CN109338200B - High-temperature high-damping high-entropy alloy and preparation method thereof - Google Patents
High-temperature high-damping high-entropy alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-temperature high-damping high-entropy alloy and a preparation method thereof, which realizes the high-temperature damping performance of the high-entropy alloy by microalloying oxygen or nitrogen elements in a refractory high-entropy alloy matrix and utilizing the high thermal stability of the high-entropy alloy matrix. The process comprises the following steps: removing oxide skin of metal raw materials Ta, Nb, Hf, Zr, Ti, Mo, V, W, Al and the like by a mechanical method, weighing according to a molar ratio, mechanically peeling other added elements, ultrasonically cleaning or pickling, weighing according to a molar ratio, adding oxygen in the form of oxide, and adding nitrogen in the form of nitride; smelting in a non-consumable vacuum arc furnace or a cold crucible suspension furnace, and obtaining the alloy by adopting vacuum suction casting or casting equipment. The invention utilizes the high structure stability of the high-entropy alloy and obviously improves the high-temperature damping performance and the mechanical property of the alloy through small-atom microalloying.
Description
Technical Field
The invention belongs to the field of metal materials and preparation thereof, and particularly relates to a high-temperature high-damping high-entropy alloy and a preparation method thereof.
Background
The technological development promotes the great improvement of the power and the running speed of mechanical equipment, and mechanical vibration and noise pollution are inevitably brought. The vibration and the noise not only greatly reduce the service life of the equipment, but also seriously affect the ecological environment and damage the physical and mental health of the public. Therefore, in recent years, high damping alloys for reducing vibration and noise and improving man-machine working environment have been paid more and more attention by researchers.
The development of high damping alloys has generally formed three types of traditional high damping alloys according to the differences of damping mechanisms: dislocation type high damping alloys such as Mg-Zr series high damping alloys; ferromagnetic type high damping alloys such as Fe-Cr series high damping alloys; a twin crystal type high damping alloy such as Mn-Cu series high damping alloy. The three types of high-damping alloys are commercially produced and applied. However, the mechanical properties of the three types of high damping alloys are still to be improved, the service stability is insufficient, and the service temperature is low. The low-dimensional defects in the three types of high-damping alloys are easy to diffuse and redistribute under continuous vibration load, and gradually enrich in a high-dimensional defect area, so that pinning is generated, and finally, the relaxation strength of the high-dimensional defects is gradually reduced until the relaxation strength disappears, so that the damping performance of the alloys is greatly deteriorated, and the service life of the alloys is shortened.
Recently, a new damping mechanism has been developed, i.e. a Snoek type high damping alloy. This type of high damping alloy utilizes the directional diffusion effect of interstitial atoms (e.g., C, B, O, N, H) induced by stress. Most of the high-damping alloys are body-centered cubic structure metals, such as beta-Ti alloy, alpha-Fe and the like. This relaxation process can occur repeatedly without destroying the body centered cubic structure of the base alloy. Therefore, the damping performance reversibility of the high-damping alloy is good, and the service life of the high-damping alloy is generally considered to be greatly higher than that of the traditional high-damping alloy.
Although the Snoek type high damping alloy makes up the defect of poor stability of the traditional alloy, the high temperature damping performance and the mechanical property of the alloy are not improved. Similar to the conventional high damping alloy, the high damping alloy is still only suitable for the low temperature region of 300-. At present, the aerospace field is rapidly developed, and the high-temperature high-damping alloy with excellent mechanical property is developed further.
Disclosure of Invention
In order to solve the problems, the invention provides the Snoek type high-temperature high-damping high-entropy alloy with the simple body-centered cubic structure alloyed by the interstitial atoms, which is obtained by adding the interstitial atoms into the high-entropy alloy matrix and promoting the directional diffusion effect of the small atoms under the induction of the stress in the high-entropy matrix by utilizing the high structural stability of the high-entropy alloy.
The technical scheme of the invention is as follows: the high-temperature high-damping high-entropy alloy comprises the following components in atomic percentage expression of TaaNbbHfcZrdTieOpNqWherein a is more than 0 and less than or equal to 35, b is more than 0 and less than or equal to 35, c is more than or equal to 0 and less than or equal to 35, d is more than or equal to 0 and less than or equal to 35, e is more than or equal to 0 and less than or equal to 35, p is more than or equal to 0 and less than or equal to 5, q is more than or equal to 0 and less than or equal to 5, and a + b + c +.
