CN113388754B - High-strength Ti-Cr-Zr-Mo-Al series titanium alloy and preparation method thereof - Google Patents
High-strength Ti-Cr-Zr-Mo-Al series titanium alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Ti-Cr-Zr-Mo-Al series titanium alloy with high strength and a preparation method thereof, wherein the titanium alloy comprises the following components in percentage by mass: 2.5 to 6.0 percent of Al,1.5 to 5.0 percent of Cr, 1.4 to 5.0 percent of Zr, 2.0 to 8.0 percent of Mo, less than or equal to 0.35 percent of O, and the balance of Ti and inevitable other impurities. The alloy is subjected to smelting, forging, solid solution and aging treatment to obtain high strength and good plasticity, and is not easy to cause component segregation, and meanwhile, the alloy raw material cost is low, and the production and manufacturing cost of the alloy is reduced to a certain extent. The alloy meets the requirement of various industrial fields on high performance of the titanium alloy structural member, and can be widely applied to the industrial fields of aviation, aerospace, automobiles and the like.
Description
Technical Field
The invention belongs to the technical field of metal materials, and particularly relates to a Ti-Cr-Zr-Mo-Al series titanium alloy with high strength and a preparation method thereof.
Background
With the consumption of traditional fossil fuels, carbon dioxide (CO) 2 ) The greenhouse effect and environmental problems caused by the emissions are attracting more and more attention, and countries around the world make strict plans to limit the use of traditional fossil fuels and the emission of greenhouse gases. Fossil fuel consumption and CO for various transportation vehicles 2 The light weight of transportation means is to reduce the consumption of fossil fuel and artificial CO 2 The key to emissions. The main approach to weight reduction is to increase the use of structural materials with high specific strength (strength to weight ratio). High specific strength materials enable component size and structural weight reductions and reduce manufacturing, transportation and installation costs. In recent years, titanium alloys have attracted great attention because of their excellent specific strength, toughness and corrosion resistance, for example, boeing 787 dream airliners use about 15% of titanium alloys for medium and long haulOne of the most fuel efficient aircraft in the air transportation.
In recent years, a few high-strength titanium alloys have been developed at home and abroad, and the beta stabilization and strengthening purposes are achieved by adding higher content of beta stabilizing elements V and Mo, wherein the V element is very expensive, and the raw material cost of the alloy is obviously increased when the V element is excessively added; the Mo element has a high melting point, and when the Mo element is excessively added, component segregation is easily caused, so that the energy consumption for processing and manufacturing is high, and the uniformity control of alloy components and structures is difficult. For example, arun et al utilize TiH 2 The tensile strength of Ti185 (Ti-1 Al-8V-5 Fe) prepared by powder sintering is about 1600MPa, the plasticity is about 5 percent, the preparation process is different from the traditional titanium alloy preparation process, and the process flow is more complex; mantri et Al prepared beta-21S (Ti-15 Mo-3Nb-2.7Al-0.2 Si) by omega-phase assisted nucleation had tensile strength of about 1880MPa and plasticity of about 4%, but the heat treatment time was over 150h, the production preparation time was longer, the production cost was high and was not suitable for commercial application; the tensile strength of Ti-7333 (Ti-7 Mo-3Nb-3Cr-3 Al) prepared by Dong et Al was about 1550MPa and the plasticity was about 8%.
Disclosure of Invention
Aiming at the defect that some high-strength titanium alloys commonly used at present have high cost caused by V, mo, nb and other elements with high content, the invention provides a Ti-Cr-Zr-Mo-Al series titanium alloy with high strength, which has excellent mechanical property, is not easy to cause component segregation and has the advantage of low cost.
The invention is realized by the following technical scheme:
a Ti-Cr-Zr-Mo-Al series titanium alloy with high strength comprises, by mass, 2.5-5.5% of Al, 1.5-4.0% of Cr, 1.4-5.0% of Zr, 3.0-8.0% of Mo and less than 0.35% of O, and the balance Ti and inevitable other impurities.
