A fusion type tantalum-silver composite double-layer functional coating material based on a metal continuous porous network structure and a preparation method thereof

Abstract

The application discloses a kind of based on metal continuous porous network structure's fusion type tantalum-silver composite double-layer functional coating material and its preparation method, its preparation method is: 1) using specific electrolyte formula, using ultra-high voltage anodic oxidation process on the surface of cleaned titanium / titanium alloy controllable construction first continuous porous metal network structure;2) vacuum heating cleaning removes titanium / titanium alloy surface impurities, carries out physical vapor deposition (PVD) on its surface, and fuses into secondary tantalum coating structure in hole;3) replace silver target material, vacuum heating cleaning twice, carry out double PVD and fuse into tertiary silver coating structure in network hole, so that it completely covers porous metal network structure;4) the sample after processing is carried out vacuum high-temperature pressure-keeping heat treatment;5) after multiple cleaning, packaging and irradiation sterilization, continuous porous network structure's fusion type tantalum-silver composite double-layer functional coating material is obtained.The application has long-acting antibacterial and promotes bone function, and can be used in orthopedics, dental field.

Description

TECHNICAL FIELD

[0001] The present application relates to the preparation technology of medical devices, in particular to a fusion type tantalum-silver composite double-layer functional coating material based on a metal continuous porous network structure and a preparation method thereof. BACKGROUND

[0002] After the occurrence of fracture, bone defect, etc., the current clinical treatment method is to use a bone implant device for fixation, and then realize bone regeneration through the self-recovery ability of the human body. However, the currently marketed bone implant device generally does not have other biological functions except for support and fixation, and the occurrence process and surgical process of fracture and bone defect will bring bacteria or impurities, which will easily cause infection at the surgical site. Secondly, the self-healing period of fracture and bone defect without external intervention is long. The above two types of problems often bring huge psychological, physiological and economic burdens to patients.

[0003] Coating technology is a platform technology that can be introduced on any shaped substrate, but the problems of the bonding strength between the coating and the substrate and the single function of the coating cannot meet the complex actual needs of the clinic, which leads to the fact that there is no mature multifunctional coating type bone implant device product on the market. In addition, the current research mainly focuses on the use of organic anti-infection or bone formation drugs to achieve the treatment of bone infection or bone defect, but in the face of various enzymes in the body and the long period of bone defect repair / bone infection treatment, we wonder whether inorganic metal materials with corresponding functions are more suitable for the application scenario of orthopedics.

[0004] Therefore, in the present application, we choose two inorganic metal materials, tantalum and silver, as the osteogenic and antibacterial active components respectively, and introduce a continuous metal network structure on the surface of the titanium substrate as a spatial loading site to prepare a fusion type tantalum-silver composite double-layer functional coating material based on a metal continuous porous network structure, which can be used for the whole cycle of bone infection and bone defect treatment. SUMMARY

[0005] The purpose of the present application is to solve the problems of insufficient bonding strength between the coating and the substrate of the current medical device surface coating and the single function of the coating which cannot meet the complex actual needs of the clinic, and to provide a fusion type tantalum-silver composite double-layer functional coating material based on a metal continuous porous network structure and a preparation method thereof by combining the biological activity and anti-infection performance of tantalum and silver metals.

[0006] The present application adopts the following technical scheme: a preparation method of a fusion type tantalum-silver composite double-layer functional coating material based on a metal continuous porous network structure, comprising the following steps:

[0007] 1) ultrasonic cleaning and chemical film removing pretreatment are first performed on the titanium / titanium alloy, a specific electrolyte is used, and a first continuous porous metal network structure is formed on the surface of the titanium / titanium alloy by using an ultrahigh voltage anodization process;

[0008] 2) vacuum heating cleaning is performed on the treated sample, and a second tantalum coating structure is integrated into the mesh holes of the first continuous porous metal network structure by using physical vapor deposition (PVD);

[0009] 3) the silver target material is replaced, vacuum heating cleaning is performed again, and a third silver coating structure is integrated into the mesh holes by double PVD to form a three-layer inlaid double-layer composite coating structure;

[0010] 4) vacuum high-temperature pressure holding heat treatment is performed on the treated sample;

[0011] 5) after multiple cleaning, packaging and irradiation sterilization, the treated sample is obtained as a metal continuous porous network structure integrated tantalum-silver composite functional coating material.

