CN112176220A - High-strength-toughness corrosion-resistant beta-type titanium-zirconium-based alloy and preparation method thereof - Google Patents
High-strength-toughness corrosion-resistant beta-type titanium-zirconium-based alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-strength-toughness corrosion-resistant beta-type titanium-zirconium-based alloy and a preparation method thereof. The alloy is a titanium-zirconium-molybdenum alloy, and the mass ratios of the three elements are respectively as follows: 20% of Zr, 5-20% of Mo and the balance of titanium, wherein impurities are ignored. Compared with the titanium-zirconium alloy, the titanium-zirconium-molybdenum series alloy obtained by the invention has optimized mechanical properties, the yield strength is improved by 500MPa and the plasticity is improved by 20% compared with the titanium-zirconium alloy.
Description
Technical Field
The invention relates to a titanium alloy material and a preparation method thereof, in particular to a high-strength-toughness corrosion-resistant beta-type titanium-zirconium-based alloy and a preparation method thereof.
Background
The titanium and the titanium alloy have wide application range and are spread in various fields of ocean engineering, aerospace, biomedical engineering and the like. Titanium and its alloys have occupied an important position in the biomedical material field due to their excellent biocompatibility, mechanical adaptability, non-magnetism, non-toxicity, workability and corrosion resistance in biological environments, and will continue to be continued and developed.
The medical titanium alloy (Ti-6Al-4V, Ti-Ni-based memory alloy and the like) which is widely used at present has certain problems, such as mismatching of elastic modulus and human skeleton, easily causing stress shielding phenomenon and causing implant loosening or fracture; the elements such as Al, Ni, V and the like can generate toxic and side effects on human bodies. Therefore, the development of a new biomedical titanium alloy with low elastic modulus, good biocompatibility, higher strength, better corrosion performance and shape memory effect becomes a new research direction and choice.
At present, the development trend of a new generation of biomedical titanium alloy is to develop a beta or near-beta phase titanium alloy which is nontoxic and has low elastic modulus, and a novel biomedical titanium alloy with good biocompatibility and biomechanical compatibility is obtained by adding beta phase alloying elements such as Nb, Mo, Ta, Zr, Sn and the like with good biocompatibility into the alloy and controlling a microstructure. In order to improve the development of titanium alloy in the biomedical field, it is very important to develop a high-toughness corrosion-resistant titanium alloy, so how to reduce the elastic modulus while improving the mechanical properties is a big difficulty.
Disclosure of Invention
The invention aims to provide an all-beta-phase high-toughness corrosion-resistant titanium-zirconium-based alloy which does not contain elements generating side effects on human bodies and a preparation method thereof, aiming at the problems in the prior art. On the basis of Ti-20Zr (mass ratio) alloy with good mechanical property, the high-strength corrosion-resistant all-beta-phase titanium alloy is prepared by adding beta stable element molybdenum under proper preparation process parameters. Compared with the titanium-zirconium alloy, the titanium-zirconium-molybdenum series alloy obtained by the invention has optimized mechanical properties, the yield strength is improved by 500MPa and the plasticity is improved by 20% compared with the titanium-zirconium alloy.
The technical scheme of the invention is as follows:
the high-strength-toughness corrosion-resistant beta-type titanium-zirconium-based alloy is a titanium-zirconium-molybdenum alloy, and the mass ratios of the three elements are respectively as follows: 20% of Zr, 5-20% of Mo and the balance of titanium, wherein impurities are ignored.
The preparation method of the all-beta high-strength-toughness corrosion-resistant titanium alloy comprises the following steps of:
(1) cleaning pure zirconium, pure titanium and pure molybdenum respectively, and then mixing according to the above proportion;
(2) placing the prepared material in a water-cooled copper crucible of a non-consumable vacuum arc melting furnace, and vacuumizing to 3.0-3.5 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon of 0.03MPa-0.05MPa into the cavity of the electric arc furnace, and then smelting for 5-7 times, wherein the time range of each time is 5-10 minutes, so as to obtain ingot casting alloy; wherein the smelting current is 240-300A/S;
(4) placing the cast ingot into a vacuum tube furnace, and pumping to below 5 × 10-3Argon is filled in the low vacuum state to form an argon atmosphere (the argon purity is 99.99%), the temperature is raised to 950-1050 ℃, the heating rate is 2-5 ℃/min, the temperature is kept for 3-6 hours, and then the titanium alloy is naturally cooled along with the furnace to obtain the all-beta high-strength-toughness corrosion-resistant titanium alloy.
