CN112941367B - Nano oxide dispersion reinforced heat-resistant zirconium alloy and preparation method thereof - Google Patents

Nano oxide dispersion reinforced heat-resistant zirconium alloy and preparation method thereof Download PDF

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CN112941367B
CN112941367B CN202110116461.5A CN202110116461A CN112941367B CN 112941367 B CN112941367 B CN 112941367B CN 202110116461 A CN202110116461 A CN 202110116461A CN 112941367 B CN112941367 B CN 112941367B
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江勇
吴华建
商佳程
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

The invention discloses a nanometer oxide dispersion reinforced heat-resistant zirconium alloy, which comprises a zirconium alloy matrix, and Y-Ti-O and Y-Zr-O nanometer oxide precipitated phases dispersed in the zirconium alloy matrix, wherein the granularity of the Y-Ti-O and Y-Zr-O nanometer oxide precipitated phases is 2-10nm, and the number density is 1-3 multiplied by 10 15 Per m 2 . According to the nanometer oxide dispersion reinforced heat-resistant zirconium alloy, a re-dissolution and re-precipitation mechanism of a solute is realized through a mechanical alloying and thermal densification mode, Y-Ti-O and Y-Zr-O nanometer oxide phases with high number density, low nanometer scale, high thermal stability and dispersion distribution are obtained in a zirconium alloy matrix, and the strength and heat resistance of the zirconium alloy can be greatly improved. The invention also provides a preparation method of the nanometer oxide dispersion reinforced heat-resistant zirconium alloy.

Description

Nano-oxide dispersion-reinforced heat-resistant zirconium alloy and preparation method thereof
Technical Field
The invention relates to the technical field of alloy materials, in particular to a nanometer oxide dispersion-strengthened heat-resistant zirconium alloy and a preparation method thereof.
Background
The zirconium alloy has the advantages of low neutron absorption cross section, corrosion resistance, easiness in processing and forming, good irradiation stability and the like, and is widely applied to manufacturing core structure components such as nuclear reactor fuel cladding tubes and the like. At present, the zirconium alloy for the nucleus is prepared by adopting a fusion casting method, and forms a precipitated phase of an intermetallic compound type through heat treatment, so as to realize dispersion strengthening of a zirconium alloy matrix. The problems that the segregation of cast ingots is serious, the structure components are not uniform, the crystal grains are large, the thermal stability of intermetallic compounds is poor, and both precipitated phases and the crystal grains are easy to coarsen rapidly under the high-temperature service condition, so that the service temperature and the strength of the zirconium alloy are severely limited, and the like exist. Due to these limitations, current nuclear zirconium alloys generally cannot operate at temperatures in excess of 350 ℃ despite the fact that pure zirconium has a melting point as high as 1850 ℃.
With the development of the advanced third generation and the fourth generation nuclear reactor technology, a high-strength heat-resistant zirconium alloy with the working temperature of more than 500 ℃ is urgently needed.
Accordingly, the present invention is directed to a novel zirconium alloy material to solve the above problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nanometer oxide dispersion reinforced heat-resistant zirconium alloy, realizing a mechanism of re-dissolution and re-precipitation of solute through a mechanical alloying and thermal densification mode, obtaining Y-Ti-O and Y-Zr-O nanometer oxide phases with high number density, low nanoscale, high thermal stability and dispersion distribution in a zirconium alloy matrix, and greatly improving the strength and heat resistance of the zirconium alloy.
In order to solve the problems, the technical scheme of the invention is as follows:
a nanometer oxide dispersion reinforced heat-resistant zirconium alloy comprises a zirconium alloy matrix, and Y-Ti-O and Y-Zr-O nanometer oxide precipitated phases dispersed in the zirconium alloy matrix, wherein the granularity of the Y-Ti-O and Y-Zr-O nanometer oxide precipitated phases is 2-10nm, and the number density is 1-3 multiplied by 10 15 Per m 2 。
Further, the structure of the precipitated phase of the nano oxide is Y 2 Ti 2 O 7 And Y 2 Zr 2 O 7 。
Further, the zirconium alloy matrix comprises the following components in percentage by weight:
1.2 to 1.6 percent of Sn, 0.2 to 0.5 percent of Fe, 0.1 to 0.3 percent of Cr, and the balance of Zr and inevitable impurities.
