CN109628866B - Heat treatment method of wrought zinc-aluminum-vanadium alloy - Google Patents
Heat treatment method of wrought zinc-aluminum-vanadium alloy Download PDFInfo
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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Abstract
The invention belongs to the technical field of non-ferrous metal material processing, and particularly relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy. The heat treatment method of the deformed zinc-aluminum-vanadium alloy adopts a multi-pass repeated heat treatment comprising quenching circulation quenching, namely: preserving the heat of the zinc-aluminum-vanadium alloy semi-finished product subjected to hot and cold plastic processing at 100-190 ℃ for 0.5-2.0 hours, and discharging the semi-finished product out of the furnace for quenching; then reheating to 100-190 ℃ and preserving heat for 0.5-2.0 hours, and discharging for quenching. This was repeated at least 2 times. After the special heat treatment, the tensile strength of the zinc-aluminum-vanadium alloy at room temperature exceeds 402MPa, and the elongation after fracture reaches more than 10%. Compared with the common heat treatment method, the invention improves the tensile strength of the zinc-aluminum-vanadium alloy by more than 60 percent and keeps good plasticity. Therefore, the heat treatment method has good engineering value.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal material processing, and particularly relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy.
Background
The zinc resource is rich in China, and the zinc alloy have the advantages of low melting point, low processing energy consumption and good comprehensive performance. At present, the zinc alloy has been widely applied to the aspects of hardware, bathroom, machinery, building materials, decoration, instruments and meters, commemorative coins and the like, and meanwhile, the zinc alloy also has potential application prospects in many aspects.
With the intensive research and application of zinc alloy, two major types of cast zinc alloy and wrought zinc alloy are formed at present, and the widely-used wrought zinc alloy structural materials mainly comprise two series of Zn-Al series and Zn-Cu series, wherein the Zn-10Al alloy containing 10% of aluminum is most applied and is registered as ZAT10 by domestic enterprises. Although the alloy has various excellent properties, the comprehensive mechanical properties are still not ideal enough, the room-temperature tensile strength of the existing Zn-Al alloy is generally about 260MPa, the elongation after fracture is 40-60%, and the alloy is used as a structural member with higher comprehensive mechanical property requirements, and the application of the alloy is limited due to low load capacity and insufficient dimensional stability in the service process.
The inventor of the patent tries to improve the comprehensive mechanical property of the alloy by adding high-melting-point vanadium element into a zinc-aluminum matrix, the tensile strength at room temperature can be improved to 360MPa, but the elongation after fracture is reduced to 3.9%. Although the tensile strength of the material is improved, the toughness is reduced, the brittleness is improved, and the comprehensive mechanical property is still not ideal.
The melting point of zinc is 419.5 ℃, the zinc alloy can generate phase change at 100-200 ℃, so the heat treatment temperature of the alloy is relatively low, after heat treatment, the conventional cooling method of the alloy mostly adopts a furnace or air cooling mode, the alloy strength, plasticity and creep resistance are low, and the alloy is difficult to be used as a structural material in engineering. Related research and reports in the field are not seen at present.
Disclosure of Invention
Aiming at the problem of lower comprehensive performance of the deformed zinc-aluminum alloy in the prior art, the invention aims to provide a heat treatment method of the deformed zinc-aluminum-vanadium alloy which has excellent tensile strength, yield strength and elongation after fracture.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy, which is characterized in that after a zinc-aluminum-vanadium alloy casting blank is subjected to homogenization treatment and plastic deformation, heat preservation and quenching at the temperature of 190 ℃ or below are carried out for at least 2 times, and the quenching speed is more than or equal to 30 ℃/s.
The heat treatment method of the deformed zinc-aluminum-vanadium alloy has the heat preservation and quenching times of 2-6 times which are not more than 190 ℃.