[0012] Further, the ultrasonic cleaning in step 1) specifically includes: first ultrasonic chemical cleaning for 10-20 min, and then deionized water ultrasonic cleaning for at least three times, each time for 5 min;

[0013] The chemical cleaning solution used in the ultrasonic chemical cleaning has the following formulation: sodium hydroxide 10-15 g / L, sodium metasilicate pentahydrate 6-10 g / L, sodium tripolyphosphate 3-5 g / L, sodium dodecyl sulfate 10-18 g / L, nitrilotriacetic acid 0.4-0.6 g / L, NP-10 (99%) 2-5 g / L, MOP-5 (99%) 0.6-1 g / L, LAB (99%) 3-5 g / L, and FMES (99%) 2-5 g / L;

[0014] The temperature of the ultrasonic chemical cleaning and the deionized water ultrasonic cleaning is 45-50°C, the ultrasonic power is 150-180 W, and the ultrasonic frequency is 80 kHz;

[0015] The chemical film removing specifically includes: the chemical film removing formulation is: nitric acid 6-8 wt%, ammonium hydrogen fluoride 2.5-4.5 wt%, urea 0.5-1.5 wt%, and the rest is deionized water, the chemical film removing time is 2 min, the temperature is 28-35°C, and then deionized water ultrasonic cleaning is performed for at least three times, each time for 2 min, the ultrasonic power is 150-180 W, and the ultrasonic frequency is 80 kHz.

[0016] Further, the superhigh voltage anodic oxidation process specifically comprises that the specific electrolyte formula is: zirconium fluoride 4.5-8.5 g / L, glycerol 650-850 ml / L, sodium phosphate 5-12 g / L, OP-10 surfactant 3-5 ml / L, ammonium carbonate 0.25-0.5 g / L, sulfamic acid 0.5-1.2 g / L, and the rest is deionized water, the pH value of the specific electrolyte is 10-12, the anode is a sample, the cathode is 304 rust-free steel, the distance between the anode and the cathode is 40-50 cm, the voltage is 80-90 V, and the reaction time is 2-5 h.

[0017] Further, in step 2), the vacuum heating cleaning specifically comprises that the vacuum furnace power is 4.5 kW, the vacuum degree is 50-100 Pa, the bias voltage is ≤200 V, the vacuum cleaning mode is heated to 480-530 ℃, and the cleaning time is 25-45 min.

[0018] The physical vapor deposition (PVD) specifically comprises that the vacuum furnace is pumped for 15-20 min, the vacuum degree in the furnace is higher than 0.06 Pa, the target material is tantalum target material with a purity greater than 99.99%, the background vacuum is higher than 4.0×10 -2 Pa, the target power density is 1-5 W / cm 2 , the target current is 0.3-1.5 A, and the temperature is 150-180 ℃.

[0019] Further, in step 3), the vacuum heating cleaning specifically comprises that the vacuum furnace power is 4.5 kW, the vacuum degree is 50-100 Pa, the bias voltage is ≤200 V, the vacuum cleaning mode is heated to 480-530 ℃, and the cleaning time is 25-45 min.

[0020] The double PVD specifically comprises that the vacuum furnace is pumped for 10-18 min, the vacuum degree in the furnace is higher than 0.1 Pa, the target material is silver target material with a purity greater than 99.99%, the background vacuum is greater than 4.0×10 -3 Pa, the target power density is 1-5 W / cm 2 , the target current is 2-5 A, and the temperature is 380-450 ℃.

[0021] Further, in step 4), the vacuum high-temperature pressure-keeping heat treatment process specifically comprises that the vacuum furnace is pumped to 4.5×10 -1 Pa, the vacuum furnace power is 100 kW, the temperature in the furnace is increased to 600-780 ℃ at a vacuum heating rate of 3-5 ℃ / min, and the temperature is kept for 2-4 h; then the micro-positive pressure in the furnace is adjusted to 150-300 Pa, and the temperature in the furnace is cooled to 25-40 ℃ at a cooling rate of 5-10 ℃ / min.

[0022] Further, in step 5), the multiple cleaning is ultrasonic cleaning using ultrapure water, the ultrasonic power is 70-90W, and the cleaning time is 10min.

[0023] The packaging is vacuum packaging.

[0024] The irradiation sterilization process uses Co 60 Sterilization, irradiation dose 5-10kGy.

[0025] A kind of based on metal continuous porous network structure's fusion type tantalum-silver composite double-layer functional coating material is prepared by any one of the methods.

[0026] Compared with the prior art, the present application has the following advantages:

[0027] 1) The present application uses titanium / titanium alloy, tantalum, silver, etc. as raw materials, and a combination process of ultrahigh voltage anodizing, vacuum heating cleaning, vacuum PVD, heat treatment, etc. to prepare a fusion type tantalum-silver composite double-layer functional coating material based on metal continuous porous network structure. The above raw material selection and process combination are unique to the present application.

