CN115109979B - Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy - Google Patents
Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy Download PDFInfo
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Abstract
The invention relates to a Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy. In the invention, tiNbZr is taken as a whole, and TaMo is taken as a whole; researching the influence of the content of TaMo as a whole on the performance of a product, then taking TiNbZrTa as a whole, taking Mo as a whole, and researching the influence of the using amount of Mo on the compression yield strength of the product; determining a mechanical property selection factor, selecting a product with better mechanical property through the mechanical property, and performing corrosion resistance test to obtain an as-cast product with excellent property; then carrying out heat treatment optimization on the eliminated as-cast product; and measuring the mechanical property and corrosion resistance of the product after the heat treatment optimization, and further obtaining the product with excellent mechanical property and corrosion resistance. The invention can greatly save the development cost of high-quality Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy and improve the development effect of high-quality products. Especially, the heat treatment optimization is carried out on the eliminated cast product, which can greatly improve the yield of high-quality products. This is advantageous for low cost industrial applications.
Description
Technical Field
The invention relates to the field of biomedical materials, in particular to a Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy.
Background
With the continuous development and development of the biomedical field, metal biomedical materials have attracted extensive attention from researchers, and due to the low compatibility of traditional metal implant materials with human bodies, development of modern materials with excellent mechanical properties and proper biocompatibility is urgently needed to solve adverse reactions caused by long-term implantation. High-entropy alloys (HEA) emerged as an innovative and advanced idea, with the development of high-entropy biomedical materials by specific HEA designs.
Biomedical HEAs are currently being studied often with group IV and V Ti and other non-toxic and hypoallergenic elements as the major components. For example, wang and Xu (2016) prepared atomic HEA such As TiZrNbTaMo by arc melting, which in the paper TiZrNbTaMo high-entropy alloy designed for orthopedic implants:As-cast microstructure and mechanical properties relates to TiZrNbTaMo high-entropy alloy, the Ecorr (mVSCE) -607+ -55, ip (μA/cm 2) of the obtained product is 0.89+ -0.06. With the intensive research of high-entropy alloy, it is found that high-entropy alloy with non-equal atomic ratio shows characteristic performance, so that in 2019 Nagase et al in paper Development of non-equiatomic Ti-Nb-Ta-Zr-Mo high-entropy alloys formetallic biomaterials, microstructure of equal-atom and non-equal-atom TiNbTaZrMo is studied, after annealing, dendrite coarsening and element segregation are found to occur in the original structure, and meanwhile, corrosion resistance of the product is not related in the paper. .
Meanwhile, according to the search, in the technology disclosed at present (comprising CN 201610407085.4), the Ecorr (mVSCE) of the obtained product is generally about-600, ip (mu A/cm) 2 ) Generally 0.8-1.45 mu A/cm 2 、Ic orr 0.03-0.05(μA/cm 2 ) The compressive yield strength is generally 950-1410MPa. However, regarding how to obtain a compressive yield strength of 1000MPa or more, and an Ecorr (mVSCE) of about-400 to-290, icorr is less than 0.02 (. Mu.A/cm) 2 ) The Ti-Ta-Nb-Zr-Mo high-entropy alloy is rarely reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention regulates and controls the mechanical property and corrosion resistance of the alloy by means of component optimization and/or regulation and control mode of heat treatment on the basis of the existing Ti-Ta-Nb-Zr-Mo high-entropy medical alloy system, and obtains as many biomedical high-entropy alloy materials with high mechanical strength and excellent corrosion resistance as possible by experiments as few as possible. The invention provides a new idea for rapidly obtaining the biomedical alloy system with excellent mechanical property, good biocompatibility and excellent corrosion resistance.
