CN113968749A - Method for connecting high-entropy ceramics and metal - Google Patents
Method for connecting high-entropy ceramics and metal Download PDFInfo
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Abstract
The invention provides a method for connecting high-entropy ceramics and metals, which comprises the following steps: step S1, carrying out vacuum diffusion welding on the high-entropy ceramic and TaZrNbHfTi refractory high-entropy alloy at high temperature to obtain a welded assembly; and step S2, carrying out vacuum diffusion welding on the TaZrNbHfTi refractory high-entropy alloy of the welded assembly and the metal to complete the connection of the high-entropy ceramic and the metal. According to the method for connecting the high-entropy ceramics and the metal, provided by the invention, TaZrNbHfTi refractory high-entropy alloy is used as the intermediate layer, so that the diffusion welding of the high-entropy ceramics and the metal is realized, the good wetting of a base material and the smooth transition of a thermal expansion coefficient can be realized, the generation of defects such as cracks is inhibited, and the strength of a joint is improved.
Description
Technical Field
The invention relates to the technical field of welding, in particular to a method for connecting high-entropy ceramics and metals.
Background
High Entropy Alloy (HEA), also known as multi-principal element alloy, where the principal elements are mixed in equal or near equal atomic ratios, with principal element atomic fractions between 5% and 35%. The high-entropy alloy has high entropy effect, delayed diffusion effect, lattice distortion effect and cocktail effect, and has attracted wide attention of scholars at home and abroad. The high-entropy ceramic is a high-entropy material which is extended from the component design concept of high-entropy alloy, and compared with the high-entropy alloy, the structural diversity and the adjustability of an electronic structure of the high-entropy ceramic provide wider space for performance regulation and application of the high-entropy ceramic. The high-entropy ceramics generally comprise carbides, nitrides, borides, oxides and the like, are formed by metal compounds formed by refractory metal elements of some transition groups, have the characteristics of high melting point and high hardness, show high temperature resistance, ablation resistance, wear resistance, low thermal conductivity and the like, and have wide application prospects in the fields of aerospace, automobiles, war industry, electronics and the like, such as thermal protection systems of aircrafts such as space shuttles, hypersonic missiles and the like. However, ceramics are brittle and have poor workability, and in practical use, they are often required to be joined to metals to form composite structures so as to exhibit their respective excellent properties to a greater extent. Therefore, the reliable connection of the high-entropy ceramics and the metal has important engineering application value.
Due to obvious differences among chemical bonds, chemical components and physical properties (such as melting point, thermal expansion coefficient, thermal conductivity and specific heat capacity), when high-entropy ceramics (HEC) and metals are welded, two key problems that base materials are difficult to wet and compatible, residual stress is too large, and joint strength is seriously reduced exist. Researches show that the problem of joint wettability can be effectively solved by metallizing the surface of the ceramic or using brazing filler metal containing an activating element, and the residual stress is relieved mainly by adding an intermediate layer material which is adaptive to the thermal expansion coefficient of the ceramic. At present, the problem to be solved at present is to select a proper interlayer material to have good balance between the welding wettability and the residual stress relief, and a report is newly made on the welding of high-entropy ceramics and metals.
In view of the above, it is necessary to provide a method for connecting high-entropy ceramics and metals to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a method for connecting high-entropy ceramics and metals, which takes TaZrNbHfTi refractory high-entropy alloy as an intermediate layer to realize diffusion welding of the high-entropy ceramics and the metals, can realize good wetting of base materials and smooth transition of thermal expansion coefficients, and inhibits the generation of defects such as cracks, thereby improving the strength of a joint.
In order to solve the problems, the technical scheme of the invention is as follows:
a method for connecting high-entropy ceramics and metals comprises the following steps:
step S1, carrying out vacuum diffusion welding on the high-entropy ceramic and TaZrNbHfTi refractory high-entropy alloy at high temperature to obtain a welded assembly;
and step S2, carrying out vacuum diffusion welding on the TaZrNbHfTi refractory high-entropy alloy of the welded assembly and the metal to complete the connection of the high-entropy ceramic and the metal.
