Medical zirconium alloy with low modulus and high yield strength and preparation method thereof
By adding trace iron, silicon and magnesium elements to the zirconium alloy and adopting hot rolling process, the problems of insufficient mechanical properties and difficult processing of zirconium alloy are solved, and the effects of high yield strength and low elastic modulus are achieved, which improves biocompatibility and processing simplicity.
Patent Information
- Application Number
- CN202510176941.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-18
- Publication Date
- 2025-05-23
AI Technical Summary
The existing zirconium alloys have insufficient mechanical properties in the human body, have low tensile strength, and have higher elastic modulus than human bones, resulting in stress shielding effects and increasing the risk of fractures. At the same time, it is difficult to process and complicated to operate.
Zirconium alloys were prepared by vacuum arc melting furnaces, and trace amounts of iron, silicon and magnesium were added, and multiple passes were processed through hot rolling process to reduce the elastic modulus and improve the yield strength.
The yield strength of zirconium alloy is significantly improved, the elastic modulus is reduced, the biocompatibility is improved, the processing technology is simplified, the processing defects are reduced, and the strength and toughness of the alloy is improved.
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Figure CN120026199A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of medical alloy materials, and in particular to a medical zirconium alloy with low modulus and high yield strength and a preparation method thereof. Background Art
[0002] Both zirconium and niobium have good biocompatibility, are less irritating to human tissues, and are not likely to cause immune and inflammatory reactions. This allows zirconium alloys to exist relatively stably in the human body. Researchers have conducted a lot of in-depth research on the biocompatibility, mechanical properties, and corrosion resistance of zirconium alloys. It was found that it has good biocompatibility and is not likely to cause immune and allergic reactions in the human environment. Although current studies have shown that zirconium alloys have good biocompatibility in the short term, their mechanical properties, such as low tensile strength and existing studies on zirconium alloys show that their elastic modulus is much higher than that of human bones. When used as implants, they will produce a higher stress shielding effect, resulting in a reduction in the stress on the surrounding bone tissue and an increased risk of fractures. In addition, zirconium alloys are difficult to process, requiring strict control of processing parameters and process conditions. Most of the processing techniques are forging and additive manufacturing processes, which are complex to operate. Summary of the invention
[0003] Purpose of the invention: To provide a medical zirconium alloy with low modulus and high yield strength and a preparation method thereof, so as to solve the above-mentioned problems existing in the prior art.
[0004] Technical solution: A medical zirconium alloy with low modulus and high yield strength and a preparation method thereof, comprising the following steps:
[0005] S1. Weighing niobium, hafnium, iron, silicon, magnesium and zirconium according to a predetermined ratio;
[0006] S2, melting the weighed raw materials to obtain a zirconium alloy;
[0007] S3, homogenizing the obtained zirconium alloy;
[0008] S4, subjecting the homogenized zirconium alloy to a multi-pass hot rolling process;
[0009] S5, cooling the hot-rolled plate by water cooling to obtain a zirconium alloy plate;
[0010] S6. Take the zirconium alloy plate obtained above and conduct a biocompatibility test.
[0011] In a further embodiment, the step S1 includes 10% to 20% niobium, 1.0% to 3.0% hafnium, 0.1% to 0.5% iron, 0.1% to 0.5% silicon, 0.1% to 0.5% magnesium, and the remainder is zirconium.
[0012] In a further embodiment, in step S2, a water-cooled copper crucible non-consumable vacuum arc furnace is used for smelting in an argon atmosphere, and the furnace is cooled to room temperature to obtain a zirconium alloy.
[0013] In a further embodiment, the zirconium alloy obtained in step S3 is homogenized by passing argon gas in a vacuum tube furnace and keeping the temperature at 950° C. for 6 hours.
[0014] In a further embodiment, in step S4, the zirconium alloy after homogenization treatment is kept at 900° C. for 30 minutes in a muffle furnace and then hot rolled, with a reduction rate of 5-10% for each pass, a heating interval of 3 minutes between each pass, and water cooling after rolling.
[0015] In a further embodiment, the thickness of the zirconium alloy plate is preferably 2-3 mm.
[0016] In a further embodiment, the biocompatibility test is designed as follows: mouse embryonic osteoblast precursor cells (MC3T3-E1 cells) are cultured, the zirconium alloy plate is placed in a cell culture medium, the cell activity is detected by the MTT method, and a cell live / dead staining experiment is performed using a laser confocal microscope.