The invention also provides a preparation method of the nanometer oxide dispersion reinforced heat-resistant zirconium alloy, which comprises the following steps:
step S1, carrying out hydrogenation dehydrogenation treatment on the zirconium alloy block to obtain pre-alloy powder;
step S2, putting powder materials containing Y, Ti and O elements and pre-alloyed powder into a high-speed pendulum vibration ball mill, and fully mixing under the protection of inert gas to obtain mixed powder;
step S3, carrying out high-energy ball milling on the mixed powder under the protection of inert gas, and dissolving solute elements back into the matrix in the form of Y, Ti and O solid solution atoms to form mechanical alloying powder with a structure exceeding that of a saturated solid solution;
step S4, cold pressing the mechanical alloying powder into a billet, filling the billet into a sheath, vacuumizing the sheath, densifying the billet, reacting and precipitating solute atoms dissolved in a zirconium alloy matrix again to form Y-Ti-O and Y-Zr-O nano oxide precipitated phases which are distributed in a dispersed way, wherein the granularity of the Y-Ti-O and Y-Zr-O nano oxide precipitated phases is 2-10nm, and the number density is 1-3 multiplied by 10 15 Per m 2 。
Further, the structure of the precipitated phase of the nano oxide is Y 2 Ti 2 O 7 And Y 2 Zr 2 O 7 。
Further, in step S1, the zirconium alloy block includes the following components by weight percent:
1.2 to 1.6 percent of Sn, 0.2 to 0.5 percent of Fe, 0.1 to 0.3 percent of Cr, and the balance of Zr and inevitable impurities;
the temperatures of the hydrogenation and dehydrogenation treatment processes are respectively 300-500 ℃;
the obtained prealloyed powder has a particle size of 5-20 μm and a hydrogen content of not more than 100 ppm.
Further, in step S2, YH is the powder material containing Y, Ti and O elements 2 Powder and TiO 2 Powder, Y 2 O 3 Powder and TiH 2 Powder, Y 2 O 3 Powder and pure Ti powder, or pure Y powder and TiO 2 One of the four combinations of powders;
wherein the average grain diameter of the powder material containing the Y element is 1-20 μm, the addition amount is 0.1-2% of the weight of the pre-alloyed powder, the average grain diameter of the powder material containing the Ti element is less than 1 μm, and the addition amount is 0.1-1% of the weight of the pre-alloyed powder.
Further, the powder material containing Y, Ti and O elements is YH 2 Powder and TiO 2 Powder, or Y 2 O 3 Powder and TiH 2 And (3) powder.
Further, in step S3, the mechanical alloying process adopts an omnibearing planetary ball mill, the disc surface rotating speed is 400-600rpm, the longitudinal rotating speed is 10-20rpm, the ball-material mass ratio is 10-20:1, and the ball milling time is 20-40 h; and stopping the ball mill for 2-3min and changing the positive and negative rotation directions after ball milling for 15-30 min.
Further, in step S4, cold pressing the mechanical alloying powder into briquettes by a tablet press, wherein the pressure is 20-40MPa, and keeping the pressure for 1 h; the sheath is vacuumized, and the vacuum degree is 10 -3 Pa; adopting hot isostatic pressing for densification, wherein the hot isostatic pressing pressure is 150-200MPa, the pressure is maintained for 4-6h, and the temperature is 1100-1300 ℃.
Compared with the prior art, the nanometer oxide dispersion reinforced heat-resistant zirconium alloy and the preparation method thereof have the beneficial effects that:
the invention provides a nanometer oxide dispersion reinforced heat-resistant zirconium alloy and a preparation method thereof, wherein mechanical alloying of zirconium alloy powder is realized by fully mixing pre-alloyed powder and powder materials containing Y and Ti elements and high-energy ball milling; further realizing complete densification through hot isostatic pressing, so that the compactness is more than 99%, no component macrosegregation exists, and the crystal grains are uniform and fine;
the added powder containing Y and Ti is easy to be broken, refined and decomposed in the process of mechanical alloying, solute elements are dissolved back into a matrix in the form of Y, Ti and O solid solution atoms to form a more than saturated solid solution, the solute atoms dissolved in the process of hot isostatic pressing react and precipitate again to form Y-Ti-O and Y-Zr-O oxide precipitated phases which are ultrahigh in number density, low in nano scale and distributed in a dispersed manner, wherein the granularity of the Y-Ti-O and Y-Zr-O nano oxide precipitated phases is 2-10nm, and the number density is 1-3 multiplied by 10 15 Per m 2 . The thermal stability and corrosion resistance of the precipitated phase of the nano oxide are high, a large amount of precipitates are precipitated in crystal interior and crystal boundary, the capability of pinning dislocation and crystal boundary is strong at high temperature, and the recrystallization of crystal grains can be inhibited, so that the strength and heat resistance of the zirconium alloy are greatly improved. The nanometer oxide dispersion reinforced heat-resistant zirconium alloy provided by the invention has higher yield strength and excellent high-temperature mechanical property when the working temperature is increased to more than 500 ℃.
