A titanium-tantalum composite implant and its preparation method

Abstract

The present invention relates to a titanium-tantalum composite implant and a preparation method thereof, comprising the following steps: dividing the titanium or titanium alloy implant into regions A and B, defining region A as tantalum and region B as titanium; covering the region B with a mask, forming a tantalum layer in the region A, and protecting the region B by the mask covering. After the preparation of the tantalum layer in the region A is completed, removing the mask to obtain an implant with a locally covered tantalum layer; performing anodic oxidation treatment on the implant with the locally covered tantalum layer, with a voltage of 10-160 V, a temperature of 10-50 °C, and a time of 30 s-300 s, to obtain a titanium-tantalum composite implant. The titanium-tantalum composite implant has a two-color film layer, which combines functional effects and functional identification. It not only solves the problem of galvanic corrosion existing in the titanium-tantalum composite, but also can identify the tantalum functional region and the titanium functional region by color, broadens the application scenarios of the composite implant material, solves clinical pain points, and has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the field of surface treatment of medical materials, and in particular to a titanium-tantalum composite implant and a preparation method thereof. Background Art

[0002] Due to its good self-passivation property and certain corrosion resistance, titanium is widely used as a material for medical implant products to be implanted into the human body to provide mechanical support. However, due to its relatively low strength, pure titanium material alone is difficult to meet the clinical strength requirements. Therefore, titanium alloy materials such as TC4 and TC20 are used more frequently to meet the strength and fatigue performance requirements of mechanical support. The addition of elements such as Al, V, and Nb in titanium alloys also increases the risk of precipitation of Al, V, Nb and other ions during the use of medical titanium alloy materials in the human body to a certain extent. The ion precipitation under body fluid immersion, especially for some products as long-term implants, further increases the corresponding precipitation probability and precipitation amount, increasing the toxicity and allergic risk to the human body. Therefore, it is necessary to perform coating treatment on titanium alloy materials to improve their surface biocompatibility and block the risk of ion precipitation from the titanium alloy matrix.

[0003] As a new type of medical implant material, tantalum has attracted certain attention in recent years. In particular, it has better biocompatibility and higher corrosion resistance, and has potential medical application value. However, due to its high cost and large density, it is difficult to be used alone as an implant. Therefore, combining titanium and tantalum as a medical implant and effectively utilizing the respective advantages of the two has important clinical application value.

[0004] However, as two metal elements, there is a large potential difference between titanium and tantalum. The electrode potential of titanium is between -1.2 and -1.4V, while the electrode potential of tantalum is about -0.6 to -0.8V. Completely different from the air environment in traditional industrial applications, medical material implants are used in a body fluid environment. Because there is a large potential difference between the two, there is a great risk of galvanic corrosion under the conduction of body fluid medium. Therefore, the electrode potentials of titanium and tantalum do not intersect, and there is a risk of galvanic corrosion during synchronous compounding, making it difficult to successfully achieve titanium-tantalum compounding.

[0005] Patent application CN110359075A discloses a titanium alloy coating material. By anodizing the titanium alloy, a dense TiO 2 oxide film is formed, and in TiO 2A tantalum coating is prepared on the oxide film by magnetron sputtering, providing a comprehensive coverage of the titanium alloy, thereby isolating the influence of aluminum and vanadium elements in the titanium alloy on the human body. However, for this method of forming an inorganic non-metallic oxide coating by oxidation on the metal substrate and then depositing a metal coating, there are significant differences in the physical and chemical properties of the materials. The metal materials Ti and Ta are combined in a metallic bond manner, while the metal oxide TiO of the inorganic non-metallic material 2 is mainly combined in an ionic bond manner. There are significant differences in the thermal expansion coefficients and thermal shock resistances of Ti, TiO 2 , and Ta. The Ti-TiO 2 -Ta "sandwich" structure formed from the inside out is prone to detachment under the high-temperature and high-humidity sterilization at 121-132 °C before the implant is clinically used, and the use risk is relatively high. Summary of the Invention

[0006] The purpose of the present invention is to overcome the problems existing in the existing titanium composite medical materials, and provide a preparation method for a titanium-tantalum composite implant. Aiming at the problem of galvanic corrosion, the implant is functionally partitioned into two regions, A and B. Region A is defined as tantalum, and region B is defined as titanium. There is a strict boundary between the two, so the risk of galvanic corrosion can be minimized.

