CN106588019A - Preparation method of Hf<x>Ta<1-x>C alloy precursor and Hf<x>Ta<1-x>C alloy prepared therefrom - Google Patents
Preparation method of Hf<x>Ta<1-x>C alloy precursor and Hf<x>Ta<1-x>C alloy prepared therefrom Download PDFInfo
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Abstract
The invention relates to a preparation method of an Hf<x>Ta<1-x>C alloy precursor and Hf<x>Ta<1-x>C alloy prepared therefrom. The method includes the following steps: (1) dispersing hafnium tetrachloride in a solvent and dropwise adding a mixture of monohydric alcohol and triethylamine, after the mixture is all added, performing heating reflux and filtering the solution to obtain a hafnium alkoxide solution; (2) dispersing tantalum pentachloride in a solvent and dropwise adding a mixture of monohydric alcohol and triethylamine, after the mixture is all added, performing heating reflux and filtering the solution to obtain a tantalum alkoxide solution; (3) mixing the hafnium alkoxide solution and the tantalum alkoxide solution, dropwise adding a chelating agent, and then performing heating reflux, dropwise adding a mixture of water and monohydric alcohol, after the mixture is all added, performing reflux and pressure reduced distillation to obtain a hafnium and tantalum polymer precursor; and (4) mixing the hafnium and tantalum polymer precursor with allyl phenolic aldehyde to prepare the Hf-Ta alloy precursor. The Hf<x>Ta<1-x>C alloy precursor has good solubility and long stable storage time and can be used as a fiber-reinforced ceramic based composite material substrate.
Description
Technical field
The present invention relates to the preparation method of superhigh temperature ceramics presoma and ceramics, more particularly to HfxTa1-xC alloy presoma
And the preparation method of alloy.
Background technology
Refractory metal ceramics are super dystectic class materials, and with fabulous resistance to ablation, scour resistance, and infusibility is golden
Category carbide is covered in material surface in oxidizing atmosphere due to generating oxide with oxygen reaction, and protection materials are not by further oxygen
Change, thus and with high-temperature oxidation resistance.
Typical refractory carbide is ZrC, HfC, TaC etc., 3880 DEG C of the fusing point of wherein TaC, and TaC's is strongly covalent
The strong connected mode of key-metal makes it that good anti-oxidant, heat shock resistance and chemical resistance of concrete performance is presented；3890 DEG C of HfC fusing points,
It is fusing point highest binary metal compound, its chemical stability is good, non-oxidizability is strong, and hardness is up to 33GPa.TaC and HfC two
Person's crystal formation is identical, and lattice constant is close to, and the two can occur solid solution reaction and form solid solution Hf with arbitrary proportionxTa1-xC, and solid solution
The ultra-temperature mechanical performance of body, oxidative attack can be better than carbide ceramics such as HfC, TaC.Because it possesses supertherm
Some characteristics of material, therefore it is referred to as hafnium tantalum alloy, its essence is hafnium tantalum carbon solid solution alloy, wherein precise stoichiometry ratio
Hf0.2Ta0.8Higher than the fusing point of simple carbide (HfC, TaC), its fusing point is up to 4215K to the fusing point of C, is known to the current mankind
Fusing point highest material.
In general, metal material possesses ductility, and typical ceramic material is (such as SiC, ZrC, ZrB2, HfC etc.) no
Possess ductility, but document report Hf0.2Ta0.8C hafnium tantalum alloys have certain ductility, i.e., the hafnium tantalum alloy material character is situated between
Between metal material and ceramic material.It can be seen that, hafnium tantalum carbon solid solution alloy not only has higher fusing point, also combines TaC
With the advantage of HfC ceramics, with the outstanding anti-oxidant erosion ability of superhigh temperature resistant, can be used for hypersonic aircraft thermal protection system
System, and rocket engine larynx shirt portion part of new generation.