The pure zirconium is industrial grade sponge zirconium, the purity of the pure titanium is 99%, and the purity of the molybdenum sheet is 99.95%.
The invention has the substantive characteristics that:
the invention reduces the content of titanium in a small amount on the premise of not influencing the mechanical property of the titanium-zirconium binary alloy, and adds Mo element to convert the titanium alloy into beta type titanium alloy, so as to obtain the ternary alloy with better mechanical property and corrosion resistance. Compared with Ti-20Zr alloy, the novel molybdenum addition improves the mechanical property, reduces the elastic modulus and improves the corrosion resistance of the alloy. In the preparation method, the titanium-zirconium-based alloy is prepared by multiple times of smelting and alloying, and the beta phase is kept to the room temperature through an annealing process, so that the full beta-phase alloy is obtained.
The invention has the beneficial effects that:
1. compared with the titanium-zirconium alloy, the mechanical property of the prepared titanium-zirconium-molybdenum series alloy is optimized, the yield strength is improved by 500MPa and the plasticity is improved by 20 percent compared with the titanium-zirconium alloy;
2. by adding Mo element, the microstructure of the alloy is easy to regulate and control, and meanwhile, the corrosion resistance of the alloy can be improved by the Mo element. On the other hand, Mo is a beta-transformation element of the titanium alloy and can play a role in refining grains and homogenizing tissues, so that the addition of the element can improve the mechanical property of the alloy and reduce the elastic modulus, the elastic modulus is reduced by 70MPa after the molybdenum element is added to form an all-beta phase, and the element can be better matched with human bones;
3. the invention strictly controls the content of various elements, and improves the corrosion resistance and the obdurability of the titanium alloy through alloying action; in the invention, Ti and Zr are easy to generate infinite solid solution, and the oxide formed by the zirconium element in a corrosive medium can effectively improve the structural performance of a passive film of the titanium alloy and obviously improve the corrosion resistance of the titanium alloy. And secondly, the thickness and compactness of the passivation film are obviously improved by molybdenum, so that the corrosion resistance can be obviously improved. In a hydrochloric acid soaking experiment, compared with a titanium-zirconium alloy, the all-beta-phase titanium-zirconium-molybdenum alloy added with molybdenum element shows stronger corrosion resistance (no obvious weight loss is found after soaking for 10 days);
4. in the titanium-zirconium-molybdenum series alloy, the titanium-zirconium-molybdenum element is proved to be non-toxic and harmless to a human body through tests, and the beta type titanium alloy has the characteristics of better matching with human bones and stability under long-time service conditions;
5. the titanium-zirconium-molybdenum series alloy has low production cost and simple processing process.
Drawings
FIG. 1 is a metallographic optical micrograph of a Ti-20Zr alloy obtained in example 1;
FIG. 2 is a metallographic optical micrograph of the Ti-20Zr alloy prepared in example 1 after immersion test;
FIG. 3 is a metallographic optical micrograph of a Ti-20Zr-5Mo alloy obtained in example 1;
FIG. 4 is a metallographic optical micrograph of the Ti-20Zr-5Mo alloy prepared in example 1 after immersion test;
FIG. 5 is a metallographic optical micrograph of a Ti-20Zr-10Mo alloy obtained in example 2;
FIG. 6 is a metallographic optical micrograph of the Ti-20Zr-10Mo alloy prepared in example 2 after immersion test;
FIG. 7 is a metallographic optical micrograph of Ti-20Zr-15Mo gold obtained in example 3;
FIG. 8 is a metallographic optical micrograph of the Ti-20Zr-15Mo alloy prepared in example 3 after immersion test;
FIG. 9 is a metallographic optical micrograph of a Ti-20Zr-20Mo alloy obtained in example 4;
FIG. 10 is a metallographic optical micrograph of the Ti-20Zr-20Mo alloy obtained in example 4 after immersion test;
FIG. 11 is an XRD pattern of a titanium-zirconium-molybdenum alloy prepared in practice;
FIG. 12 is a graph of the true stress-strain curve of the titanium-zirconium-molybdenum alloy produced in the practice.
FIG. 13 is a graph of the corrosion resistance soaking experiment weight loss of the prepared titanium-zirconium-molybdenum alloy
Detailed Description
The embodiments of the present invention are described in further detail below to make the technology, the object of the invention, and the advantages of the invention more apparent.
