CN112662903B - Preparation method of high-strength Zr-Ti-based alloy - Google Patents
Preparation method of high-strength Zr-Ti-based alloy Download PDFInfo
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Abstract
The invention provides a preparation method of a high-strength Zr-Ti-based alloy, belonging to the technical field of powder metallurgy. The preparation method provided by the invention comprises the following steps: mixing Zr powder and Ti powder to obtain mixed powder; carrying out cold isostatic pressing on the mixed powder to obtain a molded blank; and sintering the formed blank to obtain the Zr-Ti-based alloy. The invention reduces the porosity among the mixed powder through cold isostatic pressing, and improves the density of the molded green body; the compactness and the structure uniformity of the Zr-Ti-based alloy are further improved by controlling the sintering temperature, the sintering time and the sintering environment in different sintering stages and applying pressure in a third sintering stage.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a preparation method of a high-strength Zr-Ti-based alloy.
Background
The Zr-Ti-based alloy has the advantages of good corrosion resistance, heat resistance, nuclear performance and biocompatibility, and shows good application prospect in the fields of structural members of aerospace, biomedical and sports equipment and the like.
The Zr-Ti-based alloy is usually prepared by adopting an ingot metallurgy method, and the problems of component segregation, tissue shrinkage porosity, shrinkage cavity and the like of the prepared Zr-Ti-based alloy exist in the method, so that the density of the Zr-Ti-based alloy is poor, generally 95-97%, and the tissue defects need to be eliminated by subsequent processes such as heat treatment, thermal deformation and the like.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a high-strength Zr-Ti-based alloy, and the Zr-Ti-based alloy prepared by the preparation method provided by the invention has uniform structure and high density.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a high-strength Zr-Ti-based alloy, which comprises the following steps:
mixing Zr powder and Ti powder to obtain mixed powder;
carrying out cold isostatic pressing on the mixed powder to obtain a molded blank; the pressure of the cold isostatic pressing is 200-400 MPa, and the pressure maintaining time is 15-60 min;
sintering the molded blank to obtain a Zr-Ti-based alloy;
the sintering comprises a first sintering, a second sintering and a third sintering which are sequentially carried out:
the temperature of the first sintering is 300-500 ℃, the heat preservation time is 1-5 h, the temperature rising rate of rising from room temperature to the temperature of the first sintering is 5-10 ℃/min, and the first sintering is carried out in a hydrogen atmosphere; the temperature of the second sintering is 800-1000 ℃, the heat preservation time is 1-2 h, the heating rate from the temperature of the first sintering to the temperature of the second sintering is 1-2 ℃/min, and the second sintering is carried out under the vacuum condition; the temperature of the third sintering is 1300-1500 ℃, the heat preservation time is 1-4 h, and the pressure is 1-10 MPa; the third sintering is carried out in an argon atmosphere; the heating rate from the temperature of the second sintering to the temperature of the third sintering is 3-5 ℃/min, and the argon partial pressure is 10-50 mbar.
Preferably, the mixing is wet mixing, the medium of the wet mixing is absolute ethyl alcohol, and the volume ratio of the total volume of the mixed powder to the absolute ethyl alcohol is 1:2 to 5.
Preferably, the rotating speed of the mixing is 100-300 r/min, and the time is 3-10 h.
Preferably, the mixed powder comprises a dispersant, and the mass of the dispersant is 0.2-0.6 wt.% of the total mass of the Zr powder and the Ti powder.
Preferably, the mass ratio of the Zr powder to the Ti powder is 1: 99-99: 1.
Preferably, the particle diameters of the Zr powder and the Ti powder are independently 5-45 μm.
Preferably, the mixed powder further comprises a trace metal powder, wherein the trace metal powder comprises one or more of Cr powder, V powder, W powder, Cu powder, Co powder, Mo powder, Ni powder and Fe powder.
Preferably, the mass of the trace metal powder is 0.1 to 5.0 wt.% of the total mass of the Zr powder and the Ti powder.
Preferably, before the cold isostatic pressing, the method further comprises the step of performing vacuum drying treatment on the mixed powder, wherein the temperature of the vacuum drying treatment is 40-80 ℃.
Preferably, the sintered product further comprises: cooling the sintered product, wherein the cooling comprises a first cooling and a second cooling which are sequentially carried out: the temperature of the first cooling is 800-500 ℃; and the cooling rate from the third sintering temperature to the first cooling temperature is 1-3 ℃/min.
