CN102021817B - Silicon carbide fiber solid fabric for in-situ growing carbon nano tubes, composite material and preparation method thereof - Google Patents
Silicon carbide fiber solid fabric for in-situ growing carbon nano tubes, composite material and preparation method thereof Download PDFInfo
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- CN102021817B CN102021817B CN2010105401999A CN201010540199A CN102021817B CN 102021817 B CN102021817 B CN 102021817B CN 2010105401999 A CN2010105401999 A CN 2010105401999A CN 201010540199 A CN201010540199 A CN 201010540199A CN 102021817 B CN102021817 B CN 102021817B
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Abstract
The invention discloses a silicon carbide fiber solid fabric for in-situ growing carbon nano tubes, which is formed by mainly weaving silicon carbide fibers. In the invention, in-situ grown carbon nano tubes are uniformly distributed on the surfaces of the silicon carbide fibers and mutually wound to form a reticular structure. The preparation method comprises the following steps of: pretreating the silicon carbide fiber solid fabric; loading a Ni-La-Al composite catalyst by adopting a catalyst precursor vacuum impregnation-reduction method; and finally, carrying out chemical gas-phase deposition to ensure that the carbon nano tubes are in-situ grown on the silicon carbide fiber solid fabric. The invention also discloses a carbon nano tube-silicon carbide fiber mixed enhanced composite material which is prepared by using silicon carbide as a substrate and the silicon carbide fiber solid fabric as a reinforcement body by adopting a traditional precursor impregnation-conversion method. The silicon carbide fiber solid fabric has the advantages of uniform carbon nano tube dispersion, higher and controllable carbon nano tube content, good combination with fibers, and the like.
Description
Technical field
The present invention relates to a kind of Inorganic Non-metallic Materials and preparation method thereof, relate in particular to a kind of special silicon carbide fibre stereo fabric and preparation method thereof.
Background technology
CNT (Carbon nanotubes; CNTs) have bigger draw ratio and great specific area; Its tensile strength is 100 times of steel, nearly 2 times of carbon fiber, and density is merely 1/6～1/7 of steel, and the room temperature thermal conductivity that experiment records multi-walled carbon nano-tubes reaches 3000 Wm
-1K
-1The mechanical property of CNT obviously is superior to other crystal whisker materials; Its good conduction, the capacity of heat transmission can significantly be improved the functional of composite simultaneously; Strengthen the CNT of introducing proper content in the ceramic matric composite (FRCMC) in traditional fibre; Be expected to reach strengthen toughness reinforcing with improve purpose such as thermal conductivity, have tempting application prospect.But stronger Van der Waals force makes its easy reunion or winding between CNT, significantly reduces its reinforced effects, also makes the CNT of in composite, introducing high volume content become unusual difficult; Have employing now and directly add the not firm and unequal problem of dispersion of composite ubiquity interface combination of the method preparation of CNT, the performance boost amplitude is little.
At present; Those skilled in the art successfully grow CNT on carbon fiber, alumina fibre and silicon carbide fibre; But these researchs still mainly launch around one dimension fibre bundle or two-dimensional fiber cloth, combine the mode of shop layer mold pressing to prepare composite again.As the enhancing body of composite, do not have between the two-dimensional fiber tissue layer of shop layer mold pressing and the layer and be connected, this directly causes the interlaminar shear strength of composite low, easy layering.And employing three dimension stereo fabric reinforced composite materials; Its fiber is orientated in the multiaxis face of space and between face; Composite has complete globality, and the many-sided mechanical characteristic of composite all is greatly improved, and has become the research focus that high-performance composite materials strengthen body.
Summary of the invention
The technical problem that the present invention will solve is the deficiency that overcomes prior art; Provide that a kind of CNT is uniformly dispersed, content of carbon nanotubes is higher controlled and combine good growth in situ that the silicon carbide fibre stereo fabric of CNT is arranged with fiber; Also providing a kind of mechanical property better with growth in situ the silicon carbide fibre stereo fabric of CNT to be arranged is the composite that strengthens body, provides also that a kind of technical process is simple, equipment requirements is low, the technology cost is low, the silicon carbide fibre stereo fabric of wide adaptability and the preparation method of composite.
