A copper alloy material for medical devices and its preparation method

Abstract

The present invention relates to the field of medical metallic materials, and particularly to a copper alloy material for medical devices and a preparation method thereof, which is mainly based on a copper alloy and obtained by modifying the surface of the copper alloy with a high-current pulsed electron beam; the main material of the copper alloy is a copper-titanium alloy, and the copper-titanium main alloy comprises the following components in weight percentages: Mg 0.1-1.0 wt%, Fe 0.1-1.2 wt%, Ca 0.1-1.2 wt%, Ti 10-20 wt%, and the balance is Cu and inevitable impurities; the copper-titanium main alloy is modified by adding a modifier comprising the following components in parts by weight to form a thermal barrier coating on the surface of the copper-titanium main alloy. The present application can not only improve the bactericidal effect of copper ions, but also improve the surface structure of the copper alloy, thereby inhibiting the degradation of metal ions.

Description

Technical Field

[0001] The present invention relates to the field of medical metal materials, and particularly to a copper alloy material for medical devices and a preparation method thereof. Background Art

[0002] Medical metal materials have excellent comprehensive mechanical properties, processing and forming properties, and reliability in clinical use. And among them, copper alloy materials are widely used in clinical fields such as orthopedics, dentistry, and lumen stents. As China gradually enters an aging society, problems such as cardiovascular and cerebrovascular diseases, osteoporotic fractures, and tooth loss are increasing day by day. Metal medical devices used for the repair and replacement of human tissues and organs play an irreplaceable and important role.

[0003] In a physiological environment, the too-high degradation rate of copper alloys is an important problem currently faced by copper alloys. Research shows that copper alloys as implants will degrade in the human body. Among them, too-high degradation rate will lead to the release of high-concentration copper ions, which in turn will cause the alkalinity around the implant to increase, a large amount of hydrogen to be released, and the mechanical properties of the implant to gradually be lost. Although copper is one of the essential trace elements in the human body, excessive intake will cause poisoning. The World Health Organization recommends that the upper limit of daily copper intake for adults is 2 - 3g. To address this problem, researchers have tried to improve the corrosion resistance of copper alloys through surface modification methods. Commonly used surface modification methods for degradable copper alloys include acid treatment, alkali heat treatment, electrochemical deposition, anodic oxidation, micro-arc oxidation, etc. The prepared coatings are divided into inorganic coatings, organic coatings, and composite coatings, etc. Current surface modification can not only reduce the degradation rate of the copper alloy matrix, maintain the mechanical integrity of the copper alloy in the initial stage of implantation, but also promote the growth and adhesion of bone cells on the material surface.

[0004] But there are currently three explanations in medicine for the improvement of antibacterial effect by the release of Cu 2+ ions. One is that the lipoprotein on the surface of bacteria contains a large number of carboxyl groups carrying negative charges, which can attract Cu 2+ cations; the second is that after bacteria come into contact with Cu 2+ ions, the permeability of the bacterial cell membrane changes severely, and the bacterial cell wall structure is damaged; the third is that Cu 2+ ions change the ion channels of bacteria, and by changing the concentrations of potassium ions, sodium ions, calcium ions, and magnesium ions inside bacteria. When Cu 2+ ions enter the bacterial cells, they inhibit protein synthesis inside the cells and at the same time inhibit the activity of enzymes inside the cells, causing DNA deformation, inhibiting DNA replication, and promoting cell apoptosis. Therefore, Cu 2+ ions have a broad antibacterial spectrum and diverse action mechanisms. If the surface modification is too idealized, resulting in a greatly reduced degradation rate of Cu 2+ ions, it will cause a weakening of the antibacterial effect, thereby increasing the risk of human infection.

[0005] Generally, when performing surface coating modification on copper alloys, either the antibacterial effect of the copper alloy will be reduced, or the modification is not ideal, causing difficulties in human metal metabolism. Therefore, it is necessary to adopt appropriate copper alloy modification. Summary of the Invention

[0006] The purpose of the present invention is to reduce the degradation rate of copper ions in copper alloy materials and improve the antibacterial effect of copper alloy materials.