The invention relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy, wherein the heat preservation temperature is 100-190 ℃, and the heat preservation time is 0.5-2 hours; preferably, the heat preservation temperature is 120-170 ℃, and the heat preservation time is 0.5-1.5 hours; more preferably, the heat preservation temperature is 140-170 ℃ and the heat preservation time is 0.8-1.5 hours.
The invention relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy, wherein the quenching speed is 30-100 ℃/s; preferably 45-100 ℃/s; more preferably 60-100 deg.C/s.
The invention relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy.A quenching cooling medium selects one of ice water and liquid nitrogen.
The invention relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy, wherein the alloy casting blank is subjected to homogenization treatment and has the technological parameters as follows: keeping the temperature at 320-380 ℃ for 6-12 hours. .
The invention relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy, wherein a blank after homogenization treatment is subjected to plastic deformation, and the plastic deformation is selected from thermoplastic deformation and cold plastic deformation; the thermoplastic deformation is selected from one of hot rolling, hot extrusion and hot drawing; one of cold rolling, cold extrusion and cold drawing is performed on the cold plastic deformation; the total deformation amount of the plastic deformation is more than or equal to 90 percent.
The invention relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy, which comprises the following components in percentage by mass:
9.80-10% of aluminum, 0.05-1.00% of vanadium, 0.01-0.60% of titanium, 0.05-1.00% of copper and the balance of zinc.
As a further optimization, the zinc-aluminum-vanadium alloy comprises the following components in percentage by mass: 9.80-9.85% of aluminum, 0.50-0.80% of vanadium, 0.01-0.06% of titanium, 0.50-0.90% of copper and the balance of zinc.
The invention relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy, which has the following performance indexes:
the tensile strength at room temperature is more than or equal to 402 MPa;
the elongation after fracture is more than or equal to 10.4 percent;
the yield strength is more than or equal to 369 MPa.
Principles and advantages
The invention relates to a heat treatment method of a deformed zinc-aluminum-vanadium alloy, which eliminates non-equilibrium structures to the maximum extent, improves the stability of material structure components, fully exerts the beneficial effect of alloy elements and effectively improves the mechanical property of the zinc-aluminum alloy by carrying out repeated heat treatment of quenching on the zinc-aluminum-vanadium alloy subjected to hot and cold plastic processing for multiple times. The zinc-vanadium-aluminum alloy adopted by the method is subjected to an X-ray diffraction experiment, and the deformed zinc-aluminum-vanadium alloy mainly comprises a zinc-rich eta phase, an alpha + eta layer flaky, cellular and granular structure and an unbalanced beta (ZnAl) phase, wherein the eta phase is a zinc-rich phase, the alpha phase is an aluminum-rich phase, the beta phase is a ZnAl phase, and a plurality of Al phasesnVmAlZn, etc., as shown in the attached figure I. The inventor finds that the (alpha + eta) cellular and granular structures of the alloy after the conventional heat treatment are remarkably increased, and the matrix structure of the alloy is relatively uniform and stable. However, in the conventional heat treatment, the cooling rate with furnace cooling or air cooling is low, and the solid solution phase Al of the alloy in a heating and heat preservation statenVmEasy agglomeration of AlZn and the likeCoarsening is gathered, thereby reducing pinning to dislocations and grain boundaries, resulting in reduced alloy strength, plasticity, and creep resistance.
After the special heat treatment of the invention, the problem of second phase agglomeration is solved to a certain extent, and some fine second phase particles which are uniformly and dispersedly distributed are formed in the alloy, so that dislocation and crystal boundary can be effectively pinned, thereby improving the strength of the alloy and keeping good ductility. Experiments show that after the heat treatment, the tensile strength of the alloy at room temperature exceeds 400MPa, the elongation after fracture reaches more than 10 percent, and the yield strength reaches more than 360 MPa; compared with the traditional Zn-10Al alloy which is not treated by the heat treatment method, the room temperature tensile strength is improved by more than 60 percent, the yield strength is improved by more than 60 percent, and the plasticity index is equivalent; compared with the zinc-aluminum-vanadium alloy which is not treated by the heat treatment method, the room temperature tensile strength is improved by 17 percent, the elongation after fracture is improved by more than 1.8 times, and the yield strength is improved by more than 20 percent. Therefore, the high-strength steel can bear higher load, has certain toughness and has wider application prospect.