For solving the problems of the technologies described above; The technical scheme that the present invention proposes is the silicon carbide fibre stereo fabric that a kind of growth in situ has CNT; Said silicon carbide fibre stereo fabric is mainly formed by the silicon carbide fibre braiding; The even carbon nanotube of said growth in situ is distributed in said silicon carbide fibre surface, and said CNT is wound in network structure each other.
The growth in situ of the invention described above has in the silicon carbide fibre stereo fabric of CNT; The heap(ed) capacity of said CNT is preferably 4%～15%; The average length of said CNT is preferably 3 μ m～4.5 μ m, and the average diameter of said CNT is preferably 50 nm～60 nm.
As a total technical conceive, the present invention also provides a kind of above-mentioned growth in situ that the preparation method of the silicon carbide fibre stereo fabric of CNT is arranged, and may further comprise the steps: at first, prefabricated silicon carbide fibre stereo fabric is carried out preliminary treatment; Adopt catalyst precursor vacuum impregnation-reducing process that pretreated silicon carbide fibre stereo fabric is loaded the Ni-La-Al composite catalyst again; Carry out chemical vapour deposition (CVD) at last, make that growth in situ goes out CNT on the said silicon carbide fibre stereo fabric.
Among the preparation method of the invention described above; Said pretreated concrete grammar is preferably: place air to be heated to 400 ℃～500 ℃ said prefabricated silicon carbide fibre stereo fabric; Insulation 1h～2h, supersound washing in acetone again (generally wash about 6h and get final product) is to remove surface glue.
Among the preparation method of the invention described above; The concrete operations of said catalyst precursor vacuum impregnation-reducing process are preferably: press (15～5): (2～1): the mol ratio of (3～1) takes by weighing the nitrate of the nitrate of Ni, La and the nitrate of Al; Described three kinds of nitrate are dissolved in the catalyst precursor ethanolic solution that the ethanol preparation obtains containing Ni 0.1 mol/L～0.15 mol/L; With the fine said pretreated silicon carbide fibre stereo fabric of said catalyst precursor ethanolic solution vacuum impregnation, dry the back at 400 ℃～500 ℃ nitrogen (N
2) calcine 1h～3h in the atmosphere, at last at 450 ℃～600 ℃ hydrogen (H
2) reduce 10min～60 min in the atmosphere.
Among the preparation method of the invention described above; The concrete operations of said chemical vapour deposition (CVD) in-situ growing carbon nano tube are preferably: the said silicon carbide fibre stereo fabric that will be loaded with catalyst places quartz ampoule; Be warming up to 700 ℃～800 ℃ under the nitrogen atmosphere protection, feeding flow-rate ratio again is 1: 1: the acetylene-hydrogen of (1～4)-nitrogen (C
2H
2-H
2-N
2) or 1: acetylene-nitrogen (C of (2～4)
2H
2-N
2) mist (be preferably C
2H
2-H
2-N
2), in nitrogen atmosphere, lowering the temperature behind insulation 1h～6h gets final product.
As a total technical conceive; The present invention also provides a kind of CNT-silicon carbide fibre mixing reinforced composite; Said composite is to be matrix with carborundum, and with above-mentioned growth in situ the silicon carbide fibre stereo fabric of CNT being arranged serves as to strengthen body (volume fraction of said CNT in this composite is 2%～7%).
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned CNT-silicon carbide fibre mixing reinforced composite, may further comprise the steps:
(1) adopt above-mentioned preparation method of the present invention to prepare the silicon carbide fibre stereo fabric that growth in situ has CNT earlier;
(2) and then with said growth in situ the silicon carbide fibre stereo fabric of CNT to be arranged be raw material, adopt traditional precursor dipping conversion method to prepare CNT-silicon carbide/carbon silicon mixing reinforced composite.