[0007] The present invention uses titanium or a titanium alloy as the processing substrate. After forming a tantalum layer in region A, anodic oxidation is then carried out to further eliminate the risk of galvanic corrosion, and at the same time further improve the biocompatibility and galvanic corrosion resistance of the product, and reduce the clinical use risk. The inventor unexpectedly found that in anodic oxidation, by controlling the composition, voltage, temperature, and time of the anodic solution, a two-color corresponding effect can be formed, and the two colors just correspond one by one to regions A and B, playing a role in identifying and marking the functional regions. Therefore, in clinical applications, the product prepared by the present invention can identify the tantalum functional region and the titanium functional region by color, which will further broaden the application scenarios of the composite implant material and is more conducive to solving clinical pain points, such as identifying the left / right use of the implant and the front / back use of the bone plate by color marking.

[0008] Therefore, it also has important application value to obtain different functional color regions through the surface treatment of one-time anodic oxidation in the present invention.

[0009] The specific scheme is as follows:

[0010] A preparation method for a titanium-tantalum composite implant, comprising the following steps:

[0011] (1) Divide the titanium or titanium alloy implant into regions A and B, define region A as tantalum, and define region B as titanium;

[0012] (2) Mask the B region to obtain an implant with a covering mask;

[0013] (3) Form a tantalum layer in the A region of the implant with the covering mask. The B region is protected by the mask. After the tantalum layer in the A region is prepared, remove the mask to obtain an implant with a partial tantalum layer covering;

[0014] (4) Perform anodic oxidation on the implant with the partial tantalum layer covering, with a voltage of 10 - 160 V, a temperature of 10 - 50 °C, and a time of 30 s - 300 s to obtain a titanium-tantalum composite implant. The titanium-tantalum composite implant has a two-color film layer, and the colors of the A region and the B region are different.

[0015] In the present invention, before step (1), it further includes processing the titanium or titanium alloy implant to a predetermined size state, so as to facilitate the next covering of the mask, and the implant can maintain a suitable shape and a complete surface structure.

[0016] In a specific embodiment, for example, the titanium or titanium alloy implant can be processed into a screw or a bolt. The A region is the head or the cap, and the B region is the shank; or, the titanium or titanium alloy implant can be processed into a bone plate.

[0017] The method of mask covering in step (2) is to attach a high-temperature resistant film according to the predetermined morphological requirements. Here, the high-temperature resistant film can be a high-temperature resistant PVC film or a high-temperature resistant PET film.

[0018] The method of removing the mask in step (3) is to tear off the high-temperature resistant film, place the implant in a degreasing solution for degreasing and cleaning, and then rinse with purified water. The degreasing solution can use a common metal surface oil remover.

[0019] The method of forming a tantalum layer in the A region in step (3) is chemical vapor deposition, cold spraying or thermal spraying, preferably chemical vapor deposition. The process of chemical vapor deposition includes: first, clean for 10 - 60 min under a bias voltage of 500 - 1000 V. Then perform deposition, with a deposition current of 5 - 15 A, a deposition frequency of 100 - 1000 Hz, a deposition bias voltage of 50 - 1000 V, and a deposition time of 50 - 600 min; preferably, the process of chemical vapor deposition includes: first, use plasma cleaning for 10 - 40 min under a bias voltage of 650 - 1000 V, then perform deposition, with a deposition current of 5 - 15 A, a deposition frequency of 100 - 1000 Hz, a deposition bias voltage of 50 - 250 V, and a deposition time of 60 - 400 min.

[0020] In a specific embodiment, the following deposition conditions can be adopted: the deposition current is 7A, 8A, 9A, 10A, 11A, 12A, 13A, 14A; the deposition frequency is 300Hz, 400Hz, 500Hz, 600Hz, 700Hz, 800Hz; the deposition bias voltage is 50V, 100V, 150V, 200V; the deposition time is 100min, 150min, 200min, 250min, 300min, 350min.

