CN107892582A - Preparation method of carbon fiber reinforced nanoporous carbon heat-insulation composite material - Google Patents
Preparation method of carbon fiber reinforced nanoporous carbon heat-insulation composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon fiber reinforced nano-pore carbon heat-insulation composite material, and aims to provide a preparation method of a carbon fiber reinforced nano-pore carbon heat-insulation composite material which is short in period, safe and reliable and small in volume shrinkage in a carbonization process. The technical scheme is that phenols and aldehydes are used as reaction monomers, methanol is used as a solvent, hexamethylenetetramine is used as a catalyst, zinc chloride is used as a molten salt to play a role of a pore-forming agent and a supporting role, carbon fibers are used as a reinforcement, firstly, raw materials are mixed to prepare phenolic sol, the phenolic sol is used for impregnating a carbon fiber prefabricated part, the sol becomes gel, the gel is aged at room temperature and then carbonized and cracked, and finally, the carbon fiber reinforced nano-pore carbon heat insulation composite material is obtained through water washing, desalting and normal pressure drying. The method has the advantages of short period, safety, reliability, small volume shrinkage in the carbonization process, small density of the material prepared by the method, temperature resistance of 2000 ℃, no cracking phenomenon and contribution to preparing special-shaped components.
Description
Technical field
The present invention relates to a kind of preparation method of novel heat-insulation composite, more particularly to a kind of superhigh temperature resistant（Inertia or
Under oxygen free condition）Carbon fibe strengthens the preparation method of nano-pore charcoal heat-insulation composite material.
Background technology
Novel high speed aircraft（Generally more than 5 times of velocities of sound）Aerodynamic Heating problem, fuselage table can be produced in high-speed flight
The Aerodynamic Heating in face is extremely serious, and local superhigh temperature spot temperature is even up to 2000 DEG C.Effectively to prevent fuselage surface or super
The heat of high temperature position is propagated to fuselage interior, and thermal protection system active demand possesses the height that superhigh temperature resistant, lightweight and low-heat are led
Performance heat-barrier material.Nano-pore Carbon Materials have the intrinsic intrinsic property of Carbon Materials, superhigh temperature resistant（Can under inertia or vacuum atmosphere
Reach more than 2000 DEG C）【Mater Lett, 2011, 65: 3454-3456】, and due to the nano-pore structure and nanometer of uniqueness
Particle, effectively reduce gas phase heat transfer and solid phase heat transfer, charcoal nano particle has good absorption infra red radiation function again, its
High-temperature heat conductivity is relatively low, is that a kind of potential superhigh temperature resistant high-performance as high-speed aircraft thermal protection system needs is heat-insulated
Material；The conventional preparation method of nano-pore Carbon Materials is roughly divided into template charring and sol-gel process；Template charing normal plane faces
Two hang-ups：First, that organic matter carbon source is uniformly filled into technology in the nano pore of inorganic template is still immature；2nd, to pass through
Cumbersome removing template program, inorganic template is more using silicon oxide compound, goes removing template mainly to use hydrofluoric acid or highly basic
Etch, this pollutes the environment, and determines the key issue of template charing regulation modelling production multi-stage porous Carbon Materials.Colloidal sol-
Gel method production nano-pore Carbon Materials are typically combined with supercritical drying process, and wherein supercritical drying consumes a large amount of liquid
CO2Or ethanol, production cost is added, risk, the yield for improving technical process are small【Rare Metals Materials and engineering,
2009,38(2):1034-1036】.Simple nano-pore charcoal-aero gel low intensity, fragility are big, limit it and are led in superhigh temperature resistant
The application in domain, if composite can be made with fiber reinforcement, improve its mechanical property, then it is potential as high-speed aircraft
New and effective heat-barrier material.However, tradition prepares the sol-gel process of nano-pore Carbon Materials, long preparation period；Solvent is replaced
With supercritical drying process using a large amount of volatile, inflammable organic solvents, production cost and potential safety hazard are added【J.