For reunion and the scattering problem that solves CNT in the silicon carbide fibre reinforced composite; The present invention creatively adopts the chemical vapor deposition (CVD) method with in-situ growing carbon nano tube in the silicon carbide fibre stereo fabric, and then prepares " micron-nanometer " mixing reinforced composite of silicon carbide fibre-CNT; Compare with traditional preparation method; Above-mentioned technological package scheme of the present invention not only efficiently solves dispersiveness and the directionality problem of CNT in composite; And can be in composite controllability ground introduce the CNT of high-load, be the Perfected process that a kind of acquisition high-performance " silicon carbide fibre-CNT " is mixed reinforced composite.
Compared with prior art, the invention has the advantages that:
(1) CNT of the inner growth in situ of silicon carbide fibre stereo fabric of the present invention is evenly distributed, and compares with the dispersion means of routine, and the present invention efficiently solves the agglomeration traits of CNT, and CNT combines with silicon carbide fibre well;
(2) content of carbon nanotubes of introducing on the silicon carbide fibre stereo fabric of the present invention is higher and controlled; The content of carbon nanotubes of in silicon carbide fibre stereo fabric of the present invention, introducing can be up to 10 wt% more than; And through regulating pattern and the output that parameters such as catalyst concn, CVD technological temperature, carbon source carrier gas flux compare can controlling carbon nanotube, and then regulate the content of CNT in the follow-up composite;
(3) the CNTs-SiC fiber stereo fabric that obtains behind the in-situ growing carbon nano tube of the present invention can be directly as the enhancing body of existing various composites, and technology of the present invention combines to carry out the compact formed of composite with traditional precursor dipping conversion method technologies such as (PIP).
With regard to preparation method of the present invention, preparation process of the present invention is simple, and equipment requirements is low; Used process equipment mainly contains vacuum impregnation still, resistance furnace, quartz ampoule etc.; Its process route is simple, process cycle short (generally being no more than 2 days), environmentally safe in the preparation process.In addition, technology versatility of the present invention is good, though the present invention only provides the technical scheme of silicon carbide fibre stereo fabric, in fact technology of the present invention be applicable to various fiber weave structures, only requires the fiber weave structure can be at N
2Bear the growth temperature (about 750 ℃) of CNT in the atmosphere, do not have other specific (special) requirements, range of application is wide.Therefore, the fabric of other all kinds and various structures, under the prerequisite that does not break away from technical scheme basic thought of the present invention, all should be in protection scope of the present invention.
Description of drawings
The growth in situ that Fig. 1 makes for the Ni-La-Al composite catalyst of variable concentrations in the embodiment of the invention 1 has ESEM (SEM) photo of the silicon carbide fibre stereo fabric of CNT; Wherein, the product SEM photo that the Ni-La-Al composite catalyst that a schemes, b figure is dipping 0.05 mol/L obtains; C figure, d figure are the product SEM photo that the Ni-La-Al composite catalyst of dipping 0.1 mol/L obtains; E figure, f figure are the product SEM photo that the Ni-La-Al composite catalyst of dipping 0.15 mol/L obtains; G figure, h figure are the product SEM photo that the Ni-La-Al composite catalyst of dipping 0.2 mol/L obtains.
Fig. 2 carries out the SEM photo that growth in situ that chemical vapour deposition (CVD) obtains has the silicon carbide fibre stereo fabric of CNT for different carrier gas in the embodiment of the invention 2; Wherein, a figure is with N
2(C during for main carrier gas
2H
2, N
2Volume flow be respectively 100sccm, 400sccm) the product SEM photo that obtains, b figure is with H
2, N
2(C during for main carrier gas
2H
2, H
2, N
2Volume flow be respectively 100sccm, 100sccm, 300sccm) the product SEM photo that obtains.
The growth in situ that Fig. 3 makes for the embodiment of the invention 4 has the SEM photo of the silicon carbide fibre stereo fabric of CNT; Wherein, b figure is the partial enlarged drawing at a figure square frame place, and c figure is the partial enlarged drawing at b figure square frame place.
The specific embodiment
Embodiment 1:
Growth in situ of the present invention as shown in Figure 1 has the silicon carbide fibre stereo fabric of CNT; This silicon carbide fibre stereo fabric is mainly formed by the silicon carbide fibre braiding; The even carbon nanotube of this growth in situ is distributed in the silicon carbide fibre surface, and this CNT is wound in network structure each other.The heap(ed) capacity of CNT is 4.1%～6.5% in the present embodiment, and the average length of CNT is 3.8 μ m, and the average diameter of CNT is 50nm～60nm.