[0028] 2) The double-layer functional coating material of the present application has a three-level composite structure: a new type of metal continuous porous network structure is prepared using ultrahigh voltage anodizing and a specially designed electrolyte formula; a secondary tantalum coating structure and a three-level inlaid double-layer composite coating structure are respectively fused into the mesh holes of the first continuous porous metal network structure using PVD twice, i.e. a fusion type tantalum-silver composite double-layer functional coating material based on metal continuous porous network structure is obtained. The first structure is prepared based on the ultrahigh voltage anodizing and the special electrolyte formula in the present application, the metal porous structure is continuous (the continuous structure can provide complete mechanical engagement after the tantalum / silver coating is fused, so that the coating with three-level structure forms an approximately integral structure, thereby ensuring high bonding strength of the coating), the structure is smooth and flat, the internal space is large, providing physical space sites for deposition of the second and third structures, and increasing the contact area and mechanical engagement, which provides the possibility for improving the bonding strength of the second and third structures; the tantalum coating and the silver coating are fused into the metal continuous porous network structure, and the tantalum coating is located in the middle layer and the silver coating is located in the uppermost layer, which matches the time sequence of the silver coating releasing silver ions first for sterilization and the tantalum ions releasing later for promoting osteogenesis.

[0029] 3) The introduction of the tantalum / silver coating in the present application adopts a double vacuum physical vapor deposition (PVD) technology. According to the problem of high surface tension existing in the continuous porous metal network structure, the air in the pore structure can be directly stripped by vacuum physical vapor deposition, so that tantalum and silver can be easily deposited in the pore, realizing the efficient integration of tantalum and silver in the pore. After forming a three-level composite structure of a double-layer functional coating material, further combined with a vacuum heat treatment process, the molecules on the interface between the three metal layers of titanium, tantalum and silver are made to enter each other by heat treatment, the diffusion distance is increased, so that the bonding strength between the coating and the substrate is increased. And it is also clamped by the physical space site provided by the first-level metal continuous porous network structure, the tantalum and silver coating is integrated into the pore structure, increasing the contact area and mechanical occlusion, and the coating bonding strength is energized twice.

[0030] 4) The coating material in the present application has high biocompatibility, high bonding strength, anti-infection function and bone formation function. The stability of the inorganic metal titanium, tantalum and silver raw materials guarantees the high biocompatibility of the coating material; the above-mentioned porous continuous network structure and vacuum heat treatment guarantee the high bonding strength of the coating, which guarantees the long-period stable use of the coating; the silver coating on the outer layer has a high-efficiency broad-spectrum and long-period sterilization effect, and kills the bacteria at the surgical site by continuously releasing silver ions; and the tantalum coating in the middle layer is physically wrapped and blocked by the silver coating, and is released later than silver, which meets the clinical scene of anti-infection first and then bone formation, and the tantalum ion has recognized curative effect on bone formation. The organic synergy of the above-mentioned materials and structures can guarantee the perfect match of the function of the coating material and the clinical demand.

[0031] 5) The coating preparation technology of the present application has platform property, and can introduce coating on the surface of bone implant instruments of any shape, meet the needs of various bone infections and bone defects, and has obvious universality and generalizability. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 SEM image of the metal continuous porous network structure (comparative example 1);

[0033] Figure 2 SEM image of the integrated tantalum-silver composite double-layer functional coating based on the metal continuous porous network structure (example 1);

[0034] Figure 3 Photo of the integrated tantalum-silver composite double-layer functional coating material based on the metal continuous porous network structure (A is a TC4 sample without any treatment, and B is the sample in example 1);

[0035] Figure 4In vitro release curve of the integrated tantalum-silver composite double-layer functional coating material based on the continuous porous network structure of metal (Example 1);

[0036] Figure 5 Anti-infection effect of the integrated tantalum-silver composite double-layer functional coating material based on the continuous porous network structure of metal (A is Comparative Example 1, B is Example 1). DETAILED DESCRIPTION

[0037] The technical solutions of the present application will be further described in detail below in combination with the drawings and specific examples.

[0038] Comparative Example 1:

[0039] 1) Ultrasonic chemical wave cleaning of titanium alloy substrate TC4; sequentially using ultrasonic chemical cleaning for 30 minutes (ultrasonic cleaning solution formula: sodium hydroxide 10 g / L, sodium metasilicate pentahydrate 8 g / L, sodium tripolyphosphate 4 g / L, sodium dodecyl sulfate 15 g / L, nitrilotriacetic acid 0.5 g / L, NP-10 (99%) 3.4 g / L, MOP-5 (99%) 0.8 g / L, LAB (99%) 4.5 g / L, FMES (99%) 2.7 g / L), and then using deionized water ultrasonic cleaning for 3 times, 5 minutes each time, ultrasonic power is 180 W, ultrasonic frequency is 45 KHz, and temperature is 60℃.

