CN107129305A - A kind of situ-combustion synthesis prepares B4The method of fiber C - Google Patents

A kind of situ-combustion synthesis prepares B4The method of fiber C Download PDF

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CN107129305A
CN107129305A CN201710324446.3A CN201710324446A CN107129305A CN 107129305 A CN107129305 A CN 107129305A CN 201710324446 A CN201710324446 A CN 201710324446A CN 107129305 A CN107129305 A CN 107129305A
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fiber
self
situ
prepares
hydrochloric acid
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CN107129305B (en
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豆志河
张廷安
刘燕
谢恺煜
范世钢
石浩
吕国志
潘喜娟
赵秋月
牛丽萍
傅大学
张伟光
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/563—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on boron carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • C01F5/04—Magnesia by oxidation of metallic magnesium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
    • C04B35/62277—Fibres based on carbides
    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5248—Carbon, e.g. graphite

Abstract

A kind of situ-combustion synthesis prepares B4The method of fiber C, belongs to ceramic fibre technical field.This method is put into progress mechanical activation processing in high energy ball mill by the way that boron oxide and magnesium powder are mixed in molar ratio；It is well mixed, is put into mould in molar ratio with carbon fiber again, block blank is pressed into 10~60MPa, carries out self-propagating reaction；Product is immersed in watery hydrochloric acid, Strengthen education in closed reactor is placed in, last spray-wall interaction obtains high-purity boron carbide fiber product.This method prepares the good two-dimentional ceramic fibre material of high-purity, high activity, sintering character.Cost of material is low, and energy consumption is low, simple to operate, requires low to process conditions and instrument and equipment, changes the B of existing two-dimensional fiber structure4C productions high energy consumption, the present situation of low-yield.Activated using high-energy ball milling, improve the shortcoming of traditional magnesium reduction process；Using self- propagating powder-making technique, the product of gained has purity high, and size distribution is controllable, the high advantage of powder activity.

Description

A kind of situ-combustion synthesis prepares B4The method of fiber C
Technical field
The invention belongs to ceramic fibre technical field, and in particular to a kind of situ-combustion synthesis prepares B4The method of fiber C.
Background technology
Boron carbide is mainly used in making boron carbide ceramics, and boron carbide ceramics has that density is small, hardness is high, high-modulus, strong resistance to The features such as mill property, high antioxidant, stronger acid-resistant corrosion and excellent neutron-absorbing performance, before wide application Scape, is widely used in bullet resistant material, wear-resisting and self-lubricating material, cutting and grinding instrument, radiation proof material and atomic pile control System and shielding material etc..
Boron carbide is most important for impacting purposes (such as flak jackets, tank front fender and military engagement vehicle panel) Material.In military engagement, it can be greatly improved vehicle and aircraft improves depositing for survivability and activity and army personnel Motility rate.But boron carbide fragility is big, and usually based on brittle fracture, which greatly limits the application of boron carbide ceramics.Improve at present The method of ceramics toughness has a variety of, can be using particle enhancing or the arrangement with specific die orientation texture or using brilliant Palpus, nanotube and fiber reinforced mode.B4Fiber C is a kind of two-dimentional ceramic material of most important of which.Existing business Metaplasia production. art is mainly the extraordinary sintering process of superfine powder, and the method needs high temperature, and with yield rate is low, energy consumption is big, production The uppity shortcoming of product pattern.Existing laboratory route has vapour deposition process, orientation fiber elongation method etc., and these routes are typically Cost is high, yield poorly and energy consumption is big.
Based on the existing shortcoming for preparing boron carbide fibre, propose with mechanical activation, self-propagating synthesis, closed Strengthen education and The new technology route of acid solution pyrolysis cyclical produces boron carbide fibre, with technological process it is short, without intermediate step, cost be low, product The good advantage of performance, therefore be more easy to realize serialization, it is one of most potential boron carbide fibre preparation technology, meets drop The low cost of raw material, the national economic development strategy for saving the energy, the industrialized economy benefit and social benefit of this technology are all It is very considerable.
