An antibacterial zirconium alloy material and its preparation method and application

Abstract

The present invention belongs to the technical field of zirconium alloy materials, and discloses an antibacterial zirconium alloy material, its preparation method and application. The antibacterial zirconium alloy material includes the following components by mass fraction: Cu 3-7%, Ti 25-35%, Fe 0.05-0.5%, and the balance is Zr. The present invention also provides a method for preparing the antibacterial zirconium alloy material, comprising: smelting the raw materials according to the above mass fractions to obtain an alloy ingot; preheating the alloy ingot and hot pressing it to obtain a billet; homogenizing the billet and preheating it, hot rolling it to obtain a plate; packaging the plate and preheating and quenching it to obtain the antibacterial zirconium alloy material. The present invention avoids the addition of biotoxic elements, and Cu exhibits an inhibitory effect on both Escherichia coli and Staphylococcus aureus. The alloy material exhibits excellent corrosion resistance and can be used as an implant and abutment material in oral implant restoration.

Description

Technical Field

[0001] The present invention relates to the technical field of zirconium alloy materials, and in particular to an antibacterial zirconium alloy material and a preparation method and application thereof. Background Art

[0002] Teeth are indispensable organs in people's daily lives, but no new teeth will grow after the permanent teeth fall out. Periodontal disease, tooth decay, developmental abnormalities and trauma can cause permanent teeth to fall out, resulting in edentulous defect or edentulous loss. After tooth loss, not only will the patient's chewing and language functions deteriorate, but it will also affect the patient's digestive and circulatory system functions, and have an adverse effect on the patient's physical and mental health and quality of life. For the defect or loss of edentulous, the only method currently available clinically is denture restoration. Compared with other denture restoration methods, implant denture restoration has the advantages of long service life, high structural stability, low foreign body sensation and easy maintenance. It is the best and last resort for edentulous loss.

[0003] For decades, commercially pure titanium (cp-Ti) and its alloys have been widely used as dental implant materials due to their excellent biocompatibility, good corrosion resistance, and high strength-to-weight ratio. However, Ti and its alloys also have some difficult-to-overcome disadvantages. For example, cp-Ti lacks strength. Commercially available grades 1-4 Ti have low yield strengths (170-485 MPa) and fracture strengths (240-550 MPa), resulting in a significant risk of fracture when manufacturing implants with a diameter (d) of ≤ 3.5 mm, limiting the size of existing implants. Furthermore, the elastic modulus (E) of Ti and its alloys is excessively high. The elastic modulus (E) of grades 1-4 Ti (102-105 GPa) and Ti-6Al-4V alloy (wt.%, unless otherwise specified; 110 GPa) is much higher than that of human bone (10-40 GPa). This can induce stress shielding, leading to bone resorption around the metal implant, ultimately causing implant loosening and loss, and even requiring secondary surgery. Furthermore, some Ti alloys have poor biocompatibility. Previous reports have shown that the release of Al and V from Ti-6Al-4V alloys in the human body can pose risks to patients' long-term health and may even trigger psychiatric disorders such as Alzheimer's disease. Furthermore, Ti and its alloys, due to their excellent bioactivity, are easy targets for bacterial infection. Considering that oral implants are permanently exposed to a complex oral microbiome, this undoubtedly increases the risk of peri-implant tissue infection. Reports indicate that 90% of implants show signs of infection after implantation, 50% experience irreversible tissue damage, and 5-11% require secondary surgical removal. Overall, the prevalence of oral peri-implantitis is 22%, far higher than the incidence of peri-implantitis in other locations, causing long-term health concerns for patients.