[0040] 2) Normal temperature immersion chemical film removal for 90s (chemical film removal solution formula is: nitric acid 8%, ammonium hydrogen fluoride 3%, urea 0.5%, and water 89.5%), and then using deionized water ultrasonic cleaning for 3 times, 5 minutes each time.

[0041] 3) Then performing ultrahigh voltage anodic oxidation process on the sample to form a first continuous porous metal network structure on the surface of the titanium substrate (electrolyte formula is: zirconium fluoride 4.5 g / L, glycerol 650 ml / L, sodium phosphate 7 g / L, OP-10 surfactant 4 ml / L, ammonium carbonate 0.3 g / L, sulfamic acid 0.8 g / L, and the rest is deionized water), wherein the pH value of the electrolyte is controlled to be 10, a rust-free steel plate is used as the cathode, the distance between the two poles is 40 cm, the voltage is 90V, and the reaction time is 4h.

[0042] 4) The above sample is sequentially cleaned with ultrapure water for 3 times using ultrasonic cleaning, ultrasonic power is 80W, frequency is 30KHz, and cleaning time is 10min; after vacuum packaging, irradiation sterilization process Co 60 sterilization, irradiation dose is 8kGy, and finally the required sample is obtained, the SEM diagram is as Figure 1 .

[0043] The sample was subjected to bonding strength detection, and the result was 56.9 MPa; the cell survival rate was 97.3% after 7 days of CCK-8 detection compared with the control group (i.e. the original raw material TC4); the antibacterial ability was detected by the antibacterial circle experiment, and no antibacterial circle appeared; using the intramedullary infection model of rats, the sample was taken after 28 days of implantation for detection, and the results were as follows Figure 5 In the middle A, it represents that the infection is not cured, and there is basically no bone integration effect.

[0044] Example 1:

[0045] 1) The titanium alloy substrate TC4 was subjected to ultrasonic chemical wave cleaning; ultrasonic chemical cleaning was used for 30 minutes (ultrasonic cleaning solution formula: sodium hydroxide 10 g / L, sodium metasilicate pentahydrate 8 g / L, sodium tripolyphosphate 4 g / L, sodium dodecyl sulfate 15 g / L, nitrilotriacetic acid 0.5 g / L, NP-10 (99%) 3.4 g / L, MOP-5 (99%) 0.8 g / L, LAB (99%) 4.5 g / L, FMES (99%) 2.7 g / L), and then deionized water was used for ultrasonic cleaning for 3 times, 5 minutes each time, ultrasonic power was 180 W, ultrasonic frequency was 45 KHz, and temperature was 60°C.

[0046] 2) The sample was subjected to room temperature immersion chemical film removal for 90 s (chemical film removal solution formula: nitric acid 8%, ammonium hydrogen fluoride 3%, urea 0.5%, and water 89.5%), and then deionized water was used for ultrasonic cleaning for 3 times, 5 minutes each time.

[0047] 3) The sample was subjected to ultrahigh voltage anodic oxidation process to form a first continuous porous metal network structure on the surface of the titanium substrate (electrolyte formula: zirconium fluoride 4.5 g / L, glycerol 650 ml / L, sodium phosphate 7 g / L, OP-10 surfactant 4 ml / L, ammonium carbonate 0.3 g / L, sulfamic acid 0.8 g / L, and the rest is deionized water), wherein the pH value of the electrolyte was controlled to be 10, a rust-free steel plate was used as the cathode, the distance between the two electrodes was 40 cm, the voltage was 90 V, and the reaction time was 4 h.

[0048] 4) The sample was subjected to vacuum heating cleaning in a vacuum furnace with a power of 4.5 kW, a vacuum degree of 80 Pa, a bias voltage of ≤200 V, a vacuum cleaning mode heating temperature of 530°C, and a cleaning time of 35 min for surface deep cleaning.

[0049] 5) The sample was placed in the chamber, vacuumed for 18 min, the vacuum degree was higher than 0.06 Pa, the purity of the tantalum target material was 99.99%, the background vacuum was higher than 4.0 x 10 -2 Pa, the target power density was 4 W / cm 2, target current 1.2 A, temperature 168℃, PVD deposition time 1500s, further melt into the sample continuous metal hole structure to build a secondary tantalum coating structure;

[0050] 6) vacuum 15min, vacuum degree in the cavity 0.1Pa; silver target purity 99.99%, vacuum degree higher than 0.1Pa, target power density 3W / cm 2 , target current 3A, temperature 380℃, deposition time 1800s, further melt into the sample continuous metal hole structure to build a tertiary silver coating structure;

[0051] 7) vacuum high temperature pressure holding heat treatment process: vacuum the vacuum furnace bin to 4.5x10 -1 Pa, vacuum furnace power 100kW, 5℃ / min vacuum heating rate to 700℃, holding pressure 2h; step is completed, adjust the micro-positive pressure to 200Pa, 10℃ / min cooling rate to 40℃.