The invention provides a preparation method of a high-strength Zr-Ti-based alloy, which comprises the following steps: mixing Zr powder and Ti powder to obtain mixed powder; carrying out cold isostatic pressing on the mixed powder to obtain a molded blank; the pressure of the cold isostatic pressing is 200-400 MPa, and the pressure maintaining time is 15-60 min; sintering the molded blank to obtain a Zr-Ti-based alloy; the sintering comprises a first sintering, a second sintering and a third sintering which are sequentially carried out: the temperature of the first sintering is 300-500 ℃, the heat preservation time is 1-5 h, the temperature rising rate of rising from room temperature to the temperature of the first sintering is 5-10 ℃/min, and the first sintering is carried out in a hydrogen atmosphere; the temperature of the second sintering is 800-1000 ℃, the heat preservation time is 1-2 h, the heating rate from the temperature of the first sintering to the temperature of the second sintering is 1-2 ℃/min, and the second sintering is carried out under the vacuum condition; the temperature of the third sintering is 1300-1500 ℃, the heat preservation time is 1-4 h, and the pressure is 1-10 MPa; the third sintering is carried out in an argon atmosphere; the heating rate from the temperature of the second sintering to the temperature of the third sintering is 3-5 ℃/min, and the argon partial pressure is 10-50 mbar. The invention reduces the porosity among the mixed powder through cold isostatic pressing, and improves the density of the molded green body; the compactness and the structure uniformity of the Zr-Ti-based alloy are further improved by controlling the sintering temperature, the sintering time and the sintering environment in different sintering stages and applying pressure in a third sintering stage. The embodiment result shows that the Zr-Ti-based alloy prepared by the invention has high density, the density is more than 99 percent, and the structure uniformity is good.
The preparation method provided by the invention has the advantages of simple process and low production cost, can be used for preparing the Zr-Ti-based alloy with uniform structure, can flexibly regulate and control the element content, phase composition/distribution, structure morphology and the like of the Zr-Ti-based alloy, can avoid the introduction of impurity oxygen element, realizes the regulation and control of density and mechanical properties, can be used for preparing the Zr-Ti-based alloy with high density and low cost, can realize batch production, does not need heat treatment, thermal deformation and other processes compared with the traditional ingot metallurgy method, and can meet the requirements of industrial production, and meanwhile, the Zr-Ti-based alloy prepared by the invention has the characteristic of high strength.
Drawings
FIGS. 1 to 5 are photographs showing microstructures of the Zr-Ti-based alloys prepared in examples 1 to 5, respectively;
FIG. 6 is a mechanical property curve diagram of the Zr-Ti-based alloy prepared in examples 1-5 under the quasi-static compressive loading condition;
FIG. 7 is a graph showing the densification profiles of Zr-Ti-based alloys prepared in examples 1 to 5 and comparative examples 1 to 5.
Detailed Description
The invention provides a preparation method of a Zr-Ti-based alloy, which comprises the following steps:
mixing Zr powder and Ti powder to obtain mixed powder;
carrying out cold isostatic pressing on the mixed powder to obtain a molded blank;
and sintering the formed blank to obtain the Zr-Ti-based alloy.
In the invention, Zr powder and Ti powder are mixed to obtain mixed powder.
In the present invention, the mass ratio of the Zr powder to the Ti powder is preferably 1:99 to 99:1, more preferably 80:1 to 1:80, and further preferably 60:1 to 1: 60. In the present invention, the particle diameters of the Zr powder and the Ti powder are independently preferably 5 to 45 μm, and more preferably 10 to 30 μm.
In the present invention, the mixed powder preferably further includes a trace amount of metal powder. In the present invention, the trace metal powder preferably includes one or more of Cr powder, V powder, W powder, Cu powder, Co powder, Mo powder, Ni powder, and Fe powder. In the present invention, the mass of the trace metal powder is preferably 0.1 to 5.0 wt.%, more preferably 0.5 to 4.0 wt.%, and still more preferably 1 to 3.0 wt.% of the total mass of the Zr powder and the Ti powder. In the present invention, the particle size of the trace metal powder is preferably 10 to 45 μm.
In the present invention, the mixed powder preferably further includes a dispersant, and the mass of the dispersant is preferably 0.2 to 0.6 wt.%, more preferably 0.3 to 0.5 wt.%, of the total mass of the Zr powder and the Ti powder; the dispersant preferably comprises one or more of tween-80, PEG-2000 and PVA. According to the invention, the dispersant is added in the mixing process to reduce the occurrence of powder agglomeration and improve the uniformity of powder mixing.
