CN108217629A - A kind of preparation method of the compound CNTs of surface in situ generation nano SiC - Google Patents
A kind of preparation method of the compound CNTs of surface in situ generation nano SiC Download PDFInfo
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Abstract
The invention discloses the preparation methods of the compound CNTs of surface in situ generation nano SiC a kind of, pass through synchronizing ultrasound dispersion and mechanical agitation, by the nano silica fume uniform adhesion of special ratios in CNTs surfaces in PVP ethanol solutions, then by reaction in-situ in the SiC of one layer of nanometer grade thickness of CNTs Surface Creations, SiC/CNTs composite material of the formation with bud bar or shell-and-core structure.SiC/CNTs materials prepared by the method for the present invention do not destroy the structure of CNTs, and it can guarantee the dispersing uniformity of CNTs and SiC, being in direct contact between CNTs and matrix will be reduced in basis material, regulate and control the interfacial reaction between CNTs and matrix, enhance the interface cohesion between CNTs and matrix, the good conductive, heat conduction of matrix and high ductility are retained while metallic matrix mechanical property is improved.
Description
Technical field
The invention belongs to materials synthesis preparation and surface recombination modified technical fields, and in particular to a kind of surface in situ generation
The preparation method of the compound CNTs of nano SiC.
Background technology
Since carbon nanotube (Carbon nanotubes, CNTs) is found since 1991 by the Iijima of Japanese NEC Corporation,
Because the performances such as its excellent mechanics and electricity have caused worldwide research boom.CNTs is a kind of single point of novel self assembly
There is sub- material high intensity (~1TPa), great toughness and heat-resisting, corrosion-resistant, heat shock resistance, good conduction to lead
It is hot, intrinsic damp is high, has the excellent properties such as self-lubricating, be the preferable reinforced phase of composite material, have very wide application
Prospect.If the functions such as the excellent mechanics of CNTs and conductive and heat-conductive can be given full play to using CNTs enhancing metal-base composites
Characteristic makes the comprehensive performance of composite material be expected to significantly improve.C.F Deng(Deng C F,Zhang X X,Wang D
Z,et a1.Materials Letter,2007,61(8-9):Etc. 1725.) using ultrasonic disperse, ball milling in short-term after being stirred
It is broken, finally the more uniform fine and close aluminum matrix composite of CNTs dispersions is obtained by isostatic cool pressing and hot extrusion.The result shows that
The CNTs enhancing 2024A1 aluminum matrix composite elongation percentage that CNTs contents are 1.0wt.% is 17.9%, and tensile strength is
521.7MPa improves 35.7% compared with 2024 aluminium alloys, and enhancing effect is notable.Chio(Choi H J,Kwon G B,Lee G
Y,et a1.Scripta Materialia,2008,59(3)：Etc. 360.) it is prepared for using high-energy ball milling and hot extrusion technique
CNTs contents are the aluminum matrix composite of 4vol.%.The result shows that after ball milling 6h, 12h, the crystal grain refinement of composite material arrives
The addition of 200nm and 70nm, CNTs make aluminum matrix composite yield strength respectively reach 338MPa and 390MPa.
However, although CNTs can effectively promote the intensity of metallic matrix (such as aluminium, titanium, magnesium) as reinforced phase,
It is while some negative effects can be brought again (such as the reduction ductility of composite material, conduction, heat conduction functional characteristic and size are steady
It is qualitative etc.), the bottleneck present in preparation CNTs enhancing metal-base composites mainly has at present：
(1) CNTs is uniformly dispersed in metallic matrix
Since the size of CNTs is minimum, specific surface energy is big, draw ratio is big and SP2The influence of the factors such as orbital hybridization, leads
It is caused easily to generate reunion under van der Waals interaction, there are greater density differences etc. with metallic matrix additionally, due to CNTs so that
CNTs is difficult to be uniformly dispersed in metallic matrix.
