CN112779449B - Titanium carbonitride base cermet material for high-temperature structure and preparation method thereof - Google Patents
Titanium carbonitride base cermet material for high-temperature structure and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000010936 titanium Substances 0.000 title claims abstract description 27
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011195 cermet Substances 0.000 title claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims description 28
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000005238 degreasing Methods 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000001856 Ethyl cellulose Substances 0.000 claims description 12
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 12
- 229920001249 ethyl cellulose Polymers 0.000 claims description 12
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000009694 cold isostatic pressing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229910010293 ceramic material Inorganic materials 0.000 claims description 7
- 239000010953 base metal Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003870 refractory metal Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- Manufacturing & Machinery (AREA)
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Abstract
The invention provides a titanium carbonitride base cermet material for a high-temperature structure and a preparation method thereof, which solve the technical problems that high-temperature resistant materials used for furnace structural components in the prior art have obvious sintering shrinkage and deformation at high temperature, and the structural precision and the structural components are easy to crack/fit gaps, so that the structure collapses. It is prepared from TiCN, WC and Mo2C. Preparing TaC, NbC, Co and Ni; the sum of the weight percentage contents of Co and Ni is 5-14%; the weight percentage content of the whole C in the raw materials is 5.8-6.2%, and the weight ratio of the whole C to N is 3-7: 3-7. The titanium carbonitride base cermet material for the high-temperature structure can well meet the use requirements of the structural component in a furnace in a high-temperature working environment, has small sintering shrinkage and deformation at high temperature, and has high structural precision and low possibility of crack/fit clearance of the structural component.
Description
Technical Field
The invention relates to a metal ceramic material, in particular to a titanium carbonitride base metal ceramic material for a high-temperature structure and a preparation method thereof.
Background
At present, in the preparation process of some high-purity non-metallic materials (such as high-purity monocrystalline silicon, high-transmittance inorganic glass and the like), the preparation temperature is relatively high, generally 800-2O3、ZrO2The material is a high-temperature resistant material. However, as a high-temperature resistant material, there are two difficult problems to solve, first at this operating temperature, Al2O3、ZrO2Also, the sintering shrinkage and deformation are obvious, so that the structural precision and the structural part are easy to crack/fit clearance, and the structure is collapsed; second Al2O3、ZrO2Al, Zr and the like in common high-temperature resistant materials belong to light elements, and the elements are easy to generate heat migration at working temperatureAnd the detection and local enrichment of the elements of Al and Zr in the preparation environment are obvious, and great negative effects are generated in the preparation process of high-purity substances.
Among other commonly seen high-temperature resistant materials, materials such as W, Mo are the main materials, however, W, Mo and the like belong to scarce strategic reserve resources, and materials such as W, Mo and the like have high density and poor mechanical properties, so when the material is used as a structural member in a high-temperature working state, local deformation of a preparation furnace body is easily caused due to the extremely high density difference, and cracks are easily generated and cannot be effectively supported.
The modified partial metal-based high-temperature material has excellent mechanical properties, but the modified partial metal-based high-temperature material is easily volatile at working temperature, such as iron group elements of Co, Ni, Fe and the like, and the impurity components also can significantly influence the preparation process of high-purity substances.
The applicant has found that the prior art has at least the following technical problems:
1. high temperature resistant material (Al) used for furnace structural component in prior art2O3、ZrO2Materials), which has obvious sintering shrinkage and deformation at high temperature, and the structure precision and the structural member are easy to have cracks/fit gaps, thereby causing the structure collapse;
2. high temperature resistant material (Al) used for furnace structural component in prior art2O3、ZrO2Material), which is very easy to generate element heat transfer at working temperature, and generates great negative effect in the preparation process of high-purity substances;
3. in the prior art, other high-temperature resistant materials used for the structural parts in the furnace are easy to generate local deformation of the furnace body, and are easy to generate cracks, cannot be effectively supported or influence the preparation process of high-purity substances.