It is to prepare through following steps that the growth in situ of present embodiment has the silicon carbide fibre stereo fabric of CNT:
(1) silicon carbide fibre stereo fabric preliminary treatment: the three-dimensional four-way stereo fabric of prefabricated homemade KD-1 type silicon carbide fibre is placed in the Muffle furnace, heat temperature raising to 400 ℃ in air, insulation 1h, again in acetone supersound washing 6h to remove surface glue;
(2) catalyst precursor vacuum impregnation-reducing process loading catalyst: take by weighing the nitrate of Ni, the nitrate of La and the nitrate of Al by 15: 2: 3 mol ratios; These three kinds of nitrate are dissolved in the ethanol preparation obtain containing the catalyst precursor ethanolic solution that Ni concentration is respectively 0.05 mol/L, 0.1 mol/L, 0.15 mol/L, 0.2 mol/L; With the fine pretreated silicon carbide fibre stereo fabric of this catalyst precursor ethanolic solution vacuum impregnation, dry afterwards naturally under 400 ℃ of temperature, the N of 50 sccm
2Calcining 3 h are warming up to 450 ℃ again in the atmosphere, feed hydrogen reducing 60 min of 100sccm;
(3) chemical vapour deposition technique in-situ growing carbon nano tube: after the described reduction reaction of step (2) is accomplished, stop logical H
2, reacted silicon carbide fibre stereo fabric is placed quartz ampoule, in N
2Be warming up to 750 ℃ under the atmosphere protection, feed the mist (C of acetylene-nitrogen again
2H
2, N
2Volume flow be respectively 100sccm, 400sccm), continue behind the 1h at N
2Protection cooling down, the growth in situ that promptly obtains present embodiment has the silicon carbide fibre stereo fabric of CNT.
The silicon carbide fibre stereo fabric pattern that the Ni-La-Al composite catalyst of present embodiment through the vacuum impregnation variable concentrations obtains is as shown in Figure 1; Can find out by Fig. 1; When the complex catalyst precursor bulk concentration is low; The catalyst granules of silicon carbide fibre stereo fabric internal fiber surface deposition is very little seldom, and catalyst granules is coated by pyrolytic carbon easily and loses activity in the cracking process, makes the CNT that grows short, less (scheming referring to figure of a among Fig. 1 and b); Along with the increase of complex catalyst precursor bulk concentration, catalyst granules increases gradually, increases, the also all corresponding increase of the quantity of the CNT that grows and length (referring to the figure of the c figure～f among Fig. 1).When the catalyst precursor excessive concentration; The catalyst granules particle diameter is excessive; Even be coupled to thicker catalyst layer (referring to the figure of the g among Fig. 1), and be not suitable for the growth of CNT like this, can cause a large amount of pyrolytic carbons and catalyst granules to have (referring to the h figure of Fig. 1 China).It is thus clear that when the concentration of catalyst precursor was controlled at 0.1 mol/L～0.15 mol/L, the catalyst granules that obtains was tiny, even, the CNT best results of catalytic growth.
Embodiment 2:
Growth in situ of the present invention as shown in Figure 2 has the silicon carbide fibre stereo fabric of CNT; This silicon carbide fibre stereo fabric is mainly formed by the silicon carbide fibre braiding; The even carbon nanotube of this growth in situ is distributed in the silicon carbide fibre surface, and this CNT is wound in network structure each other.The heap(ed) capacity of CNT is 4.94% in the present embodiment, and the average length of CNT is 4 μ m, and the average diameter of CNT is 50nm～60 nm.