[0017] Beneficial effects: The present invention relates to a medical zirconium alloy with low modulus and high yield strength and a preparation method thereof, and relates to the technical field of medical alloy materials, including weighing niobium, hafnium, iron, silicon, magnesium and zirconium according to a predetermined ratio; smelting the weighed raw materials to obtain a zirconium alloy; homogenizing the obtained zirconium alloy; performing multiple hot rolling treatments on the zirconium alloy after homogenization; cooling the hot-rolled plate by water cooling to obtain a zirconium alloy plate and the like. The present invention uses a vacuum arc melting furnace to prepare a sample, adds trace iron, silicon and magnesium elements to the zirconium alloy, greatly improves the yield strength of the zirconium alloy, and has good biocompatibility. The sample is processed by hot rolling process, the processing process is simpler, and hot rolling can eliminate defects in the ingot, compact and homogenize the alloy structure, refine the grains, improve the microstructure, and can generate a large number of dislocations, and further improve the strength of the alloy by dislocation strengthening. Controlling the addition of different niobium contents can also reduce the elastic modulus of the alloy. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 Schematic diagram of the shape and size of the tensile specimen of medical zirconium alloy with low modulus and high yield strength
[0019] Figure 2 Tensile data of low modulus and high yield strength medical zirconium alloy
[0020] Figure 3Relative cell viability of mouse MC3T3-E1 preosteoblasts cultured on control group materials, Example 1, and Example 2 for 24 hours
[0021] Figure 4 Relative cell viability of mouse MC3T3-E1 preosteoblasts cultured on control group materials, Example 1, and Example 2 for 48 hours
[0022] Figure 5 Relative cell viability of mouse MC3T3-E1 preosteoblasts cultured on control group materials, Example 1, and Example 2 for 72 hours
[0023] Figure 6 Live / dead staining images of mouse preosteoblasts after 72 hours of culture on control group materials, Example 1, and Example 2 DETAILED DESCRIPTION
[0024] In the following description, a large number of specific details are provided to provide a more thorough understanding of the present invention. However, it is apparent to those skilled in the art that the present invention can be implemented without one or more of these details. In other examples, in order to avoid confusion with the present invention, some technical features well known in the art are not described.
[0025] The applicant believes that traditional zirconium alloys have low tensile strength and elastic modulus much higher than human bones. When used as implants, they will produce a high stress shielding effect, resulting in reduced stress on surrounding bone tissue and increased risk of fractures. At the same time, the processing is difficult and requires strict control of processing parameters and process conditions. Most of the processing processes are forging and additive manufacturing processes, which are complex to operate.
[0026] To this end, the applicant designed a medical zirconium alloy with low modulus and high yield strength and a preparation method thereof, using a vacuum arc melting furnace to prepare the sample, adding trace iron, silicon and magnesium elements to the zirconium alloy, greatly improving the yield strength of the zirconium alloy, and processing the sample through a hot rolling process. The processing process is simpler, and hot rolling can eliminate defects in the ingot, compact and homogenize the alloy structure, refine the grains, improve the microstructure, and generate a large number of dislocations, further improving the strength of the alloy through dislocation strengthening. Controlling the addition of different niobium contents can also reduce the elastic modulus of the alloy.
[0027] The present invention relates to a low modulus and high yield strength medical zirconium alloy and a preparation method thereof, which mainly comprises the following steps:
[0028] First, niobium, hafnium, iron, silicon, magnesium and zirconium are weighed as raw materials according to a predetermined ratio;
[0029] Next, the weighed raw materials are melted to obtain a zirconium alloy;
[0030] Then, the obtained zirconium alloy is subjected to homogenization treatment;
[0031] Subsequently, the homogenized zirconium alloy is subjected to a multi-pass hot rolling process;
[0032] Then, the hot-rolled plate is cooled by water cooling to obtain a zirconium alloy plate;
[0033] Finally, the zirconium alloy plate obtained above was used for biocompatibility test.
[0034] The raw materials include 10% to 20% niobium, 1.0% to 3.0% hafnium, 0.1% to 0.5% iron, 0.1% to 0.5% silicon, 0.1% to 0.5% magnesium, and the remainder is zirconium.
[0035] The zirconium alloy is prepared by melting in an argon atmosphere using a water-cooled copper crucible non-consumable vacuum arc furnace and cooling the furnace to room temperature.
[0036] The obtained zirconium alloy was homogenized in a vacuum tube furnace by passing argon gas and keeping the temperature at 950°C for 6 hours.
[0037] The zirconium alloy after homogenization treatment is kept at 900℃ in a muffle furnace for 30 minutes and then hot rolled. The reduction rate of each pass is 5-10%, and the interval between each pass is 3 minutes. After rolling, it is water-cooled. The total deformation is controlled at about 80%.
[0038] The thickness of the zirconium alloy plate is preferably 2-3 mm.
