CN107746281A - A kind of preparation method of superhigh temperature ceramics boride solid solution powder - Google Patents
A kind of preparation method of superhigh temperature ceramics boride solid solution powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 123
- 239000006104 solid solution Substances 0.000 title claims abstract description 56
- 239000000919 ceramic Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011812 mixed powder Substances 0.000 claims abstract description 69
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 34
- 229910003862 HfB2 Inorganic materials 0.000 claims abstract description 18
- 229910004533 TaB2 Inorganic materials 0.000 claims abstract description 18
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 12
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 229910007948 ZrB2 Inorganic materials 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 9
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 8
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 239000007787 solid Substances 0.000 abstract description 6
- 230000007246 mechanism Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 229910004217 TaSi2 Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000005388 borosilicate glass Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011214 refractory ceramic Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004474 Ta5Si3 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
- C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
- C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
- C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
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Abstract
A kind of preparation method of superhigh temperature ceramics boride solid solution powder, belong to the preparation method of boride solid solution powder.Weigh the single-phase boride ZrB of synthesis respectively first2、TaB2、HfB2The powder Deng needed for, then by Zr：Ta、Hf：Ta or Zr：Hf mol ratio is respectively from the single-phase boride ZrB of synthesis2、TaB2、HfB2Corresponding powder is weighed in required powder and is made into mixed powder, is finally heat-treated by superhigh temperature and carries out carbothermic reduction reaction synthesis superhigh temperature ceramics boride solid solution ZrxTa1‑xB2、HfxTa1‑xB2Or HfxZr1‑xB2Powder.Solid solution atomic molar ratio is regulated and controled by the regulation and control to each component content in mixed powder, realize and the solid solubility and microstructure of boride solid solution are control effectively, laid a solid foundation so as to for the potential oxidation protection ability of superhigh temperature ceramics boride solid solution and preventing mechanism can be made full use of, expand its application in extreme circumstances.The present invention is wide with raw material sources, and cost is relatively low, and preparation technology is simple, is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of boride solid solution powder, more particularly to a kind of superhigh temperature ceramics boride
The preparation method of solid solution powder.
Background technology
Superhigh temperature ceramics boride ZrB2、TaB2、HfB2Etc. being a kind of structural ceramics material that may apply in extreme environment
Material, it possesses high-melting-point (3245 DEG C), highly thermally conductive, high conductance, preferable chemical stability and oxidation protection power, higher ratio longevity
Numerous excellent properties such as life, cause the very big concern of researcher, and it turns into rocket engine, atmosphere reenters and supersonic speed
The candidate material of the extreme environments such as flight.Due to superhigh temperature ceramics boride ZrB2、TaB2、HfB2Deng having similar crystal
Structure, all it is hexagonal crystal system, and the atomic radius of Hf atoms, Zr atoms and Ta atoms is very close, is respectivelyWithTherefore, very likely formed in the case that two kinds of borides coexist in preparation process continuous
Type solid solution ZrxTa1-xB2、HfxTa1-xB2Or HfxZr1-xB2。
" D.Sciti, L.Silvestroni, G.Celotti, et al.Sintering the and mechanical of document 1
properties of ZrB2-TaSi2and HfB2-TaSi2ceramic composites[J].Journal of the
American Cerimic Society,2008,91(10):3285-3291 ", which is reported, is preparing ZrB2-TaSi2And HfB2-
TaSi2During ceramic composite, solid solution (Zr, Ta) B is found2With solid solution (Hf, Ta) B2Formation, research finds solid solution
Mutually presence in the composite, significantly improve the room temperature characteristic and elevated temperature strength of matrix.