As transition metal carbides of the TaC with HfC with numerous IV B with VB races, NaCl type face-centred cubic structures are respectively provided with,
Thus in principle both are capable of achieving to dissolve each other, that is, form TaxHf1-xCySolid solution.However, should due to preparing difficult and extreme temperature
With the difficult problem evaluated, the research work of the domestic material is few, has mainly carried out theoretical calculation work, calculating simulation
Hf0.2Ta0.8The dystectic origin causes of formation of C, in the world to HfxTa1-xThe research work of C hafnium tantalum alloy materials is also considerably less.It is existing to grind
Studying carefully work is prepared using high temperature powder metallurgy method, is carried out at high temperature under high pressure specifically by HfC, TaC powder solid
It is prepared by molten reaction.[the Fischer JJ.Ceram Bull 1964,43 such as Fisher:183-5.] with the TaC of 1.5 μm of particle diameter and
HfC powder is raw material, and at 2538 DEG C, pressurize, insulation a period of time, are prepared for Hf under the conditions of 48MPa0.2Ta0.8C compact blocks.
In order to reduce [the Farzin Arianpour et al.International such as sintering temperature, Farzin Arianpour
Journal of Refractory Metals and Hard Materials, 2016,56,1-7] with MoSi2Help for sintering
Agent, 2000 DEG C of vacuum SPS sintering are carried out to TaC powders and HfC powder, are prepared for relative density and are up to 99%
Ta0.8Hf0.2C blocks, and test its hardness (18-19GPa) and fracture toughness (4-4.3MPam1/2).Ghaffari etc.
[Ghaffari, S.A.et al, Journal of European Ceramic Society, 2013,33,1479-1484] with
MoSi2And TaSi2For sintering aid, SPS sintering is carried out to TaC powders and HfC powder, be prepared for a series of HfxTa1-xC (x=
0.1,0.2,0.3) alloy, and its hardness and fracture toughness are have studied, find with Hf/Ta increasing proportions, the hardness of solid solution
Become big with fracture toughness, and the species of sintering aid also has large effect to the performance of material.
In a word, in the prior art, HfxTa1-xC alloy is occurred at high temperature under high pressure admittedly using TaC and HfC powder mostly
Prepared by molten reaction, higher to equipment requirement, although adding MoSi2Or TaSi2Solid solubility temperature can be effectively reduced Deng auxiliary agent, but
It is that sintering aid exists in the material equivalent to impurity, and auxiliary agent often participates in solid solution reaction and enters HfxTa1-xThe crystalline substance of C alloy
In lattice structure, the lattice parameter for making alloy changes, and these heteroatomic introducings can most probably substantially reduce the molten of solid solution
Point.Therefore, how high-purity Hf is prepared using simple methodxTa1-xC alloy material is a difficult problem for prior art urgent need to resolve
One of.
CN104961465A discloses a kind of Ta-Hf-C ternary ceramics and preparation method thereof.The Ta-Hf-C ternary ceramics are
The continuous single phase solid solution ceramic powders of Ta-Hf-C.Preparation method includes：(1) precursor solution is prepared：Metal inorganic salt is mixed
Thing is added in the first solvent, and the metal inorganic salt mixture is containing Ta5+Inorganic salts and containing Hf4+Inorganic salts, contained
Tantalum hafnium solution；Carbon source is added in the second solvent, agitated dissolving obtains carbon source solution；By the solution of hafnium containing tantalum and described
Carbon source solution mix, it is agitated after, obtain precursor solution；(2) solvent heat treatment：Step (1) gained precursor solution is entered
Row solvent heat treatment, the treatment temperature is 150 DEG C～250 DEG C, and the process time is 5h～24h, obtains intermediate product；
(3) it is dried：Drying steps (2) gained intermediate product, obtains desciccate；(4) high-temperature calcination：Step (3) gained is dried and is produced
Thing carries out high-temperature calcination, and with the heating rate of 20 DEG C/min～100 DEG C/min 1600 DEG C～1800 DEG C are warming up to, and insulation 1h～
3h, last along with the furnace cooling obtains Ta-Hf-C ternary ceramics.The invention make use of the reaction between Hf-Ta elements and C sources to make element
Molecular level distribution is reached, therefore, its temperature for obtaining alloy is substantially reduced.But due to the reaction between hafnium tantalum solution and carbon source not
Controllable, it can only obtain the undissolvable presoma of powder, and presoma does not possess processability, it is impossible to carries out composite, apply
Layer or fiber preparation, and react need carry out under high pressure (solvent heat is exactly reaction under high pressure), condition is harsher.
