WO2021133226A1 - Method for fabrication of ultra-high-temperature ceramic material based on hafnium carbide and carbonitride - Google Patents
Method for fabrication of ultra-high-temperature ceramic material based on hafnium carbide and carbonitride Download PDFInfo
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- WO2021133226A1 WO2021133226A1 PCT/RU2020/050295 RU2020050295W WO2021133226A1 WO 2021133226 A1 WO2021133226 A1 WO 2021133226A1 RU 2020050295 W RU2020050295 W RU 2020050295W WO 2021133226 A1 WO2021133226 A1 WO 2021133226A1
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- temperature
- carbonitride
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- 238000000034 method Methods 0.000 title claims abstract description 30
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000011215 ultra-high-temperature ceramic Substances 0.000 title claims description 5
- 229910010293 ceramic material Inorganic materials 0.000 title abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 19
- 238000004137 mechanical activation Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007596 consolidation process Methods 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 230000001902 propagating effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- -1 more specifically Chemical class 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910014813 CaC2 Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 101150100117 gfm1 gene Proteins 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 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
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- MBEGFNBBAVRKLK-UHFFFAOYSA-N sodium;iminomethylideneazanide Chemical compound [Na+].[NH-]C#N MBEGFNBBAVRKLK-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- C22C29/06—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 carbides, but not containing other metal compounds
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- B22F3/23—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces involving a self-propagating high-temperature synthesis or reaction sintering step
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- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Definitions
- This invention relates to missile and space engineering and materials science, more specifically, to the development of ultra- high-temperature materials (T m > 3000 °C) on the basis of hafnium (Hf) which can be used for the protection of the most heat-affected units (air-breathing engines, nose cones and sharp leading edges) of hypersonic aircrafts, and can be furthermore used in the nuclear industry.
- T m > 3000 °C ultra- high-temperature materials
- Hf hafnium
- Transition metal nitrides fabrication method comprised of a mixture preparation, containing oxide of the metal to be nitridized, powder of the metal to be nitridized (Hf, Ti, Nb, Zr) and azide of an alkaline metal (e.g. sodium azide), pressing of the billets from mixed powders and their ignition using a tungsten wire in a nitrogen atmosphere.
- This method allows fabricating metal nitride powders with a nitride yield of at least 96% and a nitrogen content of at least 7.17% (RU 2256604, C01B21/076, 20.07.2005). Failure to deliver a 100% reaction product yield and the necessity to use powders along with their oxides, which leads to a cost increase of the method, as well as the impossibility to vary the nitrogen content in the compound are disadvantages of this fabrication method.
- Titanium carbonitride producing method comprising high- temperature synthesis of titanium-containing compounds in a nitrogen atmosphere during magnesium-thermic reduction of a titanium tetrachloride and tetrachloroethylene mixture in a ratio of 4.5 - 5.1 and the temperature range of 1010-1080 °C.
- Above-mentioned method allows fabricating titanium-containing compounds including titanium carbonitride with a minimal quantity of impurities (RU 2175021, C22B34/12, C22B5/04, C01B31/30, C01B21/076, 20.10.2001).
- Disadvantages of this method are the impossibility of varying the C/N ratio over the entire composition range, the presence of free carbon in the synthesized compound, the necessity of using a reducing metal and the high power consumption of the method caused by the necessity of maintaining high temperature for the synthesis.
- refractory metal carbides, nitrides and carbonitrides fabrication comprising mixing of a refractory metal oxide, e.g. HfO 2 , ZrO 2 or TiO 2 , with a non-metallic material, e.g.
- soot or calcium-containing compound CaC 2 , Ca 3 N 2 or CaCN 2 addition of a reducing metal (calcium), synthesis in a pipe-shaped reactor in an argon atmosphere at 450 to 800 °C and removal of the forming calcium oxide CaO by dissolving it in hydrochloric or acetic acid (RU 2225837, C01B31/30, C01B21/06, B22F3/23, 20.03.2004).
- Disadvantages of this method are the necessity to use a reducing metal oxide which should be removed from the product compound and the high power consumption of the method caused by the necessity to heat the pipe-shaped reactor to 450 - 800 °C.
- the technical result of the invention disclosed herein is simplification and significant power and time consumption reduction of the material synthesis method and the possibility of fabricating compact ceramic material of a non- stoichiometric composition.
