CN104291826A - Preparation method of carbon nanotube (CNT) enhanced SiC based nano composite material film - Google Patents

Preparation method of carbon nanotube (CNT) enhanced SiC based nano composite material film Download PDF

Info

Publication number
CN104291826A
CN104291826A CN201410475361.1A CN201410475361A CN104291826A CN 104291826 A CN104291826 A CN 104291826A CN 201410475361 A CN201410475361 A CN 201410475361A CN 104291826 A CN104291826 A CN 104291826A
Authority
CN
China
Prior art keywords
cnts
buckypaper
fluid cylinder
sample
precast body
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410475361.1A
Other languages
Chinese (zh)
Other versions
CN104291826B (en
Inventor
蔡艳芝
尹洪峰
周媛
钟兴润
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Xinyao Ceramic Composite Material Co Ltd
Original Assignee
Xian University of Architecture and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian University of Architecture and Technology filed Critical Xian University of Architecture and Technology
Priority to CN201410475361.1A priority Critical patent/CN104291826B/en
Publication of CN104291826A publication Critical patent/CN104291826A/en
Application granted granted Critical
Publication of CN104291826B publication Critical patent/CN104291826B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/591—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by reaction sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3821—Boron carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5284—Hollow fibers, e.g. nanotubes
    • C04B2235/5288—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Filtering Materials (AREA)

Abstract

The invention discloses a preparation method of a carbon nanotube (CNT) enhanced SiC based nano composite material film. The preparation method comprises the following steps: dispersing CNTs, B4C micro-powder and elemental silicon powder into water to prepare a suspension liquid, taking TritonTM X-100 as a dispersing agent, then performing pressure filtration on the suspension liquid by using a pressure filtration device, soaking a CNTs Buckypaper preform obtained by virtue of pressure filtration in a thermoplastic phenolic resin solution, and then sequentially performing soft curing, hard curing and post-curing to obtain a curing sample; and then carbonizing the curing sample under the protection of nitrogen, and finally sintering to obtain the CNT enhanced SiC based nano composite material film. The nano composite material film prepared by using the method disclosed by the invention is high in CNT volume content and good in dispersion performance, has good preferred orientation in arrangement of the CNTs, has good combination between the CNTs and a matrix, and is smooth and warping-free in film surface, uniform and compact in microscopic structure, good in thermal and electrical conduction properties, good in strength and toughness, short in period and low in cost.

