CN108503368A - A kind of fabricated in situ CNTs/ZrB2Nano composite powder and preparation method thereof - Google Patents

A kind of fabricated in situ CNTs/ZrB2Nano composite powder and preparation method thereof Download PDF

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CN108503368A
CN108503368A CN201810202882.8A CN201810202882A CN108503368A CN 108503368 A CN108503368 A CN 108503368A CN 201810202882 A CN201810202882 A CN 201810202882A CN 108503368 A CN108503368 A CN 108503368A
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zrb
powder
preparation
cnts
catalyst
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金华
孟松鹤
解维华
许承海
李金平
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6267—Pyrolysis, carbonisation or auto-combustion reactions
    • C04B35/806—
    • 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
    • C04B2235/5284—Hollow fibers, e.g. nanotubes
    • C04B2235/5288—Carbon nanotubes

Abstract

The present invention relates to a kind of fabricated in situ CNTs/ZrB2Nano composite powder and preparation method thereof, the preparation method include the following steps：(1), M is providedxOy/ZrB2Catalyst precursor, wherein M indicates that metallic catalyst, x indicate MxOyThe number of metallic atom in oxide molecule, y indicate MxOyThe number of oxygen atom in oxide molecule；(2), the M is restoredxOy/ZrB2Catalyst precursor obtains M/ZrB2Composite catalyst；(3), to M/ZrB2C is passed through in composite catalyst2H2With N2Mixed gas, make M/ZrB2Nanometer ZrB in composite catalyst2The surface in situ of powder grows CNTs, obtains CNTs/ZrB2Nano composite powder.This method is practical, self toughening effect protrudes, and the superhigh temperature heat insulation material for further sintering high temperature resistant, high tenacity, anti-yaw damper, anti-thermal shock provides raw material.

Description

A kind of fabricated in situ CNTs/ZrB2Nano composite powder and preparation method thereof
Technical field
The present invention relates to field of material technology more particularly to a kind of fabricated in situ CNTs/ZrB2The system of nano composite powder Preparation Method and by its CNTs/ZrB obtained2Nano composite powder.
Background technology
ZrB2With low-density, excellent chemical stability, high-melting-point, high rigidity, excellent thermal conductivity and electric conductivity etc. Feature so that ZrB2Based ultra-high temperature ceramic material becomes a kind of up-and-coming substitute of high-temperature structural material, such as reenters winged The nose cone and leading edge of row device and the propulsion system of rocket.But single-phase ZrB2Since fracture toughness and bending strength are relatively low, and And high temperature oxidation resistance is insufficient (900~1100s DEG C starts to aoxidize), it is caused to cannot be satisfied the requirement of hot environment.
For single-phase ZrB2Ceramics, by adding graphite flake layer, improvement sintering process and preparing the methods of ceramic layered Improve ZrB2The toughness of based ultra-high temperature ceramics, but limited by interface is thermally matched, it is unable to get excellent combination property always Material.Obviously, this by adding Section 2 or multiphase (MoSi2、CrSi2, SiC, Fe, Ni, carbon fiber) toughening mode without Method effectively provides the toughness of material under the premise of not losing other performances.
In view of the above-mentioned problems, the present invention is considered as the mode of self toughening, in ZrB2Basis on in-situ preparation toughening Phase forms the original powder of excellent toughening effect, to make up the deficiency of the Section 2 toughening such as carbon fiber, SiC and graphite flake layer. But at present about ZrB2The powder research of self toughening is very few, in ZrB2The preparation method that surface in situ generates toughening phase yet there are no report Road.
Invention content
(1) technical problems to be solved
The technical problem to be solved by the present invention is to：For in the prior art not about ZrB2Self toughening powder preparation method Relevant report, the present invention provides practicable, the self toughening effect CNTs/ZrB outstanding of one kind2Nano composite powder Preparation method can obtain the ZrB with self toughening effect2Nano composite powder, for further sintering high temperature resistant, high tenacity, The superhigh temperature heat insulation material offer raw material of anti-yaw damper, anti-thermal shock.
