CN107697916A - A kind of preparation method of metal silicon carbon compound nano-powder - Google Patents

A kind of preparation method of metal silicon carbon compound nano-powder Download PDF

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CN107697916A
CN107697916A CN201711103491.2A CN201711103491A CN107697916A CN 107697916 A CN107697916 A CN 107697916A CN 201711103491 A CN201711103491 A CN 201711103491A CN 107697916 A CN107697916 A CN 107697916A
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powder
sio
preparation
carbon
silicon
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CN107697916B (en
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高朋召
徐墨雨
廖进军
程磊
袁铮
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Hefei Cement Research and Design Institute Co Ltd
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Hunan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention discloses a kind of preparation method of metal silicon carbon compound nano-powder, this method is using aerosil as main silicon source, Phenolic resin pyrolysis Carbon is carbon charcoal source, metal powder is source metal, and the method being combined using carbon thermal reduction solid phase reaction prepares metal silicon carbon compound nano-powder.The shortcomings that reaction temperature existing for directly being reacted instant invention overcomes metal, silicon, charcoal is high, particle is larger, has a very wide distribution, and impurities phase content is higher, has good economic benefit.

Description

A kind of preparation method of metal-silicon-carbon compound nano-powder
Technical field
The present invention relates to a kind of preparation method of metal-silicon-carbon compound nano-powder, and in particular to a kind of high-purity, The preparation method of metal in height ratio surface area-silico-carbo compound.
Background technology
Metal-silicon-carbon compound (such as Al4SiC4、Mo4.8Si3C0.6And Ti3SiC2Deng) because there is metallic bond simultaneously in structure And covalent bond, therefore have a variety of premium properties of metal and ceramic material concurrently, such as good electrical and thermal conductivity, low-density, high-melting-point, High elastic modulus, high-fracture toughness, resistance to oxidation, resistance to thermal shock, easy processing and good self lubricity etc., high-temperature structural material, The field such as Electric/electronic Materials and self-lubricating bearing material has broad application prospects.And metal-silicon-carbon compound powder Purity and particle diameter have important influence to the block materials of acquisition excellent performance.Metal-silicon-carbon compound powder at present Preparation method mainly has：
As can be seen from the above table, distinct methods prepare raw material used in metal-silicon-powdered carbon body, reaction temperature, product it is pure Larger gap be present in degree and granularity.But the rare high-purity, metal in height ratio surface area-silicon-charcoal nano-powder preparation method of being related to Document.
Related patent mainly has：
Chinese patent specification CN201710240199.9 discloses a kind of lead titanium silicon-carbon composite wood of the inventions such as Wang Limin Material and preparation method thereof, its key step includes：After carbon material mixes with silica, titanyl sulfate solution is added, uses ammoniacal liquor Obtained titanium Si-C composite material is calcined after solution washing under a nitrogen atmosphere, adds lead salt solution, with acid solution wash, is done The lead sulfate obtained after dry-carbon-based material combination electrode material mixes with metal oxide, and sprays two on the surface of mixture What silica obtained.The lead titanium Si-C composite material, which has, improves the excellent of electric conductivity, charge acceptance and charge-discharge magnification Point, lead salt can be converted into active lead, suppress lead salt crystalline solid and increase and salinization；Lead titanium Si-C composite material after being combined with lead Adhesion strengthens, and it is kept some strength in charge and discharge process, will not loosely be come off because of rush of current；It is excessively electric to improve liberation of hydrogen Position, suppress negative pole and lose hydrogen too early；Improve cycle life.The patent mainly using carbon material, silica, titanyl sulfate, is led to The low-temp reaction (400 DEG C or so) crossed under inert atmosphere prepares amorphous titanium silicon-carbon and charcoal composite granule, it is desirable to increase electrode Larger difference be present in the technology path and target of the chemical property of material, its technology path and target and the application.
Chinese patent specification CN201710039809.9 discloses a kind of strong high-purity of controllability of the inventions such as Li Liejun POROUS TITANIUM silicon-carbon ceramic preparation is spent, its key step includes：1) by three kinds of titanium, silicon, graphite powder stoichiometrically 3: (1~2):After 2 ratio is sufficiently mixed, the sodium chloride particle with different-grain diameter is according to 9:1~1:4 mass ratio is in mixed powder machine Mix 8~12h；2) dry mixed-powder is poured into punching block, green compact is pressed into 100~1500MPa pressure；3) by green compact It is placed in cold water and soaks to remove sodium chloride, obtains porous green compact, be then dried for standby；4) porous green compact are placed in vacuum drying oven In, 500~2000 DEG C are warming up to 1~30 DEG C/min speed, furnace cooling after 1~5h is incubated, obtains POROUS TITANIUM silicon-carbon and answer Close ceramics.Present invention process is prepared simply, and cost is low, to Preparation equipment less-restrictive, beneficial to industrialized production.The patent is main It is that fabricated in situ-sintering process prepares POROUS TITANIUM silicon-carbon composite ceramics, its skill in a vacuum furnace using three kinds of titanium, silicon, graphite powder Larger difference be present in the technology path and target of art route and target and the application.