Disclosure of Invention
The invention aims to provide a titanium carbonitride based cermet material for a high-temperature structure and a preparation method thereof, and aims to solve the technical problems that a high-temperature resistant material used for a structural member in a furnace in the prior art has obvious sintering shrinkage and deformation at high temperature, and the structural precision and the structural member are easy to crack/fit gaps, so that the structure collapses. The technical effects that can be produced by the preferred technical scheme in the technical schemes provided by the invention are described in detail in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a titanium carbonitride base cermet material for high-temperature structures, which comprises TiCN, WC and Mo as raw materials2C. TaC, NbC, Co and Ni; wherein, the sum of the weight percentage contents of Co and Ni is 5-14%; the weight percentage content of the whole C in the raw material is 5.8-6.2%, and the weight ratio of the whole C to N in the raw material is 3-7: 3-7.
Furthermore, the sum of the weight percentage contents of Co and Ni is 8-10%, the weight percentage content of C in the raw material is 5.8-6.2%, and the weight ratio of C to N is 5-6: 4-5.
Furthermore, the sum of the weight percentage contents of Co and Ni is 9%, the weight percentage content of C in the raw material is 6%, and the weight ratio of C to N is 5.5: 4.5.
Further, the weight percentage content of the TiCN is55-65%(ii) a The weight percentage content of WC is 8-20%; mo2The weight percentage content of C is 3-10%;TaCthe content of the components is 2-10 percent by weight; the NbC content is2 to 10 percent; and saidTiCN、WC、Mo2C. The sum of the contents of TaC, NbC, Co and Ni in percentage by weight is 100%.
The invention provides a preparation method of a titanium carbonitride based cermet material for a high-temperature structure, which comprises the following steps:
(1) RTP preparation: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent for ball milling; after ball milling, the ball milled material is placed in N2Spray drying under the protection condition to obtain an RTP material for pressing;
(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressure of 1.1-1.5T/cm2;
(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing to form a pressed blank under the pressing pressure of 175-185 MPa;
(4) pre-degreasing: putting the pressed compact in the step (3) in H2Dewaxing and sintering are carried out in the atmosphere, the degreasing temperature is 780-820 ℃, the degreasing time is 11-13h, and then furnace cooling is carried out;
(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving the heat for 1.5-2.5h at the sintering temperature of 1400-1600 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.
Further, in the step (1), the dispersant is ethanol, and the addition amount of the dispersant is 5-7% of the total weight of the raw materials.
Further, in the step (1), the forming agent is paraffin or PEG, and the addition amount of the forming agent is 5-7% of the total weight of the raw materials.
Further, in the step (1), the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 1-3:0.5-1.5: 0.5-1.5; the addition amount of the forming auxiliary agent is 0.08-1.2 per mill of the total weight of the raw materials.
Further, the weight ratio of SBP, etomine and ethyl cellulose is 2:1: 1.
Furthermore, the particle size of each raw material is 1.0-2.0 um.
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
(1) according to the titanium carbonitride based cermet material for the high-temperature structure, the main high-temperature volatile elements in the material components are binder phase metals such as Co, Ni and the like, and a partial liquefaction phenomenon exists in the high-temperature (800-; according to the method for modifying and strengthening the material, a large amount of refractory metal substances are dissolved in the bonding phase in a solid solution mode, so that a strong solid solution strengthening effect can be generated, meanwhile, the refractory metal elements can play a pinning role in the structure, the melting point/liquid point of the iron group elements is greatly improved, meanwhile, the refractory metal elements cannot obviously volatilize and dissipate, and the modification of the easily oxidized bonding phase is realized through solid solution strengthening; however, if a large degree of solid solution occurs, the iron group elements can also rapidly lose the good mechanical properties, and a large amount of eta phase is precipitated, and the integral strength and carrying capacity of the material can be obviously reduced due to the occurrence of the eta phase, so that the actual solid solubility in the binding phase is adjusted by selecting the proper component content, and the special phase structure is controlled, thereby realizing the performance improvement of the material in the aspect of high-temperature oxidation resistance; when the sum of the weight percentage contents of Co and Ni is 5-14%; the weight percentage content of the whole C in the raw materials is 5.8-6.2%, and the weight ratio of the whole C to N in the raw materials is 3-7:3-7, so that an ideal solid solution strengthening effect can be obtained; the invention researches and adjusts the preparation, pressing and forming processes of the mixture compared with the common pressing and sintering process to ensure that the density of the material is more than 99.5 percent, thereby ensuring the shape precision in the continuous heating use process.