[0007] On the one hand, a copper alloy material for medical devices designed by the present invention mainly uses copper alloy as the main body and is obtained by modifying the surface of the copper alloy with a high-current pulsed electron beam; the main material of the copper alloy is a copper-titanium alloy, and the copper-titanium main alloy includes the following components in weight percentages: Mg 0.1-1.0wt%, Fe 0.1-1.2wt%, Ca 0.1-1.2wt%, Ti 40-60wt%, and the balance is Cu and inevitable impurities; the copper-titanium main alloy is modified by adding a modifier including the following components in weight parts, and a thermal barrier coating is formed on the surface of the copper-titanium main alloy; by weight, for every 100 parts of the copper-titanium main alloy, the modifier components are: TiN 0.5-2 parts, ZrN 0.5-2 parts; after the high-current pulsed electron beam, the mass of the thermal barrier coating is 0.2-2.0wt% of the copper-titanium main alloy.

[0008] Currently, thermal barrier coatings are mainly used in ceramic coatings. By depositing on the surface of high-temperature-resistant metals or alloys, they play a heat-insulating role for the substrate material, reduce the substrate temperature, and enable the devices made of them to operate at high temperatures. And by modifying the surface of the copper alloy with a high-current pulsed electron beam and forming a thermal barrier coating, the crystal structure is improved and the corrosion resistance is enhanced. In this application, a high-current pulsed electron beam is used on the surface of a copper-titanium alloy material for medical devices to form a thermal barrier coating to achieve the antibacterial effect.

[0009] Among them, the modifier components for the thermal barrier coating are TiN and ZrN. First of all, titanium is widely used in the manufacture of medical devices and is a commonly used human replacement material. Among them, titanium has biocompatibility. After being implanted to replace damaged human tissues, it can be well compatible with the tissues, which helps the better growth of human tissues; secondly, the mechanical properties of titanium are relatively similar to human bone tissues, so it can play a better replacement role without obvious stress changes, which helps the human body to adapt as soon as possible after surgery; and, the properties of titanium are stable, it can resist the erosion of human secretions, is not prone to corrosion damage, and will not have toxic and harmful effects on the human body.

[0010] Chromium is an essential trace element in the human body. Although the requirement is very small, only 6-7 milligrams are contained in a normal human body, it is very important for the human body. It is mainly distributed in bones, skin, adrenal glands, brain and muscles. It is an important element for normal growth and development and blood sugar regulation. And chromium is toxic, but the toxicity of chromium is related to its existing valence state. Trivalent chromium hardly has harmful effects on the human body, but hexavalent chromium is 100 times more toxic than trivalent chromium, is easily absorbed by the human body and accumulates in the body. Chromium entering the human body is deposited in human tissues, and the speed of metabolism and clearance is slow. However, generally only under strongly oxidizing conditions (such as ammonium persulfate / perchloric acid) will trivalent chromium be converted into hexavalent chromium.

[0011] In this application, a thermal barrier coating is applied to the surface of a copper-titanium matrix alloy by a high-current pulsed electron beam, TiN and ZrN are added to the surface of the copper-titanium matrix alloy, and modification is achieved under the irradiation of the electron beam. Under rapid high-temperature melting, a large number of trivalent titanium ions (Ti 3+ ) and trivalent chromium ions (Zr 3+ ) are sputtered. Among them, the trivalent titanium ions (Ti 3+ ) will be rapidly oxidized into tetravalent titanium ions (Ti 4+ ) at high temperature and deposited on the surface of the copper alloy material under the action of the electron beam to form a thermal barrier coating. Due to the potential difference between the tetravalent titanium ions (Ti 4+ ) and the trivalent chromium ions (Zr 3+ ) to form an electric field potential (this coating forms a micro-battery in the human body, and its voltage can reach 280 mV), and then it has a synergistic bactericidal effect with Cu 2+ . And in the vacuum environment of the high-current pulsed electron beam, a large number of nitrogen ions are enriched on the surface of the copper-titanium alloy during the heating process to form ion nitriding, improving the surface structure of the alloy crystal phase and inhibiting the degradation of metal ions.

