CN109627032A - A kind of preparation method for the high heat-conductivity conducting ceramic matric composite including three-dimensional order graphene - Google Patents

A kind of preparation method for the high heat-conductivity conducting ceramic matric composite including three-dimensional order graphene Download PDF

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CN109627032A
CN109627032A CN201910083454.2A CN201910083454A CN109627032A CN 109627032 A CN109627032 A CN 109627032A CN 201910083454 A CN201910083454 A CN 201910083454A CN 109627032 A CN109627032 A CN 109627032A
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graphene
high heat
composite
conducting ceramic
ceramic matric
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CN109627032B (en
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刘永胜
张运海
王晶
曹立阳
李精鑫
成来飞
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Northwestern Polytechnical University
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Abstract

The present invention relates to a kind of preparation methods of high heat-conductivity conducting ceramic matric composite for including three-dimensional order graphene, its technical characteristic step is to prepare graphene pretreatment, slurry configuration, ordered fabrication graphene, half densification composite material preparation, processing directed access and backfill, finally densifies again and composite material is made.Technical solution provided by the present invention can prepare graphene within a short period of time and wrap up preferable graphene/fiber core-shell structure, realize interfacial assembly；It processes directed access by double of densified composite and backfills and complete the assembling of thickness direction graphene, composite material can be made after densification.Process stabilizing of the invention, repeatability is high, and low in cost, yield is higher, the final thermal conductivity of composite material can be made to promote 10~50 times, conductivity promotes 50~300 times.

Description

A kind of system for the high heat-conductivity conducting ceramic matric composite including three-dimensional order graphene Preparation Method
Technical field
The invention belongs to the preparation methods of ceramic matric composite, are related to a kind of high thermal conductivity for including three-dimensional order graphene The preparation method of conductivity ceramics based composites.
Background technique
Carbon fiber toughened silicon carbide ceramic matric composite (Cf/ SiC) overcome single silicon carbide ceramics brittleness greatly and can By deadly defects such as property differences, have high temperature resistant, high intensity, low-density, thermal expansion is small, thermal conductivity is good, higher elevated temperature strength and The features such as anticorrosive, can be realized and integrate the functions such as ablation, heat-insulated, structural bearing, to make related aerospace structure Part realizes " structure simplification, weight saving, reuse ", reaches aerospace system and improves performance, improves reliability most Whole purpose.But with the development of aeronautical and space technology, aeroplane performance and rate request are improved, the requirement to material property Also higher and higher, it especially applies on the fields such as the thermal protection system of aero-engine, rocket engine and re-entry space vehicle Cf/ SiC ceramic matrix composite material also requires it to collect thermal conductivity magnetic cup other than requiring composite material to have preferable mechanical property Equal functional characteristics are covered in one.So, not only proof strength toughness while but also increase CfFunctionality (the high fever of/SiC ceramic matrix composite material Conductance, conductivity etc.) it is one of critical issue during the current field is urgently to be resolved.