In view of this it is special to propose the present invention.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided a kind of HfxTa1-xC alloy forerunner
The preparation method of body and its Hf for obtainingxTa1-xC alloy.The method preparation condition is gentle, low for equipment requirements；And using this
Hafnium tantalum alloy presoma dissolubility synthesized by bright method is excellent, can be miscible with arbitrary proportion with alcohols solvent, storage stability
Excellent (room temperature preservation after 1 year viscosity B coefficent be less than 10%), can use as composite matrix resin, can be used to preparing fine
Dimension strengthens hafnium tantalum alloy ceramic matric composite, also has potential application in terms of prepares coating and ceramic fibre.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of HfxTa1-xThe preparation method of C alloy presoma, wherein, described preparation method is comprised the following steps：
1) preparation of hafnium alkoxide：Hafnium tetrachloride is disperseed to instill the mixture of monohydric alcohol and triethylamine in a solvent, is added dropwise
Finish and be heated to reflux, filter, obtain hafnium alkoxide solution；
2) preparation of tantalum alkoxide：Tantalic chloride is disperseed to instill the mixture of monohydric alcohol and triethylamine in a solvent, is added dropwise
Finish and be heated to reflux, filter, obtain tantalum alkoxide solution；
3) cohydrolysis prepares hafnium tantalum polymer precursor：Hafnium alkoxide and tantalum alkoxide solution are mixed, chelating agent is added dropwise, dripped off
Backflow；Then the mixed liquor of water and monohydric alcohol is added dropwise again, backflow is dripped off, and vacuum distillation obtains hafnium tantalum polymer precursor；
4)HfxTa1-xThe preparation of C hafnium tantalum alloy presomas：Hafnium tantalum polymer precursor and the mixing of pi-allyl phenolic aldehyde is equal
It is even, hafnium tantalum alloy presoma is obtained, the quality of wherein pi-allyl phenolic aldehyde is hafnium and tantalum element quality in hafnium tantalum polymer precursor
0.4 times of sum.
CN104961465A discloses a kind of Ta-Hf-C ternary ceramics and preparation method thereof, although this process employs Hf-
Reaction between Ta elements and C sources makes element reach molecular level distribution so as to which the temperature for obtaining alloy is substantially reduced.But due to hafnium tantalum
Reaction between solution and carbon source is uncontrollable, and it can only obtain powder, undissolvable presoma, and presoma does not possess processing
Property, it is impossible to carry out the preparation of composite, coating or fiber, and react needs to enter under high pressure (solvent heat is exactly reaction under high pressure)
OK, condition is harsher.
Preparation method of the present invention is simple, it is not necessary to carry out under high pressure.More importantly using the preparation method of the present invention
Synthesized HfxTa1-xNot only dissolubility is excellent for C hafnium tantalum alloys presoma, can be miscible with arbitrary proportion with alcohols solvent, solvable
Any one solvent or several in ethanol, normal propyl alcohol, isopropanol, glycol monoethyl ether, ethylene glycol monoethyl ether, toluene, dimethylbenzene
Plant the mixed solvent of solvent；And it has excellent storage stability (room temperature preservation after 1 year viscosity B coefficent be less than 10%), can conduct
Composite matrix resin is used, and can be used to prepare fiber reinforcement hafnium tantalum alloy ceramic matric composite, in prepares coating and pottery
Porcelain fiber aspect also has potential application.
In above-mentioned preparation method, wherein, step 1) in, control temperature is -5 during the mixture of instillation monohydric alcohol and triethylamine
In the range of～10 DEG C, the time is heated to reflux for 1～5h.