[0004] Zr has better biocompatibility than Ti, which comes from its better bone compatibility, lower corrosion product toxicity and lower elastic modulus. In the field of dental implant metal materials, Zr can be considered to be a superior substitute for Ti to a large extent. However, Ti's low cost, high strength-to-weight ratio and decades of clinical experience in dental implant materials are still advantages that Ti cannot give up. Zr(4d 2 5s 2 ) and Ti(3d 2 4s 2 ) are located in the same group but different periods in the periodic table. They possess similar physical and chemical properties and can form an infinite solid solution. Zr and Ti both act as β-phase stabilizers for each other. When the α-β transition temperature is lowest, the mass ratio of Zr to Ti is approximately 66:34. The corrosion resistance of Zr-Ti alloys improves with increasing Zr content. Considering the limitations of Ti as a matrix, the development of Zr-Ti alloys as a potential new dental implant material has garnered significant attention in recent years.

[0005] Previous studies have shown that Zr-Ti alloys have better biocompatibility than cp-Ti, so Zr-Ti alloys are also subject to the risk of microbial infection. Therefore, the development of an antibacterial β-phase Zr-Ti alloy for use as a new dental implant metal material is promising. Summary of the Invention

[0006] The purpose of the present invention is to provide an antibacterial zirconium alloy material and its preparation method and application, so as to solve the problem that Zr-Ti alloy with good biocompatibility is prone to microbial infection.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides an antibacterial zirconium alloy material comprising the following components in mass fractions:

[0009] Cu 3-7%, Ti 25-35%, Fe 0.05-0.5%, and the balance is Zr.

[0010] The present invention also provides a method for preparing an antibacterial zirconium alloy material, comprising the following steps:

[0011] (1) smelting the raw materials according to the above mass fractions to obtain alloy ingots;

[0012] (2) preheating the alloy ingot and hot pressing it to obtain a billet;

[0013] (3) preheating the blank after homogenization and hot rolling to obtain a plate;

[0014] (4) After packaging, the plate is preheated and quenched to obtain an antibacterial zirconium alloy material.

[0015] Furthermore, in the method for preparing the antibacterial zirconium alloy material, in step (1), the smelting is carried out under argon protection, the smelting temperature is 2000-2200°C, the number of smelting is 6-8 times, and the time of each smelting is 3-5 minutes.

[0016] Furthermore, in the method for preparing the antibacterial zirconium alloy material, in step (2), the hot pressing temperature is 640-660°C.

[0017] Furthermore, in the method for preparing the antibacterial zirconium alloy material, in step (3), the vacuum degree of the homogenization treatment is 4×10 -3 ~6×10 -3 Pa, the temperature of the homogenization treatment is 750-850° C., and the time of the homogenization treatment is 40-60 min.

[0018] Furthermore, in the method for preparing the antibacterial zirconium alloy material, in step (3), the temperature of the hot rolling treatment is 640-660° C.; and the thickness of the plate is 1.0-1.5 mm.

[0019] Furthermore, in the method for preparing the antibacterial zirconium alloy material, in step (4), the vacuum degree of the package is 4×10 -5 ~6×10 -5 Pa, the packaging is packaging in a vacuum quartz tube.

[0020] Furthermore, in the method for preparing the antibacterial zirconium alloy material, in step (2), step (3) and step (4), the preheating temperature is independently 640-660° C., and the preheating time is independently 10-20 minutes.

[0021] Furthermore, in the method for preparing the antibacterial zirconium alloy material, in step (4), the quenching medium is water.

[0022] The present invention also provides an application of the antibacterial zirconium alloy material as a dental implant.

[0023] It can be seen from the above technical solutions that compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) The antibacterial zirconium alloy material of the present invention avoids the addition of biotoxic elements such as Al, V, Cr and Ni. At the same time, the addition of Cu enables the alloy material to exhibit a certain inhibitory effect on Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus);

[0025] (2) The antibacterial zirconium alloy material of the present invention exhibits excellent corrosion resistance in physiological saline, and its corrosion resistance is better than that of cp-Ti and Zr-30Ti alloy, and can be used as implant and abutment materials in oral implant restoration. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for describing the embodiments or the prior art.