In the invention, tiNbZr is taken as a whole, and TaMo is taken as a whole; researching the influence of the overall content of TaMo as a whole on the performance of a product, then taking TiNbZrTa as a whole, taking Mo as a whole, and researching the influence of the using amount of Mo on the compression yield strength of the product; determining a mechanical property selection factor, selecting a product with better mechanical property through the mechanical property, and performing corrosion resistance test to obtain an as-cast product with excellent property; then carrying out heat treatment optimization on the eliminated as-cast product; and measuring the mechanical property and corrosion resistance of the product after the heat treatment optimization, and further obtaining the product with excellent mechanical property and corrosion resistance. The invention can greatly save the development cost of high-quality Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy and improve the development effect of high-quality products. Especially, the heat treatment optimization is carried out on the eliminated cast product, which can greatly improve the yield of high-quality products. This is advantageous for low cost industrial applications.
The invention relates to a Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy, which comprises the following design method:
step one
Taking TiNbZr as a whole and taking TaMo as a whole; adopting TiNbZr with equal molar ratio, setting the molar contents of Ti, nb and Zr in the high-entropy alloy to be prepared as x, and setting the molar contents of Ta and Mo in the high-entropy alloy to be prepared as y; obtaining a first type of research sample through a casting process, and researching and analyzing the influence of the x/y ratio on the mechanical properties of the product; obtaining the corresponding relation between the x/y ratio in the first kind of molten cast product and the compressive yield strength of the product;
step two
Taking TiNbZrTa as a whole and Mo as a whole; adopting TiNbZrTa with equal molar ratio, setting the molar content of Ti, nb, zr, ta in the high-entropy alloy to be prepared as x1, and setting the molar content of Mo in the high-entropy alloy to be prepared as y1; obtaining a second type of research sample through a casting process, and researching and analyzing the influence of the ratio of x1/y1 on the mechanical properties of the product; obtaining the corresponding relation between the ratio of x1/y1 in the second kind of molten cast product and the compressive yield strength of the product; further obtaining the influence of the Mo consumption on the compressive yield strength of the product;
step three
Selecting products with compression yield strength larger than 1000MPa in the first step and the second step, testing corrosion resistance, and selecting products with Ecorr of-0.3 to-0.65V and Icorr smaller than 9 multiplied by 10 -9 A/cm 2 Is a sample of (a); obtaining a qualified as-cast product;
step four
Selecting products with compression yield strength greater than 1000MPa in the first and second steps, and when corrosion resistance is tested, ecorr is-0.3 to-0.65V and Icorr is greater than 9 multiplied by 10 -9 A/cm 2 Is a sample of (a); performing heat treatment experiment at 900-1200deg.C for 24 hr to obtain Ecorr of-0.3 to-0.65V with Icorr less than 9×10 -9 A/cm 2 Is a sample of (a); and obtaining a qualified heat-treated product.
The ratio of x/y of the Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy is in the range of 0.5-2. Determining this range can greatly reduce the number of experiments.
The Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy is a qualified as-cast product or a qualified heat-treated product.
The invention relates to a Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy, which has the chemical expression that: ti (Ti) 2 Nb 2 Zr 2 TaMo; i.e. x=2 and y=1.
The invention relates to a Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy, which is characterized in that the chemical expression of a qualified heat-treated product is as follows: ti (Ti) 1.5 Nb 1.5 Zr 1.5 TaMo is x=1.5 and y=1. Abbreviated as (TiNb)Zr) 1.5 TaMo. Or (b)
The invention relates to a Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy, which is characterized in that the chemical expression of a qualified heat-treated product is as follows: tiNbZrTa 1.5 Mo 1.5 I.e. x=1 and y=1.5. Abbreviated as TiNbZr (TaMo) 1.5 . Or (b)
The invention relates to a Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy, which is characterized in that the chemical expression of a qualified heat-treated product is as follows: ti (Ti) 1.5 Nb 1.5 Zr 1.5 Ta 1.5 Mo is x1=1.5 and y=1. Abbreviated as (TiNbZrTa) 1.5 Mo。
The invention relates to a Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy, which is prepared by the following steps:
step 1:
the metallurgical raw material Ti, zr, nb, ta with the purity of more than 99.9 percent and Mo metal particles are adopted, and the materials are weighed and proportioned according to the designed molar ratio for preparing alloy by melting materials;
step 2: alloy is smelted by using a vacuum non-consumable tungsten electrode arc furnace, a sample chamber is vacuumized, and when the vacuum degree reaches 5 multiplied by 10 -3 After Pa, filling industrial argon until the pressure in the furnace reaches half atmospheric pressure;
step 3: in the smelting process, in order to better and uniformly mix raw materials, after each smelting alloy is melted, the arc holding time is 30-60s, after the alloy block is cooled, the alloy block is turned over, and the process is repeated for more than 10 times; the input voltage is 380V and the current is 290-310A during smelting;
step 4: and after the master alloy is fully and uniformly smelted, obtaining a high-entropy alloy button ingot, and obtaining an as-cast product.
The Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy is cooled to room temperature along with a furnace after heat treatment.
The invention relates to a Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy; the mechanical properties are evaluated by compression experiments and microhardness; the corrosion resistance evaluation is carried out by an electrochemical experiment of quantitative analysis.
The invention has the beneficial effects that:
design method adopting the inventionAccording to the scheme, the design experiment time for obtaining the biomedical alloy system with excellent mechanical property, good biocompatibility and excellent corrosion resistance is greatly shortened. It gives products of excellent properties in a very short time, such as: chemically expressed as Ti 2 Nb 2 Zr 2 Qualified as-cast product of TaMo (its compressive yield strength is 1181.52MPa, icorr is 1.6-1.65X10) -9 A/cm 2 Ecorr is-0.34 to-0.35V), and the chemical expression of the qualified heat-treated product is as follows: ti (Ti) 1.5 Nb 1.5 Zr 1.5 Qualified heat treated product of TaMo (its compressive yield strength 1081.27MPa, icorr of 1.6-1.65X10) -9 A/cm 2 Ecorr is-0.3 to-0.305V), and is chemically expressed as TiNbZrTa 1.5 Mo 1.5 Is qualified for heat-treated products (having a compressive yield strength of 1329.21MPa, icorr of 8.35-8.4X10) -9 A/cm 2 Ecorr is-0.62 to-0.63V), and is chemically expressed as Ti 1.5 Nb 1.5 Zr 1.5 Ta 1.5 Mo 1 Is qualified for heat treatment (its compressive yield strength is 1069.43MPa, icorr is 2.2-2.25X10) -9 A/cm 2 Ecorr is-0.660-0.665V).
Drawings
FIG. 1 is a graph of compressive stress versus strain for a Ti-Nb-Zr alloy system; (b) a plot of the corresponding vickers hardness versus yield strength;
FIG. 2 is a graph of compressive stress versus strain for a Ti-Ta-Nb-Zr alloy system; (b) the Vickers hardness diagram corresponding to the alloy system;
FIG. 3 is an XRD pattern of an as-cast product and a heat-treated product in an embodiment of the present invention;
FIG. 4 is an SEM image of an as-cast product and a heat-treated product according to an embodiment of the present invention;
FIG. 5 is a graph showing compression curves of an as-cast product and a heat-treated product according to an embodiment of the present invention;
FIG. 6 is a bar graph of as-cast product and heat treated product hardness in an embodiment of the invention;
FIG. 7 is a nanoindentation P-h curve of an as-cast product and a heat treated product in an embodiment of the invention;
FIG. 8 is a graph showing corrosion voltage and current corresponding to Tafil curves for an as-cast product and a heat treated product in an embodiment of the present invention.
Remarks: c represents an as-cast state; a represents a heat treatment annealed state.
Detailed Description
The first embodiment is as follows:
component design is carried out on Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy, and the expression of the high-entropy alloy is as follows:
(TiNbZr)x(TaMo)y(x/y＝0.5-2)
further, when x/y=0.6, the chemical formula of the high-entropy alloy is (TiNbZr) 1 (TaMo) 1.5
Further, when x/y=1.5, the chemical formula of the high-entropy alloy is (TiNbZr) 1.5 (TaMo) 1
Further, when x/y=2, the chemical formula of the high-entropy alloy is (TiNbZr) 2 (TaMo) 1
The preparation method of the experimental biomedical high-entropy alloy comprises the following steps:
1) Raw material preparation: the alloy smelting raw materials adopted by the invention are high-purity (more than or equal to 99.9%) Ti, zr, nb, ta and Mo elements, the alloy smelting raw materials are accurately weighed and proportioned according to the mole ratio, and the alloy ratio is shown in components set by 1, 3, 4 and 5 in table 1, and the experiment of the first stage is carried out.