(2) technical solution
In order to solve the above technical problem, the present invention provides a kind of fabricated in situ CNTs/ZrB2Nano composite powder Preparation method includes the following steps：
(1), M is providedxOy/ZrB2Catalyst precursor, wherein M indicates that metallic catalyst, x indicate MxOyOxide molecule The number of middle metallic atom, y indicate MxOyThe number of oxygen atom in oxide molecule；
(2), the M is restoredxOy/ZrB2Catalyst precursor obtains M/ZrB2Composite catalyst；
(3), to M/ZrB2C is passed through in composite catalyst2H2With N2Mixed gas, make M/ZrB2Nanometer in composite catalyst ZrB2The surface in situ of powder grows CNTs, obtains CNTs/ZrB2Nano composite powder.
Preferably, in step (1), the offer MxOy/ZrB2The step of catalyst precursor includes：
(11), by nanometer ZrB2Powder and Mn+Solution is uniformly mixed, and then, strong base solution is added, obtains M (OH)n/ZrB2 Binary colloidal mixed liquor, wherein n indicates Mn+The valence state of middle metal ion；
(12), the M (OH) is filteredn/ZrB2Binary colloidal mixed liquor collects solid, cleans the solid to neutrality, obtain To M (OH)n/ZrB2Binary colloidal；
(13), by the M (OH)n/ZrB2Binary colloidal is dried, grinds, and obtains M (OH)n/ZrB2Powder；
(14), the M (OH) is calcinedn/ZrB2Powder obtains MxOy/ZrB2Catalyst precursor.
Preferably, in step (11), the ZrB2The granularity of powder is no more than 100nm, preferably 20~100nm, most Preferably 60nm.
Matrix ZrB2The granularity of powder is equal with the diameter of in-situ preparation CNTs as possible, is found through experiments that, this technique system Standby obtained CNTs diameters are in 60 ± 10nm, therefore the ZrB of preferably 60nm2Powder.
Preferably, in step (11), the MnFor Ni2+Or Y3+, then, work as Mn+For Ni2+When, x 1, y 1；Work as Mn+For Y3+When, x 2, y 3；And/or
The highly basic is the hydroxide of alkali metal.
Preferably, the step (2) carries out as follows：
By MxOy/ZrB2Catalyst precursor is placed in the flat-temperature zone of tube furnace, in N2Flat-temperature zone is warming up under protection 750~850 DEG C, N is closed afterwards2, it is passed through H2, to MxOy/ZrB2Catalyst precursor restores 1~2 hour, obtains M/ZrB2It is compound to urge Agent.
Preferably, the M/ZrB2In composite catalyst, the mass fraction of M is 10~35%.
Preferably, the step (3) carries out as follows：
(31), in N2Flat-temperature zone is warming up to 1150~1200 DEG C under protection；
(32), it is passed through C to flat-temperature zone2H2With N2Mixed gas, keep 2~3 hours, make M/ZrB2In composite catalyst Nanometer ZrB2The surface in situ of powder grows CNTs, obtains CNTs/ZrB2Nano composite powder.
Preferably, in step (32), C2H2With N2Velocity ratio be (10~40) mL/min:30mL/min.
Preferably, in step (13), the temperature of the drying is 70~90 DEG C, preferably 80 DEG C；And/or
In step (14), the under type such as that is calcined through carries out：By the M (OH)n/ZrB2Powder is placed in atmosphere guarantor In furnace retaining, 3h is calcined at 700 DEG C.
The present invention also provides one kind CNTs/ZrB made from above-mentioned preparation method2Nano composite powder.
(3) advantageous effect
The above-mentioned technical proposal of the present invention has the following advantages that：
The present invention provides practicable, the self toughening effect CNTs/ZrB outstanding of one kind2The system of nano composite powder Preparation Method can obtain the ZrB with self toughening effect2Nano composite powder for further sintering high temperature resistant, high tenacity, resists Ablation, anti-thermal shock superhigh temperature heat insulation material provide raw material.