(2) compatibility of CNTs and metallic matrix
Due to physics and the difference of chemical property, CNTs and most metals interface are nonwetting, and compatibility is poor to be caused
Interface cohesion is insecure between CNTs and metal, it is difficult to effectively act as transmitting the effect of load, so as to give full play to
The enhancing effect of CNTs.
(3) the excessive interfacial reaction generation crisp phase of carbide hard
During the sintering curing of metal-base composites, due to forming temperature height, CNTs holds with parent metal material
Interfacial reaction easily occurs, generates the hard crisp phase of corresponding ceramics.As CNTs and aluminium easily generate the Al of facile hydrolysis4C3Hard crisp phase, generation
Ductility, electrical and thermal conductivity and the dimensional stability of aluminum matrix composite can be then reduced when measuring excessive, is unfavorable for CNTs and strengthens effect
Performance.
(4) structural intergrity of CNTs
In mixed-powder, sintering and follow-up secondary processing process is prepared, the structure of CNTs is subject to destroy, original CNTs
Draw ratio easily reduce, cause the reinforcing decreased effectiveness of CNTs.
In view of the above problems, ameliorative way common at present has：Surface modification is carried out to CNTs, such as pickling, metal-coated membrane
Deng to improve the compatibility of CNTs and metallic matrix.But easily lead to CNTs structural damages there are pickling, metal-coated membrane technique is answered
It is miscellaneous, it is difficult to the shortcomings of controlling；Disperseed in CNTs dispersion processes using mechanical agitation or wet ball grinding, to reduce to CNTs's
Extent of the destruction, but dispersion effect is unsatisfactory；The hair that sintering parameter avoids violent interfacial reaction is adjusted in sintering process
It is raw, regulate and control the production quantity of carbide, but this method cannot fundamentally solve interfacial reaction and its control problem.It solves
Dispersions and interface cohesion and reaction problem of the CNTs in metal material, need to look for another way.
Silicon carbide (SiC) because with high specific strength, specific modulus, lightweight, anti-oxidant, anticorrosive, wear-resistant, dimensionally stable,
Non-aging, the advantages that thermal conductivity is good, the metal-base composites using SiC as reinforced phase has been applied to Aeronautics and Astronautics work
Industry and automobile, electronics industry.Wherein, the interfacial wettability of SiC and metal (such as aluminium) are good, and thermal stability and thermal conductivity are excellent
The features such as different is also an important factor for it obtains concern.But since SiC is to the strength enhancing effect mesh of metal-base composites
It is preceding still undesirable, the ductility and electric conductivity of composite material can additionally be greatly reduced, limit it to a certain extent extensively
Using.
In conclusion CNTs and SiC respectively has metallic matrix humidification, but still exist respective as reinforced phase
Deficiency, the advantages of with reference to CNTs and SiC respectively and wetability excellent between the two, can reaction in-situ the features such as preparing,
It is compound or modified to CNTs progress surface SiC, it is solve many difficulties in CNTs enhancing metal-base composites researchs one
A novelty resolving ideas.
Invention content
The object of the present invention is to provide the preparation methods of the compound CNTs of surface in situ generation nano SiC a kind of, solve existing
There is the problem of modified material dispersion effect and undesirable interface cohesion.
The technical solution adopted in the present invention is a kind of preparation method of the compound CNTs of surface in situ generation nano SiC,
It is characterized by comprising the following steps：
Step 1, dispersing binder polyvinylpyrrolidone (PVP) is scattered in absolute ethyl alcohol, obtains the anhydrous second of PVP
Alcohol dispersion liquid.
Step 2, CNTs and nano silica fume are added in PVP absolute ethyl alcohol dispersion liquids, is uniformly dispersed and filters, take what is filtered out
Mixed-powder is dried.
Step 3, mixed-powder is placed in heat-treatment furnace, hot place is carried out under vacuum environment or inert gas shielding
Reason, 1100~1300 DEG C of heat treatment temperature, heat treatment time is 1~3h, by the reaction that occurs in heat treatment process in CNTs
Surface in situ synthesizes nano SiC.