[0039] In a further preferred embodiment, the performance of the prepared zirconium alloy plate is tested. When preparing the sample, the sample surface needs to be polished and then its composition and phase structure are tested. After the tensile sample is prepared, the extensometer is used to test the extension amount at 5×10 -4 s -1 The mechanical properties results were obtained by stretching at room temperature at a speed of .
[0040] Example 1
[0041] Industrial pure zirconium, pure niobium, iron silicide and magnesium silicide are weighed by mass percentage. A water-cooled copper crucible non-consumable vacuum arc furnace is used for smelting in an argon atmosphere, and the ingot is repeatedly smelted 5-6 times during smelting. The furnace is cooled to room temperature to obtain a zirconium alloy ingot. The alloy ingot is placed in a vacuum tube furnace and heated to 950°C for 6 hours. During the homogenization process, argon is kept flowing. After the muffle furnace is heated to 900°C at a heating rate of 10°C / min, the zirconium alloy ingot is placed in the muffle furnace for 30 minutes, and then immediately taken out and rolled on a double-roll mill. The hot rolling temperature is 900°C, and multiple rolling passes are used. The reduction of each rolling deformation is 8%, and the total deformation of the alloy reaches 81.2%. Then the obtained zirconium alloy plate is water-cooled to room temperature with room temperature water. Then the surface oxide layer is polished and cleaned to obtain a zirconium alloy. The tested composition is: Zr-14.9Nb-1.86Hf-0.23Fe-0.22Si-0.1Mg. The mechanical properties are shown in Table 1.
[0042] Example 2
[0043] Industrial pure zirconium, pure niobium, iron silicide and magnesium silicide are weighed by mass percentage. A water-cooled copper crucible non-consumable vacuum arc furnace is used for smelting in an argon atmosphere, and the ingot is repeatedly smelted 5-6 times during smelting. The furnace is cooled to room temperature to obtain a zirconium alloy ingot. The alloy ingot is placed in a vacuum tube furnace and heated to 950°C for 6 hours. Argon is kept flowing during the homogenization process. After the muffle furnace is heated to 900°C at a heating rate of 10°C / min, the zirconium alloy ingot is placed in the muffle furnace for 30 minutes, and then immediately taken out and rolled on a double-roll mill. The hot rolling temperature is 900°C, and multiple rolling passes are used. The reduction of each rolling deformation is 8%, and the total deformation of the alloy reaches 83.5%. Then the obtained zirconium alloy plate is water-cooled to room temperature with room temperature water. Then the surface oxide layer is polished and cleaned to obtain a zirconium alloy. The tested composition is: Zr-17.5Nb-2.11Hf-0.2Fe-0.24Si-0.15Mg. The mechanical properties are shown in Table 1.
[0044] Table 1
[0045]
[0046] Mouse embryonic osteoblast precursor cells (MC3T3-E1 cells) were cultured in a 5% CO atmosphere. 2, cultured in a constant temperature incubator at 37°C. Cut the plates of Example 2 and Example 3 above into discs with a diameter of 8 mm, polish until the surface is smooth, and sterilize at high temperature and high pressure for later use. Divide into a control group, Example 1 group, and Example 2 group. Example 1 group and Example 2 group were added with the plate sample of Example 1 and the plate sample of Example 2, respectively, and then 2 mL of cell suspension was added, and 2 mL of cell suspension was added to the control group. According to the above-mentioned grouping treatment, the samples were placed in a 24-well plate, and mouse embryonic osteoblast-precursor cells (MC3T3-E1 cells) in the logarithmic growth period were taken, the cells were counted, the cell concentration was adjusted, and the cells were inoculated into a 24-well plate at 5% CO 2 , incubate in a 37°C incubator until cells adhere to the wall. Incubate for 24h / 48h / 72h. Remove the culture medium. Wash each well 3-4 times with phosphate buffered saline (PBS), add 2mL of culture medium containing 0.5mg / ml tetrazolium salt (MTT) to each well, and incubate at 5% CO 2 , incubate in a 37℃ constant temperature incubator for 4 hours. Discard the supernatant and add 1 mL of dimethyl sulfoxide (DMSO) to each well. After gently shaking for 10 minutes, measure the absorbance at 570 nm. The results are as follows Figure 3 , Figure 4 and Figure 5 As shown, over time, the cell activity in the samples of Example 1 and Example 2 increased significantly compared with the control group, indicating that Example 1 and Example 2 have better biocompatibility with mouse embryonic osteoblast precursor cells (MC3T3-E1 cells).