Graphene (Graphene, Gr) be one kind by carbon atom with sp2Hybridized orbit forms hexangle type in honeycomb lattice Two-dimentional carbon nanomaterial is one of highest material of known strength.Since its structure is special, graphene is also equipped with extremely excellent function Can property, as the thermal coefficient of single-layer graphene is up to 5300W/mK, and room temperature carrier mobility is up to 15000cm2/(V· S), it is optimal material as high thermal conductivity, conducing composite material reinforcement.However, due to the influence of graphene self structure, table Face can be high, and interlayer Van der Waals force is stronger, therefore is also easy to produce lamella curling, stacks and reunite, be not easy the disadvantages of dispersing.In document 1 Kinloch, I.A et al. are in article " Composites with carbon nanotubes and graphene:An Outlook " shows that the piece layer defects of graphene are more, and stacking number is more, reunites more severe, and distribution is more unordered, to graphene Performance influence it is bigger, to limit the performance of graphene performance." Fabrication of SiCf-CNTs/ in document 2 SiC composites with high thermal conductivity by vacuumfiltration combined With CVI " reports a kind of using CNTs film and SiCfAssembling preparation SiC between scrim clothfThe side of-CNTs/SiC composite material Method finally makes heat conductivity improve 2.9 times, and promotion is not obvious.This is because CNTs only is assembled in interlayer, And unstructured complete three-dimensional network channel, so that final thermal conductivity promotion is unobvious." Thermal and in document 3 mechanical properties of SiC/SiC-CNTs composites fabricated by CVI combined With electrophoretic deposition " report it is a kind of use electrophoretic deposition surface of SiC introduce the interface CNTs with The method for improving composite material heating conduction, but heating conduction only improves 1.74 times.There is a problem of with document 2 it is same, i.e., There is no effective passage of heat in thickness direction, hot-fluid can not conduct in all directions in the composite, so as to cause compound Material thermal conductivity is promoted unobvious.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that a kind of high thermal conductivity for including three-dimensional order graphene is led The preparation method of electroceramics based composites is completed graphene/fiber interface using slashing technique and is assembled, then carries out braiding system Standby fiber cloth simultaneously completes lamination assembling, or is woven into 2.5 dimensions, 3 dimension precast bodies；After the deposited boundary layer of precast body and matrix, Directed access is prepared, graphene is backfilled, so as to construct three dimentional heat conduction channel in composite material.Finally, using CVI or the side RMI Method is further introduced into matrix and is densified, and is prepared into high-heat-conductive composite material.
Technical solution
A kind of preparation method for the high heat-conductivity conducting ceramic matric composite including three-dimensional order graphene, it is characterised in that Steps are as follows:
Step 1: graphene being carried out surface activation process 0.5~12 hour using acid reagent；The graphene and acid try Mass ratio between agent is 1:40~1:120；
Step 2: pretreated graphene, dispersing agent and solvent being configured to the solution of 0.1~50mg/mL, adjust pH value Slurries are obtained to 5~10；The mass ratio of the dispersing agent and graphene is 0.1~30；
Step 3. interfacial assembly: using on slashing technique ordered fabrication graphene to fiber, one-dimensional graphene/fiber is formed Core-shell structure completes interfacial assembly after dry；
The packaging technology parameter are as follows: starching machine drying box temperature is 25~120 DEG C, and drying time is 1~60 minute, slurry Bath temperature degree is 25~100 DEG C, and walking yarn speed is 5~30m/min, the fiber after obtaining graphene interfacial assembly；
Step 4: the graphene solution for being 0.1~10mg by graphene and solvent configuration concentration, using vacuum filtration legal system Standby graphene film controls graphene film thickness at 15~1000 μm；Vacuum pump pressure control is -0.08 when the vacuum filtration ~0.096Mpa；
Step 5. precast body preparation: by the fibrage of step 3 gained at two-dimensional fiber cloth or 2.5 dimensions, 3 dimension precast bodies；With Step 4 gained graphene film carries out interlayer assembling, obtains precast body；2.5 dimensions, 3 dimension fiber preforms directly adopt graphite jig Sizing；
The two-dimensional fiber cloth of the braiding is 80~120 beams/10cm through the close control of crammed；
Step 6. deposited interfacial layer and matrix: chemical vapor infiltration deposited interfacial layer and SiC are used to precast body Matrix is prepared into half densified composite, controls its density in 1.2~1.8g/cm3；
The technological parameter of deposited interfacial layer and matrix are as follows:
Deposit PyC interface parameter are as follows: with C3H6For gas source, Ar is diluent gas, H2For carrier gas, depositing temperature 670-870 DEG C, system stagnation pressure is 5~6kPa, deposits the interface PyC phase；
Deposit SiC matrix parameter are as follows: using trichloromethyl silane as gas source, Ar is diluent gas, and H is used in a manner of bubbling2Make MTS is brought into reacting furnace for carrier gas, depositing temperature is 1000~1300 DEG C or so, and system stagnation pressure is 5~6kPa, H2With MTS Molar ratio be 10:1；
Step 7: using laser in half densified composite processing diameter for the small directed access of 0.3~1mm, interchannel Away from for 2~30mm；Control channel volume accounting is 10~60%；
The assembling of step 8. thickness direction: it is molten that the material that step 7 is punched is immersed in graphene prepared by step 2 or step 4 It in liquid, is backfilled using vacuum impregnation or injection method, impregnation pressure range is that vacuum pump pressure is controlled in -0.08~0.096MPa；
This step is repeated as many times, and backfill graphene is until directed access is opaque；
Step 9: the composite material after three-dimensional assembling further being caused using chemical vapor infiltration or the siliconising of RMI method Densification makes the final relative density of composite material reach 85~95%；The parameter is identical as step 6 depositing base parameter.