In the invention, the mixing mode is preferably wet mixing, the wet mixing mode is preferably ball milling, and the medium for ball milling is preferably absolute ethyl alcohol; when the mixed powder is preferably a mixture of Zr powder and Ti powder, the volume ratio of the total volume of the mixed powder to the anhydrous ethanol is preferably 1: 2; when the mixed powder is preferably a mixture of Zr powder, Ti powder and trace metal powder, the volume ratio of the total volume of the mixed powder to the anhydrous ethanol is preferably 1: 1; the rotation speed of the ball milling is preferably 100-300 r/min, and more preferably 150-250 r/min; the ball milling time is preferably 5-20 h, and more preferably 10-15 h; the ball material ratio is preferably 2-10: 1; the material of the ball milling tank and the ball milling ball is preferably 304 stainless steel or hard alloy; the diameter of the grinding ball is preferably 5-10 mm. In the present invention, the wet milling is preferably carried out in a planetary ball mill. In the present invention, the wet grinding is also preferably carried out in an inclined ball mill, a horizontal stirrer, a V-blender, a double cone blender or a three-dimensional blender. In the invention, when the wet grinding is preferably carried out in an inclined ball mill or a horizontal stirrer, the time for the wet grinding is preferably 10-20 h, and more preferably 13-17 h; the rotation speed of the wet grinding is preferably 50-100 r/min, and more preferably 60-80 r/min; when the wet grinding is preferably performed on a V-shaped mixer, a double-cone mixer or a three-dimensional mixer, the wet grinding time is preferably 20-48 h, and more preferably 24-36 h; the rotation speed of the wet grinding is preferably 10-30 r/min, and more preferably 15-25 r/min.
After the mixing is finished, the mixed product is preferably dried to obtain the mixed powder. In the invention, the drying treatment is preferably vacuum drying, and the temperature of the drying treatment is preferably 40-80 ℃, and more preferably 45-60 ℃; the drying time is preferably 2-10 h; the vacuum degree of the vacuum drying is preferably 101～103Pa. The invention effectively avoids the introduction of oxygen by combining the wet mixing ball milling process and the vacuum drying.
After the mixed powder is obtained, the mixed powder is subjected to cold isostatic pressing to obtain a molded blank.
In the invention, the pressure of the cold isostatic pressing is 200-400 MPa, preferably 250-350 MPa; the pressure maintaining time of the cold isostatic pressing is 15-60 min, and preferably 20-50 min. In the present invention, it is preferable that the mixed powder is charged into a rubber film and cold isostatic pressing is performed by applying an equal pressure in each direction by an oil pump in a closed environment. In the invention, the pressure and the pressure maintaining time of the cold isostatic pressing are beneficial to reducing the porosity among the powder, thereby improving the density of the formed green body.
After obtaining the molded blank, sintering the molded blank to obtain the Zr-Ti-based alloy.
In the present invention, the sintering includes a first sintering, a second sintering, and a third sintering performed in this order: the temperature of the first sintering is 300-500 ℃, and preferably 350-450 ℃; the heat preservation time of the first sintering is preferably 1-5 h, and preferably 2-4 h; the temperature rise rate from the room temperature to the first sintering temperature is 5-10 ℃/min, preferably 7-9 ℃/min; the first sintering is carried out in a hydrogen atmosphere to remove the dispersant introduced in the mixing process and oxygen in other adsorbed gases, so as to avoid the oxidation of the alloy and further improve the compactness of the alloy;
in the invention, the temperature of the second sintering is 800-1000 ℃, preferably 850-950 ℃; the heat preservation time of the second sintering is 1-2 h; the heating rate from the first sintering temperature to the second sintering temperature is 1-2 ℃/min; the second sintering is carried out under vacuum condition to remove residual H in the first sintering2；
In the invention, the temperature of the third sintering is 1300-1500 ℃, and preferably 1350-1450 ℃; the heat preservation time of the third sintering is 1-4 h; the pressure of the third sintering is 1-10 MPa, preferably 3-7 MPa; the third sintering is carried out in argon atmosphere, and preferably, argon is introduced when the temperature of the second sintering is raised; the temperature rising rate from the second sintering temperature to the third sintering temperature is 3-5 ℃/min; and heating from the temperature of the second sintering to the argon partial pressure of the third sintering is 10-50 mbar, so as to prevent Ti or Zr element from volatilizing, avoid the phenomenon that the material design component is inaccurate due to volatilization of the element, and further prevent the furnace body from being polluted.
According to the invention, by controlling the sintering temperature and time of different sintering stages, the full diffusion between Zr and Ti elements is facilitated, so that the structure uniformity and the density of the Zr-Ti-based alloy are effectively improved; by controlling the sintering environments of different sintering stages, the oxygen content in the Zr-Ti-based alloy is effectively controlled, so that the strength and the plasticity of the Zr-Ti-based alloy are improved; by applying pressure in the third sintering stage, the compactness of the Zr-Ti based alloy is further improved.