Example 1
(1) 4g of industrial grade sponge zirconium with the purity of 99.4 percent and 16g of titanium wire with the purity of 99 percent are respectively immersed in absolute ethyl alcohol, and are mixed according to the mass ratio of Ti to 20Zr after ultrasonic cleaning;
(2) placing the prepared material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, and vacuumizing to 3 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon of 0.04MPa into a cavity of an electric arc furnace as protective gas, smelting under the current of 240A/S, and in order to ensure that an ingot with uniform components is finally obtained, carrying out reverse treatment on the ingot after each smelting is finished, and repeatedly smelting and overturning the ingot for five times;
(4) after the smelting, the ingot is annealed to obtain the titanium-zirconium alloy with uniform structure. In the present invention, the annealing treatment is preferably performed in the following manner: heating the ingot to 1000 ℃ in a low vacuum state along with the furnace, preserving heat for 5 hours, and then cooling along with the furnace;
(5) cutting the annealed sample by a wire cut electric discharge machine (fast wire DK7745) to obtain a sample with the size of
The cylinder of (a) is flattened and polished to be scratch-free by using sandpaper, and a compression test is performed, which can reflect mechanical properties such as elastic modulus and plasticity of the test piece. The experimental result shows that the yield strength of the titanium-zirconium binary alloy is 503.2Mpa, the ultimate compressive strength is 1350Mpa, the deformation reaches 30 percent and the titanium-zirconium binary alloy is fractured, and the titanium-zirconium binary alloy has better compressive capacity compared with the titanium-zirconium binary alloy with other components.
(6) Slicing the annealed sample by using a wire-cut electric discharge machine to obtain a sample with the thickness of 2mm, grinding and polishing the sample by using abrasive paper until the surface of the sample has no obvious scratch, ultrasonically cleaning the sample by using absolute ethyl alcohol, and then using a Keller corrosive agent (the reagent ratio is H)2O：HNO3: HCl: HF is 95: 2.5: 1.5: 1 unit: ml) was subjected to metallographic etching to obtain FIG. 1;
(7) the phase of the material can be analyzed by immersing the corroded sample in absolute ethyl alcohol for ultrasonic cleaning and then carrying out X-ray diffraction analysis (XRD), wherein the phase of the alloy sample is analyzed by a German Bruker D8X ray diffractometer, and a Cu target K is adoptedαIrradiating, wherein lambda is 0.15406nm, the scanning range is 10-90 degrees, the scanning speed is 6 degrees/min to obtain a graph 11, the graphs obtained by the embodiments 2, 3 and 4 under the same scanning parameters are also the graph 11, and the details are not repeated in the embodiments 2, 3 and 4;
(8) cutting the ingot after smelting and cooling into cube blocks with the size of 10mm multiplied by 10mm by using an electric spark wire cutting machine tool, using sand paper to grind and polish until no scratch exists, recording the original mass of a sample, then immersing the cube blocks into a pre-prepared HCl solution with the concentration of 5mol/L, taking out the sample every 48 hours, cleaning the sample with absolute ethyl alcohol, completely drying the sample, weighing the sample, continuously immersing the sample into a newly-prepared HCl solution with the same concentration, and the steps are sharedThe procedure was repeated five times, and the value of each weighing was recorded to calculate the corrosion rate of the sample according to the formula, where is the corrosion rate of the sample, W1 is the mass of the sample before corrosion, W2 is the mass of the sample after corrosion, t is the corrosion time, and a is the total area of the sample immersed in the solution. Experimental results show that the weight of the alloy after 144 hours is almost free of loss within the error range allowed by the balance, and the corrosion rate is 15mg/cm2。
Metallographic structure observation is carried out on the titanium-zirconium alloy obtained in the embodiment, and the result is shown in fig. 1, wherein the microstructure of the alloy consists of a basket-shaped alpha phase, and the basket structure is relatively wide; the alloy after the soaking test was observed for structure enlargement, and as a result, a clear black corrosion mark appeared on the surface of the alloy as shown in fig. 2.