Further, in step S1, the diffusion temperature is 1400-2000 deg.C, the diffusion time is 5-300min, the diffusion pressure is 5-40MPa, and the vacuum degree is less than or equal to 1 × 10-3MPa。
Further, step S1 specifically includes the following steps:
setting the pressure to be 5-40MPa, firstly heating from room temperature to 1000 ℃ at the heating rate of 10-150 ℃/min, and keeping the temperature for 10-30 min;
then heating to the diffusion welding temperature of 1400-2000 ℃ at the heating rate of 10-100 ℃/min, and preserving the heat for 5-300 min;
reducing the pressure to 5MPa, reducing the temperature to 600 ℃ at the cooling rate of 10-50 ℃/min, and naturally cooling to the room temperature along with the furnace.
Furthermore, the high-entropy ceramic is composed of metal compounds formed by three or more refractory metal elements of Ta, Zr, Nb, Hf, Ti, W, Mo and V and C, N, B or O atoms, wherein each refractory metal element is proportioned according to equal atomic ratio or near equal atomic ratio.
Further, in step S2, the diffusion temperature is 800-1200 ℃, the diffusion time is 5-300min, and the vacuum degree is less than or equal to 1 × 10-3MPa。
Further, step S2 specifically includes the following steps:
setting the pressure to be 5-40MPa, firstly heating from room temperature to 600 ℃ at the heating rate of 10-150 ℃/min, and preserving the heat for 10-30 min;
then heating up to the diffusion welding temperature of 800-;
reducing the pressure to 5MPa, reducing the temperature to 600 ℃ at the cooling rate of 10-50 ℃/min, and naturally cooling to the room temperature along with the furnace.
Further, the metal used in step S2 is a refractory high-entropy alloy, a titanium alloy, a niobium alloy, or a titanium-aluminum intermetallic compound.
Furthermore, the intermediate connecting layer is formed by TaZrNbHfTi refractory high-entropy alloy, and the thickness of the intermediate connecting layer is 100-2000 mu m.
Furthermore, the TaZrNbHfTi refractory high-entropy alloy is prepared by mixing the alloy elements according to equal atomic ratio, adopting vacuum arc melting, and then carrying out homogenization annealing and water quenching.
Further, before welding, the high-entropy ceramic, the TaZrNbHfTi refractory high-entropy alloy and the metal in the steps S1 and S2 are subjected to grinding, vibration polishing, ultrasonic cleaning and drying treatment on the part to be welded in sequence.
Compared with the prior art, the method for connecting the high-entropy ceramics and the metal has the beneficial effects that:
according to the method for connecting the high-entropy ceramics and the metal, the TaZrNbHfTi refractory high-entropy alloy (RHEA) is used as an intermediate layer for connecting the high-entropy ceramics and the metal, and vacuum diffusion welding is adopted to realize the connection of the high-entropy ceramics and the metal, wherein the TaZrNbHfTi refractory high-entropy alloy is used as a novel high-temperature structural material with application potential, has certain elongation and strength, is close to the melting point of the high-entropy ceramics, and is good in wettability. In the high-temperature diffusion (not less than 1400 ℃), high solid solubility exists between refractory metal elements, and brittle intermetallic compounds are difficult to generate; according to the diffusion law, C, N, B or O atoms of the high-entropy ceramic are rapidly diffused to one side of TaZrNbHfTi refractory high-entropy alloy to form a thicker welding interface layer with smaller C, N, B or O atom concentration gradient, smooth transition of thermal expansion coefficients between parent metals is realized through the interface layer, and the problems that local residual stress is too large due to unmatched thermal expansion coefficients, cracks are generated on the welding interface, and the welding interface is rapidly expanded are solved. The welding of TaZrNbHfTi series refractory high-entropy alloy and metal generally has higher connecting strength. Therefore, the TaZrNbHfTi refractory high-entropy alloy is used as the intermediate layer for welding high-entropy ceramics and metals, good wetting of the base metal and smooth transition of the thermal expansion coefficient can be realized, the generation of defects such as cracks is inhibited, and the strength of the joint is improved.
