CN108217629B - 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 that a kind of surface in situ generates the compound CNTs of nano SiC, pass through synchronizing ultrasound dispersion and mechanical stirring, by the nano silica fume uniform adhesion of special ratios in the surface CNTs in PVP ethanol solution, then the SiC/CNTs composite material with bud bar or shell-and-core structure is formed in the SiC of one layer of nanometer grade thickness of CNTs Surface Creation by reaction in-situ.The SiC/CNTs material of the method for the present invention preparation does not destroy the structure of CNTs, and it can guarantee the dispersing uniformity of CNTs and SiC, directly contacting between CNTs and matrix will be being reduced in basis material, regulate and control the interfacial reaction between CNTs and matrix, enhance the interface cohesion between CNTs and matrix, good conductive, the thermally conductive and high ductility of reservation matrix while improving metallic matrix mechanical property.
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 technique
Since carbon nanotube (Carbon nanotubes, CNTs) is found by the Iijima of Japanese NEC Corporation since 1991,
Because the performances such as its excellent mechanics and electricity have caused worldwide research boom.CNTs is novel single point of self assembly of one kind
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 ideal 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): 1725.) etc. 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 dispersion is obtained by isostatic cool pressing and hot extrusion.The result shows that
The CNTs enhancing 2024A1 aluminum matrix composite elongation percentage that CNTs content is 1.0wt.% is 17.9%, and tensile strength is
521.7MPa improves 35.7% compared with 2024 aluminium alloys, and reinforcing effect is significant.Chio(Choi H J,Kwon G B,Lee G
2008,59 (3): Y, et a1.Scripta Materialia 360.) etc. are prepared for using high-energy ball milling and hot extrusion technique
CNTs content is the aluminum matrix composite of 4vol.%.The result shows that the crystal grain refinement of composite material arrives after ball milling 6h, 12h
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 (it is steady such as to reduce the ductility of composite material, conduction, thermally conductive functional characteristic and size again
It is qualitative etc.), the bottleneck present in preparation CNTs enhancing metal-base composites mainly has at present:
(1) CNTs is evenly 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, additionally, due to CNTs, there are greater density differences etc. with metallic matrix, so that
CNTs is difficult to be uniformly dispersed in metallic matrix.
(2) compatibility of CNTs and metallic matrix
Due to the difference of physics and 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 the effect for effectively acting as transmitting load, to cannot give full play to
The reinforcing effect of CNTs.
(3) excessive interfacial reaction generates the crisp phase of carbide hard
During the sintering curing of metal-base composites, due to forming temperature height, CNTs and parent metal material hold
Interfacial reaction easily occurs, generates the hard crisp phase of corresponding ceramics.As CNTs and aluminium are easy to generate the Al of facile hydrolysis4C3Hard crisp phase, generates
Ductility, electrical and thermal conductivity and the dimensional stability that aluminum matrix composite can be then reduced when measuring excessive, are unfavorable for CNTs strengthening effect
Performance.
(4) structural intergrity of CNTs
In preparing mixed-powder, sintering and subsequent secondary processing process, the structure of CNTs is subject to destroy, original CNTs
Draw ratio be easy reduce, cause the strengthening effect of CNTs to weaken.
In view of the above problems, ameliorative way common at present has: carrying out surface to CNTs and be modified, such as pickling, metal-coated membrane
Deng the compatibility to improve CNTs and metallic matrix.But there are pickling to easily lead to CNTs structural damage, metal-coated membrane technique is answered
It is miscellaneous, it is difficult to the disadvantages of controlling；Dispersed in CNTs dispersion process using mechanical stirring or wet ball grinding, to reduce to CNTs's
Extent of the destruction, but dispersion effect is unsatisfactory；Adjustment sintering parameter avoids the hair of violent interfacial reaction during the 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
Dispersion and interface cohesion and reaction problem of the CNTs in metal material, need to look for another way.
Silicon carbide (SiC) because have 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 as reinforced phase, has humidification to metallic matrix respectively, but still exist respective
Deficiency, in conjunction with the advantage of CNTs and SiC respectively, and wetability excellent between the two, can reaction in-situ preparation the features such as,
It is compound or modified to CNTs progress surface SiC, it is solve many difficulties in CNTs enhancing metal-base composites research one
A novelty resolving ideas.