[0052] 8) the above sample is sequentially used three times using ultrapure water for ultrasonic cleaning, ultrasonic power 80W, frequency 30KHz, cleaning time 10min; use vacuum packaging after irradiation sterilization process Co 60 sterilization, irradiation dose 8kGy, finally get the required sample.

[0053] Compared with Comparative Example 1, this embodiment increases the secondary tantalum coating structure and the tertiary silver coating structure Figure 2 . The above sample is subjected to bonding strength detection, and the result is 48.9MPa; the cell survival rate after 7 days is 88.4% compared with the control group (i.e. the original raw material TC4) using CCK-8 detection; the antibacterial ability is detected by combining the antibacterial circle experiment, and the antibacterial circle area is 3.04cm 2 ; using rat intramedullary infection model, sampling detection after 28 days of implantation found that the sample surface eluted bacteria were plated and cultured, the results are shown in B of Figure 5 , the infection treatment effect is significant, further combined with Micro-CT detection found that the sample surface has obvious bone integration phenomenon.

[0054] Example 2:

[0055] 1) ultrasonic chemical wave cleaning of titanium alloy substrate TC4; sequentially using ultrasonic chemical cleaning for 30 minutes (ultrasonic cleaning solution formula: sodium hydroxide 10 g / L, sodium metasilicate pentahydrate 8 g / L, sodium tripolyphosphate 4 g / L, sodium dodecyl sulfate 15 g / L, nitrilotriacetic acid 0.5 g / L, NP-10 (99%) 3.4 g / L, MOP-5 (99%) 0.8 g / L, LAB (99%) 4.5 g / L, FMES (99%) 2.7 g / L), and then using deionized water ultrasonic cleaning for 3 times, 5 minutes each time, ultrasonic power 180 W, ultrasonic frequency 45 KHz, temperature 60°C.

[0056] 2) normal temperature immersion chemical film removal 90s (chemical film removal solution formula: nitric acid 8%, ammonium hydrogen fluoride 3%, urea 0.5%, water 89.5%), and then using deionized water ultrasonic cleaning for 3 times, 5 minutes each time.

[0057] 3) further performing ultrahigh voltage anodic oxidation process on the sample to form a first continuous porous metal network structure on the surface of the titanium substrate (electrolyte formula: zirconium fluoride 4.5 g / L, glycerol 650 ml / L, sodium phosphate 7 g / L, OP-10 surfactant 4 ml / L, ammonium carbonate 0.3 g / L, sulfamic acid 0.8 g / L, and the rest is deionized water), wherein the pH value of the electrolyte is controlled to be 10, a rust-free steel plate is used as the cathode, the distance between the two poles is 40 cm, the voltage is 90 V, and the reaction time is 4 h.

[0058] 4) vacuum heating cleaning in a vacuum furnace with a power of 4.5 kW, a vacuum degree of 80 Pa, a bias voltage of ≤200 V, a vacuum cleaning mode heating of 530°C, and a cleaning time of 35 min to perform surface deep cleaning on the sample.

[0059] 5) placing the sample in a chamber, vacuumizing for 18 min, the vacuum degree being higher than 0.06 Pa, the purity of the tantalum target material being 99.99%, the background vacuum being higher than 4.0×10 -2 Pa, the target power density being 4 W / cm 2 , the target current being 1.2 A, the temperature being 168°C, and the PVD deposition time being 1500 s to further melt and build a second tantalum coating structure in the continuous metal pore structure of the sample;

[0060] 6) vacuumizing for 15 min, the cavity vacuum degree being 0.1 Pa; the purity of the silver target material being 99.99%, the vacuum degree being higher than 0.1 Pa, the target power density being 3 W / cm 2 , the target current being 3 A, the temperature being 380°C, and the deposition time being 1800 s to further melt and build a third silver coating structure in the continuous metal pore structure of the sample;

[0061] 7) vacuumizing for 15 min, the cavity vacuum degree being 0.1 Pa; the purity of the silver target material being 99.99%, the vacuum degree being 4.5-6.51 Pa, target power density 3 W / cm 2 , target current 3 A, temperature 170 °C. Deposition time 1800 s, further integration of the sample into the continuous metal hole structure to build a three-level silver coating structure;

[0062] 8) The above sample was sequentially cleaned with ultrapure water using ultrasonic cleaning three times in succession, ultrasonic power 80 W, frequency 30 KHz, cleaning time 10 min; vacuum packaging was used after irradiation sterilization process Co 60 60, irradiation dose 8 kGy, finally obtaining the required sample.