Preferably, the titanium alloy has a yield strength Rp =1550MPa to 1820MPa, a tensile strength Rm =1600MPa to 1880MPa, and an elongation a =3% to 10%.
A preparation method of Ti-Cr-Zr-Mo-Al series titanium alloy with high strength comprises the steps of uniformly mixing all raw materials according to the percentage, then putting the raw materials into a furnace to be smelted for multiple times to obtain ingots with uniform components, then carrying out free forging across a beta phase region after peeling and dead head cutting on the ingots, and carrying out heat treatment on the forged ingots in a two-phase region to obtain the Ti-Cr-Zr-Mo-Al series titanium alloy.
Preferably, argon is introduced during the smelting process, the induced current is 350-450A, the current frequency is 20-25 KHz, and the alloy is continuously kept for 15-20 min after being completely melted.
Preferably, the free forging includes cogging forging and forging across a beta phase region.
Preferably, the cogging temperature of the cogging forging is 1100-1200 ℃, and the heat preservation time is 90min.
Preferably, the temperature of the forging across the beta phase region is 850-980 ℃. The deformation is more than or equal to 70 percent.
Preferably, the deformation of the cogging forging is more than or equal to 60 percent, and the deformation of the forging across a beta phase region is more than or equal to 70 percent.
Preferably, the method for the heat treatment of the two-phase region comprises the following steps:
and (3) carrying out solid solution treatment on the cast ingot subjected to the forging in the beta-phase-crossing region in a two-phase region for 60min, then carrying out water quenching to room temperature, then carrying out aging treatment at 500-585 ℃, and carrying out air cooling to room temperature.
Preferably, the temperature of the two-phase region is 845 to 885 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the high-strength Ti-Cr-Zr-Mo-Al titanium alloy provided by the invention, zr and Al elements are added in the titanium alloy, so that the alpha phase is favorably compositely reinforced, and the common alpha reinforcing element Al is added, and simultaneously, the neutral element Zr is added to compositely reinforce the alpha phase, so that the dislocation slip critical slitting stress in the alpha phase can be improved, and the overall strength of the alloy is improved. Secondly, mo and Cr elements in the titanium alloy are beneficial to compositely strengthening a beta phase, mo has a strong solid solution strengthening effect on the titanium alloy, the low-temperature strength and the high-temperature strength of the alloy are improved, the eutectoid reaction speed of Cr is low, the mechanical property of the alloy is further improved, sufficient shearing resistance force is generated by an alpha/beta interface, and the average free slip path of dislocation in the alloy is reduced, so that the alloy has ultrahigh strength. The titanium alloy has yield strength Rp =1550 MPa-1820 MPa, tensile strength Rm =1600 MPa-1880 MPa and elongation A =3% -10%, so that the titanium alloy has good comprehensive mechanical properties.
The Ti-Cr-Zr-Mo-Al series titanium alloy with high strength has various smelting modes, the preparation process is simple, short-flow preparation is realized, high strength and excellent plasticity can be obtained through reasonable component design and element proportion optimization through simple heat treatment, the components and the structure of the Ti-Cr-Zr-Mo-Al series titanium alloy are optimized by utilizing the primary alpha phase and the secondary alpha phase which are separated out in multiple levels on a titanium alloy beta matrix and combining the alloying principle of the existing commercial titanium alloy, and the alloy realizes good matching of the strong plasticity of the alloy after simple heat treatment. On the basis of reducing the cost of raw materials, the processing cost is reduced, the cost of the high-strength titanium alloy is further reduced, and the requirements of various industrial fields on high-performance titanium alloy structural members are met.
Drawings
FIG. 1 is an SEM structural photograph of a Ti-Cr-Zr-Mo-Al based titanium alloy having high strength according to example 1 of the present invention;
FIG. 2 is an SEM structural photograph of a Ti-Cr-Zr-Mo-Al based titanium alloy having high strength in example 2 of the present invention;
FIG. 3 is an SEM structural photograph of a Ti-Cr-Zr-Mo-Al based titanium alloy having high strength in example 3 of the present invention;
FIG. 4 is a graph showing tensile properties of heat-treated Ti-Cr-Zr-Mo-Al based titanium alloys having high strength in examples 1 to 3 of the present invention, in which the abscissa is true strain and the ordinate is true stress.
