CN106478124A - A kind of preparation method of porous charcoal heat-insulation composite material - Google Patents
A kind of preparation method of porous charcoal heat-insulation composite material Download PDFInfo
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- CN106478124A CN106478124A CN201610846385.2A CN201610846385A CN106478124A CN 106478124 A CN106478124 A CN 106478124A CN 201610846385 A CN201610846385 A CN 201610846385A CN 106478124 A CN106478124 A CN 106478124A
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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Abstract
The invention discloses a kind of preparation method of porous charcoal heat-insulation composite material, it is therefore an objective to solve the problems such as volume contraction is big, potential safety hazard is big in existing porous charcoal heat-insulation composite material preparation method process cycle length, carbonization process.Technical scheme be using ionic liquid as charcoal precursor; eutectic saline admixture is used as pore-foaming agent; inorganic Carbon fibe prefabricated component is used as reinforcement; first by ionic liquid and eutectic saline admixture ground and mixed; heat up under high-pressure inert gas protection and mix with Carbon fibe prefabricated component after melting; continuing intensification makes ionic liquid carbonize to form porous charcoal, obtains Carbon fibe and strengthen porous charcoal/salt complex, then obtain Carbon fibe after cooling water washing dries strengthening porous charcoal heat-insulation composite material.Preparation process is simple of the present invention, cycle is short, potential safety hazard is little, environmental protection, and the Carbon fibe enhancing porous charcoal heat-insulation composite material thermal conductivity for preparing is low, and heat-proof quality is good, and surface will not be ftractureed, and is more beneficial for preparing abnormity component.
Description
Technical field
The present invention relates to a kind of preparation method of heat-barrier material, the heat-insulated composite wood of more particularly to a kind of superhigh temperature resistant porous charcoal
The preparation method of material.
Background technology
With the development of the gradually deep and military hi-tech weaponry of the external space probation of the mankind, new space travel
The flying speed of device is improved constantly, and material military service thermal environment is severe all the more, and therefore active demand lightweight, superhigh temperature resistant, low-heat are led
Novel high-performance heat-barrier material.Porous carbon material has an intrinsic intrinsic property of Carbon Materials, such as resistance under inertia or oxygen-free environment
Superhigh temperature, radiation hardness, and as unique pore structure is so as to relatively low thermal conductivity, these advantages become its great potential
Superhigh temperature resistant high-performance insulation material of new generation, is applied in the thermal protection system of new aerospace craft.Be applied at present every
The porous carbon material in hot field can be roughly divided into micron openings carbon foams, nanostructured charcoal-aero gel.Micron openings carbon foams material is
A kind of light porous material being made up of hole bubble and interconnective hole steep that wall, in absorption, catalyst carrier, anti-shielding, inhales ripple
There is huge application potential in field, become typical low-density high thermal conductivity material after graphitization processing, without graphitization
Processing warm often, conductance is minimum also 0.109W/m K, and the advantage in the heat-insulated field of superhigh temperature is not obvious.Patent document
CN201310390890.7 discloses a kind of preparation method of nano montmorillonite modified resin base carbon foams heat-barrier material, steeps charcoal
Thermal conductivity of the foam material at 800 DEG C is down to 0.588W/m K by 0.854W/m K, reduces carbon foams to a certain extent
The thermal conductivity of material, improves its heat-proof quality, but effect is undesirable.Nanostructured charcoal-aero gel is at present in all aeroges
Using temperature highest one kind (up to more than 2200 DEG C under inertia or oxygen-free environment), and the relatively low (heat under normal temperature of thermal conductivity
Conductance is less than the thermal conductivity 0.025W/m K of air), this is that have nano-pore and nanoparticle structure due to which, effectively reduces
Solid thermal conductance and heat conductivity of gas, charcoal nano particle itself have fabulous assimilation effect, reduce again to infra-red radiation
Its radiant heat conductanc.The conventional method for preparing charcoal-aero gel is needed through collosol and gel supercritical drying charing etc. mainly
Processing step, suffers from the drawback that：Complex process, cycle are long, and especially two steps of gel and supercritical drying are time-consuming very long,
Complete technological process takes around 20 days；Great volume can occur during organic aerogel carbonizes into charcoal-aero gel
Shrink, up to more than 50%, if composite is prepared, as reinforcement fiber shrinks very little, therefore can cause composite table
Face is ftractureed, and is unfavorable for preparing abnormity component；Organic solvent, organic solvent are used in a large number in gel and supercritical drying stage
Volatile, inflammable, there is larger potential safety hazard【Sol-Gel Science and technical journal, 2008,45:9-15；AIAA,
2012,5945:1-13】.Therefore the porous that a kind of short new process of simple and reliable, process cycle prepares lower thermal conductivity is found
Charcoal heat-insulation composite material is one of following main research direction, and patent document CN201310556326.8 discloses a kind of porous
The preparation method of charcoal-aero gel tiny balloon, it is spherical resistance to that patent document CN201210190952.5 discloses a kind of charcoal-aero gel base
The preparation method of corrosion magnetic material, by adding dispersant, surfactant, template in certain journey in patent documents above
The collosol and gel time is accelerated on degree, is shortened process cycle, but still is not broken through the restriction of Conventional processing methods, it is impossible to
Solve the problems, such as Conventional processing methods.