It is to prepare through following steps that the growth in situ of present embodiment has the silicon carbide fibre stereo fabric of CNT:
(1) silicon carbide fibre stereo fabric preliminary treatment: the three-dimensional four-way stereo fabric of prefabricated homemade KD-1 type silicon carbide fibre is placed in the Muffle furnace, heat temperature raising to 400 ℃ in air, insulation 1h, again in acetone supersound washing 6h to remove surface glue;
(2) catalyst precursor vacuum impregnation-reducing process loading catalyst: take by weighing the nitrate of Ni, the nitrate of La and the nitrate of Al by 15: 2: 3 mol ratios; These three kinds of nitrate are dissolved in the ethanol preparation obtain containing the catalyst precursor ethanolic solution that Ni concentration is 0.1 mol/L; With the fine pretreated silicon carbide fibre stereo fabric of this catalyst precursor ethanolic solution vacuum impregnation, dry afterwards naturally under 400 ℃ of temperature, the N of 50 sccm
2Calcining 3 h are warming up to 450 ℃ again in the atmosphere, feed hydrogen reducing 60 min of 100sccm;
(3) chemical vapour deposition technique in-situ growing carbon nano tube: after the described reduction reaction of step (2) is accomplished, stop logical H
2, reacted silicon carbide fibre stereo fabric is placed quartz ampoule, in N
2Be warming up to 750 ℃ under the atmosphere protection, feed the mist (C of acetylene-hydrogen-nitrogen again
2H
2, H
2, N
2Volume flow be respectively 100sccm, 100sccm, 300sccm) or feed the mist (C of acetylene-nitrogen
2H
2, N
2Volume flow be respectively 100sccm, 400sccm), continue behind the 1h at N
2Protection cooling down, the growth in situ that promptly obtains present embodiment has the silicon carbide fibre stereo fabric of CNT.
It is as shown in Figure 2 that present embodiment carries out the silicon carbide fibre stereo fabric pattern that chemical vapour deposition (CVD) obtains through different carrier gas, can be found out by Fig. 2, with N
2(C during for carrier gas
2H
2, N
2Volume flow be respectively 100sccm, 400sccm); CNT pattern on the silicon carbide fibre stereo fabric shows as weak point, thick shape; Length is generally in the hundreds of nanometer; Diameter Distribution is broad also, has also deposited impurity such as some carbon nano-particles, amorphous carbon on every side simultaneously, shows that catalyst has part inactivation (referring to the figure of a among Fig. 2) under this growth conditions; The H that in carrier gas, adds 100 sccm
2The back (is C
2H
2, H
2, N
2Volume flow be respectively 100sccm, 100sccm, 300sccm), the length of CNT can increase to several microns, diameter concentrates on about 50 nm, is wound in network structure each other, even compact (referring to the b among Fig. 2 figure) comparatively, its main cause is H
2Can be adsorbed on surface of metal particles, the adhesion between the reduction metallic particles makes catalyst granules evenly distribute on the silicon carbide fibre surface; The size trend is consistent; The carbide that decomposes the nickel of catalytically inactive simultaneously forms the Ni particle with activity, improves catalytic efficiency.
Embodiment 3:
A kind of growth in situ of the present invention has the silicon carbide fibre stereo fabric of CNT; This silicon carbide fibre stereo fabric is mainly formed by the silicon carbide fibre braiding; The even carbon nanotube of this growth in situ is distributed in the silicon carbide fibre surface, and this CNT is wound in network structure each other.The heap(ed) capacity of CNT is 10.8% in the present embodiment, and the average length of CNT is 4.2 μ m, and the average diameter of CNT is 50 nm～60 nm.
