CN113774253A - Wear-resistant material with wide temperature range, and preparation method and application thereof - Google Patents

Wear-resistant material with wide temperature range, and preparation method and application thereof Download PDF

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CN113774253A
CN113774253A CN202111090421.4A CN202111090421A CN113774253A CN 113774253 A CN113774253 A CN 113774253A CN 202111090421 A CN202111090421 A CN 202111090421A CN 113774253 A CN113774253 A CN 113774253A
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resistant material
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ingot
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CN113774253B (en
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郑立静
徐惠彬
张虎
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Beihang University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/023—Alloys based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

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Abstract

The invention relates to a wide temperature range wear-resistant material, a preparation method and application thereof, wherein the wear-resistant material comprises the following elements in atomic percentage: 55% -68% of Ni; 0.01-0.5% of rare earth elements, wherein the rare earth elements are selected from at least one of Y, Sc, La and Ce; 3 to 15 percent of additive elements, wherein the additive elements are at least one selected from Hf, W, Re and Ru, Ti is the rest, the atomic ratio of the Ni element to the Ti element is (1:0.5) to (1:0.8), and the atomic ratio of the additive elements to the Ni element is (0.04:1) to (0.3: 1). The wear-resistant material still keeps the characteristics of high strength, high hardness, temperature change resistance, shock resistance and the like for long-time service in a temperature difference range of approximately 800 ℃ between 196 ℃ below zero and 600 ℃; the stability of the structure performance is still kept within a short time in a high-temperature range between 700 ℃ and 900 ℃.

Description

Wear-resistant material with wide temperature range, and preparation method and application thereof
Technical Field
The invention relates to a wear-resistant material, in particular to a wide-temperature-range wear-resistant material, and a preparation method and application thereof.
Background
With the continuous update of mechanical equipment in high and new technical fields such as aerospace, nuclear power, high-speed trains, energy power, tank armor, submarines and the like of rockets, missiles, high-speed aircrafts and the like, the requirements on the performance of wear-resistant bearing parts such as gears, bearings and the like are increasingly improved. For some wear-resistant bearings, the surface temperature of the wear-resistant bearing, such as gears and bearings, may exceed 500 ℃ in high-speed, high-temperature and high-load service environments of aircraft engines in the face of instantaneous and large-scale increase of the surface temperature caused by frictional heat generation at high rotating speed. For some wear-resistant bearings, it is necessary to maintain stable structural properties under extreme service conditions, such as day and night temperature difference up to 310 ℃ in the moon (the surface temperature can be reduced to-183 ℃ at the lowest); furthermore, the surface instantaneous temperature of the wear-resistant bearing part can reach 800-900 ℃ even when the rocket and the spacecraft are launched and lifted off.
The materials of the conventional wear-resistant bearing part mainly comprise ceramics, gear bearing steel, nonferrous metals, high-temperature alloy and the like, wherein the toughness and the shock resistance of the ceramic materials are seriously insufficient, the gear bearing steel has limited high and low temperature resistance and corrosion resistance, the melting point and the strength of the nonferrous metals are low, and the wear resistance of the high-temperature alloy is insufficient, so that the wear-resistant bearing part cannot be used in the wide-temperature-range extreme environment. The prior patent CN107523719B of the applicant discloses a novel high-hardness nickel titanium-based alloy which has the friction and wear resistance superior to that of the traditional bearing steel and the like, but has limited temperature bearing range and poor tissue stability, and can not meet the requirements of aerospace, high-end equipment and other extreme working conditions, so that a wear-resistant material is needed, the wear-resistant bearing part has excellent temperature difference resistance, shock resistance, high strength, high hardness, high wear resistance and other properties within the wide temperature range of-196-600 ℃, and the stability of the tissue performance can be kept for a long time; and the stability of short-time structure performance can be still maintained in a high-temperature range of more than 700 ℃, and the requirement of instantaneous high-temperature stability under high-temperature working conditions of launching and lifting space of rockets and spacecrafts is met.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a wear-resistant material aiming at the current situation of the prior art: the temperature difference resistance, impact resistance, high strength, high hardness and high wear resistance can be realized within a wide temperature range of-196 ℃ to 600 ℃, and the stability of the structure performance can be maintained for a long time; can maintain the stability of the structure performance for a short time at the high temperature range of 700-900 ℃.