[0027] Figure 1 XRD patterns of the antibacterial zirconium alloy materials of Examples 1 and 2 and the zirconium alloy material of Comparative Example 1;

[0028] Figure 2 The inhibition of the antibacterial zirconium alloy materials of Examples 1 and 2 and the zirconium alloy material of Comparative Example 1 on Escherichia coli and Staphylococcus aureus;

[0029] Figure 3 The electrochemical impedance spectroscopy diagrams of the antibacterial zirconium alloy materials of Examples 1 and 2 and the zirconium alloy material of Comparative Example 1 in physiological saline are shown;

[0030] Figure 4 The potentiodynamic polarization curves of the antibacterial zirconium alloy materials of Examples 1-2 and the zirconium alloy material of Comparative Example 1 in physiological saline. DETAILED DESCRIPTION

[0031] The present invention provides an antibacterial zirconium alloy material comprising the following components in mass fractions:

[0032] Cu 3-7%, Ti 25-35%, Fe 0.05-0.5%, and the balance is Zr.

[0033] In the present invention, the mass fraction of Cu is preferably 3 to 7%, more preferably 4 to 6%, and even more preferably 5%.

[0034] In the present invention, the mass fraction of Ti is preferably 25 to 35%, more preferably 28 to 32%, and even more preferably 30%.

[0035] In the present invention, the mass fraction of Fe is preferably 0.05 to 0.5%, more preferably 0.1 to 0.4%, and even more preferably 0.3%.

[0036] The present invention also provides a method for preparing an antibacterial zirconium alloy material, comprising the following steps:

[0037] (1) smelting the raw materials according to the above mass fractions to obtain alloy ingots;

[0038] (2) preheating the alloy ingot and hot pressing it to obtain a billet;

[0039] (3) preheating the blank after homogenization and hot rolling to obtain a plate;

[0040] (4) After packaging, the plate is preheated and quenched to obtain an antibacterial zirconium alloy material.

[0041] In the present invention, the smelting in step (1) is preferably carried out in a non-consumable vacuum arc furnace.

[0042] In the present invention, in step (1), the smelting is preferably carried out under argon protection; the smelting temperature is preferably 2000-2200°C, more preferably 2000-2100°C, and more preferably 2000°C; the number of smeltings is preferably 6-8 times, more preferably 7-8 times, and more preferably 7 times; the time for each smelting is preferably 3-5 minutes, more preferably 4-5 minutes, and more preferably 5 minutes.

[0043] In the present invention, in step (1), in order to ensure uniformity of alloy composition, the alloy ingot is turned over each time it is smelted.

[0044] In the present invention, in step (2), the hot pressing is a process of placing the preheated alloy ingot in molds of different heights and widths and repeatedly hot pressing using a multifunctional thin plate stamping forming device; specifically, in an embodiment of the present invention, the hot pressing sequentially uses three sets of molds with heights of 26, 23 and 20 mm to obtain a billet with a thickness of about 20 mm; the temperature of the hot pressing is preferably 640-660°C, more preferably 645-655°C, and more preferably 650°C.

[0045] In the present invention, the billet obtained in step (2) is preferably a bar-shaped billet to facilitate subsequent rolling processing.

[0046] In the present invention, the blank in step (3) is preferably firstly polished with a grinding wheel to remove the surface oxide layer before homogenization treatment, and then pickled with mixed acid and rinsed with water to obtain a blank with a bright surface and no dirt.

[0047] In the present invention, during the homogenization treatment of the blank in step (3), the blank is placed in a quartz tube and heated in a tubular electric furnace.

[0048] In the present invention, in step (3), the vacuum degree of the homogenization treatment is preferably 4×10 -3~6×10 -3 Pa, more preferably 4.8×10 -3 ~5.2×10 -3 Pa, more preferably 5×10 -3 Pa; the temperature of the homogenization treatment is preferably 750-850°C, more preferably 775-815°C, and more preferably 800°C; the time of the homogenization treatment is preferably 40-60min, more preferably 45-52min, and more preferably 50min.