After the sintering is finished, the invention preferably cools the sintered product, and the cooling preferably comprises a first cooling and a second cooling which are sequentially carried out: the temperature of the first cooling is preferably 500-800 ℃; the cooling rate from the third sintering temperature to the first cooling temperature is preferably 1-3 ℃/min, so that the phenomenon that the internal stress is too high due to too high cooling speed to cause the Zr-Ti-based alloy to generate cracks is prevented, and the mechanical property of the Zr-Ti-based alloy is controlled; the second cooling is preferably furnace cooled to room temperature.
The preparation method provided by the invention adopts a process combining cold isostatic pressing and step-by-step sintering to prepare the Zr-Ti-based alloy with high density, good tissue uniformity and good mechanical property, and effectively overcomes the technical defects of poor tissue uniformity and density of the Zr-Ti-based alloy prepared by the traditional smelting and metallurgy method in the prior art.
The following examples are provided to illustrate the preparation of the Zr-Ti based alloy of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing Zr powder with the particle size of 10 microns, Ti powder with the particle size of 10 microns and Co powder with the particle size of 10 microns, wherein the mass ratio of the Zr powder to the Ti powder is 4:1, the addition amount of Co powder accounts for 1 percent of the total mass. Ball-milling the powder on a planetary ball mill, wherein a ball-milling medium is absolute ethyl alcohol, the volume ratio of the total volume of Zr powder and Ti powder to the absolute ethyl alcohol is 1:2, a dispersing agent is Tween-80, the mass of the Tween-80 is 0.2 wt% of the total mass of the Zr powder and the Ti powder, the ball-milling rotating speed is 200r/min, the ball-milling time is 6 hours, the ball-material ratio is 3:1, and the diameter of a milling ball is 10mm, so as to obtain a mixed material;
drying the mixed material in a vacuum drying oven at 30 ℃ for 5 hours to obtain mixed powder;
pressing and molding the obtained mixed powder by adopting a cold isostatic pressing process, wherein the pressure is 200MPa, and the pressure maintaining time is 30min to obtain a molded blank;
the obtained shaped body is processed toSintering in a sintering furnace, wherein the sintering process comprises the following steps: heating to 300 deg.C at a heating rate of 10 deg.C/min, maintaining at 300 deg.C for 1H, and introducing H2Protecting and sintering; heating from 300 deg.C to 800 deg.C at a rate of 5 deg.C/min, and maintaining at 800 deg.C for 1H, wherein the step is vacuum sintering to remove residual H in the sintering process2(ii) a Heating from 800 ℃ to 1300 ℃ at a heating rate of 3 ℃/min, introducing argon with the partial pressure of 10mbar in the heating process, sintering at 1300 ℃, introducing argon for protection, wherein the sintering pressure is 1MPa, and the time is 1 h; cooling from 1300 ℃ to 800 ℃ at a cooling rate of 1 ℃/min; and cooling to room temperature along with the furnace at 800 ℃ to obtain the Zr-Ti-based alloy material, wherein the Zr content is 79.2%, the Ti content is 19.8%, and the Co content is 1%.
The mechanical properties and the compactness of the Zr-Ti-based alloy prepared by the embodiment are tested, and the test results are shown in Table 1, wherein the strength test method is quasi-static compression; the critical failure strain test method is quasi-static compression, and the strain rate is 10-3S; the density testing method is an Archimedes drainage method.
Example 2
Weighing Zr powder with the particle size of 10 microns and Ti powder with the particle size of 10 microns, wherein the mass ratio of the Zr powder to the Ti powder is 9:1, carrying out ball milling on the powder on a planetary ball mill, the ball milling medium is absolute ethyl alcohol, the volume ratio of the total volume of the Zr powder and the Ti powder to the absolute ethyl alcohol is 1:3, the dispersing agent is Tween-80, the mass of the Tween-80 is 0.3 wt% of the total mass of the Zr powder and the Ti powder, the ball milling rotating speed is 250r/min, the ball milling time is 9h, the ball material ratio is 3:1, and the diameter of a milling ball is 10mm, so as to obtain a mixed material;
drying the mixed material in a vacuum drying oven at 30 ℃ for 5 hours to obtain mixed powder;
pressing and molding the obtained mixed powder by adopting a cold isostatic pressing process, wherein the pressure is 250MPa, and the pressure maintaining time is 35min to obtain a molded blank;
and placing the obtained molded blank into a sintering furnace for sintering, wherein the sintering process comprises the following steps: heating to 350 deg.C at a heating rate of 10 deg.C/min, maintaining at 350 deg.C for 1.5H, and introducing H2Protecting and sintering; heating from 350 deg.C to 800 deg.C at a heating rate of 8 deg.C/min, and maintaining at 800 deg.C for 1.5H, wherein the step is vacuum sintering to remove residual H in the sintering process2(ii) a Heating from 800 ℃ to 1350 ℃ at a heating rate of 5 ℃/min, introducing argon with a partial pressure of 15mbar in the heating process, sintering at 1350 ℃, introducing argon for protection, wherein the sintering pressure is 3MPa, and the time is 1 h; cooling from 1350 ℃ to 800 ℃ at a cooling rate of 1 ℃/min; and (3) cooling to room temperature along with the furnace at 800 ℃ to obtain the Zr-Ti-based alloy material, wherein Zr accounts for 90%, and Ti accounts for 10%.
