CN115011858B - High-strength high-plasticity CoCrNiAlTi multi-principal-element alloy and preparation method thereof - Google Patents
High-strength high-plasticity CoCrNiAlTi multi-principal-element alloy and preparation method thereof Download PDFInfo
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Abstract
A high-strength high-plasticity CoCrNiAlTi multi-principal element alloy and a preparation method thereof, wherein the alloy comprises 14-25% of Cr, 25-35% of Ni, 4-6% of Al, 4-6% of Ti, 0-1% of Mo and the balance of Co according to atomic percentage; the method comprises the following steps: preparing raw materials, and smelting and casting the raw materials to prepare an ingot; (2) homogenizing; (3) solution heat treatment; (4) cold deformation, wherein the deformation amount is 70-90%; (5) And (4) performing aging heat treatment to obtain the high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy. In the invention, the components of the entropy alloy in the CoCrNi base are precisely designed to obtain low-level fault energy and strong precipitation capacity, and the unique heterostructure of the strengthening phase with coarsening distributed in the crystal matrix with obvious structural gradient is obtained by regulating and controlling the recrystallization and the precipitation kinetics of the strengthening phase through special cold mechanical deformation and aging process.
Description
Technical Field
The invention belongs to the technical field of preparation of high-performance alloy materials, and particularly relates to a high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy and a preparation method thereof.
Background
The corrosion-resistant alloy CoCrNi system has good comprehensive mechanical property, and the alloy has excellent stress corrosion crack resistance under the stress condition, so that the alloy can obtain good service performance in a severe use environment. This property is particularly applicable in the fields of aerospace fasteners, aerospace structures, chemical processing, medical, cryogenic, marine, oil and gas, food processing, springs, non-magnetic components, instrument parts, etc. The alloy is of a face-centered cubic crystal structure, and has lower yield strength (400 MPa) at room temperature for a coarse crystal structure with a micron scale. While some parts carrying critical loads require alloys with higher yield strength and better plasticity. In order to meet the requirements of different environments, different mechanical properties can be obtained through the composition design of the alloy and the adjustment of the preparation process. From the aspect of structure regulation, the strong plasticity of the alloy can be greatly improved by a grain refining means; however, when the yield strength reaches more than 1GPa, the plastic deformation capacity of the material is obviously reduced due to the inverted relationship of strength and plasticity, so that the processability and the use safety of the material are reduced; the reason is that the ability of the crystal grains to store mobile dislocations is sharply reduced to a certain degree (ultra-fine grain size: submicron or nanometer size), so that the strain hardening rate is also reduced during deformation, resulting in premature "necking". Even if high-density stacking faults are formed during deformation by lowering the stacking fault energy, twin crystals are difficult to form in ultra-fine crystals and a sufficiently high strain hardening rate cannot be provided so that the alloy obtains sufficient plasticity; that is, in the nanocrystalline and ultrafine-grained structures, the twin toughening or transformation toughening effect cannot be achieved in the alloy system even if the stacking fault energy is low.
In order to improve the strength of the alloy, precipitation strengthening is also a more effective method in addition to fine-grained strengthening means. The elements such as Al, ti and the like are added into the CoCrNi-based alloy with the face-centered cubic lattice structure, so that strengthening particles which are coherent with a matrix can be formed, precipitation strengthening is realized, and the strengthening effect mainly comes from ordered strengthening of precipitated particles. However, the alloy obtains higher yield strength, and higher volume fraction of precipitated particles is needed, so that the space between the precipitated particles is smaller, and the stacking fault and the nucleation of twin crystals in the deformation process are seriously hindered; similarly, strengthening and toughening the alloy by this method is also difficult to overcome the "strength-plasticity" inversion relationship by twinning toughening or transformation toughening. As a result, the alloy tends to have insufficient plastic deformability at high stress levels at which the yield strength reaches 1 GPa.