The graphene are as follows: liquid phase removes graphene, electricity removing graphene, graphene oxide, redox graphene, height One of warm expanded graphite alkene, low-temperature expansion graphene or in which it is several.
The acid reagent uses one or more of nitric acid, the concentrated sulfuric acid, potassium permanganate, hydrogen peroxide.
The solvent is one or more of deionized water, N,N-dimethylformamide DMF, ethyl alcohol, isopropanol.
The dispersing agent are as follows: polyvinyl alcohol, Qula be logical, silane coupling agent, titanate coupling agent, dodecyl dimethyl benzyl Ammonium chloride, myristyl benzyl dimethyl ammonium chloride, aqueous polyurethane, cetyl trimethylammonium bromide, polyvinyl pyrrole One or more of alkanone, sodium carboxymethylcellulose, methylcellulose, sodium taurocholate, polyethylene glycol oxide, Arabic gum.
The fiber are as follows: carbon fiber, silicon carbide fibre, boron fibre or oxide and other high-temperature ceramic fibres.
Pretreated graphene or untreated graphene are used when prepared by the graphene film.
The small directed access shape is regular shape or irregular shape；The regular shape is round or rectangular
The small directed access arrangement is orderly or unordered；It is arranged side by side, annular array or Heterogeneous Permutation.
The small directed access arrangement is equidistant or non-equidistant.
Beneficial effect
A kind of preparation side of high heat-conductivity conducting ceramic matric composite including three-dimensional order graphene proposed by the present invention Method constructs graphene/carbon fiber and shell structure using the present carbon fiber surface of slashing technique, then passes through the methods of braiding preparation Precast body has constructed passage of heat in two-dimensional surface, while interlayer assembles graphene of the connection between fibrous layer and fiber and leads The passage of heat forms three-dimensional net structure；Finally by processing directed access, backfill graphene, directly get through in thickness direction Heat conduction network, progress one constructs and strengthens the three dimentional heat conduction channel in composite material, it is compound to be greatly promoted hot-fluid The transmitting of all directions in material, improves the thermal conductivity of composite material significantly.
Beneficial effects of the present invention have the following:
(1) after being pre-processed to graphene, thus it is possible to vary graphene surface property, without excessive destruction graphene Structure can be obviously improved graphene dispersion problem in conjunction with the introducing of different dispersing agents.
(2) graphene ordered fabrication is carried out using slashing technique, can make graphene it is orderly in conjunction with fiber, then by volume Weaving process can prepare the precast body of different dimensions, construct heat conduction network structure.
(3) graphene isolating problem scrim cloth being improved to fiber cloth progress interlayer assembling；It half-and-half densifies compound Material processes directed access, backfills graphene, can assemble graphene in thickness direction and be connected to interlayer and interface graphene, thus Construct 3 D stereo graphene network channel.
(4) entire technical process is easy to operate, and repeatability is high, low in cost, without upgrading existing equipment Complete composite material preparation.