Content of the invention
The technical problem to be solved in the present invention be provide a kind of short superhigh temperature resistant porous charcoal of safe and reliable, process cycle every
The preparation method of hot composite, solves the preparation process complex process of porous charcoal heat-insulation composite material, and the cycle is long, prepares
The low problem of material thermal conductivity.
In order to overcome process cycle length that conventional art is present, volume contraction is big, potential safety hazard is big in carbonization process etc. lacks
Point, the present invention propose a kind of new method, prepare superhigh temperature resistant porous charcoal using the molten-salt growth method under high ambient pressure heat-insulated multiple
Condensation material.Using ionic liquid as charcoal precursor, eutectic saline admixture as pore-foaming agent, inorganic Carbon fibe prefabricated component conduct
Reinforcement, first by ionic liquid and eutectic saline admixture ground and mixed, heat up under high-pressure inert gas protection melting
Mix with Carbon fibe prefabricated component afterwards, continuing intensification makes ionic liquid carbonize porous charcoal is formed, obtain Carbon fibe and strengthen porous charcoal/salt
Complex, then Carbon fibe enhancing porous charcoal heat-insulation composite material is obtained after cooling water washing dries.
Superhigh temperature resistant porous charcoal heat-insulation composite material of the present invention is made up of Carbon fibe prefabricated component, nanoporous carbon matrix；Charcoal
Fiber preform by inorganic Carbon fibe be chopped (3～8cm) after arrange obtain or inorganic Carbon fibe bundle braiding form, inorganic Carbon fiber
Dimension refers to the inorganic Carbon fibe of more than 2000 DEG C of heatproof, and the apparent density of Carbon fibe prefabricated component is in 0.10～0.20g/cm3Between；Receive
Meter Duo Kong carbon matrix is charcoal precursor by ionic liquid, and eutectic saline admixture is pore-foaming agent, lazy in high pressure after ground and mixed
Property gas shield under heat up melting charing after obtain；The density of superhigh temperature resistant porous charcoal heat-insulation composite material is 0.08～0.28g/
cm3, up to 2000 DEG C, 2000 DEG C of thermal conductivities are 0.312～0.401W/m K to heatproof.