Sol-Gel Sci. Technol., 2008, 45: 9-15; AIAA, 2012, 5945:1-13】, industrialization production by
Limitation；Larger volume contraction be present into the process of nano-pore Carbon Materials in organogel charing【Feng Jun ancestor charcoal-aero gels and
The preparation of its heat-insulation composite material and performance study National University of Defense technology Ph.D. Dissertations, 2012.06】, cubical contraction
Up to more than 50%, when preparing composite, because the contraction of reinforcement fiber is smaller, reinforcement and the receipts of matrix can be caused
Contracting mismatches, and causes the cracking of composite.Document【Zhi-Long Yu,Guan-Cheng Li,NinaFechler,
NingYang,Zhi-Yuan Ma,XinWang,MarkusAntonietti,and Shu-Hong Yu.Polymerization
under Hypersaline Conditions:A Robust Routeto Phenolic Polymer-Derived Carbon
Aerogels[J].Angew.Chem.Int.Ed.2016,55,1-6】Using molten-salt growth method using phenol and formaldehyde as reaction monomers system
Gone out block nanometer hole Carbon Materials, needed by solvent thermal reaction the shortcomings that the technique, and product expands several times, it is unfavorable
In preparing composite.Patent document CN201510004277.6 discloses a kind of method for preparing porous charcoal, with polycarboxylic acids and
Diamine or using acetic anhydride and diamine as reactant, in metal salt solution reaction form three-dimensional netted prepolymer, then
It is pyrolyzed, obtains porous charcoal, but more micron order macropore be present in this porous charcoal, heat-proof quality is poor；Patent document
CN201310748841.6 discloses a kind of method for preparing charcoal-aero gel, in closed container, by water-soluble saccharides compound
Water is dissolved in water soluble polymer, under the catalysis of acid or alkali, the network structure of crosslinking, warp can be formed by high temperature hydro-thermal reaction
Supercritical drying, then nano-pore charcoal-aero gel is obtained through charing, but the technique does not avoid using supercritical drying；Above specially
By selecting different material and technique, shortening prepares the cycle of porous carbon material, avoided using molten to a certain extent in sharp document
Agent is replaced, but still can not break through the limitation of Conventional processing methods, can not solve the problems, such as that Conventional processing methods are present.Therefore need
It is compound to develop the excellent Carbon fibe enhancing nano-pore charcoal of a kind of short preparation period, safe and reliable new method preparation heat-proof quality
Material.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of highest heatproof up to 2000 DEG C, while technique manufacturing cycle
The preparation method of the Carbon fibe enhancing nano-pore charcoal heat-insulation composite material short, safe and reliable, carbonization process volume contraction is small.
In order to solve the problems such as long preparation period existing for conventional art, potential safety hazard are big, carbonization process volume contraction is big,
Especially with supercritical drying, so as to cause technical process excessive risk, cost high, it is difficult to the problem of large-scale production；This hair
It is bright to propose a kind of new method, shunk by adding zinc chloride in phenolic aldehyde colloidal sol to suppress nano-pore Carbon Materials, prepare Carbon fiber
Dimension enhancing nano-pore charcoal heat-insulation composite material；Using phenols and aldehydes as reaction monomers, alcohols is solvent, and hexamethylenetetramine is to urge
Agent, zinc chloride play a part of pore-foaming agent and support as fused salt, and Carbon fibe first passes around raw material mixing system as reinforcement
Into phenolic aldehyde colloidal sol, with phenolic aldehyde sol impregnation Carbon fibe prefabricated component, after colloidal sol becomes gel, aging at room temperature, it is possible to directly
Charing cracking, whole technical process need not move through solvent displacement and supercritical drying, it is not required that solvent thermal reaction, last water
Remove salt, constant pressure and dry obtains Carbon fibe enhancing nano-pore charcoal heat-insulation composite material.Due to the base for thering is the supporting role of salt to generate
Body nano-pore Carbon Materials do not have larger volume contraction, are matched preferably with Carbon fibe reinforcement, are not in that composite is opened
The phenomenon split.