Description of the drawings
Fig. 1 is the flow diagram of preparation method provided by the invention；
Fig. 2 shows according to embodiments of the present invention 1 obtained CNTs/ZrB2The microscopic appearance of nano composite ceramic powder；
Fig. 3 shows according to embodiments of the present invention 1 obtained CNTs/ZrB2The XRD of nano composite ceramic powder.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiment of the present invention, and The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work Under the premise of the every other embodiment that is obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of fabricated in situ CNTs/ZrB2The preparation method of nano composite powder, includes the following steps：
(1), M is providedxOy/ZrB2Catalyst precursor, wherein M indicates that metallic catalyst, x indicate MxOyOxide molecule The number of middle metallic atom, y indicate MxOyThe number of oxygen atom in oxide molecule；
(2), the M is restoredxOy/ZrB2Catalyst precursor obtains M/ZrB2Composite catalyst；
(3), to M/ZrB2C is passed through in composite catalyst2H2With N2Mixed gas, make M/ZrB2Nanometer in composite catalyst ZrB2The surface in situ of powder grows CNTs, obtains CNTs/ZrB2Nano composite powder.
The brittle fracture of ceramic material is mainly the extension due to crackle, increases the potential energy overcome needed for crack propagation, disappears The methods of the energy of consumption or conversion crack propagation, dispersion crack tip stress can effectively improve the fracture toughness of ceramics.This hair In bright, using nanometer ZrB2Powder, CNTs is in nanometer ZrB2The surface in situ of powder is grown, and the crackle in ceramics is enabled to expand It deflects when exhibition, the extraction etc. of bifurcated and CNTs, consumes a large amount of energy, and then from CNTs toughenings and fine grain toughening two Aspect greatly improves ZrB2The fracture toughness and thermal shock resistance of base ceramic material.
In some embodiments, in step (1), the offer MxOy/ZrB2The step of catalyst precursor includes：
(11), by nanometer ZrB2Powder and Mn+Solution is uniformly mixed, and then, strong base solution is added, obtains M (OH)n/ZrB2 Binary colloidal mixed liquor, wherein n indicates Mn+The valence state of middle metal ion；
(12), the M (OH) is filteredn/ZrB2Binary colloidal mixed liquor collects solid, cleans the solid to neutrality, obtain To M (OH)n/ZrB2Binary colloidal；
(13), by the M (OH)n/ZrB2Binary colloidal is dried, grinds, and obtains M (OH)n/ZrB2Powder；
(14), the M (OH) is calcinedn/ZrB2Powder obtains MxOy/ZrB2Catalyst precursor.
In step (1), in order to ensure strong base solution can be homogeneously added into system, it can be added dropwise while stirring strong Aqueous slkali so that the M in systemn+Metal ion reaction generates M (OH)n, with the ZrB in system2Powder interacts to form M (OH)n/ZrB2Binary colloidal mixed liquor.The chemical principle being related to is：
Mn++OH-→M(OH)n。
The binary colloidal mixed solution of gained is filtered, filtered solid is collected, obtains M (OH)n/ZrB2Binary Colloid.It, can be by M (OH) in order to fully remove the alkaline matter in binary colloidaln/ZrB2Binary colloidal mixed liquor stands 24 hours After refilter, remove liquid solution therein, then clean the solid matter being obtained by filtration to neutral or close to neutrality.
In order to enable carbon nanotube is in ZrB2It is evenly distributed on powder, the present invention uses binary colloidal to precipitate legal system first It is standby go out MxOy/ZrB2Then catalyst precursor is reduced into M/ZrB2Composite catalyst.Nanometer ZrB2Powder is very easy to roll into a ball Poly- effect, the binary colloidal precipitation method may insure metal ions Mn+With ZrB2Powder dispersedly more uniformly, avoids a nanometer ZrB2 Powder reunite, to for follow-up carbon nanotube in ZrB2The uniform growth on powder surface establishes good basis.