In actual use, the constituent element as composite typically coexists in superhigh temperature ceramics boride simultaneously with SiC, relies on
The formation of borosilicate glass and effectively protection, present great potentiality.Due to superhigh temperature ceramics boride ZrB2、TaB2、
HfB2Deng oxide there is higher fusing point, such as ZrO2(fusing point is 2680 DEG C), Ta2O5(fusing point is 1872 DEG C), HfO2It is (molten
Point is 2850 DEG C), they often exist in borosilicate glass with incompatible phase, can not only increase borosilicate glass
Viscosity can also reduce oxygen diffusion rates and suppress B in glass so as to reduce its evaporation rate2O3Vapour pressure, so as to increase
The oxidation resistance of borosilicate glass is added.And superhigh temperature ceramics boride solid solution has two kinds of transiting group metal elements concurrently,
So as to the synergy by multicomponent transition group metallic oxide, great potentiality are shown.
" I.G.Talmy, J.A.Zaykoski, M.M.Opeka.High-temperature the chemistry and of document 2
oxidation of ZrB2ceramics containing SiC,Si3N4,Ta5Si3,and TaSi2[J].Journal of
the American Cerimic Society,2008,91(7):2250-7 " reports multicomponent transition group metallic oxide
In the presence of, be hopeful to rely on cooperative effect, further lifted composite oxidation protection effect.
" Xuanru Ren, Hejun Li, Qiangang Fu, the Kezhi Li.Ta of document 3xHf1-xB2-SiC
multiphase oxidation protective coating for SiC-coated carbon/carbon
composites.Corrosion Science,2014,87:479-488 " is reported due to TaxHf1-xB2The formation of solid solution,
TaxHf1-xB2- SiC coatings have had TaB concurrently2And HfB2Excellent specific property, show and compare TaB2- SiC coatings and HfB2- SiC coatings
More preferably oxidation protection ability.
" Xuanru Ren, Hejun Li, Kezhi Li, the Qiangang Fu.Oxidation protection of document 4
of ultra-high temperature ceramic ZrxTa1-xB2-SiC/SiC coating prepared by in-
situ reaction method for carbon/carbon composites.Journal of the European
Ceramic Society,2015,35[3]:897-907 " reports ZrxTa1-xB2Modified silicon substrate coating can be effective in 1773K
Protection carbon/carbon base body is up to 1412h, exceeds well over ZrB2Or TaB2550h that modified silicon substrate coating is under equal conditions provided and
300h protection, this is mainly due to (Zr, Ta) B2Zr, Ta two kinds of magnesium-yttrium-transition metals coexist in solid solution, and it is in oxidation
Silica, B are generated in coating surface2O3、ZrO2, tantalum pentoxide and ZrSiO4Etc. multiple oxide, so as to generate Zr-Ta-
Si-O complex phase glassy layers, show and compare ZrB2Or TaB2Modified silicon substrate coating more preferably oxidation protection power.
As can be seen here, in face of complicated harsh wide temperature range application environment, compared to the superhigh temperature ceramics boronation of one-component
Thing material, the advantage of superhigh temperature ceramics boride solid solution composite material are also more obvious.However, due to superhigh temperature ceramics boronation
Thing solid solution ZrxTa1-xB2、HfxTa1-xB2Or HfxZr1-xB2Mutually include two kinds of transiting group metal elements (Zr, Ta), (Hf, Ta) or
(Zr, Hf), the two solid solution degree difference will cause in solid solution phase double transition race metal ion ratio ripple within the specific limits
It is dynamic, thing phase, granularity and the pattern of boride solid solution can be not only influenceed, its oxidation protection mechanism and protection effect can also be produced
Considerable influence.Want to make full use of the excellent specific property of superhigh temperature ceramics boride solid solution phase, the continuous ceramic boron of elevating ultrahigh temperature
The oxidant protection under high temperature ability of compound material to its solid solubility and microstructure, it is necessary to control effectively.Therefore, excess of export is developed
Refractory ceramics boride solid-solution powder, just has great importance.
Although superhigh temperature ceramics boride solid solution has huge application potential, but at present almost not on its powder
The report of body synthesis.Among numerous methods for preparing superhigh temperature ceramics boride powder, carbothermic method is that a kind of industry is raw
The common method of superhigh temperature ceramics boride is produced, it has raw material sources wide, and cost is relatively low, simple technological process and other advantages, non-
Often it is adapted to prepare superhigh temperature ceramics boride solid solution powder.