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In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a photograph of an interface structure of a (TaZrNbHfTi) C high-entropy ceramic and a Ti2AlNb alloy joined by vacuum diffusion welding in example 1, wherein a TaZrNbHfTi refractory high-entropy alloy is used as an intermediate layer;
FIG. 2 is a photograph of an interface structure of a (TaZrNbHfTi) C high-entropy ceramic and a Ti2AlNb alloy joined by vacuum diffusion welding in example 2, wherein TaZrNbHfTi refractory high-entropy alloy is used as an intermediate layer;
FIG. 3 is a photograph of the interface structure of the (TaZrNbHfTi) C high-entropy ceramic and Ti2AlNb alloy joined by vacuum diffusion welding using TaZrNbHfTi refractory high-entropy alloy as the intermediate layer in example 3;
FIG. 4 is a photograph of the interface structure of the (TaZrNbHfTi) C high-entropy ceramic and Ti2AlNb alloy joined by vacuum diffusion welding without using an intermediate layer in the comparative example.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
A method for connecting high-entropy ceramics and metals comprises the following steps:
step S1, carrying out vacuum diffusion welding on the high-entropy ceramic and TaZrNbHfTi refractory high-entropy alloy at high temperature to obtain a welded assembly;
specifically, the high-entropy ceramic is composed of metal compounds formed by C, N, B or O atoms and three or more refractory metal elements of Ta, Zr, Nb, Hf, Ti, W, Mo and V, wherein each refractory metal element is proportioned according to equal atomic ratio or nearly equal atomic ratio;
the TaZrNbHfTi refractory high-entropy alloy is prepared by mixing alloy elements according to equal atomic ratio, adopting vacuum arc melting, and then carrying out homogenization annealing and water quenching. The specific process comprises the following steps:
proportioning and weighing metal raw material particles (with the purity of more than 99.9) according to the atomic ratio of each metal of the TaZrNbHfTi refractory high-entropy alloy;
putting the TaZrNbHfTi refractory high-entropy alloy raw material into an electric arc melting furnace, and repeatedly melting for at least 5 times under the protection of high-purity argon to obtain an ingot;
carrying out homogenization heat treatment on the cast ingot for 24h at 1200 ℃ under the protection of argon, and carrying out water quenching to obtain TaZrNbHfTi refractory high-entropy alloy with uniform components;
cutting the obtained alloy ingot into sheets of 100-2000 μm by wire cutting;
and (3) grinding the sheet by using SiC sand paper, carrying out vibration polishing, carrying out alcohol cleaning under the action of ultrasonic waves, and carrying out drying treatment in a drying oven to finally obtain the intermediate layer material with a smooth surface.
The vacuum diffusion welding process of the high-entropy ceramic and TaZrNbHfTi refractory high-entropy alloy comprises the following steps:
before welding, sequentially grinding, vibrating and polishing, ultrasonically cleaning and drying the part to be welded;
high entropy ceramicsStacking TaZrNbHfTi refractory high-entropy alloy in a graphite mold, separating the sample and the graphite mold by graphite paper with the thickness of 0.2mm, putting the sample and the graphite mold into a discharge plasma sintering furnace, ensuring that the polished surfaces of the base materials are tightly attached, vacuumizing to ensure that the vacuum degree is not more than 1 multiplied by 10-3MPa；
Setting the pressure to be 5-40MPa, firstly heating from room temperature to 1000 ℃ at the heating rate of 10-150 ℃/min, and keeping the temperature for 10-30 min; wherein the heating rate can be 10 ℃/min, 20 ℃/min, 50 ℃/min, 80 ℃/min, 100 ℃/min, 120 ℃/min, 150 ℃/min, or other heating rates within the range;
then heating to the diffusion welding temperature of 1400-2000 ℃ at the heating rate of 10-100 ℃/min, and preserving the heat for 5-300 min; wherein the heating rate can be 10 ℃/min, 20 ℃/min, 50 ℃/min, 80 ℃/min, 100 ℃/min, or other values within the range; the diffusion temperature may be 1400 ℃, 1500 ℃, 1600 ℃, 1700 ℃, 1750 ℃, 1800 ℃, 2000 ℃, or other diffusion welding temperatures within this range;
reducing the pressure to 5MPa, reducing the temperature to 600 ℃ at a cooling rate of 10-50 ℃/min, and naturally cooling to room temperature along with the furnace to obtain a welded assembly; wherein the cooling rate can be 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, or other values within the range;