ZrB2The granularity of powder is also to CNTs/ZrB2The mechanical property of nano composite powder has an impact.ZrB2The granularity of powder It is excessive to be possibly adsorbed to M (OH)nThe surface of precipitation, when undersized, then will appear a large amount of reunions, cause M in ZrB2Table EDS maps are uneven, and then influence CNTs in ZrB2The distribution situation on surface.Matrix ZrB2The granularity of powder as possible with in-situ preparation The diameter of CNTs is equal, in some embodiments, in step (11), the ZrB2The granularity of powder is no more than 100nm, example Such as, it can be 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, be found through experiments that, this technique system Standby obtained CNTs diameters are in 60 ± 10nm, therefore the ZrB of preferably 60nm2Powder.
In some embodiments, in step (11), the Mn+For Ni2+Or Y3+, then, work as Mn+For Ni2+When, x 1, y are 1；Work as Mn+For Y3+When, x 2, y 3；And/or the highly basic be alkali metal hydroxide, for example, can be sodium hydroxide, Can be potassium hydroxide, dosage will ensure Mn+Precipitation completely.
Metal M is for being catalyzed C2H2Cracking generates CNTs, the yield of species influence CNTs and the pattern of CNTs.The present invention In metal M catalyst used be selected from bivalent nickel ion or trivalent ruthenium ion, it is ensured that by carbon nanotube before not destroying its structure It puts and evenly spreads to ZrB2On powder, achieve the effect that improve CNTs yields.
Moreover, it is high using the yield of trivalent ruthenium ion not only carbon nanotube, and carbon nanotube tube wall obtained is smooth, nothing The thickness of apparent nodular structure, caliber and tube wall is uniform.
In some embodiments, the step (2) carries out as follows：
By MxOy/ZrB2Catalyst precursor is placed in the flat-temperature zone of tube furnace, in N2Flat-temperature zone is warming up under protection 750~850 DEG C, N is closed afterwards2, it is passed through H2, to MxOy/ZrB2Catalyst precursor restores 1~2 hour, obtains M/ZrB2It is compound to urge Agent.
In this step, by MxOy/ZrB2Catalyst precursor is placed in the flat-temperature zone of closed environment, under constant temperature It is interior that it is restored.Oxidant and other compositions in air or in closed environment are easy to MxOy/ZrB2Catalyst precursor Reduction process have an impact, influence the product species and content of reduction reaction.In order to eliminate these adverse effects, the present invention In preparation process, N is filled with to closed environment2, other gas components in closed environment are discharged.
It is further preferred that in some embodiments, in step (2), by MxOy/ZrB2Catalyst precursor is placed in pipe In the flat-temperature zone of formula stove, in N2Flat-temperature zone is warming up to 800~850 DEG C under protection, closes N afterwards2, it is passed through H2, to MxOy/ZrB2It urges Agent presoma restores 1.5~2 hours, obtains M/ZrB2Composite catalyst.
In some embodiments, the M/ZrB2In composite catalyst, the mass fraction of M is 10-35%.For example, can be with For 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%.
M/ZrB made from step (2)2Metal M in composite catalyst is for being catalyzed C2H2Cracking generates CNTs, works as M/ ZrB2When the mass fraction of M is 10-35% in composite catalyst, ZrB2The upgrowth situation of the CNTs on nanometer powder surface and distribution Situation is preferable.Most preferably, work as M/ZrB2When the mass fraction of Y is 15% in composite catalyst, ZrB2The CNTs's on powder surface Upgrowth situation and distribution situation are best.
In some embodiments, the step (3) carries out as follows：
(31), in N2Flat-temperature zone is warming up to 1150~1200 DEG C under protection；
(32), it is passed through C to flat-temperature zone2H2With N2Mixed gas, keep 2~3 hours, make M/ZrB2In composite catalyst Nanometer ZrB2The surface in situ of powder grows CNTs, obtains CNTs/ZrB2Nanocomposite ceramic material.
In the hot environment and M/ZrB of confined space2Under the catalytic action of composite catalyst, C2H2Cracking generates carbon nanometer Pipe CNTs.In reaction process, the reaction time of this step is 2~3 hours.C is closed after reaction time2H2, in N2Under protection Flat-temperature zone is cooled to room temperature.The CNTs generated is cracked in ZrB2The surface in situ of nanometer powder is grown, and obtains CNTs/ZrB2It receives Rice composite powder.
