CN105645382B - A kind of preparation method of the carbon aerogels with wide spectrum dimmer reflecting structure - Google Patents
A kind of preparation method of the carbon aerogels with wide spectrum dimmer reflecting structure Download PDFInfo
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- CN105645382B CN105645382B CN201610019471.6A CN201610019471A CN105645382B CN 105645382 B CN105645382 B CN 105645382B CN 201610019471 A CN201610019471 A CN 201610019471A CN 105645382 B CN105645382 B CN 105645382B
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Abstract
The invention discloses a kind of preparation method of the carbon aerogels with wide spectrum dimmer reflecting structure, the method is by adjusting the mass ratio of resorcinol and formaldehyde total mass fraction, resorcinol and sodium carbonate, control gelation time, carbonisation heating rate and its sintering temperature, obtain the carbon aerogels with wide spectrum dimmer reflecting structure.The density range for using the carbon aerogels of the inventive method preparation is 20~60mg/cm3, specific surface area scope is 1783~967m2/ g, 0.3% is below to the reflectivity of light in 400~2000nm UV, visible lights near infrared band, absorptance is all higher than 99.7%, can be applied to the fields such as Aero-Space detection sensor, solar energy photothermal converter, national defence stealth technology as a kind of novel blacker-than-black material.
Description
Technical field
The invention belongs to porous carbon materials preparation field, and in particular to a kind of carbon airsetting with wide spectrum dimmer reflecting structure
The preparation method of glue.
Background technology
Preferable black material can be transmitted and anti-such as all light that " black hole " absorption is irradiated to its surface without occurring
Penetrate, although being unable to reach perfect condition in reality, since kirchhoff elaborates that black matrix concept and Planck found black matrix
Since radiation law, blacker-than-black material attracts increasing concern with its importance to different field scientific research.Blacker-than-black material
Unfavorable reflection can effectively be reduced and discrete light is greatly absorbed, so that the efficient absorption to light is realized,
This characteristic makes blacker-than-black material hidden in veiling glare suppression device, Aero-Space detection sensor, solar energy photothermal converter, national defence
The field such as body technology extensive application.
Conventional black material relies primarily on the intrinsic extinction characteristic of material to realize the absorption to light.At present, pitch-dark and graphite
Material is 5%~10% to the reflectivity of visible ray, and platinum black, golden black, carbon black pellet coating are 1% to the average reflectance of light.
Although the absorptance of black coating can be up to 99%, illumination is mapped to black object surface, except directly being absorbed by object
Outward, there is Fresnel reflection at gas-solid interface, influence the absorbed ratio of incident light, lead to not further improve material
Absorption to light.
In recent years, studies have found that, if on the basis of the intrinsic extinction characteristic of black material, on black material top layer or interior
Anti-reflection structure is constructed in portion, realizes higher order reflection of the light in material internal, can just improve the capture rate to light, extends light and black
The action time of material, and then improve absorptance.The international and domestic research along this thinking to blacker-than-black material is in the ascendant.
Steglich etc. etches to be formed with certain thickness using inductively coupled plasma etching method (ICP-RIE) in silicon chip surface
Silicon nanowire array, the antireflective of the absorption effects of silicon and nano-wire array limit light action is combined, realize 350~
2000nm wave bands are 0.5% to the average reflectance of light.Kodama is reported after being etched through chemical method has certain surface structure
Nickel-phosphorus alloy coating, to the reflectivity of light be 0.1~0.2% in 488~1550nm wave bands.Research shows, wide spectrum anti-reflection
Penetrate the excellent carbon nano pipe array of extinction characteristic and combine carbon well to the Intrinsic Gettering effect of light and subtracting for nano-tube array
Reflection limit light action.A kind of blacker-than-black material of the research and development such as Yang is in 457~633nm wave bands to the average reflectance of visible ray
Only 0.05%, it is almost more black nearly 30 times than the carbonizable substance that National Institute of Standards and Technology is used as current black benchmark.
