CN105645382A - Preparation method of wide-spectrum-antireflection-structure carbon aerogel - Google Patents
Preparation method of wide-spectrum-antireflection-structure carbon aerogel Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a preparation method of a wide-spectrum-antireflection-structure carbon aerogel. According to the method, the total mass percent of the resorcinol and formaldehyde and the resorcinol/sodium carbonate mass ratio are regulated, and the gelation time, the heating rate in the carbonization process and the sintering temperature are controlled, thereby obtaining the wide-spectrum-antireflection-structure carbon aerogel. The density range of the carbon aerogel prepared by the method is 20-60 mg/cm<3>, the specific area range is 1783-967 m<2>/g, the light reflectivity within the 400-2000nm ultraviolet-visible-near-infrared band is respectively lower than 0.3%, and the absorbance is respectively greater than 99.7%. The carbon aerogel can be used as a novel super black material, and is applicable to the fields of aerospace detecting sensors, solar photo-thermal converters, national defense stealth technology and the like.
Description
Technical field
The invention belongs to porous carbon materials preparation field, it is specifically related to the preparation method of a kind of carbon aerogels with wide spectrum dimmer reflecting structure.
Background technology
Desirable black material can absorb as " black hole " and be irradiated to all light on its surface and transmittance and reflectance does not occur, although reality cannot reach perfect condition, but since Ji Er Hough has set forth black matrix concept and Pu Langke foundes blackbody radiation law, the importance of different field scientific research is attract more and more concerns with it by super black-materials. Super black-materials can effectively reduce disadvantageous reflection and be absorbed greatly by discrete light, thus realizing the efficient absorption to light, this characteristic makes super black-materials in field extensive application such as stray light suppression device, aerospace detection sensor, solar energy photothermal converter, national defence stealthy techniquies.
Conventional black material mainly relies on material intrinsic extinction characteristic to realize the absorption to light. At present, visible light reflectance is 5%��10% by black paint and graphite material, and platinum black, gold are black, the average reflectance of light is 1% by carbon black pellet coating. Although the light absorption ratio of black coating can up to 99%, but illumination is mapped to black object surface, except directly being absorbed by object, at gas-solid interface there is Fresnel reflection in place, affect the ratio that incident light is absorbed, cause cannot improving material further to the absorption of light.
In recent years, studies have found that, if on black material intrinsic extinction characteristic basis, at black material top layer or Internal architecture anti-reflection structure, it is achieved light, in the multistage reflection of material internal, just can improve and light is caught rate, extend the action time of light and black material, and then improve light absorption ratio. International and domestic along this thinking, the research of super black-materials is in the ascendant. Steglich etc. utilize inductively coupled plasma etching method (ICP-RIE) to have certain thickness silicon nanowire array in silicon chip surface etching formation, the antireflective of the absorption effects of silicon and nano-wire array limit light action is combined, it is achieved be 0.5% at 350��2000nm wave band to the average reflectance of light.Kodama reports has the nickel-phosphorus alloy coating of certain surface structure after chemical method etches, and is 0.1��0.2% at 488��1550nm wave band to light reflectance. Research shows, the carbon nano pipe array of wide spectrum dimmer reflecting extinction characteristic excellence well combines carbon to the antireflective limit light action of the intrinsic sorption of light and nano-tube array. The average reflectance of visible ray is only 0.05% at 457��633nm wave band by a kind of super black-materials of the research and development such as Yang, almost black nearly 30 times as the carbon species of current black benchmark than National Institute of Standards and Technology. This kind of super black-materials are made up of low density carbon nano-tube array, and incident light can be limited between narrow array gap by nano-tube array, it is to increase carbon is to the absorption of light. Researchist also makes the surface of carbon nano pipe array become rugged and rough, reduces light reflectance further. Subsequently, NASA successfully develops a kind of carbon nano pipe array, and it can realize the absorption more than 99% of ultraviolet, visible ray, near infrared and far infrared band light. 2014, " VANTAblack " super black-materials that Britain research personnel utilize carbon nano pipe array to make achieved at 2.5��15 mu m wavebands light reflectance lower than 1%.
Above-mentioned super black-materials can realize the efficient absorption to light, but still has many difficult points in actual applications. The quality of materials such as platinum black, gold are black, nickel-phosphorus alloy, black silicon are overweight, and the fields such as aerospacecraft are very harsh to specification of quality; Meanwhile, above-mentioned materials lacks heat shock resistance, acid and alkali-resistance, the characteristic such as anti-oxidant, and these all limit the range of application of material. Carbon material has the premium propertiess such as light weight, high strength, unreactiveness, wide spectral optical characteristics. The average reflectance of light is only 1% by the carbon black pellet being usually used in black coating. Although carbon nano pipe array can realize the absorption more than 99% of ultraviolet, visible ray, near infrared and far infrared band light, but carbon nano pipe array prepares accuracy requirement height, sample size is limited, workability is poor, these are not enough exists a large amount of restriction to its application equally.
