Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a construction method of the hydrophilic surface of the titanium implant, which has the advantages of simple process, convenient operation and strong surface hydrophilicity.
The technical scheme adopted by the invention is that the construction method of the hydrophilic surface of the titanium implant comprises the following steps of carrying out carbon spraying treatment on the pretreated titanium alloy, carrying out laser cladding after the carbon spraying treatment, and then cleaning and drying.
The hydrophilic surface construction method of the titanium implant provided by the application comprises the steps of firstly carrying out carbon spraying treatment, so that a layer of even and smooth carbon layer is formed on the surface of the titanium implant, then carrying out laser cladding, carrying out rapid melting and solidification on the titanium implant under the action of laser, so that a micro-nano composite structure is spontaneously formed, and carrying out carbon spraying treatment, wherein carbon deposited on the surface of the titanium implant can be partially fixed on the surface, so that the surface of the titanium implant contains carbon powder with proper content, the surface hydrophilicity of the titanium implant is further improved, and the carbon powder-fixed coating formed by laser cladding is well combined with the surface of a titanium implant matrix, so that the long-term hydrophilicity and bioactivity of the titanium implant can be ensured, and meanwhile, the roughness of the titanium implant can be ensured within a proper range in the treatment process provided by the application.
As a preferred embodiment of the method for constructing the hydrophilic surface of the titanium implant according to the present invention, the carbon spraying treatment is performed for 3 to 9 seconds.
As a preferred embodiment of the method for constructing the hydrophilic surface of the titanium implant according to the present invention, the carbon spraying treatment is carried out for a period of 5 to 7 seconds.
Preferably, the carbon spraying treatment is performed for 6 seconds.
The inventor researches and discovers that the control of the carbon spraying treatment time in the carbon spraying treatment process can ensure that the subsequent treatment contains carbon powder with a proper range in the coating, thereby realizing the high hydrophilicity of the surface of the titanium implant.
As a preferred embodiment of the method for constructing the hydrophilic surface of the titanium implant, the current in the carbon spraying treatment is 30-60A, and the power is 900-1800W.
As a preferred embodiment of the method for constructing the hydrophilic surface of the titanium implant, the current in the carbon spraying treatment is 40-50A, and the power is 1200-1500W.
Preferably, the current in the carbon spraying treatment is 45A, and the power is 1350W.
The inventor researches that the current and the power in the carbon spraying treatment process influence the uniformity and the flatness of a carbon spraying layer which is deposited later, and further influence the carbon content which is fixed on the surface later, and the hydrophilic performance of the obtained product is better under the preferential treatment current and power.
As a preferred embodiment of the method for constructing a hydrophilic surface of a titanium implant according to the present invention, the spray-coating treatment is performed under vacuum.
As a preferred embodiment of the method for constructing the hydrophilic surface of the titanium implant according to the present invention, the carbon ropes used in the carbon spraying treatment have a diameter of 0.8-2.5mm and a density of 1.2-2.5g/m 3.
The inventors have found that when the carbon rope is used within the diameter and density ranges given in the present invention, the hydrophilicity of the resulting product is excellent.
As a preferable implementation mode of the method for constructing the hydrophilic surface of the 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.
As a preferable implementation mode of the method for constructing the hydrophilic surface of the titanium implant, in the laser cladding, the laser processing speed is 40-50mm/s, the power is 60-80%, and the frequency is 35-45KHz.
Preferably, in the laser cladding, the laser processing speed is 45mm/s, the power is 70%, and the frequency is 40KHz.
The inventor researches and discovers that the processing speed, power and frequency in laser cladding can influence the content of carbon powder fixed on the final surface of a product, thereby influencing the hydrophilic performance of the surface of the product, specifically, the processing speed is too high, the surface carbon powder is quickly splashed, unnecessary loss of the carbon powder is caused, the amount of the follow-up fixed carbon powder is reduced, the processing speed is too low, the efficiency is low, the thickness of remelting is influenced by the power, the amount of the surface fixed carbon powder is finally influenced, the frequency also has a certain influence on the amount of the fixed carbon powder, and when the selected laser cladding parameters are in the range provided by the invention, the product can be ensured to have excellent hydrophilicity.