Preparation method of the present invention is comprised the following steps：
The first step, arranges clamping Carbon fibe and prepares Carbon fibe prefabricated component, as the reinforcement of porous charcoal heat-insulation composite material
The Carbon fibe prefabricated component apparent density scope of design is 0.10～0.20g/cm3, according to the body of Carbon fibe prefabricated component
Product size and Carbon fibe prefabricated component apparent density, Carbon fibe quality needed for being calculated using quality=density × volume, make when arranging
The Carbon fibe that arranges is clamped with the graphite fixture of punching by Carbon fibe arragement direction perpendicular to direction of heat flow during heat-insulated use
Fixing, obtain Carbon fibe prefabricated component；
Second step, weighs and prepares ionic liquid/salt blend thing
The 2.1 eutectic saline admixtures for weighing the pore-foaming agent as porous charcoal heat-insulation composite material：Low used by the present invention
Congruent melting saline admixture is made up of two kinds of salt, weighs preparation according to the mass ratio at eutectic point in the binary phase diagraml of both salt low
Congruent melting saline admixture；
The eutectic saline admixture is KCl/ZnCl2、LiCl/ZnCl2、NaCl/ZnCl2；
2.2 ionic liquids for weighing the carbon precursor as porous charcoal heat-insulation composite material：Common with low according to ionic liquid
The quality of load weighted eutectic saline admixture in the mass ratio of molten saline admixture and 2.1, using ionic liquid quality=
Quality × the ionic liquid of eutectic saline admixture calculates desired ion liquid matter with the mass ratio of eutectic saline admixture
Amount, and weigh and obtain desired ion liquid；
The ionic liquid be 1- ethyl-3-methylimidazole cdicynanmide, N- butyl -3- picoline cdicynanmide (N refers to nitrogen),
1- butyl -3- picoline cdicynanmide；
The ionic liquid is 0.1～0.6 with the scope of the mass ratio of eutectic saline admixture；
2.3, by load weighted eutectic saline admixture and ionic liquid ground and mixed, obtain ionic liquid/salt blend
Thing；
3rd step, using the molten-salt growth method under high ambient pressure, carries out, to ionic liquid/salt blend thing, the melting charing that heats up
Ionic liquid/salt blend thing and Carbon fibe prefabricated component are put in pressure pan, start pre- filling with inert gas (nitrogen or
Argon gas) as protective atmosphere, after the pressure of inert gas reaches pressure threshold, it is heated to according to the heating schedule for setting
600 DEG C, pressure is slowly discharged with the speed of 500kPa/min, be continuously heating to carbonize maximum temperature, ion after pressure release to normal pressure
Liquid charing cracking forms charcoal skeleton, obtains Carbon fibe and strengthen porous charcoal/salt complex after cooling；
The scope of the pressure threshold of the inert gas is 1～10MPa；
The scope of the charing maximum temperature is 900～1400 DEG C；
The heating schedule is：
When ionic liquid chooses 1- ethyl-3-methylimidazole cdicynanmide：140～160 DEG C, 240～260 DEG C, 440～
The heating rate scope of 460 DEG C of three temperature stage is 0.5～1.5 DEG C/min, in room temperature to other temperature for carbonizing maximum temperature
The heating rate scope for spending the stage is 2～10 DEG C/min；
When ionic liquid chooses N- butyl -3- picoline cdicynanmide：180～200 DEG C, 250～270 DEG C, 460～
The heating rate scope of 480 DEG C of three temperature stage is 0.5～1.5 DEG C/min, in room temperature to other temperature for carbonizing maximum temperature
The heating rate scope for spending the stage is 2～10 DEG C/min；
When ionic liquid chooses 1- butyl -3- picoline cdicynanmide：150～170 DEG C, 230～250 DEG C, 450～
The heating rate scope of 470 DEG C of three temperature stage is 0.5～1.5 DEG C/min, in room temperature to other temperature for carbonizing maximum temperature
The heating rate scope for spending the stage is 2～10 DEG C/min；
4th step, strengthening porous charcoal/salt complex to Carbon fibe carries out washing replacement Treatment
Carbon fibe is strengthened porous charcoal/salt complex carries out washing replacement Treatment, method be by Carbon fibe strengthen porous charcoal/
Salt complex is put in clean water and soaks, and changes a clean water every 2～5 hours.After changing water 4～8 times, you can obtain charcoal
Fiber reinforcement porous charcoal/water complex；
5th step, strengthening porous charcoal/water complex to Carbon fibe carries out constant pressure and dry process
Carbon fibe is strengthened porous charcoal/water complex to carry out constant pressure and dry process (constant pressure and dry refers under an atmospheric pressure
Drying), method is Carbon fibe to be strengthened porous charcoal/water complex be put in constant pressure and dry equipment, is heated to 130～150 DEG C,
Insulation 15～24 hours, is obtained superhigh temperature resistant Carbon fibe and strengthens porous charcoal heat-insulation composite material after cooling；
The constant pressure and dry equipment is chamber dryer, tunnel dryer, belt dryer.