[0049] In the present invention, step (3) further includes cooling after the homogenization treatment, and the cooling method is preferably air cooling.

[0050] In the present invention, in step (3), the temperature of the hot rolling treatment is preferably 640-660°C, more preferably 644-650°C, and more preferably 650°C; the thickness of the plate is preferably 1.0-1.5 mm, more preferably 1.2-1.4 mm, and more preferably 1.25 mm.

[0051] In the present invention, the plate in step (4) further includes mixed pickling to remove the oxide layer before packaging.

[0052] In the present invention, the mixed acid used in the blank before homogenization treatment in step (3) and in the plate before packaging in step (4) is preferably a mixed solution of nitric acid, hydrofluoric acid and water, and the volume ratio of the nitric acid, the hydrofluoric acid and the water is preferably 40-50:7-12:38-53, more preferably 43-48:9-11:41-48, and more preferably 45:10:45; the mass concentration of the nitric acid is preferably 26-34%, more preferably 27.9-32.6%, and more preferably 30%; the mass concentration of the hydrofluoric acid is preferably 2.8-4.8%, more preferably 3.6-4.4%, and more preferably 4%.

[0053] In the present invention, in step (4), the vacuum degree of the package is preferably 4×10 -5 ~6×10 -5 Pa, more preferably 4.6×10 -5 ~5.2×10 -5 Pa, more preferably 5×10 -5 Pa; the packaging is preferably packaged in a vacuum quartz tube.

[0054] In the present invention, in step (2), step (3) and step (4), the preheating temperature is independently preferably 640-660°C, more preferably 648-652°C, and more preferably 650°C; the preheating time is independently preferably 10-20 min, more preferably 13-16 min, and more preferably 15 min.

[0055] In the present invention, in step (4), the quenching medium is preferably water.

[0056] In the present invention, the quenching in step (4) is preferably performed by breaking the quartz tube so that the sample falls directly into water.

[0057] In the present invention, the antibacterial zirconium alloy material in step (4) is preferably subjected to 400 # , 800 # , 1200 # Sanding with sandpaper.

[0058] The present invention also provides an application of the antibacterial zirconium alloy material as a dental implant.

[0059] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0060] Example 1

[0061] This embodiment provides a method for preparing an antibacterial zirconium alloy material, comprising the following steps:

[0062] (1) Raw materials were weighed according to the mass fractions of Cu 3%, Ti 30%, Fe 0.3% and Zr 66.7%. The raw materials were smelted in a non-consumable vacuum arc furnace at 2000°C under high-purity Ar gas for 7 times, each smelting for 5 minutes. The raw materials were turned over after each smelting to obtain a 60g alloy ingot;

[0063] (2) The alloy ingot was preheated at 650°C for 15 min, then placed in molds with heights of 26 mm, 23 mm, and 20 mm, respectively, and hot pressed at 650°C to obtain a 20 mm thick bar-shaped billet;

[0064] (3) Use a grinding wheel to grind off the oxide layer on the surface of the blank, pickle it with a mixed acid solution of 30% nitric acid, 4% hydrofluoric acid and water in a volume ratio of 45:10:45, and rinse it with tap water until the surface is bright; place the blank with a bright surface in a vacuum chamber with a degree of vacuum of 5×10 -3Pa quartz tube, kept in a tubular electric furnace at 800 ° C for 50 minutes, then the tubular electric furnace was pushed away from the quartz tube to allow the sample to air cool, and then preheated at 650 ° C for 15 minutes, and then hot rolled at 650 ° C to obtain a plate with a thickness of 1.2 mm;

[0065] (4) Use a mixed acid solution of 30% nitric acid, 4% hydrofluoric acid and water in a volume ratio of 45:10:45 to pickle the plate surface until it is bright. After removing the oxide layer on the surface of the plate, vacuum seal it into a quartz tube. The vacuum degree of the vacuum quartz tube is 5×10 -5 Pa, after preheating at 650 °C for 15 min, the quartz tube was broken and the sample was allowed to fall into water for quenching, and an antibacterial zirconium alloy material of Zr-30Ti-3Cu-0.3Fe was obtained, which was defined as 3Cu alloy.