In the zinc-aluminum-vanadium alloy reported at present, the tensile strength is improved by adding vanadium, but the improvement on yield strength is limited, and the elongation after fracture is lower, and in the application process of the material, the comprehensive properties of the material are considered, for example, even if the tensile strength is higher, if the yield strength is not reached, the material can fail too early, so that the application is limited.
After the heat treatment process of the multistage circulating quenching treatment, the mechanical properties of the zinc-aluminum-vanadium alloy can be synchronously improved.
Compared with the prior Zn-10Al alloy and the zinc-aluminum-vanadium alloy which is not treated by the heat treatment method, the invention has the following advantages and effects:
1. good toughness: the invention relates to a zinc-aluminum-vanadium alloy, which adopts a multi-pass repeated heat treatment including quenching and quenching, the elongation after fracture is more than 10 percent, and the room-temperature tensile strength is more than 400 MPa. Compared with the zinc-vanadium-aluminum alloy which does not adopt the heat treatment method, the elongation after fracture is improved by 1.8 times. The elongation percentage of the existing Zn-10Al alloy after fracture can reach 40-60%, but the tensile strength at room temperature is only about 260MPa generally.
2. Higher room temperature tensile strength: experiments show that compared with the zinc-aluminum-vanadium alloy which does not adopt rapid cooling quenching and is repeatedly subjected to heat treatment for multiple times, the room-temperature tensile strength of the invention is improved by 17 percent; compared with the common Zn-10Al alloy which does not adopt the heat treatment method, the room-temperature tensile strength of the invention is improved by 60 percent under the same condition.
3. Excellent yield strength: compared with the zinc-aluminum-vanadium alloy which does not adopt ice water quenching and is repeatedly subjected to heat treatment for multiple times under the same condition, the yield strength at room temperature of the invention is improved by more than 20 percent; compared with the common Zn-10Al alloy which does not adopt the heat treatment method under the same condition, the yield strength at room temperature of the invention is improved by more than 60 percent.
Drawings
FIG. 1 shows the X-ray diffraction analysis results of the Zn-V-Al alloy used in the examples of the present invention.
FIG. 2 is a phase diagram of the zinc-vanadium-aluminum alloy of comparative example 2 of the invention.
FIG. 3 is a phase diagram of the Zn-V-Al alloy of example 1.
As can be seen from the results of X-ray diffraction analysis of FIG. 1: the wrought Zn-Al-V alloy mainly comprises a zinc-rich eta phase, an alpha + eta lamellar, cellular and granular structure, and a non-equilibrium beta (ZnAl) phase, wherein the eta phase is a zinc-rich phase, the alpha phase is an aluminum-rich phase, the beta phase is a ZnAl phase, and a plurality of Al phasesnVmAlZn, and the like.
As can be seen from the gold phase diagram of the attached figure 2, the matrix structure of the zinc-vanadium-aluminum alloy treated by the conventional heat treatment (furnace cooling) has a low cooling rate along with furnace cooling or air cooling in the conventional heat treatment, so that the solid solution phase Al of the alloy in a heating and heat-preserving statenVmAnd AlZn and the like are easy to agglomerate and coarsen, so that the pinning effect on dislocation and crystal boundary is reduced, and the alloy strength, plasticity and creep resistance are reduced.