The features of the present invention also characterized in that：
Preferably, the volume ratio of CNTs and nano silica fume is 0.5~10.
Preferably, CNTs can be any one in single wall CNTs, multi wall CNTs and carbon nano-fiber or arbitrary combination.
Preferably, CNTs diameter ranges are 10nm~200nm, and length range is 100nm~1cm；Nano silica fume particle is straight
Diameter range is 20nm~150nm.
Preferably, the quality of dispersing binder PVP is the 0.5~30% of CNTs mass in step 1, the quality of absolute ethyl alcohol
10~50 times for CNTs and the mixed-powder gross mass of nano silica fume.
Preferably, in step 2 dispersion using ultrasonic disperse it is synchronouss with mechanical agitation progress, ultrasonic disperse can effectively by
The nano-particle reunited together scatter, and two kinds of nanometers mutually can be dispersed in PVP ethyl alcohol first during ultrasonic vibration
In solution, the synchronous mechanical agitation that carries out can be such that CNTs and nano silica fume is sufficiently mixed uniformly, and nano silica fume is adhered at this time
In CNTs surfaces.A length of 0.5~3h during ultrasonic disperse, mechanical agitation time are 0.5~3h, and rotating speed is 50~200 revs/min.
Vacuum drying temperature is 50~100 DEG C, and drying time is 2~12h.
Heat-treatment furnace can be the equipment such as tube furnace, Muffle furnace or discharge plasma sintering in the present invention, according to not
Same Equipment for Heating Processing, can obtain similar result.
The present invention synthesizes nano SiC by solid-solid reaction in CNTs surface in situ, obtains SiC/CNTs composite materials, should
Final product has different structure and ingredient according to CNTs and silica flour volume ratio, the difference of heat treatment condition.With raw material
CNTs and the variation of silica flour volume ratio, the volume ratio of product CNTs and nano SiC also respective change, as CNTs and nano silica fume volume
(it is less than 5 when smaller:1), the nano SiC of generation mostly with graininess uniform fold at CNTs surfaces (Fig. 6), tie by formation " bud bar "
Structure；When CNTs and nano silica fume volume are bigger (more than 5:2) when, the nano SiC granule of generation is mostly with continuous shell-like structure
CNTs surfaces are coated on, are formed using CNTs as " shell core " structure (Fig. 4-5) of " core " using SiC as " shell ".Either which kind of structure,
The wetability between CNTs and matrix can be improved, and the structure of CNTs is not all destroyed.On the other hand the SiC of generation can be with
Being in direct contact between CNTs and matrix is reduced, weakens the adverse reaction between CNTs and matrix, reduces Al4C3The life of hard crisp phase
Into the bridge joint played between CNTs and metallic matrix acts on, and enhances interface cohesion between the two.Due to the physics of SiC itself
Characteristic, can also improve heat conduction and the thermal stability of metal-base composites, and with CNTs cooperative reinforcing basis materials, carrying
Retain the good conductive, heat conduction of matrix and high ductility while high metal matrix mechanical property；In addition, in-situ synthesis is compared
It is can to ensure the dispersing uniformity of CNTs and SiC in the advantages of outer addition, ensures interaction therebetween.
Description of the drawings
Fig. 1 is the technology used in the present invention route schematic diagram；
Fig. 2 is that original CNTs ((a)) used in the present invention, nano silica fume ((b)) and embodiment 1 pass through synchronizing ultrasound
The scanned photograph of CNTs-Si ((c-d)) mixed-powder made from dispersion and mechanical agitation；
Fig. 3 is that the volume ratio that embodiment 1 obtains after 1200 DEG C of reaction in-situs is 1:1 CNTs/SiC composite materials are swept
Retouch photo and energy spectrum analysis；
Fig. 4 is that the volume ratio that embodiment 1 obtains after 1200 DEG C of reaction in-situs is 5:2 CNTs/SiC composite materials are swept
Retouch photo and energy spectrum analysis；
Fig. 5 is that the volume ratio that embodiment 3 obtains after 1200 DEG C of reaction in-situs is 5:1 CNTs/SiC composite materials are swept
Retouch photo and energy spectrum analysis；
Fig. 6 is X ray diffracting spectrum of the CNTs-Si mixed-powders after different temperatures is heat-treated；
Fig. 7 is that fabricated in situ volume ratio is 1 at 1200 DEG C:The transmission photo of 1 CNTs/SiC composite materials.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description, but the present invention is not limited to
These embodiments.