[0063] Compared with Example 1, this embodiment reduces the vacuum high-temperature pressure holding heat treatment process. The above sample was subjected to bonding strength detection, and the result was 27.4 MPa; the cell survival rate after 7 days was detected using CCK-8, which was 82.1% compared with the control group (i.e. the original raw material TC4); the antibacterial ability was detected by combining the antibacterial circle experiment, and the antibacterial circle area was 3.97 cm 2 ; using the rat intramedullary infection model, sampling was detected after 28 days of implantation, and it was found that the sample surface eluted bacteria for plate culture, the infection treatment effect was significant, and further combined with Micro-CT detection found that the sample surface had obvious bone integration phenomenon.

[0064] Example 3:

[0065] 1) Ultrasonic chemical wave cleaning of titanium alloy substrate TC4; sequentially using ultrasonic chemical cleaning for 30 minutes (ultrasonic cleaning solution formula: sodium hydroxide 10 g / L, sodium metasilicate pentahydrate 8 g / L, sodium tripolyphosphate 4 g / L, sodium dodecyl sulfate 15 g / L, nitrilotriacetic acid 0.5 g / L, NP-10 (99%) 3.4 g / L, MOP-5 (99%) 0.8 g / L, LAB (99%) 4.5 g / L, FMES (99%) 2.7 g / L), then using deionized water ultrasonic cleaning 3 times, each time 5 minutes, ultrasonic power 180 W, ultrasonic frequency 45 KHz, temperature 60 °C.

[0066] 2) Normal temperature immersion chemical film removal 90 s (chemical film removal solution formula: nitric acid 8%, ammonium hydrogen fluoride 3%, urea 0.5%, water 89.5%), then using deionized water ultrasonic cleaning 3 times, each time 5 minutes.

[0067] 3) The sample is subjected to an ultrahigh voltage anodic oxidation process to form a first continuous porous metal network structure on the surface of the titanium substrate (electrolyte formula: zirconium fluoride 4.5 g / L, glycerol 650 ml / L, sodium phosphate 7 g / L, OP-10 surfactant 4 ml / L, ammonium carbonate 0.3 g / L, sulfamic acid 0.8 g / L, and the rest is deionized water), wherein the pH value of the electrolyte is controlled to be 10, a rust-free steel plate is used as the cathode, the distance between the two electrodes is 40 cm, the voltage is 90 V, and the reaction time is 4 h.

[0068] 4) The vacuum heating cleaning furnace has a power of 4.5 kW, a vacuum degree of 80 Pa, a bias voltage of less than 200 V, a vacuum cleaning mode heating temperature of 530°C, and a cleaning time of 35 min, and the sample is subjected to surface deep cleaning.

[0069] 5) The vacuum degree in the cavity is 0.1 Pa after 15 min of vacuum pumping; the silver target material has a purity of 99.99%, a vacuum degree higher than 0.1 Pa, a target power density of 3 W / cm 2 , a target current of 3 A, a temperature of 380°C, and a deposition time of 1800 s, and the sample is further integrated with a secondary silver coating structure in the continuous metal pore structure;

[0070] 6) Vacuum high-temperature pressure holding heat treatment process: the vacuum degree in the vacuum furnace bin is 4.5 x 10 -1 Pa, the vacuum furnace power is 100 kW, the vacuum temperature rising rate is 5°C / min to 700°C, and the holding pressure is 2 h; after the step is completed, the micro-positive pressure is adjusted to 200 Pa, and the cooling rate is 10°C / min to 40°C.

[0071] 7) The above sample is sequentially subjected to ultrasonic cleaning with ultrapure water for three times, an ultrasonic power of 80 W, a frequency of 30 KHz, and a cleaning time of 10 min; and Co 60 -60 sterilization is performed after vacuum packaging, and the final sample is obtained.

[0072] Compared with Comparative Example 1, the tantalum coating structure is reduced in this embodiment. The above sample is subjected to bonding strength detection, and the result is 46.5 MPa; the cell survival rate after 7 days is 84.1% compared with the control group (i.e., the original raw material TC4) by using CCK-8 detection; the antibacterial ability is detected by combining with the antibacterial circle experiment, and the antibacterial circle area is 3.46 cm 2 ; using a rat intramedullary infection model, the sample is taken after 28 days of implantation and detected, and it is found that the sample surface eluted bacteria are cultured by plating, the infection treatment effect is significant, and further Micro-CT detection shows that the sample basically has no bone integration phenomenon.