[0021] In the present invention, the anodic solution used in the anodization treatment in step (4) contains: formic acid 1 - 5wt%, acetic acid 1 - 5wt%, oxalic acid 1 - 5g / 100mL, salicylic acid 0.1 - 0.5g / 100mL, nitric acid 1 - 5wt%, manganese sulfate 0.1 - 0.5g / 100mL, citric acid 0.1 - 0.5g / 100mL, sodium ethylenediaminetetraacetate 0.1 - 0.5g / 100mL;

[0022] Preferably, the anodic solution contains: formic acid 1 - 5wt%, acetic acid 1 - 3wt%, oxalic acid 3 - 5g / 100mL, salicylic acid 0.1 - 0.2g / 100mL, nitric acid 2 - 3wt%, manganese sulfate 0.1 - 0.2g / 100mL, citric acid 0.1 - 0.2g / 100mL, sodium ethylenediaminetetraacetate 0.1 - 0.2g / 100mL.

[0023] In the present invention, different color effects are formed by controlling the voltage in the anodization treatment, including: the voltage range is 15 ± 1V, the B area is light dark red, and the A area is light khaki; in a specific embodiment, the voltage can be 14.2V, 14.5V, 14.7V, 14.8V, 15.2V, 15.5V, 15.9V.

[0024] Or, the voltage range is 18 ± 2V, the B area is deep purple, and the A area is khaki; in a specific embodiment, the voltage can be 16.5V, 16.8V, 17.2V, 17.5V, 17.8V, 18.2V, 18.5V, 18.8V, 19.5V, 19.7V, 20V.

[0025] Or, the voltage range is 24 ± 2V, the B area is blue, and the A area is deep purple; in a specific embodiment, the voltage can be 22.5V, 23V, 23.5V, 24.2V, 24.5V, 24.7V, 24.9V, 25V, 25.5V, 26V.

[0026] Alternatively, the voltage range is 30 ± 2V, the B region is light blue, and the A region is dark blue; in a specific embodiment, the voltage can be 28.5V, 29V, 29.5V, 29.8V, 30V, 30.2V, 30.4V, 30.6V, 30.8V, 31V, 31.5V, 32V.

[0027] Alternatively, the voltage range is 45 ± 2V, the B region is light green, and the A region is light blue; in a specific embodiment, the voltage can be 43.5V, 44V, 44.5V, 44.7V, 44.9V, 45V, 45.2V, 45.4V, 45.8V, 46V, 46.7V, 47V.

[0028] Alternatively, the voltage range is 68 ± 3V, the B region is light yellow, and the A region is magenta; in a specific embodiment, the voltage can be 65.5V, 66V, 66.5V, 67V, 67.5V, 68V, 68.5V, 69V, 69.5V, 70V, 70.5V, 71V.

[0029] Alternatively, the voltage range is 74 ± 2V, the B region is blue - red, and the A region is golden yellow; in a specific embodiment, the voltage can be 72.5V, 73V, 73.5V, 74V, 74.2V, 74.4V, 74.6V, 74.8V, 75V, 75.5V, 76V.

[0030] Alternatively, the voltage range is 83 ± 2V, the B region is blue - green, and the A region is dark golden yellow; in a specific embodiment, the voltage can be 81.5V, 82V, 82.5V, 83V, 83.2V, 83.4V, 83.6V, 83.8V, 84V, 84.2V, 84.5V, 85V.

[0031] Alternatively, the voltage range is 96 ± 2V, the B region is green, and the A region is magenta; in a specific embodiment, the voltage can be 94V, 94.5V, 95V, 95.6V, 95.8V, 96V, 96.2V, 96.4V, 96.8V, 97V, 97.5V, 98V.

[0032] Alternatively, the voltage range is 105 ± 2V, the B region is green, and the A region is blue - red; in a specific embodiment, the voltage can be 103.5V, 104V, 104.5V, 105V, 105.3V, 105.6V, 105.8V, 106V, 106.2V, 106.5V, 107V.

[0033] Alternatively, the voltage range is 120 ± 2V, the B area is green, and the A area is bluish green; in a specific embodiment, the voltage can be 118.5V, 119V, 119.5V, 120V, 120.2V, 120.4V, 120.6V, 120.8V, 121V, 121.4V, 121.5V, 120V.