The preparation method of the CNTs materials of the nano surface SiC In-situ reactions of the present invention, used raw material for CNTs and
Nano silica fume.CNTs can be any one in single wall CNTs, multi wall CNTs and carbon nano-fiber or arbitrarily combine, CNTs diameters
Range can be 10nm~200nm, and length range can be 100nm~1cm；Nano silica fume particle diameter range can be 20nm
~150nm.
With reference to Fig. 1, the preparation method of the material is：
Step 1, PVP absolute ethyl alcohol dispersion liquids are configured
According to CNTs and nano silica fume volume ratio weighs corresponding CNTs for 0.5~10 and nano silica fume is for use.It is fixed to measure
The absolute ethyl alcohol of amount, and add appropriate polyvinylpyrrolidone (PVP) as dispersing binder, using mechanical agitation by PVP
It is scattered in absolute ethyl alcohol.
Step 2, by nano silica fume uniform adhesion in CNTs surfaces
The CNTs and nano silica fume that step 1 is weighed in proportion are added in into the PVP absolute ethyl alcohol dispersion liquids of configuration, then
It is synchronous to carry out ultrasonic disperse and mechanical agitation, it is dried under vacuum conditions after filtering.
Step 3, fabricated in situ bud bar-shell-and-core structure CNTs/SiC
CNTs- silicon mixed-powders are placed in heat-treatment furnace and are heat-treated, by reaction in-situ in CNTs surface in situ
SiC is synthesized, obtains bud bar-shell-and-core structure CNTs/SiC.
The compound CNTs materials of surface in situ generation nano SiC being related to are further illustrated the present invention with specific embodiment below
The preparation method of material.
Embodiment 1
It is 1 to prepare a kind of CNTs-SiC volume ratios:1 SiC/CNTs composite materials.
It is for use to weigh multi wall CNTs and nano silica fume each 0.3287g, 0.2493g, measures absolute ethyl alcohol 30ml, weighs CNTs
PVP, using mechanical agitation is scattered in absolute ethyl alcohol, stirred by polyvinylpyrrolidone (PVP) 0.003287g of quality 1%
Mix time 30min, rotating speed 100rpm.Then the CNTs of weighing and nano silica fume are added in absolute ethyl alcohol dispersion liquid, same to stepping
Row ultrasonic disperse and mechanical agitation mixing, incorporation time 1h.CNTs-Si mixed-powders after dispersion are after filtering in vacuum environment
Under be dried, drying temperature be 70 DEG C, drying time 4h, obtain homodisperse CNTs-Si mixed-powders.Finally will
CNTs-Si mixed-powders, which are seated in graphite crucible in heat-treatment furnace, carries out vacuum heat, and heat treatment temperature is 1200 DEG C,
Soaking time 1h makes CNTs and nano silica fume carry out reaction in-situ, and generation volume ratio is about 1:1 CNTs-SiC composite materials.
Embodiment 2
It is 5 to prepare a kind of CNTs-SiC volume ratios:2 SiC/CNTs composite materials.
Under conditions of ensureing that other parameter is constant, only change both CNTs, SiC percent by volume in 1 product of embodiment
It is 5:2, that is, the quality for weighing CNTs and nano silica fume is respectively 0.3791g, 0.1435g.It is prepared after the same method
CNTs-SiC volume ratios are 5:2 composite material.
Embodiment 3
It is 5 to prepare a kind of CNTs-SiC volume ratios:1 SiC/CNTs composite materials.