Superhigh temperature resistant Carbon fibe of the present invention strengthens nano-pore charcoal heat-insulation composite material by Carbon fibe prefabricated component, nano-pore raw material of wood-charcoal
Expect matrix composition；Wherein Carbon fibe refers to the inorganic Carbon fibe of more than 2000 DEG C of heatproof, and Carbon fibe prefabricated component is chopped by Carbon fibe
（3~10cm）Afterwards by arranging or bundle weave forms, the apparent density of Carbon fibe prefabricated component is in 0.06 ~ 0.20g/cm3It
Between.Nano-pore Carbon Materials matrix is that the phenolic resin generated by phenols and aldehyde material is carbon precursor, and zinc chloride is pore-foaming agent,
Alcohol is solvent, is obtained by heating charing, water-washing desalting and constant pressure and dry；Phenolic aldehyde sol impregnation Carbon fibe prefabricated component, pass through
Gel aging, heating charing, water-washing desalting and constant pressure and dry obtain the superhigh temperature resistant Carbon fibe enhancing heat-insulated composite wood of nano-pore charcoal
Material, density is 0.16 ~ 0.57g/cm3, heatproof is up to 2000 DEG C.
Preparation method of the present invention comprises the following steps:
The first step, prepares Carbon fibe prefabricated component, and method is：
The volume size of Carbon fibe prefabricated component as needed and the apparent density of Carbon fibe prefabricated component, apparent density scope are
0.06~0.20g/cm3, using quality=density × Carbon fibe quality, Carbon fibe that will be weighed with mould needed for volume calculating（Will
Ask chopped（3~10cm））Heat when arranging or gripped after weaving, and making Carbon fibe arragement direction perpendicular to heat-insulated use
Direction is flowed, obtains Carbon fibe prefabricated component.
Second step, prepares phenolic aldehyde colloidal sol/salt mixture, and method is：
Using phenols and aldehyde material as raw material, alcohols is solvent, zinc chloride（ZnCl2）For fused salt, hexamethylenetetramine
(C6H12N4) it is catalyst, above-mentioned raw materials press the molar ratio weighing certain with phenols, and the mol ratio of aldehydes and phenols is 2：1, alcohol
Class and the molar ratio range of phenols are 2 ~ 12：1, the molar ratio range of zinc chloride and phenols is 0.5 ~ 5：1, hexamethylenetetramine with
The molar ratio range of phenols is 0.0075 ~ 0.015：1；Then mix, phenolic aldehyde colloidal sol/salt mixture is made；
Phenols described above refers to phenol (C6H5OH), resorcinol（C6H6O2）And hydroquinones（C6H6O2）In any one；
The aldehydes refers to furfural（C5H4O2）With any one in formaldehyde (HCHO) etc.；
The alcohols nail alcohol（CH3OH）, ethanol（C2H5OH）And isopropanol（C3H8O）Deng one kind or any several mixing
Alcohol；
3rd step, prepares Carbon fibe enhancing phenolic aldehyde gel/salt complex, and method is：
Carbon fibe prefabricated component is placed in vacuum impregnation tank, using vacuumizing（-0.1Mpa）Afterwards plus normal pressure（1 atmospheric pressure）Side
Formula carries out sol impregnation：Phenolic aldehyde colloidal sol is penetrated into Carbon fibe prefabricated component using vacuum impregnation mode first, treats that phenolic aldehyde colloidal sol oozes
After entering Carbon fibe prefabricated component, the valve of vacuum impregnation tank is opened so that the pressure in vacuum impregnation tank is changed into normal pressure, at ambient pressure
Aging 3 ~ 48 hours so that the phenolic aldehyde colloidal sol in Carbon fibe prefabricated component becomes phenolic aldehyde gel, obtain Carbon fibe enhancing phenolic aldehyde gel/
Salt complex.