This blacker-than-black material is made up of low density carbon nano-tube array, and incident light can be limited in narrow array gap by nano-tube array
Between, improve absorption of the carbon to light.Researcher also makes the surface of carbon nano pipe array become rugged and rough, further reduces right
The reflectivity of light.Then, NASA successfully develops a kind of carbon nano pipe array, and it can be realized to ultraviolet, visible
The absorption of light, near-infrared and far infrared band light more than 99%.2014, Britain research personnel utilized carbon nano pipe array
" VANTAblack " the blacker-than-black material being made is realized and is less than 1% to the reflectivity of light in 2.5~15 mu m wavebands.
Above-mentioned blacker-than-black material can realize the efficient absorption to light, but still have many difficult points in actual applications.Platinum black, gold
The quality of materials such as black, nickel-phosphorus alloy, black silicon are overweight, and the field such as aerospace vehicle is extremely harsh to quality requirement；Meanwhile, it is above-mentioned
The characteristic such as material shortage heat shock resistance, acid and alkali-resistance, anti-oxidant, these all limit the range of application of material.Carbon material has matter
Gently, the premium properties such as high intensity, chemical inertness, wide spectrum optical characteristics.The carbon black pellet for being usually used in black coating is put down to light
Equal reflectivity is only 1%.Although carbon nano pipe array can be realized to ultraviolet, visible ray, near-infrared and far infrared band light
Absorption of the line more than 99%, but carbon nano pipe array preparation required precision is high, sample size is limited, machinability is poor, these
Deficiency is equally applied to the presence of a large amount of limitations.
Carbon aerogels are a kind of novel nano porous materials, and with specific surface area very high, variable density scope is wide, hole
Structure is adjustable, and it has potential application value in fields such as mechanics, acoustics, electricity, calorifics and optics.Meanwhile, carbon aerogels
With light weight, density, structure-controllable, machinability is good, the advantages of preparing on a large scale can be met, in actual applications with pole
Big advantage.
The content of the invention
As the result of various extensive and careful research and experiment, it has been found by the inventor that by improving
The preparation technology of carbon aerogels, controls aperture and the microstructure change of carbon aerogels, and exploitation has wide spectrum dimmer reflecting structure
Carbon aerogels, be very necessary and significant as a kind of novel blacker-than-black material.Based on this discovery, this hair is completed
It is bright.
It is an object of the invention to solve at least the above and/or defect, and provide at least will be described later excellent
Point.
In order to realize these purposes of the invention and further advantage, there is provided one kind has wide spectrum dimmer reflecting structure
Carbon aerogels preparation method, comprise the following steps：
Step one, resorcinol is dissolved in deionized water, after stirring to solution clarification, adds formalin, stirring 10
~30min, is subsequently adding sodium carbonate, stirs 10~30min, then supplements deionized water, reaction solution is obtained, in stirring condition
Under, modified chitosan copper coordination compound solution is added dropwise in reaction solution, continue to stir 10~30min, obtain mixed solution；
Step 2, mixed solution is sealed, and be positioned in 60~80 DEG C of insulating box and carry out gelation, obtain wet solidifying
Glue；
Step 3, the wet gel that will be obtained be placed in trifluoroacetic acid/acetone soln carry out acidifying it is aging；
Step 4, the wet gel after acidifying is placed in exchange of solvent is carried out in acetone soln；
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extracting instrument, carries out carbon dioxide and surpass
Critical drying, obtains aeroge；
Step 6, the aeroge that will be obtained are put into temperature programmed control retort, are sintered under inert gas shielding, carbon
Change, obtain carbon aerogels.
Preferably, the preparation method of the modified chitosan copper coordination compound solution is：By weight, 5~8 parts of benzene are taken
Acid anhydride, mixes with 20~30 parts of acetone, and the shitosan and 1~5 part of pyridine for adding 3~10 parts mix, and mixed material is warming up to
75~85 DEG C and 5~10h of stirring reaction, mixture after being reacted at this temperature；Mixture after reaction is cooled to room temperature
Afterwards, filter, filtrate is dried over magnesium sulfate, obtain shitosan esterification products after organic solvent is distilled off again；Take Chitosan Ester
Change 5~10 parts of product, be added in 20~60 parts of ethanol, stir 10~30min, being subsequently adding 5~10 parts of mass concentrations is
20% copper nitrate aqueous solution, is added dropwise the pH value of triethylamine regulation solution to 7-8 under stirring condition, then stir at ambient temperature
Mix 1~2h, filter, the solid product for obtaining successively with distilled water and absolute ethanol washing 3~5 times, then at 50~70 DEG C
Dried to constant weight in baking oven, obtain modified chitosan copper coordination compound；1~5 part of modified chitosan copper coordination compound is taken, 100 parts are added
DMF, stirring obtains modified chitosan copper coordination compound solution.