It is to prepare through following steps that the growth in situ of present embodiment has the silicon carbide fibre stereo fabric of CNT:
(1) silicon carbide fibre stereo fabric preliminary treatment: the three-dimensional four-way stereo fabric of prefabricated homemade KD-1 type silicon carbide fibre is placed in the Muffle furnace, heat temperature raising to 400 ℃ in air, insulation 1h, again in acetone supersound washing 6h to remove surface glue;
(2) catalyst precursor vacuum impregnation-reducing process loading catalyst: take by weighing the nitrate of Ni, the nitrate of La and the nitrate of Al by 15: 2: 3 mol ratios; These three kinds of nitrate are dissolved in the ethanol preparation obtain containing the catalyst precursor ethanolic solution that Ni concentration is 0.1 mol/L; With the fine pretreated silicon carbide fibre stereo fabric of this catalyst precursor ethanolic solution vacuum impregnation, dry afterwards naturally under 400 ℃ of temperature, the N of 50 sccm
2Calcining 3 h are warming up to 450 ℃ again in the atmosphere, feed hydrogen reducing 60 min of 100sccm;
(3) chemical vapour deposition technique in-situ growing carbon nano tube: after the described reduction reaction of step (2) is accomplished, stop logical H
2, reacted silicon carbide fibre stereo fabric is placed quartz ampoule, in N
2Be warming up to 750 ℃ under the atmosphere protection, feed the mist (C of acetylene-hydrogen-nitrogen again
2H
2, H
2, N
2Volume flow be respectively 150sccm, 150sccm, 450sccm), continue behind the 1h at N
2Protection cooling down, the growth in situ that promptly obtains present embodiment has the silicon carbide fibre stereo fabric of CNT.
Embodiment 4:
A kind of growth in situ of the present invention shown in a figure～c figure among Fig. 3 has the silicon carbide fibre stereo fabric of CNT; This silicon carbide fibre stereo fabric is mainly formed by the silicon carbide fibre braiding; The even carbon nanotube of this growth in situ is distributed in the silicon carbide fibre surface, and this CNT is wound in network structure each other.The heap(ed) capacity of CNT is 12.9% in the present embodiment, and the average length of CNT is 4.5 μ m, and the average diameter of CNT is 50 nm～60 nm.
It is to prepare through following steps that the growth in situ of present embodiment has the silicon carbide fibre stereo fabric of CNT:
(1) silicon carbide fibre stereo fabric preliminary treatment: the three-dimensional four-way stereo fabric of prefabricated homemade KD-1 type silicon carbide fibre is placed in the Muffle furnace, heat temperature raising to 400 ℃ in air, insulation 1h, again in acetone supersound washing 6h to remove surface glue;
(2) catalyst precursor vacuum impregnation-reducing process loading catalyst: take by weighing the nitrate of Ni, the nitrate of La and the nitrate of Al by 15: 2: 3 mol ratios; These three kinds of nitrate are dissolved in the ethanol preparation obtain containing the catalyst precursor ethanolic solution that Ni concentration is 0.1 mol/L; With the fine pretreated silicon carbide fibre stereo fabric of this catalyst precursor ethanolic solution vacuum impregnation, dry afterwards naturally under 400 ℃ of temperature, the N of 50 sccm
2Calcining 3 h are warming up to 450 ℃ again in the atmosphere, feed hydrogen reducing 60 min of 100sccm;
(3) chemical vapour deposition technique in-situ growing carbon nano tube: after the described reduction reaction of step (2) is accomplished, stop logical H
2, reacted silicon carbide fibre stereo fabric is placed quartz ampoule, in N
2Be warming up to 750 ℃ under the atmosphere protection, feed the mist (C of acetylene-hydrogen-nitrogen again
2H
2, H
2, N
2Volume flow be respectively 200sccm, 200sccm, 600sccm), continue behind the 1h at N
2Protection cooling down, the growth in situ that promptly obtains present embodiment has the silicon carbide fibre stereo fabric of CNT.
The silicon carbide fibre stereo fabric pattern that present embodiment makes is as shown in Figure 3; Can find out by Fig. 3, original silicon carbide fibre surface coverage the fine and close carbon nanotube layer uniformly of one deck, about 30 nm of average diameter～50 nm; Length can reach several microns; Compare with the dispersion means of routine, it efficiently solves the agglomeration traits of CNT, and CNT combines well with fiber.
In the above embodiments of the invention 2,3,4; The contrast of CNT heap(ed) capacity and catalyst efficiency is as shown in table 1 below in the silicon carbide fibre stereo fabric that obtains under three kinds of different carbon sources (acetylene) flow condition; Can find out by following table 1; The heap(ed) capacity of CNT increases along with the increase of carbon-source gas flow, and meanwhile catalyst production also is similar to and is linear increase; In conjunction with the stereoscan photograph among Fig. 3; The carbon nano tube surface that the carbon source flow obtains when being 200 sccm is not observed the appearance of obvious deposit carbon as yet; Show that regulating the carbon-source gas flow can control the heap(ed) capacity of CNT in the stereo fabric, and then regulate the content of CNT in the follow-up composite.