As a preferable implementation mode of the method for constructing the hydrophilic surface of the titanium implant, the pretreatment is that the titanium alloy is ground and then immersed in ethanol for ultrasonic cleaning and then dried.
Preferably, the polishing is polishing with 600-3000 mesh silicon carbide abrasive paper.
The inventor researches and discovers that the carbon in the subsequent spray carbon can be assisted in adhesion deposition and fixation of the carbon in the laser cladding after being polished by sand paper with a proper mesh range.
Preferably, the ultrasonic cleaning is carried out at 20-30 ℃ for 8-12min.
As a preferred embodiment of the method for constructing the hydrophilic surface of the titanium implant, the cleaning is ultrasonic cleaning in deionized water, and the cleaning time is 8-12min.
In addition, the invention also provides a titanium implant which is constructed by adopting the hydrophilic surface construction method.
The titanium implant prepared by the construction method has a micro-nano composite structure on the surface, contains fixed carbon powder with proper content on the surface, has excellent overall hydrophilicity, has higher bioactivity and has roughness in a proper range.
Compared with the prior art, the invention has the beneficial effects that:
The method for constructing the hydrophilic surface of the titanium implant comprises the steps of spraying carbon, forming a layer of uniform and smooth carbon layer on the surface of the titanium implant, then carrying out laser cladding, and carrying out rapid melting and solidification on the titanium implant under the action of laser to spontaneously form a micro-nano composite structure. The construction method of the hydrophilic surface of the titanium implant provided by the application is simple and feasible, convenient to operate, low in cost and widely applicable to actual production.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The reagents, methods and apparatus employed in the present invention are those conventional in the art unless otherwise indicated.
Example 1
The embodiment of the invention provides a titanium implant subjected to surface hydrophilic construction, which comprises the following steps of:
(1) Pre-treating, namely polishing the surface of the titanium alloy by using 2000-mesh silicon carbide sand paper, immersing the polished titanium alloy into ethanol, ultrasonically cleaning at room temperature (25 ℃) for 10 minutes, and drying to obtain the pre-treated titanium alloy;
(2) The carbon spraying treatment, namely placing the pretreated titanium alloy into a sputtering carbon steaming instrument to perform carbon spraying treatment under the vacuum condition, wherein the carbon spraying treatment time is 6s, the carbon ropes used in the carbon spraying treatment are special carbon ropes for the sputtering carbon steaming instrument, the diameter is 1.5mm, the density is 2.0g/m 3, the current in the carbon spraying treatment is 45A, and the power is 1350W;
(3) Transferring the titanium alloy subjected to carbon spraying treatment to laser equipment, and carrying out laser cladding treatment according to a preset program, wherein the laser processing speed is 45mm/s, the power is 70%, and the frequency is 40KHz;
(4) And (3) post-treatment, namely ultrasonically cleaning the titanium alloy subjected to laser cladding in deionized water for 10min, and then placing the titanium alloy in an oven for drying to obtain the titanium implant subjected to surface hydrophilic construction.
Example 2
The embodiment of the invention provides a titanium implant subjected to surface hydrophilic construction, which comprises the following steps of:
(1) Pre-treating, namely polishing the surface of the titanium alloy by using 600-mesh silicon carbide sand paper, immersing the polished titanium alloy into ethanol, ultrasonically cleaning at room temperature (25 ℃) for 8 minutes, and drying to obtain the pretreated titanium alloy;
(2) The carbon spraying treatment, namely placing the pretreated titanium alloy into a sputtering carbon steaming instrument to perform carbon spraying treatment under a vacuum condition, wherein the carbon spraying treatment time is 5s, a carbon rope used in the carbon spraying treatment is a special carbon rope for the sputtering carbon steaming instrument, the diameter is 1mm, the density is 1.2g/m 3, the current in the carbon spraying treatment is 50A, and the power is 1500W;
(3) Transferring the titanium alloy subjected to carbon spraying treatment to laser equipment, and carrying out laser cladding treatment according to a preset program, wherein the laser processing speed is 50mm/s, the power is 60 percent, and the frequency is 45KHz;
(4) And (3) post-treatment, namely ultrasonically cleaning the titanium alloy subjected to laser cladding in deionized water for 8min, and then placing the titanium alloy in an oven for drying to obtain the titanium implant subjected to surface hydrophilic construction.