Following beneficial effect can be reached using the present invention：
The present invention based on the molten-salt growth method under high ambient pressure, with 1- ethyl-3-methylimidazole cdicynanmide, N- butyl -3- first
Yl pyridines cdicynanmide, 1- butyl -3- picoline cdicynanmide plasma liquid are charcoal precursor, KCl/ZnCl2、LiCl/ZnCl2、
NaCl/ZnCl2It is pore-foaming agent Deng eutectic saline admixture, Carbon fibe prefabricated component mixes, heats up through weighing as reinforcement
Melt, charing is cracked, then Carbon fibe is obtained after washing displacement, constant pressure and dry process strengthen porous charcoal heat-insulation composite material.
Therefore, the present invention has following advantage compared with prior art：
(1) preparation process is simple of the present invention, cycle is short.Fiber preform is made with Carbon fibe in the first step of the present invention, its
The apparent density scope of middle Carbon fibe prefabricated component is 0.10～0.20g/cm3, will be solid for Carbon fibe clamping with the graphite fixture of punching
Fixed, and make Carbon fibe arragement direction perpendicular to direction of heat flow during heat-insulated use, obtain Carbon fibe prefabricated component；In second step with
Used as charcoal precursor, eutectic saline admixture obtains ionic liquid/salt as pore-foaming agent to ionic liquid after both ground and mixed
Blend；3rd step in the 5th step by ionic liquid/salt blend thing together with Carbon fibe prefabricated component heat temperature raising, through intensification
Melting, charing cracking, washing displacement, constant pressure and dry can prepare Carbon fibe and strengthen porous charcoal heat-insulation composite material.Mainly
Processing step is the 3rd step, the 4th step, the 5th step, that is, the melting charing that heats up, washing displacement, constant pressure and dry, all only needs about 1
My god, whole technological process is only needed 3～5 days, with short production cycle, time-consuming more than 20 day with conventional method compared with, be more suitable for industrial metaplasia
Produce.
(2) the Carbon fibe enhancing porous charcoal heat-insulation composite material thermal conductivity that prepared by the present invention is low, and heat-proof quality is good.By height
It is nano material that the Carbon fibe that molten-salt growth method is prepared under ambient pressure strengthens the porous carbon matrix of porous charcoal heat-insulation composite material,
Pore structure and skeleton particle are nanoscale, and density is low, and pore size distribution is uniform, and BET specific surface area is up to 2000m2/ more than g, to solid
Body heat transferring and gas heat-transfer have good iris action, contribute to reducing thermal conductivity.The Carbon fibe that the present invention is obtained strengthens porous
1500 DEG C and 2000 DEG C thermal conductivities of charcoal heat-insulation composite material are respectively 0.233～0.298W/m K and 0.312～0.401W/m
K.And the Carbon fibe prepared using the charing of conventional sol gel supercritical drying strengthens the heat-insulated composite wood of porous charcoal
2000 DEG C of thermal conductivities of material are 0.325～0.486W/m K, it is seen that Carbon fibe prepared by the present invention strengthens the heat-insulated composite wood of porous charcoal
The thermal conductivity of material is lower, and effect of heat insulation is more preferable.
(3) Carbon fibe prepared by the present invention strengthens porous charcoal heat-insulation composite material surface and will not ftracture, and is more beneficial for preparing
Abnormity component.Ionic liquid in the 3rd step of the present invention as charcoal precursor will not occur volume to receive in charing cracking process
Contracting, has good matching and uniformity with Carbon fibe, and the Carbon fibe for preparing strengthens porous charcoal heat-insulation composite material table
Face will not be ftractureed, and solve the problems, such as to produce more than 50% volume contraction in organogel carbonization process in conventional method, more have
It is beneficial to prepare composite and abnormity component.
(4) present invention prepares that potential safety hazard is little, environmental protection.The present invention adopts 1- ethyl-3-methylimidazole cdicynanmide, N-
Butyl -3- picoline cdicynanmide, 1- butyl -3- picoline cdicynanmide plasma liquid are charcoal precursor, and ionic liquid has
There are fixedness, incombustibility；The drying process of the 5th step adopts constant pressure and dry, compares the supercritical drying process of conventional method
In in a large number using inflammable and explosive organic solvent, potential safety hazard is less；Eutectic saline admixture as pore-foaming agent is not involved in
Reaction, after the washing of the 4th step is cemented out, can recycle.Therefore potential safety hazard of the present invention is little, and environmental protection is more suitable for work
Industry metaplasia is produced.