Description

A kind of carbon nanotube strengthens the preparation method of SiC based nano composite material film
Technical field
The invention belongs to field of nanocomposite materials, be specifically related to the preparation method that a kind of carbon nanotube strengthens SiC based nano composite material film.
Background technology
Carbon nanotube (Carbon nanotubes, CNTs) is a kind of light material with excellent mechanics, electricity and thermal property.One of CNTs most potentiality application is exactly develop nano composite material.It is due to its very large length-to-diameter ratio (1000 ~ 10,000), low density, high rigidity (Young's modulus is about 1TPa) that CNTs has a large amount of potential application, high tensile strength (reaching 60GPa).And, CNTs also have excellent heat conductivity (vertically under room temperature condition, single Single Walled Carbon Nanotube (Single Wall Carbon nanotube, SWCNT), 6600W/mK; Single multi-walled carbon nano-tubes (Multi-wall carbon nanotube, MWCNT), and excellent electrical conductivity (vertically under room temperature condition >3000W/mK), the specific conductivity of MWCNT is 700 ~ 1400S/m)), this makes CNTs become the most suitable candidate material prepared and have new functional nano matrix material.
The excellent properties utilizing CNTs intrinsic can overcome the performance deficiency of traditional material.Be one at the surface coverage skim body material (multifunctional nanocomposites or hybrid material) of CNTs to have a great attraction and the research field of novelty.Engineering ceramics has high hardness, excellent thermostability and relative low density.But ceramic phase limits its application as functional materials to low electrical conductivity and heat conductivity.CNTs is introduced pottery and causes great interest in recent years.But the report overwhelming majority at present about carbon nanotube/ceramic nanocomposites is by CNTs and the blended acquisition of ceramic powder, the preparation of ceramic matric composite is limited due to CNTs strong reunion in the base, and, because its performance has obvious anisotropy, the random arrangement of CNTs in ceramic matrix also can make the performance of its excellent properties limited.Therefore, the height of the dispersiveness of CNTs, the regularity of arrangement and volume content thereof all will become the conditioning step of Nano-composite materials.And the suitable interface cohesion between CNTs and matrix obtains the key condition of many excellent properties as the mechanical property improved.
CNTs only comprises conjugated carbon atoms, therefore in unreactiveness.Unreactiveness maintains the higher oxidation-resistance of CNTs; But unreactiveness also hinders process to this material and application.At present, with carbon nanotube and Ceramic Composite for improving the obdurability of stupalith, major part test-results is all disappointing, for the report of carbon nanotube/stupalith, the even performance that has little effect the activeness and quietness of carbon nanotube to pottery does not improve, and this is because cementability weak between carbon nanotube and pottery causes.Adopt and acid treatment and chemical modification are carried out to carbon nanotube, the cementability between carbon nanotube and ceramic matrix can be improved, but acid treatment has damage eventually to carbon nanotube, and add the complicacy of experimentation.
Summary of the invention
A kind of carbon nanotube is the object of the present invention is to provide to strengthen the preparation method of SiC based nano composite material film, high and the good dispersity of the nano-composite material membrane CNTs volume content prepared of the method, the arrangement of CNTs has directivity, combine good between CNTs and matrix, film surfacing is without warpage, and uniform microstructure is fine and close, heat, electrical conductivity are good, obdurability is good, and the cycle is short, with low cost.
In order to achieve the above object, the technical solution used in the present invention comprises the following steps:
1) by CNTs, B 4c micro mist and unformed simple substance silica flour are distributed in water, with tensio-active agent Triton tMx-100 is as dispersion agent, and impulse ultrasound dispersion makes to mix, and obtains suspension; Wherein, CNTs, B in suspension 4the mass ratio of C micro mist and unformed simple substance silica flour is (1 ~ 3): (0.5 ~ 1.5): (1 ~ 5);
2) pressure filter is utilized by suspension to filter to obtain comprising B 4the CNTs Buckypaper precast body of C powder and simple substance silica flour; Then a filter screen is laid on CNTs Buckypaper precast body surface, the surface of CNTs Buckypaper precast body is made to be divided into some grids, in each grid, instill novolac resin solution, then dry, obtain flooding rear CNTs Buckypaper precast body;
3) CNTs Buckypaper precast body after dipping be put in iron plate surface and be placed in baking oven, being incubated 12 ~ 48h from room temperature to 60 ~ 90 DEG C, to carry out softcure, obtaining the sample after softcure; Wherein, DEG C period from room temperature to 60 ~ 90, often heat up 5 DEG C of insulation 3-6h;
4) two pieces of iron plates and weight are placed in baking oven and are warming up to 170 ~ 190 DEG C, then the sample after softcure is put between two pieces of iron plates, again weight is placed on iron plate, weight and iron plate is made to apply the positive pressure of 25 ~ 35MPa to the sample after softcure, then 2 ~ 3h are incubated firmly to solidify at 170 ~ 190 DEG C, the sample after firmly being solidified;
5) by firmly solidification after sample be placed in baking oven thermal treatment 6 ~ 10h at 200 ~ 280 DEG C, obtain after fixing sample;
6) under the protection of nitrogen, solidified sample is put in carbide furnace, rises to 450 ~ 650 DEG C with the heat-up rate of 1 ~ 3 DEG C/min from room temperature, isothermal holding 1 ~ 3h, be then down to room temperature with the speed of 1 ~ 3 DEG C/min, obtain pretreatment sample;
7) under the protection of nitrogen, pretreatment sample is positioned in carbide furnace, with the heat-up rate of 1 ~ 3 DEG C/min from room temperature to 550 ~ 650 DEG C, isothermal holding 5 ~ 10h, and then be warming up to 850 ~ 1000 DEG C with the heat-up rate of 1 ~ 3 DEG C/min, isothermal holding 0.5 ~ 1h, is then down to room temperature with the speed of 1 ~ 3 DEG C/min, obtains carbonized samples;
8) carbonized samples is sintered in nitrogen atmosphere stove, obtain carbon nanotube and strengthen SiC based nano composite material film.
Described step 1) in the diameter of CNTs be 20nm, length > 50 μm, density is 2.10g/cm 3; B 4the particle diameter of C micro mist is 1 ~ 2 μm, and density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour is 1 ~ 7 μm, and density is 2.34g/cm 3.
Described step 1) in the CNTs of every 1 ~ 3g be dispersed in 1000ml water, add 0.5 ~ 1.5ml tensio-active agent Triton in every 1000ml water tMx-100.
Described step 1) in time of impulse ultrasound dispersion be 0.5 ~ 1h, the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, and the frequency of ultrasonic vibration is 20kHz, and power is 1300 ~ 1400W.
Described step 2) in the pressure filter pressurizing device and top that comprise for providing pressure offer fluid inlet, the cylindrical Sheng fluid cylinder of liquid outlet is offered in bottom, described Sheng fluid cylinder is by containing fluid cylinder top cover, contain fluid cylinder sidewall, contain fluid cylinder bottom composition, and the top of containing fluid cylinder sidewall is connected with Sheng fluid cylinder top cover, the bottom of containing fluid cylinder sidewall is connected with Sheng fluid cylinder bottom, and Sheng fluid cylinder bottom is cavity configuration, the inwall of Sheng fluid cylinder bottom is provided with the annular step for laying through metal, through metal is placed with the metal screen for laying millipore filtration.
Described step 2) in CNTs Buckypaper precast body adopt and obtain with the following method:
Millipore filtration is laid on metal screen, then by Sheng fluid cylinder sidewall respectively with Sheng fluid cylinder bottom with contain fluid cylinder top cover and be connected, funnel is inserted in fluid inlet, then being poured into by fluid inlet by suspension contains in fluid cylinder, again fluid inlet is connected with pressurizing device, pressurizing device is made to apply the pressure of 0.6 ~ 0.8MPa to suspension, the water in suspension and tensio-active agent Triton tMx-100 is leached by millipore filtration and is flowed out by liquid outlet, remaining CNTs, B 4the uniform mixture of C micro mist, unformed simple substance silica flour is deposited on microporous membrane surface, form a CNTs Buckypaper, finally remove pressurizing device, millipore filtration with CNTs Buckypaper is taken out and dries, millipore filtration obtains CNTs Buckypaper precast body, then the CNTs Buckypaper precast body on millipore filtration is peeled off.
Described step 2) in the porosity of millipore filtration be 75% ~ 85%, aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm.
Described step 2) in novolac resin solution adopt and prepare with the following method: novolac resin, ethanol, acetone and the hexamethylenetetramine mass ratio by 2:0.5:0.5:0.2 is mixed, preparation novolac resin solution.
Described step 8) in sintering temperature be 1450 ~ 1700 DEG C, sintering time is 1 ~ 3h.
Compared with prior art, beneficial effect of the present invention is:
1, carbon nanotube has excellent heat and electrical conductivity vertically, high and the good dispersity of carbon nanotube by volume content in CNTs paper, the arrangement major part of CNTs is parallel to paper surface, therefore there is very high thermal conductivity and specific conductivity being parallel in paper surface direction, the weakness that pottery is warm, electrical conductivity is low can be overcome, make full use of the high thermal resistance of pottery simultaneously, make the nanometer film of the two compound have heat, electric in functionality advantage.So CNTs is made precast body to prepare CERAMIC-MATRIX NANOCOMPOSITE film by the present invention, has both improve the volume content of CNTs in ceramic composite, overcome again the shortcoming of CNTs bad dispersibility simultaneously.
2, CNTs Buckypaper precast body of the present invention is by CNTs, B 4c micro mist, Si powder form, the B adopted 4b in C micro mist 4the boron atom of C can with carbon material as the carbon atom in CNTs and resin carbon forms substitutional solid solution, carbon atom is replaced to form hexagonal aspect, eliminate the defect in random layer, boron atom has attracted the electronics of carbon atom simultaneously, result in the fracture of covalent linkage between carbon atom, carbon skeleton is reset, and carbon plane is arranged comparatively orderly, thus, the B of the present invention's employing 4c micro mist can accelerate the formation of graphite-structure.About have the carbon atom of 2% in SWCNTs in non-hexagonal rings, the defect of MWCNTs is more.Therefore, the present invention introduces on CNTs surface and comprises B 4the carbon interfacial layer of C, then B 4c can have an effect with the carbon in CNTs and carbon interfacial layer simultaneously, improves the bonding strength between carbon nanotube and carbon interfacial layer, thus improves the bonding strength between CNTs and SiC ceramic matrix, and this is simpler more effective relative to traditional CNTs surface functionalization method.
3, the present invention adopts the prepare suspension of impulse ultrasound dispersion method, and suspension obtains CNTs Buckypaper precast body through pressure filtration.Introduce B in the preparation process of CNTs Buckypaper precast body simultaneously 4c micro mist and unformed simple substance silica flour, adopt polymer impregnated-pyrolysis method (Polymer infiltration-pyrolysis again, PIP) in CNTs Buckypaper precast body, introduce resin carbon (namely novolac resin is through converting one-tenth carbon), resin carbon and unformed simple substance silica flour reaction in－situ generate SiC; And the present invention introduces unformed simple substance silica flour in CNTs Buckypaper precast body preparation process, be better than and adopt liquid Si pickling process (liquid silicon infiltration, LSI) to introduce Si powder in C/C porous preform.Reason has three:
1) the unformed simple substance silica flour of the present invention even dispersion distribution in CNTs Buckypaper precast body by ultrasonic disperse and press filtration, similarly, the distribution of CNTs Buckypaper precast body mesoporous is also uniform, thus, the resin carbon introduced in these holes also should be even dispersion distribution, Si in the unformed simple substance silica flour of such energy guarantee and carbon fully react, and the SiC generated also is even dispersion distribution.