[0012] Optionally, the copper-titanium matrix alloy is prepared by hot isostatic pressing, and the ratio of Ti to Cu in the copper-titanium matrix alloy is 1:(3-5).

[0013] The copper-titanium alloy can be prepared by hot isostatic pressing or by sintering. However, it is found in the preparation process of the copper-titanium matrix alloy that if the sintering temperature is too low, it may cause a decrease in the density of the copper alloy material, and then cause problems such as insufficient mechanical properties and corrosion resistance of the material. And if the sintering holding time is less and the sintering pressure is too low, both will increase the porosity and decrease the density of the copper-titanium alloy. Using hot isostatic pressing can quickly adjust the pressure and temperature in the static pressure preparation process, thus reducing the occurrence of the above situations, and then making the copper alloy have stronger antibacterial properties. Among them, when the ratio of Ti to Cu in the copper-titanium matrix alloy is 1:(3-5), the copper-titanium alloy generally has antibacterial properties; at the same time, it also has a wear-resistant effect.

[0014] Optionally, both TiN and ZrN in the modifier are nanoparticles; the nanoparticle TiN has a particle size of 50-150 nm, and the nanoparticle ZrN has a particle size of 50-150 nm.

[0015] Optionally, the modifier is mixed with a diffusion liquid and uniformly coated on the surface of the copper-titanium matrix alloy for modification.

[0016] By adopting the above technical solution, the modifier is uniformly mixed with the diffusion liquid and distributed on the surface of the copper-titanium matrix alloy, which can make the formation of the thermal barrier coating more uniform and dense, thereby reducing the release of copper ions in the copper alloy into the human body.

[0017] Optionally, the components of the diffusion liquid include water, ethanol, propylene glycol, triethylenetetramine, nitrilotriacetic acid, and polyacrylamide.

[0018] By adopting the above technical solution, the diffusion liquid can improve the uniformity of the modifier on the surface of the copper alloy. Among them, water dissolves ethanol and propylene glycol as the dispersion medium of the diffusion liquid, which is the carrier for diffusing the modifier; triethylenetetramine, nitrilotriacetic acid, and polyacrylamide are used as dispersants in the diffusion liquid to improve the dispersion effect. Among them, triethylenetetramine is a complexing agent and can complex with metal ions, thereby making the chelate produced by Zr metal ions diffuse more uniformly in the diffusion liquid; nitrilotriacetic acid can provide four coordination bonds for metal ions, and its molecule is small, with very strong complexing ability, and can form stable chelates with Zr and Ti metal ions in the solution; polyacrylamide is a water-soluble polymer, which can stably disperse the complex into the diffusion liquid, and when the surface of the copper alloy is irradiated with a high-current pulsed electron beam, the liquid vaporizes, and the solid media of titanium nitride and chromium nitride form a thermal barrier coating on the surface of the copper alloy.

[0019] Optionally, the main component of the diffusion liquid is water, and the following components are formulated per 100 parts of water: 20-30 parts of ethanol, 5-10 parts of propylene glycol, 1-3 parts of triethylenetetramine, 1-3 parts of nitrilotriacetic acid, and 1-3 parts of polyacrylamide.

[0020] On the other hand, the present application also provides a preparation method for a copper alloy material for medical devices.

[0021] Mixing powder and static pressing: Using pure titanium powder and pure copper powder as raw materials, putting the raw material powder into a mixer for dry mechanical mixing, then adding magnesium powder, iron powder and calcium powder in sequence for dry mechanical mixing; and forming the package containing alloy powder in a hot isostatic press through vacuum packaging, and pressing it with static pressure to obtain a densified copper-titanium matrix alloy; Coating preparation: Preparing the diffusion liquid according to the above ratio, adding the modifier to the diffusion liquid for mixing and stirring, and uniformly coating the prepared coating on the surface of the copper-titanium matrix alloy; Coating modification: Placing the copper-titanium matrix alloy coated with the modifier in a high-current pulsed electron beam, and obtaining a modified copper-titanium alloy material after being irradiated by the high-current pulsed electron beam.