Description of the drawings
Fig. 1 is the overview flow chart of the present invention.The inventive method is comprised the following steps：
The first step, arranges clamping Carbon fibe and prepares Carbon fibe prefabricated component；
Second step, weighs and prepares ionic liquid/salt blend thing；
3rd step, carries out, to ionic liquid/salt blend thing, the melting charing that heats up；
4th step, strengthening porous charcoal/salt complex to Carbon fibe carries out washing replacement Treatment；
5th step, strengthening porous charcoal/water complex to Carbon fibe carries out constant pressure and dry process.
Specific embodiment
Below for the invention will be further described in conjunction with the embodiments, but these embodiments must not be used for explaining to the present invention
The restriction of protection domain.
Embodiment 1：
(1) arrange clamping Carbon fibe and prepare Carbon fibe prefabricated component：The Carbon fibe prefabricated component apparent density of design is 0.13g/
cm3, according to volume size and the Carbon fibe prefabricated component apparent density of Carbon fibe prefabricated component, calculated using quality=density × volume
Required Carbon fibe quality, makes Carbon fibe arragement direction perpendicular to direction of heat flow during heat-insulated use, with the graphite of punching when arranging
The Carbon fibe that arranges is gripped by fixture, obtains Carbon fibe prefabricated component；
(2) weigh and prepare 1- ethyl-3-methylimidazole cdicynanmide/KCl/ZnCl2Blend：
The 2.1 eutectic saline admixture KCl/ZnCl for weighing the pore-foaming agent as porous charcoal heat-insulation composite material2：Using
KCl/ZnCl2This eutectic saline admixture, by KCl and ZnCl2Two kinds of salt compositions, according to KCl and ZnCl2Binary phase diagraml
Mass ratio 47 at middle eutectic point:100 weigh preparation KCl/ZnCl2Eutectic saline admixture；
The 2.2 ionic liquid 1- ethyl-3-methylimidazoles two for weighing the carbon precursor as porous charcoal heat-insulation composite material
Cyanamide：According to 1- ethyl-3-methylimidazole cdicynanmide and KCl/ZnCl2The mass ratio of eutectic saline admixture is 0.1 and 2.1
In load weighted KCl/ZnCl2The quality of eutectic saline admixture, using ionic liquid quality=eutectic saline admixture
Quality × 0.1 calculate needed for 1- ethyl-3-methylimidazole cdicynanmide quality, and weigh and obtain required 1- ethyl -3- methyl miaow
Azoles cdicynanmide；
2.3 by load weighted KCl/ZnCl2Eutectic saline admixture is mixed with the grinding of 1- ethyl-3-methylimidazole cdicynanmide
Close, obtain 1- ethyl-3-methylimidazole cdicynanmide/KCl/ZnCl2Blend；
(3) to 1- ethyl-3-methylimidazole cdicynanmide/KCl/ZnCl2Blend carries out the melting charing that heats up：By 1- second
Base -3- methylimidazole cdicynanmide/KCl/ZnCl2It is put in pressure pan with Carbon fibe prefabricated component, starts pre- applying argon gas as protection
Atmosphere, after the pressure of argon gas reaches 1MPa, according to room temperature to 140 DEG C of used time 20min, 140 DEG C to 160 DEG C used time 20min, 160
DEG C to 240 DEG C of used time 16min, 240 DEG C to 260 DEG C used time 20min, 260 DEG C to 440 DEG C used time 36min, 440 DEG C to 460 DEG C with
When 20min, 460 DEG C of heating schedules to 600 DEG C of used time 28min are heated to 600 DEG C, slow with the speed of 500kPa/min
Release pressure, is continuously heating to 900 DEG C with the heating rate of 5 DEG C/min after pressure release to normal pressure, 1- ethyl-3-methylimidazole dicyan
Amine charing cracking forms charcoal skeleton, obtains Carbon fibe and strengthen porous charcoal/salt complex after cooling；
(4) strengthening porous charcoal/salt complex to Carbon fibe carries out washing replacement Treatment：Carbon fibe is strengthened porous charcoal/salt
Complex carries out washing replacement Treatment, the method for washing replacement Treatment be by Carbon fibe strengthen porous charcoal/salt complex be put into dry
Soak in net water, a clean water was changed every 3 hours.After changing water 6 times, you can obtaining Carbon fibe, to strengthen porous charcoal/water multiple
Fit；
5th step, strengthening porous charcoal/water complex to Carbon fibe carries out constant pressure and dry process
Carbon fibe is strengthened porous charcoal/water complex carries out constant pressure and dry process, method be by Carbon fibe strengthen porous charcoal/
Water complex chamber dryer is in baking oven, is heated to 140 DEG C, is incubated 20 hours, superhigh temperature resistant Carbon fiber is obtained after cooling
Dimension strengthens porous charcoal heat-insulation composite material.Porous charcoal heat-insulation composite material density manufactured in the present embodiment is 0.13g/cm3, hot face
When 1500 DEG C, thermal conductivity is 0.255W/m K.