step S2, carrying out vacuum diffusion welding on TaZrNbHfTi refractory high-entropy alloy of the welded assembly and metal to complete the connection of the high-entropy ceramic and the metal;
specifically, the metal is refractory high-entropy alloy, titanium alloy, niobium alloy or titanium-aluminum intermetallic compound;
the vacuum diffusion welding process of TaZrNbHfTi refractory high-entropy alloy and metal of the welded assembly comprises the following steps:
before welding, sequentially grinding, vibrating and polishing, ultrasonically cleaning and drying the part to be welded;
stacking the welded assembly with the treated surface and Ti2AlNb alloy in a graphite mold, separating the sample and the graphite mold by graphite paper with the thickness of 0.2mm, then putting the sample and the graphite mold into a discharge plasma sintering furnace, and diffusingThe pressure is 30MPa, so that TaZrNbHfTi refractory high-entropy alloy of the welding assembly is tightly attached to the Ti2AlNb alloy polished surface, and the vacuum degree is less than or equal to 1 multiplied by 10-3MPa；
Setting the pressure to be 5-40MPa, firstly heating from room temperature to 600 ℃ at the heating rate of 10-150 ℃/min, and preserving the heat for 10-30 min; wherein the heating rate can be 10 ℃/min, 20 ℃/min, 50 ℃/min, 80 ℃/min, 100 ℃/min, 120 ℃/min, 150 ℃/min, or other values within the range;
then heating up to the diffusion welding temperature of 800-; wherein the heating rate can be 10 ℃/min, 20 ℃/min, 50 ℃/min, 80 ℃/min, 100 ℃/min, or other values within the range; the diffusion temperature may be 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, or other diffusion welding temperatures within this range;
reducing the pressure to 5MPa, reducing the temperature to 600 ℃ at a cooling rate of 10-50 ℃/min, and naturally cooling to room temperature along with the furnace to obtain a welding joint formed by connecting high-entropy ceramics and metals; wherein the cooling rate can be 10 deg.C, 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, or other values within this range.
In the welding joint, TaZrNbHfTi refractory high-entropy alloy forms an intermediate connecting layer, and the thickness of the intermediate connecting layer is 100-2000 mu m.
The method for connecting the entropy ceramics and the metal provided by the invention is explained in detail by specific examples.
Example 1
A welding method of high-entropy ceramics and metals comprises the following steps:
(1) processing (TaZrNbHfTi) C high-entropy ceramic into a cylindrical sample with the diameter phi of 15mm and the height of 6mm by adopting linear cutting, sequentially grinding surfaces to be welded by adopting 600#, 800#, 1200#, and 2000# diamond millstones, then placing the sample in a vibration polisher, respectively adopting alumina and silica gel solutions to carry out rough polishing and fine polishing until the surfaces have no scratches, then cleaning the sample by using alcohol under the action of ultrasonic waves, and finally carrying out drying treatment;
(2) preparing TaZrNbHfTi refractory high-entropy alloy, and proportioning and weighing metal raw material particles (the purity is more than 99.9%) according to the atomic ratio of each element of the TaZrNbHfTi refractory high-entropy alloy being 1:1:1:1: 1; then putting the raw materials into an electric arc melting furnace, and repeatedly melting for at least 5 times under the protection of high-purity argon to obtain an ingot; finally, packaging the cast ingot in a quartz tube under the protection of argon, carrying out homogenization heat treatment at 1200 ℃ for 24h, and carrying out water quenching;
(3) cutting TaZrNbHfTi refractory high-entropy alloy into sheets with the diameter of phi 15mm and the thickness of 1000 mu m by utilizing linear cutting; sequentially grinding the surfaces to be welded of the sheets by using 600#, 800#, 1200#, 2000# SiC abrasive paper, placing the sheets in a vibration polisher, respectively performing rough polishing and fine polishing by using alumina and silica gel solution until the surfaces are free from scratches, then cleaning the surfaces by using alcohol under the action of ultrasonic waves, and finally performing drying treatment;