2) novolac resin in novolac resin solution produces volumetric shrinkage due to mass loss and density increase in pyrolytic process, the restraint force that in CNTs Buckypaper precast body, CNTs is not strong each other, these are different from the carbon fabric perform of common braiding, thus the CNTs Buckypaper skeleton in CNTs Buckypaper precast body can produce obvious volumetric shrinkage (diameter of pyrolytic process CNTs Buckypaper has the shrinking percentage of about 20%), this can reduce the pore channel of LSI process, even if through high-temperature heat treatment because carbon base body and CNTs Buckypaper skeleton shrink simultaneously, also more pore channel can not be provided for liquid Si infiltration, and comprise the closed pore that much cannot permeate.
3) pore in CNTs/C porous preform and the dipping passage of liquid Si, Si melt infiltrate porous preform process in it around carbon reaction generate SiC, the SiC that then Si and carbon are increased gradually is separated, and needs to diffuse through SiC layer and just can contact with each other and then react further.And to be infiltrated by melt of si and process that reaction in－situ generates SiC is the process (volume of the SiC namely generated is greater than the volume of the carbon participating in reaction in－situ) of a volumetric expansion, the SiC blocking that the dipping passage of melt of si will be generated.SiC generates the more, melt of si is longer by the diffusion length of SiC layer, and blockage effect is more serious, and silicon-carbon reaction is also diffused and limits, cause large stretch of C/C substructure to remain in final C/SiC nano-composite material membrane, even center membrane infiltrates without melt of si.
4, to strengthen the preparation method of SiC based nano composite material film fairly simple for carbon nanotube of the present invention, and cost is low, and even structure, thickness about 200 ~ 1200 μm, obdurability are good, thermal characteristics and excellent electrical property.In addition, because mass loss and volumetric shrinkage will occur novolac resin in carbonization process, for preventing because novolac resin local distribution is uneven and unrelieved stress and cause sample buckling deformation, the present invention to dipping afterwards CNTs Buckypaper precast body carried out thermal treatment before carbonization.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of pressure filter of the present invention;
Wherein, 1-contains fluid cylinder, 2-fluid inlet, 3-liquid outlet, 4-rubber hose, 5-millipore filtration, 6-metal screen, 7-through metal; 101-contains fluid cylinder top cover, and 102-contains fluid cylinder sidewall, and 103-contains fluid cylinder bottom, and 104-contains step in fluid cylinder bottom.
Specific embodiments
Below in conjunction with embodiment, the present invention is described in further details.
The preparation method that CNTs of the present invention strengthens SiC based nano composite material film comprises the following steps:
1, the preparation of CNTs Buckypaper precast body
1) prepare suspension
By CNTs, B 4c micro mist and unformed simple substance silica flour are distributed in distilled water, with tensio-active agent Triton tMx-100 is as dispersion agent, and impulse ultrasound mixing makes evenly for 0.5 ~ 1 hour, obtains dispersion, even and stable suspension; Wherein, CNTs, B in suspension 4the mass ratio of C micro mist and unformed simple substance silica flour is (1 ~ 3): (0.5 ~ 1.5): (1 ~ 5); Every 1 ~ 3gCNTs is dispersed in 1000ml water, adds 0.5 ~ 1.5ml tensio-active agent Triton in every 1000ml water tMx-100; And the diameter of CNTs is about 20nm, length > 50 μm, density is 2.10g/cm 3; B 4the particle diameter of C micro mist about 1 ~ 2 μm, density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour about 1 ~ 7 μm, density is 2.34g/cm 3; Density because of unformed simple substance silica flour is 2.34g/cm 3, B 4the density of C is 2.52g/cm 3, CNTs density be 2.10g/cm 3, their density relatively, therefore in ultrasonic mixing process easily each other disperse be uniformly distributed, and can not layering; In addition, the time of impulse ultrasound dispersion is 0.5 ~ 1h, and the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, the frequency of ultrasonic vibration is 20kHz, and power is 1300 ~ 1400W.
2) pressure filter is utilized by suspension to filter to obtain CNTs Buckypaper precast body;
As shown in Figure 1, the pressure filter adopted comprises provides the pressurizing device of pressure (comprising force (forcing) pump and gas tank) and top to offer fluid inlet 2, the cylindrical Sheng fluid cylinder 1 of liquid outlet 3 is offered in bottom, fluid inlet 2 is except entering the passage containing fluid cylinder for suspension, also can be used as gas and enter the passage containing fluid cylinder, for pressure filtration; The external rubber hose 4 of liquid outlet 3; Contain fluid cylinder 1 to be made up of Sheng fluid cylinder top cover 101, Sheng fluid cylinder sidewall 102, Sheng fluid cylinder bottom 103, and the top of containing fluid cylinder sidewall 102 is connected by top flange dish with Sheng fluid cylinder top cover 101, the bottom of containing fluid cylinder sidewall 102 is connected by flange in the bottom dish with Sheng fluid cylinder bottom 103, and the top of containing fluid cylinder sidewall 102 is provided with upper sealing gasket with the junction of containing fluid cylinder top cover 101, the bottom of containing fluid cylinder sidewall 102 is provided with sealed bottom packing ring with the junction of containing fluid cylinder bottom 103; Containing fluid cylinder bottom 103 is cavity configuration, and the inwall of Sheng fluid cylinder bottom 103 is provided with the step 104 for laying through metal 7, and Sheng fluid cylinder bottom is divided into upper cavity and lower chamber by through metal 7, and lower chamber is the groove of an arc.Through metal 7 is equivalent to the upper cover containing fluid cylinder bottom cavity; Through metal 7 is placed with the metal screen 6 for laying millipore filtration 5.Wherein, the external diameter containing fluid cylinder sidewall 102 is 140mm, internal diameter is 126mm, millipore filtration 5 for diameter be the circle of 140mm, metal screen 6 is also circular, heart region has concentric(al) circles mesh area wherein, through metal 7 is also circular, and heart region has concentric(al) circles mesh area wherein, and the external diameter of metal screen 6 and through metal 7 is 140mm, internal diameter is 110mm, is annular entity between internal-and external diameter.The internal diameter of upper cavity, slightly larger than 140mm, is convenient to contain fluid cylinder sidewall 102 bottom tab and is divided embedding wherein, and be pressed on millipore filtration 5.Metal screen 6 is consistent with the diameter of the circular net bore region of through metal 7 and the diameter of press filtration gained CNTs Buckypaper precast body.Therefore, when the diameter of its mesh area changes, the diameter of gained CNTs Buckypaper precast body changes thereupon.Metal screen material is metallic aluminium, and the material of through metal and pressure filter is all stainless steel.
The concrete preparation method of CNTs Buckypaper precast body is:
By millipore filtration 5 (Isopore tMmembrane Filters) be laid in pressure filter metal screen 6 above, metal screen 6 pads below millipore filtration 5, plays an overfill protection millipore filtration 5; Millipore filtration 5 adopts diameter to be the disk of 140mm, and aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm, and porosity is 75% ~ 85%; Sheng fluid cylinder sidewall 102 bottom tab in pressure filter is divided and is pressed millipore filtration 5 and metal screen 6, prevents millipore filtration 5 from changing position or fold; Suspension is poured in the Sheng fluid cylinder 1 of pressure filter by the funnel be inserted in fluid inlet 2, then air is contained in fluid cylinder 1 through gas tank and fluid inlet 2 suction by the force (forcing) pump of pressurizing device, the pressure of 0.6 ~ 0.8MPa is applied to suspension, and pressure applies direction for down to exert pressure above suspension, forces the water in suspension and tensio-active agent Triton tMx-100 is oozed out by millipore filtration 5, flows out through liquid outlet 3 and rubber hose 4, remaining CNTs, B in suspension 4the uniform mixture of C micro mist, unformed simple substance silica flour is just deposited on millipore filtration 5 surface, forms a CNTs Buckypaper, at anhydrous and tensio-active agent Triton tMafter X-100 oozes out rear about half a minute, pressure release, millipore filtration 5 with CNTs Buckypaper is taken out, be laid in totally smooth iron plate surface, be placed in stink cupboard naturally to dry, millipore filtration 5 obtains CNTs Buckypaper precast body, and finally peeled off by the CNTs Buckypaper precast body on millipore filtration 5, then what obtain 110mm × 0.2 ~ 1.2mm comprises B 4the CNTs Buckypaper precast body of C powder and unformed simple substance silica flour.Because the liquid in suspension all could will flow out through the mesh area of metal screen 6 and through metal 7 after infiltration millipore filtration 5, therefore the filter membrane surface deposition of the solid in suspension preferentially more than mesh area, and filter membrane surface deposition outside mesh area is little, the diameter of the Buckypaper precast body therefore got off from millipore filtration 5 sur-face peeling is just consistent with the diameter of the circular net bore region of metal screen 6 and through metal 7.In addition, high pressure gas force the liquid in suspension to outbound flow very soon, and whole filtration procedure only has 1 ~ 2 minute.It is constant that force (forcing) pump can maintain the gaseous tension contained in fluid cylinder.The fluid inlet of gas tank and pressure filter is tightly connected by rubber hose, and gas tank is provided with vent valve and tensimeter.After filtration terminates, close force (forcing) pump, the vent valve on gas tank is opened, just can pressure release.
2, infiltrate resol
Novolac resin, ethanol, acetone and hexamethylenetetramine are pressed the mass ratio mixing of 2:0.5:0.5:0.2, be mixed with novolac resin solution, novolac resin solution is contained in beaker the hot water being placed in about 50 DEG C for subsequent use, to ensure that resin has good mobility; Because CNTs Buckypaper precast body is very thin, the hole of its inside is many and even, and is substantially all through pore, and therefore resol more easily infiltrates.In order to infiltrate in CNTs Buckypaper precast body with ensureing novolac resin dissolution homogeneity, at a CNTs Buckypaper precast body surface tiling filter screen woven by Plasitc fibers, be various tiny grids by CNTs Buckypaper precast body subdivision surfaces, in each grid, resol is instilled with suction pipe, be placed in stink cupboard again to dry, obtain flooding rear CNTs Buckypaper precast body.For thicker precast body, after the novolac resin solution of a side surface dries, same method dipping can be pressed to another side.
3, softcure
CNTs Buckypaper precast body after dipping to be laid on the smooth iron plate of surface clean and to be placed in baking oven, carries out softcure from room temperature to 60 ~ 90 DEG C.In order to avoid solvent is discharged too fast at sample surfaces generation bubble, 60-90 DEG C is warming up to from room temperature is stepped, (often heat up during from room temperature to top temperature 5 DEG C and be incubated 2-6h), at top temperature insulation 12-48h, make the solvent-depleted in CNTs Buckypaper precast body after dipping, and novolac resin obtains the solidification compared with low degree, the sample after the softcure obtained has certain hardness and intensity.
4, firmly solidify
Smooth for surface clean two pieces of iron plates and weight are placed in baking oven and are warming up to hard solidification value 170 ~ 190 DEG C with baking oven, then baking oven is opened, rapidly the sample after softcure is put between two pieces of iron plates, and weight is placed in topmost, be placed in weight above sample and iron plate applies the pressure of 25 ~ 35MPa to it, shut oven door, be then incubated 2 ~ 3h firmly to solidify at 170 ~ 190 DEG C, the sample after firmly being solidified; Sample after this hard solidification has higher intensity and hardness.Owing to opening baking oven, oven interior temperature is declined, therefore, in the process of placing sample, temperature in baking oven is down to 120 ~ 130 DEG C from 170 ~ 190 DEG C, sample is deliquescing at this temperature, is preheated simultaneously, and baking oven returned to hard solidification value through about 15 minutes.
5, after fixing
In order to discharge the unrelieved stress in solidification process, improving the crosslinking curing degree of novolac resin further, the sample after firmly solidifying being placed in baking oven thermal treatment 6 ~ 10h at 200 ~ 280 DEG C, obtaining after fixing sample.
6, thermal treatment before carbonization
Because mass loss and volumetric shrinkage will occur carbonization process novolac resin, CNTs Buckypaper skeleton shrinks thereupon, for preventing causing sample buckling deformation because of novolac resin local distribution inequality and unrelieved stress, thermal treatment before carbonization is carried out to solidified sample, concrete operations are: under nitrogen protection, solidified sample is put in carbide furnace, 450 ~ 650 DEG C are risen to from room temperature with the heat-up rate of 1 ~ 3 DEG C/min, isothermal holding 1 ~ 3h, then be down to room temperature with the speed of 1 ~ 3 DEG C/min, obtain pretreatment sample;