Embodiment 2～243
When second step prepares eutectic saline admixture, the mass ratio of two kinds of salt is the binary phase diagraml of two kinds of salt in congruent melting
The mass ratio at point place, determines constant, and in the 3rd step heating up process, inert gas is in the intensification of ionic liquid/salt blend thing
Protective atmosphere is provided during melting charing, composite property is had no significant effect using different inert gases, in the 3rd step
In heating up process, heating schedule is determined by ionic liquid, and different ionic liquid is in the violent journey of different temperatures elementary reaction
Degree is different, strengthens porous charcoal heat-insulation composite material to obtain high performance Carbon fibe, needs to react violent in ionic liquid
Temperature stage is slowly heated up with the severe degree for slowing down ionic liquid charing cracking, the temperature that different ionic liquid slowly need to heat up
Stage can be obtained by differential-scanning thermogravimetric analyzer, determine constant, the 4th step washing replacement process in, washing displacement time
Completely whether washing displacement is removed depending on saline admixture for number and the every time selection of time of washing displacement, is therefore washed every time
Displacement 2～5 hours, washing displacement completely is removed to wash salt after replacing 4～8 times, washes time swap with washing displacement time
Several composite property is had no significant effect, during the 5th step constant pressure and dry, constant pressure and dry equipment be in an atmospheric pressure
The container of lower drying, is had no significant effect to the performance of composite using different constant pressure and dry equipment, the 5th step constant pressure and dry
During, depending on Carbon fibe, the selection of temperature retention time and temperature strengthens whether porous carbon composite material dries safely, 130～
At 150 DEG C, insulation can be completely dried Carbon fibe enhancing porous carbon composite material, drying time and baking temperature for 15～24 hours
Composite property is had no significant effect.Therefore, conditions above all strengthens porous charcoal heat-insulation composite material performance not to Carbon fibe
Impact, the technological parameter for therefore being adopted in embodiment 2～243 as shown in table 1, not listed experimental process parameters and enforcement in table
Example 1 is identical.
1 Carbon fibe of table strengthens porous carbon composite material preparation technology parameter and material property parameter
Claims (10)
1. a kind of preparation method of porous charcoal heat-insulation composite material, it is characterised in that comprise the following steps：
The first step, arranges clamping Carbon fibe and prepares Carbon fibe prefabricated component, as the reinforcement of porous charcoal heat-insulation composite material：According to
The volume size of Carbon fibe prefabricated component and Carbon fibe prefabricated component apparent density, Carbon fiber needed for being calculated using quality=density × volume
Dimension quality, makes Carbon fibe arragement direction perpendicular to direction of heat flow during heat-insulated use, will be spread with the graphite fixture of punching when arranging
The Carbon fibe for sequencing is gripped, and obtains Carbon fibe prefabricated component；
Second step, weighs and prepares ionic liquid/salt blend thing：
The 2.1 eutectic saline admixtures for weighing the pore-foaming agent as porous charcoal heat-insulation composite material：Eutectic salt used is mixed
Compound is made up of two kinds of salt, is weighed preparation eutectic salt according to the mass ratio at eutectic point in the binary phase diagraml of both salt and is mixed
Compound；The eutectic saline admixture is KCl/ZnCl2、LiCl/ZnCl2、NaCl/ZnCl2；
2.2 ionic liquids for weighing the carbon precursor as porous charcoal heat-insulation composite material：According to ionic liquid and Eutectic molten salt