[0034] Alternatively, the voltage range is 150 ± 10V, the B area is gray, and the A area is green. In a specific embodiment, the voltage can be 141V, 143V, 145V, 146V, 148V, 150V, 152V, 154V, 156V, 158V, 160V.

[0035] The present invention also protects the titanium-tantalum composite implant prepared by the preparation method of the titanium-tantalum composite implant.

[0036] Beneficial effects:

[0037] By performing tantalum coating treatment on the titanium alloy implant product, the present invention obtains a titanium-tantalum composite functional film layer and product that can be applied to the human body environment to reduce the ion precipitation of the titanium alloy implant and improve the corrosion resistance and surface bioactivity of the titanium alloy. At the same time, on this basis, a one-time anodic oxidation treatment is carried out to oxidize the metal materials of titanium and tantalum by losing electrons, effectively preventing and eliminating the galvanic corrosion caused by the redox reaction due to the potential difference between the two metals in the body fluid environment, and further improving the overall performance.

[0038] Furthermore, in the oxidation process of the present invention, through a specific anodic oxidation solution system and process, two oxide film layers with different colors and functional identifications are obtained on the titanium side and the tantalum side during one-time anodic oxidation. The surface colors after one-time anodic oxidation on the titanium / tantalum composite surface show a strict corresponding relationship, that is, when the tantalum side is khaki, the titanium side is dark purple; when the tantalum side is dark purple, the titanium side is blue; when the tantalum side is dark blue, the titanium side is light blue; when the tantalum side is light blue, the titanium side is light green; when the tantalum side is light pink, the titanium side is light yellow; when the tantalum side is magenta, the titanium side is light yellow; when the tantalum side is golden yellow, the titanium side is blue-red; when the tantalum side is dark golden yellow, the titanium side is bluish green; when the tantalum side is magenta, the titanium side is green; when the tantalum side is blue-red, the titanium side is green; when the tantalum side is bluish green, the titanium side is green.

[0039] Finally, in the present invention, no other impurity elements are doped and introduced during the oxidation process of the implant film layer, which further ensures that there will be no corrosion problem of losing electrons and ion precipitation problem for the whole, and has the advantages of both functional effects and functional identifications. Description of the drawings

[0040] To more clearly illustrate the technical solution of the present invention, the accompanying drawings will be briefly introduced below. Obviously, the accompanying drawings in the following description only relate to some embodiments of the present invention and do not limit the present invention.

[0041] Figure 1 Schematic diagram of the titanium and tantalum composite film layer provided in Embodiment 1 of the present invention.

[0042] Figure 2 Effect diagram of the actual product obtained in Embodiment 1, where the tantalum side is light earthy yellow and the strictly corresponding titanium side is light dark red.

[0043] Figure 3 Effect diagram of the actual product obtained in Embodiment 6, where the tantalum side is magenta and the strictly corresponding titanium side is light yellow.

[0044] Figure 4 Effect diagram of the actual product obtained in Embodiment 8, where the tantalum side is deep golden yellow and the strictly corresponding titanium side is blue-green.

[0045] Figure 5 Effect diagram of the actual product obtained in Embodiment 10, where the tantalum side is blue-green and the strictly corresponding titanium side is green. Detailed implementation manners

[0046] A preparation method of a titanium-tantalum composite implant, comprising the following steps:

[0047] (1) Divide the titanium or titanium alloy implant into regions A and B, define region A as tantalum, and define region B as titanium. As Figure 1 shown, the region with the tantalum side color corresponds to region A, and the region with the titanium side color corresponds to region B;

[0048] (2) Cover the region B with a mask to obtain an implant covered with the mask; this step uses the mask to cover the local substrate of the titanium or titanium alloy, and region B will not be coated in the next step;

[0049] (3) Form a tantalum layer in region A of the implant covered with the mask, which can be carried out by vapor deposition, cold spraying or thermal spraying; region B is protected by the mask. After the tantalum layer in region A is prepared, the mask is removed to obtain an implant locally covered with the tantalum layer;

[0050] (4) Perform anodic oxidation on the implant locally covered with the tantalum layer, with a voltage of 10 - 160V, a temperature of 10 - 50°C, and a time of 30s - 300s, to obtain a titanium-tantalum composite implant. The titanium-tantalum composite implant has a two-color film layer, and the colors of region A and region B are different.

