CN104671245B - Preparation method of hafnium carbide nano-powder - Google Patents
Preparation method of hafnium carbide nano-powder Download PDFInfo
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Abstract
The invention relates to a preparation method of hafnium carbide nano-powder. The preparation method comprises steps as follows: 1) preparing hafnium-containing gel: dissolving HfCl4 and C6H8O7*H2O in deionized water, continuously stirring the mixture to fully dissolve the HfCl4 and the C6H8O7*H2O, then adjusting the pH value to range from 2 to 3 with an ammonia water solution, and performing magnetic stirring treatment at the constant temperature of 60-80 DEG C to obtain the hafnium-containing gel; 2) preparing precursor powder: placing the hafnium-containing gel into a low-temperature tube furnace for heat treatment to obtain the precursor powder; (3) preparing the hafnium carbide nano-powder: placing the precursor powder into a planetary ball-milling tank for high-energy ball milling, and placing obtained powder into a discharge plasma sintering furnace for reactions to obtain the hafnium carbide nano-powder. The method is simple in technology, low in energy consumption, good in repeatability and good in industrial prospect, and the prepared hafnium carbide nano-powder is a high-activity nano-scale product with hafnium carbide distributed evenly and is even in crystal grain distribution, high in purity and good in degree of crystallinity.
Description
Technical field
The invention belongs to ceramic powder preparing technical field, it is related to a kind of preparation method of hafnium carbide nano-powder.
Background technology
HfC is a kind of non-stoichiometric carbide that transition elements Hf is become with C-shaped, i.e. HfCx(0.5≤x≤1), it belongs to
In a kind of superhard material.According to JCPDF card, its structure is the face-centred cubic structure of NaCl type, and its lattice paprmeter is
0.46375nm, Hf atom forms close cubic lattice, and C atom is in the octahedral interstice position of lattice.HfC crystal is to lean on
Bond length is that the atom key carbon hafnium of a/2 is bonded, and this key is symmetrical.Adjacent between (111) face in HfC crystal structure
Metallic atom face and C atomic plane between be by strong bond energy atom key bonded, strong bond must be destroyed during sliding, therefore
Sliding is extremely difficult, macroscopically shows ultrahigh hardness characteristic, and its Morse hardness is 9M.Must break during due to HfC crystal melting
The atom key of bad high degree of symmetry distribution, thus very difficult, thus macroscopically showing superelevation melting point property, and the atom of HfC
The bond energy E of keyA=87.2163kJ/mol, therefore up to 3900 DEG C of the fusing point of HfC.Its specific insulation is 1.95 × 10-4Ω·cm
(2900 DEG C), thermal coefficient of expansion is 6.73 × 10-6/ DEG C, its oxidizing temperature is 400 DEG C.Because its high rigidity and high-melting-point cause
The great interest of researcher, is the key positions such as cutting tool, aircraft nose cone, the leading edge of a wing, numbers of hot-side engine both at home and abroad
Or the most promising superhigh temperature candidate material of part, have not in fields such as nuclear rocket power plant, nuclear reactor, space ships
Appreciable application prospect.
At present, few to the method report of hafnium carbide synthesis both at home and abroad, the method for report mainly has：(1) directly carbon heat is gone back
Former method, generally requires and could react more than 1900 DEG C, high energy consumption, high to equipment requirement, and the particle size growing out is big,
Need to assist by additive method and reduce reaction temperature.(2) liquid precursor conversion method, Wang Yanbin et al. is with HfOCl2, HCl,
HNO3, normal propyl alcohol, isopropanol, ethanol, acetylacetone,2,4-pentanedione etc. be raw material, prepared under the conditions of 1500 DEG C granule-morphology differ,
Size is in tens nanometers to hundreds of nanometer of HfC powder, and particle has serious agglomeration.(3) chemical vapor deposition
Method, Karlsruhe GmbH et al., with HfCl4With appropriate CH4And H2For raw material, using vapour deposition process, in the substrate of atresia
Upper successfully prepare hafnium carbide.The method reaction time is long, and power consumption is high, and yield is little.