Detailed Description
The present invention will now be described in further detail with reference to the attached drawings, which are illustrative, but not limiting, of the present invention.
A Ti-Cr-Zr-Mo-Al series titanium alloy with high strength comprises, by mass, 2.5-5.5% of Al, 1.5-4.0% of Cr, 1.4-5.0% of Zr, 3.0-8.0% of Mo and less than 0.35% of O, and the balance Ti and inevitable other impurities.
The titanium alloy has a yield strength Rp =1550MPa to 1820MPa, a tensile strength Rm =1600MPa to 1880MPa, and an elongation A =3% to 10%.
A preparation method of a high-strength Ti-Cr-Zr-Mo-Al series titanium alloy adopts a cold crucible suspension smelting method, wherein the raw materials are uniformly mixed according to the percentage, then the mixture is put into a furnace to be smelted for multiple times to obtain an ingot with uniform components, the ingot is freely forged in a beta-phase-crossing region after being scalped and a dead head is cut, and the forged ingot is subjected to heat treatment in a two-phase region to obtain the Ti-Cr-Zr-Mo-Al series titanium alloy.
And introducing high-purity argon in the cold crucible induction suspension smelting process, wherein the induction current is 350-450A, the current frequency is 20-25 KHz, continuously maintaining for 15-20 min after the alloy is completely molten, and repeatedly smelting and cooling to obtain the cast ingot.
The free forging includes cogging forging and high-temperature forging across a beta phase region.
The cogging temperature of the cogging forging is 1100-1200 ℃, the heat preservation time is 90min, and the deformation is more than or equal to 60%.
The high-temperature forging temperature across the beta phase region is 850-980 ℃, and the deformation is more than or equal to 70%.
The heat treatment process of the cast ingot comprises the following steps: dissolving in water at 845-885 deg.C for 60min, quenching to room temperature, aging at 500-585 deg.C for 120min, and cooling in air to room temperature.
Example 1
A preparation method of Ti-Cr-Zr-Mo-Al series titanium alloy with high strength comprises the following steps:
step 1, preparing the master alloy by adopting a cold crucible suspension smelting method.
The following raw materials were weighed in percentage, 4.27% of Al, 2.50% of Cr, 2.60% of Zr, 7.28% of Mo, 3242% of Ti, 83.35% and inevitable other impurities.
Uniformly mixing the high-purity Ti, the high-purity Al, the high-purity Zr, the high-purity Mo and the high-purity Cr, then, dispersedly loading the mixture into a cold crucible suspension smelting furnace, then, smelting in a high-purity argon atmosphere, wherein the smelting current is 450A, the current frequency is 20KHz, and keeping for 15min after the alloy is completely molten. Repeatedly smelting the ingot for 5 times in the furnace by turning the ingot upside down in order to ensure the components to be uniform;
and 2, cogging and forging the master alloy.
Cutting off a dead head of the ingot obtained in the step 1, and then, performing cogging forging at the temperature of 1150 ℃ for 90min, wherein three piers and three drawdowns are adopted for cogging, and the deformation is 65%;
and 3, carrying out cross-beta phase region forging on the forged master alloy.
The forging temperature range of the high-temperature beta-phase-crossing region is 890-980 ℃, and the deformation is 75%;
and 4, carrying out solid solution and aging treatment on the ingot after the forging in the beta-phase-crossing region.
Carrying out solid solution treatment on Ti-Cr-Zr-Mo-Al series titanium alloy for 60min at the temperature of 860 ℃ in an alpha + beta two-phase region, carrying out water quenching to the room temperature, then carrying out aging treatment for 120min at the temperature of 500 ℃, and carrying out air cooling to the room temperature.
