CN110079701B - High-strength zirconium alloy and preparation method thereof - Google Patents
High-strength zirconium alloy and preparation method thereof Download PDFInfo
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- CN110079701B CN110079701B CN201910365917.4A CN201910365917A CN110079701B CN 110079701 B CN110079701 B CN 110079701B CN 201910365917 A CN201910365917 A CN 201910365917A CN 110079701 B CN110079701 B CN 110079701B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
Abstract
The invention relates to a high-strength zirconium alloy and a preparation method thereof. The alloy comprises the following components in percentage by mass: aluminum (Al): 0.85-3.2%, vanadium (V): 0.6 to 3.72%, hafnium (Hf): 0.1-5%, and the balance of zirconium and inevitable impurities; in the preparation process, the obtained zirconium alloy obtains excellent tensile strength and yield strength under the condition that the cost is greatly reduced compared with that of the traditional zirconium alloy through multi-pass rolling deformation.
Description
Technical Field
The invention relates to the technical field of aerospace materials, in particular to a high-strength zirconium alloy and a preparation method thereof.
Background
Zirconium (Zr) and zirconium alloys are widely used in the nuclear industry as cladding materials due to their low thermal neutron absorption cross-section, good radiation resistance, excellent corrosion resistance, moderate mechanical properties and processability. In addition, zirconium also has the advantages of high specific strength, high melting point, good high-temperature creep resistance, atomic oxygen corrosion resistance, proton irradiation resistance, low thermal expansion coefficient and the like, and can be used as a space structure material to serve in an extreme space environment. However, most of the conventional zirconium alloys are developed for the nuclear industry, in order to control the thermal neutron absorption cross section and maintain good corrosion resistance, the alloy elements of the zirconium alloy for the nuclear are mainly niobium and tin, and the alloy content is controlled at a low level, which results in that the strength of the zirconium alloy for the nuclear is low (300 Mpa-700 Mpa), and the requirement of a high-strength structural member on mechanical properties is difficult to achieve. In addition, the raw material for preparing the zirconium alloy for the core is atomic-level sponge zirconium with hafnium content less than one ten thousandth, so the cost is extremely high. Therefore, the research and development of the novel high-strength zirconium alloy for aerospace have important significance.
Disclosure of Invention
The invention aims to solve the problem that the traditional zirconium alloy has low strength and cannot meet the requirement of a high-strength structural member on mechanical property, and provides a novel aerospace zirconium alloy with low cost and high strength and a preparation method thereof. Al and V in proper proportion are simultaneously added into metal zirconium, and the obtained zirconium alloy obtains excellent tensile strength and yield strength by multi-pass rolling deformation under the condition that the cost is greatly reduced compared with that of the traditional zirconium alloy.
The technical scheme of the invention is as follows:
a high-strength zirconium alloy comprises the following components in percentage by mass: aluminum (Al): 0.85-3.2%, vanadium (V): 0.6 to 3.72%, hafnium (Hf): 0.1-5%, and the balance of zirconium and inevitable impurities.
The preparation method of the novel high-strength zirconium alloy comprises the following steps:
(1) preparing materials: respectively weighing sponge zirconium, pure aluminum and pure vanadium according to the proportion of the components; the sponge zirconium contains 2 percent of hafnium by mass;
(2) preparing raw materials: cleaning the raw materials obtained in the step (1) in absolute ethyl alcohol by using an ultrasonic cleaner respectively, and then drying;
(3) alloy smelting: reasonably distributing the raw materials obtained in the step (2) into a water-cooled copper crucible of a non-consumable argon arc furnace according to the sequence of melting points from low to high, vacuumizing the smelting furnace until the vacuum degree reaches 1 x 10-3Pa～1*10-4Pa, filling high-purity argon into the smelting furnace to 0.05 MPa; before the alloy is smelted, smelting pure zirconium, absorbing residual oxygen in a furnace body, then beginning to smelt the alloy, wherein the smelting current is 300-500A, and repeatedly smelting for 6-8 times;
(4) alloy hot working: and (3) placing the as-cast alloy obtained in the step (3) in a muffle furnace at 800-950 ℃ for heat preservation for 30 minutes, performing 5-15 rolling with the deformation of 10-20% per pass and the total deformation of 75-95%, and performing water quenching on the alloy after the last rolling to obtain the prepared alloy.
The pure zirconium is industrial grade sponge zirconium; the pure aluminum is industrial pure aluminum, and the pure vanadium is industrial pure vanadium.