(4) stacking the (TaZrNbHfTi) C high-entropy ceramic with the processed surface and TaZrNbHfTi refractory high-entropy alloy in a graphite mold, separating the sample and the graphite mold by graphite paper with the thickness of 0.2mm, then putting the sample and the graphite mold into a discharge plasma sintering furnace together, wherein the diffusion pressure is 30MPa, so that the polished surfaces of the parent metal are tightly attached, and vacuumizing;
(5) firstly, heating from room temperature to 1000 ℃ at the heating rate of 100 ℃/min, and keeping the temperature for 10 min; then heating to 1650 ℃ at the heating rate of 50 ℃/min, and keeping the temperature for 15 min; reducing the pressure to 5MPa, reducing the temperature to 600 ℃ at a cooling rate of 20 ℃/min, and naturally cooling to room temperature along with the furnace to complete the connection of the (TaZrNbHfTi) C high-entropy ceramic and the TaZrNbHfTi refractory high-entropy alloy, thereby obtaining a welded assembly;
(6) cutting a commercialized Ti2AlNb alloy into cylindrical samples with the diameter phi of 15mm and the height of 6mm by utilizing linear cutting, sequentially grinding the surfaces of TaZrNbHfTi refractory high-entropy alloy of the welded assembly in the step (5) and the surfaces to be welded of the Ti2AlNb alloy by using SiC abrasive paper of 600#, 800#, 1200# and 2000#, placing the SiC abrasive paper into a vibration polishing machine, respectively performing rough polishing and fine polishing by using aluminum oxide and silica gel solution until the surfaces have no scratches, then cleaning by using alcohol under the action of ultrasonic waves, and finally performing drying treatment;
(7) stacking the welding assembly with the processed surface in the step (6) and the Ti2AlNb alloy in a graphite mold, separating the sample and the graphite mold by graphite paper with the thickness of 0.2mm, then putting the sample and the graphite mold into a discharge plasma sintering furnace together, wherein the diffusion pressure is 30MPa, so that the TaZrNbHfTi refractory high-entropy alloy of the welding assembly is tightly attached to the Ti2AlNb alloy polished surface, and vacuumizing;
(8) firstly, heating from room temperature to 600 ℃ at a heating rate of 50 ℃/min, and keeping the temperature for 10 min; then the temperature is raised to 1050 ℃ at the temperature raising rate of 30 ℃/min, and the temperature is preserved for 15 min; reducing the pressure to 5MPa, then reducing the temperature to 600 ℃ at the cooling rate of 20 ℃/min, naturally cooling to room temperature along with the furnace, completing the connection of the (TaZrNbHfTi) C high-entropy ceramic and the Ti2AlNb alloy, and obtaining the welding joint of the (TaZrNbHfTi) C high-entropy ceramic and the Ti2AlNb alloy.
Referring to fig. 1, a photograph of an interface structure of the (tazrnbhft) C high-entropy ceramic and the Ti2AlNb alloy joined by vacuum diffusion welding using the tazrnbheti refractory high-entropy alloy as the intermediate layer in example 1 is shown. As can be seen from FIG. 1, the welding interfaces of the (TaZrNbHfTi) C high-entropy ceramic, the TaZrNbHfTi refractory high-entropy alloy and the Ti2AlNb alloy have no obvious defects such as cracks, holes and the like, and the tissue structures are uniform.
Example 2
In the method for welding high-entropy ceramics and metals of this embodiment, the experimental steps are repeated in example 1, except that "in step 5, the diffusion welding temperature is adjusted from 1650 ℃ to 1700 ℃, and other conditions are the same as those in example 1, so that a structure in which a refractory high-entropy alloy of TaZrNbHfTi is used as an intermediate layer and vacuum diffusion welding is used to connect the (TaZrNbHfTi) C high-entropy ceramics and the Ti2AlNb alloy is finally obtained.
Referring to fig. 2, a photograph of an interface structure of the (tazrnbhft) C high-entropy ceramic and the Ti2AlNb alloy connected by vacuum diffusion welding in example 2, wherein the tazrnbhft refractory high-entropy alloy is used as an intermediate layer. As can be seen from fig. 2, the weak point of the welded joint, i.e., (tazrnbheti) C high-entropy ceramic and tazrnbheti refractory high-entropy alloy, has no obvious defects such as cracks, holes, etc., and has a uniform structure, and the thickness of the interface is obviously increased, which indicates that the diffusion distance of C atoms on the high-entropy ceramic side to the alloy side is longer, and the concentration gradient of C atoms on the interface is smaller.