[0022] Optionally, in the step of coating modification, irradiate and bombard with a high-current pulsed electron beam with an accelerating voltage of 8 - 12 kV, a pulsed current of 160 - 220 A, a pulse duration of 10 - 20 μs, a pulse frequency of 0.5 - 5 Hz, and the number of pulses is 5 - 25 times.

[0023] By adopting the above technical solution, the high-current pulsed electron beam treatment performs multiple pulsed irradiations in a short time, causing the surface layer of the copper-titanium alloy material to undergo ultra-high-speed cooling and solidification, and then enabling the tetravalent titanium ions (Ti 4+ ) and trivalent chromium ions (Zr 3+ ) in the modifier to quickly form an electric field potential, and enriching with nitrogen ions on the surface of the copper-titanium alloy during the heating process to form ion nitriding, improving the surface structure of the alloy crystal phase and inhibiting the degradation of metal ions.

[0024] In summary, a copper alloy material designed by the present invention for medical devices has the following beneficial effects:

[0025] 1. In this application, a high-current pulsed electron beam is used to apply a thermal barrier coating to the surface of the copper-titanium matrix alloy, adding TiN and ZrN to the surface of the copper-titanium matrix alloy, and realizing modification under the irradiation of the electron beam; among them, the added tetravalent titanium ions (Ti 4+ ) and trivalent chromium ions (Zr 3+ ) have a potential difference to form an electric field potential.

[0026] 2. In this application, hot isostatic pressing is used to process the copper-titanium matrix alloy, quickly adjusting the process parameters of static pressing such as pressure and temperature, and when the ratio of Ti to Cu in the copper-titanium matrix alloy is 1:(3 - 5), the copper-titanium alloy generally has antibacterial properties.

[0027] 3. In this application, a diffusion liquid is used to improve the uniformity of the modifier on the surface of the copper alloy, thereby improving the antibacterial effect of the copper-titanium alloy. Specific embodiments

[0028] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art belong to the scope of protection of the present invention.

[0029] The following further describes the present application in detail with reference to embodiments.

[0030] Raw materials

[0031] The raw materials used in the examples can all be obtained commercially.

[0032] Copper powder: CAS No. 7440-50-8, purity ≥ 99.8%, particle size 200 mesh (the particle size of commercially available copper powder is 75 ± 5 μm);

[0033] Titanium powder: CAS No. 7440-32-6, purity ≥ 99.9%, particle size 200 mesh (the particle size of commercially available titanium powder is 75 ± 5 μm);

[0034] Magnesium powder: CAS No. 11105-19-4, purity ≥ 99.5%, particle size 325 mesh (the particle size of commercially available magnesium powder is 44 ± 4 μm);

[0035] Iron powder: CAS No. 7439-89-6, purity ≥ 99.0%, particle size 400 mesh (the particle size of commercially available iron powder is 37 ± 3 μm);

[0036] Calcium powder: CAS No. 7440-70-2, purity ≥ 98.0%, particle size 400 mesh (the particle size of commercially available calcium powder is 37 ± 3 μm);

[0037] Titanium nitride: CAS No. 25583-20-4, purity ≥ 99.9%, and its particle size can be adjusted as needed. In this example, 100 ± 10 nm is taken as an example for illustration;

[0038] Chromium nitride: CAS No. 12053-27-9, purity ≥ 99.9%. In this example, 100 ± 10 nm is taken as an example for illustration;

[0039] Ethanol: CAS No. 64-17-5, purity ≥ 99.5%;

[0040] Propylene glycol: CAS No. 57-55-6, purity ≥ 99.0%;

[0041] Triethylenetetramine: CAS No. 112-24-3, purity ≥ 99.0%;

[0042] Nitrilotriacetic acid: CAS No. 556-33-2, purity ≥ 98.0%;

[0043] Polyacrylamide: CAS No. is 9003-05-8, purity ≥98.0%.