4th step, charing cracking, method are：
Carbon fibe enhancing phenolic aldehyde gel/salt complex is put into tube furnace, first vacuumize then to tube furnace be filled with argon gas or
Nitrogen, a small amount of air for remaining 1 ~ 5 time in tube furnace is replaced, then 650 are warming up to 1.0 ~ 5.0 DEG C/min programming rates ~
2000 DEG C, in this temperature 1 ~ 5 hour, then natural cooling, whole process were passed through argon gas or nitrogen with 20 ~ 200ml/min flow
Gas, obtain Carbon fibe enhancing nano-pore charcoal/salt complex.
5th step, water-washing desalting, method are：
Carbon fibe enhancing nano-pore charcoal/salt complex is immersed in the watery hydrochloric acid that mass concentration is 10%, soak time 2 ~ 6 is small
When, Carbon fibe is strengthened to zinc oxide a small amount of in nano-pore charcoal/salt complex（ZnO）Remove, then be immersed in water, every 3 ~ 12
Hour changes a water, such cyclic permutation water 4 ~ 8 times, removes zinc chloride therein（ZnCl2）, obtain Carbon fibe enhancing nano-pore
Charcoal/water complex；
6th step, constant pressure and dry, method are：
Carbon fibe enhancing nano-pore charcoal/water complex is placed in baking oven or Muffle furnace, is warming up to 100 ~ 200 DEG C, insulation 1 ~
24 hours, Carbon fibe enhancing nano-pore charcoal heat-insulation composite material is obtained after cooling.
Following beneficial effect can be reached using the present invention
The present invention is based on sol-gel technique and molten-salt growth method, reacts the phenolic resin generated as carbon precursor using phenols and aldehydes,
Alcohols is solvent, and hexamethylenetetramine is catalyst, and zinc chloride is pore-foaming agent, after being first prepared by mixing into colloidal sol, then with Carbon fibe
Prefabricated component mixes, and is cracked by gel aging, charing, then obtains Carbon fibe enhancing after water-washing desalting, constant pressure and dry processing
Nano-pore charcoal heat-insulation composite material.
Therefore, the present invention has following advantage compared with prior art：
（1）Preparation technology of the present invention is simple, and the cycle is short.Fiber preform is made with Carbon fibe in the present invention, and wherein Carbon fibe is prefabricated
The apparent density scope of part is 0.06 ~ 0.20g/cm3, the Carbon fibe weighed is gripped with mould, and arrange Carbon fibe
Direction of heat flow when cloth direction is perpendicular to heat-insulated use, obtain Carbon fibe prefabricated component.Using phenols and aldehydes as reaction monomers, alcohols
For solvent, hexamethylenetetramine is catalyst, and zinc chloride is pore-foaming agent, and after being first prepared by mixing into colloidal sol, then vacuum adds normal pressure to soak
Stain Carbon fibe prefabricated component, Carbon fibe enhancing nano-pore charcoal is obtained by gel aging, charing cracking, water-washing desalting and constant pressure and dry
Heat-insulation composite material.The main step of time-consuming step the 4th charing cracking, the 5th step water-washing desalting and the 6th step constant pressure and dry respectively need to use
Shi Yitian, whole technique is simple, about 3 ~ 4 days total used times, compared with time-consuming more than the 20 days sol-gel process of tradition, production week
Phase is short；Compared with template charring, not using template, just cumbersome removing template program is not had to, although using zinc chloride yet
As pore-foaming agent, but zinc chloride is highly soluble in water, and the can that is soaked in water removes the zinc chloride in product, and passes through evaporation
Water can recycle zinc chloride, and environment will not be polluted.