Table 1: CNT heap(ed) capacity that different carbon source flows obtain and catalyst production contrast table
| Carbon source flow (sccm) | 100 | 150 | 200 |
| CNT heap(ed) capacity (%) | 4.94 % | 10.8 % | 12.9 % |
| Catalyst production (g CNTS/g Cata） | 8.36 | 13.69 | 16.91 |
Embodiment 5:
A kind of CNT of the present invention-silicon carbide fibre mixing reinforced composite, this composite are to be matrix with carborundum, and with the growth in situ of present embodiment the silicon carbide fibre stereo fabric of CNT being arranged serves as to strengthen body.
The CNT of present embodiment-silicon carbide fibre mixing reinforced composite is mainly prepared by following steps:
(1) adopt the preparation method of above-mentioned each embodiment to prepare the silicon carbide fibre stereo fabric that growth in situ has CNT earlier;
(2) and then with this growth in situ the silicon carbide fibre stereo fabric of CNT to be arranged be raw material, adopt traditional precursor dipping conversion method to prepare CNT-silicon carbide fibre mixing reinforced composite.
The preparation method of this CNT-silicon carbide fibre mixing reinforced composite specifically may further comprise the steps:
(1) silicon carbide fibre stereo fabric preliminary treatment: the three-dimensional four-way stereo fabric of prefabricated homemade KD-1 type silicon carbide fibre is placed in the Muffle furnace, heat temperature raising to 500 ℃ in air, insulation 2h, again in acetone supersound washing 4h to remove surface glue;
(2) catalyst precursor vacuum impregnation-reducing process loading catalyst: take by weighing the nitrate of Ni, the nitrate of La and the nitrate of Al by 15: 2: 3 mol ratios; These three kinds of nitrate are dissolved in the ethanol preparation obtain containing the catalyst precursor ethanolic solution that Ni concentration is 0.1 mol/L; With the fine pretreated silicon carbide fibre stereo fabric of this catalyst precursor ethanolic solution vacuum impregnation, dry afterwards naturally under 450 ℃ of temperature, the N of 50 sccm
2Calcining 1 h is warming up to 550 ℃ again in the atmosphere, feeds hydrogen reducing 60 min of 100sccm;
(3) chemical vapour deposition technique in-situ growing carbon nano tube: after the described reduction reaction of step (2) is accomplished, stop logical H
2, reacted silicon carbide fibre stereo fabric is placed quartz ampoule, in N
2Be warming up to 700 ℃ under the atmosphere protection, feed the mist (C of acetylene-hydrogen-nitrogen again
2H
2, H
2, N
2Volume flow be respectively 200sccm, 200sccm, 600sccm), continue behind the 5h at N
2Protection cooling down promptly obtains the silicon carbide fibre stereo fabric that growth in situ has CNT;
(4) precursor infiltration and pyrolysis prepares SiC
f/ SiC composite: used precursor is a Polycarbosilane; Polycarbosilane, xylene are mixed according to 1: 2 mass ratio; The silicon carbide fibre stereo fabric that the growth in situ that above-mentioned steps (3) makes has a CNT is that steeping liq carries out high-pressure impregnation with the mixed solution of Polycarbosilane/xylene; Impregnation pressure is 2MPa, and dip time is 4h; Carry out Pintsch process again, cracking temperature is 1300 ℃, insulation 3h; Repeat said high-pressure impregnation to Pintsch process technology 18 times, obtain CNT-silicon carbide fibre and mix that to strengthen composite material of silicon carbide (be SiC
f/ SiC composite).
The SiC that present embodiment makes
fThe bending strength of/SiC composite reaches 374MPa, and fracture toughness reaches 22.7 MPam
1/2
Claims (5)
1. a growth in situ has the silicon carbide fibre stereo fabric of CNT; Said silicon carbide fibre stereo fabric is mainly formed by the silicon carbide fibre braiding; It is characterized in that: the even carbon nanotube of said growth in situ is distributed in said silicon carbide fibre surface, and said CNT is wound in network structure each other.
