CN116477952B - Preparation method of tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple - Google Patents
Preparation method of tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple Download PDFInfo
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 80
- 239000000919 ceramic Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 14
- 239000010703 silicon Substances 0.000 title claims abstract description 12
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- QKQUUVZIDLJZIJ-UHFFFAOYSA-N hafnium tantalum Chemical compound [Hf].[Ta] QKQUUVZIDLJZIJ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 117
- 238000005245 sintering Methods 0.000 claims abstract description 53
- 238000011049 filling Methods 0.000 claims abstract description 12
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910002804 graphite Inorganic materials 0.000 claims description 34
- 239000010439 graphite Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000012300 argon atmosphere Substances 0.000 claims description 22
- 238000005498 polishing Methods 0.000 claims description 19
- 238000003825 pressing Methods 0.000 claims description 17
- 239000011863 silicon-based powder Substances 0.000 claims description 12
- 229910003460 diamond Inorganic materials 0.000 claims description 9
- 239000010432 diamond Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 6
- 230000007480 spreading Effects 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 238000007731 hot pressing Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- -1 hafnium-silicon boron carbon nitrogen Chemical compound 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
A preparation method of a tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple relates to a preparation method of a diffusion couple. The invention aims to solve the problems that the existing Ta 4HfC5/SiBCN ceramic diffusion couple is difficult to combine, the interface bonding strength is poor and the diffusion behavior is not obvious. The preparation method comprises the following steps: 1. preparing amorphous SiBCN powder by high-energy ball milling; 2. filling the powder into a die; 3. and (5) hot-pressing and sintering. The preparation method is used for preparing the tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple.
Description
Technical Field
The invention relates to a preparation method of a diffusion couple.
Background
Ta 4HfC5 ceramic is used as one of carbide superhigh temperature ceramics with the highest melting point, has the advantages of high strength, high hardness, high modulus and high chemical stability, and has great application prospect in hypersonic aviation. However, the strong covalent bond between the transition metal carbide atoms makes it difficult to sinter, and has the disadvantages of low fracture toughness, poor thermal shock resistance, poor oxidation resistance when used alone, and the like. The sintering aid is added to effectively solve the problems, and the main mechanism is as follows: first, the additive may produce liquid phase sintering to promote atomic diffusion; secondly, the additive reacts with the matrix to form a new phase, which further affects the ceramic performance; third, the additives can cause segregation of atoms at grain boundaries, affect the arrangement of atoms at grain boundaries or interfaces, and thus affect interface morphology and microstructure, and thus are important for the study of interface behavior.
The effect of SiBCN as an additive on Ta 4HfC5 ceramic sintering performance has not been reported. Ta 4HfC5 and SiBCN ceramic after crystallization all belong to a cubic structure, and similar lattice constants and atomic radiuses of Ta, hf and Si atoms enable the SiC to have the capability of mutual diffusion. The covalent bonding property of Ta 4HfC5 and SiBCN ceramic makes it difficult to densify, on the one hand, the pores at the surface hinder the diffusion of atoms, and on the other hand, the point/line defects at the interface provide an atomic diffusion channel again, which means that the interface between them has a complex phenomenon. In order to explore the diffusion behavior of Si atoms with Hf and Ta atoms, diffusion coupling methods can be used for research. The diffusion couple method plays an important role in researching a solid state relationship, the diffusion phenomenon of two materials after forming the diffusion couple occurs in the direction of the two materials perpendicular to an interface, and the interface behavior between two phases can be efficiently and intuitively analyzed, but the preparation methods of the diffusion couples of different systems have great difference. The preparation difficulty of the Ta 4HfC5 -SiBCN ceramic diffusion couple is that higher energy is needed to break covalent bond combination to promote atomic interdiffusion, and the interface combination mode in the sintering process affects the interface strength; under the condition, ta 4HfC5/SiBCN ceramic diffusion couple is extremely easy to combine, interface combination strength is poor, and diffusion behavior is not obvious.
