CN113502423B - High-plasticity and high-strength cast beryllium-aluminum alloy and preparation method thereof - Google Patents
High-plasticity and high-strength cast beryllium-aluminum alloy and preparation method thereof Download PDFInfo
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- C22C25/00—Alloys based on beryllium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
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- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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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
Abstract
The invention discloses a high-plasticity and high-strength cast beryllium-aluminum alloy and a preparation method thereof, and the beryllium-aluminum alloy comprises the following components in percentage by weight: 56-65% of beryllium (Be), 33-42% of aluminum (Al), 0.7-1.0% of nickel (Ni), 0.3-0.6% of lithium (Li), 0.5-1.0% of germanium (Ge) and the balance of inevitable impurities. The casting beryllium-aluminum alloy with high sphericization degree of beryllium crystal grains and high strength and plasticity is obtained by adding metals other than rare earth elements to modify the microstructure of the alloy and combining the working procedures of high-temperature smelting, two-stage heat preservation, homogenization and hot rolling. The alloy of the invention has relatively low cost, uniform and compact alloy structure, less casting defects, short production process flow, relatively low technical difficulty, alloy strength and plasticity close to or higher than those of powder metallurgy beryllium-aluminum alloy, and good application value.
Description
Technical Field
The invention relates to the field of non-ferrous metal alloy preparation, in particular to the field of beryllium-aluminum alloy manufacture, and specifically relates to a high-plasticity and high-strength cast beryllium-aluminum alloy and a preparation method thereof.
Background
The beryllium-aluminum alloy well combines the low density and high strength of metal beryllium and the high plasticity and excellent machining performance of metal aluminum, has high specific stiffness, high thermal conductivity and excellent dimensional stability, has the characteristic of easy processing while keeping higher toughness, is a unique novel light high-strength alloy, and has wide application prospect in the fields of aerospace, nuclear industry and the like.
However, mutual solid solubility between metal beryllium and aluminum is low, melting point difference is large, and when a conventional casting method is adopted, a wider metastable miscible gap and a wider solidification interval exist in the solidification process of the alloy, which cause complete phase separation of beryllium and aluminum in the solidification process, the alloy is essentially a composite material in which pure beryllium and pure aluminum exist independently, and the beryllium and the pure aluminum form a mutually-penetrated three-dimensional network structure, wherein the beryllium phase is often represented by developed columnar dendrites, and the aluminum phase fills the gap parts between dendrite arms of beryllium grains. The difference of the solidification shrinkage rates of the two metals causes casting defects such as shrinkage porosity and shrinkage cavity to easily appear in the alloy. In addition, the coarse beryllium dendritic structure often causes anisotropy of mechanical properties of the alloy, and the density difference of two metals causes macrosegregation of the alloy when the cooling speed of the melt is slow. The structure and mechanical property of the cast beryllium-aluminum alloy can be effectively improved by adding the rare earth element as the alterant, but the micro segregation of the alloy element in the beryllium dendritic crystal gap is easy to occur when the cooling speed of the melt is not high enough. The above casting defects of various beryllium-aluminum alloys can obviously reduce the macroscopic mechanical properties such as the elastic modulus, the tensile strength, the elongation/plasticity and the like of the alloys, and greatly limit the engineering application of the cast beryllium-aluminum alloys. Therefore, there is a need to develop a new cast beryllium-aluminum alloy and a method for preparing the same to solve the above problems.
Disclosure of Invention
The invention aims to: the invention provides a high-plasticity and high-strength cast beryllium-aluminum alloy and a preparation method thereof, and solves the common problems of poor plasticity, low strength, difficult control of casting defects and the like of the beryllium-aluminum alloy prepared by the conventional casting method. The alloy microstructure is modified by adding metal elements other than rare earth elements, and finally the cast beryllium-aluminum alloy with high sphericization degree of beryllium grains and high strength and plasticity is obtained by combining smelting and hot rolling, so that the alloy raw material cost is lower. Meanwhile, the preparation process flow is short, the technical difficulty is relatively low, and the obtained alloy has excellent mechanical properties and microstructure.
The purpose of the invention is realized by the following technical scheme:
a high-plasticity and high-strength cast beryllium-aluminum alloy comprises the following components in percentage by mass: 56-65% of beryllium (Be), 33-42% of aluminum (Al), 0.7-1.0% of nickel (Ni), 0.3-0.6% of lithium (Li), 0.5-1.0% of germanium (Ge) and the balance of inevitable impurities.
Further, the lithium is added in a commercial standard aluminum lithium intermediate alloy mode, and the lithium content is 5-10% in parts by mass.
Furthermore, the purity of raw materials (except beryllium) corresponding to the alloy components is not lower than 99.9%.
