CN110078512A - High entropy carbide powder of superhigh temperature and preparation method thereof - Google Patents
High entropy carbide powder of superhigh temperature and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to ultra-high temperature ceramic powder technical fields, and in particular to a kind of high entropy carbide powder of superhigh temperature and preparation method thereof.The high entropy carbide powder of the superhigh temperature, chemical formula are (Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C, using TiO2、ZrO2、HfO2、Nb2O5、WO3、Ta2O5It is raw material with carbon black, is prepared by wet-mixing and high temperature carbothermic reduction reaction.The high entropy carbide powder of superhigh temperature of the invention, crystallite dimension is small, thermal conductivity low and high temperature stability is good, is suitable as the basis material of superhigh temperature thermal coating material, superhigh temperature heat-barrier material and superhigh temperature composite material；Preparation method of the invention, simple process, cost of material are low, and primary heating reaction at a lower temperature can be obtained the high entropy carbide powder of superhigh temperature of high-purity.
Description
Technical field
The present invention relates to ultra-high temperature ceramic powder technical fields, and in particular to a kind of high entropy carbide powder of superhigh temperature and its
Preparation method.
Background technique
The first wall of tockmark, Solid Rocket Motor combustion chamber, scramjet engine combustion chamber, it is hypersonic fly
The surface etc. of row device all suffers from ultra-high temperature environment, needs to take thermal protection measure.
The boride and carbide superhigh temperature ceramics of transition metal have high-melting-point, low-density, high rigidity, high intensity, resistance to
The advantages that environmental corrosion is the key that extreme environment thermal protection application candidate material.However transition metal boride and carbide
The thermal conductivities of superhigh temperature ceramics is high, and heat-insulated effect cannot be played while thermal protection, therefore must design and prepare and have
The novel super-high temperature ceramic material of solar heat protection and heat insulating function simultaneously.
High entropy ceramics are usually the solid solution formed by the ceramic material with same crystal structure, high entropy superhigh temperature ceramics
Both had the advantages that fusing point was high, thermal stability is good, hardness is high, intensity is high, environment resistant corrosion, while also there is lower thermal conductivity, crystalline substance
The advantages such as lattice diffusivity is low, are the novel super-high adiabators with anti-heat insulating function integrated function.
Document 1 (J.Am.Ceram.Soc.101 (2018) 4486-4491) report with high-energy ball milling HfC, ZrC, TaC,
Then discharge plasma sintering prepares (Hf for NbC and TiC powder mixing0.2Zr0.2Ta0.2Nb0.2Ti0.2) the high entropy superhigh temperature pottery of C block
The method of ceramic material.Compared with ZrC and HfC (room temperature thermal conductivity 28-35W/m.K), high entropy superhigh temperature ceramics
(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2) the room temperature thermal conductivity of C only has 6.4W/m.K.
Document 2 (Adv.Mater.30 (2018) No.1805004) reports MgxNixCuxCoxZnxSbxO (x=0.167)
Room temperature thermal conductivity down to 1.4W/m.K.
Document 3 (Scripta Mater.158 (2019) 100-104) reports ball milling metal Hf, Mo, Ta, Nb, Ti first
With the mixed-powder of B, then by from climing burning method synthesize (Hf0.2Mo0.2Ta0.2Nb0.2Ti0.2)B2High entropy ceramic powders, finally
(Hf is prepared through discharge plasma sintering0.2Mo0.2Ta0.2Nb0.2Ti0.2)B2The method of high entropy ceramic block material.
Document 4 (Scripta Materialia 142 (2018) 116-120) is reported using oxide as raw material, through high energy
Ball milling and pyroreaction prepare the high entropy ceramics Sr (Zr of Ca-Ti ore type0.2Sn0.2Ti0.2Hf0.2Mn0.2)O3、Sr
(Zr0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3、Ba(Zr0.2Sn0.2Ti0.2Hf0.2Ce0.2)O3、Ba(Zr0.2Sn0.2Ti0.2Hf0.2Y0.2)
O3-x、Ba(Zr0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3And (Sr0.5Ba0.5)(Zr0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3Method.
A kind of high entropy carbide ultra-high temperature ceramic powder and preparation method thereof is disclosed in patent CN2018111673376,
With at least two metal powders and C powder ball milling mixing in Zr, Ti, Hf, V, Nb, Ta, Cr, Mo or W, electro-plasma is pressed through nothing
Sintering is made.