Detailed description of the invention
Fig. 1 composite material preparation flow figure.
The carbon fiber SEM of (a) and (b) after assembling scheme before Fig. 2 assembling
Composite material schematic diagram after the assembling of Fig. 3 three-dimensional.
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
The present invention solves Cf/ SiC ceramic matrix composite material function poor and graphene and fiber alignment ordered fabrication problem To prepare high thermal conductivity Gr-Cf/ SiC functional composite material.The present invention completes graphene/fiber interface group using slashing technique Dress then carries out braiding preparation fiber cloth and completes lamination assembling, or is woven into 2.5 dimensions, 3 dimension precast bodies；Precast body is deposited After boundary layer and matrix, directed access is processed, graphene is backfilled, so as to construct three dimentional heat conduction channel in composite material.Most Afterwards, matrix is further introduced into using CVI or RMI method to be densified, finally prepare the composite wood for having excellent functionality Material.
To achieve the goals above, the invention adopts the following technical scheme:
Step 1. carries out graphene (Graphene, Gr) surface activation process 0.5~12 hour；
Wherein reagent treatment and treatment process are as follows: reagent used by pre-processing includes concentrated nitric acid, the concentrated sulfuric acid, potassium permanganate Or one or more of hydrogen peroxide, phosphorus pentoxide, potassium thiosulfate remove graphene to liquid phase, electricity removes graphene, One of redox graphene, high-temperature expansion graphene, low-temperature expansion graphene are pre-processed at 35~100 DEG C 0.5~24 hour；Mass ratio between graphene and reagent is 1:40~1:120.
Pretreated graphene is added in solvent by step 2., and dispersing agent is added and is configured to the molten of 0.1~50mg/mL Liquid, adjusting pH value to 5~10 obtain slurries.
Step 3. interfacial assembly: it using on graphene slurries to fiber prepared by slashing technique ordered fabrication step 1, is formed One-dimensional graphene/fiber core-shell structure completes interfacial assembly after dry.
The packaging technology parameter are as follows: starching machine drying box temperature is 25~120 DEG C, and drying time is 1~60 minute, slurry Bath temperature degree is 25~100 DEG C, and walking yarn speed is 5~30m/min, obtains fiber after graphene interfacial assembly.
Step 4. graphene solution that configuration concentration is 0.1~10mg again, it is thin to prepare graphene using vacuum filtration method Film controls graphene film thickness at 15~1000 μm.
Graphene used in the step can be pretreating graphite alkene, be also possible to untreated graphene；Vacuum pump pressure Power is controlled in -0.08~0.096MPa.
Step 5. precast body preparation: by the fibrage of step 3 gained at two-dimensional fiber cloth or 2.5 dimensions, 3 dimension precast bodies；It is fine Wei Bu is cut into certain size and step 4 gained graphene film carries out interlayer assembling, obtains precast body；2.5 dimensions, 3 dimension fibers are pre- Body processed directlys adopt graphite jig sizing.
The two-dimensional fiber cloth of braiding described in the step is 80~120 beams/10cm through the close control of crammed.
Step 6. deposited interfacial layer and matrix: chemical vapor infiltration is used at a certain temperature to step 5 gained precast body Saturating method deposited interfacial layer and a certain amount of SiC matrix, are prepared into half densified composite, control its density in 1.2~1.8g/ cm3。
The wherein technological parameter of deposited interfacial layer and matrix are as follows: deposit PyC interface parameter are as follows: wherein with C3H6For gas source, Ar is diluent gas, H2For carrier gas, depositing temperature is 670-870 DEG C, and system stagnation pressure is 5~6kPa, deposits the interface PyC phase, raw At the chemical reaction of PyC are as follows: C3H6→PyC+CxHy；Deposit SiC matrix parameter are as follows: with trichloromethyl silane (CH3SiCl3,MTS) For gas source, Ar is diluent gas, and H is used in a manner of bubbling2MTS is brought into reacting furnace as carrier gas, depositing temperature be 1000~ 1300 DEG C or so, system stagnation pressure is 5~6kPa, H2Molar ratio with MTS is 10:1, prepares the chemical reaction of SiC are as follows: CH3SiCl3+H2→SiC+HCl。
Step 7. is to half densified composite obtained by step 6 using the small directed access of laser processing, control channel diameter For 0.3~1mm；
The directed access feature are as follows: directed access shape and its arrangement have designability, and shape can be round, side The regular shapes such as shape or irregular shape, arranging, it is equidistant, non-equidistant to can be, being ordered into, unordered, It is also possible to be arranged side by side, annular array or Heterogeneous Permutation.Control directed access diameter is 0.3~1mm, interchannel away from for 2~ 30mm；It is 10~60% that control channel volume, which accounts for volume of sample ratio,.