Summary of the invention
The object of the present invention is to provide the preparation methods that a kind of surface in situ generates the compound CNTs of nano SiC, solve existing
There are modified material dispersion effect and the undesirable problem of interface cohesion.
The technical scheme adopted by the invention is that a kind of surface in situ generates the preparation method of the compound CNTs of nano SiC,
Characterized by comprising the following steps:
Step 1, it disperses dispersing binder polyvinylpyrrolidone (PVP) in dehydrated alcohol, obtains the anhydrous second of PVP
Alcohol dispersion liquid.
Step 2, CNTs and nano silica fume are added in PVP dehydrated alcohol dispersion liquid, are uniformly dispersed and filter, taken and filter out
Mixed-powder is dry.
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 any combination.
Preferably, CNTs diameter range is 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 dehydrated alcohol
It is 10~50 times of the mixed-powder gross mass of CNTs and nano silica fume.
Preferably, in step 2 dispersion using ultrasonic disperse it is synchronous with mechanical stirring progress, ultrasonic disperse can effectively by
The nanoparticle reunited together scatter, and two kinds of nanometers can mutually be dispersed in PVP ethyl alcohol first during ultrasonic vibration
In solution, the synchronous mechanical stirring that carries out can be such that CNTs and nano silica fume is sufficiently mixed uniformly at this time, and nano silica fume is adhered to
In the surface CNTs.A length of 0.5~3h when ultrasonic disperse, mechanical stirring time are 0.5~3h, and revolving 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 be obtained similar result.
The present invention synthesizes nano SiC in CNTs surface in situ by solid-solid reaction, obtains SiC/CNTs composite material, should
Difference of the final product according to CNTs and silicon powder volume than, heat treatment condition has different structure and ingredient.With raw material
CNTs and silicon powder volume are than variation, the volume ratio of product CNTs and nano SiC also corresponding change, as CNTs and nano silica fume volume
(it is less than 5:1) when smaller, the nano SiC of generation forms " bud bar " knot mostly with graininess uniform fold at the surface CNTs (Fig. 6)
Structure；As CNTs and nano silica fume volume bigger (more than 5:2), the nano SiC granule of generation is mostly with continuous shell-like structure
It is coated on the surface CNTs, being formed with CNTs is " shell core " structure (Fig. 4-5) that " core " take 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 generated can be with
Directly contacting between CNTs and matrix is reduced, the adverse reaction between CNTs and matrix is weakened, reduces Al4C3The life of hard crisp phase
At 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 the thermally conductive and thermal stability of metal-base composites, and with CNTs cooperative reinforcing basis material, mentioning
Retain matrix good conductive, thermally conductive and high ductility while high metal matrix mechanical property；In addition, in-situ synthesis is compared
It is to guarantee the dispersing uniformity of CNTs and SiC in the advantages of outer addition, guarantees interaction between the two.
Detailed description of the invention
Fig. 1 is the technology used in the present invention route schematic diagram；
Fig. 2 is that original CNTs ((a)), nano silica fume ((b)) and embodiment 1 used in the present invention pass through synchronizing ultrasound
The scanned photograph of CNTs-Si ((c-d)) mixed-powder made from dispersion and mechanical stirring；
Fig. 3 is sweeping for the CNTs/SiC composite material that the volume ratio that embodiment 1 obtains after 1200 DEG C of reaction in-situs is 1:1
Retouch photo and energy spectrum analysis；
Fig. 4 is sweeping for the CNTs/SiC composite material that the volume ratio that embodiment 1 obtains after 1200 DEG C of reaction in-situs is 5:2
Retouch photo and energy spectrum analysis；
Fig. 5 is sweeping for the CNTs/SiC composite material that the volume ratio that embodiment 3 obtains after 1200 DEG C of reaction in-situs is 5:1
Retouch photo and energy spectrum analysis；
Fig. 6 is X ray diffracting spectrum of the CNTs-Si mixed-powder after different temperatures is heat-treated；
Fig. 7 is the transmission photo for the CNTs/SiC composite material that fabricated in situ volume ratio is 1:1 at 1200 DEG C.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments, but the present invention is not limited to
These embodiments.