It is further preferred that in some embodiments, in step (31), in N2Flat-temperature zone is warming up to 1180 under protection ~1200 DEG C, in step (32), C is passed through to flat-temperature zone2H2With N2Mixed gas, keep 2.5~3 hours.
In some embodiments, in step (32), C2H2With N2Velocity ratio be (10~40) mL/min:30mL/min. Under this condition, ZrB2The even thickness and length homogeneity of the CNTs on nanometer powder surface is best.
In some embodiments, in step (13), the temperature of the drying is 70~90 DEG C, preferably 80 DEG C；And/or
In step (14), the calcining is：By the M (OH)z/ZrB2Powder is placed in atmosphere protection stove, at 700 DEG C Lower calcining 3h.
The present invention also provides one kind CNTs/ZrB made from above-mentioned preparation method2Nanocomposite ceramic material.
It is several embodiments provided by the invention below.
The key instrument list used in 1 embodiment of table
The main agents or list of materials used in 2 embodiment of table
Title Purity Source
ZrB2Nanometer powder ＞ 99% Hefei Kai Er nanometers of Energy Science Co., Ltd
Nickel nitrate ＞ 99% Nanjing chemical reagent limited liability company
Yttrium nitrate ＞ 99% Nanjing chemical reagent limited liability company
Absolute ethyl alcohol ＞ 99% Nanjing chemical reagent limited liability company
Sodium hydroxide ＞ 99% Nanjing chemical reagent limited liability company
Embodiment 1
As shown in Figure 1, the preparation method of the present embodiment includes the following steps：
1, M is prepared using deposition-precipitationxOy/ZrB2Catalyst precursor
By ZrB2Powder, which is added, contains appropriate Ni2+Deionized water solution (being dissolved in deionized water by nickel nitrate to be formulated) In, select magnetic stirring apparatus persistently to stir, while certain density NaOH aqueous solutions are added dropwise to Ni2+Precipitation completely, above-mentioned solution Through filtering, cleaning after standing 24 hours, until pH value is 7, M (OH) is obtainedn/ZrB2Binary colloidal.The colloid is placed in 80 DEG C to do Processing is dried in dry case, then by grinding, obtains M (OH)nPowder, M (OH)nPowder is placed in atmosphere protection stove, in N2 Lower 700 DEG C are protected to calcine 3 hours so that M (OH)nIt decomposes and obtains the M needed for CNTs synthesisxOy/ZrB2Catalyst precursor.
2, CNTs/ZrB is generated2Nano composite powder
Weigh the M of certain massxOy/ZrB2Catalyst precursor is put into the flat-temperature zone of tube furnace and in N2The lower heating of protection To 820 DEG C of reduction temperature, it is then shut off N2, it is passed through H2Reductase 12 hour obtains M/ZrB2Composite catalyst waits after the reaction was complete, will H2It closes, is passed through N again2, and furnace temperature is increased to 1200 DEG C of reaction temperature, it is passed through C after temperature stabilization2H2With N2Gaseous mixture Body, C2H2With N2Velocity ratio be 35 ml/mins：30 ml/mins, heat preservation make CNTs in ZrB in 2 hours2Nano powder surface Growth in situ；It waits after the completion of reacting, closes C2H2, in N2Under protection, sample is made to cool to room temperature with the furnace, obtains CNTs/ZrB2It receives Rice composite powder.
Fig. 2 shows according to embodiments of the present invention 1 obtained CNTs/ZrB2The microscopic appearance figure of nano composite powder.
Fig. 3 shows according to embodiments of the present invention 1 obtained CNTs/ZrB2The component-part diagram of nano composite powder.
Embodiment 2 is to embodiment 5
Embodiment 2 is carried out to embodiment 5 using method substantially the same manner as Example 1, and difference is as shown in table 3.
The preparation process condition of 3 each embodiment of table
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features； And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and Range.