The invention also provides a preparation method of the wear-resistant material.
A further technical problem to be solved by the present invention is to provide the use of the aforementioned wear-resistant material.
The technical scheme adopted by the invention for solving the technical problems is as follows: the wear-resistant material with the wide temperature range consists of the following elements in atomic percentage: 55% -68% of Ni; 0.01-0.5% of rare earth elements, wherein the rare earth elements are selected from at least one of Y, Sc, La and Ce; 3 to 15 percent of additive elements, wherein the additive elements are at least one selected from Hf, W, Re and Ru, Ti is the rest, the atomic ratio of the Ni element to the Ti element is (1:0.5) to (1:0.8), and the atomic ratio of the additive elements to the Ni element is (0.04:1) to (0.3: 1).
Further preferably, the wear-resistant material consists of the following elements in atomic percentage: 56-60% of Ni and 0.05-0.15% of rare earth elements, wherein the rare earth elements are selected from at least one of Y, Sc, La and Ce; 4 to 8 percent of additive elements, wherein the additive elements are at least one selected from Hf, W, Re and Ru, Ti is the rest, the atomic ratio of the Ni element to the Ti element is (1:0.7) to (1:0.8), and the atomic ratio of the additive elements to the Ni element is (0.05:1) to (0.18: 1).
More preferably, the additive elements are at least two selected from Hf, W, Re and Ru elements, and the interaction between the additive elements has better strengthening and toughening effects.
More preferably, the additive element comprises a main additive element Hf, the auxiliary additive element is at least one of W, Re and Ru, the atomic ratio of the main additive element to the auxiliary additive element is 4-1, and endpoint 1 is not included. The main alloy elements mainly have the function of strengthening precipitation and strengthening, and the auxiliary additive elements mainly have the function of solid solution strengthening.
The wear-resistant material mainly comprises an austenite B2-NiTi phase and a large number of uniformly distributed nano strengthening phases,the nano-reinforcing phase is different in content and process, including Ni4Ti3Nanophase, H phase and cubic phase, e.g. with increasing Hf content or different heat treatment processes, nanophase consisting of Ni4Ti3The nanophase is transformed into thermodynamically more stable H and cubic phases. The mass fraction of the nano phase is more than 50 percent, and the wear-resistant material can keep stable structure and performance for a long time within a wide temperature range of-196 ℃ to 600 ℃.
On the other hand, the preparation method for preparing the wear-resistant material with the wide temperature range provided by the invention comprises the following steps:
the preparation method takes simple substances with the corresponding purity of each element of more than 99.9 wt% as raw materials, and sequentially comprises the following steps: smelting ingot casting, homogenizing annealing, plastic deformation processing and solid solution and aging treatment:
smelting and ingot casting: selecting corresponding raw materials according to the component proportion of the required metal material; putting the selected raw materials into a vacuum smelting furnace (comprising a vacuum induction furnace, a vacuum non-consumable electric arc furnace, a vacuum magnetic suspension smelting furnace and a vacuum consumable electric arc furnace) protected by inert gas for smelting to obtain an ingot;
homogenizing and annealing: and carrying out homogenizing annealing on the ingot in the inert gas protection. Preferably, the temperature for carrying out homogenizing annealing on the ingot is 950-1100 ℃, the time is determined by the size of the ingot, and the ingot is cooled along with the furnace. The purpose of the homogenizing annealing is to improve the compositional uniformity of the alloy ingot.
Plastic deformation processing: the ingot is processed by adopting a forging or rolling process, so that the structure is improved, the defects are reduced, and the grains are refined. Preferably, the forging or rolling process temperature is: 800 ℃ and 1100 DEG C
Solution heat treatment: and carrying out solution heat treatment on the ingot subjected to the homogenization heat treatment in the inert gas protection. Preferably, the temperature for carrying out solution treatment on the ingot after the homogenization heat treatment is 950-1050 ℃, the time is determined by the size of the ingot, and the ingot is subjected to rapid cooling quenching. The purpose of solution heat treatment is to precipitate a large amount of nano-reinforcing phases to obtain high hardness and strength.