Step 8. thickness direction assembling: molten using graphene prepared by vacuum impregnation or injection method refilling step 2 or step 4 Liquid can carry out repeatedly backfilling graphene to guarantee graphene introduction volume, until directed access is opaque；Wherein impregnation pressure model It encloses and controls for vacuum pump pressure in -0.08~0.096MPa.
Step 9. carries out the composite material depositing base after three-dimensional assembling using chemical vapor infiltration further fine and close Change, the final relative density of composite material is made to reach 85~95%.The wherein rapid 6 depositing base ginseng of chemical vapor infiltration parameter synchronization Number.
Specific embodiment:
Embodiment 1.
Step 1: graphene slurry configurations.
2g graphene is taken, is added in the beaker for filling the 500mL concentrated sulfuric acid, hydrogen peroxide, the two volume ratio is 4:1 (note Meaning: the configuration process is relatively hazardous, and when use is careful！), it handles two hours, washs at 35 DEG C, ultrasound 30 minutes is dry.Take 2g Pretreated graphene, 4g CMC are added in 500mL deionized water, ultrasonic disperse.
Step 2: ordered fabrication.Wherein starching machine drying box temperature is 80 DEG C, and drying time is 2 minutes, and slurry groove temperature is 80 DEG C, walking yarn speed is 5~30m/min, obtains graphene assembling carbon fiber.It is used after drying and is woven into two-dimentional carbon cloth, It is 80~120 beams/10cm that it is close through crammed, which to control fiber cloth, and is cut.
Step 3: it will not be surface-treated graphene 0.5g and CMC 0.5g is added in 500mL deionized water, ultrasonic disperse, Film forming is filtered, it is dry；Step is repeated, it is several to prepare graphene film, lamination assembling is carried out with fiber cloth prepared by step 3, every two Graphene film quantity is 1 layer between layer fiber.
Step 4: assembled precast body being deposited into pyrolytic carbon PyC under certain condition, base is then deposited using CVI method Body SiC, when density reaches 1.3g/cm3When stop deposition.
The technological parameter of deposited interfacial layer and matrix are as follows:
Deposit PyC interface parameter are as follows: with C3H6For gas source, Ar is diluent gas, H2For carrier gas, depositing temperature 670-870 DEG C, system stagnation pressure is 5~6kPa, deposits the interface PyC phase；
Deposit SiC matrix parameter are as follows: using trichloromethyl silane as gas source, Ar is diluent gas, and H is used in a manner of bubbling2Make MTS is brought into reacting furnace for carrier gas, depositing temperature is 1000~1300 DEG C or so, and system stagnation pressure is 5~6kPa, H2With MTS Molar ratio be 10:1；
Step 5: half densified composite of step 4 being processed into directed access using femtosecond laser, channel diameter size is 0.3mm, pitch of holes 10mm, is arranged side by side, and channel volume accounting is 15%.