Preferably, resorcinol and the total mass fraction of formaldehyde are 1wt% in the reaction solution that the step one is obtained
~4wt%；Resorcinol and the mass ratio of sodium carbonate are 100~200 in the step one：1；Resorcinol in the step one
It is 1 with the mass ratio of modified chitosan copper coordination compound:0.5~2.
Preferably, being added dropwise in reaction solution in the step one will be molten after modified chitosan copper coordination compound solution
Liquid is placed in 30~60min of ultrasound in ultrasonic wave separating apparatus, and, in 500~1500W, supersonic frequency is 20 for the adjustable range of ultrasonic power
~40KHz.
Preferably, gelation time is 15 days~45 days in described step two.
Preferably, the inert gas in described step six is the one kind in helium, argon gas, nitrogen.
Preferably, in the step 6, the process of temperature programmed control is：Retort is risen into 150 DEG C from room temperature to vacuumize,
Insulation 2h, is then passed through inert gas with the air velocity of 50mL/min, and 200~400 are warming up to the speed of 0.5 DEG C/min
DEG C, be incubated 25~35min, be then warming up to 500~700 DEG C with the speed of 0.8 DEG C/min, be incubated 30~60min, then with
The speed of 0.6 DEG C/min is warming up to 800~900 DEG C, is incubated 1~2h, then 1000 are warming up to the speed of 0.5 DEG C/min~
1100 DEG C, 1~3h is incubated, naturally cools to room temperature, obtain carbon aerogels.
Preferably, the carbonisation heating rate in described step six is 0.5 DEG C/min~1 DEG C/min；The carbon
Change process sintering temperature is 900 DEG C~1100 DEG C.
Preferably, the temperature 45 C of supercritical drying, pressure 200bar in the step 5.
Preferably, the density of the carbon aerogels is 20~60mg/cm3, specific surface area is 1783~967m2/ g, it is described
Carbon aerogels are below 0.3% in 400~2000nm ultraviolet-visibles-near infrared band to the reflectivity of light, and absorptance is all higher than
99.7%.
In the present invention, there is addition reaction with formaldehyde using resorcinol, generate methylol group, and then it is anti-that polycondensation occurs
Should, cross-linked polymer is generated, and add modified chitosan copper coordination compound to be crosslinked simultaneously.
The present invention at least includes following beneficial effect：Can be prepared with different wide spectrums using preparation method of the invention
The carbon aerogels of anti-reflection structure, the carbon aerogels show light weight and excellent wide spectrum dimmer reflecting extinction characteristic, and
It is easy to control.Carbon aerogels with wide spectrum dimmer reflecting structure prepared by the method, can as a kind of novel blacker-than-black material,
There is extensive potential application valency in fields such as Aero-Space detection sensor, solar energy photothermal converter, national defence stealth technologies
Value.
Further advantage of the invention, target and feature embody part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph of carbon aerogels prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of carbon aerogels prepared by the embodiment of the present invention 2；
Fig. 3 is the scanning electron microscope (SEM) photograph of carbon aerogels prepared by the embodiment of the present invention 3.
Specific embodiment：
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that it is used herein such as " have ", "comprising" and " including " term do not allot one or many
The presence or addition of individual other elements or its combination.