Aging treatment: and carrying out solution heat treatment on the cast ingot and then carrying out aging treatment. Preferably, the aging treatment temperature is 300-550 ℃, and the time is determined by the size of the cast ingot.
In a further aspect the invention provides the use of the above wide temperature range wear resistant material as a wear resistant carrier in the temperature range-196 ℃ to 900 ℃. The wear-resistant material has the performances of high strength, high hardness, impact resistance, long-term stability, wear resistance and the like in a wide temperature range of-196-600 ℃, can still keep short-term structural performance stable in a high temperature range of 700-900 ℃, maintains high hardness, and has good application prospects in the aerospace fields of airplanes, aeroengines, rockets, spacecrafts and the like, military equipment fields of tank armors, submarines and the like, and advanced industrial fields of nuclear power, high-speed trains, energy power and the like.
In summary, compared with the prior art, the invention has the advantages that:
(1) compared with CN107523719B, 0.01-0.5% of rare earth elements are added, the atomic ratio of Ni elements to Ti elements is set to be (1:0.6) - (1:0.8), the atomic ratio of the added elements to the Ni elements is set to be (0.05:1) - (0.2:1), and the alloying design can effectively improve the phase stability and the toughness of the alloy in a wide temperature range;
(2) the addition of at least one of rare earth elements Y, Sc, La and Ce can reduce the influence of harmful gas elements such as oxygen, nitrogen and the like in the alloy, reduce the content of inclusions such as TiN and the like, improve the purity of the alloy, refine the grain size of the alloy and improve the toughness and the shock resistance of the alloy; in addition, Ti is easy to appear in the prior nickel titanium base alloy2The Ni fishbone phase can not be removed by heat treatment, and Ti can be avoided by adding at least one of the rare earth elements Y, Sc, La and Ce2The generation of Ni fishbone phase makes the plastic deformation processing of the alloy possible.
(3) At least one of Hf, W, Re and Ru elements is added, and the lattice mismatching degree and the interface energy of a nano phase interface are reduced, so that the thermodynamic stability of a nano strengthening phase is improved, the nano strengthening phase is not easy to change phase at high and low temperatures, and the long-term stability of a tissue structure and mechanical properties can be kept in a wide temperature range; in addition, at least two of Hf, W, Re and Ru elements are added, the main alloy element Hf plays a role in strengthening precipitation, the side additive elements play a role in strengthening solid solution, and the interaction among the additive elements has a better strengthening and toughening effect.
(4) Compared with CN107523719B, the invention processes the cast ingot by plastic deformation processing, and the high-temperature diffusion annealing is carried out on the cast ingot before the plastic processing, so that the structure and the components in the cast ingot are uniform, the structure is further refined by the plastic processing, the casting defect is eliminated, and the structure stability and the mechanical property of the material are improved.
(5) The wear-resistant material provided by the invention can still maintain the characteristics of high strength, high hardness, temperature change resistance, impact resistance and the like after being used for a long time in a temperature difference range of approximately 800 ℃ between-196 ℃ and 600 ℃: the material keeps the strength limit of 2.1-2.8GPa and the super-elastic impact resistance of 3% -8%, has high hardness of more than 650HV, and shows excellent structure and performance stability after long-time heat preservation treatment at a wide temperature range of-196-600 ℃. In addition, the wear-resistant material provided by the invention still maintains the structural performance stability within a short time in a high-temperature range of 700-900 ℃, and maintains high hardness of 650HV and above.