Content of the invention
The technical problem to be solved is for deficiency above-mentioned present in prior art, provides a kind of colloidal sol to coagulate
Glue method combines the method that being rapidly heated of discharge plasma sintering stove (SPS)-falling temperature technique prepares hafnium carbide nano-powder, energy consumption
Low, yield is high, and the hafnium carbide nano-powder purity prepared is high, better crystallinity degree.
For solving above-mentioned technical problem, the technical scheme that the present invention provides is：
There is provided a kind of preparation method of hafnium carbide nano-powder, its step is as follows：
1) prepare gel containing hafnium：By HfCl4And C6H8O7·H2O is dissolved in deionized water, HfCl4Mass volume ratio with water is
0.20-0.25g/mL, wherein HfCl4And C6H8O7·H2O mol ratio is 1:0.5-1.5, and be stirred continuously and so that it is fully dissolved, so
Adjust pH to 2-3 with ammonia spirit afterwards, and magnetic agitation is processed under 60-80 DEG C of constant temperature, obtains gel containing hafnium；
2) prepare precursor powder：By step 1) gained gel containing hafnium puts in low temperature tube furnace heat treatment, under room temperature with
The ramp of 3-10 DEG C/min is to 800 DEG C, and is incubated 1-3h, and atmosphere is Ar, obtains precursor powder；
3) prepare hafnium carbide nano-powder：By step 2) gained precursor powder puts into and carries out high energy in planetary type ball-milling tank
Ball milling, gained powder is placed in discharge plasma sintering furnace, under vacuum, with the speed of 200-400 DEG C/min under room temperature
Rate is warming up to 1500-1800 DEG C, is incubated 3-10min, then is cooled to room temperature with the speed of 100-200 DEG C/min and obtains hafnium carbide
Nano-powder.
Preferably, step 1) in HfCl4And C6H8O7·H2O mol ratio is 1:1.
By such scheme, step 1) described ammonia spirit mass concentration be 25%.
By such scheme, step 1) described magnetic agitation speed be 60-80r/min, the magnetic agitation time be 30-60min.
By such scheme, step 3) described high-energy-milling is：Planetary type ball-milling tank revolution rotating speed is 200-250r/
Min, rotation rotating speed is 400-500r/min, and Ball-milling Time is 1-3h.
By such scheme, step 3) described sintering process is：Under vacuum, with the speed of 300 DEG C/min under room temperature
It is warming up to 1600 DEG C, be incubated 5min, then the speed cooling with 200 DEG C/min.
(1) the beneficial effects of the present invention is：1st, the present invention combines low temperature tube annealing method by sol-gal process
Prepare precursor powder, then adopt high-energy-milling to pre-process precursor powder, so that C and Hf is fully contacted and be placed in discharging
Be rapidly heated-lower the temperature in plasma sintering stove sintering, hafnium carbide nano-powder is obtained at a lower temperature, the inventive method was both
The growth that reaction temperature is also beneficial to final product HfC nanocrystal, process is simple can be reduced, energy consumption is low, reproducible, have
Good industrialization prospect；2nd, the hafnium carbide nano-powder of present invention preparation is that the equally distributed High-activity nano-grade of carbon hafnium is other
Product, uniformly, purity is high, better crystallinity degree for crystal grain distribution.
Brief description
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the HfC nano-powder prepared by the embodiment of the present invention 1；
Fig. 2 is field emission scanning electron microscope (FESM) photo of the HfC nano-powder prepared by embodiment 1；
Fig. 3 is the low resolution map (Fig. 3 a) of the transmission electron microscope (TEM) of HfC nano-powder prepared by embodiment 1 and saturating
High-resolution collection of illustrative plates (Fig. 3 b) of radio mirror；
Fig. 4 is the Raman spectrogram of the HfC nano-powder prepared by embodiment 1；
Fig. 5 is the infared spectrum of the HfC nano-powder prepared by embodiment 1.
Specific embodiment
For making those skilled in the art more fully understand technical scheme, below in conjunction with the accompanying drawings the present invention is made into
One step describes in detail.
HfCl used by the embodiment of the present invention4Powder is that analysis is pure, and granularity is 200-300 mesh, and Citric Acid Mono is that analysis is pure,
Ammonia spirit concentration is 25wt%.