The content of the invention
The shortcoming of boron carbide is prepared for prior art, the present invention provides a kind of situ-combustion synthesis and prepares B4Fiber C Method, high-purity boron carbide fiber product is obtained by mechanical activation, self-propagating synthesis, closed Strengthen education and spray-wall interaction. This method is a kind of high-purity, high activity, the two-dimentional ceramic fibre material preparation method of sintering character well.This method raw material into This is low, and energy consumption is low, simple to operate, requires low to process conditions and instrument and equipment, changes the B of existing two-dimensional fiber structure4C is produced High energy consumption, the present situation of low-yield, are that industrialized production is laid a good foundation.Activated using high-energy ball milling, improve traditional magnesiothermic reduction Method raw material availability is low, and product purity is low, reaction process and the unmanageable situation of product pattern；Using self- propagating powder skill Art, the product of gained has purity high, and size distribution is controllable, the advantages of powder activity is high.
A kind of situ-combustion synthesis of the present invention prepares B4The method of fiber C, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：(2~4)；
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with carbon fiber, is put into mould, in 10~60MPa pressures Block blank is made, is placed in self-propagating reaction stove and triggers progress self-propagating reaction, reaction mass, reaction mass cooling is obtained Afterwards, B is obtained4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：(2~4)：(0.5~0.6)；
Step 3：Closed Strengthen education
By B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, it is placed in closed reactor Strengthen education, removal of impurities, filtering obtains leachate and filter residue, and leachate is reclaimed into acid cycle profit using spray-wall interaction technology With by residue washing, B is made in vacuum drying4Fiber C；
Step 4：Spray-wall interaction
Leachate is atomized, is blown into high temperature pyrolysis stove, is pyrolyzed, nanoscale magnesium and pyrolysis tail is obtained Gas；Wherein, the hydrogen chloride in pyrolysis tail gas forms hydrochloric acid after absorption, returns to sealing Strengthen education process and recycles；In height Pyrolysis temperature in warm pyrolysis oven is 200~700 DEG C, and pyrolysis time is 0.5~60min.
In described step 1, the technological parameter of described high energy ball mill is：Pellet mass ratio is 1：(5~30), ball milling Rotating speed is 150~450rpm, and Ball-milling Time is 15~150min.
In described step 2, the mode of described reaction mass cooling is water cooling or furnace cooling.
In described step 2, the initiation method of described self-propagating reaction is local methods of printing or overall heating；Its In, local methods of printing refers to local with heating wire heating response block blank in self-propagating reaction stove, initiation self-propagating reaction； Overall heating refers to block blank integrally heats up in self-propagating reaction stove, untill self-propagating reaction occurs, temperature Control is at 500~800 DEG C.
In described step 3, the molar concentration of described watery hydrochloric acid is 1~12mol/L.
It is described by B in described step 34Combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes In, hydrochloric acid and B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to rubbing for reactive chemistry equation You compare, and add the amount of hydrochloric acid 10~40% more than theoretical amount, and the chemical equation of reaction institute foundation is MgO+2H+=Mg2++H2O。
In described step 3, the technological parameter of described Strengthen education is：Extraction temperature is 20~80 DEG C, extraction time For 60~360min.
Described by residue washing in described step 3, vacuum drying concrete operation step is：Leachate will be removed Filter residue be washed with water to washing lotion for neutrality, then dried under vacuum in vacuum drying oven, drying temperature be 50~120 DEG C, the time is at least 4h.
In described step 4, the mode that described leachate carries out atomization injection is：In 0.13~0.6MPa pressure Under, leachate is carried out into high temperature pyrolysis stove by atomization injection by atomizer.
In described step 4, the mass concentration of magnesium chloride is 50~300g/L in described leachate.
In described step 4, the granularity of described nanoscale magnesium is 80~400nm.
In described step 4, the concentration for the hydrochloric acid that described hydrogen chloride is formed after absorption is 1~8mol/L.
A kind of situ-combustion synthesis of the present invention prepares B4The method of fiber C, its principle and beneficial effect are：
1st, handled by high-energy ball milling boron oxide and magnesium powder powder is subjected to deformation repeatedly, it is cold welding, broken, so as to reach The level of atomic level alloying between element；At ball milling initial stage, material is repeated extrusion, and by broken, soldering, is squeezed again Pressure, forms the composite particles of stratiform, and composite particles produce newborn atomic plane, stratiform knot under the continuous effect of mechanical mill power Structure is constantly refined；In mechanical milling process, the formation of layer structure, the reduction of synusia spacing shortens the interatomic diffusion road of solid-state Footpath, alloying process accelerates between making element, and powder grain degree substantially diminishes；Substantial amounts of collision phenomenon occurs in mechanical milling process simultaneously Between ball-powder ball, serious plastic deformation occurs under collision effect for captured powder, makes powder by two collisions " miniature " forging effect of ball；The high density of defects and nano-interface that ball milling is produced can be big during follow-up self-propagating reaction The big progress for promoting self-propagating reaction, it is ensured that the conversion ratio and product yield of reaction；Simultaneously after high-energy ball milling is handled The reaction mass of the high activity state of acquisition has higher self-propagating reaction speed and thermograde, therefore ensure that reaction product Nanocrystalline size and particle development degree.