Drawings
FIG. 1 is an X-ray diffraction pattern of the wear-resistant material of example 1 of the present invention at room temperature;
fig. 2 is a scanning back-scattered electron image of the wear-resistant material of example 1 of the present invention under room temperature conditions;
FIG. 3 is an X-ray diffraction pattern of the abrasion resistant material of example 1 of the present invention after 200 hours of incubation at-196 deg.C;
FIG. 4 is a scanning backscattered electron image of the wear-resistant material of example 1 of the present invention after 200 hours of incubation at-196 ℃;
FIG. 5 is an X-ray diffraction pattern of the wear-resistant material of example 1 of the present invention after incubation at 400 ℃ for 200 hours;
FIG. 6 is a scanning backscattered electron image of the wear-resistant material of example 1 of the present invention after incubation at 400 ℃ for 200 hours;
FIG. 7 shows transmission electron microscope images of (a) bright field images and (b) diffraction spots in selected areas of the wear-resistant material of example 1 of the present invention after heat preservation at 400 ℃ for 200 hours;
FIG. 8 is an X-ray diffraction pattern of the wear-resistant material of example 1 of the present invention after incubation at 600 ℃ for 200 hours;
FIG. 9 is a scanning backscattered electron image of the wear-resistant material of example 1 of the present invention after incubation at 600 ℃ for 200 hours;
FIG. 10 shows transmission electron microscope images of (a) bright field images and (b) diffraction spots in selected areas of the wear-resistant material of example 1 of the present invention after heat preservation at 600 ℃ for 200 hours;
FIG. 11 is a graph of compressive stress versus displacement for the abrasion resistant material prepared in accordance with example 1 of the present invention at-150 deg.C, -100 deg.C, -25 deg.C (RT), 100 deg.C, -300 deg.C, 600 deg.C;
FIG. 12 is a bar graph of room temperature microhardness of example 1 of the present invention in its aged state and after 200 hours incubation at-196/400/500/600 ℃;
FIG. 13 is a graph of room temperature compressive stress versus displacement for example 1 of the present invention in the as-aged state and after 200 hours incubation at-196/400/500/600 deg.C;
FIG. 14 is a scanning backscattered electron image of inventive example 1 after 5 hours incubation at (a)700 ℃, (b)800 ℃, (c)900 ℃;
FIG. 15 is a bar graph of room temperature microhardness of example 1 of the present invention in the aged state and after 5 hours incubation at 700/800/900 ℃;
FIG. 16 is an X-ray diffraction pattern of the wear-resistant material of comparative example 1 at room temperature;
FIG. 17 is an X-ray diffraction pattern of the wear-resistant material of comparative example 1 after heat preservation at 600 ℃ for 200 hours;
FIG. 18 shows transmission electron microscope (a) bright field image and (b) diffraction spots in selected areas of the wear-resistant material of comparative example 1 after heat preservation at 600 ℃ for 200 hours.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. The present invention is further illustrated by the following examples, but is not limited to the specific embodiments.
The raw materials used in the specific embodiment of the present invention include titanium block (Ti) with a purity of 99.95% (wt.%), nickel block (Ni) with a purity of 99.98% (wt.%), Hf rod with a purity of 99.95% (wt.%), and other elemental raw materials with a corresponding purity of 99.9 wt.% or more.
The surface of the raw material is cleaned (including removing oxide skin by acid washing and alkali washing, and removing oil stain by acetone and/or alcohol) and polished before preparation, and then the raw material is dried and weighed by a high-precision electronic balance after drying.
Preparing alloy materials according to nominal components in the following table 1:
table 1 ingredient list of examples 1-23 (element contents are all atomic percent at.%)
Figure BDA0003267198080000051
Figure BDA0003267198080000061
The alloy can be used for preparing the nickel titanium-based multi-element alloy ingot with uniform components by adopting any one of methods such as vacuum non-consumable arc melting, vacuum induction melting, vacuum consumable melting, vacuum magnetic suspension melting and the like. In the specific embodiment of the invention, the prepared raw materials with the weight are put into a water-cooled copper crucible of a vacuum non-consumable electric arc furnace and vacuumized to 3-5 multiplied by 10-3And (3) after Pa, introducing high-purity argon to ensure that the vacuum degree is 0.05MPa, repeatedly smelting for more than 5 times under the protection of argon atmosphere to ensure that the components are uniform, and cooling and smelting along with the furnace to obtain a typical button-shaped ingot.
The homogenizing annealing temperature of the alloy can be 950-1100 ℃, and the heat preservation time is 10-30 hours; the plastic deformation processing temperature can be 800-1100 ℃; the solid solution temperature can be 950-1050 ℃, and oil quenching is carried out after the heat preservation time is 2-8 hours; the aging temperature can be 300-550 ℃.