The invention has the beneficial effects that:
1. the invention adopts the industrial grade sponge zirconium which is not separated by zirconium and hafnium as the preparation raw material, and the cost is greatly reduced compared with the traditional zirconium alloy.
2. The novel zirconium alloy is deformed by multi-pass rolling, water quenching treatment is carried out on the alloy after the last pass of rolling, the equiaxed crystal structure can be obtained without carrying out heat treatment subsequently, the strength of the zirconium alloy is obviously improved, the tensile strength of the zirconium alloy is 800-1100 MPa, and the room-temperature tensile strength of the zirconium alloy is improved by about one time compared with that of the traditional zirconium alloy; the yield strength is 700-1000 MPa.
Drawings
FIG. 1 is a metallographic structure of a novel high-strength aerospace zirconium alloy prepared in example 1;
FIG. 2 is a metallographic structure of the novel high-strength aerospace zirconium alloy prepared in example 2;
FIG. 3 is a metallographic structure of the novel high-strength aerospace zirconium alloy prepared in example 3;
Detailed Description
Example 1
The invention provides a novel high-strength aerospace zirconium alloy which comprises the following components in percentage by weight:
aluminum: 0.85%, vanadium: 0.6 percent, and the balance of industrial grade sponge zirconium (containing 2 percent to the mass percent of hafnium).
The preparation method comprises the following steps:
(1) preparing materials: 98.55g of technical grade zirconium sponge, 0.85g of technical pure aluminum and 0.6g of technical pure vanadium were weighed.
(2) Preparing raw materials: respectively cleaning the raw materials obtained in the step (1) in absolute ethyl alcohol for 30 minutes by using an ultrasonic cleaner, and baking the cleaned raw materials for 10 minutes at 80 ℃;
(3) alloy smelting: reasonably distributing the raw materials obtained in the step (2) in a non-consumable argon arc furnace water-cooled copper crucible according to the sequence of melting points from low to high, vacuumizing a smelting furnace,until the vacuum degree reaches 1 x 10-3Pa, filling high-purity argon into the smelting furnace to 0.05MPa, additionally smelting 50g of sponge zirconium to absorb residual oxygen in the furnace body before the alloy is smelted, then starting to smelt the alloy, wherein the smelting current is 450A, and repeatedly smelting for 8 times;
(4) alloy hot working: and (3) placing the as-cast alloy obtained in the step (3) in a muffle furnace at 870 ℃ for heat preservation for 30 minutes, performing 6-pass rolling, wherein the deformation of each pass is 15 percent, the total deformation is 90 percent, and performing water quenching on the alloy after the last pass of rolling to obtain the prepared alloy.
Cutting a tensile sample and a metallographic sample from the obtained novel high-strength zirconium alloy: cutting 2mm thick tensile sample by linear cutting, cutting at least 3 tensile samples for each sample to ensure data repeatability, measuring by room temperature uniaxial tensile test with Instron 5982 universal material tester (manufacturer: Instron, USA), monitoring the tensile displacement of the sample with extensometer in the whole course, setting the tensile rate at 5 × 10-3s-1。
The structure was observed on a Zeiss Ax over 200MAT optical microscope, and the results of the mechanical property experiments are shown in Table 1, and the structure picture is shown in FIG. 1. The structure of the prepared high-strength zirconium alloy tends to be equiaxial, and the tensile strength of the alloy is obviously improved compared with that of the traditional zirconium alloy due to the existence of equiaxial crystals in the alloy.
Example 2
The invention provides a high-strength aerospace zirconium alloy which comprises the following components in percentage by weight:
aluminum: 2.5%, vanadium: 1.4 percent of zirconium sponge, and the balance of industrial grade sponge zirconium (containing 2 percent to the mass percent of hafnium).
The preparation method comprises the following steps:
(1) preparing materials: 96.1g of technical grade zirconium sponge, 2.5g of technical pure aluminum and 1.4g of technical pure vanadium were weighed.