Example 3
The embodiment of the invention provides a titanium implant subjected to surface hydrophilic construction, which comprises the following steps of:
(1) Pre-treating, namely polishing the surface of the titanium alloy by using silicon carbide sand paper with 3000 meshes, immersing the polished titanium alloy into ethanol, ultrasonically cleaning at room temperature (25 ℃) for 12 minutes, and drying to obtain the pretreated titanium alloy;
(2) The carbon spraying treatment, namely placing the pretreated titanium alloy into a sputtering carbon steaming instrument to perform carbon spraying treatment under the vacuum condition, wherein the carbon spraying treatment time is 7s, the carbon ropes used in the carbon spraying treatment are special carbon ropes for the sputtering carbon steaming instrument, the diameter is 2.5mm, the density is 2.5g/m 3, the current in the carbon spraying treatment is 40A, and the power is 1200W;
(3) Transferring the titanium alloy subjected to carbon spraying treatment to laser equipment, and carrying out laser cladding treatment according to a preset program, wherein the laser processing speed is 40mm/s, the power is 80%, and the frequency is 35KHz;
(4) And (3) post-treatment, namely ultrasonically cleaning the titanium alloy subjected to laser cladding in deionized water for 12min, and then placing the titanium alloy in an oven for drying to obtain the titanium implant subjected to surface hydrophilic construction.
Example 4
The embodiment of the invention provides a titanium implant subjected to surface hydrophilic construction, and the hydrophilic surface construction method of the titanium implant is only different from that of embodiment 1 in that the carbon spraying treatment time is 3s.
Example 5
The embodiment of the invention provides a titanium implant subjected to surface hydrophilic construction, and the hydrophilic surface construction method of the titanium implant is only different from that of embodiment 1 in that the carbon spraying treatment time is 9s.
Example 6
The embodiment of the invention provides a titanium implant subjected to surface hydrophilic construction, and the hydrophilic surface construction method of the titanium implant is only different from that of embodiment 1 in that the current in carbon spraying treatment is 30A, and the power is 900W.
Example 7
The embodiment of the invention provides a titanium implant subjected to surface hydrophilic construction, and the hydrophilic surface construction method of the titanium implant is only different from that of embodiment 1 in that the current in carbon spraying treatment is 60A and the power is 1800W.
Example 8
The embodiment of the invention provides a titanium implant subjected to surface hydrophilic construction, and the hydrophilic surface construction method of the titanium implant is only different from that of embodiment 1 in that in laser cladding, the laser processing speed is 20mm/s, and the power is 110%.
Example 9
The embodiment of the invention provides a titanium implant subjected to surface hydrophilic construction, and the hydrophilic surface construction method of the titanium implant is the only difference from the embodiment 1 in that in laser cladding, the laser processing speed is 60mm/s, and the power is 30%.