In combination, the above alloys rely primarily on fine grain strengthening and precipitation strengthening for strengthening, with a significant trade-off effect between "toughness-strength". Therefore, the ability to increase strength, particularly yield strength, is limited while maintaining a certain degree of plasticity; how to enable the series of alloys to obtain high strength (GPa grade) and simultaneously have good plastic deformation capability is the problem of realizing the preparation of parts bearing critical loads by the alloy system and the key point of breaking through the property inversion between toughness and strength of the series of alloys.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy and a preparation method thereof, and the multi-principal-element alloy with high yield strength and enough use elongation rate of more than 30% is formed by adding AlTi (Mo) on the basis of CoCrNi and setting the component proportion.
The invention provides a high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy which comprises, by atomic percentage, 14-25% of Cr, 25-35% of Ni, 4-6% of Al, 4-6% of Ti, 0-1% of Mo and the balance of Co.
The high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy preferably comprises, by atomic percentage, 17-22% of Cr, 28-30% of Ni, 4.5-5.5% of Al, 4.5-5.5% of Ti, 0-0.5% of Mo and the balance of Co.
The yield strength of the high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy is 1.17-1.3 GPa.
The elongation of the high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy is 27-32%.
The preparation method of the high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy comprises the following steps:
(1) Preparing raw materials according to the atomic percentage, then smelting and casting to prepare an ingot;
(2) Homogenizing the cast ingot to prepare a homogenized casting;
(3) Carrying out solution heat treatment on the homogenized casting to obtain a solid solution casting with an FCC single phase;
(4) Carrying out cold deformation on the solid solution casting, wherein the deformation amount is 70-90%, and preparing a cold deformation piece;
(5) And carrying out aging heat treatment on the cold deformation piece to obtain the high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy.
In the step (2), the homogenization treatment is to keep the cast ingot at 1000-1200 ℃ for 12-24 h, and then water quench to room temperature after the heat preservation is finished.
In the step (3), the solution heat treatment is to keep the temperature of the homogenized casting at 1150-1200 ℃ for 2-8 h, and water quench to room temperature after the heat preservation is finished.
In the step (4), the cold deformation is cold rolling, or swaging and/or drawing at room temperature.
In the step (5), the aging heat treatment is to keep the temperature of the cold deformation piece at 750-850 ℃ for 50-200 h.
In the invention, the components of the entropy alloy in the CoCrNi base are precisely designed to obtain low-layer fault energy and strong precipitation capacity, and the unique heterostructure of the coarsened strengthening phase distributed in the crystal matrix with obvious structural gradient is obtained by regulating and controlling the recrystallization and the precipitation kinetics of the strengthening phase through special cold mechanical deformation (large deformation of more than 70 percent) and an aging process (long heat preservation time in a medium temperature range), so that on the premise of effectively improving the yield strength by back stress, an additional strain hardening effect (from layer faults and nano twin crystals) is generated through local non-uniform deformation in the deformation process, thereby realizing comprehensive strengthening and toughening in the deformation process, generating the mutual coupling behavior of strengthening and toughening by back stress and precipitation, and endowing the alloy with an ultrahigh comprehensive performance index of strong plasticity. In addition, the low alloying of Mo in the present invention can produce strong solid solution strengthening effect, which is helpful for improving yield strength.
The alloy prepared by the invention is a corrosion-resistant alloy series, and by reasonably designing the components of Co-Cr-Ni-Al-Ti (Mo) and the preparation process, the uneven structure of coarse precipitated particles distributed in the crystal grain structure of the matrix can be obtained, so that the alloy has excellent comprehensive mechanical property; the alloy section can be processed into products in various forms, and has wide application in the production of fasteners used in the fields of aerospace, navigation, petroleum and natural gas, food processing, springs, non-magnetic components, instrument parts and the like; the use of Co, ni, cr, al, ti and a small amount of Mo makes the alloy moderate in price, the material preparation process is relatively simple, and the industrial investment is low.
Drawings
FIG. 1 is an electron microscope micrograph of a high strength and high plasticity CoCrNiAlTi multi-principal element alloy of example 1 of the present invention;
FIG. 2 is a stress-strain diagram of a high-strength and high-plasticity CoCrNiAlTi multi-element alloy in example 1 of the present invention.