（2）Potential safety hazard of the present invention is small, and cost is cheap.The present invention is single as reaction using cheap phenols and aldehydes
Body, raw material are easy to get, and whole technique avoids solvent displacement and the supercritical drying that traditional handicraft generally uses, solvent displacement
Need to consume substantial amounts of organic solvent, supercritical drying needs high-temperature high-pressure apparatus（Such as ethanol, 243 DEG C of critical-temperature, critical pressure
Power 6.30MPa）, dangerous high, yield is small, it is difficult to carries out large-scale production；Constant pressure and dry can is only needed to remove in the 6th step
The moisture gone in product, energy consumption is low, greatly reduces production cost, and potential safety hazard is small, is easy to large-scale production.And the technique
Compared to document【Zhi-Long Yu,Guan-Cheng Li,NinaFechler,NingYang,Zhi-Yuan Ma,XinWang,
MarkusAntonietti,and Shu-Hong Yu.Polymerization under Hypersaline Conditions:
A Robust Routeto Phenolic Polymer-Derived Carbon Aerogels[J]
.Angew.Chem.Int.Ed.2016,55,1-6 is i.e. imperial in will, Li Guancheng, Nina Fechler, Yang Ning, Ma Zhiyuan, Wang Xin,
Markus Antonietti, and the grand of Yu's book polymerize under high salt conditions：It is a kind of that charcoal airsetting is simply derived by novolac polymer
Preparation method [J] the Germany applied chemistry of glue can will .2016,55,1-6.】The method for preparing the use of nano-pore Carbon Materials, is not required to
Solvent thermal reaction is wanted, product does not expand.
（3）The Carbon fibe enhancing nano-pore charcoal heat-insulation composite material thermal conductivity prepared using the present invention is low, and heatproof is high.
Four steps carbonize cracking process, and zinc chloride plays a part of pore-foaming agent so that more nano-pore structures are formed in matrix Carbon Materials, by
There is some strength in charcoal skeleton, after water-washing desalting and constant pressure and dry, nano-pore structure remains to remain behind, nano-pore knot
Structure aperture is mainly distributed between 0.6 ~ 25nm, and specific surface area is up to 1300m2/ g, effectively suppress heat transfer, charcoal nano particle is again
With good absorption infra red radiation function, help to reduce thermal conductivity, prepared Carbon fibe enhancing nano-pore charcoal is heat-insulated multiple
Condensation material is 0.122 ~ 0.478W/mK in 2000 DEG C of thermal conductivity；Prepared Carbon fibe enhancing nano-pore charcoal is heat-insulated compound
Material has the intrinsic intrinsic property of Carbon Materials（Energy heatproof is up to 2000 DEG C under oxygen-free environment）, in 2000 DEG C of oxygen-free environment
Under, nano-pore structure will not occur significantly to cave in or shrink.
（4）The Carbon fibe enhancing nano-pore charcoal heat-insulation composite material surface prepared using the present invention will not ftracture, more favorably
In preparing abnormity component.In the 4th step carbonizes cracking process, the phenolic resin of phenols and aldehyde material reaction generation is due to having
Volume contraction will not occur for the support of salt, have good matching and uniformity with Carbon fibe so that Carbon fibe strengthens nanometer
Hole charcoal heat-insulation composite material surface will not ftracture；Solve and produce 50% in conventional method in organogel carbonization process with upper body
The problem of product is shunk, is more beneficial for preparing composite and abnormity component.
Brief description of the drawings
Fig. 1 is overview flow chart of the present invention.
Embodiment
Below for the invention will be further described in conjunction with the embodiments, but these embodiments must not be used to explain to the present invention
The limitation of protection domain.