The obtained structure is shown in figure 1, after solid solution and water quenching in a two-phase region, a typical equiaxial alpha phase appears in a beta matrix, the size is about 0.8-2 mu m, and meanwhile, a flaky secondary alpha phase with the thickness of about 30-60 nm also appears. The composite structure enables the alloy to have high strength and excellent plasticity. According to the GB/T228.1-2010 standard requirement, the measured mechanical property of the alloy is shown as a curve 1 in a figure 4: the yield strength Rp is 1810MPa, the tensile strength Rm is 1940MPa, and the total elongation at break A is 4.2%.
Example 2
A Ti-Cr-Zr-Mo-Al series titanium alloy with high strength comprises the following components in percentage by weight: 4.27% of Al, 2.50% of Cr, 2.60% of Zr, 7.28% of Mo, 8978% of Ti, 83.35% and other inevitable impurities.
According to the components, the alloy is prepared by cold crucible suspension smelting and hammering free forging, and the preparation method comprises the following steps:
step 1, preparing a master alloy: high-purity Ti, high-purity Al, high-purity Zr, high-purity Mo and high-purity Cr are accurately weighed according to the proportion, uniformly mixed and then bulk-loaded into a cold crucible suspension smelting furnace, and then smelted in the atmosphere of high-purity argon, wherein the smelting current is 400A, the current frequency is 22KHz, and the alloy is kept for 17min after being completely melted. Repeatedly smelting the ingot for 5 times in the furnace by turning the ingot upside down in order to ensure the components to be uniform;
(2) Cogging: cutting off a dead head of the ingot, and then, performing cogging forging at 1150 ℃ for 90min, wherein three piers and three pulls are adopted for cogging, and the deformation is 70%;
(3) High-temperature forging across a beta phase region: the forging temperature range of the high-temperature beta-phase-crossing region is 890-980 ℃, and the deformation is 80%;
(4) Solid solution and aging treatment: carrying out solid solution treatment on the Ti-Cr-Zr-Mo-Al series titanium alloy for 60min at the temperature of 885 ℃ in an alpha + beta two-phase region, carrying out water quenching to room temperature, carrying out aging treatment for 120min at the temperature of 585 ℃, and carrying out air cooling to the room temperature.
The obtained structure is shown in figure 2, after solid solution and water quenching in a two-phase region, a typical equiaxial alpha phase appears in a beta matrix, the size is about 1.2-3 mu m, and meanwhile, a flaky secondary alpha phase with the thickness of about 60-120 nm also appears. The composite structure enables the alloy to have high strength and excellent plasticity. According to the GB/T228.1-2010 standard requirement, the measured mechanical property of the alloy is shown as a curve 2 in a figure 4: the yield strength Rp is 1590MPa, the tensile strength Rm is 1740MPa, and the total elongation at break A is 8.2%.
Example 3
A Ti-Cr-Zr-Mo-Al series titanium alloy with high strength comprises the following components in percentage by weight: 3.21% of Al, 1.86% of Cr, 4.87% of Zr,7.24% of Mo, 8978% of Ti, 8978% of zxft 8978% and other inevitable impurities.
According to the components, the alloy is prepared by cold crucible suspension smelting and hammering free forging, and the preparation method comprises the following steps:
(1) Preparing a master alloy: high-purity Ti, high-purity Al, high-purity Zr, high-purity Mo and high-purity Cr are accurately weighed according to the proportion, uniformly mixed and then bulk-loaded into a cold crucible suspension smelting furnace, and then smelted in the atmosphere of high-purity argon, wherein the smelting current is 350A, the current frequency is 25KHz, and the alloy is kept for 20min after being completely melted. In order to ensure the components to be uniform, the ingot is repeatedly smelted for 5 times in the furnace by turning upside down;
(2) Cogging: cutting off a dead head of the ingot, and then, performing cogging forging at 1150 ℃ for 90min, wherein three piers and three pulls are adopted for cogging, and the deformation is 80%;
(3) High-temperature forging across a beta phase region: the forging temperature range of the high-temperature beta-phase-crossing region is 920-980 ℃, and the deformation is 90%;
(4) Solid solution and aging treatment: carrying out solid solution treatment on the Ti-Cr-Zr-Mo-Al series titanium alloy for 60min at 845 ℃ in an alpha + beta two-phase region, carrying out water quenching to room temperature, then carrying out aging treatment for 120min at 545 ℃, and carrying out air cooling to room temperature.