The preparation method of the beryllium-aluminum alloy comprises the following steps:
(1) an induction smelting method is adopted, high-purity argon is filled into a smelting furnace, and alloy raw materials are placed in a graphite crucible for preheating;
(2) heating, keeping the temperature to melt all the raw materials, cooling, keeping the temperature, and finally casting into ingots;
(3) homogenizing and heat-treating the alloy ingot in argon atmosphere, and then quenching;
(4) turning the uniform cast ingot to remove surface oxide skin, and then carrying out hot rolling to obtain a plate blank;
(5) and annealing the alloy plate blank.
Further, in the step (1), an induction melting method is adopted, high-purity argon gas with 0.1-0.4 atmospheric pressure is filled into a melting furnace, the alloy raw material is placed in a graphite crucible, and the graphite crucible is preheated for 10-30 minutes at the temperature of 150-200 ℃.
Further, in the step (2), the temperature is raised to 1400-1450 ℃, the temperature is kept for 12-20 minutes to melt all the raw materials, then the temperature is lowered to 1350-1380 ℃, the temperature is kept for 4-8 minutes, and finally, the raw materials are cast into ingots at 1340-1360 ℃.
Further, in the step (3), the alloy ingot is subjected to homogenization heat treatment in an argon atmosphere at 540-560 ℃ for 24-36 hours, and then quenched.
Further, in the step (5), the alloy plate blank is annealed for 0.5-2 hours at the temperature of 320-380 ℃.
Further, in the step (1), the inner surface of the graphite crucible used is coated with an alumina or calcium oxide coating.
Further, in the step (1), before filling high-purity argon, the furnace chamber needs to be vacuumized to 2.0 x 10 < -2 > Pa or below.
Further, in the step (3), the quenching mode after homogenization is room temperature water quenching or oil quenching.
Furthermore, in the step (4), the rolling temperature is 480-520 ℃, the single-pass reduction amount during rolling is 8-15%, and the total reduction amount is not more than 40%.
The invention has the beneficial effects that:
(1) the added elements of nickel, lithium and germanium have excellent structure modification and performance strengthening effects on the cast beryllium-aluminum alloy. Compared with rare earth elements, the selected alloy elements have low cost and are easy to add. Wherein the nickel contributes to improving the brittleness of the cast beryllium-aluminum alloy, and is added to form Be in the alloyxAlyNizThe ternary intermetallic compound phase is separated out along the grain boundary, so that the dislocation is effectively pinned while the beryllium crystal grains are refined; lithium can obviously strengthen the aluminum phase of the alloy in a solid solution way, improve the dislocation density and improve the hardness of the alloy in a delta' phase precipitation strengthening way, and the alloy can be further strengthened and the plasticity of the alloy can be improved after heat treatment; the germanium can obviously strengthen the alloy while improving the castability of the alloy, inhibit the formation of beryllium dendrite to a certain extent and is beneficial to the spheroidization and the grain refining of the beryllium crystal grains.
(2) The invention adopts the graphite crucible and carries out alloy smelting under inert gas, and compared with the mode of adopting the ceramic crucible under the vacuum environment, the invention can completely avoid the component deviation and the safety risk caused by the splashing of the light alloy melt. The adoption of the two-section type heat preservation mode before casting can ensure the component uniformity of the alloy melt, and the cooperation with the low-pressure argon atmosphere can realize melt degassing to the maximum extent and reduce the number or density of air holes, pinholes and the like in the ingot.
(3) The invention adopts the preparation method of hot rolling after homogenization, ensures the uniform distribution of alloy elements in the alloy, reduces the micro segregation among dendrites, eliminates the coarse primary second phase, is also the aging process of the alloy at the hot rolling heat preservation stage, and can greatly strengthen the alloy and improve the plasticity of the alloy after the precipitation of the nano second phase. The rolling deformation can eliminate partial casting defects, so that the alloy structure is more compact, and meanwhile, the alloy has a more refined completely recrystallized structure, thereby being beneficial to further improving the plasticity and the modulus of the alloy.
(4) Based on the optimization of alloy elements and the improvement of a preparation method, the cast beryllium-aluminum alloy has the advantages of lower cost, short production process flow and relatively low technical difficulty, has more excellent mechanical property and microstructure, has the properties close to or higher than the strength and plasticity of powder metallurgy beryllium-aluminum alloy, and can meet the requirements of the aerospace and nuclear industry on the structure and the properties of the beryllium-aluminum alloy material for the light structure.
The main scheme and the further selection schemes can be freely combined to form a plurality of schemes which are all adopted and claimed by the invention; in the invention, the selection (each non-conflict selection) and other selections can be freely combined. The skilled person in the art can understand that there are many combinations, which are all the technical solutions to be protected by the present invention, according to the prior art and the common general knowledge after understanding the scheme of the present invention, and the technical solutions are not exhaustive herein.