(2) The titanium carbonitride based cermet material for the high-temperature structure can well meet the use requirements of structural members in a furnace in a high-temperature working environment, has small sintering shrinkage and deformation at high temperature, and ensures that the structural precision and the structural members are not easy to crack/fit gaps, thereby ensuring the stable support of the structure; the heat migration of elements can not be generated at the high-temperature working temperature, so that the negative influence generated in the preparation process of high-purity substances can be avoided; the titanium carbonitride base cermet material for the high-temperature structure, which is prepared by the invention, can specifically achieve the following effects: firstly, under the high temperature environment of 1000-1300 ℃, the high temperature hardness of the material can reach more than 800 ℃ (HV10), so that the material can keep enough rigidity to achieve the effect of structural support; ② at above 800 ℃, the titanium carbonitride based cermet material for high temperature structure prepared by the invention has the oxidation weight gain of less than or equal to 0.015g/cm under the air environment with the high temperature oxidation speed of 100 hours2,N2Under the environment or inert gas environment, the condition of reaction weight increment is avoided; thirdly, in the high temperature environment of 800-1400 ℃, the volatilization proportion of main metal components (iron group elements such as Co, Ni, Fe, Ti and the like and transition group elements) and the like in the material is less than 0.002 mg/kg-h; high temperature structural carbonThe compactness of the titanium nitride-based cermet material is more than 99.5 percent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Description of raw materials:
the particle size of each raw material is 1.0-2.0 um.
The first embodiment is as follows:
1. raw materials:
the selection and content (weight percent) of each raw material in examples 1-6 are shown in table 1 below:
table 1 examples 1-6 raw material tables
Numbering | TiCN | WC | Mo2C | TaC | NbC | Co | Ni | C% | C:N | Co+Ni |
Example 1 | 60 | 12 | 5 | 10 | 5 | 5 | 3 | 5.85 | 5:5 | 8 |
Example 2 | 60 | 10 | 5 | 8 | 7 | 5 | 5 | 6.10 | 6:4 | 10 |
Example 3 | 65 | 15 | 3 | 8 | 5 | 3 | 2 | 5.8 | 3:7 | 5 |
Example 4 | 57 | 7 | 10 | 2 | 10 | 7.5 | 6.5 | 6.2 | 7:3 | 14 |
Example 5 | 59 | 17 | 3 | 8 | 4 | 5 | 4 | 6 | 5:5 | 9 |
Example 6 | 58 | 10 | 10 | 2 | 8 | 6.5 | 5.5 | 5.9 | 5.5:4.5 | 12 |
2. The preparation method comprises the following steps:
example 1:
the method comprises the following steps:
(1) RTP preparation: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent to perform ball milling for 56 hours; after ball milling, the ball milled material is placed in N2Spray drying under the protection condition, wherein the outlet temperature is 100 ℃, and the RTP material for pressing is obtained after drying;
the dispersing agent is ethanol, and the addition amount of the dispersing agent is 6% of the total weight of the raw materials;
the forming agent is paraffin, and the addition amount of the forming agent is 6 percent of the total weight of the raw materials;
the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 2:1: 1; the addition amount of the forming auxiliary agent is 1 per mill of the total weight of the raw materials;
(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressing pressure of 1.3T/cm2;
(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing to form a pressed blank under the pressure of 180 Mpa;
(4) pre-degreasing: putting the pressed compact in the step (3) in H2Dewaxing and sintering are carried out under the atmosphere, the degreasing temperature is 800 ℃, the degreasing time is 12 hours, and then furnace cooling is carried out;
(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving heat for 2 hours at the sintering temperature of 1500 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.
Example 2:
the method comprises the following steps:
(1) RTP systemPreparing: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent to perform ball milling for 60 hours; after ball milling, the ball milled material is placed in N2Spray drying is carried out under the protection condition, the outlet temperature is 95 ℃, and the RTP material for pressing is obtained after drying;
the dispersing agent is ethanol, and the addition amount of the dispersing agent is 5% of the total weight of the raw materials;
the forming agent is PEG4000, and the addition amount of the forming agent is 7 percent of the total weight of the raw materials;
the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 1:1.5: 0.5; the addition amount of the forming auxiliary agent is 0.08 per mill of the total weight of the raw materials;
(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressing pressure of 1.5T/cm2;
(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing the blank into a pressed blank under the pressure of 175 Mpa;
(4) pre-degreasing: putting the pressed compact in the step (3) in H2Dewaxing and sintering are carried out under the atmosphere, the degreasing temperature is 820 ℃, the degreasing time is 11 hours, and then furnace cooling is carried out;
(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving heat for 2.5 hours at the sintering temperature of 1400 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.