TABLE 1 alloy composition ratio (at%)
2) Preparation of high-entropy alloy:
the alloy was melted using a vacuum non-consumable tungsten electrode arc furnace. Respectively taking raw materials, adding into vacuum arc furnace, vacuumizing sample chamber, and keeping vacuum degree at 5×10 -3 After Pa, filling industrial argon until the pressure in the furnace reaches half atmospheric pressure; in the smelting process, in order to better and uniformly mix raw materials, the arc holding time is 30-60s after each smelting of alloy meltingThe alloy block is turned over after being cooled, and the process is repeated for more than 10 times. And after the master alloy is fully and uniformly smelted, obtaining the high-entropy alloy button ingot. The input voltage is 380V and the current is 290-310A during smelting; the smelting furnace is of the type: DHL-1250, manufacturer: shenyang a special electrician Co., ltd.
1. Characterization of the microstructure of the alloy
X-ray diffraction (XRD) test and phase composition analysis
After the test bars were cut into square pieces of 4mm×6mm×2mm by wire cutting, metallographic sandpaper of 80#,400#,800#,1000#,1500# and 2000# was used in that order to carefully grind flat. The prepared sample was subjected to phase composition analysis using an X-ray diffractometer, scanning step size 10 °/min, scanning angle 2 θ ranging from 20 ° to 100 °. Fig. 1 shows the XRD test results of the alloy, and the resulting alloy structures were all of a dual-phase BCC structure (BCC 1 and BCC2 two phases). Wherein the BCC2 diffraction peaks are weaker and the diffraction angles are smaller than those of the BCC1 phase, indicating that the BCC2 phase lattice constant is larger than that of the BCC1 phase, but the volume fraction of the BCC2 phase in the alloy is relatively low.
2. Microstructural analysis-SEM testing
Cutting an alloy spindle into square pieces with the size of 4mm multiplied by 6mm multiplied by 2mm, performing rough grinding through 80# sand paper, performing fine grinding treatment, and performing rough polishing and fine polishing on a sample sequentially on a polishing machine through grinding paste. After the sample was polished until no surface scratches were visible under a 100X optical microscope, surface etching was performed with an etching solution. The etching time is 5s each time, and the etching process adopts the principle of a few times. FIG. 2 is a scanning electron microscope image of an alloy showing two contrast ratios in the back scattering mode, further illustrating the two-phase structure of the alloy system.
2. Influence of elemental additions on the mechanical properties of alloys
1) Compression experiment
Compression experiments in the experiment are carried out on an Instron type universal electronic tester, and the compression rate in the experiment process is unified to be 1 multiplied by 10 -3 s -1 . The prepared TiTaNbZrMo alloy is processed into cylindrical samples with the diameter of 6mm and the length of 6mm by wire cutting, and the cylindrical samples are subjected to metallographic phase of 80#,400#,800#,1000#,1500# and 2000#The sides were sanded and the ends of the specimen were flattened to avoid erroneous stress strain data caused by the geometry of the specimen. The compressive engineering stress-strain curve of the TiTaNbZrMo alloy obtained through the experiment is shown in figure 5. It can be seen that: curves C1 and C4 show relatively high compression plasticity, and the yield strengths of C1, C3, C4, C2 and C5 are 1181.52, 1282.48, 1320.31, 1633.65 and 1507.74MP. The mechanical yield strengths of Ti-Ta-Nb-Zr-Mo alloy are distributed at 1000-1700MPa according to the size order of the yield strengths, so that the yield strengths of the Ti-Nb-Zr alloy system are remarkably improved. The key effect of the addition of Ta and Mo elements on the improvement of the mechanical strength of the material is illustrated; further, in (linbzr) x (TaMo) y (x/y=0.5-2): as the x/y ratio decreases, the yield strength increases. From this, it was demonstrated that the yield strength of the alloy system can be improved by increasing the ratio of (TiNbZr) x (TaMo) y.