As can be seen from the gold phase diagram shown in the attached figure 3, the structure of the zinc-vanadium-aluminum alloy matrix (example 1) treated by the heat treatment (rapid circulating cooling) of the invention solves the problem of second phase agglomeration to a certain extent, and a plurality of fine second phase particles which are uniformly and dispersedly distributed are formed in the alloy and can effectively pin dislocation and grain boundaries, so that the strength of the alloy is improved, and good ductility is maintained
Detailed Description
The technical solution of the present invention will be further specifically described below by way of examples. It should be noted that the following examples and comparative examples are only illustrative of the present invention and should not be construed as limiting the scope of the claims of the present invention.
The implementation process of the invention adopts the following method to prepare the test sample: preparing a Zn-12Al-1.5V intermediate alloy by adopting a vacuum melting method, then placing the intermediate alloy, pure zinc, pure aluminum, pure copper and pure titanium into a graphite crucible, placing the graphite crucible into a medium-frequency induction furnace, heating, properly stirring after all melts are melted, standing, and casting the melt in a steel mold to obtain a vanadium-zinc-aluminum alloy cast ingot; then the cast ingot is subjected to surface machining, homogenization treatment (keeping the temperature at 320-375 ℃ for 6-12 hours), hot and cold plastic deformation treatment (the deformation is more than or equal to 90 percent) and quenching (4-pass circulation) heat treatment. And sampling alloys with various proportions to perform room temperature tensile experiment experiments. (in the present example and comparative example, casting, homogenization treatment, hot and cold plastic deformation were conducted in a conventional zinc-aluminum alloy phase-similar manner)
The invention will now be illustrated in 7 examples:
the alloy compositions of the samples, which are not indicated in the examples and the comparative examples, are as follows:
example 1
Heat treatment process for deformed zinc-vanadium-aluminum alloy
The alloy after homogenization treatment and hot and cold plastic deformation treatment is subjected to ice water quenching circulating quenching heat treatment for 4 times:
(100 to 120 ℃) x 30min x rapid quenching (35 ℃/S) + (100 to 120 ℃) x 30min x rapid quenching (35 ℃/S) × (100 to 120 ℃)
Second, room temperature tensile test
And (4) testing the mechanical property of the finally obtained zinc-vanadium-aluminum alloy. The result is:
example 2
Heat treatment process for deformed zinc-vanadium-aluminum alloy
The alloy after homogenization treatment and hot and cold plastic deformation treatment is subjected to ice water quenching circulating quenching heat treatment for 4 times:
(120-140 ℃) x 60min x rapid quenching (not less than 55 ℃/S) + (120-140 ℃) x 60min x rapid quenching (not less than 55 ℃/S)
Second, room temperature tensile test
And (4) testing the mechanical property of the finally obtained zinc-vanadium-aluminum alloy. The result is:
example 3
Heat treatment process for deformed zinc-vanadium-aluminum alloy
The alloy after homogenization treatment and hot and cold plastic deformation treatment is subjected to ice water quenching circulating quenching heat treatment for 4 times:
(140 to 160 ℃) multiplied by 90min multiplied by rapid quenching (not less than 75 ℃/S) + (140 to 160 ℃) multiplied by 90min multiplied by rapid quenching (not less than 75 ℃/S)
Second, room temperature tensile test
And (4) testing the mechanical property of the finally obtained zinc-vanadium-aluminum alloy. The result is:
example 4
Heat treatment process for deformed zinc-vanadium-aluminum alloy
The alloy after homogenization treatment and hot and cold plastic deformation treatment is subjected to ice water quenching circulating quenching heat treatment for 4 times:
at 160-190 ℃ for 120min multiplied by rapid quenching (not less than 95 ℃/S) + (160-190 ℃) for 120min multiplied by rapid quenching (not less than 95 ℃/S)1) + (160-190 ℃) x 120min x quench quenching (more than or equal to 95 ℃/S)