[0047] For the live / dead cell staining experiment, cell culture was performed in the same manner. The plates of Example 1 and Example 2 were cut into discs with a diameter of 8 mm, polished until the surface was smooth, and sterilized at high temperature and high pressure for later use. The plates were divided into a control group, Example 1 group, and Example 2 group. The Example 1 group and Example 2 group were added with the Example 1 plate sample and the Example 2 plate sample, respectively, and then 2 mL of the cell suspension was added, and 2 mL of the cell suspension was added to the control group. According to the above grouping treatment, mouse embryonic osteoblast precursor cells (MC3T3-E1 cells) in the logarithmic growth period were taken, the cells were counted, the cell concentration was adjusted, and the cells were inoculated into a laser confocal dish at 5% CO 2, cultured in a 37°C constant temperature incubator for 24h / 48h / 72h. Use dye diluent to dilute the live / dead cell staining reagent (Calcein-AM) and propidium iodide reagent (PI) 10 times respectively; take 985.5μL serum-free culture medium and mix 10μL diluted live / dead cell staining reagent (Calcein-AM) and 4.5μL propidium iodide reagent (PI), and prepare it for use immediately. Then perform live / dead cell staining, and wash the cells in the laser confocal microscope once with phosphate buffered saline (PBS) to remove excess serum. Add staining solution at 2mL / well, incubate at room temperature in the dark for 15min, and observe and take pictures. The results are as follows Figure 6 As shown, after 72 hours of culture, the survival rate of cells increased significantly and the number of dead cells decreased, which also shows that the components of the sample are not cytotoxic and have better biocompatibility with mouse embryonic osteoblast precursor cells (MC3T3-E1 cells).
[0048] In the present invention, trace amounts of iron, silicon and magnesium are added to improve the yield strength of the zirconium alloy, and different niobium contents are adjusted to reduce the elastic modulus of the zirconium alloy by using a hot rolling process. The defects in the ingot are eliminated by hot rolling, the alloy structure is compacted and homogenized, the grains are refined, the microstructure is improved, and a large number of dislocations can be generated. The strength of the alloy is further improved by dislocation strengthening, and the uniform structure can also avoid crack extension and cracking caused by local stress concentration. The alloy has excellent toughness while having a lower elastic modulus.
[0049] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the present invention itself. Various changes in form and details may be made without departing from the spirit and scope of the present invention as defined in the appended claims.
Claims
1. A medical zirconium alloy with low modulus and high yield strength and a preparation method thereof, characterized in that The following steps are involved: S1. Weighing niobium, hafnium, iron, silicon, magnesium and zirconium according to a predetermined ratio; S2, melting the weighed raw materials to obtain a zirconium alloy; S3, homogenizing the obtained zirconium alloy; S4, subjecting the homogenized zirconium alloy to a multi-pass hot rolling process; S5. Cooling the hot-rolled plate by water cooling to obtain a zirconium alloy plate. S6. Take the zirconium alloy plate obtained above and conduct a biocompatibility test.
2. A medical zirconium alloy with low modulus and high yield strength and a preparation method thereof according to claim 1, characterized in that: The step S1 includes 10% to 20% niobium, 1.0% to 3.0% hafnium, 0.1% to 0.5% iron, 0.1% to 0.5% silicon, 0.1% to 0.5% magnesium, and the remainder is zirconium.
3. A medical zirconium alloy with low modulus and high yield strength and a preparation method thereof according to claim 2, characterized in that: In the step S2, a water-cooled copper crucible non-consumable vacuum arc furnace is used to melt in an argon atmosphere, and the furnace is cooled to room temperature to obtain a zirconium alloy.
4. A medical zirconium alloy with low modulus and high yield strength and a preparation method thereof according to claim 3, characterized in that: In step S3, the obtained zirconium alloy is homogenized by passing argon gas in a vacuum tube furnace and keeping the temperature at 950° C. for 6 hours.
5. A medical zirconium alloy with low modulus and high yield strength and a preparation method thereof according to claim 4, characterized in that: In step S4, the zirconium alloy after homogenization treatment is kept at 900° C. for 30 minutes in a muffle furnace and then hot rolled. The reduction rate of each pass is 5-10%, and the heating interval between each pass is 3 minutes. After rolling, water cooling is performed.
6. The low modulus and high yield strength medical zirconium alloy and preparation method thereof according to claim 1, characterized in that: The thickness of the zirconium alloy plate is preferably 2-3 mm.
7. The low modulus and high yield strength medical zirconium alloy and preparation method thereof according to claim 1, characterized in that: The biocompatibility experiment design in step S6 is as follows: mouse embryonic osteoblast precursor cells are cultured, the zirconium alloy plate is placed in a cell culture medium, cell activity is detected by tetrazolium salt method, and a cell live / dead staining experiment is performed using a laser confocal microscope.