Example 3
In the method for welding high-entropy ceramics and metals of this embodiment, the experimental steps are repeated in example 1, except that "in step 5, the diffusion welding temperature is adjusted from 1650 ℃ to 1750 ℃, and other conditions are the same as those in example 1, so that a structure in which a refractory high-entropy alloy of tazrnbhhfti is used as an intermediate layer and vacuum diffusion welding is used to connect (tazrnbhhtti) C high-entropy ceramics and Ti2AlNb alloy is finally obtained.
Referring to fig. 3, which is a structure photograph of an interface where the tazrnbhhtti refractory high-entropy alloy is used as an intermediate layer and the (tazrnbhhtti) C high-entropy ceramic and the Ti2AlNb alloy are connected by vacuum diffusion welding in example 3, it can be seen from fig. 3 that the weak portion of the welding joint, i.e., the welding interface of the (tazrnbhhtti) C high-entropy ceramic and the tazrnbhhtti refractory high-entropy alloy, has no obvious defects such as cracks and holes, has a uniform structure, and the thickness of the interface is significantly increased, which indicates that the diffusion distance of C atoms on the high-entropy ceramic side to the alloy side is farther and the concentration gradient of C atoms on the interface is smaller.
Comparative example 1
A welding method of high-entropy ceramics and metals comprises the following steps:
(1) processing (TaZrNbHfTi) C high-entropy ceramic and Ti2AlNb alloy into a cylindrical sample with the diameter phi of 15mm and the height of 6mm by adopting linear cutting, grinding the surface of the sample by adopting a 600#, a 800#, a 1200#, and a 2000# diamond grinding disc and SiC abrasive paper respectively, placing the sample in a vibration polisher, respectively adopting alumina and silica gel solutions to carry out rough polishing and fine polishing until the surface has no scratch, then cleaning with alcohol under the action of ultrasonic waves, and finally carrying out drying treatment;
(2) stacking the (TaZrNbHfTi) C high-entropy ceramic with the processed surface and Ti2AlNb alloy in a graphite mold, spacing the sample and the graphite mold by graphite paper with the thickness of 0.2mm, then putting the sample and the graphite mold into a discharge plasma sintering furnace together, enabling the polished surface of the base material to be tightly attached, and vacuumizing the discharge plasma sintering furnace;
(4) firstly, heating from room temperature to 1000 ℃ at the heating rate of 100 ℃/min, and keeping the temperature for 10 min; heating to 1100 deg.C at a heating rate of 50 deg.C/min, and maintaining for 15 min; reducing the pressure to 5MPa, reducing the temperature to 600 ℃ at the cooling rate of 20 ℃/min, and naturally cooling to room temperature along with the furnace to complete the connection of the (TaZrNbHfTi) C high-entropy ceramic and the Ti2AlNb alloy.
Referring to FIG. 4, the structure of the interface of the comparative example is shown, in which the (TaZrNbHfTi) C high entropy ceramic and the Ti2AlNb alloy are connected by vacuum diffusion welding without using an intermediate layer. As can be seen from fig. 4, the crack existing at the welding interface between the (TaZrNbHfTi) C high-entropy ceramic and the Ti2AlNb alloy indicates that the interface between the two materials is not well wetted at 1050 ℃, only part of the two materials are metallurgically bonded, the C atoms near the interface have a large concentration gradient, the residual stress is large, and the (TaZrNbHfTi) C high-entropy ceramic side has obvious crack. Because it is difficult to increase the diffusion temperature to accelerate the diffusion of C atoms into the alloy side due to the melting point of the Ti2AlNb alloy, it is difficult to achieve a smooth transition of the linear expansion coefficient of the base metal by generating an interface layer, and a large residual stress is present at the interface, and cracks are likely to be formed.