Thus, in the range where x/y is greater than 1, select:
(TiNbZrTa)x(Mo)y(x/y＝1.5)
the chemical formula of the high-entropy alloy is Ti 1.5 Nb 1.5 Zr 1.5 Ta 1.5 (Mo) 1
The casting experiments (i.e., second stage experiments) were performed according to the design of alloy No. 2 in table 1, and the properties were examined and found:
in (TiNbZr) x (TaMo) y (x/y=1.5): compared with (TiNbZrTa) x (Mo) y (x/y=1.5) alloy, the (TiNbZrTa) x (Mo) y shows higher yield strength, and further illustrates that Mo atoms play an important role in improving the yield strength of the Ti-Ta-Nb-Zr-Mo alloy.
Mechanical hardness test
The sample should be polished to a bright and no obvious scratch before the experiment, and the vickers hardness test is performed by using an HVS-1000 type microhardness tester, wherein the applied load is 200g during the experiment, and the dwell time is 10s. Each sample was averaged over 5 points at different locations. The experimental results show that: the hardness values of the alloy are distributed between 400 and 500HV, and the hardness of C1, C2, C1, C2 and C5 are respectively as follows: 469.2, 495.0, 438.2, 469.8 and 407.6HV. The hardness values of the alloys are distributed between 400 and 500HV. This value gives a significant increase in hardness value of about 200HV compared to the Ti-Nb-Zr alloy system.
Nanoindentation test
The hardness and elastic modulus of the constituent phases were characterized by nanoindentation tests. In the experimental process, the pressure head displacement h and the load P born by the pressure head are recorded simultaneously by means of a high-precision load displacement test technology; and analyzing the obtained P-h curve to obtain the elastic modulus and the hardness of the test sample to be tested.
The experimental results show that: the elastic moduli of the alloys C1, C2, C1, C2 and C5 are 129.41, 181.38, 142.36, 148.50 and 155.32GPa (TiNbZr) x (TaMo) y (x/y=0.5-2), and the ratio of x/y is improved, so that the elastic modulus is improved; meanwhile, (TiNbZr) x (TaMo) y (x/y=1.5) is compared with (TiNbZrTa) x (Mo) y (x/y=1.5), and the (TiNbZrTa) x (Mo) y shows higher elastic modulus, so that the elastic modulus is further improved by Mo. For biomedical materials, the elastic modulus is an important index, and the addition of Ta and Mo atoms brings about the improvement of the elastic modulus of the alloy material, which is one of factors to be considered in alloy design in the later period.
3. Corrosion resistance of alloys
1) Electrochemical performance test
Medical high-entropy alloy samples were placed in Phosphate Buffered Saline (PBS) to simulate the corrosion resistance of the samples in a human physiological environment. According to the invention, electrochemical behaviors of medical high-entropy alloy samples in PBS are researched by using an electrokinetic polarization method, an electrokinetic-current density polarization curve (Tafel curve) of the alloy is measured by using an electrochemical workstation (CHI 660E), and corrosion parameters such as corrosion potentials Ecorr and Icorr are obtained. By alloying with pure Ti and Ti-6Al-4V under the same conditions, it was found that: the corrosion voltages of alloys C1, C3, C4, C2 and C5 are-0.345, -0.652, -0.709, -0.617 and-0.605V, respectively, and the corresponding corrosion currents are 1.63×10, respectively -9 、4.20×10 -8 、5.48×10 -9 、3.30×10 -8 And 1.99X10 -8 A/cm 2 . The corrosion voltage is obviously higher than that of pure Ti and Ti-6Al-4V alloy, and the corrosion current density is 2-3 orders of magnitude smaller than that of pure Ti and Ti-6Al-4V alloy, which proves that the TiTaNbZrMo alloy has better resistanceCorrosion performance.