[0073] Example 4:

[0074] 1) ultrasonic chemical wave cleaning of titanium alloy substrate TC4; sequentially using ultrasonic chemical cleaning for 30 minutes (ultrasonic cleaning solution formula: sodium hydroxide 10 g / L, sodium metasilicate pentahydrate 8 g / L, sodium tripolyphosphate 4 g / L, sodium dodecyl sulfate 15 g / L, nitrilotriacetic acid 0.5 g / L, NP-10 (99%) 3.4 g / L, MOP-5 (99%) 0.8 g / L, LAB (99%) 4.5 g / L, FMES (99%) 2.7 g / L), and then using deionized water ultrasonic cleaning for 3 times, 5 minutes each time, ultrasonic power 180 W, ultrasonic frequency 45 KHz, temperature 60°C.

[0075] 2) normal temperature immersion chemical film removal 90s (chemical film removal solution formula: nitric acid 8%, ammonium hydrogen fluoride 3%, urea 0.5%, water 89.5%), and then using deionized water ultrasonic cleaning for 3 times, 5 minutes each time.

[0076] 3) further performing ultrahigh voltage anodic oxidation process on the sample to form a first continuous porous metal network structure on the surface of the titanium substrate (electrolyte formula: zirconium fluoride 4.5 g / L, glycerol 650 ml / L, sodium phosphate 7 g / L, OP-10 surfactant 4 ml / L, ammonium carbonate 0.3 g / L, sulfamic acid 0.8 g / L, and the rest is deionized water), wherein the pH value of the electrolyte is controlled to be 10, a rust-free steel plate is used as the cathode, the distance between the two electrodes is 40 cm, the voltage is 90 V, and the reaction time is 4 h.

[0077] 4) vacuum heating cleaning in a vacuum furnace with a power of 4.5 kW, a vacuum degree of 80 Pa, a bias voltage of ≤200 V, a vacuum cleaning mode heating at 530°C, and a cleaning time of 35 min, to perform surface deep cleaning on the sample.

[0078] 5) placing the sample in a chamber, vacuumizing for 18 min, the vacuum degree being higher than 0.06 Pa, the purity of the tantalum target material being 99.99%, the background vacuum being higher than 4.0×10 -2 Pa, the target power density being 4 W / cm 2 , the target current being 1.2 A, the temperature being 168°C, and the PVD deposition time being 1500 s, to fuse and build a secondary tantalum coating structure in the continuous metal pore structure of the sample;

[0079] 6) vacuum high-temperature pressure maintaining heat treatment process: vacuumizing in the vacuum furnace chamber to 4.5×10 -1 Pa, vacuum furnace power 100 kW, vacuum heating rate 5°C / min to 700°C, and pressure maintaining for 2 h; after the step is completed, adjusting the micro-positive pressure to 200 Pa, and cooling at a rate of 10°C / min to 40°C.

[0080] 7) The above sample is sequentially cleaned with ultrapure water for three times in succession, ultrasonic power 80W, frequency 30KHz, cleaning time 10min; after vacuum packaging, irradiation sterilization process Co 60 Sterilization, irradiation dose 8kGy, finally obtain the required sample.

[0081] Compared with Comparative Example 1, the construction of silver coating structure is reduced in the embodiment. The above sample is subjected to bonding strength detection, and the result is 45.8MPa; the cell survival rate after 7 days is detected by using CCK-8, and the cell survival rate is 94.7% compared with the control group (i.e. the original material TC4); the antibacterial ability is detected by combining the antibacterial ring experiment, and basically no antibacterial ring appears; the rat intramedullary infection model is used, and after 28 days of implantation, the sample is taken and detected, and it is found that the sample surface eluted bacteria are coated and cultured, the infection is obvious, and further combined with Micro-CT detection, it is found that the sample surface basically has no bone integration phenomenon.

[0082] The coating material of the application has long-acting antibacterial and osteogenic functions, and can be used in the fields of orthopedics, dentistry and the like.