Example 3:
the method comprises the following steps:
(1) RTP preparation: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent to perform ball milling for 50 hours; after ball milling, the ball milled material is placed in N2Spray drying is carried out under the protection condition, the outlet temperature is 105 ℃, and the RTP material for pressing is obtained after drying;
the dispersing agent is ethanol, and the addition amount of the dispersing agent is 7% of the total weight of the raw materials;
the forming agent is PEG1500, and the addition amount of the forming agent is 5 percent of the total weight of the raw materials;
the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 3:0.5: 1.5; the addition amount of the forming auxiliary agent is 1.2 per mill of the total weight of the raw materials;
(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressing pressure of 1.1T/cm2;
(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing to obtain a pressed blank with the pressing pressure of 185 Mpa;
(4) pre-degreasing: putting the pressed compact in the step (3) in H2Dewaxing and sintering are carried out under the atmosphere, the degreasing temperature is 780 ℃, the degreasing time is 13 hours, and then furnace cooling is carried out;
(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving heat for 1.5h at the sintering temperature of 1600 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.
Examples 4 to 6:
the preparation method is the same as example 1.
Second, performance detection
The finished products prepared in examples 1 to 6 were individually subjected to performance tests. The test results are shown in table 2 below:
table 2 results of performance testing
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.
Claims (9)
1. Titanium carbonitride based cermet material for high temperature structures, and preparation method thereofIs characterized in that: the raw materials comprise TiCN, WC and Mo2C. TaC, NbC, Co and Ni; wherein,
the weight percentage content of the TiCN is 55-65%; the weight percentage content of WC is 8-20%; mo2The weight percentage content of C is 3-10%; the weight percentage content of TaC is 2-10%; the weight percentage content of NbC is 2-10%; the sum of the weight percentage contents of Co and Ni is 5-14%; the TiCN, WC and Mo2C. The sum of the weight percentage contents of TaC, NbC, Co and Ni is 100 percent;
the weight percentage content of the whole C in the raw material is 5.8-6.2%, and the weight ratio of the whole C to N in the raw material is 3-7: 3-7.
2. The titanium carbonitride-based cermet material for high temperature structures as set forth in claim 1, wherein: the sum of the weight percentage of Co and Ni is 8-10%, the weight percentage of C in the raw material is 5.8-6.2%, and the weight ratio of C to N is 5-6: 4-5.
3. The titanium carbonitride-based cermet material for high temperature structures as set forth in claim 2, wherein: the sum of the weight percentage contents of Co and Ni is 9%, the weight percentage content of C in the raw material is 6%, and the weight ratio of C to N is 5.5: 4.5.
4. A method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in any one of claims 1-3, characterized in that: the method comprises the following steps:
(1) RTP preparation: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent for ball milling; after ball milling, the ball milled material is placed in N2Spray drying under the protection condition to obtain an RTP material for pressing;
(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressure of 1.1-1.5T/cm2;
(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing to form a pressed blank under the pressing pressure of 175-185 MPa;
(4) pre-degreasing: putting the pressed compact in the step (3) in H2Dewaxing and sintering are carried out in the atmosphere, the degreasing temperature is 780-820 ℃, the degreasing time is 11-13h, and then furnace cooling is carried out;
(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving the heat for 1.5-2.5h at the sintering temperature of 1400-1600 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.
5. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in claim 4, wherein: in the step (1), the dispersing agent is ethanol, and the addition amount of the dispersing agent is 5-7% of the total weight of the raw materials.
6. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in claim 4, wherein: in the step (1), the forming agent is paraffin or PEG, and the addition amount of the forming agent is 5-7% of the total weight of the raw materials.
7. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in claim 4, wherein: in the step (1), the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 1-3:0.5-1.5: 0.5-1.5; the addition amount of the forming auxiliary agent is 0.08-1.2 per mill of the total weight of the raw materials.
8. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in claim 7, wherein: the weight ratio of SBP, etomine and ethyl cellulose is 2:1: 1.
9. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in any one of claims 4-8, characterized in that: the particle size of each raw material is 1.0-2.0 um.
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