2. growth in situ according to claim 1 has the silicon carbide fibre stereo fabric of CNT; It is characterized in that: the heap(ed) capacity of said CNT is 4%～15%; The average length of said CNT is 3 μ m～4.5 μ m, and the average diameter of said CNT is 50 nm～60 nm.
3. a growth in situ according to claim 1 or claim 2 has the preparation method of the silicon carbide fibre stereo fabric of CNT, may further comprise the steps:
(1) preliminary treatment: place air to be heated to 400 ℃～500 ℃ said prefabricated silicon carbide fibre stereo fabric, insulation 1h～2h, again in acetone supersound washing to remove surface glue;
(2) adopt catalyst precursor vacuum impregnation-reducing process to load the Ni-La-Al composite catalyst: press (15～5): (2～1): the mol ratio of (3～1) takes by weighing the nitrate of the nitrate of Ni, La and the nitrate of Al; Described three kinds of nitrate are dissolved in the catalyst precursor ethanolic solution that the ethanol preparation obtains containing Ni 0.1 mol/L～0.15 mol/L; With the fine said pretreated silicon carbide fibre stereo fabric of said catalyst precursor ethanolic solution vacuum impregnation; Dry the back and in 400 ℃～500 ℃ nitrogen atmosphere, calcine 1h～3h, last 10min～60 min that in 450 ℃～600 ℃ hydrogen atmosphere, reduce;
(3) chemical vapour deposition (CVD): the said silicon carbide fibre stereo fabric that will be loaded with catalyst places quartz ampoule; Be warming up to 700 ℃～800 ℃ under the nitrogen atmosphere protection; Feeding flow-rate ratio again is 1: 1: the acetylene-hydrogen of (1～4)-nitrogen or 1: the mist of the acetylene-nitrogen of (2～4); Insulation is lowered the temperature in nitrogen atmosphere behind 1h～6h, accomplishes the growth in situ process, makes that growth in situ goes out CNT on the said silicon carbide fibre stereo fabric.
4. CNT-silicon carbide fibre mixing reinforced composite, it is characterized in that: said composite is to be matrix with carborundum, with claim 1 or 2 described growth in situ the silicon carbide fibre stereo fabric of CNT being arranged serves as to strengthen body.
5. the preparation method of CNT as claimed in claim 4-silicon carbide fibre mixing reinforced composite may further comprise the steps:
(1) adopt the described preparation method of claim 3 to prepare the silicon carbide fibre stereo fabric that growth in situ has CNT earlier;
(2) and then with said growth in situ the silicon carbide fibre stereo fabric of CNT to be arranged be raw material, adopt traditional precursor dipping conversion method to prepare CNT-silicon carbide/carbon silicon mixing reinforced composite.
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| CN105908491B (en) * | 2016-05-31 | 2018-04-10 | 哈尔滨工业大学 | Preparing superficial growth has the apparatus and method of continuous carbon fibre of CNT |
| CN106565263B (en) * | 2016-11-05 | 2019-07-30 | 天津大学 | A kind of preparation method of carbon nanotube/silicon carbide heat-conductive composite material |
| CN112624783B (en) * | 2020-12-17 | 2022-03-25 | 西南交通大学 | Preparation method of preoxidized fiber reinforced pantograph slide plate for growing carbon nano tube |
| CN114477144B (en) * | 2022-01-21 | 2023-05-30 | 西安电子科技大学 | Preparation method of carbon nanotube array |
| CN115196987B (en) * | 2022-06-02 | 2023-09-29 | 航天材料及工艺研究所 | Carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material and preparation method thereof |
| CN115538157B (en) * | 2022-10-27 | 2024-02-23 | 湖南博翔新材料有限公司 | Method for producing carbon nanotube modified silicon carbide fiber by continuous vapor deposition method |
| CN116675550A (en) * | 2023-05-29 | 2023-09-01 | 上海大学 | Electromagnetic shielding composite material and preparation method thereof |
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