- Said technical result is achieved by exposing the mixture of raw Hf and C components to preliminary mechanical activation in a high-energy planetary ball mill, subsequent self-propagating high-temperature synthesis of the prepared Hf and C mixture and consolidation of the synthesized powders.
- Said preliminary mechanical activation is carried out for 5 - 10 min, the ball-to-mixture weight ratio being 20:1 - 40:1 and the planetary disc speed being 694 - 900 rpm, said subsequent self-propagating high-temperature synthesis is carried out in a reactor containing an argon or nitrogen atmosphere at a pressure of 0.1 - 0.8 MPa, initiation of a self-sustaining exothermic reaction is performed by incandescent tungsten spiral and the consolidation of synthesized hafnium carbide (argon) or hafnium carbonitride (nitrogen) powder is carried out by means of spark plasma sintering, wherein an argon atmosphere is produced in the chamber and a pulsed current of 1000 - 5000 A is passed through the specimen being sintered at a load of 30 - 70 MPa, the consolidation temperature and exposure time being 1900 - 2200°C and 2 - 10 min, respectively.
- argon hafnium carbide
- Consolidated ultra-high-temperature materials fabricated using the method disclosed hereinabove are ceramics having the following properties: a) hafnium carbonitride of the HfC 0.5 N 0.2 composition with a relative density of 98.7 %, a Vickers hardness of 21.3 GPa and a fracture toughness of 4.7 MPa m 1/2 ; b) hafnium carbide of the HfC 0.5 composition with a relative density of 98.5
- hafnium carbide of the HfC composition with a relative density of
- the raw components for the fabrication of the ultra-high-temperature hafnium nitride, carbide and carbonitride based ceramics used for the protection of the most heat-affected units of hypersonic aircrafts are GFM-1 Grade Hf metal powder (hafnium powder) (TU Standard 48-4-176-85 (97)) and P804T Grade C powder (powdered soot) (TU Standard 38-1154-88), as well as nitrogen (GOST 9293-74) and argon (GOST 10157-79) gases.
- Preliminary mechanical activation comprising grinding and mixing of the raw hafnium powder and soot is performed in an “Activator-2S” high-energy planetary ball mill. Mechanical activation is carried out in steel vials with steel balls for 5 - 10 min at a 694 - 900 rpm main disk speed and a ball-to-powder weight ratio of 20:1 - 40:1. Mechanical activation of the raw mixtures is implemented in an argon atmosphere at an in-vial pressure of 0.4 MPa. Mechanical activation leads to the formation of new non-oxidized surfaces, uniform distribution of the particles and an increase in the contact area between the reactants which in turn accelerates the reaction between them. Preliminary mechanical activation constitutes the first stage of the method described herein.
- the second stage of the method described herein which follows the preliminary mechanical activation comprises the self-propagating high-temperature synthesis of the activated powder or Hf + xC powder mixture, where x is the quantity of carbon varying from 0.5 to 1, in order to synthesize hafnium carbide HfC x if an argon atmosphere in a laboratory reactor or hafnium carbonitride HfC x N y if a nitrogen atmosphere in a laboratory reactor.
- the gas pressure in the laboratory reactor during the process is 0.1 - 0.8 MPa.
- composition of the synthesized compounds i.e., the x and y parameters, varies depending on the quantity of carbon in the raw mixture and the nitrogen pressure in the reactor.
- the third stage of the method described herein comprises the consolidation of the non- stoichiometric HfC x and HfC x N y powders in a spark plasma sintering unit (Spark Plasma Sintering - Labox 650, SinterLand, Japan).
- the method of spark plasma sintering is based on the combined exposure to a high temperature and an axial pressure coupled with the passage of pulsed direct electric current with a high amplitude (to 5000 A) through the material being sintered and the graphite matrix in which it is contained.
- the pulsed current favors uniform heating of the specimen with a minimum impact on its microstructure.
- the consolidation load is 30 - 70 MPa, the exposure time and sintering temperature being 2 - 10 min and 1900 - 2200 °C, respectively.
- a necessary part of each stage is quality control of the as -treated specimens which is implemented either through visual inspection or with instrumental methods.
- the raw components Hf and C were mixed in a molar ratio of 2:1 (96.7wt.% Hf and 3.3 wt.% C).