Step 6: the material that step 5 is punched is immersed in graphene solution prepared by step 3, using vacuum impregnation or note Method backfill is penetrated, impregnation pressure range is that vacuum pump pressure is controlled in -0.08~0.096MPa；Repeatedly, backfill graphene is straight It is opaque to directed access；
Step 7: the densification of Multiple depositions silicon carbide being carried out using CVI method, prepares fine and close Gr-Cf/ SiC composite wood Material；The parameter is identical as step 4 depositing base parameter.
Embodiment 2.
Step 1: graphene slurry configurations.
Liquid phase is taken to remove graphene 2g, sodium taurocholate 1g, PAM 1g is added in 500mL deionized water, high speed ball milling 1 is small When, obtain finely dispersed slurries.
Step 2: interfacial assembly.Starching machine drying box temperature is 90 DEG C, and drying time is 1 minute, and slurry groove temperature is 70 DEG C, Walking yarn speed is 5~30m/min, obtains graphene assembling carbon fiber.Using two-dimentional carbon cloth is woven into after drying, control is fine It is 80~120 beams/10cm that Wei Bu is close through crammed, and is cut into a certain size.
Step 3: using pretreating graphite alkene prepared by step 1, suction filtration film forming is several, with step 3 gained scrim cloth Between assemble, control interlayer graphene film quantity, control starting two layers of carbon fiber between graphene film quantity be 1 layer, the second third It is 2 layers of graphene film between layer carbon fiber, and so on.
Step 4: assembled precast body being deposited into pyrolytic carbon PyC under certain condition, base is then deposited using CVI method Body SiC, when density reaches 1.4g/cm3When stop deposition.
The technological parameter of deposited interfacial layer and matrix are as follows:
Deposit PyC interface parameter are as follows: with C3H6For gas source, Ar is diluent gas, H2For carrier gas, depositing temperature 670-870 DEG C, system stagnation pressure is 5~6kPa, deposits the interface PyC phase；
Deposit SiC matrix parameter are as follows: using trichloromethyl silane as gas source, Ar is diluent gas, and H is used in a manner of bubbling2Make MTS is brought into reacting furnace for carrier gas, depositing temperature is 1000~1300 DEG C or so, and system stagnation pressure is 5~6kPa, H2With MTS Molar ratio be 10:1；
Step 5: half densified composite of step 4 being processed into directed access using femtosecond laser, channel diameter size is 0.5mm, pitch of holes 6mm, channel Heterogeneous Permutation, channel volume accounting are 20%.
Step 6: using graphene slurry prepared by pin hole injection refilling step 2；
Step 7: the densification of Multiple depositions silicon carbide being carried out using CVI method, prepares fine and close Gr-Cf/ SiC composite wood Material；The parameter is identical as step 4 depositing base parameter.
Embodiment 3.
Step 1: graphene slurry configurations.
Electricity is taken to remove graphene 2g, CTAB 4g is added in 500mL deionized water, ultrasonic 30min, and high speed ball milling 1 is small When, obtain finely dispersed slurries.
Step 2: ordered fabrication.Wherein starching machine drying box temperature is 60 DEG C, and drying time is 3 minutes, and slurry groove temperature is 90 DEG C, walking yarn speed is 5~30m/min, obtains graphene assembling carbon fiber.3 dimension carbon fiber precast bodies are woven into after drying.
Step 3: group precast body is deposited into pyrolytic carbon PyC under certain condition, then uses CVI method depositing base SiC, When density reaches 1.6g/cm3When stop deposition.
Step 4: half densified composite of step 3 being processed into directed access using femtosecond laser, channel diameter size is 0.8mm, using annular array, interchannel is away from being 3mm, channel ring and channel interannular away from being 10% for 5mm channel volume accounting.