An as-cast product with the compressive yield strength larger than 1000MPa is selected for corrosion resistance testing, and Ecorr is selected to be minus 0.3 to minus 0.65V and Icorr is selected to be smaller than 9 multiplied by 10 -9 A/cm 2 Is a sample of (a); obtaining a qualified as-cast product;
4. influence of the heat treatment control mode on the alloy tissue performance
Performing heat treatment regulation and control on unqualified as-cast products,
an as-cast product having a compressive yield strength of greater than 1000MPa (in particular an Ecorr of less than-0.65V or an Icorr of greater than 9X 10) -9 A/cm 2 Is subjected to a heat treatment at 1200 c for 24 hours. And respectively testing related microstructure, mechanical property and corrosion resistance of the heat-treated alloy. The XRD results of the heat treated alloy are shown in FIG. 3, and it can be seen that the phase composition of the high entropy alloy remains unchanged after heat treatment, and is still a biphasic body-centered cubic structure, indicating good structural stability of the alloy. Relevant mechanical property tests are also carried out, and the corresponding yield strength and hardness are found to be slightly reduced or not changed obviously: alloys A1, A3, A4, A2 and A5 have yield strengths 1136.58, 1081.27, 1329.21, 1069.21 and 1347.87MPa, respectively, hardness 428.1, 429.4, 438.9, 437.3 and 466.9HV, respectively, the elastic modulus does not vary much relative to the as-cast alloy: the elastic moduli of the alloys A1, A3, A4, A2 and A5 were 119.42, 141.87, 126.67, 165.65 and 140.50GPa, respectively. For corrosion resistance, after heat treatment, five biomedical high-entropy alloys still have excellent corrosion resistance in PBS solution: the corrosion voltages of alloys A1, A3, A4, A5 and A2 are-0.611, -0.302, -0.625, -0.663 and-0.610V, respectively, and the corresponding corrosion currents are 1.22×10, respectively -7 、1.63×10 -9 、8.36×10 -9 、2.21×10 -9 And 1.01X10 -6 A/cm 2 . The above shows that the alloy system still maintains good performance after heat treatment.
Table 2 mechanical index table of different medical high entropy alloys
TABLE 3 elastic modulus and microhardness of medical high entropy alloy
TABLE 4 electrochemical corrosion parameters for medical high entropy alloys and pure Ti and Ti6Al4V alloys
Through annealing experiments, ti was found 1.5 Nb 1.5 Zr 1.5 TaMo is a qualified heat-treated product (its compressive yield strength is 1081.27MPa, icorr is 1.6-1.65X10) -9 A/cm 2 Ecorr is-0.3 to-0.305V), tiNbZrTa 1.5 Mo 1.5 Is qualified for heat-treated products (having a compressive yield strength of 1329.21MPa, icorr of 8.35-8.4X10) -9 A/cm 2 Ecorr is-0.62 to-0.63V), ti 1.5 Nb 1.5 Zr 1.5 Ta 1.5 Mo 1 Is qualified as heat-treated product (its compressive yield strength is 1069.43MPa, icorr is 2.2-2.25X10) -9 A/cm 2 Ecorr is-0.660-0.665V).
Through the experiments, the invention can obtain the Ecorr with the yield strength more than 1000MPa and the Ecorr of-0.3 to-0.65V, icorr less than 9 multiplied by 10 as much as possible through fewer experiments -9 A/cm 2 The qualified product of the alloy comprises two forms of as-cast and heat treatment, which provides a good idea for rapidly obtaining high-quality Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy suitable for different human bodies and different human body parts.