Disclosure of Invention
The invention aims to solve the problems that the existing Ta 4HfC5/SiBCN ceramic diffusion couple is difficult to combine, the interface bonding strength is poor and the diffusion behavior is not obvious, and further provides a preparation method of the tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple.
The preparation method of the tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple comprises the following steps:
1. Preparing amorphous SiBCN powder by high-energy ball milling;
2. Sequentially layering and filling Ta 4HfC5 powder and amorphous SiBCN powder into a graphite mold inner sleeve to obtain a mold filled with the powder;
Or sintering Ta 4HfC5 powder to obtain a Ta 4HfC5 block, filling the Ta 4HfC5 block and amorphous SiBCN powder into a graphite mold inner sleeve, burying the Ta 4HfC5 block into the amorphous SiBCN powder, and compacting to obtain a mold filled with the powder;
Or sintering amorphous SiBCN powder to obtain SiBCN blocks, filling the SiBCN blocks and Ta 4HfC5 powder into a graphite mold inner sleeve, burying the SiBCN blocks into Ta 4HfC5 powder, and compacting to obtain a mold filled with the powder;
3. Pre-pressing the mold filled with powder, heating the pre-pressed powder to 1400-1600 ℃ under the conditions of argon atmosphere and heating rate of 20-25 ℃/min, continuously heating the sintering temperature to 1800-2100 ℃ under the conditions of argon atmosphere, heating rate of 20-25 ℃/min and pressurizing rate of 1-8 MPa/min, pressurizing to 30-60 MPa, and finally maintaining for 1-2 h under the conditions of argon atmosphere, sintering temperature of 1800-2100 ℃ and pressure of 30-60 MPa, releasing pressure at pressure release rate of 1-4 MPa/min and cooling along with a furnace to obtain the tantalum carbide hafnium-silicon boron carbon nitrogen ceramic diffusion couple.
The beneficial effects of the invention are as follows:
1. The invention adopts a mechanical alloying method and a hot-press sintering process to prepare the multilayer Ta 4HfC5/SiBCN diffusion couple, and based on the sintering characteristics of the multilayer Ta 4HfC5/SiBCN diffusion couple and the hot-press sintering, si, hf and Ta atoms are promoted to diffuse at the interface of the diffusion couple under the combination of high temperature and pressure. The prepared Ta 4HfC5/SiBCN diffusion couple has a multi-layer strong-bonding 'meshing' interface, and the reason of the 'meshing' state is attributed to non-flatness of powder filling and grain growth caused by high sintering temperature. The "meshing" feature of the interface allows the diffusion couple to remain connected after machining, forming a strong bond at the interface.
2. According to the invention, the Ta 4HfC5/SiBCN diffusion couple is prepared by adopting two hot-pressed sintering, and based on the sintering characteristics of the Ta 4HfC5/SiBCN diffusion couple, si, hf and Ta atoms are promoted to diffuse at the interface of the diffusion couple by utilizing the combination of high temperature and pressure of hot-pressed sintering. The polishing degree of the embedded small block and the sintering compactness of the peripheral block are critical, because the surface characteristics of the block inner core are not deformed along with the change of sintering pressure, temperature or sintering time, under the action of the pressure, the surrounding powder extrudes the block inner core, the powder sintering morphology at the contact position depends on the surface structure of the block inner core, diffusion occurs at the interface of the contact position of the two, and the surface impurities and macroscopic defects of the block inner core influence the atomic diffusion behavior.