[0066] Example 2

[0067] This embodiment provides a method for preparing an antibacterial zirconium alloy material, comprising the following steps:

[0068] (1) Raw materials were weighed according to the mass fractions of Cu 7%, Ti 30%, Fe 0.3% and Zr 62.7%. The raw materials were smelted in a non-consumable vacuum arc furnace at 2000°C under high-purity Ar gas for 7 times, each smelting for 5 minutes. The raw materials were turned over after each smelting to obtain a 60g alloy ingot.

[0069] (2) The alloy ingot was preheated at 650°C for 15 min, then placed in molds with heights of 26 mm, 23 mm, and 20 mm, respectively, and hot pressed at 650°C to obtain a 20 mm thick bar-shaped billet;

[0070] (3) Use a grinding wheel to grind off the oxide layer on the surface of the blank, pickle it with a mixed acid solution of 30% nitric acid, 4% hydrofluoric acid and water in a volume ratio of 45:10:45, and rinse it with tap water until the surface is bright; place the blank with a bright surface in a vacuum chamber with a degree of vacuum of 5×10 -3 Pa quartz tube, kept in a tubular electric furnace at 800 ° C for 50 minutes, then the tubular electric furnace was pushed away from the quartz tube to allow the sample to air cool, and then preheated at 650 ° C for 15 minutes, and then hot rolled at 650 ° C to obtain a plate with a thickness of 1.25 mm;

[0071] (4) Use a mixed acid solution of 30% nitric acid, 4% hydrofluoric acid and water in a volume ratio of 45:10:45 to pickle the plate surface until it is bright. After removing the oxide layer on the surface of the plate, vacuum seal it into a quartz tube. The vacuum degree of the vacuum quartz tube is 5×10 -5Pa, after preheating at 650 °C for 15 min, the quartz tube was broken and the sample was dropped into water for quenching to obtain the antibacterial zirconium alloy material of Zr-30Ti-7Cu-0.3Fe, which was defined as 7Cu alloy.

[0072] Example 3

[0073] This embodiment provides a method for preparing an antibacterial zirconium alloy material, comprising the following steps:

[0074] (1) Raw materials were weighed according to the mass fractions of Cu 5%, Ti 30%, Fe 0.3% and Zr 64.7%. The raw materials were smelted in a non-consumable vacuum arc furnace at 2000°C under high-purity Ar gas for 7 times, each smelting for 5 minutes. The raw materials were turned over after each smelting to obtain a 60g alloy ingot.

[0075] (2) The alloy ingot was preheated at 650°C for 15 min, then placed in molds with heights of 26 mm, 23 mm, and 20 mm, respectively, and hot pressed at 650°C to obtain a 20 mm thick bar-shaped billet;

[0076] (3) Use a grinding wheel to grind off the oxide layer on the surface of the blank, pickle it with a mixed acid solution of 30% nitric acid, 4% hydrofluoric acid and water in a volume ratio of 45:10:45, and rinse it with tap water until the surface is bright; place the blank with a bright surface in a vacuum chamber with a degree of vacuum of 5×10 -3 Pa quartz tube, kept in a tubular electric furnace at 800 ° C for 50 minutes, then the tubular electric furnace was pushed away from the quartz tube to allow the sample to air cool, and then preheated at 650 ° C for 15 minutes, and then hot rolled at 650 ° C to obtain a plate with a thickness of 1.2 mm;

[0077] (4) Use a mixed acid solution of 30% nitric acid, 4% hydrofluoric acid and water in a volume ratio of 45:10:45 to pickle the plate surface until it is bright. After removing the oxide layer on the surface of the plate, vacuum seal it into a quartz tube. The vacuum degree of the vacuum quartz tube is 5×10 -5 Pa, after preheating at 650 °C for 15 min, the quartz tube was broken and the sample was allowed to fall into water for quenching, and an antibacterial zirconium alloy material of Zr-30Ti-5Cu-0.3Fe was obtained, which was defined as 5Cu alloy.