Claims (4)
1. A Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy is characterized in that the design method comprises the following steps:
step one
Taking TiNbZr as a whole and taking TaMo as a whole; adopting TiNbZr with equal molar ratio, setting the molar contents of Ti, nb and Zr in the high-entropy alloy to be prepared as x, and setting the molar contents of Ta and Mo in the high-entropy alloy to be prepared as y; obtaining a first type of research sample through a casting process, and researching and analyzing the influence of the x/y ratio on the mechanical properties of the product; obtaining the corresponding relation between the x/y ratio in the first kind of molten cast product and the compressive yield strength of the product;
step two
Taking TiNbZrTa as a whole and Mo as a whole; adopting TiNbZrTa with equal molar ratio, setting the molar content of Ti, nb, zr, ta in the high-entropy alloy to be prepared as x1, and setting the molar content of Mo in the high-entropy alloy to be prepared as y1; obtaining a second type of research sample through a casting process, and researching and analyzing the influence of the ratio of x1/y1 on the mechanical properties of the product; obtaining the corresponding relation between the ratio of x1/y1 in the second kind of molten cast product and the compressive yield strength of the product; further obtaining the influence of the Mo consumption on the compressive yield strength of the product;
step three
Selecting products with compression yield strength larger than 1000MPa in the first step and the second step, testing corrosion resistance, and selecting products with Ecorr of-0.3 to-0.65V and Icorr smaller than 9 multiplied by 10 -9 A/cm 2 Is a sample of (a); obtaining a qualified as-cast product; the chemical expression of the qualified as-cast product is as follows: ti (Ti) 2 Nb 2 Zr 2 TaMo；
Step four
Selecting products with compression yield strength greater than 1000MPa in the first and second steps, wherein Ecorr is-0.3 to-0.65V and Icorr is greater than 9 multiplied by 10 when corrosion resistance is tested -9 A/cm 2 Is a sample of (a); performing heat treatment experiment at 900-1200deg.C for 24-h, and selecting Ecorr of-0.3 to-0.65V with Icorr less than 9×10 -9 A/cm 2 Is a sample of (a); obtaining a qualified heat-treated product;
the chemical expression of the qualified heat-treated product is as follows:Ti 1.5 Nb 1.5 Zr 1.5 TaMo; or (b)
The chemical expression of the qualified heat-treated product is as follows: tiNbZrTa 1.5 Mo 1.5 The method comprises the steps of carrying out a first treatment on the surface of the Or (b)
The chemical expression of the qualified heat-treated product is as follows: ti (Ti) 1.5 Nb 1.5 Zr 1.5 Ta 1.5 Mo。
2. The biomedical high-entropy alloy of Ti-Ta-Nb-Zr-Mo according to claim 1, wherein: the Ti-Ta-Nb-Zr-Mo biomedical high-entropy alloy is a qualified as-cast product or a qualified heat-treated product.
3. The biomedical high-entropy alloy of Ti-Ta-Nb-Zr-Mo according to claim 1, wherein: the biomedical high-entropy alloy of as-cast Ti-Ta-Nb-Zr-Mo is prepared by the following steps:
step 1:
the metallurgical raw material Ti, zr, nb, ta with the purity of more than 99.9 percent and Mo metal particles are adopted, and the materials are weighed and proportioned according to the designed molar ratio for preparing alloy by melting materials;
step 2: alloy is smelted by using a vacuum non-consumable tungsten electrode arc furnace, a sample chamber is vacuumized, and when the vacuum degree reaches 5 multiplied by 10 -3 After Pa, filling industrial argon until the pressure in the furnace reaches half atmospheric pressure;
step 3: in the smelting process, in order to better and uniformly mix raw materials, after each smelting alloy is melted, the arc holding time is 30-60s, and after the alloy block is cooled, the alloy block is turned over, and the process is repeated for more than 10 times; the input voltage is 380V and the current is 290-310A during smelting;
step 4: and after the master alloy is fully and uniformly smelted, obtaining a high-entropy alloy button ingot, and obtaining an as-cast product.