Claims

1. A method for preparing an integrated tantalum-silver composite bilayer functional coating material based on a continuous porous metal network structure, characterized in that: Includes the following steps: 1) The titanium / titanium alloy is first subjected to ultrasonic cleaning and chemical film removal pretreatment, and a primary continuous porous metal network structure is formed on the surface of the titanium / titanium alloy using a specific electrolyte combined with an ultra-high voltage anodizing process. 2) The processed sample is vacuum heated and cleaned, and a secondary tantalum coating structure is incorporated into the mesh of the primary continuous porous metal network structure using physical vapor deposition (PVD). 3) Replace the silver target material, vacuum heat clean it again, and perform double PVD to integrate a three-level silver coating structure into the mesh to form a three-level inlaid double-layer composite coating structure. 4) The processed sample is subjected to vacuum high-temperature pressure heat treatment; 5) After multiple cleaning, packaging and irradiation sterilization of the treated sample, an integrated tantalum-silver composite functional coating material with a continuous porous metal network structure is obtained. In step 1), the ultra-high voltage anodizing process specifically includes: the specific electrolyte formulation is: zirconium fluoride 4.5-8.5 g / L, glycerol 650-850 ml / L, sodium phosphate 5-12 g / L, OP-10 surfactant 3-5 ml / L, ammonium carbonate 0.25-0.5 g / L, aminosulfonic acid 0.5-1.2 g / L, the remainder being deionized water; the specific electrolyte pH value is 10-12; the anode is the sample; the cathode is 304 stainless steel; the distance between the anode and cathode is 40-50 cm; the voltage is 80-90 V; and the reaction time is 2-5 h. In step 2), the vacuum heating cleaning specifically includes: a vacuum furnace power of 4.5kW, a vacuum degree of 50-100Pa, a bias voltage ≤200V, a vacuum cleaning mode heating temperature of 480-530℃, and a cleaning time of 25-45min; the physical vapor deposition (PVD) specifically includes: evacuating the vacuum furnace for 15-20min, maintaining a vacuum degree higher than 0.06Pa, using a tantalum target with a purity greater than 99.99%, and maintaining a base vacuum higher than 4.0×10⁻⁶ Pa. -2 Pa, target power density is 1-5 W / cm² 2 The target current is 0.3-1.5A, and the temperature is 150-180℃; In step 3), the vacuum heating cleaning specifically includes: a vacuum furnace with a power of 4.5kW, a vacuum degree of 50-100Pa, a bias voltage ≤200V, a vacuum cleaning mode heating temperature of 480-530℃, and a cleaning time of 25-45min; the double PVD specifically includes: evacuating the vacuum furnace for 10-18min, maintaining a vacuum degree higher than 0.1Pa inside the furnace, using a silver target material with a purity greater than 99.99%, and a base vacuum greater than 4.0×10⁻⁶. -3 Pa, target power density in the range of 1-5 W / cm² 2 Target current 2-5A, temperature 380-450℃; In step 4), the vacuum high-temperature pressure holding heat treatment process specifically involves: evacuating the vacuum furnace to a vacuum level of 4.5 × 10⁻⁶. -1 Pa, vacuum furnace power 100kW, raise the furnace temperature to 600-780℃ at a vacuum heating rate of 3-5℃ / min, hold for 2-4 hours; then adjust the furnace slightly positive pressure to 150-300Pa, and cool the furnace temperature to 25-40℃ at a cooling rate of 5-10℃ / min.

2. The method for preparing the integrated tantalum-silver composite bilayer functional coating material based on a continuous porous metal network structure according to claim 1, characterized in that: The ultrasonic cleaning described in step 1) specifically includes: first ultrasonic chemical cleaning for 10-20 minutes, followed by deionized water ultrasonic cleaning at least three times, each time for 5 minutes; The chemical cleaning solution used in the ultrasonic chemical cleaning process has the following formulation: sodium hydroxide 10-15 g / L, sodium metasilicate pentahydrate 6-10 g / L, sodium tripolyphosphate 3-5 g / L, sodium dodecyl sulfate 10-18 g / L, hypozoxytriacetic acid 0.4-0.6 g / L, NP-10 (99%) 2-5 g / L, MOP-5 (99%) 0.6-1 g / L, LAB (99%) 3-5 g / L, FMES (99%) 2-5 g / L; The ultrasonic chemical cleaning and deionized water ultrasonic cleaning are both performed at a temperature of 45-50℃, with an ultrasonic power of 150-180W and an ultrasonic frequency of 80kHz. The chemical membrane removal process specifically includes the following: the chemical membrane removal formula is: 6-8 wt% nitric acid, 2.5-4.5 wt% ammonium bifluoride, 0.5-1.5 wt% urea, and the remainder is deionized water. The chemical membrane removal time is 2 minutes, and the temperature is 28-35℃. Then, ultrasonic cleaning with deionized water is performed at least three times, each time for 2 minutes, with an ultrasonic power of 150-180W and an ultrasonic frequency of 80kHz.

3. The method for preparing the integrated tantalum-silver composite bilayer functional coating material based on a continuous porous metal network structure according to claim 1, characterized in that: In step 5), the multiple cleaning is ultrasonic cleaning using ultrapure water, with an ultrasonic power of 70-90W and a cleaning time of 10 minutes. The packaging is vacuum-sealed. The irradiation sterilization process uses Co 60 Sterilization, irradiation dose 5-10 kGy.

4. An integrated tantalum-silver composite bilayer functional coating material based on a continuous porous metal network structure, characterized in that, It is prepared by the method described in any one of claims 1-3.

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