic surface for titanium implants, characterized in that, The construction method includes the following steps: carbon spraying the pretreated titanium alloy, laser cladding after carbon spraying, followed by cleaning and drying; The carbon spraying treatment time is 3-9 seconds; The current in the carbon spraying process is 30-60A, and the power is 900-1800W. The carbon rope used in the carbon spraying process has a diameter of 0.8-2.5 mm and a density of 1.2-2.5 g / m³. 3 ; In the laser cladding process, the laser processing speed is 20-60 mm / s and the power is 30-110%. The pretreatment involves grinding the titanium alloy, immersing it in ethanol for ultrasonic cleaning, and then drying it. The grinding is done with 600-3000 grit silicon carbide sandpaper.

2. The method for constructing a hydrophilic surface for titanium implants according to claim 1, characterized in that, The carbon spraying process takes 5-7 seconds.

3. The method for constructing a hydrophilic surface for titanium implants according to claim 1, characterized in that, The current in the carbon spraying process is 40-50A, and the power is 1200-1500W.

4. The method for constructing a hydrophilic surface for titanium implants according to claim 1, characterized in that, In the laser cladding process, the frequency is 35-45KHz.

5. The method for constructing a hydrophilic surface for titanium implants according to claim 1, characterized in that, In the laser cladding process, the laser processing speed is 40-50 mm / s, the power is 60-80%, and the frequency is 40 kHz.

6. A titanium implant, characterized in that, The titanium implant is constructed using the hydrophilic surface construction method as described in any one of claims 1-5.

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