[0078] Comparative Example 1

[0079] Comparative Example 1 provides a zirconium alloy material, which differs from Example 1 in that Cu is removed in step (1), the mass fraction of Zr is 69.7%, and the other steps are the same as Example 1, obtaining a Zr-30Ti-0.3Fe alloy, which is defined as a 0Cu alloy.

[0080] The antibacterial zirconium alloy materials obtained in Examples 1 and 2 and the zirconium alloy material obtained in Comparative Example 1 were respectively treated with 400 # , 800 # , 1200 # After being polished smooth with sandpaper, the sample was placed in acetone and ultrasonicated for 10 minutes, and then dried with a hair dryer. The crystal structure of the sample was analyzed using a Dutch Empyrean S2 X-ray diffractometer (XRD), with a scanning range of 20-100° and a step length of 0.02°. The diffraction peaks of the corresponding phases were marked by comparison with the standard cards in the Jade software database, and the following were obtained: Figure 1 The XRD patterns are shown.

[0081] Depend on Figure 1 It can be seen that all three alloys are primarily composed of β phase (bcc structure). The 0Cu sample also exhibits a diffraction peak for the α phase (hcp structure), which is the lamellar α phase that undergoes a martensitic transformation after quenching. The 3Cu and 7Cu samples do not show a distinct α phase diffraction peak, but do have diffraction peaks corresponding to Zr2Cu, confirming the presence of Zr2Cu precipitation in the samples. Overall, alloy samples primarily composed of β phase were obtained by quenching at 650°C, while Zr2Cu precipitation was observed in Examples 1 and 2.

[0082] The antibacterial zirconium alloy materials obtained in Examples 1 and 2 and the zirconium alloy material obtained in Comparative Example 1 were wrapped with sterile polyethylene films, and bacterial solutions containing Escherichia coli and Staphylococcus aureus were dripped into the three samples. The samples were then cultured at 37±2°C for 24 hours. The samples were taken out and the surfaces were completely cleaned with a quantitative sterilized saline solution (100 mL). The cleaning solution was then inoculated onto a TSA plate. After culturing for 24 hours under the same conditions, the number of colonies was counted under a light microscope. The statistical results and the percentage of colony count reduction relative to the 0Cu alloy (i.e., the antibacterial activity R) are shown in Figure 2. Figure 2 shown.

[0083] Depend on Figure 2 The results show that, based on the number of colonies attached to the surface of the 0Cu alloy, the antibacterial activity R of the 3Cu alloy against Escherichia coli and Staphylococcus aureus was 39.8% and 50.9%, respectively, while that of the 7Cu alloy was 90.6% and 81.1%. This suggests that the addition of Cu imparts an inhibitory effect on both bacteria, and the inhibitory effect increases with increasing Cu content.

[0084] The antibacterial zirconium alloy materials obtained in Examples 1 and 2 and the zirconium alloy material obtained in Comparative Example 1 were respectively placed in physiological saline (0.9 wt.% NaCl aqueous solution) as working electrodes, a saturated calomel electrode was used as a reference electrode, and a platinum electrode was used as a counter electrode. Electrochemical impedance spectroscopy and potentiodynamic polarization curve tests were performed. The results are shown in FIG. Figure 3 and Figure 4 As shown; Figure 4 The corrosion parameters are shown in Table 1.