B of the present invention2O3Mechanical activation pretreatment is carried out first with Mg, can obtain B2O3It is very refined and abundant with Mg The presoma for the high activity that disperse is combined；The presoma is uniformly mixed with carbon fiber again, both can ensure C fiber morphology not Destroyed, ensure that boracic presoma obtains mechanical activation again, improve material reaction activity.Mixture is carried out from climing together When prolonging reaction, boracic presoma is understood itself occurs the ultra-fine high activity B simple substance of strong exothermic reaction generation first；Due to superelevation Thermal discharge newly-generated B can be triggered to be attached to fibrous C immediately carry out combination reaction, directly generate fibrous B4C Product, therefore the morphology controllable of this handicraft product, raw material availability are high.
High-energy ball milling processing, obtains the active presoma of boracic, it is ensured that the carry out degree of reaction, improves reactant Conversion ratio；Self-propagating reaction pattern is used simultaneously, is taken full advantage of and is reacted the reaction heat of itself, reduces energy consumption；It is simple to operate, Low, the B of gained is required to process conditions4Fiber C has purity high, morphology controllable, the advantages of agglutinating property is good.
2nd, leaching process of the invention is carried out in enclosed high pressure kettle, it is ensured that B4The purity and leaching efficiency of C products；From climing Prolong that the MgO impurity generated in course of reaction is loose, product is easily broken, MgO impurity reactivity is high, MgO impurity is wrapped in B4C Surface, beneficial to the leaching of hydrochloric acid.Because acidleach process is carried out in enclosed high pressure kettle, leachate less turbulence is greatly carried Height, wherein diffusion mass transfer process is also greatly strengthened, so as to ensure that MgO thorough removal, it is ensured that B4C products it is high-purity Degree., need to be by salt excessive acid, while to ensure clean result, in washing process to ensure that MgO is removed completely in leaching process Washed using dynamic circulation, i.e., washing lotion keeps constant water level in sink in washing process, how many washing lotion discharge is with regard to how many Fresh water is supplemented, washing to neutrality.
3rd, the beneficial effects of the present invention are magnesium chloride solution is handled by the way of spray-wall interaction, reaction efficiency is high, Nanoscale magnesium products can be obtained, added value of product is improved, while acid and water that production process is produced were by thermally decomposing Journey can be realized and recycled, and realize whole process without useless clean manufacturing.
4th, the logical equation of above-mentioned self-propagating reaction is as follows：2B2O3+ 6Mg+C=B4C+6MgO+ △ H, wherein △ H are represented certainly Spread the reaction heat of reaction generating process reaction release；
Leaching process reaction is as follows in the above method：MgO+2HCl=MgCl2+H2O；
The reaction of thermal decomposition process is as follows in the above method：MgCl2+H2O=MgO+2HCl.
5th, self-propagating reaction of the invention can be triggered using local methods of printing, easy with operation, energy-conservation it is excellent Point.
6th, this process efficient, energy-conservation, flow are short, low for equipment requirements, are the production technologies of clean and effective safety, it is easy to work Industry is promoted.This method may also used to prepare the ceramic fibres such as SiC.
Brief description of the drawings
Fig. 1 is the method production B using the present invention4The process chart of fiber C.
Embodiment
With reference to embodiment, the present invention is described in further detail.
Boron oxide, magnesium powder, the hydrochloric acid used in following examples is technical grade product.
Boron oxide, magnesium powder, the granularity of carbon dust are respectively less than 0.5mm.
Carbon fiber powder used is high-purity carbon fiber powder to commercially produce, and granularity is less than 100 mesh, 0.5~30 μm of diameter, Draw ratio 10~50.
The self-propagating reaction stove used in following examples self- propagating disclosed in patent " ZL200510047308.2 " is anti- Stove is answered, the reacting furnace is made up of reaction vessel, heater, sight glass, transformer, function recording instrument, thermocouple, gas valve.