Chinese patent specification CN201610994818.9 discloses one kind silicon-carbon containing aluminium Compound Negative of the inventions such as Liu Lijun Pole material and preparation method thereof, silicon-carbon composite cathode material containing aluminium is prepared using following steps：Tetraethyl orthosilicate is dissolved in Ethyl acetate, catalyst is added, obtains solution A；Aluminium isopropoxide is added in isopropanol and dissolved, obtains solution B；By solution B It is added in solution A and is uniformly mixing to obtain mixed solution C；Single-walled carbon nanotube is scattered in ethanol solution, it is even to add silane Join agent, ultrasonic disperse is uniform；Mixed solution C is added while stirring；Distilled water is stirring evenly and then adding into, is stirred at 150-250 DEG C 3-8h is reacted, vacuum filtration, washing, is dried, obtains being deposited on the aluminium doping silica-base material presoma of single-walled carbon nanotube；Then 600-800 DEG C of high temperature keeps 6-10h under reducing atmosphere, obtains unbodied silicon-carbon composite cathode material containing aluminium.Using this hair Bright technical scheme, the electrical conductivity of material is improved, improve the cycle performance of material；With higher capacity and life-span.The patent Mainly first prepare SiO2-Al2O3Complex sol, gel after being then well mixed with surface treated carbon nanotube, finally Low-temp reaction (800 DEG C) prepares the unbodied powder of silicon-carbon composite cathode containing aluminium, to improve the chemical property of material, its technology Larger difference be present in the technology path and target of route and target and the application.
Chinese patent specification CN201410225845.0 discloses a kind of fine and close niobium aluminium silicon-carbon solid solution that poplar such as builds at the invention Body material and preparation method thereof, its main contents include：The chemical structural formula of niobium aluminium silicon carbon solid-solution material is Nb4Al1- xSixC3, wherein x span is 0.03≤x≤0.08.Synthesized using in-situ hot pressing technique：By raw material niobium powder, aluminium powder, silicon Powder and graphite powder are by feed molar proportioning：n(Nb):n(Al):n(Si):N (C)=4:(1.02~1.07):(0.03~ 0.08):2.7, after physical mechanical method is well mixed, it is fitted into surface and scribbles and be cold-pressed into the graphite jig of BN protective coatings Type, the then hot pressed sintering in the vacuum hotpressing stove for be connected with protective atmosphere.Present invention process is simple, excellent material performance.This is special Profit is raw material using niobium powder, aluminium powder, silica flour and graphite powder, and fine and close niobium aluminium silicon is prepared by the method for reaction in-situ-hot pressed sintering Larger difference be present in the technology path and target of carbon solid-solution material, its technology path and target and the application.
The modification lithium-ion battery graphite that Chinese patent specification CN201410168843.2 discloses Yang Maoping inventions is born Pole material and preparation method thereof, its key step include：Titanium source, silicon source and graphite are weighed, under inert gas shielding, addition point Powder simultaneously carries out spheroidal graphite or ultrasonic mixing processing, dries；Dried feed is sintered under hydrogen and the protection of inert gas mixed atmosphere Processing.Modification lithium-ion battery graphite cathode material, surface is smooth, and surface nature is homogeneous, has higher electronic conductivity.Table The formation of roll cover effectively reduces graphite cathode and contacted with the direct of electrolyte, reduces the erosion of electrolyte.Titanium silicon-carbon Surface coating layer chemical stability is good, good conductivity, can effectively keep crystal structure stable in charge and discharge process repeatedly, and Electric conductivity is obviously improved.Coulombic efficiency, high rate performance and cycle performance are obviously improved first for it.Patent master If using the solid phase reaction of titanium source, silicon source and graphite, by the Ti of generation2SiC2Material in situ is coated on graphite particle surface, shape Into conductive network, the chemical property of graphite cathode, its technology path and the technology path and target of target and the application are improved Larger difference be present.
Chinese patent specification CN201310014932.7 discloses a kind of firm highly anticorrosive rare earth-siderochrome for waiting invention of dragon Silicon-carbon magneto-caloric material and preparation method thereof, its main contents include：The invention belongs to technical field of magnetic, there is provided one Kind highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material.Contain portion in highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material of the present invention Divide and substitute the chromium atom of iron atom, as C atoms existing for interstitial atom.Highly anticorrosive rare earth-siderochrome silicon-carbon magnetic of the present invention Hot material soaks 12 hours in the running water that temperature is 25 degrees Celsius, and corrosion rate is less than 0.2g/m2.h.Above-mentioned high corrosion-resistant Rare-earth-iron chrome-silicon carbon magneto-caloric material is made up of two kinds of chemical molecular formulas, and a kind of chemical molecular formula is La1-xRx(Fe1-y- mCryMm)13-zSizCa, another chemical molecular formula LaFeSi.The highly anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material is rotten Lose less than half that speed is general rare-earth-iron silicon magneto-caloric material, and above-mentioned highly anticorrosive rare earth-siderochrome silicon-carbon magnetic hot-cast ingot After short time annealing, there is high magnetic entropy change value, Applied Materials can be used as to be used in magnetic Refrigeration Technique.The patent it is main 2 groups of alloys is will be put into melting in vaccum sensitive stove by preparation method in proportion, and then fast quenching obtains in ingot casting and frozen water Powder, it is desirable to obtain corrosion-resistant and excellent magnetic heating performance powder, the technology path of its technology path and target and the application and Bigger difference be present in target.