In view of the oxidation protection behavior that superhigh temperature ceramics boride solid solution is potential, develops superhigh temperature ceramics boronation
Thing solid solution ZrxTa1-xB2、HfxTa1-xB2Or HfxZr1-xB2Powder, for superhigh temperature ceramics boride answering in extreme circumstances
With having great importance.
The content of the invention
Wide the invention aims to provide a kind of raw material sources, cost is relatively low, and powder preparation process is simply super
The preparation method of refractory ceramics boride solid solution powder, realizes and its solid solubility and microstructure is control effectively, so as to
Reach the oxidation protection ability and mechanism for making full use of superhigh temperature ceramics boride solid solution potential, expand it in extreme ring
Application under border.
The object of the present invention is achieved like this：Weigh the single-phase boride ZrB of synthesis respectively first2、TaB2、HfB2It is required
Powder, then by Zr：Ta、Hf：Ta or Zr：Hf mol ratio is respectively from the single-phase boride ZrB of synthesis2、TaB2、HfB2Required powder
In weigh corresponding powder and be made into mixed powder, be finally heat-treated by superhigh temperature and carry out carbothermic reduction reaction synthesis superhigh temperature pottery
Porcelain boride solid solution ZrxTa1-xB2、HfxTa1-xB2Or HfxZr1-xB2Powder.
Concretely comprise the following steps：
Step 1：By Ta2O5Powder, C powder and B2O3Powder is according to 1：11：2~4 molar ratio weighs synthesis TaB2Required mixing
Powder a；
Step 2：By ZrO2Powder, C powder and B2O3Powder is according to 1：5：1~2 molar ratio weighs synthesis ZrB2Required mixed powder
Expect b；
Step 3：By HfO2Powder, C powder and B2O3Powder is according to 1：5：1~2 molar ratio weighs synthesis HfB2Required mixed powder
Expect c；
Step 4：By load weighted mixed powder a, b, c are respectively charged into ball grinder, then ball grinder is positioned over into ball mill
Upper carry out ball milling, the mixed powder A, B, C being uniformly mixed after ball milling sieving drying later；
Step 5：Optional 2 kinds of mixed powders from uniform mixed mixed powder A, B, C, according to 0.05~0.95
Zr：Ta、Hf：Ta or Zr：Hf ratios weigh corresponding powder A*, B* or C* from mixed powder A, B or C, further mix
To mixed powder x, wherein x=A*+B*, A*+C* or B*+C*；
Step 6：Load weighted mixed powder x is fitted into ball grinder, then ball grinder is positioned on ball mill and carries out ball
Mill, the mixed powder X being uniformly mixed after ball milling sieving drying later；
Step 7：Mixed uniformly mixed powder X is first placed into graphite crucible, places into superhigh temperature heat-treatment furnace, enters
Row heat treatment, obtains superhigh temperature ceramics boride solid solution powder.
Further, in step 4 and 6, powder ball milling is arranged to dry or wet ball milling, ratio of grinding media to material 3:1~15:1,
Ball grinding cylinder rotating speed is 200~800 turns/min, and Ball-milling Time is 0.5~24h.
Further, in step 7, the Technology for Heating Processing of mixed powder is protected for argon gas atmosphere, and heating rate is 3~20
DEG C/min, heat treatment temperature is 1300~2000 DEG C, and soaking time is 0.5~5h.
Further, in step 7, the superhigh temperature ceramics boride solid solution powder of synthesis is ZrxTa1-xB2、HfxTa1-xB2
Or HfxZr1-xB2Powder.
Described powdered carbon is graphite powder.
Beneficial effect and advantage：As a result of such scheme, realize to superhigh temperature ceramics boride solid solution
ZrxTa1-xB2、HfxTa1-xB2Or HfxZr1-xB2Effective control of the solid solubility and microstructure of powder, so as to control solid solution
Thing phase, granularity and the pattern of body.