- the prepared mixture of the raw components was exposed to preliminary mechanical activation in a planetary ball mill in an argon atmosphere at a pressure of 0.4 MPa and a mill speed of 900 rpm with a ball-to- powder weight ratio of 20:1 in order to mix, grind and clean powder surface from oxides.
- the ball diameter was 6 mm.
- the time of preliminary mechanical activation was 10 min.
- the resultant reaction powder mixture was exposed to self-propagating high-temperature synthesis in a reactor at a nitrogen pressure of 0.8 MPa and a self- sustaining exothermic reaction was initiated with an incandescent tungsten spiral.
- the resultant hafnium carbonitride powder had the HfC 0.5 N 0.2 composition.
- the as-synthesized HfC 0.5 N 0.2 powder was consolidated using the method of spark plasma sintering.
- the powder was placed in a cylindrical graphite matrix and clamped between two punches which simultaneously acted as electrodes, the matrix was placed into the working space of the spark plasma sintering unit, a argon atmosphere was produced in the chamber and pulsed electric current was passed through the specimen being sintered at a load of 50 MPa applied to the specimen.
- the consolidation temperature was 2000 °C and the exposure time was 10 min.
- the heating rate to the sintering temperature was 100 °C/min.
- the specimens had disc shapes and were 15 - 50 mm in diameter and 2 - 10 mm in thickness.
- the ultra-high-temperature material has the following parameters: relative density 98.7 %, Vickers hardness 21.3 GPa and fracture toughness 4.7 MPa m 1/2 .
- Figure 1 and 2 shows a diffraction pattern and the microstructure of HfC 0.5 N 0.2 -
- the raw components Hf and C were mixed in a molar ratio of 2:1 (96.7wt.% Hf and 3.3 wt.% C).
- the prepared mixture of the raw components was exposed to preliminary mechanical activation in a planetary ball mill in an argon atmosphere at a pressure of 0.4 MPa and a mill speed of 694 rpm with a ball-to- powder weight ratio of 20:1 in order to mix, grind and clean powder surface from oxides.
- the ball diameter was 6 mm.
- the time of preliminary mechanical activation was 5 min.
- the resultant reaction powder mixture was exposed to self-propagating high-temperature synthesis in a reactor at a argon pressure of 0.8 MPa and a self- sustaining exothermic reaction was initiated with an incandescent tungsten spiral.
- the as-synthesized HfC 0.5 powder was consolidated using the method of spark plasma sintering.
- the powder was placed in a cylindrical graphite matrix and clamped between two punches which simultaneously acted as electrodes, the matrix was placed into the working space of the spark plasma sintering unit, a argon atmosphere was produced in the chamber and pulsed electric current of 1000 - 5000 A was passed through the specimen being sintered at a load of 70 MPa applied to the specimen.
- the consolidation temperature was 2200 °C and the exposure time was 10 min.
- the heating rate to the sintering temperature was 100 °C/min.
- the specimens had disc shapes and were 15 - 50 mm in diameter and 2 - 10 mm in thickness.
- the ultra-high-temperature HfC 0.5 ceramic has the following parameters: relative density 98.5 %, Vickers hardness 16.2 GPa and fracture toughness 3.6 MPa m 1/2 .
- Figure 3 and 4 shows a diffraction pattern and the microstructure of HfC 0.5
- the raw components Hf and C were mixed in a molar ratio of 1:1 (93.7wt.% Hf and 6.3 wt.% C).
- the prepared mixture of the raw components was exposed to preliminary mechanical activation in a planetary ball mill in an argon atmosphere at a pressure of 0.4 MPa and a mill speed of 900 rpm with a ball-to- powder weight ratio of 20:1 in order to mix, grind and clean powder surface from oxides.
- the ball diameter was 6 mm.
- the time of preliminary mechanical activation was 5 min.
- the resultant reaction powder mixture was exposed to self-propagating high-temperature synthesis in a reactor at a argon pressure of 0.4 MPa and a self- sustaining exothermic reaction was initiated with an incandescent tungsten spiral.
- the as- synthesized HfC powder was consolidated using the method of spark plasma sintering.
- the powder was placed in a cylindrical graphite matrix and clamped between two punches which simultaneously acted as electrodes, the matrix was placed into the working space of the spark plasma sintering unit, a argon atmosphere was produced in the chamber and pulsed electric current was passed through the specimen being sintered at a load of 30 MPa applied to the specimen.