However, the above-mentioned method for preparing high entropy ceramics or needing high-energy ball milling or needing discharge plasma sintering, no
It is suitble to the large-scale production high entropy ceramic powder of superhigh temperature.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of high entropy carbide powder of superhigh temperature, crystal grain rulers
It is very little it is small, thermal conductivity low and high temperature stability is good, be suitable as superhigh temperature thermal coating material, superhigh temperature heat-barrier material and superhigh temperature
The basis material of composite material；The present invention also provides preparation method, cost of material is low, simple process, and at a lower temperature one
Secondary heating reaction can be obtained the high entropy carbide powder of superhigh temperature of high-purity.
The high entropy carbide powder of superhigh temperature of the present invention, chemical formula are (Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C,
Using TiO2、ZrO2、HfO2、Nb2O5、WO3、Ta2O5It is raw material with carbon black, passes through wet-mixing and high temperature carbothermic reduction reaction system
It is standby to obtain.
Molar ratio TiO2:ZrO2:HfO2:Nb2O5:WO3:Ta2O5: C=1-1.5:1-1.5:1-1.5:0.25-0.5:0.5-
1.0:1-1.5:3.0-6.0, the carbide powder solid solubility prepared under the molar ratio are high.
TiO in raw material2、ZrO2、HfO2、Nb2O5、WO3、Ta2O5Purity >=99.9%, partial size be 2 ± 0.5 μm；Carbon black
Purity >=99%.
The preparation method of the high entropy carbide powder of superhigh temperature of the present invention, steps are as follows:
(1) all raw materials are mixed using the method for wet-mixing, and dry, obtains mixed raw material；
(2) mixed raw material is placed in graphite furnace, is warming up to 1650-2000 DEG C, kept the temperature 0.5-4h, ground after cooling
Mill, obtains the high entropy carbide powder of superhigh temperature.
Wet-mixing condition in step (1) are as follows: using distilled water as medium, revolving speed 100-300r/min, time 12-
48h.Raw material can be made mixedly more uniform using wet-mixing.
Drying temperature is 40-120 DEG C in step (1), drying time 24-72h.
Atmosphere in step (2) in graphite furnace is the argon gas of vacuum or flowing.Using vacuum or the argon atmosphere of flowing
Carbothermic reduction reaction is carried out, solves the problems, such as that carbide diffusion coefficient is low, it is difficult to form multicomponent solid solution.
The heating rate of step (2) is 10-20 DEG C/min.
The reaction process of step (2) high temperature carbothermic reduction reaction is as follows:
TiO2+3C→TiC+2CO (1)
ZrO2+3C→ZrC+2CO (2)
HfO2+3C→HfC+2CO (3)
Nb2O5+7C→2NbC+5CO (4)
WO3+4C→WC+3CO (5)
Ta2O5+7C→TaC+5CO (6)
0.2TiC+0.2ZrC+0.2Hf+0.1NbC+0.1WC+0.2TaC→(Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2)C (7)。
Compared with prior art, the invention has the following beneficial effects:
(1) present invention uses TiO2、ZrO2、HfO2、Nb2O5、WO3、Ta2O5It is raw material with carbon black, raw material sources are wide, price
It is low, it is lower with metal carbides cost of material than pure metal powder raw material；
(2) present invention protects lower pyrocarbon heat by vacuum or argon gas from transition metal oxide and carbon black raw material
Reduction reaction synthesis obtains the high entropy carbide (Ti of superhigh temperature0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder, equipment requirement is low, instead
Mild condition is answered, process is simple, can be obtained the high entropy carbide powder of superhigh temperature of high-purity by being once heated at high temperature；
(3) present invention is using the carbothermic reduction reaction in the argon gas of vacuum or flowing, solve carbide diffusion coefficient it is low,
Form the problem of multicomponent solid solution hardly possible, the high entropy carbide (Ti of the superhigh temperature of preparation0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder
Crystallite dimension is small, thermal conductivity is low, and solid solubility is high, exists without impurity phase；High-temperature stability is good, both can be used as superhigh temperature it is anti-every
Heating integrated coating material can be used as the framework material of superhigh temperature porous material again.
Detailed description of the invention
Fig. 1 is the high entropy carbide (Ti of superhigh temperature prepared by the embodiment of the present invention 10.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder
The x-ray diffraction pattern of body；
Fig. 2 is the high entropy carbide (Ti of superhigh temperature prepared by the embodiment of the present invention 30.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder
The transmission electron microscope photo of body.
Specific embodiment
The present invention will be further described with reference to embodiments, but protection scope of the present invention is not limited only to this.