Under conditions of ensureing that other parameter is constant, only change both CNTs, SiC percent by volume in 1 product of embodiment
It is 5:1, that is, the quality for weighing CNTs and nano silica fume is respectively 0.4068g, 0.0837g.It is prepared after the same method
CNTs-SiC volume ratios are 5:1 composite material.
Embodiment 4
It is 1 to prepare a kind of CNTs-SiC volume ratios:1 SiC/CNTs composite materials.
Under conditions of ensureing that other parameter is constant, it is 1100 DEG C only to change heat treatment temperature in embodiment 1, according to similary
Method CNTs-SiC volume ratios are prepared as 1:1 composite material.
Embodiment 5
It is 1 to prepare a kind of CNTs-SiC volume ratios:1 SiC/CNTs composite materials.
Under conditions of ensureing that other parameter is constant, it is 1300 DEG C only to change heat treatment temperature in embodiment 1, according to similary
Method CNTs-SiC volume ratios are prepared as 1:1 composite material.
Embodiment 6
It is 1 to prepare a kind of CNTs-SiC volume ratios:1 SiC/CNTs composite materials.
Multi wall CNTs and the 0.2493g grain size that a diameter of 20nm-200nm length of 0.3287g is 100nm-1cm is weighed to exist
Nano silica fume in the range of 20nm~150nm so that volume ratio shared by CNTs, SiC the two is 1 in product:1.Measure anhydrous second
Alcohol 30ml is weighed polyvinylpyrrolidone (PVP) 0.0986g of CNTs mass 30%, is scattered in PVP using mechanical agitation
In absolute ethyl alcohol, mixing time 3h, rotating speed 200rpm.Then the CNTs of weighing and nano silica fume are added into absolute ethyl alcohol dispersion liquid
In, it is carried out at the same time ultrasonic disperse and mechanical agitation mixing, incorporation time 3h.CNTs-Si mixed-powders after dispersion are after filtering
It is dried under vacuum conditions, drying temperature is 50 DEG C, drying time 12h, obtains homodisperse CNTs-Si mixed powders
End.CNTs-Si mixed-powders are finally seated in vacuum heat in graphite crucible, heat treatment temperature is 1200 DEG C, during heat preservation
Between 3h, CNTs and nano silica fume is made to carry out reaction in-situ, generation volume ratio is 1:1 CNTs-SiC composite materials.
Embodiment 7
It is 1 to prepare a kind of CNTs-SiC volume ratios:1 SiC/CNTs composite materials.
Multi wall CNTs and the 0.2493g grain size that a diameter of 20nm-200nm length of 0.3287g is 100nm-1cm is weighed to exist
Nano silica fume in the range of 20nm~150nm so that volume ratio shared by CNTs, SiC the two is 1 in product:1.Measure anhydrous second
Alcohol 5ml is weighed polyvinylpyrrolidone (PVP) 0.001644g of CNTs mass 0.5%, is disperseed PVP using mechanical agitation
In absolute ethyl alcohol, mixing time 0.5h, rotating speed 50rpm.Then load weighted CNTs and nano silica fume are added into absolute ethyl alcohol
In dispersion liquid, it is carried out at the same time ultrasonic disperse and mechanical agitation mixing, incorporation time 0.5h.CNTs-Si mixed-powders after dispersion
It is dried under vacuum conditions after filtering, drying temperature is 100 DEG C, and drying time 2h obtains homodisperse CNTs-Si
Mixed-powder.Finally CNTs-Si mixed-powders are seated in graphite crucible and are heat-treated, heat treatment temperature is 1200 DEG C,
Soaking time 1h, argon gas atmosphere protection make CNTs and nano silica fume carry out reaction in-situ, and generation volume ratio is 1:1 CNTs-
SiC ceramic matrix composite material.
In order to which CNTs is managed before and after the dispersion effect and reaction in-situ of the mixed-powder obtained explicitly by above-mentioned preparation method
The microstructure of the synthesis situation of surface SiC, phase composition and SiC/CNTs, the present invention are prepared for respectively by taking embodiment 1 as an example
The composite materials of 1000 DEG C of heat treatment of mixed powder and process of CNTs and nano silica fume are as a comparison.