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In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a Transmission Electron Microscope (TEM) photograph of a nano-oxide dispersion-strengthened heat-resistant zirconium alloy prepared in example 1 of the present invention;
FIG. 2 is a selected area electron diffraction (SAD) analysis diagram of the microstructure of the nano-oxide dispersion-strengthened heat-resistant zirconium alloy prepared in example 1 of the present invention;
FIG. 3 is a comparison graph of the mechanical properties of the nano-oxide dispersion-strengthened heat-resistant zirconium alloy prepared in the example of the present invention and the zirconium alloy prepared in the comparative example under different temperature conditions.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
A preparation method of a nanometer oxide dispersion reinforced heat-resistant zirconium alloy comprises the following steps:
step S1, carrying out hydrogenation dehydrogenation treatment on the zirconium alloy block to obtain pre-alloy powder;
specifically, the zirconium alloy block comprises the following components in percentage by weight:
1.2 to 1.6 percent of Sn, 0.2 to 0.5 percent of Fe, 0.1 to 0.3 percent of Cr, and the balance of Zr and inevitable impurities;
a gas tube furnace is adopted for hydrogenation, the hydrogenation temperature is 300-; then the pre-alloyed powder with the average grain diameter of 5-20 mu m and the hydrogen content of not more than 100ppm is obtained by dehydrogenation treatment at the temperature of 300 ℃ and 500 ℃.
Step S2, putting powder materials containing Y, Ti and O elements and pre-alloyed powder into a high-speed pendulum vibration ball mill, and fully mixing under the protection of inert gas to obtain mixed powder;
Specifically, the powder material containing Y, Ti and O is YH 2 Powder and TiO 2 Powder, Y 2 O 3 Powder and TiH 2 Powder, Y 2 O 3 Powder and pure Ti powder, or pure Y powder and TiO 2 One of the four combinations of powders; preferred is YH 2 Powder and TiO 2 Powder, or Y 2 O 3 Powder and TiH 2 The powder, the two combined powder materials can be uniformly dispersed when being added into the prealloyed powder, so that the precipitated phase structure of the oxide formed in the later period is more stable. Wherein, the purity of the powder is: TiO 2 2 99.9% of YH 2 99.9%, or Y 2 O 3 99.9% of TiH 2 99.9%; the addition amount of the powder material containing the Y element is 0.1-2% of the weight of the pre-alloyed powder, and the addition amount of the powder material containing the Ti element is 0.1-1% of the weight of the pre-alloyed powder;
premixing by a high-speed oscillating ball mill, and fully mixing under the protection of inert gas to ensure that the average grain diameter of the powder containing the Y element is 1-20 mu m, and the average grain diameter of the powder containing the Ti element is less than 1 mu m. The content of H, O elements in the alloy is effectively controlled by argon protection and adjustment of the introduction mode and the addition amount of Y, Ti and O elements, and the preparation of the high-activity metal zirconium alloy in a powder metallurgy mode is realized.
Step S3, carrying out high-energy ball milling on the mixed powder under the protection of inert gas, and dissolving solute elements back into the matrix in the form of Y, Ti and O solid solution atoms to form mechanical alloying powder with a structure exceeding that of a saturated solid solution;
Specifically, the mechanical alloying process adopts an omnibearing planetary ball mill, the disc surface rotating speed is 400-600rpm, the longitudinal rotating speed is 10-20rpm, the ball-material mass ratio is 10-20:1, and the ball milling time is 20-40 h; and each ball milling is carried out for 15-30min, the machine is stopped for 2-3min, and the positive and negative rotation directions are changed, thus being beneficial to ensuring the mechanical alloying effect.