In view of the oxidation protection behavior that superhigh temperature ceramics boride solid solution is potential, develops solid solubility and microcosmic knot
The controllable superhigh temperature ceramics boride solid solution Zr of structurexTa1-xB2、HfxTa1-xB2Or HfxZr1-xB2Powder, it can make full use of super
The potential oxidation protection ability of refractory ceramics boride solid solution and preventing mechanism, realize and expand it in extreme circumstances
Using.And the present invention has the advantages of raw material sources are wide, and cost is relatively low, and powder preparation process is simple, is adapted to industrialization
Production.
Brief description of the drawings：
Fig. 1 is the Zr prepared using the present invention0.5Ta0.5B2The XRD diffraction patterns of powder.
Fig. 2 is the Zr prepared using the present invention0.5Ta0.5B2The SEM photograph of powder.
Fig. 3 is the Hf prepared using the present invention0.8Ta0.2B2The XRD diffraction patterns of powder.
Fig. 4 is the Hf prepared using the present invention0.8Ta0.2B2The SEM photograph of powder.
Fig. 5 is the Hf prepared using the present invention0.6Zr 0.4B2The XRD diffraction patterns of powder.
Fig. 6 is the Hf prepared using the present invention0.6Zr 0.4B2The SEM photograph of powder.
Embodiment
The preparation method of the superhigh temperature ceramics boride solid solution powder of the present invention, weigh the single-phase boronation of synthesis respectively first
Thing ZrB2、TaB2、HfB2Required powder, then by Zr：Ta、Hf：Ta or Zr：Hf mol ratio is respectively from the single-phase boride of synthesis
ZrB2、TaB2、HfB2Corresponding powder is weighed in required powder and is made into mixed powder, is finally heat-treated by superhigh temperature and carries out carbon
Thermal reduction reaction synthesis superhigh temperature ceramics boride solid solution XB2Powder, wherein X=(Zr, Ta), (Hf, Ta) or (Zr, Hf),
That is superhigh temperature ceramics boride solid solution ZrxTa1-xB2、HfxTa1-xB2Or HfxZr1-xB2Powder.
Concretely comprise the following steps：
Step 1：By Ta2O5Powder, C powder and B2O3Powder is according to 1：11：2~4 molar ratio weighs synthesis TaB2Required mixing
Powder a；
Step 2：By ZrO2Powder, C powder and B2O3Powder is according to 1：5：1~2 molar ratio weighs synthesis ZrB2Required mixed powder
Expect b；
Step 3：By HfO2Powder, C powder and B2O3Powder is according to 1：5：1~2 molar ratio weighs synthesis HfB2Required mixed powder
Expect c；
Step 4：By load weighted mixed powder a, b, c are respectively charged into ball grinder, then ball grinder is positioned over into ball mill
Upper carry out ball milling, the mixed powder A, B, C being uniformly mixed after ball milling sieving drying later；
Step 5：Optional 2 kinds of mixed powders from uniform mixed mixed powder A, B, C, according to 0.05~0.95
Zr：Ta、Hf：Ta or Zr：Hf ratios weigh corresponding powder A*, B* or C* from mixed powder A, B or C, further mix
To mixed powder x, wherein x=A*+B*, A*+C* or B*+C*；
Step 6：Load weighted mixed powder x is fitted into ball grinder, then ball grinder is positioned on ball mill and carries out ball
Mill, the mixed powder X being uniformly mixed after ball milling sieving drying later；
Step 7：Mixed uniformly mixed powder X is first placed into graphite crucible, places into superhigh temperature heat-treatment furnace, enters
Row heat treatment, obtains superhigh temperature ceramics boride solid solution powder.
Further, in step 4 and 6, powder ball milling is arranged to dry or wet ball milling, ratio of grinding media to material 3:1~15:1,
Ball grinding cylinder rotating speed is 200~800 turns/min, and Ball-milling Time is 0.5~24h.
Further, in step 7, the Technology for Heating Processing of mixed powder is protected for argon gas atmosphere, and heating rate is 3~20
DEG C/min, heat treatment temperature is 1300~2000 DEG C, and soaking time is 0.5~5h.