Comparative example 1
Prepare a kind of CNTs-Si mixed powders.
It is for use to weigh CNTs and nano silica fume each 0.3287g, 0.2493g.Absolute ethyl alcohol 30ml is measured, weighs CNTs mass
PVP, is scattered in absolute ethyl alcohol by 1% polyvinylpyrrolidone (PVP) 0.003287g using mechanical agitation, during stirring
Between 30min, rotating speed 100rpm.Then the CNTs of weighing and nano silica fume are added in PVP absolute ethyl alcohol dispersion liquids, it is synchronous to carry out
Ultrasonic disperse and mechanical agitation mixing, incorporation time 1h.CNTs-Si mixed-powders after dispersion are after filtering under vacuum conditions
It is dried, drying temperature is 70 DEG C, drying time 4h, obtains homodisperse CNTs-Si mixed-powders.
Comparative example 2
It is 1 to prepare a kind of CNTs-SiC volume ratios:1 SiC/CNTs composite materials.
It is 1 according to CNTs, generation SiC volume ratios:1 weighing CNTs and nano silica fume each 0.3287g, 0.2493g is for use.Amount
Absolute ethyl alcohol 30ml is taken, weighs polyvinylpyrrolidone (PVP) 0.003287g of CNTs mass 1%, it will using mechanical agitation
PVP is scattered in absolute ethyl alcohol, mixing time 30min, rotating speed 100rpm.Then the CNTs of weighing and nano silica fume are added to
In PVP absolute ethyl alcohol dispersion liquids, it is carried out at the same time ultrasonic disperse and mechanical agitation mixing, incorporation time 1h.CNTs-Si after dispersion
Mixed-powder is dried under vacuum conditions after filtering, and drying temperature is 70 DEG C, and drying time 4h is obtained homodisperse
CNTs-Si mixed-powders.Finally CNTs-Si mixed-powders are seated in graphite crucible and carry out vacuum heat, heat treatment temperature
It is 1000 DEG C, soaking time 1h to spend, and CNTs and nano silica fume is made to carry out reaction in-situ, to generate volume ratio as 1:1 CNTs-
SiC ceramic matrix composite material.
Microstructure is carried out with comparative example material to CNTs-SiC composite materials prepared by the present invention and phase composition compares.
Fig. 2 is the microscopic appearance of starting powder and mixed-powder.(a) is original nano silica fume in Fig. 2, and (b) is original
CNTs, (c) and (d) (partial enlarged view) are the mixed-powder of CNTs and silica flour made from embodiment 1, it can be seen that after dispersion
CNTs and nano silica fume wound upon themselves and agglomeration weaken, and individually dispersion are presented uniformly, and nano silica fume is glued in the form of single
Invest CNTs surfaces.
Fig. 3 is the stereoscan photograph of composite material and energy spectrum analysis after CNTs-Si made from embodiment 1 is heat-treated.By
(a) and (b) can be seen that the nano SiC granule generated and mostly be uniformly wrapped on CNTs surfaces with continuous shell-like structure in Fig. 3,
It is " core " using SiC as " shell core " the shape structure of " shell " to be formed using CNTs, reacts and is started simultaneously constantly to CNTs internal layers from CNTs outer layers
Diffusion obtains a kind of compound CNTs of surface in situ generation nano SiC, and the thickness of SiC generation layers is about 25nm.Be computed when by
It is 1 according to CNTs and SiC volume ratios:During 1 proportioning, the theoretic throat for generating SiC layer is 25nm, theoretical value and experiment value kissing
It closes, that is, the SiC for illustrating reaction in-situ generation can equably be coated on CNTs surfaces according to design thickness.By (c-e) composite powder
The power spectrum of body can be seen that structure distribution of the element silicon along CNTs, and using original CNTs as substrate, nano silica fume and CNTs's is outer
Layer occurs reaction in-situ generation SiC and is coated on CNTs surfaces first, and core still keeps CNTs prototype structures and ingredient.This shell core
The SiC/CNTs of shape structure can both retain the original excellent comprehensive performances of CNTs, and the SiC for being coated on CNTs surfaces can
To effectively improve the wetability between CNTs and metallic matrix (such as aluminium, titanium), directly connecing between CNTs and matrix is reduced
It touches, weakens unfavorable interfacial reaction, inhibit the generation of the crisp phase of carbide hard, assist CNTs reinforced metal matrixes, further improve
The mechanical property and functional characteristic of metal-base composites are (such as：Thermal conductivity and thermal stability etc.).