The temperature of the all-round planet high-energy ball mill is set to be 0 ℃, and the grinding balls and the ball milling tank are made of zirconia materials, so that the high-activity zirconium alloy mechanical alloying process is safely and efficiently carried out.
Step S4, cold pressing the mechanical alloying powder into a billet, filling the billet into a sheath, vacuumizing the sheath, densifying the billet, reacting and precipitating solute atoms dissolved in a zirconium alloy matrix again to form Y-Ti-O and Y-Zr-O nano oxide precipitated phases which are distributed in a dispersed way, wherein the granularity of the Y-Ti-O and Y-Zr-O nano oxide precipitated phases is 2-10nm, and the number density is 1-3 multiplied by 10 15 Per m 2 。
In the process, the high-surface-activity mechanical alloying powder is mechanically and cold pressed into a compact in an argon glove box, and the compact is sheathed and then vacuumized, so that the problem of oxidative flammability of direct hot isostatic pressing of the powder can be effectively solved.
Specifically, cold pressing the mechanical alloying powder into briquettes by a tablet press, keeping the pressure at 20-40MPa for 1 h; the sheath is vacuumized, and the vacuum degree is 10 -3 Pa; performing densification by hot isostatic pressing, wherein the hot isostatic pressing pressure is 150-200MPa, the pressure is maintained for 4-6h, and the temperature is 1100-1300 ℃; the structure of the formed nano oxide precipitated phase is Y 2 Ti 2 O 7 And Y 2 Zr 2 O 7 。
The cold pressing mode can be replaced by a cold isostatic pressing mode, and the hot isostatic pressing densification mode can be replaced by a hot extrusion mode or a spark plasma sintering mode.
The nano-oxide dispersion-strengthened heat-resistant zirconium alloy and the preparation method thereof provided by the invention are explained in detail by specific examples below.
Example 1
A preparation method of a nanometer oxide dispersion reinforced heat-resistant zirconium alloy comprises the following steps:
step S1, prealloyed powder preparation: putting the zirconium alloy block into a gas tube furnace, hydrogenating at 500 ℃ to obtain a zirconium hydride alloy block, putting the zirconium hydride alloy block into a ball mill, rapidly crushing at the rotating speed of 300rpm for 5h to obtain hydrogenated alloy powder, and dehydrogenating the hydrogenated alloy powder at 500 ℃ to obtain pre-alloy powder, wherein the average particle size of the pre-alloy powder is 5-20 mu m, and the hydrogen content is not more than 100 ppm;
the zirconium alloy block comprises the following components in percentage by weight:
1.3% of Sn, 0.2% of Fe, 0.1% of Cr and the balance of Zr and inevitable impurities;
Step S2, powder premixing: 0.4 wt% TiO of prealloyed powder weight 2 Powder, 0.4 wt% YH 2 Putting the powder and the prealloying powder into a high-speed shimmying ball mill for premixing, wherein the vibration time is 1h, and the frequency is 1400rpm, so as to obtain mixed powder;
step S3, mechanical alloying: putting the mixed powder into a zirconia ball milling tank, carrying out ball milling under the protection of argon, wherein the ball milling time is 30h, the plate surface rotating speed is 300rpm, the longitudinal rotating speed is 20rpm, the mass ratio of ball materials is 10:1, the temperature of a cooling system is set to be 0 ℃, solute elements are re-dissolved into a matrix in the form of solid solution atoms of Y, Ti and O, and mechanical alloying powder exceeding a saturated solid solution structure is formed;
step S4, densification forming: mechanically cold pressing the mechanical alloying powder for 1h under 50MPa to form a billet, filling the billet into a sheath, vacuumizing the sheath, and keeping the vacuum degree at 10 -3 Pa; and (3) performing densification by adopting hot isostatic pressing, wherein the hot isostatic pressing pressure is 200MPa, the pressure is maintained for 4h, the temperature is 1200 ℃, solute atoms dissolved in the zirconium alloy matrix react and precipitate again, and the Y-Ti-O and Y-Zr-O nano oxide dispersion reinforced zirconium alloy is obtained.