Chinese patent specification CN201110139958.5 discloses a kind of hafnium aluminium silicon carbon-silicon carbide of the inventions such as Zhou Yanchun Composite and preparation method thereof, its main technological route include：Using the Hf powder of certain stoichiometric proportion, Al powder, Si powder and C Powder is raw material, and raw material mixes 5~50 hours by physical mechanical method, is cold-pressed into pie with 5~20MPa pressure, loads stone In black mould, 1600 DEG C~2400 DEG C original positions are heated in hot pressing furnace of the inert gas as protection gas (or under vacuum) is connected with Hot pressure reaction 0.1~4 hour, hot pressing pressure are 20~40MPa.The present invention can synthesize high at a lower temperature, in the short time The hafnium aluminium silicon carbon fiber reinforced silicon carbide matrix composite of the performances such as hardness, high intensity, high tenacity, superhigh temperature resistant, is obtained using the inventive method Material can be used at a high temperature of more than 1600 DEG C.The essence of the patent is to utilize Hf powder, Al powder, Si powder and C powder as original Material, hafnium aluminium silicon carbon fiber reinforced silicon carbide matrix composite, its technology path and target and the application are prepared by reaction in-situ-pressure sintering Bigger difference be present in technology path and target.
Chinese patent specification CN201010120226.7 discloses a kind of synthesis side of aluminium silicon-carbon of the inventions such as Zhao Jianli Method, its key step include：With Al2O3And SiO2For raw material, using C as reducing agent, in air atmosphere, it is heated to 2500~ After 3200 DEG C of 5~72h of synthesis, cooling obtains aluminium silicon-carbon, wherein the percent mass proportioning of each raw material is：Al2O3Raw material 50~ 60%th, SiO2Raw material 10~20%, C raw materials 25~35%.The present invention makes it possible the large-scale application of aluminium silicon-carbon, synthesis Aluminium silicon-carbon can be applied to refractory ceramics component, aircraft surface high-temperaure coating, metal smelt container inside lining, high temperature exothermic The fields such as body.The patent is used with Al2O3And SiO2For raw material, using C as reducing agent, in air atmosphere, it is heated to 2500~ After 3200 DEG C of 5~72h of synthesis, cooling obtains aluminium silicon-carbon, and its reaction temperature is higher, based on raw material proportioning and reaction condition, it is contemplated that Its impurity is more, and particle size is larger, larger difference be present with the technology path and target of the application.
Chinese patent specification CN201010581357.5 discloses a kind of zirconium niobium aluminium silicon-carbon solid solution of the inventions such as Zhou Yanchun Body material and preparation method thereof, it is characterised in that：The chemical formula of zirconium niobium aluminium silicon carbon solid-solution material is (Zr1-zNbz)2(Al1- ySiy)4C5, wherein, Nb substitutions Zr atomic molar substitution amount z span is rubbed for 0 ＜ z≤0.3, Si substitutions Al atom Your substitution amount y span is 0 ＜ y≤0.2.First, using zirconium powder, niobium powder, silica flour, aluminium powder and graphite powder as raw material, through thing Mechanical means mixing is managed, is fitted into cold moudling in graphite jig, is sintered in the hot pressing furnace for be connected with protective atmosphere, obtains zirconium niobium aluminium Silicon carbon solid-solution material.The present invention can prepare single-phase zirconium niobium aluminium silicon carbon solid-solution material, and this material is not damaging zirconium Its antioxygenic property is significantly improved on the basis of aluminium silicon-carbon Mechanical Property of Ceramics.The essence of the patent is zirconium powder, niobium powder, silicon Powder, aluminium powder and graphite powder are raw material, and zirconium niobium aluminium silicon-carbon compact block material, its technology are prepared by fabricated in situ-hot pressed sintering Bigger difference be present in the technology path and target of route and target and the application.
Chinese patent specification CN200910010561.9 discloses a kind of zirconium-aluminum-silicon-carbon-carborundum of the inventions such as Zhou Yanchun Composite and preparation method thereof, its key step include：Use Zr powder, Al powder, Si powder and the C powder of certain stoichiometric proportion for Raw material, raw material mix 5~50 hours by physical mechanical method, are cold-pressed into pie with 5~20MPa pressure, load graphite mo(u)ld In tool, 1600 DEG C~2400 DEG C in-situ hot pressings are heated in hot pressing furnace of the inert gas as protection gas (or under vacuum) is connected with Reaction 0.1~4 hour, hot pressing pressure is 20~40MPa.The present invention can at a lower temperature, synthesis high rigidity in the short time, The zirconium-aluminum-silicon-carbon-silicon carbide composite material of the performances such as high intensity, high tenacity, superhigh temperature resistant, the material obtained using the inventive method Material can use under the superhigh temperature more than 1600 DEG C.It using Zr powder, Al powder, Si powder and C powder is raw material that the essence of the patent, which is, Zirconium-aluminum-silicon-carbon-silicon carbide composite material is prepared by reaction in-situ-pressure sintering, the technology path and target and the application of the patent Technology path and target bigger difference be present.
One kind that Chinese patent specification CN200410009220.7 discloses the inventions such as Li Shibo prepares titanium silicon carbide ceramics The method of powder, its specific steps include：First, by three kinds of titanium (Ti), silicon (Si), graphite powder (C) massages that proportionings 3: (1 ~2): (1.5~2) dispensing, using stainless steel ball, the weight of ball and material is than 10: 1~100: 1；Ball and material are put into ball grinder, Ball grinder vacuumizes, and rotating speed is 150~350r/min；At room temperature, by the ball milling of 1~4 hour, synthesis of titanium silicon carbon is principal phase Ceramic powder.Secondly, by the fine powder of synthesis through hydrofluoric acid solution pickling 0.5~2 hour, silicide is removed；Powder is again through distilled water Rinse, drying, handled 1~4 hour in 400~500 DEG C of internal oxiditions, remove titanium carbide；Mixing again through ammonium sulfate and sulfuric acid is molten Oxide is removed in liquid processing, washes, and drying, obtains titanium silicon carbide ceramics powder.The titanium that this method technique is simple, cost is low, prepares Silicon-carbon ceramic powders purity is high.The primary raw material of the patent is titanium (Ti), silicon (Si), graphite powder (C), and titanium is prepared by ball milling Silicon-carbon ceramic powder；The application is mainly source metal using metal powder, SiO2Aeroge is main silicon source, and PF cracking charcoals are charcoal source, The metal-silicon of high-purity-carbon compound nano particle is prepared by more single-step solid phase reactions under high temperature inert atmosphere.The patent Technology path, it is contemplated that purity, particle diameter and the specific surface area of product and the presence bigger difference of the application.