The preparation method of the CNTs material of nano surface SiC In-situ reaction of the invention, used raw material be CNTs and
Nano silica fume.CNTs can be any one in single wall CNTs, multi wall CNTs and carbon nano-fiber or any combination, CNTs diameter
Range can be 10nm~200nm, and length range can be 100nm~1cm；Nano silica fume particle diameter range can be 20nm
~150nm.
Referring to Fig.1, the material the preparation method comprises the following steps:
Step 1, PVP dehydrated alcohol dispersion liquid is configured
It is that the corresponding CNTs of 0.5~10 weighing and nano silica fume are stand-by according to CNTs and nano silica fume volume ratio.It is fixed to measure
The dehydrated alcohol of amount, and add appropriate polyvinylpyrrolidone (PVP) as dispersing binder, using mechanical stirring by PVP
It is scattered in dehydrated alcohol.
Step 2, by nano silica fume uniform adhesion in the surface CNTs
CNTs and nano silica fume that step 1 weighs in proportion are added into the PVP dehydrated alcohol dispersion liquid of configuration, then
It is synchronous to carry out ultrasonic disperse and mechanical stirring, it is dried under vacuum conditions after filtering.
Step 3, fabricated in situ bud bar-shell-and-core structure CNTs/SiC
CNTs- silicon mixed-powder is placed in heat-treatment furnace and is heat-treated, by reaction in-situ in CNTs surface in situ
SiC is synthesized, bud bar-shell-and-core structure CNTs/SiC is obtained.
Further illustrate that surface in situ of the present invention generates the compound CNTs material of nano SiC below with specific embodiment
The preparation method of material.
Embodiment 1
Prepare a kind of SiC/CNTs composite material that CNTs-SiC volume ratio is 1:1.
It is stand-by to weigh multi wall CNTs and nano silica fume each 0.3287g, 0.2493g, measures dehydrated alcohol 30ml, weighs CNTs
Polyvinylpyrrolidone (PVP) 0.003287g of quality 1%, is dispersed PVP in dehydrated alcohol using mechanical stirring, stirred
Mix time 30min, revolving speed 100rpm.Then the CNTs of weighing and nano silica fume are added in dehydrated alcohol dispersion liquid, same to stepping
Row ultrasonic disperse and mechanical stirring mixing, incorporation time 1h.CNTs-Si mixed-powder after dispersion is after filtering in vacuum environment
Under be dried, drying temperature be 70 DEG C, drying time 4h, obtain evenly dispersed CNTs-Si mixed-powder.Finally will
CNTs-Si mixed-powder, which is seated in graphite crucible in heat-treatment furnace, carries out vacuum heat treatment, and heat treatment temperature is 1200 DEG C,
Soaking time 1h makes CNTs and nano silica fume carry out reaction in-situ, generates the CNTs-SiC composite material that volume ratio is about 1:1.
Embodiment 2
Prepare a kind of SiC/CNTs composite material that CNTs-SiC volume ratio is 5:2.
Under conditions of guaranteeing that other parameters are constant, only change both CNTs, SiC percent by volume in 1 product of embodiment
For 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 ratio is the composite material of 5:2.
Embodiment 3
Prepare a kind of SiC/CNTs composite material that CNTs-SiC volume ratio is 5:1.
Under conditions of guaranteeing that other parameters are constant, only change both CNTs, SiC percent by volume in 1 product of embodiment
For 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 ratio is the composite material of 5:1.
Embodiment 4
Prepare a kind of SiC/CNTs composite material that CNTs-SiC volume ratio is 1:1.
Under conditions of guaranteeing that other parameters are constant, only changing heat treatment temperature in embodiment 1 is 1100 DEG C, according to same
Method be prepared CNTs-SiC volume ratio be 1:1 composite material.
Embodiment 5
Prepare a kind of SiC/CNTs composite material that CNTs-SiC volume ratio is 1:1.