The technological parameter of deposited interfacial layer and matrix are as follows:
Deposit PyC interface parameter are as follows: with C3H6For gas source, Ar is diluent gas, H2For carrier gas, depositing temperature 670-870 DEG C, system stagnation pressure is 5~6kPa, deposits the interface PyC phase；
Deposit SiC matrix parameter are as follows: using trichloromethyl silane as gas source, Ar is diluent gas, and H is used in a manner of bubbling2Make MTS is brought into reacting furnace for carrier gas, depositing temperature is 1000~1300 DEG C or so, and system stagnation pressure is 5~6kPa, H2With MTS Molar ratio be 10:1；
Step 6: using graphene slurry prepared by pin hole injection refilling step 2；
Step 7: the densification of Multiple depositions silicon carbide being carried out using CVI method, prepares fine and close Gr-Cf/ SiC composite wood Material；The parameter is identical as step 4 depositing base parameter.
Preparation method of the invention, be primarily applicable for superhigh temperature functionality ceramic based composites enhancing it is modifies and In functional composite material field.Its technical characteristic step is to prepare graphene pretreatment, slurry configuration, ordered fabrication graphite Alkene, half densification composite material preparation, processing directed access and backfill, finally densify again and composite material are made.The present invention Provided technical solution can prepare graphene within a short period of time and wrap up preferable graphene/fiber core-shell structure, real Existing interfacial assembly；It processes directed access by double of densified composite and backfills and complete the assembling of thickness direction graphene, it is fine and close Composite material can be made after change.Process stabilizing of the invention, repeatability is high, and low in cost, yield is higher, can make composite material Final thermal conductivity promotes 10~50 times, and conductivity promotes 50~300 times.

Claims (10)

1. a kind of preparation method for the high heat-conductivity conducting ceramic matric composite for including three-dimensional order graphene, it is characterised in that step It is rapid as follows:
Step 1: graphene being carried out surface activation process 0.5~12 hour using acid reagent；The graphene and acid reagent it Between mass ratio be 1:40~1:120；
Step 2: pretreated graphene, dispersing agent and solvent be configured to the solution of 0.1~50mg/mL, adjust pH value to 5~ 10 obtain slurries；The mass ratio of the dispersing agent and graphene is 0.1~30；
Step 3. interfacial assembly: using on slashing technique ordered fabrication graphene to fiber, one-dimensional graphene/fiber nucleocapsid is formed Structure completes interfacial assembly after dry；
The packaging technology parameter are as follows: starching machine drying box temperature is 25~120 DEG C, and drying time is 1~60 minute, stock tank temperature Degree is 25~100 DEG C, and walking yarn speed is 5~30m/min, the fiber after obtaining graphene interfacial assembly；
Step 4: the graphene solution for being 0.1~10mg by graphene and solvent configuration concentration prepares stone using vacuum filtration method Black alkene film controls graphene film thickness at 15~1000 μm；When the vacuum filtration vacuum pump pressure control -0.08~ 0.096Mpa；
Step 5. precast body preparation: by the fibrage of step 3 gained at two-dimensional fiber cloth or 2.5 dimensions, 3 dimension precast bodies；With step 4 Gained graphene film carries out interlayer assembling, obtains precast body；2.5 dimensions, 3 dimension fiber preforms directly adopt graphite jig sizing；
The two-dimensional fiber cloth of the braiding is 80~120 beams/10cm through the close control of crammed；
Step 6. deposited interfacial layer and matrix: using chemical vapor infiltration deposited interfacial layer and SiC matrix to precast body, It is prepared into half densified composite, controls its density in 1.2~1.8g/cm3；
The technological parameter of deposited interfacial layer and matrix are as follows:
Deposit PyC interface parameter are as follows: with C3H6For gas source, Ar is diluent gas, H2For carrier gas, depositing temperature is 670-870 DEG C, System stagnation pressure is 5~6kPa, deposits the interface PyC phase；
Deposit SiC matrix parameter are as follows: using trichloromethyl silane as gas source, Ar is diluent gas, and H is used in a manner of bubbling2As carrier gas MTS is brought into reacting furnace, depositing temperature is 1000~1300 DEG C or so, and system stagnation pressure is 5~6kPa, H2With mole of MTS Than for 10:1；
Step 7: use laser half densified composite processing diameter for the small directed access of 0.3~1mm, interchannel away from for 2~30mm；Control channel volume accounting is 10~60%；
The assembling of step 8. thickness direction: the material that step 7 is punched is immersed in graphene solution prepared by step 2 or step 4, It is backfilled using vacuum impregnation or injection method, impregnation pressure range is that vacuum pump pressure is controlled in -0.08~0.096MPa；
This step is repeated as many times, and backfill graphene is until directed access is opaque；
Step 9: the composite material after three-dimensional assembling being carried out using chemical vapor infiltration or the siliconising of RMI method further fine and close Change, the final relative density of composite material is made to reach 85~95%；The parameter is identical as step 6 depositing base parameter.