Embodiment 1：
（1）Prepare Carbon fibe prefabricated component：It is real according to the volume size of Carbon fibe prefabricated component and the apparent density of Carbon fibe prefabricated component
The apparent density for applying the Carbon fibe prefabricated component of the design of example 1 is 0.10g/cm3, the Carbon fibe weighed is gripped with mould, and
And direction of heat flow when making Carbon fibe arragement direction perpendicular to heat-insulated use, obtain Carbon fibe prefabricated component；
（2）Prepare phenolic aldehyde colloidal sol/salt mixture：Using resorcinol and furfural as reaction monomers, methanol is solvent, and zinc chloride is molten
Salt is as pore-foaming agent, detailed process：First zinc chloride is placed in beaker, sequentially adds methanol and furfural, is stirred 25 points
Zhong Hou, adds resorcinol and hexamethylenetetramine, stirs 20 minutes, resorcinol is fully dissolved, obtain phenolic aldehyde colloidal sol/
Salt mixture；Wherein, furfural：Methanol：Zinc chloride：Hexamethylenetetramine：The mol ratio of resorcinol is 2：12：5：0.015：1；
（3）Prepare Carbon fibe enhancing phenolic aldehyde gel/salt complex：The Carbon fibe prefabricated component prepared is placed on vacuum impregnation tank
In, add normal pressure mode to carry out sol impregnation using after vacuumizing：Phenolic aldehyde colloidal sol is penetrated into by Carbon fiber using vacuum impregnation mode first
Tie up in prefabricated component, after phenolic aldehyde colloidal sol penetrates into Carbon fibe prefabricated component, open valve and cause the pressure in impregnating autoclave to be changed into normal pressure,
Aging 24 hours under normal pressure so that the colloidal sol in Carbon fibe prefabricated component becomes gel, and it is multiple to obtain Carbon fibe enhancing phenolic aldehyde gel/salt
It is fit；
（4）Heating charing：Carbon fibe enhancing phenolic aldehyde gel/salt complex is put into tube furnace, first vacuumizes and is then charged with argon
Gas, replaces air therein 2 times, is then warming up to 650 DEG C with 2 DEG C/min, is incubated 2 hours at 650 DEG C, then natural cooling,
Whole process is passed through argon gas with 50mL/min Ventilation Rate；Obtain Carbon fibe enhancing nano-pore charcoal/salt complex；
（5）Water-washing desalting：Carbon fibe enhancing nano-pore charcoal/salt complex is immersed in the watery hydrochloric acid that mass concentration is 10%, leaching
4 hours time is steeped, removes zinc oxide a small amount of in Carbon fibe enhancing nano-pore charcoal/salt complex（ZnO）, then it is immersed in
In deionized water, a water is changed within 4 hours, such cyclic permutation water 6 times, remove zinc chloride therein（ZnCl2）, obtain Carbon fibe
Strengthen nano-pore charcoal/water complex；
（6）Constant pressure and dry：Carbon fibe enhancing nano-pore charcoal/water complex is placed in normal pressure baking oven, 120 DEG C is warming up to, protects
Temperature 24 hours, Carbon fibe enhancing nano-pore charcoal heat-insulation composite material is can obtain after cooling.Carbon fibe manufactured in the present embodiment increases
Strong nano-pore charcoal heat-insulation composite material density is 0.19g/cm3, thermal conductivity is 0.152W/mK at 2000 DEG C.
Embodiment 2 ~ 243
When second step prepares phenolic aldehyde colloidal sol, furfural：The mol ratio of resorcinol is 2:1 determines constant, aldehydes and aldehydes matter
Generation phenolic resin react mainly as charcoal source, in the case where dosage is consistent, which kind of aldehydes described above or phenol used
Class material has no significant effect to product property；Cracking process is carbonized in the 4th step, argon gas or nitrogen are filled with tube furnace, is to make
Phenolic aldehyde gel/salt complex is under inert atmosphere, prevents it to be oxidized in the case of a high temperature, the anaerobic ring in tube furnace is ensured
In the case of border, be filled with argon gas or nitrogen, displaced air number, be passed through the flow of argon gas or nitrogen to product property without obvious shadow
Ring, according to the differential of phenolic aldehyde gel-scanning thermogravimetric analysis, rational heating schedule is set, can so slow down the charing of phenolic aldehyde gel
The severe degree of cracking；5th step water-washing desalting process, this process mainly remove zinc oxide and zinc chloride in product, first will
Product, which is immersed in watery hydrochloric acid, removes zinc oxide, then product is immersed in water, and soak time is longer or replaces the number of water more