Embodiment 1
Weigh 15g HfCl4、9.84g C6H8O7·H2O(HfCl4And C6H8O7·H2O mol ratio is 1:1) put into 1000mL
In beaker, add 65mL deionized water, be stirred continuously with glass bar, make HfCl4And C6H8O7·H2O is substantially dissolved in deionized water
In, then add appropriate NH with buret3·H2The pH that O solution (mass concentration be 25%) adjusts solution is 2-3, and 80
Carry out magnetic agitation process, magnetic stirring speed is 60r/min, mixing time is 30min, obtains gel containing hafnium under DEG C constant temperature.
Hafnium gel will be contained it is placed in alumina crucible to put into and in low temperature tube furnace, be thermally treated resulting in precursor powder, annealing process will be room temperature
Under be raised to 800 DEG C with the programming rate of 4 DEG C/min, be incubated 2h, atmosphere be high-purity Ar, Ar flow be 0.5L/min.At annealing
The precursor powder obtaining after reason takes out, and puts in planetary type ball-milling tank, ball milling revolution 250r/min, rotation 500r/min, ball
Consume time as 3 hours.Ball milling material is taken out, is placed in graphite jig, put into synthesis, vacuum in discharge plasma sintering furnace
For 10Pa, with the ramp of 300 DEG C/min to 1600 DEG C under room temperature, temperature retention time is 5min, then the speed with 200 DEG C/min
It is cooled to room temperature, you can obtain grey HfC nano-powder 11.356g, product yield is 87.3%.
It is illustrated in figure 1 the XRD spectrum of embodiment of the present invention gained HfC nano-powder, as seen from the figure, X-ray diffraction peak
Match with HfC standard diffraction card PDF#65-8748.Diffraction maximum d value is 2.6650,2.3076,1.6322,1.3937,Place, corresponds respectively to (111), (200), (220), (311), (222) crystal face of hafnium carbide, by XRD each crystal face d value,
Calculating product lattice constant is a=0.4619nm, basically identical with standard card a=0.4621nm, shows that product is hafnium carbide.
It can be seen that diffraction maximum is very strong from XRD spectra, illustrate that product crystallinity is fine；Find there is not crystallization in diffraction maximum simultaneously
The diffraction maximum of other materials such as carbon, illustrates that product purity is very high.
It is illustrated in figure 2 the FESM photo of the present embodiment gained HfC nano-powder, as seen from the figure, powder granule size
150-350nm, average grain diameter 250nm, particle assumes irregularly shaped, even particle distribution, does not find obvious amorphous carbon
Exist.
It is illustrated in figure 3 the TEM picture of the HfC nano-powder prepared by the present embodiment, Fig. 3 a is HfC nano sized powder sample
TEM picture, as seen from the figure, powder granule size average grain diameter is in 250nm.Because Hf element belongs to heavy metal, so
Deep black back end is shown in TEM electromicroscopic photograph.Fig. 3 b is the HRTEM photo of sample, as seen from the figure, sample crystallization
Property good, interplanar distance is 0.268nm, corresponding to (111) crystal face of HfC crystal.
It is illustrated in figure 4 the Raman spectrogram of the HfC nano-powder prepared by the present embodiment, HfC also right and wrong similar with ZrC
, there is carbon room in stoichiometric proportion compound in HfC lattice, therefore may contain free carbon in the product, using Raman light
Spectrum is measured to free carbon, and in figure D peak and G peak it is known that containing free carbon in product, but D peak and G all ratios are shallower,
Illustrate that free carbon content is less.
It is illustrated in figure 5 the infared spectrum of the HfC nano-powder prepared by the present embodiment, in figure is observed that three ratios
Significantly absworption peak, is located at 3442,1635 and 1036cm respectively-1Place.Wherein 3442cm-1And 1635cm-1Absworption peak can be returned
Because of the vibration peak of-OH group in absorption water and H-O-H key, and it is located at 1036cm-1The absworption peak going out is due to Hf-C-O key
Vibration caused by.