Further, the high entropyThe atomic percentage expression of the alloy material component is TaaNbbHfcZrdTieMfOpNqWherein M is I, J, K or L, I is selected from at least one of C, B, Al, Si, P, Ga, In, Sn, Pb, Ge, As, Sb or Te, J is at least one of Mn, Fe, Co, Ni, Cu, Zn, Au, Ag, Pd, Pt, Cd or Ru, K is at least one of V, Cr, W, Mo, Y, Mg, Ca, L is at least one of rare earth elements, a is more than 0 and less than or equal to 35, B is more than 0 and less than or equal to 35, C is more than or equal to 0 and less than or equal to 35, d is more than or equal to 0 and less than or equal to 35, f is more than or equal to 0 and less than or equal to 35, P is more than or equal to 0 and less than or equal to 5, and a + B + C + d + e + f + P + q is 100.
Further, when q is 2, p is 0, a is 12.5, b is 12.5, c is 24.5, d is 24.5, and e is 24.5, the atomic percent expression of the high-entropy alloy material component is Ta12.25Nb12.25Hf24.5Zr24.5Ti24.5O2。
Further, when q is 0, p is 2, a is 12.5, b is 12.5, c is 24.5, d is 24.5, and e is 24.5, the atomic percent expression of the high-entropy alloy material component is Ta12.25Nb12.25Hf24.5Zr24.5Ti24.5O2。
Further, when q is 2, p is 0, a is 16.33, b is 16.33, c is 32.67, d is 16.33, and e is 32.67, the atomic percent expression of the high-entropy alloy material component is Ti32.67Hf32.67Nb16.33Ta16.33O2。
Further, when q is 0, p is 2, a is 16.33, b is 16.33, c is 32.67, d is 16.33, and e is 32.67, the atomic percent expression of the high-entropy alloy material component is Ti32.67Hf32.67Nb16.33Ta16.33N2。
Further, when q is 1.0, p is 1.0, a is 4.67, b is 23.33, c is 23.33, d is 23.33, and e is 23.33, the atomic percent expression of the high-entropy alloy material component is Ti23.33Zr23.33Hf23.33Nb23.33Ta4.67O1.0N1.0。
Further, when q is 1.5, p is 1.5, aWhen the alloy material component is 6.77, b is 22.56, c is 22.56, d is 22.56, and e is 22.56, the atomic percentage expression of the high-entropy alloy material component is Ti22.56Zr22.56Hf22.56Nb22.56Ta6.77O1.5N1.5。
The invention also aims to provide a preparation method of the alloy, which specifically comprises the following steps:
step 1, raw material cleaning: removing oxide skin on the surface of metal in the selected raw material by using sand paper or a grinding machine, cleaning the raw material by using industrial ethanol ultrasonic oscillation, removing the oxide skin on the surface of the metal by using a mechanical method or an acid washing method for other metal elements, and cleaning the raw material by using the industrial ethanol ultrasonic oscillation for later use;
step 2: weighing the following raw materials: converting the treated raw materials, the oxide and the nitride into mass ratio according to the atomic percentage of the expression, and proportioning the materials, wherein the O or N element is added in a powder or block oxide or nitride mode, and the purity of the oxide and the nitride is not lower than 99.9%;
step 3, smelting: stacking the weighed raw materials, oxide and nitride in a non-consumable vacuum arc furnace or a cold crucible suspension furnace according to the sequence of melting point to smelt, placing the metalloid, the oxide and the nitride at the bottom of the crucible, vacuumizing until the vacuum degree reaches 5 multiplied by 10-3After Pa, the chamber was filled with argon to half atmospheric pressure and then evacuated again to 5X 10-3Pa, filling argon into the furnace chamber to half atmospheric pressure, and beginning to smelt the alloy; before the alloy is smelted, firstly smelting a titanium ingot to absorb free gases such as oxygen, nitrogen and the like in a furnace cavity, after the alloy is smelted, keeping the electric arc for 60-120 seconds, turning over the alloy block after the alloy block is cooled, repeating the process for at least 4 times, vacuumizing and refilling argon after the alloy is smelted twice, and after the mother alloy is fully smelted uniformly, carrying out suction casting on the alloy by using vacuum suction casting equipment to enter a water-cooling copper mold, thus obtaining the high-entropy alloy material with a simple body-centered cubic structure.