Chinese patent specification CN200410009589.8 disclose the inventions such as Zhai Hongxiang a kind of titanium silicon carbide powder and Its atmospheric synthesizing method using aluminium as reaction promoter, it is characterised in that：Using titanium Ti, silicon Si and graphite C powder as raw material, using aluminium Al as The ratio dispensing of reaction promoter, in molar ratio Ti: Si: C: Al=3: 1: 2: 0.1~0.2, ball mill mixing 2~6 hours, 60~70 DEG C oven drying, by dry mixed material under 8~10MPa briquet, be placed in high temperature furnace, argon gas protection, with 20~ Furnace temperature is risen to 1430~1480 DEG C by 40 DEG C/min heating rate, is incubated 5~8min, cold with 10~15 DEG C/min speed But, that is, the titanium silicon carbide powder of the present invention is obtained.The application is mainly source metal using metal powder, SiO2Aeroge is main silicon Source, PF cracking charcoals are charcoal source, and metal-silicon-carbonization of high-purity is prepared by more single-step solid phase reactions under high temperature inert atmosphere Compound nano particle.The patent is in terms of the particle diameter of expected product and specific surface area, the presence bigger difference with the application.
The content of the invention
It is contemplated that overcoming, reaction temperature existing for the direct reaction of metal, silicon, charcoal is high, particle is larger, has a very wide distribution, The shortcomings that impurities phase content is higher.
The technical scheme is that, there is provided a kind of preparation method of metal-silicon-carbon compound nano powder, methods described Comprise the following steps：
(1) (1-10) is pressed：(0.2-8)：(0.2-8)：The mol ratio of (0.5-40) weighs metal powder, heat treatment SiO2Airsetting Glue, silica flour and Phenolic resin pyrolysis Carbon, by above-mentioned material mixing and ball milling, obtain mixed powder；
It is heat-treated SiO2The preparation of aeroge：First prepare SiO2Aeroge, then by SiO under air atmosphere2Aeroge exists 0.5-4h is incubated at 400-1200 DEG C, obtains being heat-treated SiO2Aeroge；
The preparation of Phenolic resin pyrolysis Carbon：The phenolic resin after solidification is incubated at 600-1400 DEG C under an inert atmosphere 0.5-4h, obtain Phenolic resin pyrolysis Carbon；
(2) mixed powder is carried out old, is then pressed into green compact；
(3) green compact are incubated 1-4h at inert atmosphere, 1200-1800 DEG C, then cool down, be levigate, obtain head product；
(4) head product is obtained into metal-silicon-carbon compound nano powder by carbon removal and except silica.
Preferably, in step (1), SiO2The preparation method of aeroge is：
A) under agitation, salpeter solution is added dropwise in the ethanol solution of silester, continues to stir after being added dropwise Mix, then sealing and standing 40-60h, obtain SiO2Colloidal sol, by SiO2Colloidal sol is thermally formed SiO in a water bath2Gel；
B) under protective atmosphere, by SiO2Gel carries out supercritical drying under 280-320 DEG C, 10-14MPa, obtains SiO2 Aeroge.
Preferably, the concentration of salpeter solution is 0.01-0.3mol/L；Salpeter solution is the aqueous solution of nitric acid.Silicic acid second The ethanol solution of ester is (0.5-10) by volume ratio：The ethanol of 1 silester and ethanol composition, salpeter solution and silester The volume ratio of solution is (1-4):(2-1), preferably 1：(0.8-2).
Preferably, in step (2), old technique is：Polyvinyl alcohol adhesive and water are added in mixed powder, grinding is equal It is even, then seal, room temperature places 12-48h.
Preferably, in step (1), by SiO2Aeroge is warming up to 400-1200 DEG C in the case where speed is 2-15 DEG C/min.
Preferably, in step (1), the phenolic resin after solidification is warming up to 600-1400 in the case where speed is 2-15 DEG C/min ℃。
Preferably, in step (1), the metal powder is aluminium powder, molybdenum powder, chromium powder and/or titanium valve.
Preferably, in step (1), the purity of metal powder is more than 99%, and granularity is 1-3 microns, and silica flour purity is more than 99%, Granularity is 1-3 microns.
Preferably, in step (1), by (2-8)：(0.8-6)：(0.4-2)：The mol ratio of (2-20) weighs metal powder, heat Handle SiO2Aeroge, silica flour and Phenolic resin pyrolysis Carbon.It is highly preferred that press (3-5)：(1-5)：(0.5-1)：(8-15's) rubs You are than weighing metal powder, heat treatment SiO2Aeroge, silica flour and Phenolic resin pyrolysis Carbon.
Preferably, perchloric acid solution carbon removal is utilized；Silica is removed using hydrofluoric acid solution.