The mechanical properties and the compactness of the Zr-Ti based alloy prepared in this example are tested, the test results are shown in table 1, and the methods for testing the mechanical properties and the compactness are the same as those in example 1.
Example 3
Weighing Zr powder with the particle size of 10 microns, Ti powder with the particle size of 10 microns and Mo powder with the particle size of 10 microns, wherein the mass ratio of the Zr powder to the Ti powder is 1:1, the adding amount of Mo is 2% of the total mass, ball-milling the powders on a planetary ball mill, the ball-milling medium is absolute ethyl alcohol, the volume ratio of the total volume of the Zr powder, the Ti powder and the Mo powder to the absolute ethyl alcohol is 1:3, the dispersing agent is Tween-80, the mass of the Tween-80 is 0.5 wt% of the total mass of the Zr powder, the Ti powder and the Mo powder, the ball-milling rotating speed is 200r/min, the ball-milling time is 8h, the ball-to-material ratio is 4:1, and the diameter of a milling ball is 10mm, so as to obtain a mixed material;
drying the mixed material in a vacuum drying oven at 40 ℃ for 6 hours to obtain mixed powder;
pressing and molding the obtained mixed powder by adopting a cold isostatic pressing process, wherein the pressure is 350MPa, and the pressure maintaining time is 45min to obtain a molded blank;
and placing the obtained molded blank into a sintering furnace for sintering, wherein the sintering process comprises the following steps: heating to 400 deg.C at a heating rate of 10 deg.C/min, maintaining at 400 deg.C for 2H, and introducing H2Protecting and sintering; heating from 400 deg.C to 800 deg.C at a rate of 5 deg.C/min, and maintaining at 800 deg.C for 1.5H, wherein the step is vacuum sintering to remove residual H in the sintering process2(ii) a At 3 deg.C/min, raising the temperature from 800 ℃ to 1400 ℃, introducing argon with the partial pressure of 15mbar in the temperature raising process, sintering at 1400 ℃, introducing argon for protection, wherein the sintering pressure is 3MPa, and the time is 1 h; cooling from 1400 ℃ to 800 ℃ at a cooling rate of 2 ℃/min; and (3) cooling to room temperature along with the furnace at 800 ℃ to obtain the Zr-Ti-based alloy material, wherein the Zr content is 49%, the Ti content is 49%, and the Mo content is 2%.
The mechanical properties and the compactness of the Zr-Ti based alloy prepared in this example are tested, the test results are shown in table 1, and the methods for testing the mechanical properties and the compactness are the same as those in example 1.
Example 4
Weighing Zr powder with the particle size of 10 microns and Ti powder with the particle size of 10 microns, wherein the mass ratio of the Zr powder to the Ti powder is 25: 8, ball-milling the powder on a planet ball mill, wherein the ball-milling medium is absolute ethyl alcohol, the volume ratio of the total volume of the Zr powder, the Ti powder and the Mo powder to the absolute ethyl alcohol is 1:2, the dispersing agent is tween-80, the mass of the tween-80 is 0.5 wt% of the total mass of the Zr powder, the Ti powder and the Mo powder, the ball-milling rotating speed is 200r/min, the ball-milling time is 8h, the ball-material ratio is 4:1, and the diameter of a milling ball is 10mm to obtain a mixed material;
drying the mixed material in a vacuum drying oven at 40 ℃ for 8 hours to obtain mixed powder;
pressing and molding the obtained mixed powder by adopting a cold isostatic pressing process, wherein the pressure is 350MPa, and the pressure maintaining time is 40min to obtain a molded blank;
and placing the obtained molded blank into a sintering furnace for sintering, wherein the sintering process comprises the following steps: heating to 500 deg.C at a heating rate of 10 deg.C/min, maintaining at 500 deg.C for 2H, introducing H2Protecting and sintering; heating from 500 deg.C to 900 deg.C at a rate of 5 deg.C/min, and maintaining at 900 deg.C for 1.5H, wherein the step is vacuum sintering to remove residual H in the sintering process2(ii) a Heating from 800 ℃ to 1450 ℃ at a heating rate of 3 ℃/min, introducing argon with partial pressure of 15mbar in the heating process, sintering at 1450 ℃, introducing argon for protection, wherein the sintering pressure is 10MPa, and the time is 1 h; decrease at 2 ℃/minThe temperature is reduced from 1500 ℃ to 800 ℃; and cooling to room temperature along with the furnace at 800 ℃ to obtain the Zr-Ti-based alloy material, wherein Zr accounts for 75%, Ti accounts for 24% and Mo accounts for 1%.