Example 2
(1) 4g of industrial grade sponge zirconium with the purity of 99.4%, 15g of titanium wire with the purity of 99% and 1g of electrolytic molybdenum sheet with the purity of 99.95% are respectively immersed in absolute ethyl alcohol, and are mixed according to the mass ratio of Ti-20Zr-5Mo after ultrasonic cleaning;
(2) placing the prepared material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, and vacuumizing to 3 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon with the purity of 99.99% and the pressure of 0.04MPa into a cavity of an electric arc furnace as protective gas, smelting under the current of 240A/S, and in order to ensure that an ingot with uniform components is finally obtained, performing reverse treatment on the ingot after each smelting is finished, and repeatedly smelting and turning the ingot for five times;
(4) after the smelting, the ingot is annealed to obtain the titanium-zirconium alloy with uniform structure. In the present invention, the annealing treatment is preferably performed in the following manner: after being pumped to less than 5 x 10-3Argon is filled in the furnace under a low vacuum state to form an argon atmosphere, the ingot is heated to 1000 ℃ along with the furnace, and then is kept warm for 5 hours and is cooled along with the furnace;
(5) the annealed sample was cut into a size of
The cylinder of (a) is carefully smoothed and polished with sandpaper to be scratch-free, and a compression test is performed, which reflects the mechanical properties of the test piece, such as modulus of elasticity and plasticity. The experimental result shows that the yield strength of the titanium-zirconium-molybdenum alloy is 689Mpa, the ultimate compressive strength is 1500Mpa, and the titanium-zirconium-molybdenum alloy is fractured when the deformation reaches 35 percent, and has good toughness and compressive capacity compared with the titanium-zirconium binary alloy.
(6) Slicing the annealed sample by using a wire-cut electric discharge machine to obtain a sample with the thickness of 2mm, grinding and polishing the sample by using abrasive paper until the surface of the sample has no obvious scratch, ultrasonically cleaning the sample by using absolute ethyl alcohol, and then using a Keller corrosive agent (the reagent ratio is H)2O：HNO3: HCl: HF is 95: 2.5: 1.5: 1 unit: ml) was subjected to metallographic etching to obtain FIG. 3;
(7) cutting the ingot after smelting and cooling into cube blocks with the size of 10mm multiplied by 10mm by using an electric spark wire cutting machine, carefully grinding and polishing the cube blocks by using sand paper until no scratch is formed, recording the original mass of the sample, then immersing the cube blocks into a pre-prepared HCl solution with the concentration of 5mol/L, taking out the sample every 48 hours, washing the sample by using absolute ethyl alcohol, completely drying the sample, weighing the sample, continuously immersing the sample into a new HCl solution with the same concentration, repeating the steps for five times, recording the numerical value of each weighing, calculating the corrosion rate of the sample according to a formula, wherein the corrosion rate of the sample is represented by the formula, W1 is the mass before corrosion of the sample, W2 is the mass after corrosion of the sample, t is the corrosion time, and A is the total area of the sample immersed in the solution. Experimental results show that the weight of the alloy after 144 hours has the corrosion rate of 43mg/cm within the error range allowed by the balance2And exhibits poor corrosion resistance.
Metallographic structure observation is carried out on the titanium-zirconium-chromium alloy obtained in the embodiment, and the result is shown in fig. 3, wherein the microstructure of the alloy consists of needle-shaped structures which are orderly arranged, and the basket structure becomes thin; the alloy after the soaking test was subjected to a structure magnification observation, and the result is shown in fig. 4, in which the corrosion was accelerated by the thinning of the strip compared to the Ti-20Zr alloy.
Example 3
(1) 4g of industrial grade sponge zirconium with the purity of 99.4%, 14g of titanium wire with the purity of 99% and 2g of electrolytic molybdenum sheet with the purity of 99.95% are respectively immersed in absolute ethyl alcohol, and are mixed according to the mass ratio of Ti-20Zr-10Mo after ultrasonic cleaning;
(2) placing the prepared material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, and vacuumizing to 3 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon with the purity of 99.999 percent and the pressure of 0.04MPa into a cavity of an electric arc furnace as protective gas, smelting under the current of 240A/S, and in order to ensure that an ingot with uniform components is finally obtained, carrying out reverse treatment on the ingot after each smelting is finished, and repeatedly smelting and turning the ingot for five times;
(4) after the smelting, the ingot is annealed to obtain the titanium-zirconium alloy with uniform structure. In the present invention, the annealing treatment is preferably performed in the following manner: after being pumped to less than 5 x 10-3Argon is filled in the furnace under a low vacuum state to form an argon atmosphere, the ingot is heated to 1000 ℃ along with the furnace, and then is kept warm for 5 hours and is cooled along with the furnace;
(5) the annealed sample was cut into a size of
The cylinder of (a) is carefully smoothed and polished with sandpaper to be scratch-free, and a compression test is performed, which reflects the mechanical properties of the test piece, such as modulus of elasticity and plasticity. The experimental result shows that the yield strength of the titanium-zirconium-molybdenum alloy is 1247.2Mpa, the ultimate compressive strength is 1500Mpa, and the titanium-zirconium-molybdenum alloy is fractured when the deformation reaches 40%, and has good toughness and compressive capacity compared with the titanium-zirconium binary alloy.