7, carbonization
Pretreatment sample is carried out carbonizing treatment; its concrete operations are; under the protection of nitrogen, pretreatment sample is positioned in carbide furnace, with the heat-up rate of 1 ~ 3 DEG C/min from room temperature to 450 ~ 650 DEG C; isothermal holding 5 ~ 10h; and then be warming up to 850 ~ 1000 DEG C with the heat-up rate of 1 ~ 3 DEG C/min, isothermal holding 0.5 ~ 1h, and then be down to room temperature with the speed of 1 ~ 3 DEG C/min; obtain carbonized samples
8, silicon-carbon reaction and sintering
Carbonized samples is carried out reaction sintering in nitrogen atmosphere stove, sintering temperature: 1450 ~ 1700 DEG C, be incubated in sintering temperature: 1 ~ 3h (sintering time), obtain carbon nanotube and strengthen SiC based nano composite material film; Nano-composite material membrane (being of a size of 110mm × 0.2 ~ 1.2mm) prepared by the method, high and the good dispersity of CNTs volume content, the arrangement of CNTs has directivity, combine good between CNTs and matrix, film surfacing is without warpage, and uniform microstructure is fine and close, heat, electrical conductivity are good, obdurability is good, and the cycle is short, with low cost.
Using CNTs Buckypaper as precast body, can ensure that the volume content that CNTs is high and good dispersiveness and good preferred orientation are arranged; Between CNTs and ceramic matrix, carbon interfacial layer is introduced with phenolic resin carbonized, and with B 4c micro mist improves the bonding strength of carbon interfacial layer, strengthens the combination between CNTs and matrix, for the obdurability of matrix material is given security; By B 4c powder, Si powder and CNTs with ultrasonic disperse Homogeneous phase mixing, and prepare Buckypaper precast body in conjunction with pressure filtration, ensure that each uniform composition Dispersed precipitate; Because Buckypaper precast body and matrix shrink in carbonization and sintering process simultaneously, the compactness of composite material film can be ensured; Each uniform composition Dispersed precipitate in composite material film, and the regulation and control of combined process system, control the temperature field in material preparation process and stress field, make composite material film surfacing without warpage; The electricity of carbon nanotube excellence and heat conductivity ensure that electricity and the heat conductivity of composite material film excellence.
Below by embodiment, the present invention is described in further detail, but is not limited only to this.
Embodiment 1:
1) by 2g CNTs, 1g B 4c micro mist and the unformed simple substance silica flour of 3.5g are distributed in 1000ml distilled water, instillation 0.9ml tensio-active agent Triton tMx-100, through pulse ultrasonic disperse 50min, obtains dispersion, even and stable suspension; Wherein, the diameter of CNTs is about 20nm, length > 50 μm, and density is 2.10g/cm 3; B 4the particle diameter of C micro mist is 1 ~ 2 μm, and density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour 1 ~ 7 μm, density is 2.34g/cm 3.In addition, the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, the frequency of ultrasonic vibration is 20kHz, and power is 1300W.
2) by millipore filtration 5 (Isopore tMmembrane Filters) be laid in pressure filter metal screen 6 above, metal screen 6 pads below millipore filtration 5, plays an overfill protection millipore filtration 5; Millipore filtration 5 adopts diameter to be the disk of 140mm, and aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm, and porosity is 75% ~ 85%; Press millipore filtration 5 and metal screen 6 bottom Sheng fluid cylinder sidewall 102 in pressure filter, prevent millipore filtration 5 from changing position or fold; Suspension is poured in the Sheng fluid cylinder 1 of pressure filter by the funnel be inserted in fluid inlet 2, then air is contained in fluid cylinder 1 through fluid inlet 2 suction by pressurizing device such as force (forcing) pump, force (forcing) pump is made to apply the pressure of 0.65MPa to suspension, and pressure applies direction for down to exert pressure to suspension above suspension, forces the water in suspension and tensio-active agent Triton tMx-100 is oozed out by millipore filtration, flows out through liquid outlet 3 and rubber hose 4, remaining CNTs, B in suspension 4the uniform mixture of C micro mist, unformed simple substance silica flour is just deposited on millipore filtration 5 surface, forms a CNTs Buckypaper, at anhydrous and tensio-active agent Triton tMafter X-100 oozes out rear about half a minute, pressure release, millipore filtration 5 with CNTs Buckypaper is taken out, be laid in totally smooth iron plate surface, be placed in stink cupboard naturally to dry, millipore filtration 5 obtains CNTs Buckypaper precast body, and finally peeled off by the CNTs Buckypaper precast body on millipore filtration 5, then what obtain 110mm × 0.65mm comprises B 4the CNTs Buckypaper precast body of C powder and unformed simple substance silica flour.
3) novolac resin, ethanol, acetone and hexamethylenetetramine are pressed the mass ratio mixing of 2:0.5:0.5:0.2, be mixed with novolac resin solution, novolac resin solution is contained in beaker the hot water being placed in about 50 DEG C for subsequent use, to ensure that resin has good mobility; At a CNTs Buckypaper precast body surface tiling filter screen woven by Plasitc fibers, be various tiny grids by CNTs Buckypaper precast body subdivision surfaces, in each grid, resol is instilled with suction pipe, be placed in stink cupboard again to dry, obtain flooding rear CNTs Buckypaper precast body.In this step, the tow sides of CNTs Buckypaper precast body are all processed by the method.
4) CNTs Buckypaper precast body after dipping to be laid on the smooth iron plate of surface clean and to be placed in baking oven, 80 DEG C are warming up to from room temperature is stepped, at 80 DEG C of insulation 24h, the resin portion after making dipping in CNTs Buckypaper precast body is solidified, and obtains the sample after softcure; Wherein, from room temperature to 80 DEG C period, often heat up 5 DEG C of insulation 3h;
5) smooth for surface clean two pieces of iron plates and weight are placed in baking oven and are warming up to hard solidification value 190 DEG C, then baking oven is opened, rapidly the sample after softcure is put between two pieces of iron plates, and be placed in topmost with weight, weight and iron plate is made to apply the positive pressure of 30MPa to the sample after softcure, shut oven door, be then incubated 3h firmly to solidify at 190 DEG C, the sample after firmly being solidified;
6) by firmly solidification after sample be placed in baking oven thermal treatment 8h at 260 DEG C, obtain after fixing sample.
7) under the protection of nitrogen, after fixing sample is put in carbide furnace, rises to 600 DEG C with the heat-up rate of 2 DEG C/min from room temperature, isothermal holding 3h, be then down to room temperature with the speed of 2 DEG C/min, obtain pretreatment sample.
8) under the protection of nitrogen; pretreatment sample is positioned in carbide furnace; with the heat-up rate of 2 DEG C/min from room temperature to 600 DEG C; isothermal holding 8h; and then be warming up to 850 DEG C with the heat-up rate of 1 DEG C/min, isothermal holding 0.5h, then be down to room temperature with the speed of 2 DEG C/min; make novolac resin matrix be converted into carbon base body completely, obtain carbonized samples.
9) carbonized samples is carried out reaction sintering in nitrogen atmosphere stove, sintering temperature: 1550 DEG C, be incubated in sintering temperature: 2h, obtain carbon nanotube and strengthen SiC based nano composite material film.
Embodiment 2:
1) by the B of CNTs, 1.5g of 3g 4the unformed simple substance silica flour of C micro mist and 5g is distributed in 1000ml distilled water, instillation 1.3ml tensio-active agent Triton tMx-100, makes evenly through pulse ultrasonic disperse 1h, obtains dispersion, even and stable suspension; Wherein, the diameter of CNTs is about 20nm, length > 50 μm, and density is 2.10g/cm 3; B 4the particle diameter of C micro mist is 1 ~ 2 μm, and density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour is 1 ~ 7 μm, and density is 2.34g/cm 3; In addition, the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, the frequency of ultrasonic vibration is 20kHz, and power is 1370W.
2) by millipore filtration 5 (Isopore tMmembrane Filters) be laid in pressure filter metal screen 6 above, metal screen 6 pads below millipore filtration 5, plays an overfill protection millipore filtration 5; Millipore filtration 5 adopts diameter to be the disk of 140mm, and aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm, and porosity is 75% ~ 85%; Press millipore filtration 5 and metal screen 6 bottom Sheng fluid cylinder sidewall 102 in pressure filter, prevent millipore filtration 5 from changing position or fold; Suspension is poured in the Sheng fluid cylinder 1 of pressure filter by the funnel be inserted in fluid inlet 2, then air is contained in fluid cylinder 1 through fluid inlet 2 suction by pressurizing device such as force (forcing) pump, force (forcing) pump is made to apply the pressure of 0.75MPa to suspension, and pressure applies direction for down to exert pressure to suspension above suspension, forces the water in suspension and tensio-active agent Triton tMx-100 is oozed out by millipore filtration 5, flows out through liquid outlet 3 and rubber hose 4, remaining CNTs, B in suspension 4the uniform mixture of C micro mist, unformed simple substance silica flour is just deposited on millipore filtration 5 surface, forms a CNTs Buckypaper, at anhydrous and tensio-active agent Triton tMafter X-100 oozes out rear about half a minute, pressure release, millipore filtration 5 with CNTs Buckypaper is taken out, be laid in totally smooth iron plate surface, be placed in stink cupboard naturally to dry, millipore filtration 5 obtains CNTs Buckypaper precast body, and finally peeled off by the CNTs Buckypaper precast body on millipore filtration 5, then what obtain 110mm × 1.2mm comprises B 4the CNTs Buckypaper precast body of C powder and unformed simple substance silica flour.
3) novolac resin, ethanol, acetone and hexamethylenetetramine are pressed the mass ratio mixing of 2:0.5:0.5:0.2, be mixed with novolac resin solution, novolac resin solution is contained in beaker the hot water being placed in about 50 DEG C for subsequent use, to ensure that resin has good mobility; At a CNTs Buckypaper precast body surface tiling filter screen woven by Plasitc fibers, be various tiny grids by CNTs Buckypaper precast body subdivision surfaces, in each grid, resol is instilled with suction pipe, be placed in stink cupboard again to dry, obtain flooding rear CNTs Buckypaper precast body.In this step, the tow sides of CNTs Buckypaper precast body are all processed by the method.
4) CNTs Buckypaper precast body after dipping to be laid on the smooth iron plate of surface clean and to be placed in baking oven, 75 DEG C are warming up at 75 DEG C of insulation 24h from room temperature is stepped, resin portion after making dipping in CNTs Buckypaper precast body is solidified, and obtains the sample after softcure; Wherein, from room temperature to 75 DEG C period, often heat up 5 DEG C of insulation 4h;
5) smooth for surface clean two pieces of iron plates and weight are placed in baking oven and are warming up to hard solidification value 180 DEG C, then baking oven is opened, rapidly the sample after softcure is put between two pieces of iron plates, and weight is placed in topmost, weight and iron plate is made to apply the positive pressure of 30MPa to the sample after softcure, shut oven door, be then incubated 3h firmly to solidify at 180 DEG C, the sample after firmly being solidified;
6) by firmly solidification after sample be placed in baking oven thermal treatment 8h at 260 DEG C, obtain after fixing sample.
7) under nitrogen protection, solidified sample is put in carbide furnace, rises to 600 DEG C with the heat-up rate of 2 DEG C/min from room temperature, isothermal holding 2.5h, be then down to room temperature with the speed of 2 DEG C/min, obtain pretreatment sample.
8) under nitrogen protection; pretreatment sample is positioned in carbide furnace; with the heat-up rate of 2 DEG C/min from room temperature to 600 DEG C; isothermal holding 9h; and then be warming up to 900 DEG C with the heat-up rate of 1 DEG C/min, isothermal holding 1h, then be down to room temperature with the speed of 2 DEG C/min; make novolac resin matrix be converted into carbon base body completely, obtain carbonized samples.
9) carbonized samples is carried out reaction sintering in nitrogen atmosphere stove, sintering temperature: 1550 DEG C, at sintering temperature insulation 2h, obtain carbon nanotube and strengthen SiC based nano composite material film.
Embodiment 3:
1) by the B of CNTs, 0.5g of 1g 4the unformed simple substance silica flour of C micro mist and 1g is distributed in 1000ml distilled water, instillation 0.5ml tensio-active agent Triton tMx-100, makes evenly through pulse ultrasonic disperse 40min, obtains dispersion, even and stable suspension; Wherein, the diameter of CNTs is about 20nm, length > 50 μm, and density is 2.10g/cm 3; B 4the particle diameter of C micro mist 1 ~ 2 μm, density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour is 1 ~ 7 μm, and density is 2.34g/cm 3.In addition, the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, the frequency of ultrasonic vibration is 20kHz, and power is 1400W.
2) by millipore filtration 5 (Isopore tMmembrane Filters) be laid in pressure filter metal screen 6 above, metal screen 6 pads below millipore filtration 5, plays an overfill protection millipore filtration 5; Millipore filtration 5 adopts diameter to be the disk of 140mm, and aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm, and porosity is 75% ~ 85%; Press millipore filtration 5 and metal screen 6 bottom Sheng fluid cylinder sidewall 102 in pressure filter, prevent millipore filtration 5 from changing position or fold; Suspension is poured in the Sheng fluid cylinder 1 of pressure filter by the funnel be inserted in fluid inlet 2, then air is contained in fluid cylinder 1 through fluid inlet 2 suction by pressurizing device such as force (forcing) pump, force (forcing) pump is made to apply the pressure of 0.6MPa to suspension, and pressure applies direction for down to exert pressure to suspension above suspension, forces the water in suspension and tensio-active agent Triton tMx-100 is oozed out by millipore filtration 5, flows out through liquid outlet 3 and rubber hose 4, remaining CNTs, B in suspension 4c micro mist, unformed simple substance silica flour uniform mixture are just deposited on millipore filtration 5 surface, form a CNTs Buckypaper, at anhydrous and tensio-active agent Triton tMafter X-100 oozes out rear about half a minute, pressure release, millipore filtration 5 with CNTs Buckypaper is taken out, be laid in totally smooth iron plate surface, be placed in stink cupboard naturally to dry, millipore filtration 5 obtains CNTs Buckypaper precast body, and finally peeled off by the CNTs Buckypaper precast body on millipore filtration 5, then what obtain 110mm × 0.2mm comprises B 4the CNTs Buckypaper precast body of C powder and unformed simple substance silica flour.
3) novolac resin, ethanol, acetone and hexamethylenetetramine are pressed the mass ratio mixing of 2:0.5:0.5:0.2, be mixed with novolac resin solution, novolac resin solution is contained in beaker the hot water being placed in about 50 DEG C for subsequent use, to ensure that resin has good mobility; At a CNTs Buckypaper precast body surface tiling filter screen woven by Plasitc fibers, be various tiny grids by CNTs Buckypaper precast body subdivision surfaces, in each grid, resol is instilled with suction pipe, be placed in stink cupboard again to dry, obtain flooding rear CNTs Buckypaper precast body.
4) CNTs Buckypaper precast body after dipping to be laid on the smooth iron plate of surface clean and to be placed in baking oven, 80 DEG C are warming up to from room temperature is stepped, at 80 DEG C of insulation 24h, the resin portion in CNTs Buckypaper precast body is solidified, obtains the sample after softcure; Wherein, from room temperature to 80 DEG C period, often heat up 5 DEG C of insulation 6h;
5) smooth for surface clean two pieces of iron plates and weight are placed in baking oven and are warming up to hard solidification value 180 DEG C, then baking oven is opened, rapidly the sample after softcure is put between two pieces of iron plates, and weight is placed in topmost, weight and iron plate is made to apply the positive pressure of 25MPa to the sample after softcure, shut oven door, be then incubated 3h firmly to solidify at 180 DEG C, the sample after firmly being solidified;
6) by firmly solidification after sample be placed in baking oven thermal treatment 10h at 230 DEG C, obtain after fixing sample.
7) under the protection of nitrogen, after fixing sample is put in carbide furnace, rises to 600 DEG C with the heat-up rate of 2 DEG C/min from room temperature, isothermal holding 2h, be then down to room temperature with the speed of 2 DEG C/min, obtain pretreatment sample.
8) under nitrogen protection; pretreatment sample is positioned in carbide furnace; with the heat-up rate of 2 DEG C/min from room temperature to 600 DEG C; isothermal holding 8h; and then be warming up to 850 DEG C with the heat-up rate of 1 DEG C/min, isothermal holding 0.5h, then be down to room temperature with the speed of 2 DEG C/min; make novolac resin matrix be converted into carbon base body completely, obtain carbonized samples.
9) carbonized samples is carried out reaction sintering in nitrogen atmosphere stove, sintering temperature: 1550 DEG C, be incubated in sintering temperature: 2h, obtain carbon nanotube and strengthen SiC based nano composite material film.
Embodiment 4:
1) by the B of CNTs, 1g of 2g 4the unformed simple substance silica flour of C micro mist and 2.5g is distributed in 1000ml distilled water, instillation 0.8ml tensio-active agent Triton tMx-100, makes evenly through pulse ultrasonic disperse 1h, obtains dispersion, even and stable suspension; Wherein, the diameter of CNTs is about 20nm, length > 50 μm, and density is 2.10g/cm 3; B 4the particle diameter of C micro mist 1 ~ 2 μm, density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour 1 ~ 7 μm, density is 2.34g/cm 3.In addition, the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, the frequency of ultrasonic vibration is 20kHz, and power is 1300W.
2) by millipore filtration 5 (Isopore tMmembrane Filters) be laid in pressure filter metal screen 6 above, metal screen 6 pads below millipore filtration 5, plays an overfill protection millipore filtration 5; Millipore filtration 5 adopts diameter to be the disk of 140mm, and aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm, and porosity is 75% ~ 85%; Press millipore filtration 5 and metal screen 6 bottom Sheng fluid cylinder sidewall 102 in pressure filter, prevent millipore filtration 5 from changing position or fold; Suspension is poured in the Sheng fluid cylinder 1 of pressure filter by the funnel be inserted in fluid inlet 2, then air is contained in fluid cylinder 1 through fluid inlet 2 suction by pressurizing device such as force (forcing) pump, force (forcing) pump is made to apply the pressure of 0.65MPa to suspension, and pressure applies direction for down to exert pressure to suspension above suspension, forces the water in suspension and tensio-active agent Triton tMx-100 is oozed out by millipore filtration 5, flows out through liquid outlet 3 and rubber hose 4, remaining CNTs, B in suspension 4the uniform mixture of C micro mist, unformed simple substance silica flour is just deposited on millipore filtration 5 surface, forms a CNTs Buckypaper, at anhydrous and tensio-active agent Triton tMafter X-100 oozes out rear about half a minute, pressure release, millipore filtration 5 with CNTs Buckypaper is taken out, be laid in totally smooth iron plate surface, be placed in stink cupboard naturally to dry, millipore filtration 5 obtains CNTs Buckypaper precast body, and finally peeled off by the CNTs Buckypaper precast body on millipore filtration 5, then what obtain 110mm × 0.63mm comprises B 4the CNTs Buckypaper precast body of C powder and unformed simple substance silica flour.
3) novolac resin, ethanol, acetone and hexamethylenetetramine are pressed the mass ratio mixing of 2:0.5:0.5:0.2, be mixed with novolac resin solution, novolac resin solution is contained in beaker the hot water being placed in about 50 DEG C for subsequent use, to ensure that resin has good mobility; At a CNTs Buckypaper precast body surface tiling filter screen woven by Plasitc fibers, be various tiny grids by CNTs Buckypaper precast body subdivision surfaces, in each grid, resol is instilled with suction pipe, be placed in stink cupboard again to dry, obtain flooding rear CNTs Buckypaper precast body.In this step, the tow sides of CNTs Buckypaper precast body are all processed by the method.
4) CNTs Buckypaper precast body after dipping to be laid on the smooth iron plate of surface clean and to be placed in baking oven, 80 DEG C are warming up to from room temperature is stepped, at 80 DEG C of insulation 24h, the resin portion after making dipping in CNTs Buckypaper precast body is solidified, and obtains the sample after softcure; Wherein, from room temperature to 80 DEG C period, often heat up 5 DEG C of insulation 4h;
5) smooth for surface clean two pieces of iron plates and weight are placed in baking oven and are warming up to hard solidification value 185 DEG C, then baking oven is opened, rapidly the sample after softcure is put between two pieces of iron plates, and weight is placed in topmost, weight and iron plate is made to apply the positive pressure of 25MPa to the sample after softcure, shut oven door, be then incubated 2.5h firmly to solidify at 185 DEG C, the sample after firmly being solidified;
6) by firmly solidification after sample be placed in baking oven thermal treatment 6h at 280 DEG C, obtain after fixing sample.
7) under the protection of nitrogen, after fixing sample is put in carbide furnace, rises to 600 DEG C with the heat-up rate of 2 DEG C/min from room temperature, isothermal holding 2.5h, be then down to room temperature with the speed of 2 DEG C/min, obtain pretreatment sample.
8) under nitrogen protection; pretreatment sample is positioned in carbide furnace; with the heat-up rate of 2 DEG C/min from room temperature to 600 DEG C; isothermal holding 8h; and then be warming up to 900 DEG C with the heat-up rate of 1 DEG C/min, isothermal holding 0.5h, then be down to room temperature with the speed of 2 DEG C/min; make novolac resin matrix be converted into carbon base body completely, obtain carbonized samples.
9) carbonized samples is carried out reaction sintering in nitrogen atmosphere stove, sintering temperature: 1500 DEG C, be incubated in sintering temperature: 3h, obtain carbon nanotube and strengthen SiC based nano composite material film.
Embodiment 5:
1) by 2g CNTs, 1.2g B 4c micro mist and the unformed simple substance silica flour of 3g are distributed in 1000ml distilled water, instillation 0.9ml tensio-active agent Triton tMx-100, makes evenly through ultrasonic disperse 50min, obtains dispersion, even and stable suspension; Wherein, the diameter of CNTs is about 20nm, length > 50 μm, and density is 2.10g/cm 3; B 4the particle diameter of C micro mist is 1 ~ 2 μm, and density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour is 1 ~ 7 μm, and density is 2.34g/cm 3.In addition, the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, the frequency of ultrasonic vibration is 20kHz, and power is 1370W.
2) by millipore filtration 5 (Isopore tMmembrane Filters) be laid in pressure filter metal screen 6 above, metal screen 6 pads below millipore filtration 5, plays an overfill protection millipore filtration 5; Millipore filtration 5 adopts diameter to be the disk of 140mm, and aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm, and porosity is 75% ~ 85%; Press millipore filtration 5 and metal screen 6 bottom Sheng fluid cylinder sidewall 102 in pressure filter, prevent millipore filtration 5 from changing position or fold; Suspension is poured in the Sheng fluid cylinder 1 of pressure filter by the funnel be inserted in fluid inlet 2, then air is contained in fluid cylinder 1 through fluid inlet 2 suction by pressurizing device such as force (forcing) pump, force (forcing) pump is made to apply the pressure of 0.65MPa to suspension, and pressure applies direction for down to exert pressure to suspension above suspension, forces the water in suspension and tensio-active agent Triton tMx-100 is oozed out by millipore filtration, flows out, remaining CNTs, B in suspension through liquid outlet and rubber hose 4c micro mist, unformed simple substance silica flour uniform mixture are just deposited on microporous membrane surface, form a CNTs Buckypaper, at anhydrous and tensio-active agent Triton tMafter X-100 oozes out rear about half a minute, pressure release, millipore filtration 5 with CNTs Buckypaper is taken out, be laid in totally smooth iron plate surface, be placed in stink cupboard naturally to dry, millipore filtration 5 obtains CNTs Buckypaper precast body, and finally peeled off by the CNTs Buckypaper precast body on millipore filtration 5, then what obtain 110mm × 0.72mm comprises B 4the CNTs Buckypaper precast body of C powder and unformed simple substance silica flour.
3) novolac resin, ethanol, acetone and hexamethylenetetramine are pressed the mass ratio mixing of 2:0.5:0.5:0.2, be mixed with novolac resin solution, novolac resin solution is contained in beaker the hot water being placed in about 50 DEG C for subsequent use, to ensure that resin has good mobility; At a CNTs Buckypaper precast body surface tiling filter screen woven by Plasitc fibers, be various tiny grids by CNTs Buckypaper precast body subdivision surfaces, in each grid, resol is instilled with suction pipe, be placed in stink cupboard again to dry, obtain flooding rear CNTs Buckypaper precast body.In this step, the tow sides of CNTs Buckypaper precast body are all processed by the method.