The mechanical properties and the compactness of the Zr-Ti based alloy prepared in this example are tested, the test results are shown in table 1, and the methods for testing the mechanical properties and the compactness are the same as those in example 1.
Example 5
Weighing Zr powder with the particle size of 10 microns and Ti powder with the particle size of 10 microns, wherein the mass ratio of the Zr powder to the Ti powder is 9:1, ball-milling the powder on a planet ball mill with Cu accounting for 2% of the total mass of Zr and Ti, wherein the ball-milling medium is absolute ethyl alcohol, the volume ratio of the total volume of the Zr powder, the Ti powder and the Cu powder to the absolute ethyl alcohol is 1:2.5, the dispersing agent is tween-80, the mass of the tween-80 is 0.3 wt% of the total mass of the Zr powder, the Ti powder and the Cu powder, the ball-milling rotation speed is 200r/min, the ball-milling time is 9h, the ball-material ratio is 4:1, and the diameter of a milling ball is 10mm to obtain a mixed material;
drying the mixed material in a vacuum drying oven at 45 ℃ for 8 hours to obtain mixed powder;
pressing and molding the obtained mixed powder by adopting a cold isostatic pressing process, wherein the pressure is 300MPa, and the pressure maintaining time is 40min, so as to obtain a molded blank;
and placing the obtained molded blank into a sintering furnace for sintering, wherein the sintering process comprises the following steps: heating to 450 deg.C at a heating rate of 10 deg.C/min, maintaining at 450 deg.C for 3H, introducing H2Protecting and sintering; heating from 450 deg.C to 950 deg.C at a rate of 15 deg.C/min, and maintaining at 950 deg.C for 1.5H, wherein the step is vacuum sintering to remove residual H in the sintering process2(ii) a Heating from 950 ℃ to 1450 ℃ at a heating rate of 3 ℃/min, introducing argon with partial pressure of 40mbar in the heating process, sintering at 1450 ℃, introducing argon for protection, wherein the sintering pressure is 10MPa, and the time is 1 h; cooling from 1500 ℃ to 800 ℃ at a cooling rate of 2 ℃/min; and (3) cooling to room temperature along with the furnace at 800 ℃ to obtain the Zr-Ti-based alloy material, wherein the Zr content is 88.2%, the Ti content is 9.8%, and the Cu content is 2%.
The mechanical properties and the compactness of the Zr-Ti based alloy prepared in this example are tested, the test results are shown in table 1, and the methods for testing the mechanical properties and the compactness are the same as those in example 1.
The microstructures of the Zr-Ti-based alloys prepared in examples 1 to 5 are detected, and FIGS. 1 to 5 are photographs of the microstructures of the Zr-Ti-based alloys prepared in examples 1 to 5, wherein a is 80Zr-20Ti-1Co, b is 60Zr-40Ti, c is 90Zr-10Ti-0.5Co, d is 85Zr-15Ti, and e is 90Zr-10 Ti.
The Zr-Ti-based alloy prepared in the embodiment 1-5 is subjected to mechanical property test under the quasi-static compression loading condition, and the specific quasi-static compression loading condition is as follows: strain rate of 10-3·s-1The maximum strain is set to be 50%, the size of the sample is phi 4 x 4mm, two end faces of the sample are parallel, flat and smooth before testing, each group of experiments are repeated for 3 times, and the average value and the error are calculated. FIG. 6 is a mechanical property curve diagram of the Zr-Ti-based alloy prepared in examples 1-5 under the quasi-static compressive loading condition, and it can be seen from the diagram that the Zr-Ti-based alloy prepared by the invention has the strength of more than 1400MPa, has different obdurability matching and can meet different application requirements.
Comparative example 1
The Zr-Ti-based alloy prepared by adopting the traditional smelting metallurgy method comprises the following specific steps:
1. taking sponge zirconium and a metal titanium wire as raw materials, and mixing the sponge zirconium and the metal titanium wire to obtain a mixed material, wherein Zr and Ti are 60: 40;
2. putting the obtained mixed material into an argon arc furnace, vacuumizing until the vacuum degree in the argon arc furnace reaches 3 multiplied by 10-3When in use, argon is filled in the argon arc furnace to ensure that the pressure in the argon arc furnace reaches-0.5 MPa;
3. heating the metal by adopting a non-consumable tungsten electrode until the temperature of the mixed material instantly reaches a very high temperature so as to be melted into molten metal, and simultaneously, opening an electromagnetic stirring function to stir and mix the molten alloy during smelting in order to fully melt and mix the raw materials;
4. after the smelting is finished, cooling the smelted molten metal to room temperature;
5. repeating the heating-smelting-cooling steps for 5 times to obtain the Zr-Ti-based alloy.