Embodiment 1：
Step one, 0.647g resorcinols are dissolved in 50mL deionized waters, after stirring to solution clarification, added
0.871mL formalins, stir 20min, are subsequently adding 0.147mL sodium carbonate liquors, stir 20min, then supplement 20mL and go
Ionized water, obtains reaction solution, under agitation, 30mL modified chitosan copper coordination compounds is added dropwise in reaction solution molten
Liquid, continues to stir 30min, obtains mixed solution；The density 1.066g/mL of the formalin, formaldehyde mass percent is
38%；The substance withdrawl syndrome of the sodium carbonate liquor is 0.2mol/L；
Step 2, mixed solution is sealed, and be positioned over gel 30 days in 80 DEG C of insulating box, obtain wet gel；
Step 3, the wet gel that will be obtained are placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution and carry out acid
Change aging 7 days；
Wet gel after step 4, just acidifying burin-in process is placed in and solvent friendship is carried out in the container equipped with fresh acetone
Change, acetone is changed daily, continue 5 days；
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extracting instrument, in T=45 DEG C, P=
Through CO under 200bar experiment conditions2Supercritical drying obtains aeroge；
Step 6, the aeroge that will be obtained are carbonized under flowing argon gas protection in tube furnace, and 150 are slowly increased to from room temperature
DEG C vacuumize, keep 2h；Then argon gas is passed through with the air velocity of 50mL/min, it is slow from 150 DEG C with 0.6 DEG C/min heating rates
It is slow to rise to 1050 DEG C of holding carbonization 3h, room temperature is naturally cooled to, obtain carbon aerogels；The density of the carbon aerogels is 20mg/
cm3, specific surface area is 1783m2/ g, is less than in 400~2000nm ultraviolet-visibles-near infrared band to the reflectivity of light
0.24%, absorptance is more than 99.76%, and electromicroscopic photograph is shown in Fig. 1.
The preparation method of the modified chitosan copper coordination compound solution is：8g phthalic anhydrides are taken, is mixed with 20g acetone, added
5g shitosans and 2g pyridines mix, and mixed material is warming up into 85 DEG C and at this temperature stirring reaction 8h, are mixed after being reacted
Compound；After mixture after reaction is cooled into room temperature, filtering, filtrate is dried over magnesium sulfate, again after organic solvent is distilled off
Obtain shitosan esterification products；Shitosan esterification products 8g is taken, is added in 30g ethanol, stir 30min, be subsequently adding 8g matter
Amount concentration is 20% copper nitrate aqueous solution, the pH value of triethylamine regulation solution is added dropwise under stirring condition to 7, then in room temperature bar
2h is stirred under part, is filtered, the solid product for obtaining successively with distilled water and absolute ethanol washing 3 times, then in 70 DEG C of baking oven
Middle drying obtains modified chitosan copper coordination compound to constant weight；2g modified chitosan copper coordination compounds are taken, 100g N, N- diformazans are added
Base formamide, stirring obtains modified chitosan copper coordination compound solution；The shitosan is dissolved in 1% acetic acid solution and then enters
Row esterification.
Embodiment 2：
Step one, 1.941g resorcinols are dissolved in 50mL deionized waters, after stirring to solution clarification, added
2.614mL formalins, stir 20min, are subsequently adding 0.441mL sodium carbonate liquors, stir 20min, then supplement 20mL and go
Ionized water, obtains reaction solution, under agitation, 30mL modified chitosan copper coordination compounds is added dropwise in reaction solution molten
Liquid, continues to stir 30min, obtains mixed solution；The density 1.066g/mL of the formalin, formaldehyde mass percent is
38%；The substance withdrawl syndrome of the sodium carbonate liquor is 0.2mol/L；The preparation of the modified chitosan copper coordination compound solution
Method is using the method described in embodiment 1；
Step 2, mixed solution is sealed, and be positioned over gel 30 days in 80 DEG C of insulating box, obtain wet gel；
Step 3, the wet gel that will be obtained are placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution and carry out acid
Change aging 7 days；
Wet gel after step 4, just acidifying burin-in process is placed in and solvent friendship is carried out in the container equipped with fresh acetone
Change, acetone is changed daily, continue 5 days；
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extracting instrument, in T=45 DEG C, P=
Through CO under 200bar experiment conditions2Supercritical drying obtains aeroge；
Step 6, the aeroge that will be obtained are carbonized under flowing argon gas protection in tube furnace, and 150 are slowly increased to from room temperature
DEG C vacuumize, keep 2h；Then argon gas is passed through with the air velocity of 50mL/min, it is slow from 150 DEG C with 0.6 DEG C/min heating rates
It is slow to rise to 1050 DEG C of holding carbonization 3h, room temperature is naturally cooled to, obtain carbon aerogels；The density of the carbon aerogels is 40mg/
cm3, specific surface area is 997m2/ g, 0.21% is less than in 400~2000nm ultraviolet-visibles-near infrared band to the reflectivity of light,
Absorptance is more than 99.79%, and electromicroscopic photograph is shown in Fig. 2.