Drawings
FIG. 1 is a microstructure of a conventionally cast beryllium-aluminum alloy.
FIG. 2 is a microstructure of a high strength, high plasticity cast beryllium aluminum alloy prepared in example 1.
Detailed Description
The following non-limiting examples serve to illustrate the invention.
Example 1:
a high-plasticity and high-strength cast beryllium-aluminum alloy comprises the following components in percentage by mass: 60% of beryllium (Be), 38% of aluminum (Al), 1.0% of nickel (Ni), 0.5% of lithium (Li), 0.5% of germanium (Ge) and the balance of inevitable impurities.
The preparation method of the beryllium-aluminum alloy comprises the following steps: the furnace chamber of the vacuum induction melting furnace is vacuumized to 2.0 multiplied by 10-2After Pa, high-purity argon gas with 0.1 standard atmospheric pressure is filled, and the prepared alloy raw materials are placed in a graphite crucible and preheated for 10 minutes at 200 ℃. Starting a power supply to heat the raw materials to 1430 ℃ and then preserving heat for 15 minutes, then cooling to 1380 ℃ and continuing preserving heat for 4 minutes, and finally casting the raw materials into ingots at 1360 ℃. After discharging, the alloy ingot is subjected to homogenization heat treatment in argon at 560 ℃ for 24 hours, and then water quenching is carried out at room temperature. Turning the uniform post-state alloy billet to remove surface oxide skin, and then carrying out hot rolling at 520 ℃, wherein the single-pass reduction is 15%, and the total reduction is 40%, so as to obtain a hot-rolled slab. And annealing the alloy plate blank at 380 ℃ for 0.5h to obtain the alloy product.
The prepared high-strength and high-plasticity cast beryllium-aluminum alloy plate is processed into a standard tensile sample, room-temperature tensile test is carried out on the standard tensile sample under the premise of meeting the national standard GB-T228.1-2010-Metal Room temperature tensile test to detect the mechanical property of the alloy, and the obtained result is shown in Table 1.
Table 1 example 1 tensile mechanical properties data at room temperature for cast beryllium-aluminum alloys
| Sample number | Tensile strength/MPa | Modulus of elasticity/GPa | Elongation/percent |
| 1-1 | 416 | 206 | 6.4 |
| 1-2 | 423 | 213 | 6.0 |
| 1-3 | 419 | 200 | 6.1 |
As can be seen from Table 1, the average values of tensile strength, elastic modulus and elongation of the high-strength and high-plasticity cast beryllium-aluminum alloy in example 1 are 419.3MPa, 206.3GPa and 6.16%, respectively, and some data are close to or exceed those of the AlBeMet AM162 (i.e. 426MPa, 202GPa and 4.2%) corresponding to the high-strength and high-plasticity powder metallurgy beryllium-aluminum alloy product developed by Brush Wellman in the United states.
Example 2:
a high-plasticity and high-strength cast beryllium-aluminum alloy comprises the following components in percentage by mass: 65% of beryllium (Be), 33% of aluminum (Al), 0.7% of nickel (Ni), 0.3% of lithium (Li), 1.0% of germanium (Ge), and the balance of unavoidable impurities.
The preparation method of the beryllium-aluminum alloy comprises the following steps: the furnace chamber of the vacuum induction melting furnace is vacuumized to 1.5 x 10-2After Pa, high-purity argon gas with 0.2 standard atmospheric pressure is filled, and the prepared alloy raw materials are placed in a graphite crucible and preheated for 30 minutes at 150 ℃. Starting a power supply to heat the raw materials to 1450 ℃, preserving heat for 12 minutes, then cooling to 1360 ℃, continuously preserving heat for 6 minutes, and casting the raw materials into ingots at 1350 ℃ after the process is finished. After discharging, the alloy ingot is subjected to homogenization heat treatment at 540 ℃ in argon for 36 hours, and then water quenching is carried out at room temperature. Turning the uniform post-state alloy ingot to remove surface oxide skin, and then carrying out hot rolling at the temperature of 506 ℃, wherein the single-pass reduction is 10%, and the total reduction is 32%, so as to obtain a hot-rolled slab. Alloy slab 3And annealing at 50 ℃ for 1.7h to obtain an alloy product.
The room temperature tensile mechanical properties of the cast beryllium aluminum alloy of example 2, prepared according to the above procedure, are shown in table 2.