Drawings
FIG. 1 is a schematic diagram of hot press sintering in step three in a preparation method of a tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple according to the invention;
FIG. 2 is an optical photograph of Ta 4HfC5/SiBCN diffusion couple prepared in example one prior to cleavage;
FIG. 3 is an optical photograph of a cross section of Ta 4HfC5/SiBCN diffusion couple prepared in example one after cutting;
FIG. 4 is an SEM image of the polished Ta 4HfC5/SiBCN diffusion couple interface microscopic morphology of example one;
FIG. 5 is a graph showing the relative amounts of Ta 4HfC5/SiBCN diffusion couple SEM and atoms as a function of diffusion distance after polishing according to example one;
FIG. 6 is an XRD pattern of the Ta 4HfC5/SiBCN diffusion couple interface after polishing according to example one;
FIG. 7 is a schematic illustration of the "engaged" morphology of the Ta 4HfC5/SiBCN diffusion couple interface prepared in example one;
FIG. 8 is a photograph of a Ta 4HfC5/SiBCN diffusion dipole optical image of a second embodiment polished to remove SiBCN ceramic from the surface.
Detailed Description
The first embodiment is as follows: the preparation method of the tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple comprises the following steps:
1. Preparing amorphous SiBCN powder by high-energy ball milling;
2. Sequentially layering and filling Ta 4HfC5 powder and amorphous SiBCN powder into a graphite mold inner sleeve to obtain a mold filled with the powder;
Or sintering Ta 4HfC5 powder to obtain a Ta 4HfC5 block, filling the Ta 4HfC5 block and amorphous SiBCN powder into a graphite mold inner sleeve, burying the Ta 4HfC5 block into the amorphous SiBCN powder, and compacting to obtain a mold filled with the powder;
Or sintering amorphous SiBCN powder to obtain SiBCN blocks, filling the SiBCN blocks and Ta 4HfC5 powder into a graphite mold inner sleeve, burying the SiBCN blocks into Ta 4HfC5 powder, and compacting to obtain a mold filled with the powder;
3. Pre-pressing the mold filled with powder, heating the pre-pressed powder to 1400-1600 ℃ under the conditions of argon atmosphere and heating rate of 20-25 ℃/min, continuously heating the sintering temperature to 1800-2100 ℃ under the conditions of argon atmosphere, heating rate of 20-25 ℃/min and pressurizing rate of 1-8 MPa/min, pressurizing to 30-60 MPa, and finally maintaining for 1-2 h under the conditions of argon atmosphere, sintering temperature of 1800-2100 ℃ and pressure of 30-60 MPa, releasing pressure at pressure release rate of 1-4 MPa/min and cooling along with a furnace to obtain the tantalum carbide hafnium-silicon boron carbon nitrogen ceramic diffusion couple.
In the embodiment, the upper and lower pressure heads apply pressure from above, but the upper and lower surfaces of the powder are loaded with the pressure head as described in detail with reference to fig. 1.
The amorphous phase SiBCN powder prepared in the step one of the present embodiments is stored in argon or vacuum environment.
The beneficial effects of this embodiment are:
1. The embodiment adopts a mechanical alloying method and a hot-press sintering process to prepare the multilayer Ta 4HfC5/SiBCN diffusion couple, and based on the sintering characteristics of the multilayer Ta 4HfC5/SiBCN diffusion couple and the multilayer Ta diffusion couple, si, hf and Ta atoms are promoted to be diffused at the interface of the diffusion couple by using the combination of high temperature and pressure of hot-press sintering. The prepared Ta 4HfC5/SiBCN diffusion couple has a multi-layer strong-bonding 'meshing' interface, and the reason of the 'meshing' state is attributed to non-flatness of powder filling and grain growth caused by high sintering temperature. The "meshing" feature of the interface allows the diffusion couple to remain connected after machining, forming a strong bond at the interface.