Embodiment 3：
Step one, 2.588g resorcinols are dissolved in 50mL deionized waters, after stirring to solution clarification, added
3.485mL formalins, stir 20min, are subsequently adding 0.588mL sodium carbonate liquors, stir 20min, then supplement 20mL and go
Ionized water, obtains reaction solution, under agitation, 30mL modified chitosan copper coordination compounds is added dropwise in reaction solution molten
Liquid, continues to stir 30min, obtains mixed solution；The density 1.066g/mL of the formalin, formaldehyde mass percent is
38%；The substance withdrawl syndrome of the sodium carbonate liquor is 0.2mol/L；The preparation of the modified chitosan copper coordination compound solution
Method is using the method described in embodiment 1；
Step 2, mixed solution is sealed, and be positioned over gel 30 days in 80 DEG C of insulating box, obtain wet gel；
Step 3, the wet gel that will be obtained are placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution and carry out acid
Change aging 7 days；
Wet gel after step 4, just acidifying burin-in process is placed in and solvent friendship is carried out in the container equipped with fresh acetone
Change, acetone is changed daily, continue 5 days；
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extracting instrument, in T=45 DEG C, P=
Through CO under 200bar experiment conditions2Supercritical drying obtains aeroge；
Step 6, the aeroge that will be obtained are carbonized under flowing argon gas protection in tube furnace, and 150 are slowly increased to from room temperature
DEG C vacuumize, keep 2h；Then argon gas is passed through with the air velocity of 50mL/min, it is slow from 150 DEG C with 0.6 DEG C/min heating rates
It is slow to rise to 1050 DEG C of holding carbonization 3h, room temperature is naturally cooled to, obtain carbon aerogels；The density of the carbon aerogels is 60mg/
cm3, specific surface area is 967m2/ g, 0.19% is less than in 400~2000nm ultraviolet-visibles-near infrared band to the reflectivity of light,
Absorptance is more than 99.81%, and electromicroscopic photograph is shown in Fig. 3.
Embodiment 4：
Step one, 1.941g resorcinols are dissolved in 50mL deionized waters, after stirring to solution clarification, added
2.614mL formalins, stir 30min, are subsequently adding 0.441mL sodium carbonate liquors, stir 20min, then supplement 30mL and go
Ionized water, obtains reaction solution, under agitation, 20mL modified chitosan copper coordination compounds is added dropwise in reaction solution molten
Liquid, continues to stir 30min, obtains mixed solution；The density 1.066g/mL of the formalin, formaldehyde mass percent is
38%；The substance withdrawl syndrome of the sodium carbonate liquor is 0.2mol/L；The preparation of the modified chitosan copper coordination compound solution
Method is：6g phthalic anhydrides are taken, is mixed with 25g acetone, add 8g shitosans and the mixing of 4g pyridines, mixed material is warming up to 80 DEG C
And stirring reaction 10h, mixture after being reacted at this temperature；After mixture after reaction is cooled into room temperature, filtering, filtrate
It is dried over magnesium sulfate, shitosan esterification products are obtained after organic solvent is distilled off again；Shitosan esterification products 10g is taken, plus
Enter in 50g ethanol, stir 20min, be subsequently adding the copper nitrate aqueous solution that 7g mass concentrations are 20%, be added dropwise under stirring condition
Then the pH value of triethylamine regulation solution stirs 1h at ambient temperature to 7, filters, and the solid product for obtaining is successively with distillation
Water and absolute ethanol washing 5 times, then dry to constant weight in 70 DEG C of baking oven, obtain modified chitosan copper coordination compound；Take 5g
Modified chitosan copper coordination compound, adds 100g DMFs, and stirring obtains modified chitosan copper coordination compound solution；
The shitosan is dissolved in 1% acetic acid solution and then carries out esterification.