The model for the planetary high-energy ball mill that high-energy ball milling processing is used is Pulveristte4, ball in following examples Mill rotating speed is 100~450rpm.
The time of self-propagating reaction is 5~90s in following examples.
Drying time is at least 4h in following examples.
" metal chloride disclosed in CN 103771344A " is molten for patent for the spray pyrolysis unit used in following examples Liquid jet is blown rapid pyrolysis apparatus.The device includes jet pyrolysis system, cyclone separation system, tail gas absorbing system.
Embodiment 1
A kind of situ-combustion synthesis prepares B4The method of fiber C, its process chart is shown in Fig. 1, specifically enters according to the following steps OK：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：3；The technological parameter of high energy ball mill is：Pellet mass ratio is 1：10, rotational speed of ball-mill is 300rpm, and Ball-milling Time is 30min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with carbon fiber, is put into mould, is pressed into 10MPa Block blank, is placed in self-propagating reaction stove to be triggered using local methods of printing and carries out self-propagating reaction, temperature control at 500 DEG C, Reaction mass is obtained, after reaction mass furnace cooling, B is obtained4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：3：0.5；
Step 3：Closed Strengthen education
By B4Combustion product of the C products Dispersed precipitate in MgO matrixes immerses molar concentration in 5mol/L watery hydrochloric acid, to put In closed reactor, in 80 DEG C of Strengthen education 120min, removal of impurities, filtering obtains leachate and filter residue, leachate is used Spray-wall interaction technology reclaim acid solution recycle, by filter residue be washed with water to washing lotion for neutrality, then in vacuum drying oven Dried under vacuum condition, drying temperature is 50 DEG C, and the time is 24h, B is made4Fiber C；
By B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid and B4C products disperse point The addition of combustion product of the cloth in MgO matrixes, according to the mol ratio of reactive chemistry equation, adds the amount of hydrochloric acid than theoretical Amount many 10%, the chemical equation of reaction institute foundation is MgO+2H+=Mg2++H2O。
Wherein, the mass concentration of magnesium chloride is 300g/L in leachate.
Step 4：Spray-wall interaction
Under 0.2MPa pressure, leachate is atomized by atomizer, is blown into high temperature pyrolysis stove, is carried out Pyrolysis, obtains nanoscale magnesium and pyrolysis tail gas that granularity is 80nm；Wherein, the shape after absorption of the hydrogen chloride in pyrolysis tail gas Into the hydrochloric acid that molar concentration is 6mol/L, return to sealing Strengthen education process and recycle；Pyrolysis temperature in high temperature pyrolysis stove Spend for 400 DEG C, pyrolysis time is 10min.
Embodiment 2
A kind of situ-combustion synthesis prepares B4The method of fiber C, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：2.5；The technological parameter of high energy ball mill is：Pellet mass ratio For 1：15, rotational speed of ball-mill is 200rpm, and Ball-milling Time is 60min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with carbon fiber, is put into mould, is pressed into 20MPa Block blank, is placed in self-propagating reaction stove to be triggered using local methods of printing and carries out self-propagating reaction, temperature control at 800 DEG C, Reaction mass is obtained, after reaction mass furnace cooling, B is obtained4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：2.5：0.5；
Step 3：Closed Strengthen education
By B4Combustion product of the C products Dispersed precipitate in MgO matrixes immerses molar concentration in 8mol/L watery hydrochloric acid, to put In closed reactor, in 80 DEG C of Strengthen education 100min, removal of impurities, filtering obtains leachate and filter residue, leachate is used Spray-wall interaction technology reclaim acid solution recycle, by filter residue be washed with water to washing lotion for neutrality, then in vacuum drying oven Dried under vacuum condition, drying temperature is 120 DEG C, and the time is 4h, B is made4Fiber C；
By B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid and B4C products disperse point The addition of combustion product of the cloth in MgO matrixes, according to the mol ratio of reactive chemistry equation, adds the amount of hydrochloric acid than theoretical Amount many 40%, the chemical equation of reaction institute foundation is MgO+2H+=Mg2++H2O。
Wherein, the mass concentration of magnesium chloride is 50g/L in leachate.