Second, room temperature pull-up test
And (4) testing the mechanical property of the finally obtained zinc-vanadium-aluminum alloy. The result is:
example 5
Heat treatment process for deformed zinc-vanadium-aluminum alloy
The alloy after homogenization treatment and hot and cold plastic deformation treatment is subjected to ice water quenching circulating quenching heat treatment for 4 times:
(200-230 ℃) x 150min x rapid quenching (75 ℃/S) + (200-230 ℃) x 150min x rapid quenching (75 ℃/S) ×
Second, room temperature tensile test
And (4) testing the mechanical property of the finally obtained zinc-vanadium-aluminum alloy. The result is:
example 6
Heat treatment process for deformed zinc-vanadium-aluminum alloy
The alloy after homogenization treatment and hot and cold plastic deformation treatment is subjected to 5 times of quenching heat treatment of quenching circulation: (140-160 ℃) x 90min x rapid quenching (not less than 75 ℃/S) + (140-160 ℃) x 90min x rapid quenching (not less than 75 ℃/S)
Second, room temperature tensile test
And (4) testing the mechanical property of the finally obtained zinc-vanadium-aluminum alloy. The result is:
comparative example 1
The deformed zinc-vanadium-aluminum alloy is not subjected to heat treatment, and is subjected to cold-hot deformation after homogenization treatment and then is directly subjected to tensile test:
and (4) testing the mechanical property of the finally obtained zinc-vanadium-aluminum alloy. The result is:
comparative example 2
Firstly, carrying out conventional heat treatment after homogenizing treatment and hot and cold plastic deformation treatment on the deformed zinc-vanadium-aluminum alloy, wherein the conventional heat treatment process comprises the following steps:
360 ℃ x 30min x furnace cooling +270 ℃ x 10min x furnace cooling +100 ℃ x 10-13 h x air cooling
Second, room temperature tensile test
And (4) testing the mechanical property of the finally obtained zinc-vanadium-aluminum alloy. The result is:
comparative example 3
Conventional heat treatment process for deformed Zn-10Al alloy
First, the component proportion of the alloy
Second, conventional heat treatment process for deformation Zn-10Al alloy
360 ℃ x 30min x furnace cooling +270 ℃ x 10min x furnace cooling +100 ℃ x 10-13 h x air cooling
Third, room temperature pull-up test
And (4) testing the mechanical property of the finally obtained zinc-vanadium-aluminum alloy. The result is:
by comparing the above-mentioned examples with comparative examples,
1. examples 1, 2, 3, 4, 5 and 6 are a multi-pass repeated heat treatment method using quenching in a quench cycle,
examples of experiments were conducted on hot and cold deformed zinc-aluminium-vanadium alloys, wherein examples 1, 2, 3, 4 are described in the summary of the invention;
2. comparative example 1 is an experimental example of a hot-cold deformation zinc-aluminum-vanadium alloy material which is repeatedly subjected to heat treatment for multiple times and does not adopt quenching circulation;
3. comparative example 2 is an experimental example of hot and cold deformation of a zinc-aluminum-vanadium alloy material by adopting a conventional heat treatment process;
4. comparative example 3 is an example of an experiment on a general hot and cold deformation Zn-10Al alloy material using a conventional heat treatment process;
5. the experimental result shows that in the examples 1, 2, 3, 4, 5 and 6, the hot-deformation zinc-aluminum-vanadium alloy material and the cold-deformation zinc-aluminum-vanadium alloy material are subjected to repeated heat treatment of multiple times of quenching in a quenching cycle, and the room-temperature tensile strength and the yield strength of the material are improved along with the increase of the single heat preservation temperature and the prolongation of the heat preservation time. However, under the same multi-pass quenching cycle quenching condition, when the single-time heat preservation temperature exceeds 160 ℃ and the single-time heat preservation time exceeds 90 minutes, the room-temperature tensile strength and the yield strength of the material are reduced, and the test scheme is optimal as that of example 3, optimal as that of example 4 and worst as that of example 5.