Under conditions of guaranteeing that other parameters are constant, only changing heat treatment temperature in embodiment 1 is 1300 DEG C, according to same
Method be prepared CNTs-SiC volume ratio be 1:1 composite material.
Embodiment 6
Prepare a kind of SiC/CNTs composite material that CNTs-SiC volume ratio is 1:1.
Weighing 0.3287g diameter is that multi wall CNTs and the 0.2493g partial size that 20nm-200nm length is 100nm-1cm exists
Nano silica fume within the scope of 20nm~150nm, so that volume ratio shared by CNTs, SiC the two is 1:1 in product.Measure anhydrous second
Alcohol 30ml is weighed polyvinylpyrrolidone (PVP) 0.0986g of CNTs mass 30%, is dispersed PVP in using mechanical stirring
In dehydrated alcohol, mixing time 3h, revolving speed 200rpm.Then the CNTs of weighing and nano silica fume are added into dehydrated alcohol dispersion liquid
In, while carrying out ultrasonic disperse and mechanical stirring mixing, incorporation time 3h.CNTs-Si mixed-powder after dispersion is after filtering
It is dried under vacuum conditions, drying temperature is 50 DEG C, drying time 12h, obtains evenly dispersed CNTs-Si mixed powder
End.CNTs-Si mixed-powder is finally seated in vacuum heat treatment in graphite crucible, heat treatment temperature is 1200 DEG C, when heat preservation
Between 3h, so that CNTs and nano silica fume is carried out reaction in-situ, generate the CNTs-SiC composite material that volume ratio is 1:1.
Embodiment 7
Prepare a kind of SiC/CNTs composite material that CNTs-SiC volume ratio is 1:1.
Weighing 0.3287g diameter is that multi wall CNTs and the 0.2493g partial size that 20nm-200nm length is 100nm-1cm exists
Nano silica fume within the scope of 20nm~150nm, so that volume ratio shared by CNTs, SiC the two is 1:1 in product.Measure anhydrous second
Alcohol 5ml is weighed polyvinylpyrrolidone (PVP) 0.001644g of CNTs mass 0.5%, is dispersed PVP using mechanical stirring
In dehydrated alcohol, mixing time 0.5h, revolving speed 50rpm.Then load weighted CNTs and nano silica fume are added into dehydrated alcohol
In dispersion liquid, while carrying out ultrasonic disperse and mechanical stirring mixing, incorporation time 0.5h.CNTs-Si mixed-powder after dispersion
It is dried under vacuum conditions after filtering, drying temperature is 100 DEG C, and drying time 2h obtains evenly dispersed CNTs-Si
Mixed-powder.Finally CNTs-Si mixed-powder is seated in graphite crucible and is heat-treated, heat treatment temperature is 1200 DEG C,
Soaking time 1h, argon atmosphere protection make CNTs and nano silica fume carry out reaction in-situ, generate the CNTs- that volume ratio is 1:1
SiC ceramic matrix composite material.
For CNTs pipe 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 material of 1000 DEG C of heat treatment of mixed powder and process of CNTs and nano silica fume is as a comparison.
Comparative example 1
Prepare a kind of CNTs-Si mixed powder.
It is stand-by to weigh CNTs and nano silica fume each 0.3287g, 0.2493g.Dehydrated alcohol 30ml is measured, CNTs mass is weighed
1% polyvinylpyrrolidone (PVP) 0.003287g, is dispersed PVP in dehydrated alcohol using mechanical stirring, when stirring
Between 30min, revolving speed 100rpm.Then the CNTs of weighing and nano silica fume are added in PVP dehydrated alcohol dispersion liquid, it is synchronous to carry out
Ultrasonic disperse and mechanical stirring mixing, incorporation time 1h.CNTs-Si mixed-powder after dispersion is after filtering under vacuum conditions
It is dried, drying temperature is 70 DEG C, drying time 4h, obtains evenly dispersed CNTs-Si mixed-powder.
Comparative example 2
Prepare a kind of SiC/CNTs composite material that CNTs-SiC volume ratio is 1:1.