Detailed Description
In the embodiment of the invention, after the aging heat treatment is finished, the furnace is cooled to room temperature.
In the embodiment of the invention, the raw materials are metal chromium, metal nickel, metal cobalt, metal aluminum, metal titanium and metal molybdenum.
The high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy in the embodiment of the invention is a plate or a bar.
Example 1
The high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy comprises 19.9% of Cr, 29.85% of Ni, 4.975% of Al, 4.975% of Ti, 0.5% of Mo and 39.8% of Co by atomic percentage;
the method comprises the following steps:
(1) Preparing raw materials according to the atomic percentage, then smelting and casting to prepare an ingot;
(2) Homogenizing the cast ingot to prepare a homogenized casting; homogenizing, namely keeping the temperature of the cast ingot at 1200 ℃ for 12h, and quenching to room temperature after the heat preservation is finished;
(3) Carrying out solution heat treatment on the homogenized casting to obtain a solid solution casting with an FCC single phase; the solid solution heat treatment is to keep the temperature of the homogenized casting at 1200 ℃ for 2h, and quench the homogenized casting to room temperature after the heat preservation is finished;
(4) Carrying out cold deformation on the solid solution casting, wherein the deformation amount is 80%, and manufacturing a cold deformation piece; cold deformation is cold rolling;
(5) Carrying out aging heat treatment on the cold deformation piece to obtain high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy; the aging heat treatment is to keep the temperature of the cold deformation piece at 800 ℃ for 100h;
the microstructure is shown in figure 1, and it can be seen from the figure that the microstructure of the alloy has both a nano-scale recrystallized matrix grain structure and a micron-scale unrecrystallized structure to form a strong heterostructure structure;
at 10 -3 s -1 Tensile test was performed on the obtained alloy sample, and as a result, as shown in fig. 2, the tensile plasticity (elongation) was 30% and the yield strength was 1200MPa at room temperature.
Example 2
The high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy comprises the following components in percentage by atom of Cr 15%, ni 30%, al 6%, ti 6% and Co 43%;
the method is the same as example 1, except that:
(1) Homogenizing at 1000 deg.C for 20h;
(2) The solution heat treatment temperature is 1200 ℃, and the time is 3h;
(3) The deformation amount of cold deformation is 75%;
(4) The aging heat treatment temperature is 800 ℃, and the time is 110h;
(5) The elongation is 29 percent, and the yield strength is 1190MPa.
Example 3
The high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy comprises 19.8% of Cr, 29.7% of Ni, 4.95% of Al, 4.95% of Ti, 1% of Mo and 39.6% of Co by atomic percentage;
the method is the same as example 1, except that:
(1) The homogenization treatment temperature is 1100 ℃, and the time is 24 hours;
(2) The solution heat treatment temperature is 1200 ℃, and the time is 4 hours;
(3) The deformation amount of cold deformation is 75%; cold deformation is rotary swaging at room temperature;
(4) The aging heat treatment temperature is 850 ℃, and the time is 100h;
(5) Elongation of 31 percent and yield strength of 1230MPa.
Example 4
The high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy comprises the following components in percentage by atom of Cr 14.925%, ni 29.85%, al 5.97%, ti 5.97%, mo 0.5% and Co 42.57%;
the method is the same as example 1, except that:
(1) Homogenizing at 1200 deg.C for 13h;
(2) The temperature of the solution heat treatment is 1150 ℃, and the time is 8 hours;
(3) The deformation amount of cold deformation is 80%; cold deformation is rotary swaging at room temperature;
(4) The aging heat treatment temperature is 750 ℃, and the time is 200h;
(5) The elongation is 28 percent, and the yield strength is 1300MPa.
Example 5
The high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy comprises 14.85% of Cr, 29.7% of Ni, 5.94% of Al, 5.94% of Ti, 1% of Mo and 42.57% of Co by atomic percentage;
the method is the same as example 1, except that:
(1) Homogenizing at 1200 deg.C for 14h;
(2) The solution heat treatment temperature is 1200 ℃, and the time is 4 hours;
(3) The deformation amount of cold deformation is 80%; cold deformation is drawing;
(4) The aging heat treatment temperature is 850 ℃, and the time is 200h;
(5) The elongation is 28 percent, and the yield strength is 1290MPa.