The chemical composition analysis result of the HfC nano-powder prepared by the present embodiment is as follows：
Plasma emission spectrum (ICP) result shows, hafnium element mass percent is 90.05%, sulphur carbon analyzer result
Show, in sample, total carbon content is 6.08%, and free carbon content is 0.94%, and oxygen nitrogen analysis show that in sample, oxygen content is
1.27%.This absolutely proves, has the characteristics that high-purity, low oxygen content, low free carbon with the hafnium carbide of the method preparation.
Embodiment 2
Weigh 15g HfCl4、6.27g C6H8O7·H2O(HfCl4And C6H8O7·H2O mol ratio is 1:0.64) put into
In 1000mL beaker, add 60mL deionized water, be stirred continuously with glass bar, make HfCl4And C6H8O7·H2O is substantially dissolved in
In ionized water, then add appropriate NH with buret3·H2The pH that O solution adjusts solution is 2-3, and enters under 60 DEG C of constant temperature
Row magnetic agitation is processed, and magnetic stirring speed is 60r/min, and mixing time is 30min, obtains gel containing hafnium.Hafnium gel will be contained
Be placed in alumina crucible to put into and in low temperature tube furnace, be thermally treated resulting in precursor powder, annealing process be room temperature under with 3 DEG C/
The programming rate of min is raised to 800 DEG C, is incubated 1h, and atmosphere is high-purity Ar, and Ar flow is 0.5L/min.Obtain after annealing
Precursor powder take out, put in planetary type ball-milling tank, ball milling revolve round the sun 200r/min, rotation 400r/min, Ball-milling Time be 1
Hour.Ball milling material is taken out, is placed in graphite jig, put into synthesis in discharge plasma sintering furnace, vacuum is 10Pa, room
With the ramp of 200 DEG C/min to 1800 DEG C under temperature, temperature retention time is 10min, then is cooled to room with the speed of 100 DEG C/min
Temperature, you can obtain grey powder 8.657g.
Through XRD, FSEM and tem analysis, the present embodiment products therefrom comprises only a small amount of HfC, most of HfO2Not anti-
Should, in this explanation reactant, C content is very few, does not have can react HfO completely2, the average grain diameter of product is 600nm.Due to
During colloidal sol, the amount that citric acid adds is very few, leads to the carbon source of the presoma of production very few, and the carbon content of presoma is not enough, makes anti-
Should be not exclusively.
Embodiment 3
Weigh 15g HfCl4、14.7g C6H8O7·H2O(HfCl4And C6H8O7·H2O mol ratio is 1:1.5) put into
In 1000mL beaker, add 70mL deionized water, be stirred continuously with glass bar, make HfCl4And C6H8O7·H2O is substantially dissolved in
In ionized water, then add appropriate NH with buret3·H2The pH that O solution adjusts solution is 2-3, and enters under 80 DEG C of constant temperature
Row magnetic agitation is processed, and magnetic stirring speed is 80r/min, and mixing time is 60min, obtains gel containing hafnium.Hafnium gel will be contained
Be placed in alumina crucible to put into and in low temperature tube furnace, be thermally treated resulting in precursor powder, annealing process be room temperature under with 10 DEG C/
The programming rate of min is raised to 800 DEG C, is incubated 3h, and atmosphere is high-purity Ar, and Ar flow is 0.4L/min.Obtain after annealing
Precursor powder take out, put in planetary type ball-milling tank, ball milling revolve round the sun 500r/min, rotation 250r/min, Ball-milling Time be 3
Hour.Ball milling material is taken out, is placed in graphite jig, put into synthesis in discharge plasma sintering furnace, vacuum is 10Pa, room
With the ramp of 400 DEG C/min to 1500 DEG C under temperature, temperature retention time is 3min, then is cooled to room with the speed of 200 DEG C/min
Temperature, you can obtain grey powder 13.542g.
Through XRD, FESEM and tem analysis, the present embodiment products therefrom is pure HfC powder, but because carbon hafnium ratio is excessive, produces
Remain substantial amounts of free carbon in thing, and free carbon is wrapped in HfC particle, observe in FESEM and can see that, hafnium carbide particle is big
Little for 60nm.