Step 4：Spray-wall interaction
Under 0.3MPa pressure, leachate is atomized by atomizer, is blown into high temperature pyrolysis stove, is carried out Pyrolysis, obtains nanoscale magnesium and pyrolysis tail gas that granularity is 400nm；Wherein, the hydrogen chloride in pyrolysis tail gas is after absorption The hydrochloric acid that molar concentration is 3mol/L is formed, sealing Strengthen education process is returned and recycles；Pyrolysis in high temperature pyrolysis stove Temperature is 500 DEG C, and pyrolysis time is 20min.
Embodiment 3
A kind of situ-combustion synthesis prepares B4The method of fiber C, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：3；The technological parameter of high energy ball mill is：Pellet mass ratio is 1：20, rotational speed of ball-mill is 400rpm, and Ball-milling Time is 100min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with carbon fiber, is put into mould, is pressed into 40MPa Block blank, is placed in self-propagating reaction stove to be triggered using local methods of printing and carries out self-propagating reaction, temperature control at 600 DEG C, Reaction mass is obtained, after reaction mass furnace cooling, B is obtained4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：3：0.6；
Step 3：Closed Strengthen education
By B4C products Dispersed precipitate in MgO matrixes combustion product immersion molar concentration be 10mol/L watery hydrochloric acid in, It is placed in closed reactor, in 60 DEG C of Strengthen education 120min, removal of impurities, filtering obtains leachate and filter residue, leachate is adopted Acid solution is reclaimed with spray-wall interaction technology to recycle, it is neutrality that filter residue is washed with water into washing lotion, then in vacuum drying oven Dry under vacuum, drying temperature is 100 DEG C, and the time is 8h, B is made4Fiber C；
By B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid and B4C products disperse point The addition of combustion product of the cloth in MgO matrixes, according to the mol ratio of reactive chemistry equation, adds the amount of hydrochloric acid than theoretical Amount many 30%, the chemical equation of reaction institute foundation is MgO+2H+=Mg2++H2O。
Wherein, the mass concentration of magnesium chloride is 50g/L in leachate.
Step 4：Spray-wall interaction
Under 0.4MPa pressure, leachate is atomized by atomizer, is blown into high temperature pyrolysis stove, is carried out Pyrolysis, obtains nanoscale magnesium and pyrolysis tail gas that granularity is 320nm；Wherein, the hydrogen chloride in pyrolysis tail gas is after absorption The hydrochloric acid that molar concentration is 3mol/L is formed, sealing Strengthen education process is returned and recycles；Pyrolysis in high temperature pyrolysis stove Temperature is 300 DEG C, and pyrolysis time is 15min.
Embodiment 4
A kind of situ-combustion synthesis prepares B4The method of fiber C, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：2.7；The technological parameter of high energy ball mill is：Pellet mass ratio For 1：8, rotational speed of ball-mill is 250rpm, and Ball-milling Time is 40min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with carbon fiber, is put into mould, is pressed into 40MPa Block blank, is placed in self-propagating reaction stove to be triggered using local methods of printing and carries out self-propagating reaction, temperature control at 520 DEG C, Reaction mass is obtained, after reaction mass furnace cooling, B is obtained4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：2.7：0.5；
Step 3：Closed Strengthen education
By B4Combustion product of the C products Dispersed precipitate in MgO matrixes immerses molar concentration in 2mol/L watery hydrochloric acid, to put In closed reactor, in 50 DEG C of Strengthen education 180min, removal of impurities, filtering obtains leachate and filter residue, leachate is used Spray-wall interaction technology reclaim acid solution recycle, by filter residue be washed with water to washing lotion for neutrality, then in vacuum drying oven Dried under vacuum condition, drying temperature is 110 DEG C, and the time is 6h, B is made4Fiber C；
By B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid and B4C products disperse point The addition of combustion product of the cloth in MgO matrixes, according to the mol ratio of reactive chemistry equation, adds the amount of hydrochloric acid than theoretical Amount many 30%, the chemical equation of reaction institute foundation is MgO+2H+=Mg2++H2O。
Wherein, the mass concentration of magnesium chloride is 50g/L in leachate.
Step 4：Spray-wall interaction
Under 0.2MPa pressure, leachate is atomized by atomizer, is blown into high temperature pyrolysis stove, is carried out Pyrolysis, obtains nanoscale magnesium and pyrolysis tail gas that granularity is 260nm；Wherein, the hydrogen chloride in pyrolysis tail gas is after absorption The hydrochloric acid that molar concentration is 6mol/L is formed, sealing Strengthen education process is returned and recycles；Pyrolysis in high temperature pyrolysis stove Temperature is 600 DEG C, and pyrolysis time is 30min.