2. According to the embodiment, the Ta 4HfC5/SiBCN diffusion couple is prepared by adopting two hot-press sintering, and based on the sintering characteristics of the Ta 4HfC5/SiBCN diffusion couple and the Ta atoms are promoted to diffuse at the interface of the diffusion couple by utilizing the combination of high temperature and pressure of hot-press sintering. The polishing degree of the embedded small block and the sintering compactness of the peripheral block are critical, because the surface characteristics of the block inner core are not deformed along with the change of sintering pressure, temperature or sintering time, under the action of the pressure, the surrounding powder extrudes the block inner core, the powder sintering morphology at the contact position depends on the surface structure of the block inner core, diffusion occurs at the interface of the contact position of the two, and the surface impurities and macroscopic defects of the block inner core influence the atomic diffusion behavior.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the preparation of amorphous SiBCN powder by high-energy ball milling in the first step is specifically carried out according to the following steps: weighing Si powder, h-BN and graphite in a glove box, loading the weighed Si powder, h-BN and graphite into a ball milling tank, and performing high-energy ball milling for 20-40 hours under the conditions of argon atmosphere, ball milling rotating speed of 600-800 rpm and ball material ratio of (10-20): 1 to obtain amorphous SiBCN powder. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the mol ratio of the Si powder to the h-BN is 1 (0.5-1). The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the molar ratio of the Si powder to the graphite is 1 (1-2). The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: and step two, ta 4HfC5 powder and amorphous SiBCN powder are obtained after passing through a 200-mesh sieve. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: in the second step, ta 4HfC5 powder and amorphous SiBCN powder are sequentially and hierarchically filled in a graphite die inner sleeve, specifically, the steps are carried out as follows: spreading an amorphous phase SiBCN powder on the bottom surface of the inner sleeve of the graphite mold, vibrating up and down to spread the powder, compacting the powder by an upper pressing head, spreading a layer of Ta 4HfC5 powder on the compacted powder, vibrating up and down to spread the powder, compacting the powder by the upper pressing head, and repeatedly alternating the spreading and compacting of the amorphous phase SiBCN powder and the Ta 4HfC5 powder until reaching 3 layers of amorphous phase SiBCN powder and 2 layers of Ta 4HfC5 powder, thereby obtaining the mold filled with the powder. The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the Ta 4HfC5 block and the SiBCN block in the second step are prepared according to the following steps: heating to a sintering temperature of 1400-1550 ℃ under an argon atmosphere and a heating rate of 20-25 ℃/min, continuously heating to 1600-2100 ℃ under the conditions of 20-25 ℃/min and a pressurizing speed of 1-4 MPa/min, pressurizing to 30-40 MPa, maintaining for 0.5-1 h under the conditions of 1600-2100 ℃ and a pressure of 30-40 MPa under the conditions of 1-4 MPa to obtain ceramic, cutting the ceramic into six-sided blocks, and polishing the six sides of the blocks. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: the grinding and polishing treatment is specifically that the diamond polishing agent with the grain diameter of 0.25 mu m is sequentially ground by a diamond grinding disc with the grain diameter of 500-3000 meshes, and ground by sand paper with the grain diameter of 500-3000 meshes. The other is the same as in embodiments one to seven.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: the inner surface of the graphite mold inner sleeve in the second step is provided with graphite paper with the thickness of 0.01 mm-0.03 mm; and step two, compacting the powder by using an upper pressing head, and separating the powder from the upper pressing head by using graphite paper with the thickness of 0.1-0.5 mm in the compacting process. The others are the same as in embodiments one to eight.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: the pre-pressing in the third step is specifically carried out according to the following steps: under the condition of a press, the mould filled with powder is pressurized to 1 t-5 t at a pressurizing speed of 0.05 t/s-0.1 t/s, the pressure is maintained for 10 min-60 min under the condition of the pressure of 1 t-5 t, and then the pressure is relieved at a pressure relief speed of 0.2 t/s-0.5 t/s. The others are the same as in embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