4) CNTs Buckypaper precast body after dipping to be laid on the smooth iron plate of surface clean and to be placed in baking oven, 75 DEG C are warming up to from room temperature is stepped, at 75 DEG C of insulation 30h, the resin portion after making dipping in CNTs Buckypaper precast body is solidified, and obtains the sample after softcure; Wherein, from room temperature to 75 DEG C period, often heat up 5 DEG C of insulation 6h;
5) smooth for surface clean two pieces of iron plates and weight are placed in baking oven and are warming up to hard solidification value 170 DEG C, then baking oven is opened, rapidly the sample after softcure is put between two pieces of iron plates, and be placed in topmost with weight, weight and iron plate is made to apply the positive pressure of 35MPa to the sample after softcure, shut oven door, be then incubated 2h firmly to solidify at 170 DEG C, the sample after firmly being solidified;
6) by firmly solidification after sample be placed in baking oven thermal treatment 7h at 200 DEG C, obtain after fixing sample.
7) under the protection of nitrogen, solidified sample is put in carbide furnace, rises to 550 DEG C with the heat-up rate of 1 DEG C/min from room temperature, isothermal holding 1.5h, be then down to room temperature with the speed of 2 DEG C/min, obtain pretreatment sample.
8) under the protection of nitrogen; pretreatment sample is positioned in carbide furnace; with the heat-up rate of 3 DEG C/min from room temperature to 550 DEG C; isothermal holding 10h; and then be warming up to 1000 DEG C with the heat-up rate of 2 DEG C/min, isothermal holding 0.5h, then be down to room temperature with the speed of 3 DEG C/min; make novolac resin matrix be converted into carbon base body completely, obtain carbonized samples.
9) carbonized samples is carried out reaction sintering in nitrogen atmosphere stove, sintering temperature: 1500 DEG C, be incubated in sintering temperature: 3h, obtain carbon nanotube and strengthen SiC based nano composite material film.
Embodiment 6:
1) by 2g CNTs, 0.5g B 4c micro mist and the unformed simple substance silica flour of 3g are distributed in 1000ml distilled water, instillation 1ml tensio-active agent Triton tMx-100, makes evenly through ultrasonic disperse 50min, obtains dispersion, even and stable suspension; Wherein, the diameter of CNTs is about 20nm, length > 50 μm, and density is 2.10g/cm 3; B 4the particle diameter of C micro mist is 1 ~ 2 μm, and density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour is 1 ~ 7 μm, and density is 2.34g/cm 3.In addition, in addition, the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, the frequency of ultrasonic vibration is 20kHz, and power is 1400W.
2) by millipore filtration 5 (Isopore tMmembrane Filters) be laid in pressure filter metal screen 6 above, metal screen 6 pads below millipore filtration 5, plays an overfill protection millipore filtration 5; Millipore filtration 5 adopts diameter to be the disk of 140mm, and aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm, and porosity is 75% ~ 85%; Press millipore filtration 5 and metal screen 6 bottom Sheng fluid cylinder sidewall 102 in pressure filter, prevent millipore filtration 5 from changing position or fold; Suspension is poured in the Sheng fluid cylinder 1 of pressure filter by the funnel be inserted in fluid inlet 2, then air is contained in fluid cylinder 1 through fluid inlet 2 suction by pressurizing device such as force (forcing) pump, force (forcing) pump is made to apply the pressure of 0.60MPa to suspension, and pressure applies direction for down to exert pressure to suspension above suspension, forces the water in suspension and tensio-active agent Triton tMx-100 is oozed out by millipore filtration, flows out through liquid outlet 3 and rubber hose 4, remaining CNTs, B in suspension 4the uniform mixture of C micro mist, unformed simple substance silica flour is just deposited on millipore filtration 5 surface, forms a CNTs Buckypaper, at anhydrous and tensio-active agent Triton tMafter X-100 oozes out rear about half a minute, pressure release, millipore filtration 5 with CNTs Buckypaper is taken out, be laid in totally smooth iron plate surface, be placed in stink cupboard naturally to dry, millipore filtration 5 obtains CNTs Buckypaper precast body, and finally peeled off by the CNTs Buckypaper precast body on millipore filtration 5, then what obtain 110mm × 0.56mm comprises B 4the CNTs Buckypaper precast body of C powder and Si powder.
3) novolac resin, ethanol, acetone and hexamethylenetetramine are pressed the mass ratio mixing of 2:0.5:0.5:0.2, be mixed with novolac resin solution, novolac resin solution is contained in beaker the hot water being placed in about 50 DEG C for subsequent use, to ensure that resin has good mobility; At a CNTs Buckypaper precast body surface tiling filter screen woven by Plasitc fibers, be various tiny grids by CNTs Buckypaper precast body subdivision surfaces, in each grid, resol is instilled with suction pipe, be placed in stink cupboard again to dry, obtain flooding rear CNTs Buckypaper precast body.In this step, the tow sides of CNTs Buckypaper precast body are all processed by the method.
4) CNTs Buckypaper precast body after dipping is laid in the smooth iron plate of surface clean and is placed in baking oven, 90 DEG C are warming up to from room temperature is stepped, at 90 DEG C of insulation 12h, the resin portion after making dipping in CNTs Buckypaper precast body is solidified, and obtains the sample after softcure; Wherein, from room temperature to 90 DEG C period, often heat up 5 DEG C of insulation 5h;
5) smooth for surface clean two pieces of iron plates and weight are placed in baking oven and are warming up to hard solidification value 170 DEG C, then baking oven is opened, rapidly the sample after softcure is put between two pieces of iron plates, and be placed in topmost with weight, weight and iron plate is made to apply the positive pressure of 35MPa to the sample after softcure, shut oven door, be then incubated 2h firmly to solidify at 170 DEG C, the sample after firmly being solidified;
6) by firmly solidification after sample be placed in baking oven thermal treatment 7h at 280 DEG C, obtain after fixing sample.
7) under the protection of nitrogen, solidified sample is put in carbide furnace, rises to 650 DEG C with the heat-up rate of 3 DEG C/min from room temperature, isothermal holding 1h, be then down to room temperature with the speed of 3 DEG C/min, obtain pretreatment sample.
8) under the protection of nitrogen; pretreatment sample is positioned in carbide furnace; with the heat-up rate of 1 DEG C/min from room temperature to 650 DEG C; isothermal holding 5h; and then be warming up to 1000 DEG C with the heat-up rate of 2 DEG C/min, isothermal holding 45min, then be down to room temperature with the speed of 3 DEG C/min; make novolac resin matrix be converted into carbon base body completely, obtain carbonized samples.
9) carbonized samples is carried out reaction sintering in nitrogen atmosphere stove, sintering temperature: 1700 DEG C, be incubated in sintering temperature: 1.5h, obtain carbon nanotube and strengthen SiC based nano composite material film.
Embodiment 7:
1) by 2.5g CNTs, 1.5g B 4c micro mist and the unformed simple substance silica flour of 1.5g are distributed in 1000ml distilled water, instillation 0.9ml tensio-active agent Triton tMx-100, makes evenly through ultrasonic disperse 50min, obtains dispersion, even and stable suspension; Wherein, the diameter of CNTs is about 20nm, length > 50 μm, and density is 2.10g/cm 3; B 4the particle diameter of C micro mist is 1 ~ 2 μm, and density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour is 1 ~ 7 μm, and density is 2.34g/cm 3.In addition, the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, the frequency of ultrasonic vibration is 20kHz, and power is 1370W.
2) by millipore filtration 5 (Isopore tMmembrane Filters) be laid in pressure filter metal screen 6 above, metal screen 6 pads below millipore filtration 5, plays an overfill protection millipore filtration 5; Millipore filtration 5 adopts diameter to be the disk of 140mm, and aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm, and porosity is 75% ~ 85%; Press millipore filtration 5 and metal screen 6 bottom Sheng fluid cylinder sidewall 102 in pressure filter, prevent millipore filtration 5 from changing position or fold; Suspension is poured in the Sheng fluid cylinder 1 of pressure filter by the funnel be inserted in fluid inlet 2, then air is contained in fluid cylinder 1 through fluid inlet 2 suction by pressurizing device such as force (forcing) pump, force (forcing) pump is made to apply the pressure of 0.80MPa to suspension, and pressure applies direction for down to exert pressure to suspension above suspension, forces the water in suspension and tensio-active agent Triton tMx-100 is oozed out by millipore filtration, flows out through liquid outlet 3 and rubber hose 4, remaining CNTs, B in suspension 4the uniform mixture of C micro mist, unformed simple substance silica flour is just deposited on millipore filtration 5 surface, forms a CNTs Buckypaper, at anhydrous and tensio-active agent Triton tMafter X-100 oozes out rear about half a minute, pressure release, millipore filtration 5 with CNTs Buckypaper is taken out, be laid in totally smooth iron plate surface, be placed in stink cupboard naturally to dry, millipore filtration 5 obtains CNTs Buckypaper precast body, finally the CNTs Buckypaper precast body on millipore filtration 5 is peeled off, then obtain 110mm × 0.79mm and comprise B 4the CNTs Buckypaper precast body of C powder and unformed simple substance silica flour.
3) novolac resin, ethanol, acetone and hexamethylenetetramine are pressed the mass ratio mixing of 2:0.5:0.5:0.2, be mixed with novolac resin solution, novolac resin solution is contained in beaker the hot water being placed in about 50 DEG C for subsequent use, to ensure that resin has good mobility; At a CNTs Buckypaper precast body surface tiling filter screen woven by Plasitc fibers, be various tiny grids by CNTs Buckypaper precast body subdivision surfaces, in each grid, resol is instilled with suction pipe, be placed in stink cupboard again to dry, obtain flooding rear CNTs Buckypaper precast body.In this step, the tow sides of CNTs Buckypaper precast body are all processed by the method.
4) CNTs Buckypaper precast body after dipping to be laid on the smooth iron plate of surface clean and to be placed in baking oven, 60 DEG C are warming up to from room temperature is stepped, at 60 DEG C of insulation 48h, the resin portion after making dipping in CNTs Buckypaper precast body is solidified, and obtains the sample after softcure; Wherein, from room temperature to 60 DEG C period, often heat up 5 DEG C of insulation 6h;
5) smooth for surface clean two pieces of iron plates and weight are placed in baking oven and are warming up to hard solidification value 180 DEG C, then baking oven is opened, rapidly the sample after softcure is put between two pieces of iron plates, and be placed in topmost with weight, weight and iron plate is made to apply the positive pressure of 35MPa to the sample after softcure, shut oven door, be then incubated 2h firmly to solidify at 180 DEG C, the sample after firmly being solidified;
6) by firmly solidification after sample be placed in baking oven thermal treatment 7h at 200 DEG C, obtain after fixing sample.
7) under the protection of nitrogen, solidified sample is put in carbide furnace, rises to 450 DEG C with the heat-up rate of 1 DEG C/min from room temperature, isothermal holding 3h, be then down to room temperature with the speed of 2 DEG C/min, obtain pretreatment sample.
8) under the protection of nitrogen; pretreatment sample is positioned in carbide furnace; with the heat-up rate of 1 DEG C/min from room temperature to 600 DEG C; isothermal holding 10h; and then be warming up to 1000 DEG C with the heat-up rate of 3 DEG C/min, isothermal holding 0.5h, then be down to room temperature with the speed of 1 DEG C/min; make novolac resin matrix be converted into carbon base body completely, obtain carbonized samples.
9) carbonized samples is carried out reaction sintering in nitrogen atmosphere stove, sintering temperature: 1500 DEG C, be incubated in sintering temperature: 3h, obtain carbon nanotube and strengthen SiC based nano composite material film.
The CNTs that the present invention's four-point probe method tests prepared heterogeneity proportioning strengthens SiC-B 4c CERAMIC-MATRIX NANOCOMPOSITE film resistivity at ambient temperature, the resistivity of film surface point-to-point transmission is 30 ~ 45 μ Ω m, close to the resistivity (being about 25 μ Ω m) of carbon, the resistivity of carbon nanotube axis is about 1 μ Ω about m, and pure SiC is isolator or the semi-insulator of electricity, can become semi-conductor after doping, general, the resistivity of SiC is 1000 more than Ω m.Therefore, the CNTs/SiC-B prepared by the present invention 4c ceramic matric composite film has become excellent electric conductor.And, B here 4adding of C also has a positive effect, without B 4c adds fashionable, and the resistivity of CNTs/SiC film is 100 μ Ω about m, and this should owing to B 4c is to the modifying function at CNTs/SiC interface.