The mechanical properties and the compactness of the Zr-Ti-based alloy prepared by the comparative example are tested, and the test results are shown in the table 1, wherein the strength test method is quasi-static stretching; the critical failure strain test method is quasi-static tension with a strain rate of 10-3S; the density testing method is an Archimedes drainage method.
Comparative example 2
The Zr-Ti-based alloy prepared by adopting the traditional smelting metallurgy method comprises the following specific steps:
1. taking sponge zirconium and a metal titanium wire as raw materials, and mixing the sponge zirconium and the metal titanium wire to obtain a mixed material, wherein Zr and Ti are 80: 20;
2. putting the obtained mixed material into an argon arc furnace, vacuumizing until the vacuum degree in the argon arc furnace reaches 3 multiplied by 10-3When in use, argon is filled in the argon arc furnace to ensure that the pressure in the argon arc furnace reaches-0.5 MPa;
3. heating the metal by adopting a non-consumable tungsten electrode until the temperature of the mixed material instantly reaches a very high temperature so as to be melted into molten metal, and simultaneously, opening an electromagnetic stirring function to stir and mix the molten alloy during smelting in order to fully melt and mix the raw materials;
4. after the smelting is finished, cooling the smelted molten metal to room temperature;
5. repeating the heating-smelting-cooling steps for 5 times to obtain the Zr-Ti-based alloy.
The mechanical properties and the compactness of the Zr-Ti-based alloy prepared by the comparative example are tested, the test results are shown in the table 1, and the test methods of the mechanical properties and the compactness are the same as those of the example 1.
Comparative example 3
The Zr-Ti-based alloy prepared by adopting the traditional smelting metallurgy method comprises the following specific steps:
1. taking sponge zirconium and a metal titanium wire as raw materials, and mixing the sponge zirconium and the metal titanium wire to obtain a mixed material, wherein Zr and Ti are 90: 10;
2. mixing the obtained mixturePutting the mixture into an argon arc furnace, vacuumizing until the vacuum degree in the argon arc furnace reaches 3 multiplied by 10-3When in use, argon is filled in the argon arc furnace to ensure that the pressure in the argon arc furnace reaches-0.5 MPa;
3. heating the metal by adopting a non-consumable tungsten electrode until the temperature of the mixed material instantly reaches a very high temperature so as to be melted into molten metal, and simultaneously, opening an electromagnetic stirring function to stir and mix the molten alloy during smelting in order to fully melt and mix the raw materials;
4. after the smelting is finished, cooling the smelted molten metal to room temperature;
5. repeating the heating-smelting-cooling steps for 5 times to obtain the Zr-Ti-based alloy.
The mechanical properties and the compactness of the Zr-Ti-based alloy prepared by the comparative example are tested, the test results are shown in the table 1, and the test methods of the mechanical properties and the compactness are the same as those of the example 1.
Comparative example 4
The Zr-Ti-based alloy prepared by adopting the powder metallurgy normal-pressure one-step sintering process comprises the following specific steps:
1. ball-milling metal zirconium powder with the particle size of 10 mu m and metal titanium powder on a planetary ball mill, wherein the rotating speed of the ball mill is 200r/min, the ball-material ratio is 3:1, the ball-milling time is 6h, and the diameter of a milling ball is 10mm to obtain mixed powder with the component of 60Zr-40 Ti;
2. carrying out cold isostatic pressing on the mixed powder, wherein the pressure is 250MPa, and the time is 15min, so as to obtain a molded blank;
3. and sintering the molded blank at 1400 ℃ for 4h to obtain the Zr-Ti-based alloy.
The mechanical properties and the density of the Zr-Ti-based alloy prepared by the comparative example are tested, the test results are shown in Table 1, and the test methods of the mechanical properties and the density are the same as those of the example 1.
Comparative example 5
The Zr-Ti-based alloy prepared by adopting the powder metallurgy normal-pressure one-step sintering process comprises the following specific steps:
1. performing ball milling on metal zirconium powder and metal titanium powder with the particle size of 30 mu m on a planetary ball mill, wherein the rotating speed of the ball mill is 150r/min, and the ball-material ratio is 3:1, obtaining mixed powder with the component of 80Zr-20 Ti;
2. carrying out cold isostatic pressing on the mixed powder, wherein the pressure is 250MPa, and the time is 15min, so as to obtain a molded blank;
3. sintering the formed blank at 1400 ℃ for 4h to obtain the Zr-Ti-based alloy
The mechanical properties and the density of the Zr-Ti-based alloy prepared by the comparative example are tested, the test results are shown in Table 1, and the test methods of the mechanical properties and the density are the same as those of the example 1.