(6) Slicing the annealed sample by using a wire-cut electric discharge machine to obtain a sample with the thickness of 2mm, grinding and polishing the sample by using abrasive paper until the surface of the sample has no obvious scratch, ultrasonically cleaning the sample by using absolute ethyl alcohol, and then using a Keller corrosive agent (the reagent ratio is H)2O：HNO3: HCl: HF is 95: 2.5: 1.5: 1 unit: ml) is subjected to metallographic etchingFIG. 3 is obtained;
(7) cutting the ingot after smelting and cooling into cube blocks with the size of 10mm multiplied by 10mm by using an electric spark wire cutting machine, carefully grinding and polishing the cube blocks by using sand paper until no scratch is formed, recording the original mass of the sample, then immersing the cube blocks into a pre-prepared HCl solution with the concentration of 5mol/L, taking out the sample every 48 hours, washing the sample by using absolute ethyl alcohol, completely drying the sample, weighing the sample, continuously immersing the sample into a new HCl solution with the same concentration, repeating the steps for five times, recording the numerical value of each weighing, calculating the corrosion rate of the sample according to a formula, wherein the corrosion rate of the sample is represented by the formula, W1 is the mass before corrosion of the sample, W2 is the mass after corrosion of the sample, t is the corrosion time, and A is the total area of the sample immersed in the solution. Experimental results show that the weight of the alloy after 144 hours has the corrosion rate of 5mg/cm within the error range allowed by the balance2And exhibits poor corrosion resistance.
Metallographic structure observation is carried out on the titanium-zirconium-chromium alloy obtained in the embodiment, and the result is shown in fig. 5, wherein the microstructure of the alloy consists of needle-shaped structures which are orderly arranged, and the basket structure becomes thin; as a result of structure enlargement observation of the alloy after the soaking test, as shown in fig. 6, the alloy of this composition was a dual-phase structure, and the lath at the grain boundary and the trace of α -phase corrosion within the grain boundary were significant, and weight loss was also caused thereby.
Example 4
(1) 4g of industrial grade sponge zirconium with the purity of 99.4 percent, 13g of titanium wire with the purity of 99 percent and 3g of molybdenum sheet with the purity of 99.95 percent are respectively immersed in absolute ethyl alcohol, and are mixed according to the alloy atomic ratio Ti-20Zr-15Mo after ultrasonic cleaning;
(2) placing the prepared material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, and vacuumizing to 3 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon with the purity of 99.999 percent and the pressure of 0.04MPa into a cavity of an electric arc furnace as protective gas, smelting under the current of 240A/S, and in order to ensure that an ingot with uniform components is finally obtained, carrying out reverse treatment on the ingot after each smelting is finished, and repeatedly smelting and turning the ingot for five times;
(4) after the smelting, the ingot is annealed to obtain the titanium-zirconium alloy with uniform structure. In the present invention, the annealing treatment is preferably performed in the following manner: after being pumped to less than 5 x 10-3Argon is filled in the furnace under a low vacuum state to form an argon atmosphere, the ingot is heated to 1000 ℃ along with the furnace, and then is kept warm for 5 hours and is cooled along with the furnace;
(5) the annealed sample was cut into a size of
The cylinder of (a) is flattened and polished to be scratch-free by using sandpaper, and a compression test is performed, which can reflect mechanical properties such as elastic modulus and plasticity of the test piece. The experimental result shows that the yield strength of the titanium-zirconium-molybdenum alloy is 750Mpa, the ultimate compressive strength is 1600Mpa, the deformation can reach 40%, and the titanium-zirconium-molybdenum alloy has good toughness compared with the Ti-20Zr alloy.