Embodiment one:
The preparation method of the tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple comprises the following steps:
1. Weighing Si powder, h-BN and graphite in a glove box, loading the weighed Si powder, h-BN and graphite into a ball milling tank, and performing high-energy ball milling for 20 hours under the conditions of argon atmosphere, ball milling rotating speed of 600rpm and ball material ratio of 20:1 to obtain amorphous SiBCN powder;
the molar ratio of the Si powder to the h-BN is 2:1; the molar ratio of the Si powder to the graphite is 2:3;
2. Paving a layer of amorphous SiBCN powder with the diameter of 1.2g on the bottom surface of a graphite die inner sleeve with the diameter of 20mm, vibrating up and down to enable the powder to be paved, then compacting the powder by an upper pressing head under the condition that the pressure is 3MPa, paving a layer of 4gTa 4HfC5 powder on the compacted powder, vibrating up and down to enable the powder to be paved, compacting the powder by the upper pressing head under the condition that the pressure is 3MPa, and repeatedly and alternately paving and compacting the amorphous SiBCN powder and the Ta 4HfC5 powder until the powder reaches 3 layers of amorphous SiBCN powder and 2 layers of Ta 4HfC5 powder, thereby obtaining a die filled with the powder;
3. Pre-pressing a mould filled with powder, heating the pre-pressed powder to a sintering temperature of 1400 ℃ under the conditions of an argon atmosphere and a heating rate of 25 ℃/min, continuously heating the sintering temperature to 2100 ℃ under the conditions of an argon atmosphere, a heating rate of 25 ℃/min and a pressurizing rate of 1.1MPa/min, pressurizing to 30MPa, and finally maintaining for 2 hours under the conditions of an argon atmosphere, a sintering temperature of 2100 ℃ and a pressure of 30MPa, decompressing at a decompressing rate of 1.1MPa/min and cooling along with a furnace to obtain the Ta 4HfC5/SiBCN diffusion couple.
And step two, ta 4HfC5 powder and amorphous SiBCN powder are obtained after passing through a 200-mesh sieve.
And step two, the graphite die inner sleeve is a high-strength graphite die inner sleeve.
The inner surface of the graphite mold inner sleeve in the second step is provided with graphite paper with the thickness of 0.03 mm; and step two, compacting the powder by using an upper pressing head, and separating the powder from the upper pressing head by using graphite paper with the thickness of 0.2mm in the compacting process.
The pre-pressing in the third step is specifically carried out according to the following steps: the powder-filled mold was pressurized to 1.2t at a pressurizing speed of 0.05t/s under a press, and maintained for 20 minutes under a pressure of 1.2t, and then depressurized at a pressure releasing speed of 0.4 t/s.
In the first step of the embodiment, the raw materials are simple substance silicon (Si), hexagonal boron nitride (h-BN) and graphite. The Ta 4HfC5 powder in the second step is purchased commercial powder; and in the second step, weighing corresponding 4gTa 4HfC5 powder or 1.2g amorphous SiBCN powder in each layer, and ensuring that each layer has similar thickness (about 2 mm) after sintering.
The Ta 4HfC5/SiBCN diffusion couple prepared in the first embodiment is cut into sections along the axial direction, sequentially polished by using diamond grinding discs of 500 meshes and 800 meshes, sequentially polished by using abrasive paper of 1000 meshes, 1500 meshes and 2000 meshes, finally polished by using a diamond polishing agent with the particle size of 0.25 μm under the condition of the rotating speed of 1000rpm, and the polished sample is dried after being ultrasonically cleaned by using alcohol, so that the polished Ta 4HfC5/SiBCN diffusion couple is obtained.
FIG. 2 is an optical photograph of Ta 4HfC5/SiBCN diffusion couple prepared in example one prior to cleavage; FIG. 3 is an optical photograph of a cross section of Ta 4HfC5/SiBCN diffusion couple prepared in example one after cutting; the figure shows that five layers of diffusion couple samples obtained after sintering are tightly combined, and the interface bonding strength can meet the requirement of subsequent machining.
FIG. 4 is an SEM image of the Ta 4HfC5/SiBCN diffusion couple interface microscopic morphology after polishing according to example one. The interface is tightly combined and presents a tooth-shaped characteristic.
FIG. 5 is a graph showing the relative amounts of Ta 4HfC5/SiBCN diffusion couple SEM and atoms as a function of diffusion distance after polishing in accordance with example one. As can be seen, the apparent diffusion behavior of Si, hf, ta atoms occurs at the diffusion couple interface prepared under the process of example one.