Step 2, mixed solution is sealed, and be positioned in 70 DEG C of insulating box and coagulate 45 days, obtain wet gel；
Step 3, the wet gel that will be obtained are placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution and carry out acid
Change aging 7 days；
Wet gel after step 4, just acidifying burin-in process is placed in and solvent friendship is carried out in the container equipped with fresh acetone
Change, acetone is changed daily, continue 5 days；
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extracting instrument, in T=45 DEG C, P=
Through CO under 200bar experiment conditions2Supercritical drying obtains aeroge；
Step 6, the aeroge that will be obtained are added in retort, retort is risen into 150 DEG C from room temperature and is vacuumized, and are incubated
2h, is then passed through nitrogen with the air velocity of 50mL/min, and 200 DEG C are warming up to the speed of 0.5 DEG C/min, is incubated 25min, so
500 DEG C are warming up to the speed of 0.8 DEG C/min afterwards, 30min is incubated, then 900 DEG C is warming up to the speed of 0.6 DEG C/min, protected
Warm 2h, is then warming up to 1100 DEG C with the speed of 0.5 DEG C/min, is incubated 1h, naturally cools to room temperature, obtains carbon aerogels；Should
The density of carbon aerogels is 45mg/cm3, specific surface area is 971m2/ g, the carbon aerogels are in 400~2000nm ultraviolet-visibles-near
Infrared band is below 0.08% to the reflectivity of light, and absorptance is all higher than 99.92%.
Embodiment 5：
Step one, 2.588g resorcinols are dissolved in 50mL deionized waters, after stirring to solution clarification, added
3.485mL formalins, stir 20min, are subsequently adding 0.588mL sodium carbonate liquors, stir 20min, then supplement 20mL and go
Ionized water, obtains reaction solution, under agitation, 30mL modified chitosan copper coordination compounds is added dropwise in reaction solution molten
Liquid, is then placed in ultrasound 50min in ultrasonic wave separating apparatus by solution, and ultrasonic power is 1200W, and supersonic frequency is in 28KHz；Complete
Into after ultrasound, continue to stir 30min, obtain mixed solution；The density 1.066g/mL of the formalin, formaldehyde quality percentage
Than being 38%；The substance withdrawl syndrome of the sodium carbonate liquor is 0.2mol/L；The modified chitosan copper coordination compound solution
Preparation method is using the method described in embodiment 4；
Step 2, mixed solution is sealed, and be positioned over gel 30 days in 80 DEG C of insulating box, obtain wet gel；
Step 3, the wet gel that will be obtained are placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution and carry out acid
Change aging 7 days；
Wet gel after step 4, just acidifying burin-in process is placed in and solvent friendship is carried out in the container equipped with fresh acetone
Change, acetone is changed daily, continue 5 days；
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extracting instrument, in T=45 DEG C, P=
Through CO under 200bar experiment conditions2Supercritical drying obtains aeroge；
Step 6, the aeroge that will be obtained are added in retort, retort is risen into 150 DEG C from room temperature and is vacuumized, and are incubated
2h, is then passed through nitrogen with the air velocity of 50mL/min, and 200 DEG C are warming up to the speed of 0.5 DEG C/min, is incubated 25min, so
500 DEG C are warming up to the speed of 0.8 DEG C/min afterwards, 30min is incubated, then 900 DEG C is warming up to the speed of 0.6 DEG C/min, protected
Warm 2h, is then warming up to 1100 DEG C with the speed of 0.5 DEG C/min, is incubated 1h, naturally cools to room temperature, obtains carbon aerogels；Should
The density of carbon aerogels is 58mg/cm3, specific surface area is 980m2/ g, the carbon aerogels are in 400~2000nm ultraviolet-visibles-near
Infrared band is below 0.06% to the reflectivity of light, and absorptance is all higher than 99.94%.