Claims (9)

1. carbon nanotube strengthens a preparation method for SiC based nano composite material film, it is characterized in that, comprises the following steps:
1) by CNTs, B 4c micro mist and unformed simple substance silica flour are distributed in water, with tensio-active agent Triton tMx-100 is as dispersion agent, and impulse ultrasound dispersion makes to mix, and obtains suspension; Wherein, CNTs, B in suspension 4the mass ratio of C micro mist and unformed simple substance silica flour is (1 ~ 3): (0.5 ~ 1.5): (1 ~ 5);
2) pressure filter is utilized by suspension to filter to obtain comprising B 4the CNTs Buckypaper precast body of C powder and simple substance silica flour; Then a filter screen is laid on CNTs Buckypaper precast body surface, the surface of CNTs Buckypaper precast body is made to be divided into some grids, in each grid, instill novolac resin solution, then dry, obtain flooding rear CNTs Buckypaper precast body;
3) CNTs Buckypaper precast body after dipping be put in iron plate surface and be placed in baking oven, being incubated 12 ~ 48h from room temperature to 60 ~ 90 DEG C, to carry out softcure, obtaining the sample after softcure; Wherein, DEG C period from room temperature to 60 ~ 90, often heat up 5 DEG C of insulation 3-6h;
4) two pieces of iron plates and weight are placed in baking oven and are warming up to 170 ~ 190 DEG C, then the sample after softcure is put between two pieces of iron plates, again weight is placed on iron plate, weight and iron plate is made to apply the positive pressure of 25 ~ 35MPa to the sample after softcure, then 2 ~ 3h are incubated firmly to solidify at 170 ~ 190 DEG C, the sample after firmly being solidified;
5) by firmly solidification after sample be placed in baking oven thermal treatment 6 ~ 10h at 200 ~ 280 DEG C, obtain after fixing sample;
6) under the protection of nitrogen, solidified sample is put in carbide furnace, rises to 450 ~ 650 DEG C with the heat-up rate of 1 ~ 3 DEG C/min from room temperature, isothermal holding 1 ~ 3h, be then down to room temperature with the speed of 1 ~ 3 DEG C/min, obtain pretreatment sample;
7) under the protection of nitrogen, pretreatment sample is positioned in carbide furnace, with the heat-up rate of 1 ~ 3 DEG C/min from room temperature to 550 ~ 650 DEG C, isothermal holding 5 ~ 10h, and then be warming up to 850 ~ 1000 DEG C with the heat-up rate of 1 ~ 3 DEG C/min, isothermal holding 0.5 ~ 1h, is then down to room temperature with the speed of 1 ~ 3 DEG C/min, obtains carbonized samples;
8) carbonized samples is sintered in nitrogen atmosphere stove, obtain carbon nanotube and strengthen SiC based nano composite material film.
2. carbon nanotube according to claim 1 strengthens the preparation method of SiC based nano composite material film, it is characterized in that: described step 1) in the diameter of CNTs be 20nm, length > 50 μm, density is 2.10g/cm 3; B 4the particle diameter of C micro mist is 1 ~ 2 μm, and density is 2.52g/cm 3; The particle diameter of unformed simple substance silica flour is 1 ~ 7 μm, and density is 2.34g/cm 3.
3. carbon nanotube according to claim 1 strengthens the preparation method of SiC based nano composite material film, it is characterized in that: described step 1) in the CNTs of every 1 ~ 3g be dispersed in 1000ml water, add 0.5 ~ 1.5ml tensio-active agent Triton in every 1000ml water tMx-100.
4. carbon nanotube according to claim 1 strengthens the preparation method of SiC based nano composite material film, it is characterized in that: described step 1) in impulse ultrasound dispersion time be 0.5 ~ 1h, the cycle of impulse ultrasound is 1min, and every ultrasonic 45s interval 15s, the frequency of ultrasonic vibration is 20kHz, and power is 1300 ~ 1400W.
5. carbon nanotube according to claim 1 strengthens the preparation method of SiC based nano composite material film, it is characterized in that: described step 2) in pressure filter comprise for providing the pressurizing device of pressure and top to offer fluid inlet (2) to pressurizing device, the cylindrical Sheng fluid cylinder (1) of liquid outlet (3) is offered in bottom, described Sheng fluid cylinder (1) is by Sheng fluid cylinder top cover (101), contain fluid cylinder sidewall (102), contain fluid cylinder bottom (103) composition, and the top of containing fluid cylinder sidewall (102) is connected with Sheng fluid cylinder top cover (101), the bottom of containing fluid cylinder sidewall (102) is connected with Sheng fluid cylinder bottom (103), and Sheng fluid cylinder bottom (103) is cavity configuration, the inwall of Sheng fluid cylinder bottom (103) is provided with the annular step (104) for laying through metal (7), through metal (7) is placed with the metal screen (6) for laying millipore filtration (5).
6. carbon nanotube according to claim 5 strengthens the preparation method of SiC based nano composite material film, it is characterized in that: described step 2) in CNTs Buckypaper precast body adopt and obtain with the following method:
Millipore filtration (5) is laid on metal screen (6), then will contain fluid cylinder sidewall (102) respectively with Sheng fluid cylinder bottom (103) with contain fluid cylinder top cover (101) and be connected, funnel is inserted in fluid inlet (2), then being poured into by fluid inlet (2) by suspension contains in fluid cylinder (1), again fluid inlet (2) is connected with pressurizing device, pressurizing device is made to apply the pressure of 0.6 ~ 0.8MPa to suspension, the water in suspension and tensio-active agent Triton tMx-100 is leached by millipore filtration (5) and is flowed out by liquid outlet (3), remaining CNTs, B 4the uniform mixture of C micro mist, unformed simple substance silica flour is deposited on millipore filtration (5) surface, form a CNTs Buckypaper, finally remove pressurizing device, millipore filtration (5) with CNTsBuckypaper is taken out and dries, millipore filtration (5) obtains CNTsBuckypaper precast body, then the CNTs Buckypaper precast body on millipore filtration (5) is peeled off.
7. carbon nanotube according to claim 5 strengthens the preparation method of SiC based nano composite material film, it is characterized in that: described step 2) in the porosity of millipore filtration be 75% ~ 85%, aperture is unimodal distribution and narrow distribution range, and aperture averaging is 0.45 μm.
8. carbon nanotube according to claim 1 strengthens the preparation method of SiC based nano composite material film, it is characterized in that, described step 2) in novolac resin solution adopt and prepare with the following method: novolac resin, ethanol, acetone and the hexamethylenetetramine mass ratio by 2:0.5:0.5:0.2 is mixed, preparation novolac resin solution.
9. carbon nanotube according to claim 1 strengthens the preparation method of SiC based nano composite material film, it is characterized in that: described step 8) in sintering temperature be 1450 ~ 1700 DEG C, sintering time is 1 ~ 3h.
CN201410475361.1A 2014-09-17 2014-09-17 A kind of CNT strengthens the preparation method of SiC based nano composite material film Active CN104291826B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410475361.1A CN104291826B (en) 2014-09-17 2014-09-17 A kind of CNT strengthens the preparation method of SiC based nano composite material film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410475361.1A CN104291826B (en) 2014-09-17 2014-09-17 A kind of CNT strengthens the preparation method of SiC based nano composite material film