It is that 1:1 weighing CNTs and nano silica fume each 0.3287g, 0.2493g is stand-by according to CNTs, generation SiC volume ratio.Amount
Dehydrated alcohol 30ml is taken, polyvinylpyrrolidone (PVP) 0.003287g of CNTs mass 1% is weighed, it will using mechanical stirring
PVP is scattered in dehydrated alcohol, mixing time 30min, revolving speed 100rpm.Then the CNTs of weighing and nano silica fume are added to
In PVP dehydrated alcohol dispersion liquid, while carrying out ultrasonic disperse and mechanical stirring 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 evenly dispersed
CNTs-Si mixed-powder.Finally CNTs-Si mixed-powder is seated in graphite crucible and carries out vacuum heat treatment, heat treatment temperature
Degree is 1000 DEG C, soaking time 1h, so that CNTs and nano silica fume is carried out reaction in-situ, to generate volume ratio as the CNTs- of 1:1
SiC ceramic matrix composite material.
Microstructure is carried out to CNTs-SiC composite material prepared by the present invention and comparative example material 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, (b) is original
The mixed-powder that CNTs, (c) and (d) (partial enlarged view) are CNTs and silicon powder 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 the surface CNTs.
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 the surface CNTs with continuous shell-like structure in Fig. 3,
Being formed with CNTs be " shell core " shape structure that " core " take SiC as " shell ", reacts and is started simultaneously from CNTs outer layer constantly to CNTs internal layer
Diffusion obtains a kind of compound CNTs of surface in situ generation nano SiC, and the thickness of SiC generation layer is about 25nm.Be computed when by
When matching according to CNTs and SiC volume ratio for 1:1, the theoretic throat for generating SiC layer is 25nm, theoretical value and experiment value kissing
It closes, that is, the SiC for illustrating that reaction in-situ generates can equably be coated on the surface CNTs according to design thickness.By (c-e) composite powder
The power spectrum of body can be seen that element silicon along the structure distribution of CNTs, and using original CNTs as substrate, nano silica fume and CNTs's is outer
Reaction in-situ generation SiC occurs first and is coated on the surface CNTs for layer, and core still keeps CNTs prototype structure and ingredient.This shell core
The SiC/CNTs of shape structure can both retain the original excellent comprehensive performance of CNTs, and the SiC for being coated on the surface CNTs can
To effectively improve the wetability between CNTs and metallic matrix (such as aluminium, titanium), directly connecing between CNTs and matrix is reduced
Touching weakens unfavorable interfacial reaction, inhibits the generation of the crisp phase of carbide hard, assists CNTs reinforced metal matrix, further increases
The mechanical property and functional characteristic (such as: thermal conductivity and thermal stability) of metal-base composites.
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 proportion of CNTs and nano silica fume, the volume ratio of CNTs and nano SiC is 5:2 after reaction in-situ, generates the theory of SiC
With a thickness of 10nm.(a) and (b) can see in Fig. 4, have both bud bar-shell-and-core structure SiC/ in CNTs Surface Creation
CNTs.SiC a part of generation is in continuous shell-like structure, is coated on the surface CNTs；Another part nano SiC is then equal with graininess
It is even to be covered on the surface CNTs then and be 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 the surface CNTs, 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 generated is coated on the surface CNTs, composite granule integrally still keeps the fibre structure of original CNTs.Institute as above
It states, this structure can sufficiently be sent out under the premise of improving the wetability of CNTs and metallic matrix, weakening unfavorable interfacial reaction
The strengthening effect for waving CNTs 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 proportion of CNTs and nano silica fume, the volume ratio of CNTs and the SiC of generation are 5:1 after reaction in-situ, generate the reason of SiC
By with a thickness of 5nm.It is about 18nm by statistics SiC generation layer thickness, and there are deviations for theoretical value.To find out its cause, working as silicone content
It is difficult to form shell in the SiC of the surface CNTs synthesis when proportion 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 causing part to occur, 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 that is generated receives
Rice SiC forms the bud rod-like structure with CNTs for " bar " mostly with graininess uniform fold on the surface CNTs.By above embodiments knot
Fruit is it is envisioned that with the increase for designing SiC content in reaction product, then continuous shell core shape structure proportion increases therewith.