Embodiment 1
By raw material TiO2、ZrO2、HfO2、Nb2O5、WO3、Ta2O5With carbon black example TiO in molar ratio2ZrO2:HfO2:Nb2O5:
WO3:Ta2O5: C=1:1:1:0.25:0.5:1:4 weighing is subsequently placed in zirconium oxide mixing tank, distilled water is added, uses zirconium oxide
Ball mixes 48h under 100r/min revolving speed, then does uniformly mixed raw material under 80 DEG C of steady temperature in drying box
Raw material powder after drying process is put into graphite crucible, is added in Vacuum graphite oven with the heating rate of 10 DEG C/min by dry 72h
Heat keeps the temperature 2h, cools to room temperature with the furnace, grinding resulting powder is the high entropy carbide of superhigh temperature to 1800 DEG C
(Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder.
The X-ray diffraction spectrogram of the powder of preparation is as shown in Figure 1, it can be seen from the figure that through X-ray diffraction analytical table
Bright is the pure high entropy carbide (Ti of superhigh temperature0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder, without impurity phase.
Embodiment 2
By raw material TiO2、ZrO2、HfO2、Nb2O5、WO3、Ta2O5With carbon black example TiO in molar ratio2:ZrO2:HfO2:Nb2O5:
WO3:Ta2O5: C=1.2:1.2:1.2:0.4:0.7:1.2:4.5 weighing is subsequently placed in zirconium oxide mixing tank, distillation is added
Water mixes 36h with zirconia ball under 150r/min revolving speed, then by uniformly mixed raw material in drying box at 100 DEG C
Dry 64h, the raw material powder after drying process is put into graphite crucible, with 15 DEG C/min in argon gas graphite furnace under steady temperature
Heating rate be heated to 1980 DEG C, keep the temperature 1h, cool to room temperature with the furnace, grinding resulting powder is the high entropy carbonization of superhigh temperature
Object (Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder.
The transmission electron microscope picture of the powder of preparation is as shown in Fig. 2, it can be seen from the figure that be shown to be brilliant through transmission electron microscope analysis
The tiny high entropy carbide (Ti of superhigh temperature of grain0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder, 100-300 nanometers of crystallite dimension.
Embodiment 3
By raw material TiO2、ZrO2、HfO2、Nb2O5、WO3、Ta2O5With carbon black example TiO in molar ratio2:ZrO2:HfO2:Nb2O5:
WO3:Ta2O5: C=1.5:1.5:1.5:0.4:0.75:1.5:6 weighing is subsequently placed in zirconium oxide mixing tank, distilled water is added,
40h is mixed under 120r/min revolving speed with zirconia ball, it is then that uniformly mixed raw material is constant at 120 DEG C in drying box
At a temperature of it is dry for 24 hours, the raw material powder after drying process is put into graphite crucible, with the liter of 15 DEG C/min in argon gas graphite furnace
Warm rate is heated to 1900 DEG C, keeps the temperature 1.5h, cools to room temperature with the furnace, grinding resulting powder is the high entropy carbide of superhigh temperature
(Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder.
The powder of preparation is sintered through 2200 DEG C of plasma discharging, obtains the high entropy carbide ceramics of superhigh temperature
(Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C block materials, the relative densities of block materials is 96%, Vickers hardness 28GPa,
Thermal conductivity is 5.9W/mK.
Embodiment 4
By raw material TiO2、ZrO2、HfO2、Nb2O5、WO3、Ta2O5With carbon black example TiO in molar ratio2:ZrO2:HfO2:Nb2O5:
WO3:Ta2O5: C=1:1:1:0.25:0.5:1:3 weighing is subsequently placed in zirconium oxide mixing tank, distilled water is added, uses zirconium oxide
Ball mixes for 24 hours under 200r/min revolving speed, then does uniformly mixed raw material under 40 DEG C of steady temperature in drying box
Raw material powder after drying process is put into graphite crucible, is added in argon gas graphite furnace with the heating rate of 10 DEG C/min by dry 72h
Heat keeps the temperature 4h, cools to room temperature with the furnace, grinding resulting powder is the high entropy carbide of superhigh temperature to 1650 DEG C
(Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C powder.
The powder of preparation is obtained into the high entropy carbide ceramics of superhigh temperature after thermal spraying
(Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C coating, do not occur in thermal spray process to aoxidize and decompose, coating density 94%, heat
Conductance is 4.8W/m.K.
Claims (8)
1. a kind of high entropy carbide powder of superhigh temperature, it is characterised in that: chemical formula is (Ti0.2Zr0.2Hf0.2Nb0.1W0.1Ta0.2) C,
Using TiO2、ZrO2、HfO2、Nb2O5、WO3、Ta2O5It is raw material with carbon black, passes through wet-mixing and high temperature carbothermic reduction reaction system
It is standby to obtain.