Fig. 4 is the stereoscan photograph of composite material and energy spectrum analysis after CNTs-Si made from embodiment 2 is heat-treated.It presses
According to the proportioning of CNTs and nano silica fume, the volume ratio of CNTs and nano SiC is 5 after reaction in-situ:2, generate the theory of SiC
Thickness is 10nm.(a) and (b) can see in Fig. 4, and the SiC/ of bud bar-shell-and-core structure is had both in CNTs Surface Creations
CNTs.A SiC parts for generation are in continuous shell-like structure, are coated on CNTs surfaces；Another part nano SiC is then equal with graininess
It is even to be covered in CNTs surfaces then in spherical, the SiC/CNTs of similar bud rod structure is formed with CNTs.Compared with Example 1, it coats
It decreases in the continuity degree of the SiC on CNTs surfaces, bud rod structure ratio increased.By counting SiC generation layer thickness
About 12.5nm, close to theoretical value.The distribution kissing of carbon and element silicon it can be seen from the power spectrum of (c-e) composite granule
It closes, that is, illustrates that the SiC of generation is coated on CNTs surfaces, composite granule integrally still keeps the fibre structure of original CNTs.As above institute
It states, this structure can fully be sent out under the premise of improving the wetability of CNTs and metallic matrix, weakening unfavorable interfacial reaction
The reinforcing effect of CNTs is waved, improves the comprehensive performance of composite material.
Fig. 5 is the stereoscan photograph of composite material and energy spectrum analysis after CNTs-Si made from embodiment 3 is heat-treated.It presses
According to the proportioning of CNTs and nano silica fume, the volume ratio of CNTs and the SiC of generation are 5 after reaction in-situ:1, generate the reason of SiC
It is 5nm by thickness.It is about 18nm, and there are deviations for theoretical value by counting SiC generation layer thickness.To find out its cause, work as silicone content
Its SiC in the synthesis of CNTs surfaces, which is difficult to form shell, when proportioning is reduced uniformly coats CNTs, forms continuous shell core shape structure,
The ratio of bud rod-like structure further increases and shell core shape structure is reduced, and part is caused to occur, and generation layer is thicker and non-uniform feelings
Condition.Carbon matches with element silicon distribution it can be seen from the power spectrum of (c-e) composite granule in Fig. 5, that is, illustrates receiving for generation
Rice SiC on CNTs surfaces, forms the bud rod-like structure using CNTs as " bar " mostly with graininess uniform fold.By above example knot
Fruit is it is envisioned that with the increase of SiC content in design reaction product, then continuous shell core shape structure proportion increases therewith.
Conversely, then increase by the bud rod-like structure ratio of bar, SiC for bud of CNTs.
Fig. 6 is the X ray diffracting spectrum of CNTs-SiC composite materials made from comparative example 1,2 and embodiment 1,4,5.It can be with
Find out, the mixed-powder of CNTs and nano silica fume only has the diffraction maximum of carbon and silicon, and heat treatment temperature equally only has when being 1000 DEG C
The diffraction maximum of carbon and silicon.With the raising of heat treatment temperature, at 1100 DEG C other than the diffraction maximum of original carbon and silicon, go back
There is the diffraction maximum of SiC, that is, show at 1100 DEG C, have occurred that hair is answered between CNTs and silica flour, generate SiC, but
It is that reaction is insufficient, still with the presence of unreacted silicon.When heat treatment temperature be increased to 1200 DEG C and more than when, composite material X is penetrated
The result of line diffraction then only has carbon and the diffraction maximum of SiC, that is, shows that the reaction was complete for the nano silica fume added in quilt, on the surface layer of CNTs
SiC is generated, constitutes the SiC/CNTs composite materials of bud bar-shell-and-core structure shown in figure (4,5,6).