[0051] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. For those not specifying specific techniques or conditions in the examples, the techniques or conditions described in the literature in this field or according to the product specifications are followed. For reagents or instruments not indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase. In the following examples, unless otherwise specified, "%" refers to weight percentage.

[0052] In the examples, the acquisition of the tantalum layer is illustrated by taking chemical vapor deposition as an example. Cold spraying or thermal spraying of tantalum belongs to the prior art and can be carried out according to conventional processes, which will not be elaborated here.

[0053] Example 1

[0054] Titanium alloy bars are processed into screws of a predetermined size. After degreasing and cleaning, the screws in a state to be treated are obtained. According to the predetermined requirements, a temperature-resistant mask is used to cover and protect the screw head without coating treatment, which is defined as area B, and the screw shank and other areas are to be coated with a tantalum layer, which is defined as area A.

[0055] A high-temperature resistant film is attached according to the predetermined morphological requirements to ensure clear boundaries.

[0056] Subsequently, the screws are hung in a vacuum furnace for chemical vapor deposition. The deposition process is a bias voltage of 650 V, a cleaning time of 10 min, a deposition current of 5 A, a deposition frequency of 100 Hz, a deposition bias voltage of 90 V, and a deposition time of 270 min. After deposition, the obtained products are placed in a degreasing solution (PWC-401 cleaning agent) for degreasing and cleaning after removing the high-temperature mask. After rinsing with purified water, the whole screw product is immersed in an anodic solution for anodic coloring. The anodic solution contains 1 wt% formic acid, 1 wt% acetic acid, 5 g / 100 mL oxalic acid, 0.2 g / 100 mL salicylic acid, 2 wt% nitric acid, 0.1 g / 100 mL manganese sulfate, 0.2 g / 100 mL citric acid, and 0.1 g / 100 mL sodium ethylenediaminetetraacetate; among them, the oxidation voltage is set to 15 ± 0.6 V, the temperature is 25 °C, and the oxidation time is 60 s. After oxidation, rinsing with purified water can obtain the final titanium / tantalum composite two-color functional film layer screw product. The color of area A on the tantalum side is light khaki, and the color of area B on the titanium side corresponding to it is light dark red, as Figure 2 shown.

[0057] Example 2

[0058] This example is an improvement based on Example 1. The only difference is that the voltage setting range for the anodic oxidation reaction is 18 ± 2 V. The color of the titanium side is dark purple, and the color of the tantalum side corresponding exactly to it is khaki. The color distinction is very obvious, making it easy to identify the corresponding functional areas and facilitating clinical application.

[0059] Example 3

[0060] This example is an improvement based on Example 1. The only difference is that the voltage setting range for the anodic oxidation reaction is 24 ± 2V. The color on the titanium side is blue, and the strictly corresponding color on the tantalum side is dark purple. The color distinction is very obvious, making it easy to identify the corresponding functional areas and facilitating clinical application.

[0061] Example 4

[0062] This example is an improvement based on Example 1. The only difference is that the voltage setting range for the anodic oxidation reaction is 30 ± 2V. The color on the titanium side is light blue, and the strictly corresponding color on the tantalum side is dark blue. The color distinction is very obvious, making it easy to identify the corresponding functional areas and facilitating clinical application.

[0063] Example 5

[0064] This example is an improvement based on Example 1. The only difference is that the voltage setting range for the anodic oxidation reaction is 45 ± 2V. The color on the titanium side is light green, and the strictly corresponding color on the tantalum side is light blue. The color distinction is very obvious, making it easy to identify the corresponding functional areas and facilitating clinical application.

[0065] Example 6

[0066] The titanium alloy bar is processed into screws of a predetermined size. After degreasing and cleaning, the screws are in a state to be processed. According to the predetermined requirements, a heat-resistant mask is used to cover and protect the screw head without coating treatment, which is defined as area B. The screw shank and other areas are to be coated with a tantalum layer, which is defined as area A.

[0067] The method of covering the heat-resistant mask is the same as that in Example 1.