2. the high entropy carbide powder of superhigh temperature according to claim 1, it is characterised in that: the molar ratio of raw material is TiO2:
ZrO2:HfO2:Nb2O5:WO3:Ta2O5: C=1-1.5:1-1.5:1-1.5:0.25-0.5:0.5-1.0:1-1.5:3.0-6.0.
3. the high entropy carbide powder of superhigh temperature according to claim 1, it is characterised in that: TiO in raw material2、ZrO2、HfO2、
Nb2O5、WO3、Ta2O5Purity >=99.9%, partial size be 2 ± 0.5 μm；Purity >=99% of carbon black.
4. a kind of preparation method of the high entropy carbide powder of the described in any item superhigh temperature of claim 1-3, it is characterised in that: step
It is rapid as follows:
(1) all raw materials are mixed using the method for wet-mixing, and dry, obtains mixed raw material；
(2) mixed raw material is placed in graphite furnace, is warming up to 1650-2000 DEG C, kept the temperature 0.5-4h, ground, obtained after cooling
To the high entropy carbide powder of superhigh temperature.
5. the preparation method of the high entropy carbide powder of superhigh temperature according to claim 4, it is characterised in that: in step (1)
Wet-mixing condition are as follows: using distilled water as medium, revolving speed 100-300r/min, time 12-48h.
6. the preparation method of the high entropy carbide powder of superhigh temperature according to claim 4, it is characterised in that: in step (1)
Drying temperature is 40-120 DEG C, drying time 24-72h.
7. the preparation method of the high entropy carbide powder of superhigh temperature according to claim 4, it is characterised in that: in step (2)
Atmosphere in graphite furnace is the argon gas of vacuum or flowing.
8. the preparation method of the high entropy carbide powder of superhigh temperature according to claim 4, it is characterised in that: step (2)
Heating rate is 10-20 DEG C/min.
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| CN201910411748.3A CN110078512A (en) | 2019-05-17 | 2019-05-17 | High entropy carbide powder of superhigh temperature and preparation method thereof |
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| CN111254376A (en) * | 2020-03-15 | 2020-06-09 | 河北工业大学 | Preparation method of high-entropy ceramic composite coating |
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| CN113045332A (en) * | 2021-02-08 | 2021-06-29 | 中国科学院金属研究所 | Ultrahigh-porosity high-entropy carbide ultrahigh-temperature ceramic and preparation method thereof |
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| CN114180965A (en) * | 2021-12-27 | 2022-03-15 | 安徽工业大学 | High-entropy carbide nano powder material with high sphericity and high activity, and preparation method and application thereof |
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| DE102019127518A1 (en) * | 2019-10-11 | 2021-04-15 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | CARBIDE METALS AND METHOD FOR PRODUCING THEM |
| DE102019127518A8 (en) * | 2019-10-11 | 2021-06-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | CARBIDE METALS AND THE METHOD OF MANUFACTURING THEM |
| CN111410536A (en) * | 2020-03-06 | 2020-07-14 | 中国科学院上海硅酸盐研究所 | Method for preparing compact (HfZrTaNbTi) C high-entropy ceramic sintered body by normal-pressure sintering |
| CN111254376A (en) * | 2020-03-15 | 2020-06-09 | 河北工业大学 | Preparation method of high-entropy ceramic composite coating |
| CN111533559A (en) * | 2020-03-30 | 2020-08-14 | 东华大学 | Carbon-deficiency type high-entropy transition metal carbide ceramic material and preparation method thereof |
| CN111732436A (en) * | 2020-06-18 | 2020-10-02 | 山东合创明业精细陶瓷有限公司 | Easy-to-sinter titanium and tungsten co-doped zirconium carbide powder and preparation method thereof |
| CN111995400B (en) * | 2020-09-10 | 2021-07-20 | 中国科学院兰州化学物理研究所 | High-entropy ceramic material with excellent tribological property and preparation method thereof |
| CN111995400A (en) * | 2020-09-10 | 2020-11-27 | 中国科学院兰州化学物理研究所 | High-entropy ceramic material with excellent tribological property and preparation method thereof |
| CN112341199A (en) * | 2020-10-22 | 2021-02-09 | 航天材料及工艺研究所 | High-entropy wave-absorbing carbide ceramic powder material, preparation method and application thereof |