In the specific embodiment of the invention, the ingot is put into a vacuum heat treatment furnace for homogenizing annealing, and the annealing temperature is 1Keeping the temperature at 050 ℃ for 24 hours, and then cooling along with the furnace; performing plastic deformation processing by forging: the temperature is 950 ℃; cutting round bar with diameter of 12mm from the ingot by using a wire cutting machine, packaging in a quartz glass tube, and drawing to 10 deg.C in the glass tube-3And introducing argon as protective gas after the vacuum degree of Pa level. And (3) carrying out solid solution oil cold quenching on the sample subjected to tube sealing at 1050 ℃/4h in a tube furnace, wherein the aging temperature is 400 ℃, and the aging time is 4 h.
The Vickers hardness of the alloy prepared above was measured using a microscopic Vickers hardness tester, and ten sets of data were tested per sample to calculate the average value in order to avoid the deviation caused by the non-uniform structure.
A cylindrical sample with the diameter d of 3mm and the height h of 6mm is cut from the prepared alloy by a wire cutting method to be used as a compression performance test sample, and a SANS-5504 type universal material tester is used for carrying out compression test, wherein the compression rate is 0.05 mm/min.
A cuboid sample with the length of a preformed notch a being 3mm is taken as a fracture toughness test sample, wherein the length L being 30mm, the length W being 6mm, the length B being 3mm and the length a being 3mm is cut by linear cutting. A SANS-5504 type universal material testing machine is adopted to carry out three-point bending test, and the strain rate is 0.1 mm/min.
The mechanical properties of examples 1-23 are shown in Table 2:
TABLE 2 mechanical Properties of examples 1-23
Figure BDA0003267198080000071
Figure BDA0003267198080000081
As shown in Table 2, the addition of the alloying elements Hf, W, Re and Ru increases the hardness and strength of the alloy, and the excessively high Ni content decreases the hardness and improves the toughness. Hf element has better strengthening effect, and the multi-element alloy has better comprehensive performance; however, the atomic ratio of the main additive element Hf to the auxiliary additive elements W, Re, and Ru should be maintained at a certain ratio, which would otherwise reduce the strength of the alloy, and it is preferable that the atomic ratio of the main additive element Hf to the auxiliary additive elements W, Re, and Ru be 4-1, excluding endpoint 1.
The friction and wear test is carried out on a UMT-2 type friction and wear testing machine, the lubricating condition is oil lubrication friction, the ball-disk contact is adopted to carry out the reciprocating friction and wear test, and a test sample on a friction pair is used
Figure BDA0003267198080000083
Si of (2)3N4The ball, lower sample, was processed according to the alloy composition of Table 1
Figure BDA0003267198080000084
The alloy disc of (1) has the load of 20N, the frequency of 5Hz, the step length of 6mm and the abrasion time of 4 h. The mass before and after the time of abrasion was weighed with an analytical balance having a sensitivity of 0.1mg, and the difference between the two was the abrasion loss.
The results of the frictional wear test are shown in table 3:
TABLE 3 frictional wear Performance Table for examples 1-23
Figure BDA0003267198080000082
Figure BDA0003267198080000091
As can be seen from Table 3, the higher the alloy hardness, the smaller the wear amount and the friction coefficient, and therefore, the better the frictional wear properties. Examples 1-23 all had good wear resistance and were used to make wear resistant bearing articles.
As shown in FIGS. 1 and 2, which are respectively an X-ray diffraction pattern and a scanning back scattering electron image of the wear-resistant material prepared in example 1 of the invention at room temperature, it can be seen that the main composition phases of the wear-resistant material after solution treatment in example 1 are B2-NiTi and Ni4Ti3Two phases, semi-quantitative analysis by RIR value method, Ni4Ti3The mass fraction of phases is greater than 50 wt%. The alloy presents a relatively uniform structure, no obvious precipitated phase and only a small amount of HfO2The particles and TiC phase are distributed in the matrix. Ni in alloy4Ti3The phase size is on the order of nanometers and is difficult to observe in scanned images. The X-ray diffraction pattern and the scanning back scattering electron image under the room temperature condition of other embodiments of the invention are similar to the embodiment 1, and the main composition phases are B2-NiTi and Ni4Ti3Two phases, Ni4Ti3The mass fraction of the phase is more than 50 wt%, the alloy presents a relatively uniform structure, no obvious precipitated phase exists, and only a small amount of HfO exists2The particles and the TiC phase are distributed in the matrix.