Further, in step 7, the superhigh temperature ceramics boride solid solution powder of synthesis is ZrxTa1-xB2、HfxTa1-xB2
Or HfxZr1-xB2Powder.
Described powdered carbon is graphite powder.
The present invention is described in further detail with reference to the accompanying drawings and examples
Embodiment 1：
Step 1：By Ta2O5Powder, B2O3Powder and C powder are according to 1:2:11 molar ratio weighs synthesis TaB2Required mixing
Powder a；
Step 2：By ZrO2Powder, B2O3Powder and C powder are according to 1:1:5 molar ratio weighs synthesis ZrB2Required mixing
Powder b；
Step 3：By HfO2Powder, B2O3Powder and C powder are according to 1:1:5 molar ratio weighs synthesis HfB2Required mixing
Powder c；
Step 4：By load weighted mixed powder a, b, c are respectively charged into ball grinder, then ball grinder is positioned over into ball mill
Upper progress dry or wet ball milling, ratio of grinding media to material 3:1, ball grinding cylinder rotating speed is 300 turns/min, Ball-milling Time 6h, after ball milling
The mixed powder A, B, C being uniformly mixed after sieving drying.
Step 5：From uniform mixed mixed powder A, two kinds of mixed powders of A and B are selected in B, C, according to 1:1 Zr：
Ta mol ratios weigh corresponding powder from mixed powder A and B, are further mixed to get mixed powder x.
Step 6：Load weighted mixed powder x is fitted into ball grinder, then ball grinder is positioned on ball mill and done
Method or wet ball grinding, ratio of grinding media to material 3:1, ball grinding cylinder rotating speed is 300 turns/min, Ball-milling Time 2h, and ball milling sieves drying later
The mixed powder X being uniformly mixed afterwards.
Step 7：Mixed uniformly mixed powder X is first placed into graphite crucible, placed into superhigh temperature heat-treatment furnace, is led to
Enter argon gas atmosphere protection, and with 5 DEG C/min heating rates by superhigh temperature heat-treatment furnace be warming up to 1500 DEG C carry out carbon thermal reductions it is anti-
Should, 2h is incubated, obtains solid solution Zr0.5Ta0.5B2Powder.
Zr0.5Ta0.5B2The material phase analysis of powder is as shown in figure 1, its surface topography is as shown in Figure 2；
Embodiment 2：
Step 1：By Ta2O5Powder, B2O3Powder and C powder are according to 1:2.5:11 molar ratio weighs synthesis TaB2It is required mixed
Close powder a；
Step 2：By ZrO2Powder, B2O3Powder and C powder are according to 1:1.3:5 molar ratio weighs synthesis ZrB2It is required mixed
Close powder b；
Step 3：By HfO2Powder, B2O3Powder and C powder are according to 1:1.3:5 molar ratio weighs synthesis HfB2It is required mixed
Close powder c；
Step 4：By load weighted mixed powder a, b, c are respectively charged into ball grinder, then ball grinder is positioned over into ball mill
Upper progress dry or wet ball milling, ratio of grinding media to material 5:1, ball grinding cylinder rotating speed is 500 turns/min, Ball-milling Time 4h, after ball milling
The mixed powder A, B, C being uniformly mixed after sieving drying.
Step 5：From uniform mixed mixed powder A, two kinds of mixed powders of A and C are selected in B, C, according to 8:2 Hf：
Ta mol ratios weigh corresponding powder from mixed powder A and C, are further mixed to get mixed powder x.
Step 6：Load weighted mixed powder x is fitted into ball grinder, then ball grinder is positioned on ball mill and done
Method or wet ball grinding, ratio of grinding media to material 5:1, ball grinding cylinder rotating speed is 500 turns/min, Ball-milling Time 4h, and ball milling sieves drying later
The mixed powder X being uniformly mixed afterwards.
Step 7：Mixed uniformly mixed powder X is first placed into graphite crucible, placed into superhigh temperature heat-treatment furnace, is led to
Enter argon gas atmosphere protection, and with 10 DEG C/min heating rates by superhigh temperature heat-treatment furnace be warming up to 1600 DEG C carry out carbon thermal reductions it is anti-
Should, 2h is incubated, obtains solid solution Hf0.8Ta0.2B2Powder.