Specifically, specific implementation step of the invention is as follows：
(1) by certain volume and the HNO of concentration3Add a certain amount of H2Stirring is allowed to well mixed in O, is named as A；Will A certain amount of TEOS (silester) adds stirring in a certain amount of EtOH (ethanol) and is allowed to well mixed, is named as B；
(2) with vigorous stirring, A is added dropwise in B according to certain rate of addition and volume ratio, one section of stirring is added dropwise Time, seal the system and stand 48h, obtain SiO2Colloidal sol, the colloidal sol is put into 60 DEG C of water-baths to gelling；
(3) a certain amount of SiO is taken2Gel is put into reactor, seals reactor, the Ar gas of preliminary filling certain pressure intensity, according to one Fixed heating schedule and pressure require supercritical drying SiO2Gel prepares SiO2Aeroge；
(4) by gained SiO2Aeroge carries out hot place in air atmosphere, according to certain heating process and soaking time Reason, obtain being heat-treated SiO2Aeroge, the main silicon source as solid phase reaction；
(5) a certain amount of PF (phenolic resin) is solidified into 24h at 80 DEG C, then under an inert atmosphere, according to certain heating Technique and soaking time cracking, obtain PF cracking charcoals, the charcoal source as solid phase reaction；
(6) metal powder, heat treatment SiO are weighed respectively by a certain percentage2Aeroge and silica flour, PF cracking charcoals, by these powder Material is fitted into ball grinder, using ZrO2Ball is abrasive material, and EtOH is medium, carries out wet-milling, after completing ball milling, by slurry from ball grinder It is transferred in porcelain container, constant weight is dried at 80 DEG C in air dry oven；
(7) it is a certain amount of binding agent of powder addition of mixing and water progress is old, old rear powder compression molding is made Green compact, green compact are then dried in 80 DEG C of baking ovens to constant weight；
(8) green compact are put into high temperature furnace, solid phase is carried out according to certain heating process and soaking time under inert atmosphere Synthetic reaction, obtain product；
(9) after product is ground in mortar, it is fitted into ball grinder, using ZrO2Ball is abrasive material, and EtOH is medium, is carried out Wet-milling, after completing ball milling, slurry is transferred in glass container from ball grinder, perseverance is dried at 80 DEG C in air dry oven Weight, then uses HClO respectively4The charcoal and SiO that may be remained in powder are removed with HF2, produce high-purity, high-specific area nano gold Category-silico-carbo compound particle.
A kind of preferred scheme, the above-mentioned specific steps the step of in (1), HNO3Concentration be 0.3-1.2mol/L, HNO3With H2O volume ratio is (1-5):(1-15)；TEOS and EtOH volume ratio is (1-5):1.
A kind of preferred scheme, the above-mentioned specific steps the step of in (2), the rate of addition that A is added dropwise in B is 10-40ml/h, The volume ratio of solution A and B solution is (1-4):(2-1)；It is 18-30h that rear mixing time, which is added dropwise,.
A kind of preferred scheme, the above-mentioned specific steps the step of in (3), after sealing reactor, the pressure of preliminary filling Ar gas is 2.0-5.0MPa, SiO2Gel supercritical drying process is：Heating cycle：Room temperature is to 300 DEG C, 0.5-1.5 DEG C/min, 300 DEG C It is incubated 1-3h；Pressure requirement：At 300 DEG C, reactor pressure is more than or equal to 10MPa, less than or equal to 14MPa.Insulation finishes beginning Release, stress-relief process maintenance reaction kettle is temperature-resistant, and release finishes, and closes heating, waits reactor to cool down, you can obtains SiO2Airsetting Glue.
A kind of preferred scheme, the above-mentioned specific steps the step of in (4), SiO2Aeroge Technology for Heating Processing is：Room temperature arrives The heating rate of target temperature (600-1000 DEG C) is 5-10 DEG C/min, target temperature insulation 0.5-3h.
A kind of preferred scheme, the above-mentioned specific steps the step of in (5), inert atmosphere is Ar gas, and PF cracking technologies are：Room Temperature is 4-10 DEG C/min to the heating rate of target temperature (800-1200 DEG C), and target temperature is incubated 0.5-3h.
A kind of preferred scheme, the above-mentioned specific steps the step of in (6), metal dust refers to Mo, Ti, Al and Cr powder, metal The purity of powder is all higher than 99%, and granularity is 2.0 ± 1.0 μm, and silica flour purity is all higher than 99%, and granularity is 2.0 ± 1.0 μm；Gold Belong to powder:The SiO of pretreatment2Aeroge:Silica flour:PF cracking charcoal mol ratio be：(2-8):(0.5-6):(0.5-6):(1.0- 30)。
A kind of preferred scheme, the above-mentioned specific steps the step of in (6), in wet-grinding technology and relative device, powder:Abrasive material:The matter of medium Amount is than being 1:2:5, the rotating speed of ball mill is 350-450r/min, Ball-milling Time 80-160min.
A kind of preferred scheme, the above-mentioned specific steps the step of in (7), old technique：Powder after drying is put into mortar, Add PVA binding agent and H of a certain amount of mass percent for 3-7% (specific such as 5%)2O, account for the quality of final binding agent (the quality summation of powder, 5%PVA and water is denominator to the 0.2-0.6% of powder gross mass after drying, and PVA quality is point Son, gained mass percent), then grinding is uniform, is fitted into polybag and seals, and room temperature places 18-36h and realizes uniform moisture Change；Mould pressing process is：Powder after old is put into mould, with press under 60-100MPa pressure pressurize 0.5-2min.