Comparative example 1
The invention provides a titanium implant subjected to surface hydrophilic construction, and the method for constructing the hydrophilic surface of the titanium implant comprises the following steps of:
(1) Pre-treating, namely polishing the surface of the titanium alloy by using 2000-mesh silicon carbide sand paper, immersing the polished titanium alloy into ethanol, ultrasonically cleaning at room temperature (25 ℃) for 10 minutes, and drying to obtain the pre-treated titanium alloy;
(2) Transferring the pretreated titanium alloy to laser equipment, and carrying out laser cladding treatment according to a preset program, wherein the laser processing speed is 45mm/s, the power is 70 percent, and the frequency is 40KHz;
(3) The carbon spraying treatment, namely placing the titanium alloy subjected to the laser cladding treatment into a sputtering carbon steaming instrument to perform carbon spraying treatment under a vacuum condition, wherein the carbon spraying treatment time is 6s, a carbon rope used in the carbon spraying treatment is a special carbon rope for the sputtering carbon steaming instrument, the diameter is 1.5mm, the density is 2.0g/m 3, the current in the carbon spraying treatment is 45A, and the power is 1350W;
(4) And (3) post-treatment, namely ultrasonically cleaning the titanium alloy subjected to carbon spraying treatment in deionized water for 10min, and then placing the titanium alloy in an oven for drying to obtain the titanium implant subjected to surface hydrophilic construction.
Comparative example 2
The invention provides a titanium implant subjected to surface hydrophilic construction, and the method for constructing the hydrophilic surface of the titanium implant comprises the following steps of:
(1) Pre-treating, namely polishing the surface of the titanium alloy by using 2000-mesh silicon carbide sand paper, immersing the polished titanium alloy into ethanol, ultrasonically cleaning at room temperature (25 ℃) for 10 minutes, and drying to obtain the pre-treated titanium alloy;
(2) The carbon spraying treatment, namely placing the pretreated titanium alloy into a sputtering carbon steaming instrument to perform carbon spraying treatment under the vacuum condition, wherein the carbon spraying treatment time is 6s, the carbon ropes used in the carbon spraying treatment are special carbon ropes for the sputtering carbon steaming instrument, the diameter is 1.5mm, the density is 2.0g/m 3, the current in the carbon spraying treatment is 45A, and the power is 1350W;
(3) And (3) post-treatment, namely ultrasonically cleaning the titanium alloy subjected to carbon spraying treatment in deionized water for 10min, and then placing the titanium alloy in an oven for drying to obtain the titanium implant subjected to surface hydrophilic construction.
Comparative example 3
The invention provides a titanium implant subjected to surface hydrophilic construction, and the method for constructing the hydrophilic surface of the titanium implant comprises the following steps of:
(1) Pre-treating, namely polishing the surface of the titanium alloy by using 2000-mesh silicon carbide sand paper, immersing the polished titanium alloy into ethanol, ultrasonically cleaning at room temperature (25 ℃) for 10 minutes, and drying to obtain the pre-treated titanium alloy;
(2) Transferring the pretreated titanium alloy to laser equipment, and carrying out laser cladding treatment according to a preset program, wherein the laser processing speed is 45mm/s, the power is 70 percent, and the frequency is 40KHz;
(3) And (3) post-treatment, namely ultrasonically cleaning the titanium alloy subjected to laser cladding in deionized water for 10min, and then placing the titanium alloy in an oven for drying to obtain the titanium implant subjected to surface hydrophilic construction.
Comparative example 4
The comparative example of the present invention provides a titanium implant after surface hydrophilic construction, which is unique from example 1 in that the carbon spraying treatment time is 2s.
Comparative example 5
The comparative example of the present invention provides a titanium implant after surface hydrophilic construction, which is unique in that the carbon spraying treatment time is 10s from example 1.
Comparative example 6
The comparative example of the present invention provides a titanium implant after surface hydrophilic construction, which is unique from example 1 in that the current in the carbon spraying treatment is 20A and the power is 600W.
Comparative example 7
The comparative example of the present invention provides a titanium implant after surface hydrophilic construction, which is unique from example 1 in that the current in the carbon spraying treatment is 70A and the power is 2100W.
Comparative example 8
The comparative example of the present invention provides a titanium implant after surface hydrophilic construction, which is unique in that the laser machining speed is 70mm/s in laser cladding.
Comparative example 9
The comparative example of the present invention provides a titanium implant after surface hydrophilic construction, which is unique in that the power in laser cladding is 20% from example 1.