Step 2) in, control temperature is heated back in the range of -5～10 DEG C during the mixture of instillation monohydric alcohol and triethylamine
The stream time is 1～5h.
Step 3) in, when chelating agent is added dropwise control temperature in the range of room temperature～80 DEG C, drip off return time for 0.5～
5h；Control temperature drips off the mixed liquor of water and monohydric alcohol in the range of room temperature～80 DEG C during the mixed liquor of dropwise addition water and monohydric alcohol
Afterwards return time is 1～5h.
Further, step 3) described in hafnium alkoxide, tantalum alkoxide, chelating agent, the mol ratio of water and monohydric alcohol be X：(1-
X)：(0.5～2.0)：(0.9～1.5)：(4～8), wherein 0<X<1.
Step 1) described in hafnium tetrachloride, solvent, the mol ratio of monohydric alcohol and triethylamine be 1：(30～50)：(4.5～
7)：(4～5)；Step 2) described in tantalic chloride, solvent, monohydric alcohol and triethylamine mol ratio be 1：(40～60)：(6～
9)：(5～6).
Step 4) in, the quality of pi-allyl phenolic aldehyde is 0.4 of hafnium and tantalum element quality sum in hafnium tantalum polymer precursor
Times.
Pi-allyl phenolic aldehyde is the allylation phenolic resin synthesized with phenolic resin using allyl chloride, including O- pi-allyls
Phenolic resin and C- allyl phenol urea formaldehydes, introduce unsaturated group, using unsaturated double-bond in thermoplastic phenolic resin
Solidification is realized in addition, makes to be crosslinked between molecule by the addition reaction between unsaturated group, is improved it and was being solidified
Cheng Zhonghui produces the problem of lower-molecular substance, affects insulation and other performances of product, improves the processability of material.
In the present invention, pi-allyl phenolic aldehyde can adopt the method synthesis of prior art obtain, such as using this research group it
Front article " the Thermosetting Resin System Based on Novolak and Bismaleimide for having delivered
for Resin-Transfer Molding”【Journal of Applied Polymer Science,83,1651(2002)】
Middle reported method synthesis.The allylation degree of the allyl phenol urea formaldehyde used by the present invention is more than 85%.
Step 1) and step 2) described in solvent be n-hexane, normal heptane, toluene, dimethylbenzene, petroleum ether, tert-butyl group first
One kind in ether, glycol dimethyl ether or ethylene glycol diethyl ether.
Step 1), step 2) and step 3) described in monohydric alcohol be normal propyl alcohol, isopropanol, n-butanol, isobutanol, second two
One kind in alcohol monomethyl ether or ethylene glycol monoethyl ether.
Step 3) described in chelating agent be one or two mixture in acetylacetone,2,4-pentanedione or ethyl acetoacetate.
The present invention also provides a kind of HfxTa1-xC alloy, wherein, described HfxTa1-xC alloy is by using of the present invention
Preparation method prepare HfxTa1-xC hafnium tantalum alloys presoma solidify, then vacuum or argon gas protection under, in temperature 1600-
Crack at 2000 DEG C, obtain final product described HfxTa1-xC alloy.
In the prior art, HfxTa1-xC alloy is that solid solution reaction occurs at high temperature under high pressure using TaC and HfC powder mostly
Prepare, it is higher to equipment requirement, although adding MoSi2Or TaSi2Solid solubility temperature can be effectively reduced Deng auxiliary agent, but is sintered
Auxiliary agent exists in the material equivalent to impurity, and auxiliary agent often participates in solid solution reaction and enters HfxTa1-xThe lattice structure of C alloy
In, the lattice parameter for making alloy changes, so that obtained alloy purity is not high, and these heteroatomic introducings also pole
The fusing point of solid solution may be substantially reduced.