Embodiment 5
A kind of situ-combustion synthesis prepares B4The method of fiber C, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：4；The technological parameter of high energy ball mill is：Pellet mass ratio is 1：30, rotational speed of ball-mill is 200rpm, and Ball-milling Time is 30min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with carbon fiber, is put into mould, is pressed into 30MPa Block blank, is placed in self-propagating reaction stove to be triggered using overall methods of printing and carries out self-propagating reaction, temperature control at 700 DEG C, Reaction mass is obtained, after reaction mass furnace cooling, B is obtained4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：4：0.6；
Step 3：Closed Strengthen education
By B4C products Dispersed precipitate in MgO matrixes combustion product immersion molar concentration be 10mol/L watery hydrochloric acid in, It is placed in closed reactor, in 40 DEG C of Strengthen education 120min, removal of impurities, filtering obtains leachate and filter residue, leachate is adopted Acid solution is reclaimed with spray-wall interaction technology to recycle, it is neutrality that filter residue is washed with water into washing lotion, then in vacuum drying oven Dry under vacuum, drying temperature is 70 DEG C, and the time is 12h, B is made4Fiber C；
By B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid and B4C products disperse point The addition of combustion product of the cloth in MgO matrixes, according to the mol ratio of reactive chemistry equation, adds the amount of hydrochloric acid than theoretical Amount many 25%, the chemical equation of reaction institute foundation is MgO+2H+=Mg2++H2O。
Wherein, the mass concentration of magnesium chloride is 100g/L in leachate.
Step 4：Spray-wall interaction
Under 0.5MPa pressure, leachate is atomized by atomizer, is blown into high temperature pyrolysis stove, is carried out Pyrolysis, obtains nanoscale magnesium and pyrolysis tail gas that granularity is 380nm；Wherein, the hydrogen chloride in pyrolysis tail gas is after absorption The hydrochloric acid that molar concentration is 5mol/L is formed, sealing Strengthen education process is returned and recycles；Pyrolysis in high temperature pyrolysis stove Temperature is 600 DEG C, and pyrolysis time is 15min.
Embodiment 6
A kind of situ-combustion synthesis prepares B4The method of fiber C, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：2；The technological parameter of high energy ball mill is：Pellet mass ratio is 1：30, rotational speed of ball-mill is 450rpm, and Ball-milling Time is 15min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with carbon fiber, is put into mould, is pressed into 60MPa Block blank, is placed in self-propagating reaction stove to be triggered using local methods of printing and carries out self-propagating reaction, temperature control at 800 DEG C, Reaction mass is obtained, after reaction mass furnace cooling, B is obtained4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：2：0.5；
Step 3：Closed Strengthen education
By B4C products Dispersed precipitate in MgO matrixes combustion product immersion molar concentration be 12mol/L watery hydrochloric acid in, It is placed in closed reactor, in 20 DEG C of Strengthen education 360min, removal of impurities, filtering obtains leachate and filter residue, leachate is adopted Acid solution is reclaimed with spray-wall interaction technology to recycle, it is neutrality that filter residue is washed with water into washing lotion, then in vacuum drying oven Dry under vacuum, drying temperature is 120 DEG C, and the time is 4h, B is made4Fiber C；
By B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid and B4C products disperse point The addition of combustion product of the cloth in MgO matrixes, according to the mol ratio of reactive chemistry equation, adds the amount of hydrochloric acid than theoretical Amount many 10%, the chemical equation of reaction institute foundation is MgO+2H+=Mg2++H2O。
Wherein, the mass concentration of magnesium chloride is 50g/L in leachate.
Step 4：Spray-wall interaction
Under 0.13MPa pressure, leachate is atomized by atomizer, is blown into high temperature pyrolysis stove, enters Row pyrolysis, obtains nanoscale magnesium and pyrolysis tail gas that granularity is 400nm；Wherein, the hydrogen chloride in pyrolysis tail gas is through absorbing The hydrochloric acid that molar concentration is 1mol/L is formed afterwards, is returned to sealing Strengthen education process and is recycled；Heat in high temperature pyrolysis stove It is 700 DEG C to solve temperature, and pyrolysis time is 0.5min.