Publications (2)

Publication Number Publication Date
CN104291826A true CN104291826A (en) 2015-01-21
CN104291826B CN104291826B (en) 2015-12-30

Family

ID=52311820

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410475361.1A Active CN104291826B (en) 2014-09-17 2014-09-17 A kind of CNT strengthens the preparation method of SiC based nano composite material film

Country Status (1)

Country Link
CN (1) CN104291826B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106676092A (en) * 2016-12-09 2017-05-17 西安建筑科技大学 Preparation method of low-dimensional carbon nanomaterial/quorum quenching enzyme composite film material
CN109351202A (en) * 2018-12-19 2019-02-19 安徽工业大学 It is a kind of based on ceramic tube be the compound carbon membrane of supporter preparation method
CN110981490A (en) * 2019-11-28 2020-04-10 赛福纳米科技(徐州)有限公司 CNT toughening of B4C-SiC laminated composite ceramic and preparation method thereof
CN116161962A (en) * 2023-02-06 2023-05-26 中国科学院上海硅酸盐研究所 Silicon carbide pressure-sensitive ceramic with anisotropic electrical property and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106676092A (en) * 2016-12-09 2017-05-17 西安建筑科技大学 Preparation method of low-dimensional carbon nanomaterial/quorum quenching enzyme composite film material
CN106676092B (en) * 2016-12-09 2019-07-12 西安建筑科技大学 Low-dimensional carbon nanomaterial/Quorum quenching enzymes composite film material preparation method
CN109351202A (en) * 2018-12-19 2019-02-19 安徽工业大学 It is a kind of based on ceramic tube be the compound carbon membrane of supporter preparation method
CN110981490A (en) * 2019-11-28 2020-04-10 赛福纳米科技(徐州)有限公司 CNT toughening of B4C-SiC laminated composite ceramic and preparation method thereof
CN116161962A (en) * 2023-02-06 2023-05-26 中国科学院上海硅酸盐研究所 Silicon carbide pressure-sensitive ceramic with anisotropic electrical property and preparation method thereof

Also Published As

Publication number Publication date
CN104291826B (en) 2015-12-30

Similar Documents

Publication Publication Date Title
Lei et al. Phase change material with anisotropically high thermal conductivity and excellent shape stability due to its robust cellulose/BNNSs skeleton
CN104291826B (en) A kind of CNT strengthens the preparation method of SiC based nano composite material film
Ramakrishnan et al. Heat transfer performance enhancement of paraffin/expanded perlite phase change composites with graphene nano-platelets
CN104311090B (en) A kind of hot pressed sintering/presoma cracking process prepares the method for Cf/ZrC-SiC ultrahigh temperature ceramic composite
CN104030716B (en) The method of sol-gel method in-situ synthesis of SiC nano wire modifying carbon/carbon composite material precast body
Zhang et al. Biocompatible, ultralight, strong hydroxyapatite networks based on hydroxyapatite microtubes with excellent permeability and ultralow thermal conductivity
CN106633652A (en) Preparation method of bicontinuous-phase alumina/epoxy resin composite material
Zhang et al. Three-dimensional reticulated, spongelike, resilient aerogels assembled by SiC/Si3N4 nanowires
CN106631079B (en) Carbon nanotube composite material of silicon carbide and preparation method thereof
Zhou et al. Wood‐Derived, Vertically Aligned, and Densely Interconnected 3D SiC Frameworks for Anisotropically Highly Thermoconductive Polymer Composites
Zhuang et al. Realizing high ceramic yield and low shrinkage of in-situ formed lightweight 3D-SiC (rGO) px polymer-derived ceramics with excellent fracture toughness
Du et al. One‐step fabrication of ceramic and carbon nanotube (CNT) composites by in situ growth of CNTs
Wang et al. MXene reconciles concurrent enhancement of thermal conductivity and mechanical robustness of SiC-based thermal energy storage composites
CN105272229A (en) Ceramic containing pyrochlore phase zirconic acid gadolinium powder and preparation method of ceramic
Ortona et al. Fabrication of cylindrical SiCf/Si/SiC-based composite by electrophoretic deposition and liquid silicon infiltration
CN112592188A (en) Preparation method of graphene composite silicon carbide ceramic material
Ma et al. Study on microstructures and properties of porous TiC ceramics fabricated by powder metallurgy
CN206828402U (en) A kind of ceramic membrane materials component
CN106478120B (en) A kind of preparation method of the modified C/C composite material of binary ceramic
JP2015071519A (en) POROUS SiC SINTERED BODY AND METHOD OF PRODUCING POROUS SiC SINTERED BODY
CN107082641A (en) A kind of ceramic membrane materials component
CN104177113B (en) SiC bonded ceramic matrix composite material and preparation method thereof
CN106119741A (en) A kind of CNT and the preparation method of aluminum borate whisker hybrid reinforced aluminum-matrix composite material
Li et al. Conversion of wood flour/SiO2/phenolic composite to porous SiC ceramic containing SiC whiskers
Mei et al. Fabrication and mechanical properties of SiC composites toughened by buckypaper and carbon fiber fabrics alternately laminated

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20230113

Address after: 710065 No.912, West Section of Biyuan 1st Road, High-tech Zone, Xi'an, Shaanxi Province

Patentee after: Xi'an Xinyao Ceramic Composite Co.,Ltd.

Address before: 710055 No. 13, Yanta Road, Shaanxi, Xi'an

Patentee before: XIAN University OF ARCHITECTURE AND TECHNOLOG

TR01 Transfer of patent right