FIG. 6 is an XRD pattern of the Ta 4HfC5/SiBCN diffusion couple interface after polishing for example one. The interface is mainly composed of Ta 4HfC5 phase and amorphous SiBCN crystallization phase.
FIG. 7 is a schematic illustration of the "engaged" morphology of the Ta 4HfC5/SiBCN diffusion couple interface prepared in example one; the five-layer diffusion couple interface prepared by the embodiment has the characteristic of meshing, can keep a connected state after being machined, and forms stronger combination at the interface.
Comparison experiment: the first difference between this comparative experiment and the example is: and thirdly, continuously heating the sintering temperature to 1700 ℃ and pressurizing to 30MPa under the conditions of argon atmosphere, heating rate of 25 ℃/min and pressurizing speed of 1.1MPa/min, and finally keeping for 2 hours under the conditions of argon atmosphere, sintering temperature of 1700 ℃ and pressurizing pressure of 30 MPa. The other is the same as in the first embodiment.
The sintering temperature of the comparative experiment is 1700 ℃, the bonding strength between diffusion couples is low, cracking occurs along the interface of two materials during mechanical processing, and the diffusion behavior at the interface is not obvious.
Embodiment two: the first difference between this embodiment and the first embodiment is that: sintering the Ta 4HfC5 powder to obtain a Ta 4HfC5 block, filling the Ta 4HfC5 block and amorphous SiBCN powder into a graphite mold inner sleeve, burying the Ta 4HfC5 block into the amorphous SiBCN powder, and compacting to obtain a mold filled with the powder;
The Ta 4HfC5 block is prepared according to the following steps: heating to 1400 ℃ under the condition of argon atmosphere and heating rate of 25 ℃/min, continuously heating to 2000 ℃ under the condition of argon atmosphere, heating rate of 25 ℃/min and pressurizing rate of 1.25MPa/min, pressurizing to 30MPa, maintaining for 1h under the condition of argon atmosphere, sintering temperature of 2000 ℃ and pressure of 30MPa, releasing pressure at pressure release rate of 1.25MPa/min, cooling with a furnace to obtain ceramic, cutting the ceramic into six-sided blocks, and polishing six sides respectively; the grinding and polishing treatment comprises the steps of sequentially grinding by using diamond grinding discs with 500 meshes and 1000 meshes, sequentially grinding by using abrasive paper with 1000 meshes, 1500 meshes and 2000 meshes, and finally polishing by using a diamond polishing agent with the particle size of 0.25 mu m. The other is the same as in the first embodiment.
The Ta 4HfC5/SiBCN diffusion couple prepared in example two was polished to remove the surface SiBCN ceramic, exposing the internal Ta 4HfC5 bulk and performing optical photography. FIG. 8 is a photograph of a Ta 4HfC5/SiBCN diffusion dipole optical image of a second embodiment polished to remove SiBCN ceramic from the surface. In the figure, the yellow core is a Ta 4HfC5 ceramic block, the black is SiBCN ceramic, and the Ta 4HfC5 ceramic block and the SiBCN ceramic block are well combined.
