CN113388754A - 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 vehicles2The light weight of transportation means is to reduce the consumption of fossil fuel and artificial CO2The 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 dreams use about 15% of titanium alloys in passenger aircraft, one of the most fuel efficient aircraft in medium and long haul transport.
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 TiH2The 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-15Mo-3Nb-2.7Al-0.2Si) 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-7Mo-3Nb-3Cr-3Al) prepared by Dong et Al is about1550MPa and plasticity of about 8 percent.
Disclosure of Invention
Aiming at the defect that some high-strength titanium alloys commonly used at present have high cost caused by elements such as V, Mo, Nb and the like with high content, the invention provides a Ti-Cr-Zr-Mo-Al series titanium alloy with high strength, which not only has excellent mechanical property, but also 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 of 1550 to 1820MPa, a tensile strength Rm of 1600 to 1880MPa, and an elongation a of 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 in 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.
Preferably, the free forging includes cogging forging and cross- β phase region forging.
Preferably, the cogging temperature of the cogging forging is 1100-1200 ℃, and the heat preservation time is 90 min.
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) performing solid solution treatment on the ingot subjected to the forging in the beta-phase region in a two-phase region for 60min, then performing water quenching to room temperature, then performing aging treatment at the temperature of 500-585 ℃, and cooling in air to room temperature.
Preferably, the temperature of the two-phase region is 845-885 ℃.
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 of 1550-1820 MPa, tensile strength Rm of 1600-1880 MPa and elongation A of 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 high-strength Ti-Cr-Zr-Mo-Al-based titanium alloys according to examples 1 to 3 of the present invention, in which the abscissa represents true strain and the ordinate represents 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 yield strength Rp of 1550-1820 MPa, tensile strength Rm of 1600-1880 MPa, and elongation A of 3-10%.
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 gas in the cold crucible induction suspension smelting process, wherein the induction current is 350-450A, the current frequency is 20-25 KHz, continuously keeping 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: carrying out solid solution at 845-885 ℃ in a two-phase region for 60min, then carrying out water quenching to room temperature, then carrying out aging treatment at 500-585 for 120min, and carrying out air cooling 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, 83.35% of Ti 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 requirements of the GB/T228.1-2010 standard, the measured mechanical properties of the alloy are shown as a curve 1 in 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, 83.35% of Ti 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 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 requirements of the GB/T228.1-2010 standard, the measured mechanical properties of the alloy are shown as a curve 2 in 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, 82.82% of Ti 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. 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 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, carrying out aging treatment for 120min at 545 ℃, and carrying out air cooling to room temperature.
The obtained structure is shown in figure 3, 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 0.8-2.5 mu m, and meanwhile, a flaky secondary alpha phase with the thickness of about 80-160 nm also appears. The composite structure enables the alloy to have high strength and excellent plasticity. The mechanical properties of the alloy measured according to the requirements of the GB/T228.1-2010 standard are shown as a curve 3 in figure 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 (10)
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, 3.0-8.0% of Mo and less than 0.35% of O by mass percent, and the balance of Ti and inevitable other impurities.
2. The titanium alloy according to claim 1, wherein the titanium alloy has a yield strength Rp of 1550 to 1820MPa, a tensile strength Rm of 1600 to 1880MPa, and an elongation a of 3 to 10%.
3. The method for producing a high-strength Ti-Cr-Zr-Mo-Al titanium alloy according to claim 1 or 2, wherein the raw materials are mixed uniformly in the above-mentioned percentages, and then the mixture is put into a furnace to be melted for a plurality of times to obtain an ingot with uniform composition, and then the ingot is subjected to free forging across a β -phase region after being scalped and a riser cut, and the forged ingot is subjected to heat treatment in a two-phase region to obtain the Ti-Cr-Zr-Mo-Al titanium alloy.
4. The method for preparing the high-strength Ti-Cr-Zr-Mo-Al titanium alloy according to claim 3, wherein argon is introduced during the smelting process, the induction current is 350-450A, the current frequency is 20-25 KHz, and the alloy is kept for 15-20 min after being completely melted.
5. The method for producing a Ti-Cr-Zr-Mo-Al series titanium alloy with high strength according to claim 3, wherein said free forging includes cogging forging and cross- β phase region forging.
6. The method for producing a high-strength Ti-Cr-Zr-Mo-Al-based titanium alloy according to claim 5, wherein the cogging temperature in the cogging forging is 1100 to 1200 ℃ and the holding time is 90 minutes.
7. The method for producing a high-strength Ti-Cr-Zr-Mo-Al-based titanium alloy according to claim 5, wherein the temperature of the forging step spanning the beta phase region is 850 to 980 ℃ and the deformation is 70% or more.
8. The method for producing a high-strength Ti-Cr-Zr-Mo-Al-based titanium alloy according to claim 5, wherein the deformation amount in the cogging forging is 60% or more and the deformation amount in the beta-phase-region-crossing forging is 70% or more.
9. The method for producing a Ti-Cr-Zr-Mo-Al based titanium alloy having high strength according to claim 4, wherein said two-phase region heat treatment is carried out by:
and (3) performing solid solution treatment on the ingot subjected to the forging in the beta-phase region in a two-phase region for 60min, then performing water quenching to room temperature, then performing aging treatment at the temperature of 500-585 ℃, and cooling in air to room temperature.
10. The method for producing a high-strength Ti-Cr-Zr-Mo-Al-based titanium alloy according to claim 2, wherein the temperature of the two-phase region is 845 to 885 ℃.
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| CN114959362A (en) * | 2022-06-20 | 2022-08-30 | 长安大学 | High-strength high-plasticity laser additive manufacturing titanium alloy based on equiaxial fine grain strengthening |
| CN115233035A (en) * | 2022-08-23 | 2022-10-25 | 西安稀有金属材料研究院有限公司 | High-strength corrosion-resistant titanium alloy and preparation method thereof |
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