Carbon aerogels is a kind of novel nano porous material, has very high specific surface area, and variable density scope is wide, and pore texture is adjustable, and it has potential using value in fields such as mechanics, acoustics, electricity, calorifics and optics. Meanwhile, carbon aerogels has light weight, and density, structure are controlled, and workability is good, can meet the advantages such as extensive preparation, have great advantage in actual applications.
Summary of the invention
As the result of various extensive and careful research and experiment, the present inventor has been found that, by improving the preparation technology of carbon aerogels, the aperture of control carbon aerogels and microstructure change, exploitation has the carbon aerogels of wide spectrum dimmer reflecting structure, and the super black-materials as a kind of novelty are very necessary and meaningful. Find based on this kind, complete the present invention.
It is an object of the invention to solve at least the problems referred to above and/or defect, and the advantage that will illustrate at least below is provided.
In order to realize these objects according to the present invention and other advantage, it provides the preparation method of a kind of carbon aerogels with wide spectrum dimmer reflecting structure, comprises the following steps:
Step one, Resorcinol is dissolved in deionized water, after being stirred to solution clarification, add formaldehyde solution, stir 10��30min, then sodium carbonate is added, stir 10��30min, then supplement deionized water, obtain reaction soln, under agitation, reaction soln dropwise adds modified chitosan copper coordination compound solution, continues stirring 10��30min, obtain mixing solutions;
Step 2, mixing solutions is sealed, and it is positioned in the thermostat container of 60��80 DEG C and carries out gelation, obtain wet gel;
Step 3, that the wet gel obtained is placed in trifluoroacetic acid/acetone soln carries out acidifying is aging;
Step 4, the wet gel after acidifying is placed in acetone soln carries out exchange of solvent;
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extraction instrument, carry out CO 2 supercritical drying, obtain aerogel;
Step 6, the aerogel obtained is put into temperature programmed control charring furnace, carries out sintering under protection of inert gas, carbonization, obtain carbon aerogels.
Preferably, the preparation method of described modified chitosan copper coordination compound solution is: by weight, get 5��8 parts of phthalic anhydrides, mix with 20��30 parts of acetone, add chitosan and 1��5 part of pyridine mixing of 3��10 parts again, mixture is warming up to 75��85 DEG C and stirring reaction 5��10h at this temperature, obtains reacting rear mixture; After mixture after reaction is cooled to room temperature, filtering, filtrate is through dried over mgso, remove and obtain chitosan esterification products after organic solvent again through distillation; Get chitosan esterification products 5��10 parts, join in 20��60 parts of ethanol, stir 10��30min, then adding 5��10 parts of mass concentrations is the copper nitrate aqueous solution of 20%, and lower of agitation condition adds triethylamine and regulates the pH value of solution to 7-8, then stirs 1��2h at ambient temperature, filter, the solid product obtained with distilled water and absolute ethanol washing 3��5 times, is then dried to constant weight in the baking oven of 50��70 DEG C, obtains modified chitosan copper coordination compound successively; Get 1��5 part of modified chitosan copper coordination compound, add 100 parts of N, dinethylformamide, stir and obtain modified chitosan copper coordination compound solution.
Preferably, in the reaction soln that described step one obtains, the total mass mark of Resorcinol and formaldehyde is 1wt%��4wt%; In described step one, the mass ratio of Resorcinol and sodium carbonate is 100��200:1; In described step one, the mass ratio of Resorcinol and modified chitosan copper coordination compound is 1:0.5��2.
Preferably, solution being placed in after dropwise adding modified chitosan copper coordination compound solution in reaction soln in described step one the ultrasonic 30��60min of ultrasonic wave separating apparatus, the regulation range of ultrasonic power is at 500��1500W, and ultrasonic frequency is at 20��40KHz.
Preferably, in described step 2, gelation time is 15 days��45 days.
Preferably, the described rare gas element in step 6 is the one in helium, argon gas, nitrogen.