It is more, be more advantageous to desalination, soak time length, replacing the number of water can accordingly be reduced, as long as the salt in product is depleted, be further added by
Replace the number of water or extend soak time and the performance of product is had no significant effect.5th step constant pressure and dry process, is mainly removed
Whether the water that the water gone in composite, drying temperature and soaking time are depended primarily in composite eliminates completely, 100
The 24 hours water that can be eliminated completely in composite of ~ 200 DEG C of insulations, drying time and soaking time strengthen nanometer to Carbon fibe
The performance impact of hole carbon composite is little.Therefore, conditions above strengthens Carbon fibe the property of nano-pore charcoal heat-insulation composite material
It can not produce and significantly affect, therefore technological parameter is as shown in table 1 used by embodiment 2 ~ 243, not listed experiment work in table
Skill parameter is same as Example 1.As it can be seen from table 1 the Carbon fibe enhancing nano-pore charcoal prepared using the present invention is heat-insulated compound
Material is 0.122 ~ 0.478W/mK in 2000 DEG C of thermal conductivity, and least density is only 0.16g/cm3, and due to there is the branch of salt
Support, which acts on, causes the matrix nano hole Carbon Materials of generation not have larger volume contraction, is matched with Carbon fibe reinforcement preferably,
It is not in the phenomenon of composite cracking.So using the composite for preparing of the present invention can high temperature resistant, and lightly, be adapted to
High temperature inert atmosphere furnace or high-speed aircraft thermal protection system field.
The Carbon fibe of table 1 strengthens nano-pore charcoal heat-insulation composite material preparation technology parameter and material property parameter
Claims (10)
1. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material, it is characterised in that comprise the following steps:
The first step, prepares Carbon fibe prefabricated component, and method is：
The volume size of Carbon fibe prefabricated component as needed and the apparent density of Carbon fibe prefabricated component, using quality=density ×
Carbon fibe quality needed for volume calculating, is gripped, and make Carbon fibe after the Carbon fibe weighed is arranged or woven with mould
Direction of heat flow when arragement direction is perpendicular to heat-insulated use, obtain Carbon fibe prefabricated component；
Second step, prepares phenolic aldehyde colloidal sol, and method is：
Using phenols and aldehyde material as raw material, alcohols is solvent, and zinc chloride is ZnCl2For fused salt, hexamethylenetetramine is C6H12N4
For catalyst, above-mentioned raw materials press the molar ratio weighing certain with phenols, and the mol ratio of aldehydes and phenols is 2：1, alcohols and phenols
Molar ratio range be 2 ~ 12：1, the molar ratio range of zinc chloride and phenols is 0.5 ~ 5：1, hexamethylenetetramine and phenols rub
You are 0.0075 ~ 0.015 than scope：1；Then mix, phenolic aldehyde colloidal sol is made；
3rd step, prepares Carbon fibe enhancing phenolic aldehyde gel/salt complex, and method is：
Carbon fibe prefabricated component is placed in vacuum impregnation tank, adds normal pressure mode to carry out sol impregnation using after vacuumizing：First
Phenolic aldehyde colloidal sol is penetrated into Carbon fibe prefabricated component using vacuum impregnation mode, after phenolic aldehyde colloidal sol penetrates into Carbon fibe prefabricated component, beaten
The valve of vacuum impregnation tank is opened so that the pressure in vacuum impregnation tank is changed into normal pressure, aging at ambient pressure so that Carbon fibe is prefabricated
Phenolic aldehyde colloidal sol in part becomes phenolic aldehyde gel, obtains Carbon fibe enhancing phenolic aldehyde gel/salt complex；
4th step, Carbon fibe is strengthened into phenolic aldehyde gel/salt complex and carries out charing cracking, obtain Carbon fibe enhancing nano-pore charcoal/
Salt complex；
5th step, Carbon fibe is strengthened into nano-pore charcoal/salt complex and carries out water-washing desalting, obtain Carbon fibe enhancing nano-pore charcoal/
Water complex；
6th step, Carbon fibe is strengthened into nano-pore charcoal/water complex and carries out constant pressure and dry, obtain Carbon fibe enhancing nano-pore charcoal every
Hot composite.
2. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material as claimed in claim 1, its feature exist
Refer to the inorganic Carbon fibe of more than 2000 DEG C of heatproof in Carbon fibe described in the first step, and require to be chopped into 3 ~ 10cm, the Carbon fibe
The apparent density scope of prefabricated component is 0.06 ~ 0.20g/cm3。
3. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material as claimed in claim 1, its feature exist
Refer to phenol i.e. C in phenols described in second step6H5OH, resorcinol are C6H6O2It is C with hydroquinones6H6O2In any one.
4. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material as claimed in claim 1, its feature exist
Refer to furfural i.e. C in aldehydes described in second step5H4O2It is any one in HCHO with formaldehyde.
5. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material as claimed in claim 1, its feature exist
In alcohols nail alcohol described in second step be CH3OH, ethanol are C2H5OH and isopropanol are C3H8One kind in O is any several mixed
Close alcohol.
6. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material as claimed in claim 1, its feature exist
It is -0.1Mpa to refer to air pressure in vacuum described in the 3rd step, and the normal pressure refers to 1 atmospheric pressure.
7. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material as claimed in claim 1, its feature exist
In ageing time described in the 3rd step be 3 ~ 48 hours.
8. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material as claimed in claim 1, its feature exist
It is that Carbon fibe enhancing phenolic aldehyde gel/salt complex is put into tube furnace in the method for carbonizing cracking described in the 4th step, first takes out true
It is empty to be then filled with argon gas or nitrogen, the air remained in displacement tube furnace 1 ~ 5 time, then with 1.0 ~ 5.0 DEG C/min to tube furnace
Programming rate is warming up to 650 ~ 2000 DEG C, and in this temperature 1 ~ 5 hour, then natural cooling, whole process was with 20 ~ 200ml/min
Flow be passed through argon gas or nitrogen, obtain Carbon fibe enhancing nano-pore charcoal/salt complex.
9. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material as claimed in claim 1, its feature exist
It is in the method for water-washing desalting described in the 5th step：Carbon fibe enhancing nano-pore charcoal/salt complex is immersed in mass concentration as 10%
Watery hydrochloric acid in, soak time 2 ~ 6 hours, it is that ZnO is removed that Carbon fibe is strengthened into zinc oxide a small amount of in nano-pore charcoal/salt complex
Go, then be immersed in water, changed a water every 3 ~ 12 hours, such cyclic permutation water 4 ~ 8 times, remove zinc chloride therein, obtain
To Carbon fibe enhancing nano-pore charcoal/water complex.
10. a kind of preparation method of Carbon fibe enhancing nano-pore charcoal heat-insulation composite material as claimed in claim 1, its feature exist
It is in the method for constant pressure and dry described in the 6th step：Carbon fibe enhancing nano-pore charcoal/water complex is placed on baking oven or Muffle furnace
In, 100 ~ 200 DEG C are warming up to, is incubated 1 ~ 24 hour, Carbon fibe enhancing nano-pore charcoal heat-insulation composite material is obtained after cooling.
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| CN108640699A (en) * | 2018-04-28 | 2018-10-12 | 中国人民解放军国防科技大学 | Method for preparing carbon/carbon preformed body by recycling carbon fiber reinforced resin matrix composite material |
| CN110698169A (en) * | 2019-11-21 | 2020-01-17 | 哈尔滨工业大学 | Preparation method of high-temperature-resistant quartz fiber needled felt/phenolic resin composite carbonized derivative |
| CN110774604A (en) * | 2019-10-10 | 2020-02-11 | 江阴海达橡塑股份有限公司 | Method for opening holes in foamed sponge product |
| WO2020127214A1 (en) * | 2018-12-19 | 2020-06-25 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Process for producing a porous fibre composite material, fibre composite material and use of said fibre composite material |
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