Hf of the present inventionxTa1-xOnly need to be by Hf obtained in the present invention in the preparation process of C alloyxTa1-xC hafnium tantalum alloy presomas
Solidification, then under vacuum or argon gas protection, the cracking at temperature 1600-2000 DEG C, obtains final product；MoSi need not be added2Or
TaSi2Deng auxiliary agent, the introducing of impurity is fundamentally avoided, improve the purity of the alloy of gained.
In the present invention, described is cured as HfxTa1-xC hafnium tantalum alloy presomas are 100 DEG C in baking oven, 150 DEG C, 200
DEG C, 250 DEG C of each insulation 2h are allowed to solidify.
After above-mentioned technical proposal, the present invention has the advantages that compared with prior art.
The present invention first synthesizes the polymer containing hafnium tantalum element using precursor process, then by multiple with carbon source pi-allyl phenolic aldehyde
With hafnium tantalum alloy presoma is prepared for, hafnium tantalum alloy nano-powder can be formed after presoma negative pressure or the lower cracking of normal pressure Ar protections,
Preparation condition is gentle, low for equipment requirements；And the hafnium tantalum alloy presoma dissolubility synthesized by the present invention is excellent, storage stability
Excellent (room temperature preservation after 1 year viscosity B coefficent be less than 10%), can use as composite matrix resin, therefore can be used to make
Standby fiber reinforcement hafnium tantalum alloy ceramic matric composite, also has potential application in terms of prepares coating and ceramic fibre.
The specific embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Description of the drawings
Fig. 1 is the Hf of the gained of the embodiment of the present invention 10.2Ta0.8The XRD of C alloy；
Fig. 2 is the Hf of the gained of the embodiment of the present invention 10.2Ta0.8The SEM figures of C alloy；
Fig. 3 is the Hf of the gained of the embodiment of the present invention 20.8Ta0.2The XRD of C alloy.
It should be noted that these accompanying drawings and word description are not intended as limiting the design model of the present invention by any way
Enclose, but be that those skilled in the art illustrate idea of the invention by reference to specific embodiment.
Specific embodiment
To make purpose, technical scheme and the advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in embodiment is clearly and completely described, following examples be used for illustrate the present invention, but
It is not limited to the scope of the present invention.
Embodiment 1
Hf in the present embodiment0.2Ta0.8C presomas synthesize according to the following steps：
1. the preparation of hafnium alkoxide：1mol hafnium tetrachlorides are dispersed in 30mol n-hexanes, -5 DEG C of instillation 4.5mol normal propyl alcohols
With the mixture of 4mol triethylamines, completion of dropping is heated to reflux 1h, filters, and obtains hafnium alkoxide solution；
2. the preparation of tantalum alkoxide：4mol tantalic chlorides are dispersed in 240mol glycol dimethyl ethers, 10 DEG C of instillation 24mol
The mixture of isopropanol and 24mol triethylamines, completion of dropping is heated to reflux 5h, filters, and obtains tantalum alkoxide solution；
3. cohydrolysis prepares hafnium tantalum polymer precursor：Hafnium alkoxide, the mixing of tantalum alkoxide solution that step 1 and 2 are obtained, room
Temperature is lower to be added dropwise 2.5mol acetylacetone,2,4-pentanediones, drips off backflow 0.5h, is down to room temperature, instills the mixing of 4.5mol water and 20mol normal propyl alcohols
Liquid, drips off backflow 1h, and vacuum distillation obtains hafnium tantalum polymer precursor；
4.Hf0.2Ta0.8The preparation of C hafnium tantalum alloy presomas：The hafnium tantalum polymer that step 3 is obtained and 360.9g pi-allyls
Phenolic aldehyde is well mixed, and obtains hafnium tantalum alloy presoma.
By presoma 100 DEG C in baking oven, 150 DEG C, 200 DEG C, 250 DEG C of each insulation 2h be allowed to solidify, be subsequently placed in graphite
In stove, heating in vacuum obtains Hf to 1600 DEG C0.2Ta0.8C alloy, the Hf of inductive coupling plasma emission spectrum beta alloy is first
Cellulose content is 18.3wt%, and Ta constituent contents are 74.9wt%, and C element content is 6.2wt% in carbon and sulfur analytical instrument beta alloy,
Corresponding element mol ratio Hf:Ta:C=1:4.04:5.04, close theoretical ratio.Its XRD is as shown in figure 1, the SEM figures of sample
As shown in Figure 2.