Fig. 7 is the transmission electron microscope photo of SiC/CNTs composite materials made from embodiment 1.(a) and (b) display is logical in Fig. 7
Cross reaction in-situ generation SiC particulate with shell shape uniform fold on CNTs surfaces.By the height for analyzing A1 and A2 regions in (b)
Differentiate the diffraction fringe of picture and lattice image it is found that in (c) diffraction fringe of the high resolution picture and lattice image in A1 regions interplanar
Away from for 0.34nm, (002) crystal face of corresponding graphite, the interplanar of the diffraction fringe of A2 regions high resolution picture and lattice image in (d)
Away from for 0.25nm, (111) crystal face of corresponding SiC.Illustrating can be in CNTs surface in situ synthesis nano by the method for the present invention
SiC, and its original structure and ingredient are still maintained inside CNTs, this structure is conducive to give full play to CNTs in Metal Substrate
Enhancing effect in body.
The present invention is raw material according to different CNTs, nano silica fume, using different preparation parameter and heat treatment method,
Above-described embodiment 1 is substituted using other embodiment, also can obtain similar result.
Claims (7)
1. a kind of preparation method of the compound CNTs of surface in situ generation nano SiC, which is characterized in that include the following steps：
Step 1, dispersing binder polyvinylpyrrolidone (PVP) is scattered in absolute ethyl alcohol, obtains PVP absolute ethyl alcohols point
Dispersion liquid；
Step 2, CNTs and nano silica fume are added in PVP absolute ethyl alcohol dispersion liquids, is uniformly dispersed and filters, take the mixing filtered out
Powder is dried；
Step 3, mixed-powder is placed in heat-treatment furnace, is heat-treated under vacuum environment or inert gas shielding, heat
1100~1300 DEG C for the treatment of temperature, heat treatment time is 1~3h, by the reaction in-situ that occurs in heat treatment process in CNTs tables
Nano SiC of the face synthesis with different structure.
2. the preparation method of the compound CNTs materials of surface in situ generation nano SiC according to claim 1, feature exist
In the volume ratio of the CNTs and nano silica fume is 0.5~10.
3. the preparation method of the compound CNTs materials of surface in situ generation nano SiC according to claim 1, feature exist
In the CNTs is any one in single wall CNTs, multi wall CNTs and carbon nano-fiber or arbitrary combination.
4. the preparation method of the compound CNTs materials of surface in situ generation nano SiC according to claim 1, feature exist
In the CNTs diameter ranges are 10nm~200nm, and length range is 100nm~1cm；Nano silica fume particle diameter range is
20nm~150nm.
5. the preparation method of the compound CNTs materials of surface in situ generation nano SiC according to claim 1, feature exist
In the quality of, dispersing binder PVP described in step 1 be the 0.5~30% of CNTs mass, the quality of absolute ethyl alcohol for CNTs and
10~50 times of the mixed-powder gross mass of nano silica fume.
6. the preparation method of the compound CNTs materials of surface in situ generation nano SiC according to claim 1, feature exist
In dispersion described in step 2 is using ultrasonic disperse progress synchronouss with mechanical agitation, a length of 0.5~3h during ultrasonic disperse, and machinery stirs
The time is mixed as 0.5~3h, rotating speed is 50~200 revs/min.
7. the preparation method of the compound CNTs materials of surface in situ generation nano SiC according to claim 1, feature exist
In vacuum drying temperature described in step 2 is 50~100 DEG C, and drying time is 2~12h.
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| CN110172180B (en) * | 2019-04-12 | 2021-07-09 | 西安理工大学 | Inorganic fiber/silicon dioxide nano material and preparation method and application thereof |
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