The diffusion welded joints obtained in examples 1 to 3 and comparative example 1 were placed on a universal testing machine to test the shear strength thereof, and the results are shown in table 1:
table 1: shear strength of joints of examples and comparative examples
As can be seen from the joint shear strength results in table 1, the diffusion weld joint strength of the (tazrnbhtti) C high-entropy ceramic and the Ti2AlNb alloy can be significantly improved by using the tazrnbheti refractory high-entropy alloy as the intermediate layer, and the joint strength gradually improves as the diffusion temperature of the (tazrnbheti) C high-entropy ceramic and the tazrnbheti refractory high-entropy alloy increases. The combination of the structural analysis and the inference, the higher diffusion temperature is favorable for the C atoms to generate the interstitial diffusion to TaZrNbHfTi refractory high-entropy alloy, so as to achieve good metallurgical bonding; further increasing the diffusion temperature, forming a thicker interface layer with smaller concentration gradient of C atoms, realizing smoother transition of the thermal expansion coefficients between the base materials, reducing the residual stress near the interface, and inhibiting the formation and the expansion of cracks, thereby improving the joint strength of the high-entropy ceramics and the metal.
The invention is helpful to solve the difficult problems of large residual stress caused by difficult welding and wetting of high-entropy ceramics and metals and large difference of linear expansion coefficients. By introducing TaZrNbHfTi refractory high-entropy alloy as an intermediate layer, firstly, the intermediate layer and the high-entropy ceramic are in diffusion connection at a higher temperature (more than or equal to 1400 ℃), and in the temperature range, the two materials have good wettability, elements are diffused mutually, metal elements are dissolved mutually, and brittle intermetallic compounds are difficult to generate. Interstitial atoms diffuse to TaZrNbHfTi refractory high-entropy alloy, an interface layer with uniformly distributed tissues is formed by means of a high-entropy effect, the smooth transition of a thermal expansion coefficient from high-entropy ceramic to TaZrNbHfTi refractory high-entropy alloy is realized, the local residual stress is reduced, the formation and the expansion of cracks are inhibited, and the joint strength is improved. And then diffusion welding is carried out on the intermediate layer and metals such as titanium-aluminum intermetallic compounds, titanium alloy, refractory high-entropy alloy and the like at a lower temperature, higher joint strength can be easily obtained by welding with the alloys, and the welding difficulty is smaller. Therefore, the TaZrNbHfTi refractory high-entropy alloy is used as the intermediate layer, and the high-strength connection between the (TaZrNbHfTi) C high-entropy ceramic and the metal can be realized by adopting vacuum diffusion welding.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (10)
1. A method for connecting high-entropy ceramics and metals is characterized by comprising the following steps:
step S1, carrying out vacuum diffusion welding on the high-entropy ceramic and TaZrNbHfTi refractory high-entropy alloy at high temperature to obtain a welded assembly;
and step S2, carrying out vacuum diffusion welding on the TaZrNbHfTi refractory high-entropy alloy of the welded assembly and the metal to complete the connection of the high-entropy ceramic and the metal.
2. The method for connecting a high-entropy ceramic and a metal according to claim 1, wherein in step S1, the diffusion temperature is 1400 ℃ to 2000 ℃, the diffusion time is 5 to 300min, the diffusion pressure is 5 to 40MPa, and the degree of vacuum is 1 x 10 or less-3MPa。
3. The method for connecting high-entropy ceramics and metals according to claim 2, wherein step S1 specifically includes the steps of:
setting the pressure to be 5-40MPa, firstly heating from room temperature to 1000 ℃ at the heating rate of 10-150 ℃/min, and keeping the temperature for 10-30 min;
then heating to the diffusion welding temperature of 1400-2000 ℃ at the heating rate of 10-100 ℃/min, and preserving the heat for 5-300 min;
reducing the pressure to 5MPa, reducing the temperature to 600 ℃ at the cooling rate of 10-50 ℃/min, and naturally cooling to the room temperature along with the furnace.
4. A method according to claim 1, wherein the high-entropy ceramic is composed of a metal compound of C, N, B or O atoms and three or more refractory metal elements selected from Ta, Zr, Nb, Hf, Ti, W, Mo and V, wherein the refractory metal elements are mixed at equal or near equal atomic ratios.
5. The method for connecting high-entropy ceramics and metals according to claim 1, wherein in step S2, the diffusion temperature is 800 ℃ to 1200 ℃, the diffusion time is 5 to 300min, and the vacuum degree is less than or equal to 1 x 10-3MPa。
6. The method for connecting high-entropy ceramics and metals according to claim 5, wherein step S2 specifically includes the steps of:
setting the pressure to be 5-40MPa, firstly heating from room temperature to 600 ℃ at the heating rate of 10-150 ℃/min, and preserving the heat for 10-30 min;
then heating up to the diffusion welding temperature of 800-;
reducing the pressure to 5MPa, reducing the temperature to 600 ℃ at the cooling rate of 10-50 ℃/min, and naturally cooling to the room temperature along with the furnace.