A kind of preferred scheme, the above-mentioned specific steps the step of in (8), inert atmosphere is Ar gas, solid phase synthesis Temperature increasing schedule is：Room temperature is 5-15 DEG C/min to the heating rate of target temperature (1400-1800 DEG C), and target temperature is incubated 1- 3h。
A kind of preferred scheme, the above-mentioned specific steps the step of in (9), in wet-grinding technology and relative device, powder:Abrasive material:The matter of medium Amount is than being 1:2:20, drum's speed of rotation 350-450r/min, Ball-milling Time 180-360min；Carbon removal technique is：HClO4's Concentration of volume percent is 50-100%, and temperature is 40-80 DEG C, soaking time 4-8h；Except SiO2Technique is：Dose volume ratio For 1 (water):Powder after carbon removal, is then put into the HF aqueous solution, is stored at room temperature 20-60h by the HF aqueous solution of 3 (HF concentrated solutions), Then powder is washed to pH equal to 7 with distilled water.
This method is using aerosil as main silicon source, and Phenolic resin pyrolysis Carbon is charcoal source, and metal powder is source metal, The method being combined using carbon thermal reduction-solid phase reaction prepares metal-silicon-charcoal compound nano powder.
The invention has the advantages that this method is based on the small particle size of aerosil and very high ratio table Area, it is easily obtained the product of the nano-scale of high-specific surface area；The unformed charcoal that phenolic resin cracking is obtained has very high Reactivity, the driving force as solid phase reaction, it is possible to achieve reaction carry out at a lower temperature；As major impurity phase Aerosil be easily removed in the product, the product of high-purity can be obtained；Instant invention overcomes metal, silicon, charcoal are straight It is reversed to answer the shortcomings that existing reaction temperature is high, particle is larger, has a very wide distribution, and impurities phase content is higher, there is good warp Ji benefit.
Brief description of the drawings
Fig. 1 is gained aluminium-silico-carbo (Al in embodiment 14SiC4) nano particle stereoscan photograph.
Fig. 2 is gained aluminium-silico-carbo (Al in embodiment 14SiC4) nano particle XRD spectrum.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
Aluminium silicon-carbon (the Al4SiC4) preparation method of nano powder comprises the following steps：
(1) by 30ml 1.0mol/L HNO3Add in 200ml distilled water, stirring is allowed to mix, and is named as A；250ml TEOS is added in 90ml EtOH, and stirring is allowed to mix, and is named as B；
(2) with vigorous stirring, by A be added dropwise B in, rate of addition 20ml/h, after stir 24h, stood after sealing 48h obtains SiO2Colloidal sol, colloidal sol is put into 60 DEG C of water-bath to gel；
(3) take about 50ml wet gels to be put into reactor, seal reactor, preliminary filling 2.5MPa Ar gas, then start to add Heat, program be room temperature to 300 DEG C, 1 DEG C/min, 300 DEG C of insulation 2h, start release after insulation, stress-relief process maintains 300 DEG C, release finishes, and closes heating, waits reactor to be cooled to room temperature, takes out product SiO2Aeroge；
(4) by SiO2Aeroge is heat-treated in air atmosphere, and program is：Room temperature is to 700 DEG C, 10 DEG C/min, 700 DEG C insulation 2h, obtain the heat treatment SiO as main silicon source2Aeroge；
(5) a certain amount of PF is solidified into 24h at 80 DEG C, then cracked in tube furnace under Ar atmosphere, program is：Room temperature arrives 900 DEG C, 5 DEG C/min, 900 DEG C of insulation 1h, obtain PF cracking charcoals；
(6) it is 4 according to mol ratio:1.5:0.5:15 ratio weighs Al powder, heat treatment SiO respectively2Aeroge and Si powder, PF cracks charcoal, these powders is added in ball grinder, by powder:ZrO2Abrading-ball:EtOH mass ratioes are 1:2:5 by abrading-ball and EtOH Add in ball grinder, wet-milling 120min, drum's speed of rotation 400r/min.After ball milling, slurry is shifted in porcelain container, Remove ZrO2Ball, constant weight is dried at 80 DEG C in air dry oven；
(7) the mixed powder progress after drying is old, old technique is：To mixed powder add 5%PVA binding agents and H2O, the quality of final binding agent account for the 0.2% of powder gross mass, and then grinding is uniform, is fitted into polybag and seals, in plastics Aperture is pricked on bag, prevents the bag that rises, room temperature places 24h and realizes homogeneity of water.Powder after will be old is put into mould, uses press The pressurize 1min under 70MPa pressure, prepare green sheet；
(8) green sheet is put into high temperature furnace, leads to Ar gas shieldeds, be warming up to 1590 DEG C according to 10 DEG C/min speed, protect Warm 1.5h, obtains product；
(9) after product is roughly ground in mortar, it is fitted into ball grinder, according to powder:ZrO2Abrading-ball:EtOH mass ratioes are 1: 2:20 add in ball grinder, ball milling 240min, drum's speed of rotation 400r/min.Ball milling is finished, and slurry is shifted from ball grinder Into glass container, abrading-ball is removed, constant weight is dried at 80 DEG C in air dry oven.Then by powder after drying at 70 DEG C, Percent by volume is 70% HClO4Solution insulation 8h carries out carbon removal processing, after powder washing and drying after carbon removal, is then transferred to Volume ratio is 1 (H2O):In the HF aqueous solution of 3 (HF concentrated solutions), 48h is stood at room temperature and removes SiO2, then with distillation water washing Powder is equal to 7 to pH, is dried to constant weight at 80 DEG C in air dry oven, produces high-purity, the nanometer of high-specific surface area Al4SiC4Particle.