[0044] Example

[0045] Example 1

[0046] A preparation method of a copper alloy material for medical devices disclosed in Example 1 includes the following steps:

[0047] S1 Powder mixing and static pressing: Using 30 kg of pure titanium powder and 10 kg of pure copper powder in the above raw materials as raw materials, putting the raw material powder into a mixer for dry mechanical mixing, with a rotation speed of 12 rpm and a time of 30 min, then adding 1 kg of magnesium powder, 1 kg of iron powder, and 1 kg of calcium powder in the above raw materials in sequence, and continuing dry mechanical mixing, with a rotation speed of 20 rpm and a time of 15 min; using a vacuum pump to extract the air in the jacket, putting the jacket filled with the mixed powder into a heating furnace, the air pressure in the jacket is 4.0×10 -3 Pa, then heating the jacket, with a heating temperature of 800 °C, keeping warm and vacuum for 3 hours, and sealing and removing air holes under vacuum conditions to form a jacket closed structure; putting the jacket into a hot isostatic press for hot isostatic pressing treatment, with a treatment temperature of 1200 °C, a pressure of 160 MPa, a heat preservation and pressure holding time of 3 hours, and cooling in the furnace to 200 °C after the heat preservation and pressure holding are completed and then taking out of the furnace.

[0048] S2 Coating preparation: Adding 1 kg of pure water, 0.2 kg of ethanol, and 0.05 kg of propylene glycol in the above raw materials and stirring and mixing evenly; then adding 0.5 kg of titanium nitride and 0.5 kg of chromium nitride, and during the stirring process, adding 0.1 kg of triethylenetetramine, 0.1 kg of nitrilotriacetic acid, and 0.1 kg of polyacrylamide, stirring for 10 minutes, and evenly coating on the surface of the copper-titanium matrix alloy; the TiN concentration in the modifier mixed solution is 20 wt%, and the ZrN concentration is 20 wt%; in this example, the modifier mixed solution coated on the surface of 10 kg of the statically shaped copper-titanium matrix alloy is 0.25 kg. Specifically, for every 100 parts by weight of the copper-titanium matrix alloy, TiN is 0.5 part and ZrN is 0.5 part;

[0049] S3 Coating modification: Placing the copper-titanium matrix alloy coated with the modifier in a high-current pulsed electron beam, the solvent of the modifier mixed solution volatilizes under vacuum and the remaining temperature of the copper-titanium matrix alloy, and the volatilized solvent is post-treated by a vacuum pump, then irradiating the surface of the copper-titanium matrix alloy with a high-current pulsed electron beam, with an acceleration voltage of 8 kV, a pulse current of 160 A for irradiation bombardment, a pulse duration of 10 μs, a pulse frequency of 0.5 Hz, and the number of pulses being 5 times. Obtaining the modified copper-titanium alloy material.

[0050] Example 2-6

[0051] On the basis of the preparation method of Example 1, the component contents of nano-titanium nitride and nano-chromium nitride in the modifier mixed solution were adjusted in Example 2-6.

[0052] The specific component adjustment situations of the above Examples 1-6 are shown in Table 1 below, with the unit being: kg.

[0053] Table 1. Component Table of Preparation Raw Materials for Surface Modification of Copper Alloy Materials

[0054] Copper-titanium matrix alloy Nanometer titanium nitride Nanometer chromium nitride Example 1 10 0.05 0.05 Example 2 10 0.10 0.05 Example 3 10 0.10 0.50 Example 4 10 0.50 0.50 Example 5 10 1.00 1.00 Example 6 10 1.00 0.50 Example 7 10 0.50 1.00 Example 8 10 1.00 2.00 Example 9 10 2.00 1.00 Example 10 10 2.00 2.00

[0055] Comparative Example

[0056] Comparative Example 1

[0057] The difference between Comparative Example 1 and Example 1 is that the surface of the copper-titanium matrix alloy was not modified with a thermal barrier coating.