Embodiment 2
Hf in the present embodiment0.8Ta0.2C presomas synthesize according to the following steps：
1. the preparation of hafnium alkoxide：4mol hafnium tetrachlorides are dispersed in 200mol normal heptanes, 10 DEG C of instillation 28mol isopropanols
With the mixture of 20mol triethylamines, completion of dropping is heated to reflux 5h, filters, and obtains hafnium alkoxide solution；
2. the preparation of tantalum alkoxide：1mol tantalic chlorides are dispersed in 40mol dimethylbenzene, -5 DEG C instill 9mol n-butanols and
The mixture of 5mol triethylamines, completion of dropping is heated to reflux 1h, filters, and obtains tantalum alkoxide solution；
3. cohydrolysis prepares hafnium tantalum polymer precursor：Hafnium alkoxide, the mixing of tantalum alkoxide solution that step 1 and 2 are obtained, 80
DEG C 5mol ethyl acetoacetates are added dropwise, drip off backflow 5h, be down to 50 DEG C, instill the mixed liquor of 7.5mol water and 40mol n-butanols,
Backflow 5h is dripped off, vacuum distillation obtains hafnium tantalum polymer precursor；
4.Hf0.8Ta0.2The preparation of C hafnium tantalum alloy presomas：The hafnium tantalum polymer that step 3 is obtained and 358.0g pi-allyls
Phenolic aldehyde is well mixed, and obtains hafnium tantalum alloy presoma.
By presoma 100 DEG C in baking oven, 150 DEG C, 200 DEG C, 250 DEG C of each insulation 2h be allowed to solidify, be subsequently placed in graphite
In stove, 2000 DEG C are heated under Ar gas shieldeds, obtain Hf0.8Ta0.2C alloy, inductive coupling plasma emission spectrum beta alloy
Hf constituent contents be 74.8wt%, Ta constituent contents be 18.9wt%, C element content is in carbon and sulfur analytical instrument beta alloy
6.3wt%, corresponding element mol ratio Hf:Ta:C=4.01:1:5.03, close theoretical ratio.Its XRD is as shown in Figure 3.
Embodiment 3
Hf in the present embodiment0.5Ta0.5C presomas synthesize according to the following steps：
1. the preparation of hafnium alkoxide：1mol hafnium tetrachlorides are dispersed in 40mol toluene, 5 DEG C instill 5mol isobutanols and
The mixture of 4.5mol triethylamines, completion of dropping is heated to reflux 2h, filters, and obtains hafnium alkoxide solution；
2. the preparation of tantalum alkoxide：1mol tantalic chlorides are dispersed in 50mol glycol dimethyl ethers, 3 DEG C of instillation 7mol second
The mixture of glycol monomethyl ether and 5.5mol triethylamines, completion of dropping is heated to reflux 3h, filters, and obtains tantalum alkoxide solution；
3. cohydrolysis prepares hafnium tantalum polymer precursor：Hafnium alkoxide, the mixing of tantalum alkoxide solution that step 1 and 2 are obtained, room
Temperature is lower to be added dropwise 3mol acetylacetone,2,4-pentanediones, drips off backflow 2h, 80 DEG C, instills the mixed liquor of 2.0mol water and the positive isobutanol alcohol of 12mol, drop
Complete backflow 2h, vacuum distillation obtains hafnium tantalum polymer precursor；
4.Hf0.5Ta0.5The preparation of C hafnium tantalum alloy presomas：The hafnium tantalum polymer that step 3 is obtained and 143.8g pi-allyls
Phenolic aldehyde is well mixed, and obtains hafnium tantalum alloy presoma.