Claims (10)

1. fabricated in situ CNTs/ZrB2The preparation method of nano composite powder, which is characterized in that include the following steps：
(1), M is providedxOy/ZrB2Catalyst precursor, wherein M indicates that metallic catalyst, x indicate MxOyIt is golden in oxide molecule Belong to the number of atom, y indicates MxOyThe number of oxygen atom in oxide molecule；
(2), the M is restoredxOy/ZrB2Catalyst precursor obtains M/ZrB2Composite catalyst；
(3), to M/ZrB2C is passed through in composite catalyst2H2With N2Mixed gas, make M/ZrB2Nanometer ZrB in composite catalyst2 The surface in situ of powder grows CNTs, obtains CNTs/ZrB2Nano composite powder.
2. preparation method according to claim 1, which is characterized in that in step (1), the offer MxOy/ZrB2Catalysis The step of agent presoma includes：
(11), by nanometer ZrB2Powder and Mn+Solution is uniformly mixed, and then, strong base solution is added, obtains M (OH)n/ZrB2Binary Colloid mixed liquor, wherein n indicates Mn+The valence state of middle metal ion；
(12), the M (OH) is filteredn/ZrB2Binary colloidal mixed liquor collects solid, cleans the solid to neutrality, obtain M (OH)n/ZrB2Binary colloidal；
(13), by the M (OH)n/ZrB2Binary colloidal is dried, grinds, and obtains M (OH)n/ZrB2Powder；
(14), the M (OH) is calcinedn/ZrB2Powder obtains MxOy/ZrB2Catalyst precursor.
3. preparation method according to claim 2, which is characterized in that in step (11), the ZrB2The granularity of powder is No more than 100nm, preferably 20~100nm, most preferably 60nm.
4. preparation method according to claim 2, which is characterized in that in step (11), the Mn+For Ni2+Or Y3+, Then, work as Mn+For Ni2+When, x 1, y 1；Work as Mn+For Y3+When, x 2, y 3；And/or
The highly basic is the hydroxide of alkali metal.
5. preparation method according to claim 1, which is characterized in that the step (2) carries out as follows：
By MxOy/ZrB2Catalyst precursor is placed in the flat-temperature zone of tube furnace, in N2Flat-temperature zone is warming up to 750 under protection~ 850 DEG C, N is closed afterwards2, it is passed through H2, to MxOy/ZrB2Catalyst precursor restores 1~2 hour, obtains M/ZrB2Composite catalyst.
6. preparation method according to claim 5, which is characterized in that the M/ZrB2In composite catalyst, the quality point of M Number is 10~35%.
7. preparation method according to claim 5, which is characterized in that the step (3) carries out as follows：
(31), in N2Flat-temperature zone is warming up to 1150~1200 DEG C under protection；
(32), it is passed through C to flat-temperature zone2H2With N2Mixed gas, keep 2~3 hours, make M/ZrB2Nanometer in composite catalyst ZrB2The surface in situ of powder grows CNTs, obtains CNTs/ZrB2Nano composite powder.
8. preparation method according to claim 6, which is characterized in that in step (32), C2H2With N2Velocity ratio be (10~40) mL/min:30mL/min.
9. according to claim 2~8 any one of them preparation method, which is characterized in that in step (13), the drying Temperature is 70~90 DEG C, preferably 80 DEG C；And/or
In step (14), the under type such as that is calcined through carries out：By the M (OH)n/ZrB2Powder is placed in atmosphere protection stove In, calcine 3h at 700 DEG C.
10. one kind CNTs/ZrB made from claim 1~9 any one of them preparation method2Nano composite powder.
CN201810202882.8A 2018-03-13 2018-03-13 A kind of fabricated in situ CNTs/ZrB2Nano composite powder and preparation method thereof Pending CN108503368A (en)

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CN102199872A (en) * 2011-03-29 2011-09-28 北京航空航天大学 Method for in-situ growing carbon nanotubes on fiber surfaces
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CN102199872A (en) * 2011-03-29 2011-09-28 北京航空航天大学 Method for in-situ growing carbon nanotubes on fiber surfaces
CN104150939B (en) * 2014-07-24 2015-12-30 西北工业大学 A kind of electrophoretic deposition CNTs strengthens the preparation method of ceramic matric composite
US20180056435A1 (en) * 2016-08-23 2018-03-01 University Of Connecticut Multi-scale manufacturing of carbon nanotube composites

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