Gained Al4SiC4Powder XRD tests free from admixture phase, particle diameter about 80-150nm, specific surface area 10.7533m2/ g。
Embodiment 2
Molybdenum silicon-carbon (the Mo4.8Si3C0.6) preparation method of nano powder comprises the following steps：
(1) by 30ml 0.7mol/L HNO3Add in 200ml distilled water, stirring is allowed to mix, and is named as A；180ml TEOS is added in 90ml EtOH, and stirring is allowed to mix, and is named as B；
(2) with vigorous stirring, by A be added dropwise B in, rate of addition 20ml/h, after stir 24h, stood after sealing 48h obtains SiO2Colloidal sol, colloidal sol is put into 60 DEG C of water-bath to gel；
(3) take about 50ml wet gels to be put into reactor, seal reactor, preliminary filling 3MPa Ar gas, then begin to warm up, Program be room temperature to 300 DEG C, 1 DEG C/min, 300 DEG C of insulation 2h, start release after insulation, stress-relief process maintains 300 DEG C, unloaded Pressure finishes, and closes heating, waits reactor to be cooled to room temperature, takes out product SiO2Aeroge；
(4) by SiO2Aeroge is heat-treated in air atmosphere, and program is：Room temperature is to 800 DEG C, 10 DEG C/min, 800 DEG C insulation 2h, obtain the heat treatment SiO as main silicon source2Aeroge；
(5) a certain amount of PF is solidified into 24h at 80 DEG C, then cracked in tube furnace under Ar atmosphere, program is：Room temperature arrives 1000 DEG C, 5 DEG C/min, 1000 DEG C of insulation 1h, obtain PF cracking charcoals；
(6) it is 5 according to mol ratio:4:1:8 ratio weighs Mo powder, heat treatment SiO respectively2Aeroge and Si powder, PF split Charcoal is solved, these powders are added in ball grinder, by powder:ZrO2Abrading-ball:EtOH mass ratioes are 1:2:5 add abrading-ball and EtOH In ball grinder, wet-milling 120min, drum's speed of rotation 400r/min.After ball milling, slurry is shifted in porcelain container, removed ZrO2Ball, constant weight is dried at 80 DEG C in air dry oven；
(7) the mixed powder progress after drying is old, old technique is：To mixed powder add 5%PVA binding agents and H2O, the quality of final binding agent account for the 0.4% of powder gross mass, and then grinding is uniform, is fitted into polybag and seals, room temperature is put Put 24h and realize homogeneity of water.Powder after will be old is put into mould, with press under 70MPa pressure pressurize 1min, system Standby green sheet；
(8) green sheet is put into high temperature furnace, leads to Ar gas shieldeds, be warming up to 1550 DEG C according to 10 DEG C/min speed, protect Warm 1.5h, obtains product；
(9) after product is roughly ground in mortar, it is fitted into ball grinder, according to powder:ZrO2Abrading-ball:EtOH mass ratioes are 1: 2:20 add in ball grinder, ball milling 240min, drum's speed of rotation 400r/min.Ball milling is finished, and slurry is shifted from ball grinder Into glass container, abrading-ball is removed, constant weight is dried at 80 DEG C in air dry oven.Then by powder after drying at 70 DEG C, Percent by volume is 70% HClO4Solution insulation 8h carries out carbon removal processing, after powder washing and drying after carbon removal, is then transferred to Volume ratio is 1 (H2O):In the HF aqueous solution of 3 (HF concentrated solutions), 48h is stood at room temperature and removes SiO2, then with distillation water washing Powder is equal to 7 to pH, is dried to constant weight at 80 DEG C in air dry oven, produces high-purity, high-specific area nano Mo4.8Si3C0.6Particle.
Gained Mo4.8Si3C0.6Powder XRD tests free from admixture phase, particle diameter about 70-200nm, and specific surface area is 8.3248m2/g。
Embodiment 3
Titanium silicon-carbon (the Ti3SiC2) preparation method of nano powder comprises the following steps：
(1) by 30ml 1.0mol/L HNO3Add in 180ml distilled water, stirring is allowed to mix, and is named as A；120ml TEOS is added in 90ml EtOH, and stirring is allowed to mix, and is named as B；
(2) with vigorous stirring, by A be added dropwise B in, rate of addition 20ml/h, after stir 24h, stood after sealing 48h obtains SiO2Colloidal sol, colloidal sol is put into 60 DEG C of water-bath to gel；
(3) take about 50ml wet gels to be put into reactor, seal reactor, preliminary filling 4MPa Ar gas, then begin to warm up, Program be room temperature to 300 DEG C, 1 DEG C/min, 300 DEG C of insulation 2h, start release after insulation, stress-relief process maintains 300 DEG C, unloaded Pressure finishes, and closes heating, waits reactor to be cooled to room temperature, takes out product SiO2Aeroge；
(4) by SiO2Aeroge is heat-treated in air atmosphere, and program is：Room temperature is to 800 DEG C, 10 DEG C/min, 800 DEG C insulation 2h, obtain the heat treatment SiO as main silicon source2Aeroge；
(5) a certain amount of PF is solidified into 24h at 80 DEG C, then cracked in tube furnace under Ar atmosphere, program is：Room temperature arrives 900 DEG C, 5 DEG C/min, 900 DEG C of insulation 1h, obtain PF cracking charcoals；
(6) it is 3 according to mol ratio:1.4:0.6:12 ratio weighs Ti powder, heat treatment SiO respectively2Aeroge and Si powder, PF cracks charcoal, these powders is added in ball grinder, by powder:ZrO2Abrading-ball:EtOH mass ratioes are 1:2:5 by abrading-ball and EtOH Add in ball grinder, wet-milling 120min, drum's speed of rotation 400r/min.After ball milling, slurry is shifted in porcelain container, Remove ZrO2Ball, constant weight is dried at 80 DEG C in air dry oven；
(7) the mixed powder progress after drying is old, old technique is：To mixed powder add 5%PVA binding agents and H2O, the quality of final binding agent account for the 0.6% of powder gross mass, and then grinding is uniform, is fitted into polybag and seals, room temperature is put Put 24h and realize homogeneity of water.Powder after will be old is put into mould, with press under 70MPa pressure pressurize 1min, system Standby green sheet；
(8) green sheet is put into high temperature furnace, leads to Ar gas shieldeds, be warming up to 1400 DEG C according to 10 DEG C/min speed, protect Warm 3h, obtains product；
(9) after product is roughly ground in mortar, it is fitted into ball grinder, according to powder:ZrO2Abrading-ball:EtOH mass ratioes are 1: 2:20 add in ball grinder, ball milling 240min, drum's speed of rotation 400r/min.Ball milling is finished, and slurry is shifted from ball grinder Into glass container, abrading-ball is removed, constant weight is dried at 80 DEG C in air dry oven.Then by powder after drying at 70 DEG C, Percent by volume is 70% HClO4Solution insulation 8h carries out carbon removal processing, after powder washing and drying after carbon removal, is then transferred to Volume ratio is 1 (H2O):In the HF aqueous solution of 3 (HF concentrated solutions), 48h is stood at room temperature and removes SiO2, then with distillation water washing Powder is equal to 7 to pH, is dried to constant weight at 80 DEG C in air dry oven, produces high-specific surface area, high-purity nano Ti3SiC2Particle.