[0068] Subsequently, the screws are hung in a vacuum furnace for vapor deposition. The deposition process includes a bias voltage of 500V, a cleaning time of 30min, a deposition current of 5A, a deposition frequency of 500Hz, a deposition bias voltage of 150V, and a deposition time of 240min. After deposition, the obtained product is removed from the high-temperature mask and placed in a degreasing solution for degreasing and cleaning. After rinsing with purified water, the entire screw product is immersed in an anodic solution for oxidation coloring. The anodic solution contains 5wt% formic acid, 3wt% acetic acid, 3g / 100mL oxalic acid, 0.1g / 100mL salicylic acid, 3wt% nitric acid, 0.2g / 100mL manganese sulfate, 0.1g / 100mL citric acid, and 0.2g / 100mL sodium ethylenediaminetetraacetate. Among them, the oxidation voltage is set to 68 ± 3V, the temperature is 30°C, and the oxidation time is 60S. After oxidation, rinsing with purified water can obtain the final titanium / tantalum composite double-color functional film layer screw product. The color of area A on the tantalum side is magenta, and the corresponding color of area B on the titanium side is light yellow, asFigure 3 as shown

[0069] Example 7

[0070] This example is an improvement based on Example 6. The only difference is that the voltage setting range for the anodic oxidation reaction is 74 ± 2 V. The color on the titanium side is blue - red, and the strictly corresponding color on the tantalum side is golden yellow. The color distinction is very obvious, making it easy to identify the corresponding functional areas and facilitating clinical application.

[0071] Example 8

[0072] The titanium alloy bar is processed into screws of a predetermined size. After degreasing and cleaning, the screws in a state to be processed are obtained. According to the predetermined requirements, a heat - resistant mask is used to cover and protect the screw head without coating treatment, which is defined as area B. The screw rod and other areas of the screw are to be coated with a tantalum layer, which is defined as area A.

[0073] The method of covering the heat - resistant mask is the same as that in Example 1.

[0074] Subsequently, the screws are hung in a vacuum furnace for vapor deposition. The deposition process parameters are: bias voltage 700 V, cleaning for 25 min, deposition current 10 A, deposition frequency 300 Hz, deposition bias voltage 100 V, deposition time 60 min. After deposition, the obtained products are placed in a degreasing solution for degreasing and cleaning after removing the high - temperature mask. After rinsing with purified water, the whole screw product is immersed in an anodic solution for oxidation coloring. The anodic solution contains 3 wt% formic acid, 2 wt% acetic acid, 4 g / 100 mL oxalic acid, 0.1 g / 100 mL salicylic acid, 2 wt% nitric acid, 0.1 g / 100 mL manganese sulfate, 0.1 g / 100 mL citric acid, and 0.2 g / 100 mL sodium ethylenediaminetetraacetate. Among them, the oxidation voltage is set to 83 ± 2 V, the temperature is 40 °C, and the oxidation time is 60 s. After oxidation, rinsing with purified water can obtain the final titanium / tantalum composite two - color functional film - layer screw product. The color of area A on the tantalum side is dark golden yellow, and the corresponding color of area B on the titanium side is blue - green, as Figure 4 as shown

[0075] Example 9

[0076] This example is an improvement based on Example 8. The only difference is that the voltage setting range for the anodic oxidation reaction is 96 ± 2 V. The color on the titanium side is green, and the strictly corresponding color on the tantalum side is magenta. The color distinction is very obvious, making it easy to identify the corresponding functional areas and facilitating clinical application.

[0077] Example 10

[0078] This embodiment is an improvement based on Embodiment 8. The only difference is that the voltage setting range for the anodic oxidation reaction is 105 ± 2V. The color on the titanium side is green, and the strictly corresponding color on the tantalum side is blue - red. The color distinction is very obvious, making it easy to identify the corresponding functional areas and facilitating clinical application.

[0079] Embodiment 11

[0080] The titanium alloy bar is processed into screws of a predetermined size. After degreasing and cleaning, the screws in a to - be - treated state are obtained. According to the predetermined requirements, a heat - resistant mask is used to cover and protect the screw head without coating treatment, which is defined as area B. The screw rod and other areas are to be coated with a tantalum layer, which is defined as area A.