[0058] Comparative Example 2

[0059] The difference between Comparative Example 2 and Example 1 is that only titanium nitride was used to modify the surface of the copper-titanium matrix alloy, and 0.05 kg of nano-titanium nitride particles were used to modify the surface of 10 kg of the copper-titanium matrix alloy.

[0060] Comparative Example 3

[0061] The difference between Comparative Example 3 and Example 1 is that only chromium nitride was used to modify the surface of the copper-titanium matrix alloy, and 0.05 kg of nano-chromium nitride particles were used to modify the surface of 10 kg of the copper-titanium matrix alloy.

[0062] Performance Detection Test

[0063] Performance detection tests were carried out on the copper-titanium alloys provided in Examples 1-10 and Comparative Examples 1-3 of this application.

[0064] 1. Qualitative and Quantitative Analysis of Degradation Products of Copper Alloy

[0065] The copper alloy materials prepared in this application were subjected to performance detection according to GB / T16886.15-2003. Specifically, it is the 15th part of the biological evaluation of medical devices: qualitative and quantitative analysis of degradation products of metals and alloys. Detection was carried out according to the means designed in the research, the potential of the degradation products was measured as +50 mV, and the polarization time was selected as 5 h; this detection standard mainly detects the degradation concentration of copper ions.

[0066] 2. Toxicokinetics Detection of Degradation Products and Leachables of Copper Alloy

[0067] The copper alloy material prepared in this application was subjected to performance testing in accordance with GB / T 16886.16-2013. Specifically, it was for the biological evaluation of medical devices - Part 16: Toxicokinetics study design of degradation products and leachables, and the testing was carried out according to the research design methods therein. This testing mainly targeted the indicators of the metabolism and absorption of metal ions (including copper ions, titanium ions, magnesium ions, iron ions, calcium ions) in experimental animals, and comprehensively evaluated the harm of copper ions to organisms from the absorption rate, area under the plasma concentration-time curve, area under the plasma concentration-time curve, apparent distribution volume, c max 、t max 、half-life, mean residence time, elimination rate, and clearance rate.

[0068] 3. Antibacterial ability experiment

[0069] The copper alloy material obtained in this invention was subjected to antibacterial tests on standard strains such as Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Bacillus subtilis. 2 ml of a bacterial solution with a concentration of 10 5 was inoculated on the surface of each specimen and cultured at 37°C for 1 day. The specimens were rinsed 3 times with PBS to remove unadhered bacteria, and then the bacteria adhered to the specimens were eluted into 2 ml of distilled water by ultrasonic oscillation for 5 min. The eluate was used to detect the number of viable bacteria in the bacteria adhered to the specimen surface, and the antibacterial rate was calculated according to the national standard WS / T 650-2019 to evaluate the antibacterial effect on the specimen surface in the culture dish.

[0070] Table 2. Performance test data table

[0071]

[0072] * This is the toxicokinetic biological residue hazard assessment for this testing. "+" / "-" represent the indicators of metabolism and absorption in experimental animals;

[0073] "+" represents that the metal ion residue causes greater harm to the experimental animal body and causes irreversible damage;

[0074] "-" represents that the metal ion residue causes less harm to the experimental animal body.

[0075] The following details this application in combination with the test data provided in Table 2.

[0076] In Examples 1-10, the component contents of nano titanium nitride and nano chromium nitride in the modifier mixed solution were changed to improve the modification effect in the copper-titanium alloy. Among them, as the component contents of nano titanium nitride and nano chromium nitride increased, the logarithmic volume of copper ions in the electrolyte decreased continuously under static potential measurement within the same time, that is, the electrolyte volume of copper ions decreased continuously, and the thermal barrier coating played a certain inhibitory role in the degradation of copper ions; moreover, as the component contents of nano titanium nitride and nano chromium nitride increased, due to the existence of the thermal barrier coating, the degradation of copper ions was inhibited, and the antibacterial effects of the copper-titanium alloy against standard strains such as Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Bacillus subtilis gradually weakened. However, microbatteries were formed by titanium ions and chromium ions in the thermal barrier coating and had a significant antibacterial effect. Specifically, it could be seen that with the increase of titanium nitride and chromium nitride, the antibacterial effect did not weaken rapidly, and Example 5 was obtained as the optimal example.