The precipitated crystal plane of the nano-oxide dispersion-strengthened heat-resistant zirconium alloy of example 1 was measured, and the measurement results are shown in table 1:
Table 1: precipitated phase interplanar spacing calibration results for nano-oxide dispersion strengthened zirconium alloy prepared in example 1
Figure BDA0002920583550000061
According to the calibration results in Table 1, it can be preliminarily determined that the precipitated phase is Y 2 Ti 2 O 7 And Y 2 Zr 2 O 7 A nano-oxide phase. Since the crystal structures of these two phases are identical and the lattice constants are very close (about 4% difference), the two phases have a coexistence characteristic in view of the measured dispersion of interplanar spacings.
Referring to fig. 1 and fig. 2, fig. 1 is a Transmission Electron Microscope (TEM) photograph of a nano-oxide dispersion-strengthened heat-resistant zirconium alloy prepared in example 1 of the present invention; FIG. 2 is a selected area electron diffraction (SAD) analysis diagram of the microstructure of the nano-oxide dispersion-strengthened heat-resistant zirconium alloy prepared in example 1 of the present invention. The crystal phase structures in the figures 1 and 2 show that a large amount of dispersed precipitated phases of low-nanometer oxides are formed in the alloy matrix, and the granularity of the precipitated phases is 2-10nm through detection, and the number density can reach 1-3 multiplied by 10 15 Per m 2 。
Example 2
Step S1, prealloyed powder preparation: putting the zirconium alloy block into a gas tube furnace, hydrogenating at 500 ℃ to obtain a zirconium hydride alloy block, putting the zirconium hydride alloy block into a ball mill, rapidly crushing at the rotating speed of 300rpm for 5 hours to obtain hydrogenated alloy powder, and dehydrogenating the hydrogenated alloy powder at 500 ℃ to obtain pre-alloyed powder;
The zirconium alloy block comprises the following components in percentage by weight:
1.3% of Sn, 0.2% of Fe, 0.1% of Cr and the balance of Zr and inevitable impurities;
step S2, powder premixing: pre-alloyed powder 0.4 wt% by weight of Y 2 O 3 Powder, 0.4 wt% TiH 2 Putting the powder and the prealloying powder into a high-speed shimmying ball mill for premixing, wherein the vibration time is 1h, and the frequency is 1400rpm, so as to obtain mixed powder;
step S3, mechanical alloying: putting the mixed powder into a zirconia ball milling tank, carrying out ball milling under the protection of argon, wherein the ball milling time is 40h, the plate surface rotating speed is 300rpm, the longitudinal rotating speed is 20rpm, the mass ratio of ball materials is 10:1, the temperature of a cooling system is set to be 0 ℃, solute elements are re-dissolved into a matrix in the form of solid solution atoms of Y, Ti and O, and mechanical alloying powder exceeding a saturated solid solution structure is formed;
step S4, densification forming: mechanically cold pressing the mechanical alloying powder for 1h under 50MPa to form a billet, filling the billet into a sheath, vacuumizing the sheath, and keeping the vacuum degree at 10 -3 Pa; and (3) performing densification by adopting hot isostatic pressing, wherein the hot isostatic pressing pressure is 200MPa, the pressure is maintained for 4h, the temperature is 1200 ℃, solute atoms dissolved in the zirconium alloy matrix react and precipitate again, and the Y-Ti-O and Y-Zr-O nano oxide dispersion reinforced zirconium alloy is obtained.
The crystal phase structure of the zirconium alloy of example 2 was examined and was similar to that of example 1. The detection shows that the structure of the Y-Ti-O and Y-Zr-O nano oxides is Y 2 Ti 2 O 7 And Y 2 Zr 2 O 7 (ii) a The granularity of the precipitated phase is 2-10nm, and the number density can reach 1-3 multiplied by 10 15 Per m 2 。
Comparative example 1
Zirconium alloy without introduction of Y, Ti and O elements was prepared, the alloy composition was the same as that of the prealloy in example 1, and the preparation process was the same as that of example 1.
Comparative example 2
Preparation of a separate addition of 0.4 wt% Y 2 O 3 The composition of the zirconium alloy of (1) was the same as that of the prealloy in example 1, and the preparation process was the same as that of example 1.