Table 2 example 2 data on tensile mechanical properties at room temperature for cast beryllium-aluminum alloys
| Sample number | Tensile strength/MPa | Modulus of elasticity/GPa | Elongation/percent |
| 2-1 | 393 | 193 | 5.4 |
| 2-2 | 402 | 197 | 5.6 |
| 2-3 | 398 | 192 | 5.4 |
Example 3:
a high-plasticity and high-strength cast beryllium-aluminum alloy comprises the following components in percentage by mass: 56% of beryllium (Be), 42% of aluminum (Al), 0.8% of nickel (Ni), 0.6% of lithium (Li), 0.6% of germanium (Ge) and the balance of inevitable impurities.
The preparation method of the beryllium-aluminum alloy comprises the following steps: the preparation method of the high-strength and high-plasticity cast beryllium-aluminum alloy comprises the following steps: the furnace chamber of the vacuum induction melting furnace is vacuumized to 2.0 x 10-2After Pa, high-purity argon gas with 0.4 standard atmospheric pressure is filled, and the prepared alloy raw materials are placed in a graphite crucible and preheated for 20 minutes at 180 ℃. Starting a power supply to heat the raw materials to 1400 ℃, preserving heat for 20 minutes, then cooling to 1350 ℃, preserving heat for 8 minutes continuously, and casting the raw materials into ingots at 1340 ℃ after the process is finished. After discharging, the alloy billet is subjected to homogenization heat treatment in argon at 550 ℃ for 30 hours, and then oil quenching is carried out at room temperature. Turning the uniform post-state alloy billet to remove surface oxide skin, and then carrying out hot rolling at 480 ℃, wherein the single-pass reduction is 8%, and the total reduction is 30%, so as to obtain a hot-rolled slab. And annealing the alloy plate blank at 320 ℃ for 2.0h to obtain an alloy product.
The room temperature tensile mechanical properties of the cast beryllium aluminum alloy of example 2, prepared according to the above procedure, are shown in table 3.
Table 3 example 3 tensile mechanical properties data at room temperature for cast beryllium-aluminum alloys
| Sample number | Tensile strength/MPa | Modulus of elasticity/GPa | Elongation/percent |
| 3-1 | 366 | 193 | 7.7 |
| 3-2 | 375 | 197 | 7.2 |
| 3-3 | 369 | 192 | 7.6 |
The foregoing basic embodiments of the invention and their various further alternatives can be freely combined to form multiple embodiments, all of which are contemplated and claimed herein. In the scheme of the invention, each selection example can be combined with any other basic example and selection example at will. For example, fig. … … can also be regarded as a combination of the basic example and the option … …, fig. … … can also be regarded as a combination of the basic example and the option … …, and so on, which are not exhaustive, and those skilled in the art can recognize many combinations.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. The preparation method of the beryllium-aluminum alloy is characterized by comprising the following steps:
(1) introducing high-purity argon into the smelting furnace, placing alloy raw materials into a graphite crucible, and preheating;
(2) heating, keeping the temperature to melt all the raw materials, cooling, keeping the temperature, and finally casting into ingots;
(3) homogenizing and heat-treating the alloy ingot in argon atmosphere, and then quenching;
(4) turning the uniform cast ingot to remove surface oxide skin, and then carrying out hot rolling to obtain a plate blank;
(5) annealing the alloy plate blank;
the beryllium-aluminum alloy comprises the following components in percentage by mass: 56-65% of beryllium, 33-42% of aluminum, 0.7-1.0% of nickel, 0.3-0.6% of lithium, 0.5-1.0% of germanium and the balance of inevitable impurities;
in the step (2), heating to 1400-1450 ℃, preserving heat for 12-20 minutes to melt all raw materials, then cooling to 1350-1380 ℃, preserving heat for 4-8 minutes, and finally casting into ingots at 1340-1360 ℃;
in the step (3), carrying out homogenization heat treatment on the alloy ingot at 540-560 ℃ in an argon atmosphere for 24-36 hours, and then quenching;
in the step (4), the rolling temperature is 480-520 ℃, the single-pass reduction during rolling is 8-15%, and the total reduction is not more than 40%.
2. The method of claim 1, wherein: the lithium is added in a commercial standard aluminum lithium intermediate alloy mode, and the lithium content is 5-10% in parts by mass.
3. The method of claim 1, wherein: in the step (1), high-purity argon gas with 0.1-0.4 atmospheric pressure is filled into the smelting furnace, the alloy raw material is placed in a graphite crucible, and the graphite crucible is preheated for 10-30 minutes at the temperature of 150-200 ℃.
4. The method of claim 1, wherein: in the step (5), the alloy plate blank is annealed for 0.5-2 hours at the temperature of 320-380 ℃.
5. The method of claim 1, wherein: in the step (1), the inner surface of the graphite crucible is coated with an alumina or calcium oxide coating.
6. The production method according to claim 1 or 5, characterized in that: in the step (1), before filling high-purity argon, the furnace chamber needs to be vacuumized to 2.0 x 10-2Pa andthe following steps.
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