- the consolidation temperature was 1900 °C and the exposure time was 10 min.
- the heating rate to the sintering temperature was 100 °C/min.
- the specimens had disc shapes and were 15 - 50 mm in diameter and 2 - 10 mm in thickness.
- the ultra-high-temperature ceramic has the following parameters: relative density 99.3 %, Vickers hardness 20.5 GPa and fracture toughness 4.1 MPa m 1/2 .
- Figure 5 and 6 shows a diffraction pattern and the microstructure of HfC.
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Abstract
This invention relates to space engineering and materials science. The technical result of the invention disclosed herein regarding the method is facilitation and significant reduction of power and time consumption for the material synthesis, and regarding the material is providing a compact ceramic material of a nonstoichiometric composition. Said technical result is achieved by providing the method of synthesizing ultrahigh-temperature materials on the basis of hafnium carbide and carbonitride comprising preliminary mechanical activation of the initial hafnium and carbon powders in a high-energy planetary ball mill, self-propagating high-temperature synthesis in argon or nitrogen atmosphere and subsequent sintering of the synthesized mixture. Consolidation of the synthesized powder is achieved using the spark plasma sintering method.
Description
Method for Fabrication of Ultra-High-Temperature Ceramic material based on Hafnium Carbide and Carbonitride
Field of the Invention. This invention relates to missile and space engineering and materials science, more specifically, to the development of ultra- high-temperature materials (Tm > 3000 °C) on the basis of hafnium (Hf) which can be used for the protection of the most heat-affected units (air-breathing engines, nose cones and sharp leading edges) of hypersonic aircrafts, and can be furthermore used in the nuclear industry.
Prior Art. Fabrication of this type of the materials for operation at ultrahigh temperatures (above 2000 °C) requires providing a combination of the following key properties: efficient heat removal, high oxidation resistance and refractory quality. Of greatest interest from this viewpoint are binary and ternary non- stoichiometric compounds, more specifically, carbides, nitrides and carbonitrides of transition metals of groups 4B and 5B of the Periodic Table including hafnium. Fabrication of these non- stoichiometric compounds is a complex task due to the difficulties associated with the nitrogen and/or carbon quantity adjustment in the system and the high melting points of the main components.
Transition metal nitrides fabrication method is known, comprised of a mixture preparation, containing oxide of the metal to be nitridized, powder of the metal to be nitridized (Hf, Ti, Nb, Zr) and azide of an alkaline metal (e.g. sodium azide), pressing of the billets from mixed powders and their ignition using a tungsten wire in a nitrogen atmosphere. This method allows fabricating metal nitride powders with a nitride yield of at least 96% and a nitrogen content of at least 7.17% (RU 2256604, C01B21/076, 20.07.2005).
Failure to deliver a 100% reaction product yield and the necessity to use powders along with their oxides, which leads to a cost increase of the method, as well as the impossibility to vary the nitrogen content in the compound are disadvantages of this fabrication method.
Titanium carbonitride producing method is known, comprising high- temperature synthesis of titanium-containing compounds in a nitrogen atmosphere during magnesium-thermic reduction of a titanium tetrachloride and tetrachloroethylene mixture in a ratio of 4.5 - 5.1 and the temperature range of 1010-1080 °C. Above-mentioned method allows fabricating titanium-containing compounds including titanium carbonitride with a minimal quantity of impurities (RU 2175021, C22B34/12, C22B5/04, C01B31/30, C01B21/076, 20.10.2001).
Disadvantages of this method are the impossibility of varying the C/N ratio over the entire composition range, the presence of free carbon in the synthesized compound, the necessity of using a reducing metal and the high power consumption of the method caused by the necessity of maintaining high temperature for the synthesis.
The closest counterpart of the material and method of its fabrication disclosed herein is the method of refractory metal carbides, nitrides and carbonitrides fabrication, comprising mixing of a refractory metal oxide, e.g. HfO2, ZrO2 or TiO2, with a non-metallic material, e.g. soot or calcium-containing compound CaC2, Ca3N2 or CaCN2, addition of a reducing metal (calcium), synthesis in a pipe-shaped reactor in an argon atmosphere at 450 to 800 °C and removal of the forming calcium oxide CaO by dissolving it in hydrochloric or acetic acid (RU 2225837, C01B31/30, C01B21/06, B22F3/23, 20.03.2004).