Comparative example 10
The comparative example of the present invention provides a titanium implant after surface hydrophilic construction, which is unique in that the power in laser cladding is 120% from example 1.
Comparative example 11
The comparative example of the present invention provides a titanium implant having a surface hydrophilically built, which is unique from example 1 in that the silicon carbide sandpaper used for polishing in the pretreatment is 200 mesh.
Comparative example 12
The comparative example of the present invention provides a titanium implant after surface hydrophilic construction, which is unique from example 1 in that the carbon rope has a diameter of 3mm and a density of 3.5g/m 3.
Comparative example 13
The comparative example of the present invention provides a titanium implant after surface hydrophilic construction, which is unique from example 1 in that the carbon rope has a diameter of 0.5mm and a density of 0.8g/m 3.
Effect example
The method for testing the hydrophilia performance and roughness data of the titanium implant after the surface hydrophilia construction, which are prepared in the embodiment and the comparative example, is to test a static water contact angle by using a sitting drop method on a contact angle tester, to obtain 3 mu L of deionized water to be dropped on the surface of the titanium implant sample after the surface hydrophilia construction, to measure a corresponding water contact angle, wherein the smaller the value of the water contact angle is, the better the hydrophilicity is, the roughness is tested by using a surface roughness measuring instrument to represent the roughness value of the sample surface, and the water contact angle and the roughness value are measured for 3 times, and the obtained data are shown in a table 1;
TABLE 1
As can be seen from Table 1, when the hydrophilic surface construction method of the present invention is adopted, the obtained product has excellent hydrophilic performance and a proper roughness range, wherein the water contact angle is below 23.1 DEG, the roughness value is between 60.1 and 68.8 mu m, in addition, the surface microscopic morphology of the product prepared in example 1 is shown as a graph in FIG. 1 to 3, wherein the scale in FIG. 1 is 50 mu m, the scale in FIG. 2 is 5 mu m, the scale in FIG. 3 is 200nm, the titanium surface can be obviously formed into a micro-nano composite structure through carbon spraying and laser cladding treatment, the micro-nano composite structure is presented in a nano scale, which is favorable for forming the hydrophilic surface, and meanwhile, the surface energy of the product prepared in example 1 is shown as a graph in FIG. 4, the surface of the titanium surface treated is fixed with carbon elements (black and white pictures in the graph, but the surface of the titanium surface is fixed with red color in the original pictures displayed on the scanning electron microscope of the characterization equipment is shown as a graph, and the surface of the surface is very important carbon elements is very important to improve the hydrophilic performance of the carbon surface.
As can be seen from example 1 and comparative examples 1 to 3, when the treatment sequence in the present invention was not adopted or one of the treatment sequences in the present invention was absent, the hydrophilicity of the obtained product was significantly reduced, and the data increase range of the water contact angle in comparative examples 1 to 3 was 411.9 to 518.5% as compared with example 1. As can be seen from examples 1, 4-5 and comparative examples 4-5, the carbon spraying time during the carbon spraying treatment had an effect on the hydrophilicity of the product, and when the carbon spraying time was outside the range given by the present invention, the hydrophilicity of the obtained product was significantly reduced, and the water contact angle of the product in comparative examples 4-5 was increased by 311.9-503.7% as compared with example 1. It can be seen from examples 1, examples 6 to 9 and comparative examples 6 to 10 that the selection of parameters in the carbon spraying treatment and the laser cladding treatment also has a significant effect on the hydrophilicity of the product, and the increase of the water contact angle of the product in comparative examples 6 to 10 is 102.2% or more when the parameters are out of the range of the present invention as compared with example 1. It can be seen from example 1 and comparative example 11 that polishing of the titanium alloy surface during pretreatment also has some effect on hydrophilicity. It can be seen from example 1 and comparative examples 12-13 that the selection of the density and diameter of carbon in the carbon spray treatment also affects the overall performance of the product.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that changes can be made to the technical solutions of the invention or equivalents thereof without departing from the spirit and scope of the technical solutions of the invention.