Claims (2)
1. The preparation method of the tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple is characterized by comprising the following steps of:
1. Preparing amorphous SiBCN powder by high-energy ball milling;
2. Spreading a layer of amorphous SiBCN powder on the bottom surface of the inner sleeve of the graphite mold, vibrating up and down to spread the powder, compacting the powder by using an upper pressing head, spreading a layer of Ta 4HfC5 powder on the compacted powder, vibrating up and down to spread the powder, compacting the powder by using the upper pressing head, and repeatedly alternating the spreading and compacting of the amorphous SiBCN powder and the Ta 4HfC5 powder until reaching 3 layers of amorphous SiBCN powder and 2 layers of Ta 4HfC5 powder, thereby obtaining a mold filled with the powder;
Or sintering Ta 4HfC5 powder to obtain a Ta 4HfC5 block, filling the Ta 4HfC5 block and amorphous SiBCN powder into a graphite mold inner sleeve, burying the Ta 4HfC5 block into the amorphous SiBCN powder, and compacting to obtain a mold filled with the powder;
Or sintering amorphous SiBCN powder to obtain SiBCN blocks, filling the SiBCN blocks and Ta 4HfC5 powder into a graphite mold inner sleeve, burying the SiBCN blocks into Ta 4HfC5 powder, and compacting to obtain a mold filled with the powder;
The Ta 4HfC5 block and the SiBCN block are prepared according to the following steps: heating to a sintering temperature of 1400-1550 ℃ under an argon atmosphere and a heating rate of 20-25 ℃/min, continuously heating to 1600-2100 ℃ under the conditions of 20-25 ℃/min and a pressurizing speed of 1-4 MPa/min, pressurizing to 30-40 MPa, maintaining for 0.5-1 h under the conditions of 1600-2100 ℃ and a pressure of 30-40 MPa under the conditions of 1-4 MPa to obtain ceramic, cutting the ceramic into six-sided blocks, and polishing the six sides of the blocks;
the Ta 4HfC5 powder and the amorphous phase SiBCN powder are obtained after passing through a 200-mesh sieve;
3. Pressurizing a die filled with powder to 1 t-5 t at a pressurizing speed of 0.05 t/s-0.1 t/s under a press, maintaining the pressure for 10 min-60 min under the condition of 1 t-5 t, then releasing the pressure at a pressure releasing speed of 0.2 t/s-0.5 t/s, then heating the pre-pressed powder to a sintering temperature of 1400-1600 ℃ under the conditions of an argon atmosphere and a heating rate of 20 ℃/min-25 ℃/min, continuously heating the sintering temperature to 1800-2100 ℃ under the conditions of an argon atmosphere, a heating rate of 20 ℃/min-25 ℃/min and a pressurizing speed of 1-8 MPa/min, pressurizing to 30-60 MPa, finally maintaining for 1-2 h under the conditions of an argon atmosphere, a sintering temperature of 1800-2100 ℃ and a pressure of 30-60 MPa, releasing the pressure at a pressure releasing speed of 1-4 MPa/min, and cooling along with a furnace to obtain tantalum carbide-hafnium silicon boron nitride diffusion ceramic;
The preparation of amorphous SiBCN powder by high-energy ball milling in the first step is specifically carried out according to the following steps: weighing Si powder, h-BN and graphite in a glove box, loading the weighed Si powder, h-BN and graphite into a ball milling tank, and performing high-energy ball milling for 20-40 hours under the conditions of argon atmosphere, 600-800 rpm of ball milling rotating speed and (10-20): 1 of ball material ratio to obtain amorphous SiBCN powder; the mol ratio of the Si powder to the h-BN is 1 (0.5-1); the molar ratio of the Si powder to the graphite is 1 (1-2);
The inner surface of the graphite mold inner sleeve is provided with graphite paper with the thickness of 0.01 mm-0.03 mm; and step two, compacting the powder by using an upper pressing head, and separating the powder from the upper pressing head by using graphite paper with the thickness of 0.1-0.5 mm in the compacting process.
2. The method for preparing the tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple according to claim 1, wherein the grinding and polishing treatment is specifically that the polishing is sequentially performed by a diamond grinding disc with 500-3000 meshes, a diamond abrasive paper with 500-3000 meshes and a diamond polishing agent with the particle size of 0.25 μm.
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| CN110845238A (en) * | 2019-11-29 | 2020-02-28 | 中南大学 | Long-time ablation-resistant ultrahigh-melting-point nitrogen-containing carbide ultrahigh-temperature ceramic and application thereof |
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| CN111217610A (en) * | 2019-06-19 | 2020-06-02 | 哈尔滨工业大学 | Nanocrystalline tantalum carbide reinforced silicon-boron-carbon-nitrogen composite ceramic material and preparation method thereof |
| CN111196726A (en) * | 2020-01-06 | 2020-05-26 | 哈尔滨工业大学 | SiBCN-Ta4HfC5Complex phase ceramic and preparation method thereof |
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