[0085] Depend on Figure 3 It can be seen that the capacitive reactance arcs of all three alloys are part of a circular arc curve. As the Cu content of the alloy increases, the radius of the corresponding capacitive reactance arc increases. In the Nyquist plot, the larger the radius of the corresponding arc of the material, the greater the polarization resistance and the better the corrosion resistance. In other words, the addition of Cu increases the resistance of the alloy's passivation film, thereby improving the corrosion resistance of the alloy.

[0086] Table 1. Corrosion parameters of the antibacterial zirconium alloy materials of Examples 1 to 2 and the zirconium alloy material of Comparative Example 1

[0087]

[0088] Depend on Figure 4 It can be seen that with the increase of Cu content, the curve shifts slightly to the left. Combined with Table 1, it can be seen that the addition of Cu leads to the self-corrosion potential E corr The value decreases, and the self-corrosion current i corr The value also becomes smaller. In thermodynamics, E corr A decrease in the value indicates that the alloy has a higher tendency to corrode. Kinetically, i corr A smaller value indicates a slower corrosion rate, so the addition of Cu increases the alloy's tendency to corrode but slows the corrosion rate. For the 0Cu sample, after entering the strong polarization zone, the current value rapidly increases with increasing scan potential before entering the passivation zone. However, for the 3Cu and 7Cu samples, there is no rapid increase in current value with increasing scan potential after entering the strong polarization zone, indicating that Cu-containing alloys are more likely to enter the passivation zone and that the passivation zone is relatively large.

[0089] It can be concluded that the matrix of the antibacterial zirconium alloy obtained in the present invention is mainly β phase, and its corrosion resistance in physiological saline is significantly better than that of Zr-30Ti-0.3Fe alloy. At the same time, both copper-containing alloys have a certain inhibitory effect on Escherichia coli and Staphylococcus aureus.

[0090] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. An antibacterial zirconium alloy material, characterized in that: The following components by mass fraction composition: Cu 3~7%, Ti 25~35%, Fe 0.05~0.5%, and the balance is Zr.

2. The method for preparing an antibacterial zirconium alloy material according to claim 1, characterized in that: The following steps are involved: (1) melting the raw materials according to the mass fraction of claim 1 to obtain an alloy ingot; (2) preheating the alloy ingot and hot pressing it to obtain a billet; (3) preheating the blank after homogenization and hot rolling to obtain a plate; (4) After packaging, the plate is preheated and quenched to obtain an antibacterial zirconium alloy material.

3. The method for preparing an antibacterial zirconium alloy material according to claim 2, wherein: In step (1), the smelting is carried out under argon protection, the smelting temperature is 2000-2200°C, the smelting is repeated 6-8 times, and the time for each smelting is 3-5 minutes.

4. The method for preparing an antibacterial zirconium alloy material according to claim 2 or 3, characterized in that: In step (2), the hot pressing temperature is 640-660°C.

5. The method for preparing an antibacterial zirconium alloy material according to claim 4, characterized in that: In step (3), the vacuum degree of the homogenization treatment is 4×10 -3 ~6×10 -3 Pa, the temperature of the homogenization treatment is 750-850° C., and the time of the homogenization treatment is 40-60 min.

6. The method for preparing an antibacterial zirconium alloy material according to claim 2 or 5, characterized in that: In step (3), the temperature of the hot rolling treatment is 640-660° C.; the thickness of the plate is 1.0-1.5 mm.

7. The method for preparing an antibacterial zirconium alloy material according to claim 6, characterized in that: In step (4), the vacuum degree of the package is 4×10 -5 ~6×10 -5 Pa, the packaging is packaging in a vacuum quartz tube.

8. The method for preparing an antibacterial zirconium alloy material according to claim 5 or 7, characterized in that: In step (2), step (3) and step (4), the preheating temperature is independently 640-660° C., and the preheating time is independently 10-20 minutes.

9. The method for preparing an antibacterial zirconium alloy material according to claim 8, characterized in that: In step (4), the quenching medium is water.

10. Use of the antibacterial zirconium alloy material according to claim 1 as a dental implant.

Images