As shown in FIGS. 3 and 4, which are respectively an X-ray diffraction pattern and a scanning back scattering electron image of the wear-resistant material prepared in example 1 of the invention after heat preservation at-196 ℃ for 200 hours, it can be seen from FIG. 3 that the main composition phases of the alloy are B2-NiTi and Ni4Ti3Two phases, semi-quantitative analysis by RIR value method, Ni4Ti3The mass fraction of phases is greater than 50 wt%; as shown in FIG. 4, the alloy exhibited a relatively uniform structure, no significant precipitated phase, and only a small amount of HfO2The particles and TiC phase are distributed. Ni in alloy4Ti3The phase size is on the order of nanometers and is difficult to observe in scanned images. The X-ray diffraction pattern and the scanning back scattering electron image of other embodiments of the invention after the temperature is kept at 196 ℃ below zero for 200 hours are similar to the embodiment 1, and the main composition phases are B2-NiTi and Ni4Ti3Two phases, Ni4Ti3The mass fraction of the phase is more than 50 wt%, the alloy presents a relatively uniform structure, no obvious precipitated phase exists, and only a small amount of HfO exists2The particles and the TiC phase are distributed in the matrix.
As shown in FIGS. 5 and 6, which are respectively the X-ray diffraction pattern and the scanning back scattering electron image of the wear-resistant material prepared in example 1 of the invention after heat preservation at 400 ℃ for 200 hours, as shown in FIG. 5, the main composition phases of the alloy are B2-NiTi and Ni4Ti3Two phases, semi-quantitative analysis by RIR value method, Ni4Ti3The mass fraction of phases is greater than 50 wt%; as shown in FIG. 6, the alloy structure is uniform, no obvious precipitated phase exists, and only a small amount of HfO exists2The particles and TiC phase are distributed. Ni4Ti3The phase size is on the order of nanometers and is difficult to observe in scanned images. As shown in FIG. 7 for implementationThe transmission electron microscope bright field image and diffraction spots of the wear-resistant material of example 1 after heat preservation at 400 ℃ for 200 hours were observed, from which Ni4Ti3The phases are ellipsoidal and have dimensions of about 75nm in length and about 25nm in width. Double halo Ni around B2 reflection4Ti3Phase reflection, an additional single point reflection between the two point reflections indicates the presence of the H phase.
The X-ray diffraction pattern and the scanning back scattering electron image of other embodiments of the invention after heat preservation at 400 ℃ for 200 hours are similar to those of the embodiment 1, and the main composition phases are B2-NiTi and Ni4Ti3Two phases, Ni4Ti3The mass fraction of the phase is more than 50 wt%, the alloy presents a relatively uniform structure, no obvious precipitated phase exists, and only a small amount of HfO exists2The particles and the TiC phase are distributed in the matrix.
As shown in FIGS. 8 and 9, which are respectively the X-ray diffraction pattern and the scanning back scattering electron image of the wear-resistant material prepared in example 1 of the invention after heat preservation at 600 ℃ for 200 hours, as shown in FIG. 8, the main composition phases of the alloy are B2-NiTi and Ni4Ti3Two phases, semi-quantitative analysis by RIR value method, Ni4Ti3The mass fraction of phases is greater than 50 wt%; as shown in FIG. 9, the alloy exhibited a relatively uniform structure, no significant precipitated phase, and only a small amount of HfO2The particles and TiC phase are distributed. As shown in FIG. 10, the transmission electron microscope bright field image and diffraction spots of example 1 after heat preservation at 600 ℃ for 200 hours are shown, from which Ni is observed4Ti3The phases are ellipsoidal and have dimensions of about 110nm in length and about 60nm in width. Double halo Ni around B2 reflection4Ti3Phase reflection, an additional single point reflection between the two point reflections indicates the presence of the H phase.