Disadvantages of this method are the necessity to use a reducing metal oxide which should be removed from the product compound and the high power
consumption of the method caused by the necessity to heat the pipe-shaped reactor to 450 - 800 °C.
Disclosure of the Invention. The technical result of the invention disclosed herein is simplification and significant power and time consumption reduction of the material synthesis method and the possibility of fabricating compact ceramic material of a non- stoichiometric composition.
Said technical result is achieved by exposing the mixture of raw Hf and C components to preliminary mechanical activation in a high-energy planetary ball mill, subsequent self-propagating high-temperature synthesis of the prepared Hf and C mixture and consolidation of the synthesized powders. Said preliminary mechanical activation is carried out for 5 - 10 min, the ball-to-mixture weight ratio being 20:1 - 40:1 and the planetary disc speed being 694 - 900 rpm, said subsequent self-propagating high-temperature synthesis is carried out in a reactor containing an argon or nitrogen atmosphere at a pressure of 0.1 - 0.8 MPa, initiation of a self-sustaining exothermic reaction is performed by incandescent tungsten spiral and the consolidation of synthesized hafnium carbide (argon) or hafnium carbonitride (nitrogen) powder is carried out by means of spark plasma sintering, wherein an argon atmosphere is produced in the chamber and a pulsed current of 1000 - 5000 A is passed through the specimen being sintered at a load of 30 - 70 MPa, the consolidation temperature and exposure time being 1900 - 2200°C and 2 - 10 min, respectively.
Embodiments of the Invention. Consolidated ultra-high-temperature materials fabricated using the method disclosed hereinabove are ceramics having the following properties:
a) hafnium carbonitride of the HfC0.5N0.2 composition with a relative density of 98.7 %, a Vickers hardness of 21.3 GPa and a fracture toughness of 4.7 MPa m1/2; b) hafnium carbide of the HfC0.5 composition with a relative density of 98.5
%, a Vickers hardness of 10.2 GPa and a fracture toughness of 3.6 MPa m1/2; c) hafnium carbide of the HfC composition with a relative density of
99.3 %, a Vickers hardness of 20.5 GPa and a fracture toughness of 4.1 MPa m1/2.
The raw components for the fabrication of the ultra-high-temperature hafnium nitride, carbide and carbonitride based ceramics used for the protection of the most heat-affected units of hypersonic aircrafts are GFM-1 Grade Hf metal powder (hafnium powder) (TU Standard 48-4-176-85 (97)) and P804T Grade C powder (powdered soot) (TU Standard 38-1154-88), as well as nitrogen (GOST 9293-74) and argon (GOST 10157-79) gases.
Preliminary mechanical activation comprising grinding and mixing of the raw hafnium powder and soot is performed in an “Activator-2S” high-energy planetary ball mill. Mechanical activation is carried out in steel vials with steel balls for 5 - 10 min at a 694 - 900 rpm main disk speed and a ball-to-powder weight ratio of 20:1 - 40:1. Mechanical activation of the raw mixtures is implemented in an argon atmosphere at an in-vial pressure of 0.4 MPa. Mechanical activation leads to the formation of new non-oxidized surfaces, uniform distribution of the particles and an increase in the contact area between the reactants which in turn accelerates the reaction between them. Preliminary mechanical activation constitutes the first stage of the method described herein.
The second stage of the method described herein which follows the preliminary mechanical activation comprises the self-propagating high-temperature synthesis of the activated powder or Hf + xC powder mixture, where x is the
quantity of carbon varying from 0.5 to 1, in order to synthesize hafnium carbide HfCx if an argon atmosphere in a laboratory reactor or hafnium carbonitride HfCxNy if a nitrogen atmosphere in a laboratory reactor. The gas pressure in the laboratory reactor during the process is 0.1 - 0.8 MPa.
The composition of the synthesized compounds, i.e., the x and y parameters, varies depending on the quantity of carbon in the raw mixture and the nitrogen pressure in the reactor.
The third stage of the method described herein comprises the consolidation of the non- stoichiometric HfCx and HfCxNy powders in a spark plasma sintering unit (Spark Plasma Sintering - Labox 650, SinterLand, Japan).