The resulting structure is shown in fig. 3, and after solution and water quenching in the two-phase region, a typical equiaxial alpha phase appears in the beta matrix, with dimensions of about 0.8-2.5 μm, and a flaky secondary alpha phase with a thickness of about 80-160 nm. The composite structure enables the alloy to have high strength and excellent plasticity. The mechanical properties of the alloy measured according to the GB/T228.1-2010 standard are shown in curve 3 in FIG. 4: the yield strength Rp is 1620MPa, the tensile strength Rm is 1760MPa, and the total elongation at break A is 5.6%.
The Ti-Cr-Zr-Mo-Al series titanium alloy with high strength provided by the invention has the advantages that through reasonable component design and element proportion optimization, the alloy can obtain high strength and better plasticity after being smelted, forged, solid-dissolved and aged, the components and the structure of the Ti-Cr-Zr-Mo-Al series titanium alloy are optimized by utilizing the primary alpha phase and the secondary alpha phase which are separated out on a titanium alloy beta matrix and are in multiple levels and combined with the alloying principle of the existing commercial titanium alloy, meanwhile, the alloy raw material cost is lower, and the production and manufacturing cost of the alloy is reduced to a certain extent; secondly, the alloy realizes good matching of alloy strength and plasticity after simple heat treatment, further reduces the processing cost, has excellent mechanical property, is not easy to cause component segregation, ensures that the Ti-Cr-Zr-Mo-Al series high-strength titanium alloy has the advantage of low cost, meets the requirement of various industrial fields on high performance of titanium alloy structural members, and can be widely used in the industrial fields of aviation, aerospace, automobiles and the like.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (3)
1. A Ti-Cr-Zr-Mo-Al series titanium alloy with high strength is characterized by comprising 2.5-5.5% of Al, 1.5-4.0% of Cr, 1.4-5.0% of Zr, 7.24-8.0% of Mo and less than 0.35% of O by mass percent, and the balance of Ti and inevitable other impurities;
the preparation method of the Ti-Cr-Zr-Mo-Al series titanium alloy comprises the following steps:
step 1, uniformly mixing all the raw materials according to the percentage, and then putting the raw materials into a furnace for smelting for multiple times to obtain ingots with uniform components;
step 2, performing cogging forging and beta-phase-crossing region forging on the cast ingot after peeling and riser cutting;
the cogging temperature of the cogging forging is 1100-1200 ℃, the holding time is 90min, the deformation is more than or equal to 60 percent, the temperature of the forging across the beta phase region is 850-980 ℃, and the deformation is more than or equal to 70 percent;
step 3, carrying out heat treatment on the forged cast ingot in a two-phase region to obtain a Ti-Cr-Zr-Mo-Al series titanium alloy;
the two-phase region heat treatment method comprises the steps of carrying out solid solution treatment on the ingot after forging in the cross-phase region for 60min in the two-phase region, then carrying out water quenching to room temperature, carrying out aging treatment at the temperature of 500-585 ℃ after the temperature of the two-phase region is 845-885 ℃, and carrying out air cooling to room temperature.
2. The high-strength Ti-Cr-Zr-Mo-Al titanium alloy according to claim 1, wherein said titanium alloy has a yield strength Rp =1550MPa to 1820MPa, a tensile strength Rm =1600MPa to 1880MPa, and an elongation a =3% to 10%.
3. The Ti-Cr-Zr-Mo-Al series titanium alloy with high strength as claimed in claim 1, wherein argon is introduced during the smelting process, the induced current is 350-450A, the current frequency is 20-25 KHz, and the alloy is kept for 15-20 min after being completely melted.
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