The X-ray diffraction pattern and the scanning back scattering electron image of other embodiments of the invention after heat preservation at 600 ℃ for 200 hours are similar to those of the embodiment 1, and the main composition phases are B2-NiTi and Ni4Ti3Two phases, Ni4Ti3The mass fraction of the phase is more than 50 wt%, the alloy presents a relatively uniform structure, no obvious precipitated phase exists, and only a small amount of HfO exists2The particles and the TiC phase are distributed in the matrix.
According to the experimental results, the wear-resistant material disclosed by the invention can keep stable structure and performance for a long time in a wide temperature range of-196-600 ℃.
As shown in FIG. 11, the compressive stress-displacement curve of example 1 at-150 ℃, 100 ℃, 25 ℃ (RT), 100 ℃, 200 ℃, 600 ℃ was measured using a SANS Universal tester, and the dimension of the compressed sample was φ 3X 6 mm. Within the wide temperature range of-150 to 300 ℃, the alloy has higher strength limit and basically keeps linear elasticity, and the compressive strength is reduced along with the rise of the temperature and is 2795MPa, 2678MPa, 2640MPa, 2486MPa, 2389MPa and 2190MPa respectively. The displacement is corrected to estimate the strain limit, taking into account equipment tolerances, over this wide temperature range the alloy has a linear elastic strength limit of 2.1-2.8GPa and a linear elastic strain limit of 3.5% -8%. Also, other embodiments of the present invention have similar performance.
FIG. 12 is a bar graph of room temperature microhardness after treatment under different conditions in example 1. The data show that the material of the embodiment can keep warm for a long time in a temperature range of-196-600 ℃, the material still keeps certain stability, and the hardness value is kept above 670 HV.
As shown in FIG. 13, the room temperature compressive stress-displacement curves of the samples treated under different conditions in example 1 are shown, and the dimensions of the compressed samples are φ 3X 6 mm. After long-term heat preservation treatment in a wide temperature range, the room-temperature compressive strength of the alloy is kept above 2160MPa and high elasticity is kept. And correcting the displacement to estimate the strain limit by considering equipment errors, wherein the alloy has a linear elastic strength limit of 2.1-2.8GPa and a linear elastic strain limit of 3.8% -8% after long-time heat preservation treatment in a temperature range of-196-600 ℃. The metal material obtained in this example has excellent mechanical properties over this wide temperature range and maintains stable structure properties over a long period of time. Also, other embodiments of the present invention have similar performance.
According to the content, the wear-resistant material prepared by the invention has excellent mechanical properties in a wide temperature range of-196-600 ℃, and the mechanical properties are still stable after long-term heat preservation treatment.
FIG. 14 shows the present embodiment1, keeping the temperature at 700 ℃, 800 ℃ and 900 ℃ for 5 hours, and then carrying out scanning back scattering electron image; it can be seen that the tissue performance remains stable over this temperature range: the main composition phases are B2-NiTi and Ni4Ti3Two phases, Ni4Ti3The mass fraction of the phase is more than 50 wt%, the alloy presents a relatively uniform structure, no obvious precipitated phase exists, and only a small amount of HfO exists2The particles and the TiC phase are distributed in the matrix.
FIG. 15 is a bar graph showing the room temperature microhardness of this example 1 in the aged state and after 5 hours of incubation at 700/800/900 ℃, which is stable in performance in this temperature range and maintains a high hardness of 650HV and above.
Comparative example 1
The raw materials used for this comparative example included 99.95% (wt.%) titanium chunks (Ti), 99.98% (wt.%) nickel chunks (Ni), 99.95% (wt.%) Hf rods.
The surface of the raw material is cleaned (including removing oxide skin by acid washing and alkali washing, and removing oil stain by acetone and/or alcohol) and polished before preparation, and then the raw material is dried and weighed by a high-precision electronic balance after drying.
Preparing an alloy material according to the following nominal components:
55at％Ni，42at％Ti，3at％Hf
the raw materials with the prepared weight are put into a water-cooled copper crucible of a vacuum non-consumable electric arc furnace and vacuumized to 3-5 multiplied by 10-3And (3) after Pa, introducing high-purity argon to ensure that the vacuum degree is 0.05MPa, repeatedly smelting for more than 5 times under the protection of argon atmosphere to ensure that the components are uniform, and cooling and smelting along with the furnace to obtain a typical button-shaped ingot.