Example 6
The high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy comprises the following components in percentage by atom of Cr 13.875%, ni 27.75%, al 5.55%, ti 5.55%, mo 0.75%, and Co 39.775%;
the method is the same as example 1, except that:
(1) Homogenizing at 1200 deg.C for 24h;
(2) The solution heat treatment temperature is 1200 ℃, and the time is 4 hours;
(3) The deformation amount of cold deformation is 80%; cold deformation is rotary swaging and drawing at room temperature;
(4) The aging heat treatment temperature is 700 ℃, and the time is 150h;
(5) Elongation of 31 percent and yield strength of 1210MPa.
Example 7
The high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy comprises 19.8% of Cr, 29.7% of Ni, 4.95% of Al, 4.95% of Ti, 1% of Mo and 39.6% of Co by atomic percentage;
the method is the same as example 1, except that:
(1) Homogenizing at 1200 deg.C for 18h;
(2) The solution heat treatment temperature is 1200 ℃, and the time is 4h;
(3) The deformation amount of cold deformation is 80%; cold deformation is rotary swaging at room temperature;
(4) The aging heat treatment temperature is 850 ℃, and the time is 50h;
(5) The elongation is 30 percent, and the yield strength is 1200MPa.
Example 8
The high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy comprises the following components in percentage by atom of Cr 20%, ni 30%, al 5%, ti 5% and Co 40%;
the method is the same as example 1, except that:
(1) Homogenizing at 1200 deg.C for 24h;
(2) The solution heat treatment temperature is 1200 ℃, and the time is 4h;
(3) The deformation amount of cold deformation is 80%; cold deformation is rotary swaging at room temperature;
(4) The aging heat treatment temperature is 750 ℃, and the time is 100h;
(5) Elongation 32% and yield strength 1170MPa.
Claims (5)
1. A preparation method of high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy is characterized by comprising the following steps:
(1) Preparing raw materials according to atomic percentage, then smelting and casting to prepare an ingot;
(2) Homogenizing the cast ingot to prepare a homogenized casting;
(3) Carrying out solution heat treatment on the homogenized casting to obtain a solid solution casting with an FCC single phase;
(4) Carrying out cold deformation on the solid solution casting, wherein the deformation amount is 70-90%, and preparing a cold deformation piece;
(5) Performing aging heat treatment on the cold deformation piece, and keeping the temperature at 750-850 ℃ for 50-200 h to obtain the high-strength and high-plasticity CoCrNiAlTi multi-principal-element alloy;
the alloy comprises, by atomic percentage, 14-25% of Cr, 25-35% of Ni, 4-6% of Al, 4-6% of Ti, 0-1% of Mo and the balance of Co;
the alloy yield strength is 1.17-1.3 GPa;
the elongation of the alloy is 27-32%.
2. The method for preparing high-strength high-plasticity CoCrNiAlTi multi-principal element alloy according to claim 1, wherein the preferable components comprise, by atomic percentage, 17-22% of Cr, 28-30% of Ni, 4.5-5.5% of Al, 4.5-5.5% of Ti, 0-0.5% of Mo, and the balance of Co.
3. The preparation method of the high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy according to claim 1, wherein in the step (2), the homogenization treatment is to keep the temperature of the cast ingot at 1000-1200 ℃ for 12-24 h, and then water quench to room temperature after the heat preservation is finished.
4. The method for preparing the high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy according to claim 1, wherein in the step (3), the solution heat treatment is to keep the temperature of the homogenized casting at 1150-1200 ℃ for 2-8 h and then carry out water quenching to room temperature after the heat preservation is finished.
5. The method for preparing a high-strength high-plasticity CoCrNiAlTi multi-principal-element alloy according to claim 1, wherein in the step (4), the cold deformation is cold rolling, or swaging and/or drawing at room temperature.
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