The mass ratio of class mixture and the quality of load weighted eutectic saline admixture, using ionic liquid quality=eutectic salt
Quality × the ionic liquid of mixture calculates desired ion liquid quality with the mass ratio of eutectic saline admixture, and weighs
To desired ion liquid；The ionic liquid be 1- ethyl-3-methylimidazole cdicynanmide, N- butyl -3- picoline cdicynanmide,
1- butyl -3- picoline cdicynanmide；
2.3, by load weighted eutectic saline admixture and ionic liquid ground and mixed, obtain ionic liquid/salt blend thing；
3rd step, using the molten-salt growth method under high ambient pressure, carries out, to ionic liquid/salt blend thing, the melting charing that heats up：Will be from
Sub- liquid/salt blend thing and Carbon fibe prefabricated component are put in pressure pan, start pre- filling with inert gas as protective atmosphere, indifferent gas
After the pressure of body reaches pressure threshold, 600 DEG C are heated to, pressure is slowly discharged with the speed of 500kPa/min, pressure release is extremely
It is continuously heating to carbonize maximum temperature after normal pressure, ionic liquid charing cracking forms charcoal skeleton, obtains Carbon fibe enhancing after cooling
Porous charcoal/salt complex；
4th step, to Carbon fibe strengthen porous charcoal/salt complex carry out washing replacement Treatment, obtain Carbon fibe strengthen porous charcoal/
Water complex；
5th step, strengthening porous charcoal/water complex to Carbon fibe carries out constant pressure and dry process, obtains the enhancing of superhigh temperature resistant Carbon fibe
Porous charcoal heat-insulation composite material.
2. a kind of preparation method of porous charcoal heat-insulation composite material as claimed in claim 1, it is characterised in that the ionic liquid
Body is 0.1～0.6 with the scope of the mass ratio of eutectic saline admixture.
3. a kind of preparation method of porous charcoal heat-insulation composite material as claimed in claim 1, it is characterised in that the indifferent gas
Body refers to nitrogen or argon gas.
4. a kind of preparation method of porous charcoal heat-insulation composite material as claimed in claim 1, it is characterised in that the indifferent gas
The scope of the pressure threshold of body is 1～10MPa.
5. a kind of preparation method of porous charcoal heat-insulation composite material as claimed in claim 1, it is characterised in that the charing is most
The scope of high-temperature is 900～1400 DEG C.
6. a kind of preparation method of porous charcoal heat-insulation composite material as claimed in claim 1, it is characterised in that the 3rd step heats up
Melting is warming up to the method for charing maximum temperature when carbonizing：
When ionic liquid chooses 1- ethyl-3-methylimidazole cdicynanmide：140～160 DEG C, 240～260 DEG C, 440～460
The heating rate scope of DEG C three temperature stage is 0.5～1.5 DEG C/min, in room temperature to other temperature ranks for carbonizing maximum temperature
The heating rate scope of section is 2～10 DEG C/min；
When ionic liquid chooses N- butyl -3- picoline cdicynanmide：180～200 DEG C, 250～270 DEG C, 460～480
The heating rate scope of DEG C three temperature stage is 0.5～1.5 DEG C/min, in room temperature to other temperature ranks for carbonizing maximum temperature
The heating rate scope of section is 2～10 DEG C/min；
When ionic liquid chooses 1- butyl -3- picoline cdicynanmide：150～170 DEG C, 230～250 DEG C, 450～470
The heating rate scope of DEG C three temperature stage is 0.5～1.5 DEG C/min, in room temperature to other temperature ranks for carbonizing maximum temperature
The heating rate scope of section is 2～10 DEG C/min.
7. a kind of preparation method of porous charcoal heat-insulation composite material as claimed in claim 1, it is characterised in that the 4th step is to charcoal
It is Carbon fibe to be strengthened porous charcoal/salt complex put that fiber reinforcement porous charcoal/salt complex carries out washing the method for replacement Treatment
Enter in clean water and soak, changed a clean water every 2～5 hours, after changing water 4～8 times, you can obtain Carbon fibe strengthen many
Hole charcoal/water complex.