Embodiment 7
A kind of situ-combustion synthesis prepares B4The method of fiber C, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：2.5；The technological parameter of high energy ball mill is：Pellet mass ratio For 1：15, rotational speed of ball-mill is 200rpm, and Ball-milling Time is 60min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with carbon fiber, is put into mould, is pressed into 20MPa Block blank, is placed in self-propagating reaction stove to be triggered using local methods of printing and carries out self-propagating reaction, temperature control at 800 DEG C, Reaction mass is obtained, after reaction mass furnace cooling, B is obtained4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：2.5：0.5；
Step 3：Closed Strengthen education
By B4Combustion product of the C products Dispersed precipitate in MgO matrixes immerses molar concentration in 1mol/L watery hydrochloric acid, to put In closed reactor, in 80 DEG C of Strengthen education 60min, removal of impurities, filtering obtains leachate and filter residue, leachate is used Spray-wall interaction technology reclaim acid solution recycle, by filter residue be washed with water to washing lotion for neutrality, then in vacuum drying oven Dried under vacuum condition, drying temperature is 50 DEG C, and the time is 12h, B is made4Fiber C；
By B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid and B4C products disperse point The addition of combustion product of the cloth in MgO matrixes, according to the mol ratio of reactive chemistry equation, adds the amount of hydrochloric acid than theoretical Amount many 40%, the chemical equation of reaction institute foundation is MgO+2H+=Mg2++H2O。
Wherein, the mass concentration of magnesium chloride is 300g/L in leachate.
Step 4：Spray-wall interaction
Under 0.6MPa pressure, leachate is atomized by atomizer, is blown into high temperature pyrolysis stove, is carried out Pyrolysis, obtains nanoscale magnesium and pyrolysis tail gas that granularity is 80nm；Wherein, the shape after absorption of the hydrogen chloride in pyrolysis tail gas Into the hydrochloric acid that molar concentration is 8mol/L, return to sealing Strengthen education process and recycle；Pyrolysis temperature in high temperature pyrolysis stove Spend for 200 DEG C, pyrolysis time is 60min.

Claims (10)

1. a kind of situ-combustion synthesis prepares B4The method of fiber C, it is characterised in that carry out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains before boracic Drive body mixture；Wherein, in molar ratio, B2O3：Mg=1：(2~4)；
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with carbon fiber, is put into mould, is pressed into 10~60MPa Block blank, is placed in self-propagating reaction stove and triggers progress self-propagating reaction, obtains reaction mass, after reaction mass cooling, obtains To B4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：(2~4)：(0.5~0.6)；
Step 3：Closed Strengthen education
By B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, it is placed in closed reactor and strengthens Leach, removal of impurities, filtering obtains leachate and filter residue, leachate is reclaimed into acid solution using spray-wall interaction technology recycles, will B is made in residue washing, vacuum drying4Fiber C；
Step 4：Spray-wall interaction
Leachate is atomized, is blown into high temperature pyrolysis stove, is pyrolyzed, nanoscale magnesium and pyrolysis tail gas is obtained； Wherein, the hydrogen chloride in pyrolysis tail gas forms hydrochloric acid after absorption, returns to sealing Strengthen education process and recycles；In high warm It is 200~700 DEG C to solve the pyrolysis temperature in stove, and pyrolysis time is 0.5~60min.
2. situ-combustion synthesis as claimed in claim 1 prepares B4The method of fiber C, it is characterised in that in described step 1, The technological parameter of described high energy ball mill is：Pellet mass ratio is 1：(5~30), rotational speed of ball-mill is 150~450rpm, ball milling Time is 15~150min.
3. situ-combustion synthesis as claimed in claim 1 prepares B4The method of fiber C, it is characterised in that in described step 2, The mode of described reaction mass cooling is water cooling or furnace cooling；
In described step 2, the initiation method of described self-propagating reaction is local methods of printing or overall heating；Wherein, office Portion's methods of printing refers to local with heating wire heating response block blank in self-propagating reaction stove, initiation self-propagating reaction；It is overall Heating refers to block blank integrally heats up in self-propagating reaction stove, untill self-propagating reaction occurs, temperature control At 500~800 DEG C.
4. situ-combustion synthesis as claimed in claim 1 prepares B4The method of fiber C, it is characterised in that in described step 3, The molar concentration of described watery hydrochloric acid is 1~12mol/L.