4. The biomedical high-entropy alloy of Ti-Ta-Nb-Zr-Mo according to claim 1, wherein: after heat treatment, cooling to room temperature along with the furnace.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962721A (en) * | 2010-11-02 | 2011-02-02 | 中南大学 | Powder metallurgy titanium alloy and preparation method thereof |
| CN103602872A (en) * | 2013-10-31 | 2014-02-26 | 北京科技大学 | TiZrNbVMo[x] high entropy alloy and preparation method thereof |
| CN105734312A (en) * | 2016-03-10 | 2016-07-06 | 北京科技大学 | Biomedical TiZrNbTa high-entropy alloy and preparation method thereof |
| CN107488803A (en) * | 2016-06-12 | 2017-12-19 | 中国科学院金属研究所 | Magnesium-yttrium-transition metal high-entropy alloy before a kind of bio-medical |
| JP2018070949A (en) * | 2016-10-28 | 2018-05-10 | 国立大学法人大阪大学 | Alloy made of multicomponent system |
| CN108220741A (en) * | 2018-02-14 | 2018-06-29 | 哈尔滨工业大学 | A kind of bio-medical high-entropy alloy and preparation method thereof |
| KR20210035574A (en) * | 2019-09-24 | 2021-04-01 | 한국과학기술원 | Mri compatible-high entropy alloys and implant comprising same |
| CN112725678A (en) * | 2020-12-14 | 2021-04-30 | 中南大学 | Non-equal atomic ratio medium/high entropy alloy containing NiCoCr and preparation method thereof |
| CN113652593A (en) * | 2021-07-28 | 2021-11-16 | 中国科学院金属研究所 | MoxNbTayTiV high-entropy alloy and preparation method thereof |
| RU2762897C1 (en) * | 2020-12-22 | 2021-12-23 | федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский политехнический университет Петра Великого" (ФГАОУ ВО "СПбПУ") | Method for obtaining carbide powder of a high-entropy alloy with a spherical particle shape |
-
2022
- 2022-05-16 CN CN202210528167.XA patent/CN115109979B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962721A (en) * | 2010-11-02 | 2011-02-02 | 中南大学 | Powder metallurgy titanium alloy and preparation method thereof |
| CN103602872A (en) * | 2013-10-31 | 2014-02-26 | 北京科技大学 | TiZrNbVMo[x] high entropy alloy and preparation method thereof |
| CN105734312A (en) * | 2016-03-10 | 2016-07-06 | 北京科技大学 | Biomedical TiZrNbTa high-entropy alloy and preparation method thereof |
| CN107488803A (en) * | 2016-06-12 | 2017-12-19 | 中国科学院金属研究所 | Magnesium-yttrium-transition metal high-entropy alloy before a kind of bio-medical |
| JP2018070949A (en) * | 2016-10-28 | 2018-05-10 | 国立大学法人大阪大学 | Alloy made of multicomponent system |
| CN108220741A (en) * | 2018-02-14 | 2018-06-29 | 哈尔滨工业大学 | A kind of bio-medical high-entropy alloy and preparation method thereof |
| KR20210035574A (en) * | 2019-09-24 | 2021-04-01 | 한국과학기술원 | Mri compatible-high entropy alloys and implant comprising same |
| CN112725678A (en) * | 2020-12-14 | 2021-04-30 | 中南大学 | Non-equal atomic ratio medium/high entropy alloy containing NiCoCr and preparation method thereof |
| RU2762897C1 (en) * | 2020-12-22 | 2021-12-23 | федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский политехнический университет Петра Великого" (ФГАОУ ВО "СПбПУ") | Method for obtaining carbide powder of a high-entropy alloy with a spherical particle shape |
| CN113652593A (en) * | 2021-07-28 | 2021-11-16 | 中国科学院金属研究所 | MoxNbTayTiV high-entropy alloy and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Mechanical, corrosion, and wear properties of biomedical Ti–Zr–Nb–Ta–Mo high entropy alloys;Nengbin Hua;《Journal of Alloys and Compounds》;第861卷;1-18 * |
| 粉末冶金高熵合金研究进展;刘咏;《中国有色金属学报》;第29卷(第9期);2155-2184 * |
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