7. The method for connecting high-entropy ceramics and metals according to claim 1, wherein the metal used in step S2 is a refractory high-entropy alloy, a titanium alloy, a niobium alloy or a titanium-aluminum intermetallic compound.
8. A method for joining high-entropy ceramics and metals according to claim 1, characterized in that the intermediate joining layer is formed of tazrnbti refractory high-entropy alloy, the thickness of which is 100 μm to 2000 μm.
9. The method for connecting high-entropy ceramics and metals according to claim 1, wherein the TaZrNbHfTi refractory high-entropy alloy is prepared by mixing alloy elements according to an equal atomic ratio, performing vacuum arc melting, performing homogenization annealing, and performing water quenching.
10. The method for connecting high-entropy ceramics and metals according to claim 1, wherein the high-entropy ceramics, the TaZrNbHfTi refractory high-entropy alloy and the metals of the step S1 and the step S2 are subjected to grinding, vibration polishing, ultrasonic cleaning and drying treatment in sequence on the part to be welded before welding.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114951880A (en) * | 2022-06-13 | 2022-08-30 | 宁波江丰电子材料股份有限公司 | Method for welding three-layer structure ceramic target |
| CN115057715A (en) * | 2022-06-17 | 2022-09-16 | 中广核研究院有限公司 | Silicon carbide cladding connecting material, silicon carbide ceramic connecting piece and manufacturing method and application thereof |
| CN115353408A (en) * | 2022-08-31 | 2022-11-18 | 歌尔股份有限公司 | Metal and ceramic composite part, preparation method thereof, shell and electronic equipment |
| CN115991609A (en) * | 2023-01-09 | 2023-04-21 | 南京理工大学 | Ceramic-metal discharge plasma connection method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107363359A (en) * | 2017-08-09 | 2017-11-21 | 北京工业大学 | A kind of method of compound high-entropy alloy solder ceramic soldering and metal |
| CN108299006A (en) * | 2018-01-24 | 2018-07-20 | 北京工业大学 | A kind of method of compound high entropy solder coated laser ceramic soldering and metal |
| CN110438386A (en) * | 2019-09-20 | 2019-11-12 | 南方科技大学 | A kind of Preparation method and use of high-entropy alloy solder |
-
2021
- 2021-10-26 CN CN202111245353.4A patent/CN113968749B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107363359A (en) * | 2017-08-09 | 2017-11-21 | 北京工业大学 | A kind of method of compound high-entropy alloy solder ceramic soldering and metal |
| CN108299006A (en) * | 2018-01-24 | 2018-07-20 | 北京工业大学 | A kind of method of compound high entropy solder coated laser ceramic soldering and metal |
| CN110438386A (en) * | 2019-09-20 | 2019-11-12 | 南方科技大学 | A kind of Preparation method and use of high-entropy alloy solder |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114951880A (en) * | 2022-06-13 | 2022-08-30 | 宁波江丰电子材料股份有限公司 | Method for welding three-layer structure ceramic target |
| CN114951880B (en) * | 2022-06-13 | 2024-05-14 | 宁波江丰电子材料股份有限公司 | Method for welding three-layer ceramic target |
| CN115057715A (en) * | 2022-06-17 | 2022-09-16 | 中广核研究院有限公司 | Silicon carbide cladding connecting material, silicon carbide ceramic connecting piece and manufacturing method and application thereof |
| CN115353408A (en) * | 2022-08-31 | 2022-11-18 | 歌尔股份有限公司 | Metal and ceramic composite part, preparation method thereof, shell and electronic equipment |
| CN115353408B (en) * | 2022-08-31 | 2023-09-01 | 歌尔股份有限公司 | Metal and ceramic composite part, preparation method thereof, shell and electronic equipment |
| CN115991609A (en) * | 2023-01-09 | 2023-04-21 | 南京理工大学 | Ceramic-metal discharge plasma connection method |
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