(6) Slicing the annealed sample by using a wire-cut electric discharge machine to obtain a sample with the thickness of 2mm, grinding and polishing the sample by using abrasive paper until the surface of the sample has no obvious scratch, ultrasonically cleaning the sample by using absolute ethyl alcohol, and then using a Keller corrosive agent (the reagent ratio is H)2O：HNO3: HCl: HF is 95: 2.5: 1.5: 1 unit: ml) was subjected to metallographic etching to obtain FIG. 7;
(7) cutting the ingot after smelting and cooling into cube blocks with the size of 10mm multiplied by 10mm by using an electric spark wire cutting machine, using sand paper to grind and polish until no scratch is formed, recording the original mass of the sample, then immersing the cube blocks into a pre-prepared HCl solution with the concentration of 5mol/L, taking out the sample every 48 hours, washing the sample with absolute ethyl alcohol, completely drying the sample, weighing the sample, continuously immersing the sample into a newly-prepared HCl solution with the same concentration, repeating the steps for five times, recording the numerical value of each weighing, calculating the corrosion rate of the sample according to a formula, wherein the corrosion rate of the sample is represented by the formula, W1 represents the mass before corrosion of the sample, W2 represents the mass after corrosion of the sample, t represents the corrosion time, and A represents the total area of the sample immersed in the solution. Results of the experiment the weight of the alloy after 144 hours was determined to beThe corrosion rate is 0mg/cm within the allowable error range of the balance2And the corrosion resistance is better.
Metallographic structure observation is carried out on the titanium-zirconium-chromium alloy obtained in the embodiment, and the result is shown in fig. 7, wherein the microstructure of the alloy consists of beta grains, and acicular alpha phase is precipitated on grain boundaries; the alloy after the soaking test was subjected to structure magnification observation, and the result is shown in fig. 8, in which the corrosion area was significantly reduced compared to the Ti-20Zr alloy.
Example 5
(1) Respectively soaking 12g of industrial grade sponge zirconium with the purity of 99.4%, 4g of titanium wire with the purity of 99% and 4g of molybdenum sheet with the purity of 99.95% in absolute ethyl alcohol, and preparing materials according to the alloy atomic ratio Ti-20Zr-20Mo after ultrasonic cleaning;
(2) placing the prepared material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, and vacuumizing to 3 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon with the purity of 99.99% and the pressure of 0.04MPa into a cavity of an electric arc furnace as protective gas, smelting under the current of 240A/S, and in order to ensure that an ingot with uniform components is finally obtained, performing reverse treatment on the ingot after each smelting is finished, and repeatedly smelting and turning the ingot for five times;
(4) after the smelting, the ingot is annealed to obtain the titanium-zirconium alloy with uniform structure. In the present invention, the annealing treatment is preferably performed in the following manner: after being pumped to less than 5 x 10-3Argon is filled in the furnace under a low vacuum state to form an argon atmosphere, the ingot is heated to 1000 ℃ along with the furnace, and then is kept warm for 5 hours and is cooled along with the furnace;
(5) the annealed sample was cut into a size of
The cylinder of (a) is flattened and polished to be scratch-free by using sandpaper, and a compression test is performed, which can reflect mechanical properties such as elastic modulus and plasticity of the test piece. The experimental result shows that the yield strength of the titanium-zirconium-molybdenum alloy is 705Mpa, the ultimate compressive strength is 1552.3Mpa, and the deformation can reach 35 percentCompared with Ti-20Zr alloy, the alloy has good toughness.
(5) Cutting the ingot after smelting and cooling into cube blocks with the size of 10mm multiplied by 10mm by using an electric spark wire cutting machine, carefully grinding and polishing the cube blocks by using sand paper until no scratch is formed, recording the original mass of the sample, then immersing the cube blocks into a pre-prepared HCl solution with the concentration of 5mol/L, taking out the sample every 48 hours, washing the sample by using absolute ethyl alcohol, completely drying the sample, weighing the sample, continuously immersing the sample into a new HCl solution with the same concentration, repeating the steps for five times, recording the numerical value of each weighing, calculating the corrosion rate of the sample according to a formula, wherein the corrosion rate of the sample is represented by the formula, W1 is the mass before corrosion of the sample, W2 is the mass after corrosion of the sample, t is the corrosion time, and A is the total area of the sample immersed in the solution. The experimental result shows that the weight of the alloy is not lost within the error range allowed by the balance after 144 hours, the corrosion rate is zero, and the alloy shows better corrosion resistance.