| CN112441837A (en) * | 2020-12-09 | 2021-03-05 | 安徽工业大学 | High-performance (VNbTaMoW) C high-entropy carbide ceramic and preparation method thereof |
| RU2762897C1 (en) * | 2020-12-22 | 2021-12-23 | федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский политехнический университет Петра Великого" (ФГАОУ ВО "СПбПУ") | Method for obtaining carbide powder of a high-entropy alloy with a spherical particle shape |
| CN112851352A (en) * | 2021-01-27 | 2021-05-28 | 陕西科技大学 | Ultrahigh-temperature high-entropy carbide powder and preparation method thereof |
| CN113045332A (en) * | 2021-02-08 | 2021-06-29 | 中国科学院金属研究所 | Ultrahigh-porosity high-entropy carbide ultrahigh-temperature ceramic and preparation method thereof |
| CN113045332B (en) * | 2021-02-08 | 2022-05-31 | 中国科学院金属研究所 | Ultrahigh-porosity high-entropy carbide ultrahigh-temperature ceramic and preparation method thereof |
| CN113387724A (en) * | 2021-06-10 | 2021-09-14 | 西北工业大学 | High-temperature-resistant long-life composite coating on surface of carbon/carbon composite material and preparation method thereof |
| CN113387724B (en) * | 2021-06-10 | 2022-09-02 | 西北工业大学 | High-temperature-resistant long-life composite coating on surface of carbon/carbon composite material and preparation method |
| CN113603490A (en) * | 2021-07-22 | 2021-11-05 | 中广核研究院有限公司 | High-entropy ceramic inert matrix dispersion fuel pellet and preparation method thereof |
| CN113620712A (en) * | 2021-08-13 | 2021-11-09 | 华南理工大学 | High-entropy carbide ceramic nano powder and preparation method and application thereof |
| CN113582696A (en) * | 2021-08-30 | 2021-11-02 | 郑州航空工业管理学院 | (ZrTiCoNb) C high-entropy carbide ceramic material and preparation method thereof |
| CN113788679A (en) * | 2021-09-14 | 2021-12-14 | 河海大学 | High-entropy carbide ceramic powder for deep sea environment and preparation method and application thereof |
| CN113788679B (en) * | 2021-09-14 | 2022-04-15 | 河海大学 | High-entropy carbide ceramic powder for deep sea environment and preparation method and application thereof |
| CN113880580A (en) * | 2021-11-12 | 2022-01-04 | 内蒙古工业大学 | High-entropy carbide ultra-high temperature ceramic powder and preparation method thereof |
| CN113880580B (en) * | 2021-11-12 | 2023-01-03 | 内蒙古工业大学 | High-entropy carbide ultra-high temperature ceramic powder and preparation method thereof |
| CN114180965A (en) * | 2021-12-27 | 2022-03-15 | 安徽工业大学 | High-entropy carbide nano powder material with high sphericity and high activity, and preparation method and application thereof |
| CN114180965B (en) * | 2021-12-27 | 2023-01-31 | 安徽工业大学 | High-entropy carbide nano powder material with high sphericity and high activity, and preparation method and application thereof |
| CN114853506A (en) * | 2022-03-30 | 2022-08-05 | 西北工业大学 | Carbon/carbon composite surface (HfZrTi) C 3 Medium-entropy carbide anti-ablation coating and preparation method thereof |
| CN114853506B (en) * | 2022-03-30 | 2023-11-10 | 西北工业大学 | Carbon/carbon composite surface (HfZrTi) C 3 Mid-entropy carbide anti-ablation coating and preparation method thereof |
| CN115368163A (en) * | 2022-08-11 | 2022-11-22 | 中国科学院金属研究所 | Ultra-light medium-entropy carbide ultra-high temperature heat insulation material and preparation method thereof |
| CN115536398A (en) * | 2022-10-13 | 2022-12-30 | 北方民族大学 | Method for preparing high-entropy nitride submicron powder by soft mechanical force chemical assisted nitride thermal reduction |
| CN115536398B (en) * | 2022-10-13 | 2023-03-14 | 北方民族大学 | Method for preparing high-entropy nitride submicron powder by soft mechanical force chemical assisted nitride thermal reduction |
| RU2806562C1 (en) * | 2022-12-09 | 2023-11-01 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | METHOD FOR PRODUCING HIGH ENTROPY CARBIDE TiNbZrHfTaC5 |
| CN117105664A (en) * | 2023-09-19 | 2023-11-24 | 北方民族大学 | High entropy carbide ceramic (MonbTaTiW) C 5 And a method for preparing the same |
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