The method of spark plasma sintering is based on the combined exposure to a high temperature and an axial pressure coupled with the passage of pulsed direct electric current with a high amplitude (to 5000 A) through the material being sintered and the graphite matrix in which it is contained. The pulsed current favors uniform heating of the specimen with a minimum impact on its microstructure. The consolidation load is 30 - 70 MPa, the exposure time and sintering temperature being 2 - 10 min and 1900 - 2200 °C, respectively.
A necessary part of each stage is quality control of the as -treated specimens which is implemented either through visual inspection or with instrumental methods.
For the microstructure and phase composition investigations of the as- synthesized and as-consolidated powders we used scanning electron microscopy (SEM) and X-ray diffraction (X-ray phase analysis) methods. For consolidated ultra-high-temperature non- stoichiometric hafnium carbide, nitride and carbonitride based ceramics we further controlled the porosity, hardness, fracture toughness and microstructure.
The subject matter of the method disclosed herein will be further supported with examples.
Example 1.
Fabrication of ultra-high-temperature HfC0.5N0.2 ceramic.
The raw components Hf and C were mixed in a molar ratio of 2:1 (96.7wt.% Hf and 3.3 wt.% C). The prepared mixture of the raw components was exposed to preliminary mechanical activation in a planetary ball mill in an argon atmosphere at a pressure of 0.4 MPa and a mill speed of 900 rpm with a ball-to- powder weight ratio of 20:1 in order to mix, grind and clean powder surface from oxides. The ball diameter was 6 mm. The time of preliminary mechanical activation was 10 min.
The resultant reaction powder mixture was exposed to self-propagating high-temperature synthesis in a reactor at a nitrogen pressure of 0.8 MPa and a self- sustaining exothermic reaction was initiated with an incandescent tungsten spiral. The resultant hafnium carbonitride powder had the HfC0.5N0.2 composition.
The as-synthesized HfC0.5N0.2 powder was consolidated using the method of spark plasma sintering. For this purpose the powder was placed in a cylindrical graphite matrix and clamped between two punches which simultaneously acted as electrodes, the matrix was placed into the working space of the spark plasma sintering unit, a argon atmosphere was produced in the chamber and pulsed electric current was passed through the specimen being sintered at a load of 50 MPa applied to the specimen. The consolidation temperature was 2000 °C and the exposure time was 10 min. The heating rate to the sintering temperature was 100 °C/min. As a result, the specimens had disc shapes and were 15 - 50 mm in diameter and 2 - 10 mm in thickness.
The ultra-high-temperature material has the following parameters: relative density 98.7 %, Vickers hardness 21.3 GPa and fracture toughness 4.7 MPa m1/2. Figure 1 and 2 shows a diffraction pattern and the microstructure of HfC0.5N0.2-
Example 2.
Fabrication of ultra-high-temperature HfC0.5 ceramic.
The raw components Hf and C were mixed in a molar ratio of 2:1 (96.7wt.% Hf and 3.3 wt.% C). The prepared mixture of the raw components was exposed to preliminary mechanical activation in a planetary ball mill in an argon atmosphere at a pressure of 0.4 MPa and a mill speed of 694 rpm with a ball-to- powder weight ratio of 20:1 in order to mix, grind and clean powder surface from oxides. The ball diameter was 6 mm. The time of preliminary mechanical activation was 5 min.
The resultant reaction powder mixture was exposed to self-propagating high-temperature synthesis in a reactor at a argon pressure of 0.8 MPa and a self- sustaining exothermic reaction was initiated with an incandescent tungsten spiral.
The as-synthesized HfC0.5 powder was consolidated using the method of spark plasma sintering. For this purpose the powder was placed in a cylindrical graphite matrix and clamped between two punches which simultaneously acted as electrodes, the matrix was placed into the working space of the spark plasma sintering unit, a argon atmosphere was produced in the chamber and pulsed electric current of 1000 - 5000 A was passed through the specimen being sintered at a load of 70 MPa applied to the specimen. The consolidation temperature was 2200 °C and the exposure time was 10 min. The heating rate to the sintering temperature was 100 °C/min. As a result, the specimens had disc shapes and were 15 - 50 mm in diameter and 2 - 10 mm in thickness.