Hf0.8Ta0.2B2The material phase analysis of powder is as shown in figure 3, its surface topography is as shown in Figure 4；
Embodiment 3：
Step 1：By Ta2O5Powder, B2O3Powder and C powder are according to 1:3:11 molar ratio weighs synthesis TaB2Required mixing
Powder a；
Step 2：By ZrO2Powder, B2O3Powder and C powder are according to 1:1.5:5 molar ratio weighs synthesis ZrB2It is required mixed
Close powder b；
Step 3：By HfO2Powder, B2O3Powder and C powder are according to 1:1.5:5 molar ratio weighs synthesis HfB2It is required mixed
Close powder c；
Step 4：By load weighted mixed powder a, b, c are respectively charged into ball grinder, then ball grinder is positioned over into ball mill
Upper progress dry or wet ball milling, ratio of grinding media to material 7:1, ball grinding cylinder rotating speed is 700 turns/min, Ball-milling Time 2h, after ball milling
The mixed powder A, B, C being uniformly mixed after sieving drying.
Step 5：From uniform mixed mixed powder A, two kinds of mixed powders of B and C are selected in B, C, according to 6:4 Hf：
Zr mol ratios weigh corresponding powder from mixed powder B and C, are further mixed to get mixed powder x.
Step 6：Load weighted mixed powder x is fitted into ball grinder, then ball grinder is positioned on ball mill and done
Method or wet ball grinding, ratio of grinding media to material 5:1, ball grinding cylinder rotating speed is 700 turns/min, Ball-milling Time 2h, and ball milling sieves drying later
The mixed powder X being uniformly mixed afterwards.
Step 7：Mixed uniformly mixed powder X is first placed into graphite crucible, placed into superhigh temperature heat-treatment furnace, is led to
Enter argon gas atmosphere protection, and with 10 DEG C/min heating rates by superhigh temperature heat-treatment furnace be warming up to 1800 DEG C carry out carbon thermal reductions it is anti-
Should, 2h is incubated, obtains solid solution Hf0.6Zr 0.4B2Powder.
Hf0.6Zr 0.4B2The material phase analysis of powder is as shown in figure 5, its surface topography is as shown in Figure 6；
It is described above, it is only the preferable embodiment of the present invention, therefore the scope that the present invention is implemented can not be implemented according to more than
Example is defined, and the equivalent modification carried out according to the scope of the claims of the present invention and description and change, is still contained for the present invention
The scope of lid.
Claims (7)
- A kind of 1. preparation method of superhigh temperature ceramics boride solid solution powder, it is characterised in that：It is single to weigh synthesis respectively first Boride phase ZrB2、TaB2、HfB2Required powder, then by Zr：Ta、Hf：Ta or Zr：Hf mol ratio is respectively from the single-phase boron of synthesis Compound ZrB2、TaB2、HfB2Corresponding powder is weighed in required powder and is made into mixed powder, finally by superhigh temperature be heat-treated into Row carbothermic reduction reaction synthesis superhigh temperature ceramics boride solid solution ZrxTa1-xB2、HfxTa1-xB2Or HfxZr1-xB2Powder.