Comparative example 3
Preparation of addition of 0.4 wt% Y 2 O 3 And 0.4 wt% Ti, the alloy composition being the same as the prealloyed composition in example 1, and the preparation process being the same as in example 1.
Comparative example 4
A zirconium alloy was prepared with the addition of 0.4 wt% Y and 0.4 wt% Ti, the alloying constituents were the same as in the prealloyed composition of example 1, and the preparation process was the same as in example 1.
Comparative example 5
Preparation of 0.4 wt% Y and 0.4 wt% TiO addition 2 The composition of the zirconium alloy of (1) was the same as that of the prealloy in example 1, and the preparation process was the same as that of example 1.
Performance test of zirconium alloy:
the tensile test selects a sheet sample with the length of a parallel segment of 30mm, and the tensile test with the tensile speed of 0.15mm/min is carried out under the vacuum conditions of 25, 300, 400, 500 and 600 ℃. Referring to fig. 3, a graph comparing the mechanical properties of the nano-oxide dispersion-strengthened heat-resistant zirconium alloy prepared according to the present invention and the zirconium alloy prepared according to the comparative example under different temperature conditions is shown.
As can be seen from FIG. 3, the room temperature yield strength and the high temperature yield strength of the nano-oxide dispersion strengthened zirconium alloy prepared in the embodiments 1 and 2 of the invention are both significantly better than those of the zirconium alloy without introducing Y, Ti and O elements (comparative example 1), and the zirconium alloy with only Y added 2 O 3 Zirconium alloy of (comparative example 2), addition of Y 2 O 3 And pure Ti (comparative example 3), pure Y and pure Ti (comparative example 4), and pure Y and TiO 2 The zirconium alloy (comparative example 5) of the present invention shows that the zirconium alloy provided by the present invention realizes excellent high-strength heat resistance.
In the present invention, the hydride YH is used 2 And oxide TiO 2 Or hydride TiH 2 And oxide Y 2 O 3 Compared with the mode of directly adding pure Y and pure Ti and only adding pure Ti in an oxide form, the method has the advantages that powder is crushed and refined, the dispersion is uniform, the solute is fully dissolved back in the subsequent high-energy ball milling process, and the mechanical alloying effect is improved; on the other hand, the proportion of hydride and oxide is regulated, and the excessive H, O is combined to generate water in the mechanical alloying process, so that part of heat is absorbed, and the ball milling efficiency is improved.
It should be noted that the zirconium alloy block in the present invention may be replaced with pure zirconium or other zirconium alloys, such as alloys of the Zr-Nb, Zr-Sn-Nb, etc. series.
The invention provides a nanometer oxide dispersion reinforced heat-resistant zirconium alloy and a preparation method thereof, wherein mechanical alloying of zirconium alloy powder is realized by fully mixing pre-alloy powder, powder containing Y and powder containing Ti and high-energy ball milling; further realizing complete densification through hot isostatic pressing, so that the compactness is more than 99%, no component macrosegregation exists, and the crystal grains are uniform and fine;
the added powder containing Y and Ti is easy to be broken, refined and decomposed in the process of mechanical alloying, solute elements are dissolved back into a matrix in the form of Y, Ti and O solid solution atoms to form a more than saturated solid solution, the solute atoms dissolved in the process of hot isostatic pressing react and precipitate again to form Y-Ti-O and Y-Zr-O oxide precipitated phases which are ultrahigh in number density, low in nano scale and distributed in a dispersed manner, wherein the granularity of the Y-Ti-O and Y-Zr-O nano oxide precipitated phases is 2-10nm, and the number density is 1-3 multiplied by 10 15 Per m 2 The thermal stability and corrosion resistance of the precipitated phase of the nano oxide are high, a large amount of precipitates are precipitated in crystal interior and crystal boundary, the capability of pinning dislocation and crystal boundary at high temperature is strong, and the recrystallization of crystal grains can be inhibited, so that the strength and heat resistance of the zirconium alloy are greatly improved. The nanometer oxide dispersion reinforced heat-resistant zirconium alloy provided by the invention has higher yield strength and excellent high-temperature mechanical property when the working temperature is increased to more than 500 ℃.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.