By presoma 100 DEG C in baking oven, 150 DEG C, 200 DEG C, 250 DEG C of each insulation 2h be allowed to solidify, be subsequently placed in graphite
In stove, heating in vacuum obtains Hf to 1800 DEG C0.5Ta0.5C alloy, the Hf of inductive coupling plasma emission spectrum beta alloy is first
Cellulose content is 46.7wt%, and Ta constituent contents are 47.3wt%, and C element content is 6.3wt% in carbon and sulfur analytical instrument beta alloy,
Corresponding element mol ratio Hf:Ta:C=1:1:2.1, close theoretical ratio.
Embodiment 4
Hf in the present embodiment0.2Ta0.8C presomas synthesize according to the following steps：
1. the preparation of hafnium alkoxide：1mol hafnium tetrachlorides are dispersed in into 30mol petroleum ethers, 0 DEG C of instillation 4.5mol ethylene glycol list
The mixture of ether and 4mol triethylamines, completion of dropping is heated to reflux 1h, filters, and obtains hafnium alkoxide solution；
2. the preparation of tantalum alkoxide：4mol tantalic chlorides are dispersed in 240mol t-butyl methyl ethers, 0 DEG C of instillation 24mol second
The mixture of glycol monomethyl ether and 24mol triethylamines, completion of dropping is heated to reflux 5h, filters, and obtains tantalum alkoxide solution；
3. cohydrolysis prepares hafnium tantalum polymer precursor：Hafnium alkoxide, the mixing of tantalum alkoxide solution that step 1 and 2 are obtained, room
Temperature is lower to be added dropwise 10mol ethyl acetoacetates, drips off backflow 0.5h, is down to room temperature, instills the mixing of 5mol water and 20mol normal propyl alcohols
Liquid, drips off backflow 1h, and vacuum distillation obtains hafnium tantalum polymer precursor；
4.Hf0.2Ta0.8The preparation of C hafnium tantalum alloy presomas：The hafnium tantalum polymer that step 3 is obtained and 360.9g pi-allyls
Phenolic aldehyde is well mixed, and obtains hafnium tantalum alloy presoma.
By presoma 100 DEG C in baking oven, 150 DEG C, 200 DEG C, 250 DEG C of each insulation 2h be allowed to solidify, be subsequently placed in graphite
In stove, 1900 DEG C are heated under Ar protections, obtain Hf0.2Ta0.8C alloy, inductive coupling plasma emission spectrum test result with
Embodiment 1 is similar.
Test example 1, storage stability test
This test example has investigated the storage stability of hafnium tantalum alloy presoma obtained in the embodiment of the present invention.
Test method：The initial viscosity and room temperature for determining the hafnium tantalum alloy presoma obtained by the embodiment of the present invention respectively is protected
The viscosity after 1 year is deposited, its rate of change in viscosity is investigated.
Result of the test is as shown in table 1 below：
Table 1, storage stability investigates result
| Hafnium tantalum alloy presoma | Initial viscosity (PaS) | Room temperature preservation viscosity (PaS) after 1 year | Rate of change in viscosity |
| Embodiment 1 | 30 | 31 | 3.33% |
| Embodiment 2 | 32 | 34 | 6.25% |
| Embodiment 3 | 31 | 33 | 6.45% |
| Embodiment 4 | 29 | 29.5 | 1.72% |
Can be seen that from above-mentioned result of the test and be stored at room temperature using hafnium tantalum alloy presoma obtained in the method for the present invention
Viscosity B coefficent is less than 10% after 1 year, shows that its storage stability is good.
The above is only presently preferred embodiments of the present invention, and any pro forma restriction is not made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, the technology people of any familiar present invention
Member in the range of without departing from technical solution of the present invention, when using the technology contents of above-mentioned prompting make it is a little change or be modified to
The Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, according to the technical spirit pair of the present invention
Any simple modification, equivalent variations and modification that above example is made, still fall within the range of the present invention program.