Furthermore, the high-entropy alloy material prepared by the method has a simple body-centered cubic structure and has the damping performance of tan deltamaxNot less than 0.01, resistThe peak temperature of the relaxation is over 700K, the tensile yield strength is over 1.0GPa, the tensile plasticity is over 10.0 percent, and the damping material is suitable for high-temperature damping.
The invention has the advantages that:
1. the high-temperature high-damping high-entropy alloy provided by the invention has a large component application range and wide preparation conditions.
2. Different mechanical properties and damping properties can be obtained by adjusting the alloy components and subsequent heat treatment, cold working and other technical means.
3. The main elements of the high-temperature high-damping high-entropy alloy material provided by the invention are common pure metal raw materials, and the oxide and the nitride are more common ceramic raw materials, so that the high-temperature high-damping high-entropy alloy material is low in price and has the advantages of convenience in preparation, simple process, safety in use and the like.
4. The high-entropy alloy prepared by the invention has excellent mechanical properties, the tensile yield strength exceeds 1.0GPa, and the tensile plasticity exceeds 10.0%.
5. The high-entropy alloy prepared by the invention has excellent high-temperature damping performance, and fills the blank of high-temperature application of the damping alloy.
6. The high-entropy alloy prepared by the invention has excellent mechanical property and high-temperature damping property, and can be widely applied to the fields of structures and damping application.
Drawings
FIG. 1 shows Ta, an example of the present invention12.25Nb12.25Hf24.5Zr24.5Ti24.5O2The damping performance curve of the high-entropy alloy is shown schematically.
FIG. 2 shows Ta12.25Nb12.25Hf24.5Zr24.5Ti24.5N2The damping performance curve of the high-entropy alloy is shown schematically.
FIG. 3 shows an embodiment of the present invention Ti32.67Hf32.67Nb16.33Ta16.33O2The damping performance curve of the high-entropy alloy is shown schematically.
FIG. 4 shows an embodiment of the present invention Ti32.67Hf32.67Nb16.33Ta16.33N2The damping performance curve of the high-entropy alloy is shown schematically.
FIG. 5 shows an embodiment of the present invention Ti23.33Zr23.33Hf23.33Nb23.33Ta4.67O1.0N1.0The damping performance curve of the high-entropy alloy is shown schematically.
FIG. 6 shows an embodiment of the present invention Ti22.56Zr22.56Hf22.56Nb22.56Ta6.77O1.5N1.5The damping performance curve of the high-entropy alloy is shown schematically.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
The invention relates to a high-temperature high-damping high-entropy alloy and a preparation method thereof, wherein the atomic percentage expression of the components of the high-entropy alloy material is TaaNbbHfcZrdTieOpNqWherein a is more than 0 and less than or equal to 35, b is more than 0 and less than or equal to 35, c is more than or equal to 0 and less than or equal to 35, d is more than or equal to 0 and less than or equal to 35, e is more than or equal to 0 and less than or equal to 35, p is more than or equal to 0 and less than or equal to 5, q is more than or equal to 0 and less than or equal to 5, and a + b + c +.
The atomic percentage expression of the components of the high-entropy alloy material is TaaNbbHfcZrdTieMfOpNqWherein M is I, J, K or L, I is selected from at least one of C, B, Al, Si, P, Ga, In, Sn, Pb, Ge, As, Sb or Te, J is at least one of Mn, Fe, Co, Ni, Cu, Zn, Au, Ag, Pd, Pt, Cd or Ru, K is at least one of V, Cr, W, Mo, Y, Mg, Ca, L is at least one of rare earth elements, a is more than 0 and less than or equal to 35, B is more than 0 and less than or equal to 35, C is more than or equal to 0 and less than or equal to 35, d is more than or equal to 0 and less than or equal to 35, f is more than or equal to 0 and less than or equal to 35, P is more than or equal to 0 and less than or equal to 5, and a + B + C + d + e + f + P + q is 100.