The ultra-high-temperature HfC0.5 ceramic has the following parameters: relative density 98.5 %, Vickers hardness 16.2 GPa and fracture toughness 3.6 MPa m1/2. Figure 3 and 4 shows a diffraction pattern and the microstructure of HfC0.5
Example 3.
Fabrication of ultra-high-temperature HfC ceramic.
The raw components Hf and C were mixed in a molar ratio of 1:1 (93.7wt.% Hf and 6.3 wt.% C). The prepared mixture of the raw components was exposed to preliminary mechanical activation in a planetary ball mill in an argon atmosphere at a pressure of 0.4 MPa and a mill speed of 900 rpm with a ball-to- powder weight ratio of 20:1 in order to mix, grind and clean powder surface from oxides. The ball diameter was 6 mm. The time of preliminary mechanical activation was 5 min.
The resultant reaction powder mixture was exposed to self-propagating high-temperature synthesis in a reactor at a argon pressure of 0.4 MPa and a self- sustaining exothermic reaction was initiated with an incandescent tungsten spiral.
The as- synthesized HfC powder was consolidated using the method of spark plasma sintering. For this purpose the powder was placed in a cylindrical graphite matrix and clamped between two punches which simultaneously acted as electrodes, the matrix was placed into the working space of the spark plasma sintering unit, a argon atmosphere was produced in the chamber and pulsed electric current was passed through the specimen being sintered at a load of 30 MPa applied to the specimen. The consolidation temperature was 1900 °C and the exposure time was 10 min. The heating rate to the sintering temperature was 100
°C/min. As a result, the specimens had disc shapes and were 15 - 50 mm in diameter and 2 - 10 mm in thickness.
The ultra-high-temperature ceramic has the following parameters: relative density 99.3 %, Vickers hardness 20.5 GPa and fracture toughness 4.1 MPa m1/2. Figure 5 and 6 shows a diffraction pattern and the microstructure of HfC.
Claims
What is claimed is a
Method of fabrication of ultra-high-temperature ceramics on the basis of hafnium carbide or carbonitride ultra-high-temperature ceramics fabrication method, comprising preliminary mechanical activation of the Hf and C raw components mixture in a high-energy planetary ball mill, subsequent self- propagating high-temperature synthesis of the prepared Hf and C mixture and consolidation of the synthesized powders, wherein said preliminary mechanical activation is implemented for 5 - 10 min at a ball-to-powder weight ratio of 20:1 - 40:1 and a main disc speed of 694 - 900 rpm, said subsequent self-propagating high-temperature synthesis is carried out in a reactor with an argon or nitrogen atmosphere at a pressure of 0.1 - 0.8 MPa, a self-sustaining exothermic reaction is initiated with an incandescent tungsten spiral and the synthesized hafnium carbide or carbonitride powder is consolidated by means of spark plasma sintering, further wherein a argon atmosphere is produced in the reaction chamber and a pulsed current of 1000 - 5000 A is passed through the specimen being sintered at a load of 30 - 70 MPa, the consolidation temperature and exposure time being 1900 - 2200°C and 2 - 10 min, respectively.
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| US20220009838A1 (en) * | 2019-11-29 | 2022-01-13 | Central South University | Long-term ablation-resistant nitrogen-containing carbide ultra-high temperature ceramic with ultra-high melting point and application thereof |
| CN115806277A (en) * | 2021-09-15 | 2023-03-17 | 中南大学 | Novel preparation method of ultrahigh-melting-point hafnium carbonitride powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20220009838A1 (en) * | 2019-11-29 | 2022-01-13 | Central South University | Long-term ablation-resistant nitrogen-containing carbide ultra-high temperature ceramic with ultra-high melting point and application thereof |
| US12012364B2 (en) * | 2019-11-29 | 2024-06-18 | Central South University | Long-term ablation-resistant nitrogen-containing carbide ultra-high temperature ceramic with ultra-high melting point and application thereof |
| CN115806277A (en) * | 2021-09-15 | 2023-03-17 | 中南大学 | Novel preparation method of ultrahigh-melting-point hafnium carbonitride powder |
Also Published As
| Publication number | Publication date |
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| CN115151358B (en) | 2024-05-24 |
| CN115151358A (en) | 2022-10-04 |
| RU2729277C1 (en) | 2020-08-05 |
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