Conversely, then increasing using CNTs as bar, SiC for the bud rod-like structure ratio of bud.
Fig. 6 is the X ray diffracting spectrum of CNTs-SiC composite material 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, also
There is the diffraction maximum of SiC, that is, shows to have occurred that hair is answered between CNTs and silicon powder at 1100 DEG C, generate SiC, but
It is that reaction is insufficient, still with the presence of unreacted silicon.When heat treatment temperature is increased to 1200 DEG C or more, composite material X is penetrated
The result of line diffraction then only has the diffraction maximum of carbon and SiC, that is, shows the nano silica fume being added by fully reacting, on the surface layer of CNTs
SiC is generated, bud bar-shell-and-core structure SiC/CNTs composite material shown in figure (4,5,6) is constituted.
Fig. 7 is the transmission electron microscope photo of SiC/CNTs composite material 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 the surface CNTs.Pass through the height in the region A1 and A2 in analysis (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 the region A1 interplanar
Away from for 0.34nm, (002) crystal face of corresponding graphite, (d) in the diffraction fringe of the region A2 high resolution picture and lattice image interplanar
Away from for 0.25nm, (111) crystal face of corresponding SiC.Illustrating by the method for the invention can be in CNTs surface in situ synthesis nano
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
Reinforcing 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 embodiments, similar result also can be obtained.
Claims (5)
1. the preparation method that a kind of surface in situ generates the compound CNTs of nano SiC, which comprises the following steps:
Step 1, it disperses dispersing binder polyvinylpyrrolidone (PVP) in dehydrated alcohol, obtains PVP dehydrated alcohol point
Dispersion liquid；
Step 2, CNTs and nano silica fume are added in PVP dehydrated alcohol dispersion liquid, are uniformly dispersed and filter, takes the mixing filtered out
Powder is dry；The volume ratio of the CNTs and nano silica fume is 0.5~10；Dispersion described in step 2 uses ultrasonic disperse and machine
Tool stirring is synchronous to be carried out, when ultrasonic disperse a length of 0.5~3h, the mechanical stirring time is 0.5~3h, and revolving speed is 50~200 revs/min
Clock；
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 table
Face synthesis has the nano SiC of different structure.
2. a kind of surface in situ according to claim 1 generates the preparation method of the compound CNTs of nano SiC, feature exists
In the CNTs is any one in single wall CNTs, multi wall CNTs and carbon nano-fiber or any combination.
3. a kind of surface in situ according to claim 1 generates the preparation method of the compound CNTs of nano SiC, feature exists
In the CNTs diameter range is 10nm~200nm, and length range is 100nm~1cm；Nano silica fume particle diameter range is
20nm~150nm.
4. a kind of surface in situ according to claim 1 generates the preparation method of the compound CNTs of nano SiC, feature exists
In the quality of, dispersing binder PVP described in step 1 be the 0.5~30% of CNTs mass, the quality of dehydrated alcohol be CNTs and
10~50 times of the mixed-powder gross mass of nano silica fume.
5. a kind of surface in situ according to claim 1 generates the preparation method of the compound CNTs of nano SiC, feature exists
In dry to be dried in vacuo described in step 2, vacuum drying temperature is 50~100 DEG C, and drying time is 2~12h.
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| CN103754878A (en) * | 2014-01-06 | 2014-04-30 | 上海交通大学 | Method for preparing carbon nano tubes on surfaces of silicon carbide particles through in-situ synthesis |
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| CN103058167A (en) * | 2012-12-05 | 2013-04-24 | 天津大学 | Composite material of carbon nanotube and carbon, and preparation method thereof |
| CN103754878A (en) * | 2014-01-06 | 2014-04-30 | 上海交通大学 | Method for preparing carbon nano tubes on surfaces of silicon carbide particles through in-situ synthesis |
| CN107176604A (en) * | 2016-03-10 | 2017-09-19 | 中国科学院金属研究所 | A kind of method that carbon materials surface in situ generates nano-carbide coating |
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