FIG. 7 is a graph showing the compactness of the Zr-Ti-based alloys prepared in examples 1 to 5 and comparative examples 1 to 5, and it can be seen that the compactness of the Zr-Ti-based alloy prepared by the present invention is significantly better than that of the Zr-Ti-based alloy prepared by the conventional smelting metallurgy method and the powder metallurgy process normal pressure one-step sintering process.
The mechanical properties and density test results of the Zr-Ti-based alloy prepared in the embodiments 1-5 and the comparative examples 1-5 are shown in Table 1, and it can be seen that the strength and density of the Zr-Ti-based alloy prepared by the method are obviously superior to the density of the Zr-Ti-based alloy prepared by the conventional smelting metallurgy method and the normal-pressure one-step sintering process of the powder metallurgy process, the alloy strength can be effectively improved, and the technical defects of poor density and low strength of the Zr-Ti-based alloy prepared by the conventional smelting metallurgy method are overcome.
TABLE 1 mechanical Properties and compactness test results of Zr-Ti-based alloys obtained in examples 1 to 5 and comparative examples 1 to 5
The experimental data show that the compactness of the Zr-Ti-based alloy prepared by the method is obviously superior to that of the Zr-Ti-based alloy prepared by the traditional smelting and metallurgy method, the technical defect that the Zr-Ti-based alloy prepared by the traditional smelting and metallurgy method is poor in compactness can be effectively overcome, and the mechanical property of the Zr-Ti-based alloy prepared by the method is more excellent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a high-strength Zr-Ti-based alloy comprises the following steps:
mixing Zr powder and Ti powder to obtain mixed powder; the mass ratio of the Zr powder to the Ti powder is 1: 99-99: 1;
carrying out cold isostatic pressing on the mixed powder to obtain a molded blank; the pressure of the cold isostatic pressing is 200-400 MPa, and the pressure maintaining time is 15-60 min;
sintering the molded blank to obtain a Zr-Ti-based alloy;
the sintering comprises a first sintering, a second sintering and a third sintering which are sequentially carried out:
the temperature of the first sintering is 300-500 ℃, the heat preservation time is 1-5 h, and the temperature rising rate from the room temperature to the temperature of the first sintering is 5-10 ℃/min; the first sintering is performed in a hydrogen atmosphere; the temperature of the second sintering is 800-1000 ℃, and the heat preservation time is 1-2 h; the heating rate from the first sintering temperature to the second sintering temperature is 1-2 ℃/min; the second sintering is carried out under vacuum conditions; the temperature of the third sintering is 1300-1500 ℃, the heat preservation time is 1-4 h, and the pressure is 1-10 MPa; the third sintering is carried out in an argon atmosphere; the heating rate from the temperature of the second sintering to the temperature of the third sintering is 3-5 ℃/min, and the argon partial pressure is 10-50 mbar;
the sintered ceramic further comprises: cooling the sintered product, wherein the cooling comprises a first cooling and a second cooling which are sequentially carried out: the temperature of the first cooling is 800-500 ℃; and the cooling rate from the third sintering temperature to the first cooling temperature is 1-3 ℃/min.
2. The method according to claim 1, wherein the mixing is wet mixing, the medium for wet mixing is absolute ethanol, and a volume ratio of the total volume of the mixed powder to the absolute ethanol is 1:2 to 5.
3. The method according to claim 1 or 2, wherein the mixing is performed at a rotation speed of 100 to 300r/min for 3 to 10 hours.
4. The production method according to claim 1 or 2, characterized in that a dispersant is included in the mixed powder, and the mass of the dispersant is 0.2 to 0.6 wt.% of the total mass of the Zr powder and the Ti powder.
5. The method according to claim 1, wherein the particle diameters of the Zr powder and the Ti powder are independently 5 to 45 μm.
6. The method according to claim 1, wherein the mixed powder further includes a trace amount of metal powder including one or more of Cr powder, V powder, W powder, Cu powder, Co powder, Mo powder, Ni powder, and Fe powder.
7. The production method according to claim 6, wherein the mass of the trace metal powder is 0.1 to 5.0 wt.% of the total mass of the Zr powder and the Ti powder.
8. The preparation method according to claim 1, further comprising a step of subjecting the mixed powder to a vacuum drying treatment before the cold isostatic pressing, wherein the temperature of the vacuum drying treatment is 40 to 80 ℃.
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