The present invention by controlling response parameter and condition, by resorcinol, formaldehyde and modified chitosan copper coordination compound through hand over
Connection reaction is made hydrogel, then can prepare the carbon with wide spectrum dimmer reflecting structure through supercritical drying, high temperature cabonization
Aeroge, the raw material used during preparation in ratio of the present invention, parameters in described scope, preparation
Carbon aerogels density is less than 60mg/cm3, specific surface area is more than 950m2/ g, gained carbon aerogels 400~2000nm it is ultraviolet-can
See-near infrared band to the reflectivity of light less than 0.3%, absorptance is more than 99.7%, and because modified chitosan copper coordinates
There is interaction of hydrogen bond in the presence of thing, amino and the resorcinol of modified chitosan copper coordination compound molecular surface, and formaldehyde is
Can be reacted with modified chitosan copper coordination compound, promote the crosslinking of modified chitosan copper coordination compound, can form hydroxyl with resorcinol again
Methyl groups, so that further by phenol and formaldehyde molecule absorption around the skeleton of shitosan, making the stability of crosslinking strengthens, together
When aeroge by the carbon aerogels that obtain of carbonization, comprising nano oxidized steel structure, the application of carbon aerogels can be expanded, can
As a kind of novel blacker-than-black material, in the neck such as Aero-Space detection sensor, solar energy photothermal converter, national defence stealth technology
Domain has extensive potential using value.Additionally, being processed mixed solution using ultrasound, ultrasonic wave energy discharges huge
Energy, localized hyperthermia's hyperbaric environment and the microjet with strong impacts of generation, easily realizes that each phase uniformly mixes, and eliminates
Local concentration is uneven, improves reaction speed, stimulates the formation of cenotype, and may also operate as shear action to reunion, favorably
In the formation of nanocluster, and the presence that can stablize.And temperature programming is used during carbonization, temperature programming can
The greatest benefit of each temperature section is played, the mean temperature of whole process is reduced, total energy loss is reduced, overall energy is improved
Amount utilization rate, meanwhile, temperature programming reduces the heater working time at high temperature, resistance to heater so as to reduce
The requirement of hot properties, improves the utilization rate and reliability of firing equipment.
Although embodiment of the present invention is disclosed as above, it is not restricted to listed in specification and implementation method
Using, it can be applied to various suitable the field of the invention completely, for those skilled in the art, can be easily
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here as the legend with description.
Claims (9)
1. a kind of preparation method of the carbon aerogels with wide spectrum dimmer reflecting structure, it is characterised in that comprise the following steps：
Step one, resorcinol is dissolved in deionized water, after stirring to solution clarification, adds formalin, stirring 10~
30min, is subsequently adding sodium carbonate, stirs 10~30min, then supplements deionized water, reaction solution is obtained, in stirring condition
Under, modified chitosan copper coordination compound solution is added dropwise in reaction solution, continue to stir 10~30min, obtain mixed solution；
Step 2, mixed solution is sealed, and be positioned in 60~80 DEG C of insulating box and carry out gelation, obtain wet gel；
Step 3, the wet gel that will be obtained be placed in trifluoroacetic acid/acetone soln carry out acidifying it is aging；
Step 4, the wet gel after acidifying is placed in exchange of solvent is carried out in acetone soln；
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extracting instrument, carries out CO 2 supercritical
Dry, obtain aeroge；
Step 6, the aeroge that will be obtained are put into temperature programmed control retort, are sintered under inert gas shielding, are carbonized,
Obtain carbon aerogels；
The preparation method of the modified chitosan copper coordination compound solution is：By weight, 5~8 parts of phthalic anhydrides are taken, with 20~30 part third
Ketone mixes, and the shitosan and 1~5 part of pyridine for adding 3~10 parts mix, and mixed material is warming up into 75~85 DEG C and herein temperature
Degree lower 5~10h of stirring reaction, mixture after being reacted；After mixture after reaction is cooled into room temperature, filtering, filtrate is through sulphur
Sour magnesium is dried, obtains shitosan esterification products after organic solvent is distilled off again；5~10 parts of shitosan esterification products are taken, plus
Enter in 20~60 parts of ethanol, stir 10~30min, be subsequently adding the copper nitrate aqueous solution that 5~10 parts of mass concentrations are 20%,
The pH value of triethylamine regulation solution is added dropwise under stirring condition to 7-8,1~2h is then stirred at ambient temperature, filtering is obtained
Solid product with distilled water and absolute ethanol washing 3~5 times, is then dried to constant weight in 50~70 DEG C of baking oven successively, is obtained
To modified chitosan copper coordination compound；1~5 part of modified chitosan copper coordination compound is taken, 100 parts of DMFs are added, stirred
Mix and obtain modified chitosan copper coordination compound solution.
2. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterised in that
Resorcinol and the total mass fraction of formaldehyde are 1wt%~4wt% in the reaction solution that the step one is obtained；The step one
Middle resorcinol is 100~200 with the mass ratio of sodium carbonate：1；Resorcinol coordinates with modified chitosan copper in the step one
The mass ratio of thing is 1:0.5~2.
3. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterised in that
Solution is placed in ultrasonic wave dispersion after being added dropwise over modified chitosan copper coordination compound solution in reaction solution in the step one
30~60min of ultrasound in instrument, in 500~1500W, supersonic frequency is in 20~40kHz for the adjustable range of ultrasonic power.
4. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterised in that
Gelation time is 15 days~45 days in described step two.
5. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterised in that
Inert gas in described step six is the one kind in helium, argon gas, nitrogen.
6. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterised in that
In the step 6, the process of temperature programmed control is：Retort is risen into 150 DEG C from room temperature to vacuumize, be incubated 2h, then with
The air velocity of 50mL/min is passed through inert gas, and 200~400 DEG C are warming up to the speed of 0.5 DEG C/min, and insulation 25~
35min, is then warming up to 500~700 DEG C with the speed of 0.8 DEG C/min, 30~60min is incubated, then with the speed of 0.6 DEG C/min
Degree is warming up to 800~900 DEG C, is incubated 1~2h, is then warming up to 1000~1100 DEG C with the speed of 0.5 DEG C/min, and insulation 1~
3h, naturally cools to room temperature, obtains carbon aerogels.
7. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterised in that
Carbonisation heating rate in described step six is 0.5 DEG C/min~1 DEG C/min；The carbonisation sintering temperature is
900 DEG C~1100 DEG C.
8. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterised in that
The temperature 45 C of supercritical drying, pressure 200bar in the step 5.
9. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, its feature exists
In the density of the carbon aerogels is 20~60mg/cm3, specific surface area is 1783~967m2/ g, the carbon aerogels are 400
~2000nm ultraviolet-visibles-near infrared band is below 0.3% to the reflectivity of light, and absorptance is all higher than 99.7%.
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| CN106340726B (en) * | 2016-10-31 | 2019-01-25 | 中国工程物理研究院激光聚变研究中心 | Magnetic conductive nano metal/carbon aerogels absorbing material and preparation method thereof |
| CN106542517A (en) * | 2016-12-06 | 2017-03-29 | 绵阳泛博新材料科技有限公司 | The preparation method of carbon aerogels |
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| CN109734448B (en) * | 2019-03-19 | 2020-07-21 | 电子科技大学 | Preparation method of carbon aerogel-based electromagnetic shielding material |
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| CN110791192A (en) * | 2019-11-18 | 2020-02-14 | 复旦大学 | Super-black coating and preparation method thereof |
| CN111960402B (en) * | 2020-08-28 | 2022-02-08 | 国网山东综合能源服务有限公司 | Preparation method of photo-thermal material for solar water evaporation |
| CN114479659B (en) * | 2022-01-05 | 2023-03-17 | 上海卫星装备研究所 | Carbon-based super-black stray light eliminating nano composite coating and preparation method thereof |
| CN115010882A (en) * | 2022-06-22 | 2022-09-06 | 南京林业大学 | Phenolic resin ionic liquid gel for photo-thermal water evaporation and preparation method thereof |
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