2. including the preparation side of the high heat-conductivity conducting ceramic matric composite of three-dimensional order graphene according to claim 1 Method, it is characterised in that: the graphene are as follows: liquid phase removes graphene, electricity removing graphene, graphene oxide, oxygen reduction fossil One of black alkene, high-temperature expansion graphene, low-temperature expansion graphene or in which it is several.
3. including the preparation side of the high heat-conductivity conducting ceramic matric composite of three-dimensional order graphene according to claim 1 Method, it is characterised in that: the acid reagent uses one or more of nitric acid, the concentrated sulfuric acid, potassium permanganate, hydrogen peroxide.
4. including the preparation side of the high heat-conductivity conducting ceramic matric composite of three-dimensional order graphene according to claim 1 Method, it is characterised in that: the solvent is one of deionized water, n,N-Dimethylformamide DMF, ethyl alcohol, isopropanol or several Kind.
5. including the preparation side of the high heat-conductivity conducting ceramic matric composite of three-dimensional order graphene according to claim 1 Method, it is characterised in that: the dispersing agent are as follows: polyvinyl alcohol, Qula be logical, silane coupling agent, titanate coupling agent, dodecyl two Methylbenzyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, aqueous polyurethane, cetyl trimethylammonium bromide, poly- second One of alkene pyrrolidone, sodium carboxymethylcellulose, methylcellulose, sodium taurocholate, polyethylene glycol oxide, Arabic gum are several Kind.
6. including the preparation side of the high heat-conductivity conducting ceramic matric composite of three-dimensional order graphene according to claim 1 Method, it is characterised in that: the fiber are as follows: carbon fiber, silicon carbide fibre, boron fibre or oxide and other high-temperature ceramic fibres.
7. including the preparation side of the high heat-conductivity conducting ceramic matric composite of three-dimensional order graphene according to claim 1 Method, it is characterised in that: pretreated graphene or untreated graphene are used when prepared by the graphene film.
8. including the preparation side of the high heat-conductivity conducting ceramic matric composite of three-dimensional order graphene according to claim 1 Method, it is characterised in that: the small directed access shape is regular shape or irregular shape；The regular shape be it is round or It is rectangular.
9. including the preparation side of the high heat-conductivity conducting ceramic matric composite of three-dimensional order graphene according to claim 1 Method, it is characterised in that: the small directed access arrangement is orderly or unordered；It is arranged side by side, annular array or Heterogeneous Permutation.
10. including the preparation of the high heat-conductivity conducting ceramic matric composite of three-dimensional order graphene according to claim 1 or 8 Method, it is characterised in that: the small directed access arrangement is equidistant or non-equidistant.
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CN112358315A (en) * 2020-11-27 2021-02-12 西北工业大学 Preparation method of ceramic matrix composite material containing cooling pore channel
CN113831139A (en) * 2021-09-29 2021-12-24 湖北瑞宇空天高新技术有限公司 C/SiC composite material for gas rudder of aerospace engine and preparation method thereof
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CN101484628A (en) * 2006-05-02 2009-07-15 罗尔股份有限公司 Modification of reinforcing fiber tows used in composite materials by using nanoreinforcements
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