A method for preparing the high-temperature high-damping high-entropy alloy specifically comprises the following steps:
step 1, raw material cleaning: removing oxide skin on the surface of metal in the selected raw material by using sand paper or a grinding machine, cleaning the raw material by using industrial ethanol ultrasonic oscillation, removing the oxide skin on the surface of the metal by using a mechanical method or an acid washing method for other metal elements, and cleaning the raw material by using the industrial ethanol ultrasonic oscillation for later use;
step 2: weighing the following raw materials: converting the treated raw materials, the oxide and the nitride into mass ratio according to the atomic percentage of the expression, and proportioning the materials, wherein the O or N element is added in a powder or block oxide or nitride mode, and the purity of the oxide and the nitride is not lower than 99.9%;
step 3, smelting: stacking the weighed raw materials, oxide and nitride in a non-consumable vacuum arc furnace or a cold crucible suspension furnace according to the sequence of melting point to smelt, placing the metalloid, the oxide and the nitride at the bottom of the crucible, vacuumizing until the vacuum degree reaches 5 multiplied by 10-3After Pa, the chamber was filled with argon to half atmospheric pressure and then evacuated again to 5X 10-3Pa, filling argon into the furnace chamber to half atmospheric pressure, and beginning to smelt the alloy; before the alloy is smelted, firstly smelting a titanium ingot to absorb free gases such as oxygen, nitrogen and the like in a furnace cavity, after the alloy is smelted, keeping the electric arc for 60-120 seconds, turning over the alloy block after the alloy block is cooled, repeating the process for more than 4 times, vacuumizing and refilling argon after the alloy is smelted twice, and after the mother alloy is fully smelted uniformly, carrying out suction casting on the alloy by using vacuum suction casting equipment to enter a water-cooling copper mold to obtain the high-entropy alloy material.
The high-entropy alloy material prepared by the method has a simple body-centered cubic structure and has the damping property of tan deltamaxNot less than 0.01, the damping relaxation peak temperature also exceeds 700K, the tensile yield strength exceeds 1.0GPa, the tensile plasticity exceeds 10.0 percent, and the damping material is suitable for high-temperature shock absorption.
Example 1
A high-temperature high-damping high-entropy alloy comprises the following components (atomic ratio): ta12.25Nb12.25Hf24.5Zr24.5Ti24.5O2As shown in FIG. 1, the alloy is a high damping alloy (tan. delta.)maxNot less than 0.01) and the damping relaxation peak temperature is more than 700K, which indicates that the alloy can be applied to the high-temperature damping field.
Example 2
High temperatureThe damping high-entropy alloy comprises the following components (atomic ratio): ta12.25Nb12.25Hf24.5Zr24.5Ti24.5N2As shown in FIG. 2, tan. delta. thereofmaxThe damping relaxation peak temperature is more than or equal to 0.01, the alloy is high-damping alloy, and the damping relaxation peak temperature is more than 700K, which shows that the alloy can be suitable for the high-temperature damping field.
Example 3
A high-temperature high-damping high-entropy alloy comprises the following components (atomic ratio): ti32.67Hf32.67Nb16.33Ta16.33O2As shown in FIG. 3, tan. delta. thereofmaxNot less than 0.01, is a high damping alloy, and the damping relaxation peak temperature is more than 700K, which shows that the alloy can also be suitable for high-temperature shock absorption.
Example 4
A high-temperature high-damping high-entropy alloy comprises the following components (atomic ratio): ti32.67Hf32.67Nb16.33Ta16.33N2As shown in FIG. 4, tan. delta. thereofmaxNot less than 0.01, is a high damping alloy, and the damping relaxation peak temperature of the alloy exceeds 700K, which indicates that the alloy can also be suitable for high-temperature shock absorption.
Example 5
A high-temperature high-damping high-entropy alloy comprises the following components (atomic ratio): ti23.33Zr23.33Hf23.33Nb23.33Ta4.67O1. 0N1.0As shown in FIG. 5, when oxygen and nitrogen atoms are added simultaneously, tan. delta. ismaxNot less than 0.01, the alloy still shows high damping performance, and the damping relaxation peak temperature is higher than 700K, so that the alloy is suitable for high-temperature shock absorption.