6. The experimental result shows that the hot and cold deformation zinc-aluminum-vanadium alloy material is repeatedly subjected to quenching heat treatment by adopting multiple quenching cycles, the room-temperature tensile strength and the yield strength of the material can be obviously improved, the good elongation after fracture is kept, and the experimental scheme takes the embodiment 3 as the best. However, under the same holding temperature and holding time conditions, when the quenching heat treatment of the quenching cycle is repeated more than 4 times, the room-temperature tensile strength and yield strength of the material are reduced.
7. Compared with the same heat treatment method and different alloy component ratios (comparative examples 2 and 3), the experimental result shows that: under the condition of conventional heat treatment, the hot and cold deformation zinc-aluminum-vanadium alloy materials and the common hot and cold deformation Zn-10Al alloy materials have lower room temperature tensile strength, and the comprehensive mechanical property of the zinc-aluminum-vanadium alloy materials subjected to the conventional heat treatment is even slightly lower than that of the common Zn-10Al alloy materials;
8. the experimental results of the experimental examples (examples 1, 2, 3 and 4 and comparative examples 1 and 2) of different heat treatment methods comparing the same alloy composition ratio longitudinally show that: the hot and cold deformation zinc-aluminum-vanadium alloy adopting the multi-pass repeated heat treatment method of quenching circulation has the room temperature tensile strength improved by more than 60 percent compared with the hot and cold deformation zinc-aluminum-vanadium alloy adopting the conventional heat treatment method, the yield strength improved by more than 60 percent, and the elongation after the material is broken improved by more than 60 percent.
Therefore, the heat treatment method of the deformed zinc-aluminum-vanadium alloy adopts a multi-pass repeated heat treatment including quenching cycle quenching, so that the zinc-aluminum-vanadium alloy has better room-temperature tensile strength and keeps good ductility, the defect of low bearing capacity in the service process of the alloy is overcome, the comprehensive mechanical property of the material is greatly improved, and an effective technical approach is provided for the development of new zinc-based alloy products.
While the invention has been described with respect to specific embodiments, many modifications and variations are possible. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.
Claims (5)
1. A heat treatment method of a deformed zinc-aluminum-vanadium alloy is to carry out heat preservation and quenching for 2 to 6 times after homogenizing treatment and plastic deformation of a zinc-aluminum-vanadium alloy casting blank, wherein the heat preservation temperature is 100 to 190 ℃, the heat preservation time is 0.5 to 2 hours, and the quenching speed is more than or equal to 30 ℃/s;
the alloy casting blank is subjected to homogenization treatment with the following technological parameters: preserving heat for 6-12 hours at 320-380 ℃; the total deformation amount of the plastic deformation is more than or equal to 90 percent;
the zinc-aluminum-vanadium alloy comprises the following components in percentage by mass:
9.80-10% of aluminum, 0.05-1.00% of vanadium, 0.01-0.60% of titanium, 0.05-1.00% of copper and the balance of zinc.
2. The method for heat-treating a wrought zinc-aluminum-vanadium alloy according to claim 1, wherein: the quenching speed is 30-100 ℃/s.
3. The method for heat-treating a wrought zinc-aluminum-vanadium alloy according to claim 1, wherein: the quenching cooling medium is selected from one of ice water and liquid nitrogen.
4. The method for heat-treating a wrought zinc-aluminum-vanadium alloy according to claim 1, wherein: subjecting the homogenized blank to plastic deformation selected from the group consisting of thermoplastic deformation and cold plastic deformation; the thermoplastic deformation is selected from one of hot rolling, hot extrusion and hot drawing; and the cold plastic deformation is one of cold rolling, cold extrusion and cold drawing.
5. The method for heat-treating a wrought zinc-aluminum-vanadium alloy according to claim 1, wherein: the performance indexes of the processed deformed zinc-aluminum-vanadium alloy are as follows:
the tensile strength at room temperature is more than or equal to 402 MPa;
the elongation after fracture is more than or equal to 10.4 percent;
the yield strength is more than or equal to 369 MPa.
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