Metallographic structure observation is carried out on the titanium-zirconium-molybdenum alloy obtained in the embodiment, and the result is shown in fig. 9, wherein the microstructure of the alloy consists of beta grains, and no low-temperature alpha phase is observed; the alloy after the soaking test was subjected to structure enlargement observation, and the result is shown in fig. 10, in which the corrosion area was significantly reduced compared to the Ti-20Zr alloy.
FIG. 11 is the XRD result of the alloy obtained, and it can be seen that the addition of Mo element to the Ti-Zr alloy makes the original alpha-phase Ti-Zr alloy transform to beta-phase;
FIG. 12 is a graph of the true stress-strain curve of a compression test performed on a resulting alloy, wherein the compressive plasticity of the resulting alloy is improved during the transformation of the zirconium-titanium alloy to the all-beta phase by adding Mo to the zirconium-titanium alloy, and the strain is improved by 20% compared to the alpha phase of the zirconium-titanium alloy;
fig. 13 is a result of soaking the prepared alloy in hydrochloric acid with a concentration of 5mol/L, and it can be clearly seen that the soaking weight loss is substantially 0 after molybdenum element is added into the titanium zirconium alloy to form an all-beta phase alloy, so that the corrosion resistance of the alloy can be improved by adding molybdenum element into the titanium zirconium alloy.
Table 1 shows the mechanical properties in corrosion of all examples of the inventionResults of the measurements of the properties, which were carried out on an Instron5982 testing machine at a strain rate of 5X 10-4s-1Compression test of (2). To prevent non-uniformity of stress, the samples were each a cylinder with a diameter of 4mm and a height of 8mm, and each set was tested in an average of three times to reduce errors.
The results show that the yield strength and ultimate compression strength of examples 2, 3 and 4 are higher than those of example 1, and exhibit more excellent toughness, while the elastic modulus of examples 2, 3 and 4 is lower than that of example 1. Therefore, according to the experimental results in the table and by combining the metallographic structure diagram of each example with the enlarged structure diagram of the structure after the soaking experiment, the strength, toughness and corrosion resistance of the novel Ti-Zr-Mo alloy provided by the invention are obviously improved.
Table 1: mechanical property test results of examples 1, 2, 3, 4 and 5 of the present invention
The present invention is described by way of example, but not by way of limitation, and reference to the description of the invention is made to the other variations of the disclosed examples which are readily guessable by researchers in the field of titanium and zirconium alloys and which fall within the limits of the claims of the present invention.
The invention is not the best known technology.
Claims (4)
1. The high-strength-toughness corrosion-resistant beta-type titanium-zirconium-based alloy is characterized in that the alloy is a titanium-zirconium-molybdenum alloy, and the mass ratios of the three elements are respectively as follows: 20% of Zr, 5-20% of Mo and the balance of titanium.
2. The preparation method of the all-beta high-toughness corrosion-resistant titanium alloy according to claim 1, characterized by comprising the following steps:
(1) cleaning pure zirconium, pure titanium and pure molybdenum respectively, and then mixing according to the above proportion;
(2) placing the prepared material in non-consumable vacuumIn a water-cooled copper crucible of an arc melting furnace, high vacuum is pumped to 3.0-3.5 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon of 0.03MPa-0.05MPa into the cavity of the electric arc furnace, and then smelting for 5-7 times, wherein the time range of each time is 5-10 minutes, so as to obtain ingot casting alloy; wherein the smelting current is 240-300A/S;
(4) placing the cast ingot into a vacuum tube furnace, and vacuumizing to less than 5 x 10-3And (3) filling argon to form an argon atmosphere in a low vacuum state, heating to 950-1050 ℃, wherein the heating rate is 2-5 ℃/min, preserving heat for 3-6 hours, and naturally cooling along with the furnace to obtain the all-beta high-strength-toughness corrosion-resistant titanium alloy.
3. The method for preparing the all-beta high-toughness corrosion-resistant titanium alloy according to claim 2, wherein the pure zirconium is industrial grade sponge zirconium, the purity of the pure titanium is 99%, and the purity of the molybdenum sheet is 99.95%.
4. The method for preparing the full-beta high-toughness corrosion-resistant titanium alloy according to claim 2, wherein the purity of argon gas is 99.99%.
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| TWI755263B (en) * | 2021-01-27 | 2022-02-11 | 國立清華大學 | High strength and low modulus alloy and use thereof |
| CN114318057A (en) * | 2021-11-10 | 2022-04-12 | 河北工业大学 | High-strength-toughness corrosion-resistant zirconium-cobalt binary alloy and preparation method thereof |
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