Claims (7)

1. A preparation method of a nanometer oxide dispersion reinforced heat-resistant zirconium alloy is characterized by comprising the following steps:
step S1, carrying out hydrogenation dehydrogenation treatment on the zirconium alloy block to obtain pre-alloy powder;
the zirconium alloy block comprises the following components in percentage by weight:
1.2 to 1.6 percent of Sn, 0.2 to 0.5 percent of Fe, 0.1 to 0.3 percent of Cr, and the balance of Zr and inevitable impurities;
step S2, putting powder materials containing Y, Ti and O elements and pre-alloyed powder into a high-speed pendulum vibration ball mill, and fully mixing under the protection of inert gas to obtain mixed powder;
step S3, carrying out high-energy ball milling on the mixed powder under the protection of inert gas, and dissolving solute elements back into the matrix in the form of Y, Ti and O solid solution atoms to form mechanical alloying powder with a structure exceeding that of a saturated solid solution;
step S4, cold pressing the mechanical alloying powder into a billet, filling the billet into a sheath, vacuumizing the sheath, densifying the billet, reacting and precipitating solute atoms dissolved in the zirconium alloy matrix again to form Y-Ti-O and Y-Zr-O nano oxide precipitated phases which are distributed in a dispersed way, wherein the structure of the nano oxide precipitated phase is Y 2 Ti 2 O 7 And Y 2 Zr 2 O 7 With a particle size of 2-10nm and a number density of 1-3X 10 15 Per m 2 。
2. The method for preparing the nano-oxide dispersion-strengthened heat-resistant zirconium alloy as claimed in claim 1, wherein the temperatures of the hydrogenation and dehydrogenation processes in step S1 are 300-500 ℃ respectively;
the obtained prealloyed powder has a particle size of 5-20 μm and a hydrogen content of not more than 100 ppm.
3. The method of claim 1, wherein in step S2, the powder material containing Y, Ti and O elements is YH 2 Powder and TiO 2 Powder, Y 2 O 3 Powder and TiH 2 Powder, Y 2 O 3 Powder and pure Ti powder, or pure Y powder and TiO 2 One of the four combinations of powders;
wherein the average grain diameter of the powder material containing the Y element is 1-20 μm, the addition amount is 0.1-2% of the weight of the pre-alloyed powder, the average grain diameter of the powder material containing the Ti element is less than 1 μm, and the addition amount is 0.1-1% of the weight of the pre-alloyed powder.
4. The preparation method of the nano-oxide dispersion-reinforced heat-resistant zirconium alloy as claimed in claim 1, wherein in step S3, the mechanical alloying process adopts an omnibearing planetary ball mill, the disc surface rotation speed is 400-600rpm, the longitudinal rotation speed is 10-20rpm, the ball-material mass ratio is 10-20:1, and the ball milling time is 20-40 h; and stopping the ball mill for 2-3min and changing the positive and negative rotation directions after ball milling for 15-30 min.
5. The method for preparing a nano-oxide dispersion-strengthened heat-resistant zirconium alloy according to claim 1, wherein in step S4, the mechanically alloyed powder is cold-pressed into briquettes by a tablet press, the pressure is 20 to 40MPa, and the pressure is maintained for 1 hour; the sheath is vacuumized with the vacuum degree of 10 -3 Pa; adopting hot isostatic pressing for densification, wherein the hot isostatic pressing pressure is 150-200MPa, the pressure is maintained for 4-6h, and the temperature is 1100-1300 ℃.
6. The method for preparing the nano-oxide dispersion-strengthened heat-resistant zirconium alloy as claimed in claim 5, wherein the cold pressing mode is replaced by a cold isostatic pressing mode, and the hot isostatic pressing densification mode is replaced by a hot extrusion or spark plasma sintering mode.
7. The nano-oxide dispersion-strengthened heat-resistant zirconium alloy prepared by the preparation method of the nano-oxide dispersion-strengthened heat-resistant zirconium alloy according to any one of claims 1 to 6, which is characterized by comprising a zirconium alloy matrix and Y-Ti-O and Y-Zr-O nano-oxide precipitated phases dispersed in the zirconium alloy matrix, wherein the Y-Ti-O and Y-Zr-O nano-oxide precipitated phases have a structure of Y 2 Ti 2 O 7 And Y 2 Zr 2 O 7 With a particle size of 2-10nm and a number density of 1-3X 10 15 Per m 2 。
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