(2) Preparing raw materials: respectively cleaning the raw materials obtained in the step (1) in absolute ethyl alcohol for 30 minutes by using an ultrasonic cleaner, and baking the cleaned raw materials for 10 minutes at 80 ℃;
(3) alloy smelting: reasonably distributing the raw materials obtained in the step (2) into a water-cooled copper crucible of a non-consumable argon arc furnace according to the sequence of melting points from low to high, vacuumizing the smelting furnace until the vacuum degree reaches 1 x 10-3Introducing high-purity argon to 0.05MPa below Pa, additionally smelting 50g of sponge zirconium to absorb residual oxygen in the furnace body before alloy smelting, then starting to smelt the alloy, wherein the smelting current is 450A, and repeatedly smelting for 8 times;
(4) alloy hot working: and (3) placing the as-cast alloy obtained in the step (3) in a muffle furnace at 870 ℃ for heat preservation for 30 minutes, performing 6-pass rolling, wherein the deformation of each pass is 15 percent, the total deformation is 90 percent, and performing water quenching on the alloy after the last pass of rolling to obtain the prepared alloy.
Tensile samples and metallographic samples are cut from the obtained novel high-strength aerospace zirconium alloy, mechanical property experiments are carried out on the novel high-strength aerospace zirconium alloy on an Instron 5892 stretcher, the structure of the novel high-strength aerospace zirconium alloy is observed on a Zeiss Ax overt 200MAT optical microscope, the obtained mechanical property experiment results are listed in a table 1, and a structure picture is shown in a figure 2. The prepared high-strength zirconium alloy has a structure of a two-state structure, and consists of laths and a large number of isometric crystals, and the tensile strength of the alloy is further improved due to the lath structure in the alloy.
Example 3
The invention provides a high-strength aerospace zirconium alloy which comprises the following components in percentage by weight:
aluminum: 3.2%, vanadium: 3.72 percent of the total weight of the alloy, and the balance of industrial-grade sponge zirconium (containing 2 percent to the mass percent of hafnium).
The preparation method comprises the following steps:
(1) preparing materials: 93.08g of technical grade zirconium sponge, 3.2g of technical pure aluminum and 3.72g of technical pure vanadium were weighed.
(2) Preparing raw materials: respectively cleaning the raw materials obtained in the step (1) in absolute ethyl alcohol for 30 minutes by using an ultrasonic cleaner, and baking the cleaned raw materials for 10 minutes at 80 ℃;
(3) alloy smelting: reasonably distributing the raw materials obtained in the step (2) in a non-consumable argon arc furnace according to the sequence of melting points from low to highIn the water-cooled copper crucible, the smelting furnace is vacuumized until the vacuum degree reaches 1 x 10-3Introducing high-purity argon to 0.05MPa below Pa, additionally smelting 50g of sponge zirconium to absorb residual oxygen in the furnace body before alloy smelting, then starting to smelt the alloy, wherein the smelting current is 450A, and repeatedly smelting for 8 times;
(4) alloy hot working: and (3) placing the as-cast alloy obtained in the step (3) in a muffle furnace at 870 ℃ for heat preservation for 30 minutes, performing 6-pass rolling, wherein the deformation of each pass is 15 percent, the total deformation is 90 percent, and performing water quenching on the alloy after the last pass of rolling to obtain the prepared alloy.
Tensile samples and metallographic samples are cut from the obtained novel high-strength aerospace zirconium alloy, mechanical property experiments are carried out on the novel high-strength aerospace zirconium alloy on an Instron 5892 stretcher, the structure of the novel high-strength aerospace zirconium alloy is observed on a Zeiss Ax overt 200MAT optical microscope, the obtained mechanical property experiment results are listed in a table 1, and a structure picture is shown in a figure 3. The prepared high-strength zirconium alloy structure is a two-state structure and consists of laths and equiaxed crystals, and the tensile strength of the alloy reaches the maximum value due to further refinement of the equiaxed crystals.
TABLE 1 mechanical property experiment data of novel high-strength aerospace zirconium alloy in examples 1-3
Based on the data shown in table 1, those skilled in the art can find that the alloy of the present invention has higher strength, and the strength of the zirconium alloy is improved correspondingly with the increase of the alloy elements (examples 1-3).
The novel high-strength aerospace zirconium alloy takes industrial grade sponge zirconium which is not separated from zirconium and hafnium as a preparation raw material, and the preparation raw material of the nuclear zirconium alloy is atomic level sponge zirconium with hafnium content less than one ten thousandth, so that the cost is extremely high. Therefore, compared with the nuclear zirconium alloy, the cost of the novel high-strength aerospace zirconium alloy can be reduced by 50-80%.