Example 6
A high-temperature high-damping high-entropy alloy comprises the following components (atomic ratio): ti22.56Zr22.56Hf22.56Nb22.56Ta6.77O1. 5N1.5As shown in FIG. 6, when oxygen and nitrogen atoms are added simultaneously, tan. delta. ismaxNot less than 0.01, the alloy still shows high damping performance, and the damping relaxation peak temperature of the alloy also exceeds 700K, and the alloy is suitable for high-temperature shock absorption.
The high-entropy alloy with high thermal stability is innovatively used as a substrate, and the relaxation effect of interstitial atoms under stress induction is utilized, so that the high-temperature and high-damping characteristics of the high-entropy alloy are realized, and the interstitial solid solution strengthened high-entropy alloy also has excellent mechanical properties.
Claims (6)
1. The high-temperature high-damping high-entropy alloy is characterized in that the atomic percent expression of the components of the high-entropy alloy material is Ta12.25Nb12.25Hf24.5Zr24.5Ti24.5O2The alloy has a simple body-centered cubic structure and has a damping property of tan deltamaxNot less than 0.01, the damping relaxation peak temperature also exceeds 700K, the tensile yield strength exceeds 1.0GPa, the tensile plasticity exceeds 10.0 percent, and the damping material is suitable for high-temperature shock absorption.
2. The high-temperature high-damping high-entropy alloy is characterized in that the atomic percent expression of the components of the high-entropy alloy material is Ta12.25Nb12.25Hf24.5Zr24.5Ti24.5O2The alloy has a simple body-centered cubic structure and has a damping property of tan deltamaxNot less than 0.01, the damping relaxation peak temperature also exceeds 700K, the tensile yield strength exceeds 1.0GPa, the tensile plasticity exceeds 10.0 percent, and the damping material is suitable for high-temperature shock absorption.
3. The high-temperature high-damping high-entropy alloy is characterized in that the atomic percent expression of the components of the high-entropy alloy material is Ti32.67Hf32.67Nb16.33Ta16.33O2The alloy has a simple body-centered cubic structure and has a damping property of tan deltamaxNot less than 0.01, the damping relaxation peak temperature also exceeds 700K, the tensile yield strength exceeds 1.0GPa, the tensile plasticity exceeds 10.0 percent, and the damping material is suitable for high-temperature shock absorption.
4. The high-temperature high-damping high-entropy alloy is characterized in that the atomic percent expression of the components of the high-entropy alloy material is Ti32.67Hf32.67Nb16.33Ta16.33N2The alloy has simple body-centered cubic structure and resistanceThe damping property is tan deltamaxNot less than 0.01, the damping relaxation peak temperature also exceeds 700K, the tensile yield strength exceeds 1.0GPa, the tensile plasticity exceeds 10.0 percent, and the damping material is suitable for high-temperature shock absorption.
5. The high-temperature high-damping high-entropy alloy is characterized in that the atomic percent expression of the components of the high-entropy alloy material is Ti23.33Zr23.33Hf23.33Nb23.33Ta4.67O1.0N1.0The alloy has a simple body-centered cubic structure and has the damping property of tan deltamaxNot less than 0.01, the damping relaxation peak temperature also exceeds 700K, the tensile yield strength exceeds 1.0GPa, the tensile plasticity exceeds 10.0 percent, and the damping material is suitable for high-temperature shock absorption.
6. The high-temperature high-damping high-entropy alloy is characterized in that the atomic percent expression of the components of the high-entropy alloy material is Ti22.56Zr22.56Hf22.56Nb22.56Ta6.77O1.5N1.5The alloy has a simple body-centered cubic structure and has a damping property of tan deltamaxNot less than 0.01, the damping relaxation peak temperature also exceeds 700K, the tensile yield strength exceeds 1.0GPa, the tensile plasticity exceeds 10.0 percent, and the damping material is suitable for high-temperature shock absorption.
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| CN108130470A (en) * | 2018-01-15 | 2018-06-08 | 湘潭大学 | A kind of MoNbTaZrHf high-entropy alloys and preparation method thereof |
| CN108220742A (en) * | 2018-03-14 | 2018-06-29 | 北京理工大学 | A kind of microalloying Ti-Zr-Hf-V-Nb-Ta infusibility high-entropy alloys and preparation method thereof |
| CN108911751A (en) * | 2018-06-30 | 2018-11-30 | 华南理工大学 | A kind of high entropy ceramic material of ZrHfTaNbTiC superhigh temperature and preparation method thereof |
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