5. situ-combustion synthesis as claimed in claim 1 prepares B4The method of fiber C, it is characterised in that in described step 3, It is described by B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid and B4C product Dispersed precipitates The addition of combustion product in MgO matrixes, according to the mol ratio of reactive chemistry equation, the amount for adding hydrochloric acid compares theoretical amount Many 10~40%, the chemical equation of reaction institute foundation is MgO+2H+=Mg2++H2O；
In described step 3, the technological parameter of described Strengthen education is：Extraction temperature is 20~80 DEG C, and extraction time is 60 ~360min.
6. situ-combustion synthesis as claimed in claim 1 prepares B4The method of fiber C, it is characterised in that in described step 3, It is described by residue washing, vacuum drying concrete operation step is：The filter residue for removing leachate is washed with water into washing lotion is Neutrality, is then dried under vacuum in vacuum drying oven, and drying temperature is 50~120 DEG C, and the time is at least 4h.
7. situ-combustion synthesis as claimed in claim 1 prepares B4The method of fiber C, it is characterised in that in described step 4, The mode that described leachate carries out atomization injection is：Under 0.13~0.6MPa pressure, by atomizer by leachate Atomization injection is carried out into high temperature pyrolysis stove.
8. situ-combustion synthesis as claimed in claim 1 prepares B4The method of fiber C, it is characterised in that in described step 4, The mass concentration of magnesium chloride is 50~300g/L in described leachate.
9. situ-combustion synthesis as claimed in claim 1 prepares B4The method of fiber C, it is characterised in that in described step 4, The granularity of described nanoscale magnesium is 80~400nm.
10. situ-combustion synthesis as claimed in claim 1 prepares B4The method of fiber C, it is characterised in that described step 4 In, the concentration for the hydrochloric acid that described hydrogen chloride is formed after absorption is 1~8mol/L.
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Publication number Priority date Publication date Assignee Title
CN109574014A (en) * 2018-10-22 2019-04-05 西安建筑科技大学 A kind of B4Fiber C felt and preparation method thereof
CN109970066A (en) * 2019-04-23 2019-07-05 桂林理工大学 A method of quickly preparing the dendritic nanofiber of boron carbide
WO2020168883A1 (en) * 2019-02-21 2020-08-27 刘丽 Method for preparing metal powder material
CN114873596A (en) * 2022-04-29 2022-08-09 淄博晟钛复合材料科技有限公司 Method for preparing boron carbide powder by dilution self-propagating method
CN114956842A (en) * 2022-05-05 2022-08-30 武汉工程大学 Boron carbide fiber/boron carbide ceramic composite material and preparation method thereof

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CN1408639A (en) * 2002-09-23 2003-04-09 中国科学院长春应用化学研究所 Process for preparing boron carbide powder
CN103466648A (en) * 2013-08-28 2013-12-25 东北大学 Cleaner production method for preparing superfine powder through self-propagating metallurgy method

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CN1408639A (en) * 2002-09-23 2003-04-09 中国科学院长春应用化学研究所 Process for preparing boron carbide powder
CN103466648A (en) * 2013-08-28 2013-12-25 东北大学 Cleaner production method for preparing superfine powder through self-propagating metallurgy method

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109574014A (en) * 2018-10-22 2019-04-05 西安建筑科技大学 A kind of B4Fiber C felt and preparation method thereof
CN109574014B (en) * 2018-10-22 2022-04-19 西安建筑科技大学 B4C fiber felt and preparation method thereof
WO2020168883A1 (en) * 2019-02-21 2020-08-27 刘丽 Method for preparing metal powder material
US11491544B2 (en) 2019-02-21 2022-11-08 Li Liu Preparation method of metal powder material
CN109970066A (en) * 2019-04-23 2019-07-05 桂林理工大学 A method of quickly preparing the dendritic nanofiber of boron carbide
CN109970066B (en) * 2019-04-23 2022-09-30 桂林理工大学 Method for rapidly preparing boron carbide dendritic nano-fibers
CN114873596A (en) * 2022-04-29 2022-08-09 淄博晟钛复合材料科技有限公司 Method for preparing boron carbide powder by dilution self-propagating method
CN114956842A (en) * 2022-05-05 2022-08-30 武汉工程大学 Boron carbide fiber/boron carbide ceramic composite material and preparation method thereof

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