[0081] The method of covering with the heat - resistant mask is the same as that in Embodiment 1.

[0082] Subsequently, the screws are hung in a vacuum furnace for vapor deposition. The deposition process is as follows: bias voltage 900V, cleaning for 20 min, deposition current 13A, deposition frequency 300Hz, deposition bias voltage 230V, deposition time 300 min. After deposition, the obtained product is removed from the high - temperature mask and then placed in a degreasing solution for degreasing and cleaning. After rinsing with purified water, the whole screw product is immersed in an anodic solution for oxidation coloring. The anodic solution contains formic acid 2wt%, acetic acid 2wt%, oxalic acid 4g / 100mL, salicylic acid 0.2g / 100mL, nitric acid 3wt%, manganese sulfate 0.1g / 100mL, citric acid 0.1g / 100mL, sodium ethylenediaminetetraacetate 0.1g / 100mL. Among them, the oxidation voltage is set to 120 ± 2V, the oxidation time is 30S, the temperature is room temperature. After oxidation, rinsing with purified water can obtain the final titanium / tantalum composite double - color functional film - layer screw product. The color of area A on the tantalum side is blue - green, and the corresponding color of area B on the titanium side is green, as Figure 5 shown.

[0083] Embodiment 12

[0084] This embodiment is an improvement based on Embodiment 10. The only difference is that the voltage setting range for the anodic oxidation reaction is 150 ± 10V. The color on the titanium side is gray, and the strictly corresponding color on the tantalum side is green. The color distinction is very obvious, making it easy to identify the corresponding functional areas and facilitating clinical application.

[0085] Comparative Example 1

[0086] The titanium alloy bar is processed into screws of a predetermined size. After degreasing and cleaning, the screws in a to - be - treated state are obtained. According to the predetermined requirements, a heat - resistant mask is used to cover and protect the screw head without coating treatment, which is defined as area B. The screw rod and other areas are to be coated with a tantalum layer, which is defined as area A.

[0087] Attach a high-temperature resistant film according to the predetermined morphological requirements to ensure clear boundaries.

[0088] Subsequently, hang the screws in a vacuum furnace for vapor deposition. The deposition process includes a bias voltage of 650V, a cleaning time of 10 minutes, a deposition current of 5A, a deposition frequency of 100Hz, a deposition bias voltage of 900V, and a deposition time of 270 minutes. After deposition, remove the high-temperature mask from the obtained product and place it in a degreasing solution (PWC-401 cleaning agent) for degreasing and cleaning. After rinsing with purified water, immerse the entire screw product in an anodic solution for anodic coloring. The anodic solution contains 0.5wt% sodium fluoride and 2wt% nitric acid. Among them, the anodic voltage is set to 15 ± 0.6V, the temperature is 25°C, and the anodic time is 60 seconds. After anodization, rinse with purified water to obtain the final titanium / tantalum composite two-color functional film layer screw product. The color of the tantalum side region A is light earthy yellow, and the color of the corresponding titanium side region B is light gray, and the distinction effect between the two is not obvious.

[0089] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0090] In addition, it should be noted that in the above specific embodiments, the various specific technical features described can be combined in any suitable manner without conflict. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0091] In addition, any combination can be made between various different embodiments of the present invention as long as it does not violate the idea of the present invention, and it should also be regarded as the content disclosed by the present invention.

Claims

1. A method for preparing a titanium-tantalum composite implant, characterized in that: It includes the following steps: (1) Divide the titanium or titanium alloy implant into regions A and B, define region A as tantalum, and define region B as titanium; (2) Cover the region B with a mask to obtain an implant covered with the mask; (3) Form a tantalum layer in region A of the implant covered with the mask, and region B is protected by the mask. After the preparation of the tantalum layer in region A is completed, remove the mask to obtain an implant partially covered with the tantalum layer; (4) Perform anodic oxidation on the implant partially covered with the tantalum layer, with a voltage of 10 - 160V, a temperature of 10 - 50°C, and a time of 30s - 300s, to obtain a titanium-tantalum composite implant. The titanium-tantalum composite implant has a two-color film layer, and the colors of region A and region B are different.

2. The method for preparing a titanium-tantalum composite implant according to claim 1, characterized in that: Before step (1), it further includes processing the titanium or titanium alloy implant to a predetermined dimensional state.