[0077] Combined with Comparative Example 1, the modification of the surface of the copper-titanium alloy by the thermal barrier coating could inhibit the degradation of copper ions therein, and it was obtained from the toxicokinetic bioresidue hazard assessment that the metal surface coating could effectively reduce the harm of the released metal ions to organisms; combined with Comparative Examples 2-3, the thermal barrier coating could effectively inhibit the harm of metal ions in organisms, but the antibacterial effect would also weaken, and the degradation rate of copper ions was faster than that in Example 1 compared with Example 1, thereby increasing the risk of copper ions to organisms.

[0078] Example

[0079] Examples 11-14

[0080] In Examples 11-14, based on the preparation method of Example 5, the ratio of Cu to Ti in the copper-titanium main alloy was changed.

[0081] The specific component adjustment situations of the above Examples 11-14 are shown in Table 3 below, with the unit: kg.

[0082] Table 3. Raw material component table of copper-titanium main alloy

[0083] Pure titanium powder Pure iron powder Example 5 30 10 Example 11 35 10 Example 12 40 10 Example 13 45 10 Example 14 50 10

[0084] The copper alloy materials prepared in the above Examples 14-15 were tested according to the above performance detection tests, and the test results are shown in Table 4 below.

[0085] Table 4. Performance detection data table

[0086]

[0087] The present application will be described in detail below in combination with the detection data provided in Table 4.

[0088] In Examples 11-14, the ratio of Cu to Ti in the copper-titanium matrix alloy was changed. Since the ratio of Cu to Ti in the copper-titanium alloy is highly related to the antibacterial effect, it was found that when the ratio of Cu to Ti in the copper-titanium matrix alloy is 1:4, the antibacterial effect is the best, and Example 12 is the optimal example.

[0089] Example

[0090] Examples 15-20

[0091] In Examples 15-20, based on the preparation method of Example 12, the composition of the diffusion liquid in the modified mixed solution was changed, and the ratio was adjusted as shown in Table 5. Unit: kg.

[0092] Table 5. Composition Table of Modified Diffusion Liquid

[0093] Pure water Ethanol Propylene glycol Triethylenetetramine Nitrilotriacetic acid Polyacrylamide Example 12 1 0.20 0.05 0.1 0.1 0.1 Example 15 1 0.20 0.10 0.2 0.2 0.2 Example 16 1 0.25 0.05 0.3 0.1 0.3 Example 17 1 0.25 0.10 0.1 0.2 0.1 Example 18 1 0.25 0.05 0.2 0.3 0.1 Example 19 1 0.30 0.10 0.3 0.1 0.2 Example 20 1 0.30 0.05 0.1 0.2 0.3

[0094] The copper alloy materials prepared in Examples 15-20 were tested according to the above performance detection tests, and the test results are shown in Table 6 below.

[0095] Table 6. Performance Detection Data Table

[0096]

[0097] The present application will be described in detail below in combination with the detection data provided in Table 6.

[0098] In Examples 15-20, the composition of the diffusion liquid in the modified mixed solution was changed. Using the diffusion liquid can improve the uniformity of the modifier on the surface of the copper alloy, which has a beneficial effect on the antibacterial effect of the copper-titanium alloy. At the same time, it was found that the diffusion liquid composition in Example 18 has the best antibacterial effect and can also reduce the harm of metal ions to organisms. Example 18 is the optimal example.