Claims (10)
1. a kind of HfxTa1-xThe preparation method of C alloy presoma, it is characterised in that described preparation method is comprised the following steps：
1) preparation of hafnium alkoxide：Hafnium tetrachloride is disperseed to instill the mixture of monohydric alcohol and triethylamine, completion of dropping in a solvent
It is heated to reflux, filters, obtains hafnium alkoxide solution；
2) preparation of tantalum alkoxide：Tantalic chloride is disperseed to instill the mixture of monohydric alcohol and triethylamine, completion of dropping in a solvent
It is heated to reflux, filters, obtains tantalum alkoxide solution；
3) cohydrolysis prepares hafnium tantalum polymer precursor：Hafnium alkoxide and tantalum alkoxide solution are mixed, chelating agent is added dropwise, dripped off back
Stream；Then the mixed liquor of water and monohydric alcohol is added dropwise again, backflow is dripped off, and vacuum distillation obtains hafnium tantalum polymer precursor；
4)HfxTa1-xThe preparation of C hafnium tantalum alloy presomas：Hafnium tantalum polymer precursor and pi-allyl phenolic aldehyde are well mixed, are obtained
Hafnium tantalum alloy presoma.
2. preparation method as claimed in claim 1, it is characterised in that step 1) in, instill the mixing of monohydric alcohol and triethylamine
Temperature is controlled during thing in the range of -5～10 DEG C, the time is heated to reflux for 1～5h.
3. preparation method as claimed in claim 1, it is characterised in that step 2) in, instill the mixing of monohydric alcohol and triethylamine
Temperature is controlled during thing in the range of -5～10 DEG C, the time is heated to reflux for 1～5h.
4. preparation method as claimed in claim 1, it is characterised in that step 3) in, control temperature is in room when chelating agent is added dropwise
In the range of temperature～80 DEG C, return time is dripped off for 0.5～5h；When the mixed liquor of water and monohydric alcohol is added dropwise control temperature room temperature～
In the range of 80 DEG C, it is 1～5h to drip off return time after the mixed liquor of water and monohydric alcohol.
5. the preparation method as described in claim 1-4 any one, it is characterised in that step 3) described in hafnium alkoxide, tantalum
The mol ratio of alkoxide, chelating agent, water and monohydric alcohol is X：(1-X)：(0.5～2.0)：(0.9～1.5)：(4～8), wherein 0<X<
1。
6. preparation method as claimed in claim 5, it is characterised in that step 1) described in hafnium tetrachloride, solvent, monohydric alcohol
It is 1 with the mol ratio of triethylamine：(30～50)：(4.5～7)：(4～5)；Step 2) described in tantalic chloride, solvent, unitary
Alcohol is 1 with triethylamine mol ratio：(40～60)：(6～9)：(5～6).
7. the preparation method as described in claim 1-6 any one, it is characterised in that step 4) in, the matter of pi-allyl phenolic aldehyde
Amount is 0.4 times of hafnium and tantalum element quality sum in hafnium tantalum polymer precursor.
8. the preparation method as described in claim 1-7 any one, it is characterised in that step 1) and step 2) described in it is molten
Agent is in n-hexane, normal heptane, toluene, dimethylbenzene, petroleum ether, t-butyl methyl ether, glycol dimethyl ether or ethylene glycol diethyl ether
One kind；Step 1), step 2) and step 3) described in monohydric alcohol be normal propyl alcohol, isopropanol, n-butanol, isobutanol, second two
One kind in alcohol monomethyl ether or ethylene glycol monoethyl ether.
9. the preparation method as described in claim 1-8 any one, it is characterised in that step 3) described in chelating agent for
One or two mixture in acetylacetone,2,4-pentanedione or ethyl acetoacetate.
10. a kind of HfxTa1-xC alloy, it is characterised in that described HfxTa1-xC alloy is by using any one of claim 1-9
Hf prepared by described preparation methodxTa1-xC hafnium tantalum alloys presoma solidify, then vacuum or argon gas protection under, in temperature
Crack at 1600-2000 DEG C, obtain final product described HfxTa1-xC alloy.
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