- A kind of 2. preparation method of superhigh temperature ceramics boride solid solution powder according to claim 1, it is characterised in that： Concretely comprise the following steps：Step 1：By Ta2O5Powder, C powder and B2O3Powder is according to 1：11：2 ~ 4 molar ratio weighs synthesis TaB2Required mixed powder a；Step 2：By ZrO2Powder, C powder and B2O3Powder is according to 1：5：1 ~ 2 molar ratio weighs synthesis ZrB2Required mixed powder b；Step 3：By HfO2Powder, C powder and B2O3Powder is according to 1：5：1 ~ 2 molar ratio weighs synthesis HfB2Required mixed powder c；Step 4：By load weighted mixed powder a, b, c are respectively charged into ball grinder, then that ball grinder is positioned over into ball mill is enterprising Row ball milling, the mixed powder A, B, C being uniformly mixed after ball milling sieving drying later；Step 5：Optional 2 kinds of mixed powders from uniform mixed mixed powder A, B, C, according to 0.05 ~ 0.95 Zr：Ta、 Hf：Ta or Zr：Hf ratios weigh corresponding powder A*, B* or C* from mixed powder A, B or C, are further mixed to get mixing Powder x, wherein x=A*+B*, A*+C* or B*+C*；Step 6：Load weighted mixed powder x is fitted into ball grinder, then ball grinder is positioned on ball mill and carries out ball milling, ball The mixed powder X being uniformly mixed after honed after sieving drying；Step 7：Mixed uniformly mixed powder X is first placed into graphite crucible, placed into superhigh temperature heat-treatment furnace, carries out heat Processing, obtains superhigh temperature ceramics boride solid solution powder.
- A kind of 3. preparation method of superhigh temperature ceramics boride solid solution powder according to claim 2, it is characterised in that： In step 1-3, initial feed used in mixed powder a, b and c is Ta2O5Powder, ZrO2Powder, HfO2Powder, C powder and B2O3Powder.
- A kind of 4. preparation method of superhigh temperature ceramics boride solid solution powder according to claim 2, it is characterised in that： In step 4 and 6, powder ball milling is arranged to dry or wet ball milling, ratio of grinding media to material 3:1~15:1, ball grinding cylinder rotating speed be 200 ~ 800 turns/min, Ball-milling Time is 0.5 ~ 24h.
- A kind of 5. preparation method of superhigh temperature ceramics boride solid solution powder according to claim 2, it is characterised in that： In step 7, the Technology for Heating Processing of mixed powder is protected for argon gas atmosphere, and heating rate is 3 ~ 20 DEG C/min, and heat treatment temperature is 1300 ~ 2000 DEG C, soaking time is 0.5 ~ 5h.
- A kind of 6. preparation method of superhigh temperature ceramics boride solid solution powder according to claim 2, it is characterised in that： In step 7, the superhigh temperature ceramics boride solid solution powder of synthesis is ZrxTa1-xB2、HfxTa1-xB2Or HfxZr1-xB2。
- A kind of 7. preparation method of superhigh temperature ceramics boride solid solution powder according to claim 2, it is characterised in that： Described C powder is powdered carbon or graphite powder.
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| CN108455623A (en) * | 2018-05-29 | 2018-08-28 | 广东工业大学 | A kind of ultra fine transition metal boride powder and its preparation method and application |
| CN109534825A (en) * | 2019-01-16 | 2019-03-29 | 电子科技大学 | A kind of ZrB of fabricated in situ inertia glass phase cladding2And preparation method thereof |
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| CN109534825A (en) * | 2019-01-16 | 2019-03-29 | 电子科技大学 | A kind of ZrB of fabricated in situ inertia glass phase cladding2And preparation method thereof |
| CN109665848B (en) * | 2019-01-16 | 2021-07-09 | 广东工业大学 | Ultrahigh-temperature SiC-HfB2Composite ceramic and preparation method and application thereof |
| WO2020212692A1 (en) * | 2019-04-15 | 2020-10-22 | The University Of Birmingham | Hafnium and zirconium diboride containing ceramics |
| CN110079775A (en) * | 2019-04-30 | 2019-08-02 | 江苏理工学院 | A kind of molybdenum alloy surface MoSi2The preparation method of coating |
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| CN116253569A (en) * | 2023-01-04 | 2023-06-13 | 河南省科学院碳基复合材料研究院 | Preparation of (Hf, ta) B by using self-propagating auxiliary solid solution doping technology 2 -MoSi 2 Method for preparing oxygen-resistant coating |
| CN116253569B (en) * | 2023-01-04 | 2023-12-01 | 河南省科学院碳基复合材料研究院 | Preparation of (Hf, ta) B by using self-propagating auxiliary solid solution doping technology 2 -MoSi 2 Method for preparing oxygen-resistant coating |
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