[0099] And in this application, a life test was conducted on the copper-titanium alloy material of Example 18. In the strong electric field and oxidation experiments, it was found that the life of the copper-titanium alloy is more than 10 years. Since there is a potential difference between the tetravalent titanium ion (Ti4+) and the trivalent chromium ion (Zr3+) to form an electric field potential, and this coating forms a micro-battery in the human body, which has a synergistic bactericidal effect with Cu2+. However, as the copper ions degrade, the electric field potential of the micro-battery will decrease over time, thereby reducing the antibacterial effect of the copper-titanium alloy.

[0100] The present invention is not limited to the above best embodiment. Anyone can obtain other various forms of products under the inspiration of the present invention. However, no matter what changes are made in its shape or structure, as long as it has the same or similar technical solutions as the present application, it falls within the protection scope of the present invention.

Claims

1. A copper alloy material for medical devices, characterized in that, it is mainly composed of a copper alloy as the main body, and is obtained by modifying the surface of the copper alloy with a high-current pulsed electron beam; the main material of the copper alloy is a copper-titanium alloy, and the copper-titanium alloy includes the following components in weight percentages: Mg 0.1-1.0wt%, Fe 0.1-1.2wt%, Ca 0.1-1.2wt%, Ti 40-60wt%, and the balance is Cu and unavoidable impurities; the copper-titanium alloy is modified by adding a modifier including the following components in parts by weight, and a thermal barrier coating is formed on the surface of the copper-titanium alloy; by weight, for every 100 parts of the copper-titanium alloy, the modifier components are: 0.5-2 parts of TiN and 0.5-2 parts of ZrN; after being irradiated by the high-current pulsed electron beam, the mass of the thermal barrier coating is 0.2-2.0wt% of the copper-titanium alloy.

2. The copper alloy material for medical devices according to claim 1, characterized in that, both TiN and ZrN in the modifier are nanoparticles; the particle size of the TiN is 50-150nm, the particle size of the ZrN is 50-150nm.

3. The copper alloy material for medical devices according to claim 1, characterized in that, the modifier is mixed with a diffusion liquid and uniformly coated on the surface of the copper-titanium alloy for modification.

4. The copper alloy material for medical devices according to claim 3, characterized in that, the components of the diffusion liquid include water, ethanol, propylene glycol, triethylenetetramine, nitrilotriacetic acid, and polyacrylamide.

5. The copper alloy material for medical devices according to claim 4, characterized in that, the main component of the diffusion liquid is water, and the following components are mixed with every 100 parts of water: 20-30 parts of ethanol, 5-10 parts of propylene glycol, 1-3 parts of triethylenetetramine, 1-3 parts of nitrilotriacetic acid, and 1-3 parts of polyacrylamide.

6. The preparation method of the copper alloy material for medical devices according to any one of claims 1-5, characterized in that, includes the following steps: Powder mixing and static pressing: Using pure titanium powder and pure copper powder as raw materials, putting the raw material powder into a mixer for dry mechanical mixing, then adding magnesium powder, iron powder, and calcium powder in sequence for dry mechanical mixing; and forming the package containing the alloy powder in a hot isostatic press through vacuum packaging, and pressing it with static pressure to obtain a densified copper-titanium alloy; Coating preparation: Diffusion liquid: The following components are mixed with every 100 parts of water: 20-30 parts of ethanol, 5-10 parts of propylene glycol, 1-3 parts of triethylenetetramine, 1-3 parts of nitrilotriacetic acid, and 1-3 parts of polyacrylamide, and adding the modifier to the diffusion liquid for mixing and stirring, and uniformly coating the prepared coating on the surface of the copper-titanium alloy; Coating modification: Placing the copper-titanium alloy coated with the modifier in a high-current pulsed electron beam, and obtaining a modified copper-titanium alloy material after being irradiated by the high-current pulsed electron beam.

7. The preparation method of the copper alloy material for medical devices according to claim 6, characterized in that, In the step of coating modification, it is irradiated and bombarded by a high-current pulsed electron beam with an accelerating voltage of 8 - 12 kV, a pulsed current of 160 - 220 A, a pulse duration of 10 - 20 μs, a pulse frequency of 0.5 - 5 Hz, and the number of pulses is 5 - 25 times.

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