3. The method for preparing a titanium-tantalum composite implant according to claim 2, characterized in that: Process the titanium or titanium alloy implant into a screw or bolt, where region A is the head or cap, and region B is the shank; or, process the titanium or titanium alloy implant into a bone plate.

4. The method for preparing a titanium-tantalum composite implant according to claim 1, characterized in that: In step (2), the method of mask covering is to perform mask covering in accordance with the predetermined morphological requirements by using a high-temperature resistant film or encapsulation method.

5. The method for preparing a titanium-tantalum composite implant according to claim 4, characterized in that: In step (3), the method for removing the mask is to place the implant in a degreasing solution for degreasing and cleaning, and then rinse with purified water.

6. The method for preparing a titanium-tantalum composite implant according to claim 1, characterized in that: In step (3), the method for forming the tantalum layer in region A is physical vapor deposition, cold spraying or thermal spraying.

7. The method for preparing a titanium-tantalum composite implant according to claim 1, characterized in that: In step (3), the method for forming the tantalum layer in region A is physical vapor deposition, and the process of physical vapor deposition includes: first, clean for 10 - 60 min under a bias voltage of 500 - 1000V, then perform deposition, with a deposition current of 5 - 15A, a deposition frequency of 100 - 1000Hz, a deposition bias voltage of 50 - 1000V, and a deposition time of 50 - 600 min.

8. The method for preparing a titanium-tantalum composite implant according to claim 6 or 7, characterized in that: The process of physical vapor deposition includes: first, use plasma cleaning for 10 - 40 min under a bias voltage of 650 - 1000V, then perform deposition, with a deposition current of 5 - 15A, a deposition frequency of 100 - 1000Hz, a deposition bias voltage of 50 - 250V, and a deposition time of 60 - 400 min.

9. The method for preparing a titanium-tantalum composite implant according to claim 1, characterized in that: In step (4), the anodic solution used in the anodizing treatment contains: formic acid 1-5 wt%, acetic acid 1-5 wt%, oxalic acid 1-5 g / 100 mL, salicylic acid 0.1-0.5 g / 100 mL, nitric acid 1-5 wt%, manganese sulfate 0.1-0.5 g / 100 mL, citric acid 0.1-0.5 g / 100 mL, and sodium ethylenediaminetetraacetate 0.1-0.5 g / 100 mL.

10. The method for preparing a titanium-tantalum composite implant according to claim 9, wherein: the anodic solution contains: formic acid 1-5 wt%, acetic acid 1-3 wt%, oxalic acid 3-5 g / 100 mL, salicylic acid 0.1-0.2 g / 100 mL, nitric acid 2-3 wt%, manganese sulfate 0.1-0.2 g / 100 mL, citric acid 0.1-0.2 g / 100 mL, and sodium ethylenediaminetetraacetate 0.1-0.2 g / 100 mL.

11. The method for preparing a titanium-tantalum composite implant according to claim 9 or 10, wherein: different color effects are formed by controlling the voltage in the anodizing treatment, including: the voltage range is 15±1 V, the B area is light dark red, and the A area is light earthy yellow; alternatively, the voltage range is 24±2 V, the B area is blue, and the A area is dark purple; alternatively, the voltage range is 30±2 V, the B area is light blue, and the A area is dark blue; alternatively, the voltage range is 45±2 V, the B area is light green, and the A area is light blue; alternatively, the voltage range is 68±3 V, the B area is light yellow, and the A area is magenta; alternatively, the voltage range is 74±2 V, the B area is blue-red, and the A area is golden yellow; alternatively, the voltage range is 83±2 V, the B area is blue-green, and the A area is dark golden yellow; alternatively, the voltage range is 96±2 V, the B area is green, and the A area is magenta; alternatively, the voltage range is 105±2 V, the B area is green, and the A area is blue-red; alternatively, the voltage range is 120±2 V, the B area is green, and the A area is blue-green; alternatively, the voltage range is 150±10 V, the B area is gray, and the A area is green.

12. A titanium-tantalum composite implant prepared by the method for preparing a titanium-tantalum composite implant according to any one of claims 1-11.

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