Putting the cast ingot into a vacuum heat treatment furnace for homogenizing annealing, wherein the annealing temperature is 1050 ℃, and cooling along with the furnace after heat preservation for 24 hours; cutting round bar with diameter of 12mm from the ingot by using a wire cutting machine, packaging in a quartz glass tube, and drawing to 10 deg.C in the glass tube-3And introducing argon as protective gas after the vacuum degree of Pa level. And (3) carrying out solid solution oil cold quenching on the sample subjected to tube sealing at 1050 ℃/4h in a tube furnace, wherein the aging temperature is 400 ℃, and the aging time is 4 h.
As shown in FIGS. 16 and 17,18 is X-ray diffraction pattern of the prepared material at room temperature and 600 deg.C for 200 hr, and transmission electron microscope bright field image and diffraction spot of the material at 600 deg.C for 200 hr. The main composition phases of B2-NiTi and Ni at room temperature4Ti3Two phases, the main component phases are B2-NiTi and Ni after heat preservation for 200 hours at 600 DEG C4Ti3、Ni3Ti2Three-phase, i.e. nanophase Ni in long-term service at high temperatures4Ti3Conversion to Ni3Ti2The structural transformation will cause the hardness of the material to decrease, and the service condition cannot be met.
The technical means disclosed in the invention scheme are not limited to the technical means disclosed in the above embodiments, but also include the technical scheme formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.

Claims (8)

1. The wide-temperature-range wear-resistant material is characterized by comprising the following elements in atomic percentage: 55% -68% of Ni; 0.01-0.5% of rare earth elements, wherein the rare earth elements are selected from at least one of Y, Sc, La and Ce; 3 to 15 percent of additive elements, wherein the additive elements are at least one selected from Hf, W, Re and Ru, Ti is the rest, the atomic ratio of the Ni element to the Ti element is (1:0.5) to (1:0.8), and the atomic ratio of the additive elements to the Ni element is (0.04:1) to (0.3: 1).
2. The wide temperature range, wear resistant material of claim 1, characterized by consisting of the following elements in atomic percent: 56-60% of Ni, 0.05-0.15% of rare earth elements and 4-8% of additive elements, the balance being Ti, wherein the atomic ratio of the Ni element to the Ti element is (1:0.7) - (1:0.8), and the atomic ratio of the additive elements to the Ni element is (0.05:1) - (0.18: 1).
3. The wide temperature range wear resistant material of claim 1 or 2, wherein: the additive elements are at least two elements selected from Hf, W, Re and Ru.
4. The wide temperature range wear resistant material of claim 1 or 2, wherein: the additive element comprises a main additive element Hf, the auxiliary additive element is at least one of W, Re and Ru, the atomic ratio of the main additive element to the auxiliary additive element is 4-1, and endpoint 1 is not included.
5. A method for producing the wear-resistant material as claimed in any one of claims 1 to 4, characterized by comprising the steps of: smelting ingot casting, homogenizing annealing, plastic deformation processing, solid solution heat treatment and aging treatment.
6. The production method according to claim 5,
the ingot casting is smelted, corresponding raw materials are selected according to the component proportion of the required metal material, and the selected raw materials are put into a vacuum smelting furnace protected by inert gas for smelting to obtain an ingot casting;
carrying out homogenization annealing on the ingot in inert gas protection, wherein the temperature is 950-1100 ℃, the time is determined by the size of the ingot, and the ingot is cooled along with the furnace;
the plastic deformation processing is to process the cast ingot by adopting a forging or rolling process;
performing solution heat treatment on the cast ingot subjected to plastic deformation processing in inert gas protection, wherein the temperature is 950-1050 ℃, the time is determined by the size of the cast ingot, and performing rapid cold quenching;
and the aging treatment is carried out after the ingot is subjected to solution heat treatment, the temperature of the aging treatment is 300-550 ℃, and the time is determined by the size of the ingot.
7. The production method according to claim 6,
the forging or rolling process temperature is as follows: 800 ℃ and 1100 ℃.
8. Use of the wear resistant material according to any of claims 1 to 4 as a wear resistant carrier in the temperature range-196 ℃ to 900 ℃.
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