8. a kind of preparation method of porous charcoal heat-insulation composite material as claimed in claim 1, it is characterised in that the 5th step is to charcoal
It is Carbon fibe to be strengthened porous charcoal/water complex put that fiber reinforcement porous charcoal/water complex carries out the method for constant pressure and dry process
Enter in constant pressure and dry equipment, 130～150 DEG C are heated to, 15～24 hours are incubated, after cooling, obtain the enhancing of superhigh temperature resistant Carbon fibe
Porous charcoal heat-insulation composite material.
9. a kind of preparation method of porous charcoal heat-insulation composite material as claimed in claim 1, it is characterised in that constant pressure and dry refers to
Drying under one atmospheric pressure.
10. a kind of preparation method of porous charcoal heat-insulation composite material as claimed in claim 1, it is characterised in that constant pressure and dry sets
Standby finger chamber dryer, tunnel dryer, belt dryer.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200597A (en) * | 2017-05-26 | 2017-09-26 | 华中科技大学 | A kind of Direct Coagulation Casting preparation method of the complicated porous ceramics of high porosity |
| CN107892582A (en) * | 2017-12-12 | 2018-04-10 | 中国人民解放军国防科技大学 | Preparation method of carbon fiber reinforced nanoporous carbon heat-insulation composite material |
| CN108329046A (en) * | 2018-02-26 | 2018-07-27 | 中国人民解放军国防科技大学 | Preparation method of carbon aerogel heat insulation composite material |
| CN108607510A (en) * | 2018-05-14 | 2018-10-02 | 西北民族大学 | Carbon dioxide adsorption adulterates porous carbon material, preparation method and its usage with N- |
| 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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830703A (en) * | 2010-04-06 | 2010-09-15 | 中南大学 | Carbon fiber reinforced boron carbide composite material and preparation method thereof |
| CN103936464A (en) * | 2014-03-27 | 2014-07-23 | 西北工业大学 | Preparation method of HfC-SiC modified carbon/carbon composite material |
| CN104230366A (en) * | 2014-09-06 | 2014-12-24 | 丹阳丹金汽车部件有限公司 | Activated carbon fiber-reinforced porous composite material and preparation method thereof |
-
2016
- 2016-09-23 CN CN201610846385.2A patent/CN106478124B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830703A (en) * | 2010-04-06 | 2010-09-15 | 中南大学 | Carbon fiber reinforced boron carbide composite material and preparation method thereof |
| CN103936464A (en) * | 2014-03-27 | 2014-07-23 | 西北工业大学 | Preparation method of HfC-SiC modified carbon/carbon composite material |
| CN104230366A (en) * | 2014-09-06 | 2014-12-24 | 丹阳丹金汽车部件有限公司 | Activated carbon fiber-reinforced porous composite material and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200597A (en) * | 2017-05-26 | 2017-09-26 | 华中科技大学 | A kind of Direct Coagulation Casting preparation method of the complicated porous ceramics of high porosity |
| CN107200597B (en) * | 2017-05-26 | 2019-12-13 | 华中科技大学 | direct solidification injection molding preparation method of high-porosity complex porous ceramic |
| CN107892582A (en) * | 2017-12-12 | 2018-04-10 | 中国人民解放军国防科技大学 | Preparation method of carbon fiber reinforced nanoporous carbon heat-insulation composite material |
| CN107892582B (en) * | 2017-12-12 | 2020-01-24 | 中国人民解放军国防科技大学 | Preparation method of carbon fiber reinforced nanoporous carbon heat-insulation composite material |
| CN108329046A (en) * | 2018-02-26 | 2018-07-27 | 中国人民解放军国防科技大学 | Preparation method of carbon aerogel heat insulation composite material |
| CN108329046B (en) * | 2018-02-26 | 2020-09-11 | 中国人民解放军国防科技大学 | Preparation method of carbon aerogel heat insulation composite material |
| CN108607510A (en) * | 2018-05-14 | 2018-10-02 | 西北民族大学 | Carbon dioxide adsorption adulterates porous carbon material, preparation method and its usage with N- |
| CN108607510B (en) * | 2018-05-14 | 2021-06-01 | 西北民族大学 | N-doped porous carbon material for carbon dioxide adsorption, preparation method and application thereof |
| 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 |
| CN111686478A (en) * | 2020-06-30 | 2020-09-22 | 成都大学 | Carbon foam membrane material for oil-water emulsion separation, preparation method and application |
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