Claims (5)
1. a kind of preparation method of hafnium carbide nano-powder is it is characterised in that step is as follows：
1) prepare gel containing hafnium：By HfCl4And C6H8O7·H2O is dissolved in deionized water, HfCl4Mass volume ratio with water is
0.20-0.25g/mL, wherein HfCl4And C6H8O7·H2O mol ratio is 1:0.5-1.5, and be stirred continuously and so that it is fully dissolved, so
Adjust pH to 2-3 with ammonia spirit afterwards, and magnetic agitation is processed under 60-80 DEG C of constant temperature, obtains gel containing hafnium；
2) prepare precursor powder：By step 1) gained gel containing hafnium puts in low temperature tube furnace heat treatment, with 3-10 under room temperature
DEG C/ramp of min is to 800 DEG C, and it is incubated 1-3h, atmosphere is Ar, obtains precursor powder；
3) prepare hafnium carbide nano-powder：By step 2) gained precursor powder puts into and carries out high energy ball in planetary type ball-milling tank
Mill, gained powder is placed in discharge plasma sintering furnace, under vacuum, with the speed of 200-400 DEG C/min under room temperature
It is warming up to 1500-1800 DEG C, is incubated 3-10min, then room temperature is cooled to the speed of 100-200 DEG C/min obtains hafnium carbide and receive
Ground rice body.
2. hafnium carbide nano-powder according to claim 1 preparation method it is characterised in that：Step 1) described ammoniacal liquor is molten
Liquid mass concentration is 25%.
3. hafnium carbide nano-powder according to claim 1 preparation method it is characterised in that：Step 1) described magnetic force stirs
Mixing speed is 60-80r/min, and the magnetic agitation time is 30-60min.
4. hafnium carbide nano-powder according to claim 1 preparation method it is characterised in that：Step 3) described high energy ball
Grinding process is：Planetary type ball-milling tank revolution rotating speed is 200-250r/min, and rotation rotating speed is 400-500r/min, and Ball-milling Time is
1-3h.
5. hafnium carbide nano-powder according to claim 1 preparation method it is characterised in that：Step 3) described agglomerant
Skill is：Under vacuum, under room temperature with the ramp of 300 DEG C/min to 1600 DEG C, be incubated 5min, then with 200 DEG C/min
Speed cooling.
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| CN105753477B (en) * | 2016-01-22 | 2018-08-14 | 中国人民解放军国防科学技术大学 | A kind of preparation method of HfC ceramic precursors and application |
| CN105780123B (en) * | 2016-02-04 | 2018-02-09 | 武汉科技大学 | A kind of hafnium carbide nano whisker and preparation method thereof |
| CN106588018B (en) * | 2016-11-15 | 2019-05-07 | 上海交通大学 | A kind of preparation method of superhigh temperature hafnium carbide ceramic nano-powder body |
| CN107601508B (en) * | 2017-09-12 | 2020-02-14 | 江苏理工学院 | Hafnium carbide nano material and preparation method thereof |
| CN109678511B (en) | 2018-12-23 | 2021-09-10 | 上海交通大学 | Dense HfC (Si) -HfB2Preparation method of complex phase ceramic |
| US20220185677A1 (en) * | 2019-04-15 | 2022-06-16 | Chubu Electric Power Co., Inc. | Hafnium carbide powder for plasma electrodes, method for producing same, hafnium carbide sintered body, and plasma electrode |
| RU2729277C1 (en) * | 2019-12-24 | 2020-08-05 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method of producing ultrahigh-temperature ceramic material based on hafnium carbonitride |
| CN116854092A (en) * | 2023-07-28 | 2023-10-10 | 北京华威锐科化工有限公司 | Hafnium carbide precursor production system and preparation method |
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| CN102162057A (en) * | 2011-03-30 | 2011-08-24 | 北京矿冶研究总院 | High-strength low-magnetism light hard alloy for dynamic pressure gas bearing and preparation method thereof |
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| CN102162057A (en) * | 2011-03-30 | 2011-08-24 | 北京矿冶研究总院 | High-strength low-magnetism light hard alloy for dynamic pressure gas bearing and preparation method thereof |
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