The alloy elements of the novel high-strength aerospace zirconium alloy comprise two elements, namely aluminum and vanadium. Aluminum has a solid solution strengthening effect on zirconium, is an alpha stabilizing element and can increase the alpha → beta transition temperature. The deformation at higher temperature is beneficial to the zirconium alloy to obtain an equiaxial structure or a two-state structure with better comprehensive mechanical property. Vanadium has a solid solution strengthening effect on zirconium. The addition of a small amount of vanadium can lead the zirconium alloy to retain a small amount of beta phase at room temperature, thereby strengthening the alpha/beta interface. In addition, vanadium is a beta stabilizing element, lowering the alpha → beta transition temperature. The combination of the aluminum and the vanadium elements can enlarge the temperature range of the alpha + beta two-phase region of the alloy, thereby being beneficial to regulating and controlling the alloy structure through the thermal deformation of the two-phase region. Hafnium is introduced for preparing alloy raw material industrial grade sponge zirconium. The hafnium and the zirconium are infinitely solid-dissolved at room temperature, and can play a role in solid-solution strengthening.
In summary, the novel aerospace zirconium alloy has the advantages of low cost, high strength and the like besides the physical and chemical advantages of zirconium.
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.
The invention is not the best known technology.
Claims (3)
1. A high-strength zirconium alloy is characterized in that the alloy comprises the following components in percentage by mass: aluminum (Al): 0.85-3.2%, vanadium (V): 0.6 to 3.72%, hafnium (Hf): 0.1-5%, and the balance of zirconium and inevitable impurities;
the preparation method of the novel high-strength zirconium alloy is characterized by comprising the following steps of:
(1) preparing materials: respectively weighing sponge zirconium, pure aluminum and pure vanadium according to the proportion of the components; the sponge zirconium contains 2 percent of hafnium by mass;
(2) preparing raw materials: cleaning the raw materials obtained in the step (1) in absolute ethyl alcohol by using an ultrasonic cleaner respectively, and then drying;
(3) alloy smelting: reasonably distributing the raw materials obtained in the step (2) in a water-cooled copper crucible of a non-consumable argon arc furnace according to the sequence of melting points from low to high, vacuumizing the smelting furnace, and filling high-purity argon into the smelting furnace to 0.05 MPa; before the alloy is smelted, smelting pure zirconium, absorbing residual oxygen in a furnace body, then beginning to smelt the alloy, wherein the smelting current is 300-500A, and repeatedly smelting for 6-8 times;
(4) alloy hot working: and (3) placing the as-cast alloy obtained in the step (3) in a muffle furnace at 800-950 ℃ for heat preservation for 30 minutes, performing rolling for 5-15 times, wherein the deformation of each time is 10% -20%, the total deformation is 75% -95%, and performing water quenching on the alloy after the last rolling to obtain the prepared alloy.
2. The high strength zirconium alloy of claim 1 wherein said pure zirconium is technical grade zirconium sponge; the pure aluminum is industrial pure aluminum, and the pure vanadium is industrial pure vanadium.
3. The high strength zirconium alloy according to claim 1, wherein the degree of vacuum in step (3) of the method is 1 x 10-3Pa~1*10-4Pa。
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| CN1796579A (en) * | 2004-12-21 | 2006-07-05 | 成都思摩纳米技术有限公司 | New technique for preparing getter of zirconium - barium - iron |
| CN102925749A (en) * | 2012-10-16 | 2013-02-13 | 常州大学 | Bismuth, zirconium and iron alloy for environment-friendly high-strength free cutting steel and preparation method for bismuth, zirconium and iron alloy |
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| JPS59116350A (en) * | 1982-12-23 | 1984-07-05 | Masaaki Naga | Alloy foil strip formed by quick liquid cooling for brazing |
| EP1632584A1 (en) * | 2004-09-06 | 2006-03-08 | Eidgenössische Technische Hochschule Zürich | Amorphous alloys on the base of Zr and their use |
| US9334553B2 (en) * | 2012-03-29 | 2016-05-10 | Washington State University | Zirconium based bulk metallic glasses |
| CN105603258B (en) * | 2015-12-25 | 2017-09-26 | 燕山大学 | A kind of high intensity zircaloy and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1796579A (en) * | 2004-12-21 | 2006-07-05 | 成都思摩纳米技术有限公司 | New technique for preparing getter of zirconium - barium - iron |
| CN102925749A (en) * | 2012-10-16 | 2013-02-13 | 常州大学 | Bismuth, zirconium and iron alloy for environment-friendly high-strength free cutting steel and preparation method for bismuth, zirconium and iron alloy |
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