Gained Ti3SiC2Powder XRD tests free from admixture phase, particle diameter 90-150nm, specific surface area 12.75m2/g。

Claims (10)

1. the preparation method of a kind of metal-silicon-carbon compound nano-powder, it is characterised in that methods described comprises the following steps：
(1) press（1-10）：（0.2-8）：（0.2-8）：（0.5-40）Mol ratio weigh metal powder, heat treatment SiO2Aeroge, Silica flour and Phenolic resin pyrolysis Carbon, by above-mentioned material mixing and ball milling, obtain mixed powder；
It is heat-treated SiO2The preparation method of aeroge is as follows：First prepare SiO2Aeroge, then in air atmosphere by SiO2Airsetting Glue is incubated 0.5-4 h at 400-1200 DEG C, obtains being heat-treated SiO2Aeroge；
The preparation method of Phenolic resin pyrolysis Carbon is as follows：Under an inert atmosphere by the phenolic resin after solidification at 600-1400 DEG C 0.5-4 h are incubated, obtain Phenolic resin pyrolysis Carbon；
(2) mixed powder is carried out old, is then pressed into green compact；
(3) green compact are incubated 1-4h at inert atmosphere, 1200-1800 DEG C, then cool down, be levigate, obtain head product；
(4) head product is obtained into metal-silicon-carbon compound nano-powder by carbon removal and except silica.
2. preparation method as claimed in claim 1, it is characterised in that step（1）In, SiO2The preparation method of aeroge is： A) under agitation, salpeter solution is added dropwise in the ethanol solution of silester, continues to stir after being added dropwise, then Sealing and standing 40-60 h, obtain SiO2Colloidal sol, by SiO2Colloidal sol is thermally formed SiO in a water bath2Gel；
B) under protective atmosphere, by SiO2Gel supercritical drying under 280-320 DEG C, 10-14MPa, obtains SiO2Aeroge.
3. preparation method as claimed in claim 2, it is characterised in that the concentration of salpeter solution is 0.01-0.3mol/L；Silicic acid The ethanol solution of ethyl ester is by volume ratio（0.5-10）：The second of 1 silester and ethanol composition, salpeter solution and silester The volume ratio of alcoholic solution is 1：（0.8-2）.
4. preparation method as claimed in claim 1, it is characterised in that step（2）In, old technique is：In mixed powder Polyvinyl alcohol adhesive and water are added, grinding is uniform, then seals, and room temperature places 12-48 h.
5. preparation method as claimed in claim 1, it is characterised in that step（1）In, by SiO2Aeroge is 2-15 in speed DEG C/min under be warming up to 400-1200 DEG C.
6. preparation method as claimed in claim 1, it is characterised in that step（1）In, by the phenolic resin after solidification in speed To be warming up to 600-1400 DEG C under 2-15 DEG C/min.
7. preparation method as claimed in claim 1, it is characterised in that step（1）In, the metal powder is aluminium powder, molybdenum powder, chromium Powder and/or titanium valve.
8. preparation method as claimed in claim 1, it is characterised in that step（1）In, the purity of metal powder is more than 99%, granularity For 1.0-3.0 microns, the purity of silica flour is more than 99%, and granularity is 1.0-3.0 microns.
9. preparation method as claimed in claim 1, it is characterised in that step（1）In, press（3-5）：（1-5）：（0.5-1）： （8-15）Mol ratio weigh metal powder, heat treatment SiO2Aeroge, silica flour and Phenolic resin pyrolysis Carbon.
10. preparation method as claimed in claim 1, it is characterised in that utilize perchloric acid solution carbon removal；Utilize hydrofluoric acid solution Except silica.
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CN111681816B (en) * 2020-05-26 2022-03-01 浙江万马股份有限公司 High-current-carrying-capacity modified polypropylene insulated cable and modified polypropylene insulating material used by same
CN116477955A (en) * 2023-04-07 2023-07-25 中国工程物理研究院材料研究所 High-heat-conductivity silicon nitride material and preparation method thereof

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