Preferably, in described step 6, the process of temperature programmed control is: from room temperature, charring furnace is risen to 150 DEG C and vacuumizes, insulation 2h, then lead to into rare gas element with the gas velocity of 50mL/min, it is warming up to 200��400 DEG C with the speed of 0.5 DEG C/min, insulation 25��35min, then it is warming up to 500��700 DEG C with the speed of 0.8 DEG C/min, insulation 30��60min, then it is warming up to 800��900 DEG C with the speed of 0.6 DEG C/min, insulation 1��2h, then it is warming up to 1000��1100 DEG C with the speed of 0.5 DEG C/min, insulation 1��3h, naturally cool to room temperature, obtain carbon aerogels.
Preferably, the carbonization process temperature rise rate in described step 6 is 0.5 DEG C/min��1 DEG C/min; Described carbonization process sintering temperature is 900 DEG C��1100 DEG C.
Preferably, the temperature 45 DEG C of supercritical drying, pressure 200bar in described step 5.
Preferably, the density of described carbon aerogels is 20��60mg/cm3, specific surface area is 1783��967m2/ g, described carbon aerogels at 400��2000nm ultraviolet-visible-near-infrared band to light reflectance all lower than 0.3%, light absorption ratio is all greater than 99.7%.
In the present invention, utilize Resorcinol with formaldehyde generation addition reaction, generate methylol group, and then polycondensation occurs, generate cross-linked polymer, and add modified chitosan copper coordination compound simultaneously and be cross-linked.
The present invention at least comprises following useful effect: adopting the preparation method of the present invention can prepare the carbon aerogels with different wide spectrum dimmer reflecting structures, this carbon aerogels shows the wide spectrum dimmer reflecting extinction characteristic of light weight and excellence, and is convenient to control. Prepared by this method has the carbon aerogels of wide spectrum dimmer reflecting structure, can be used as the super black-materials of a kind of novelty, and the fields such as sensor, solar energy photothermal converter, national defence stealthy technique that detect in aerospace have potential using value widely.
Part is embodied by other advantage of the present invention, target and feature by explanation below, and the technician by this area by the research and practice to the present invention is also understood by part.
Accompanying drawing illustrates:
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.
Embodiment:
Below in conjunction with accompanying drawing, the present invention is described in further detail, to make those skilled in the art can implement according to this with reference to specification sheets word.
Such as " have " it is to be understood that used herein, other element one or more do not allotted in " comprising " and " comprising " term or its combination existence or interpolation.
Embodiment 1:
Step one, 0.647g Resorcinol is dissolved in 50mL deionized water, after being stirred to solution clarification, add 0.871mL formaldehyde solution, stir 20min, then 0.147mL sodium carbonate solution is added, stir 20min, then supplement 20mL deionized water, obtain reaction soln, under agitation, reaction soln dropwise adds 30mL modified chitosan copper coordination compound solution, continues to stir 30min, obtain mixing solutions; The density 1.066g/mL of described formaldehyde solution, formaldehyde mass percent is 38%; The substance withdrawl syndrome of described sodium carbonate solution is 0.2mol/L;
Step 2, mixing solutions is sealed, and it is positioned in the thermostat container of 80 DEG C gel 30 days, obtain wet gel;
Step 3, the wet gel obtained is placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution carries out acidifying aging 7 days;
Wet gel after step 4, just acidifying burin-in process is placed in the container that fresh acetone is housed and carries out exchange of solvent, and every day changes acetone, continues 5 days;
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extraction instrument, at T=45 DEG C, through CO under P=200bar experiment condition2Supercritical drying obtains aerogel;
Step 6, the aerogel carbonization in tube furnace under flowing argon gas shielded that will obtain, slowly rise to 150 DEG C from room temperature and vacuumize, keep 2h; Then lead to into argon gas with the gas velocity of 50mL/min, slowly rise to 1050 DEG C with 0.6 DEG C/min temperature rise rate from 150 DEG C and keep carbonization 3h, naturally cool to room temperature, obtain carbon aerogels; The density of this carbon aerogels is 20mg/cm3, specific surface area is 1783m2/ g, at 400��2000nm ultraviolet-visible-near-infrared band to light reflectance lower than 0.24%, light absorption ratio is greater than 99.76%, and electromicroscopic photograph is shown in Fig. 1.
The preparation method of described modified chitosan copper coordination compound solution is: gets 8g phthalic anhydride, mixes with 20g acetone, then adds 5g chitosan and the mixing of 2g pyridine, mixture is warming up to 85 DEG C and stirring reaction 8h at this temperature, obtains reacting rear mixture; After mixture after reaction is cooled to room temperature, filtering, filtrate is through dried over mgso, remove and obtain chitosan esterification products after organic solvent again through distillation; Get chitosan esterification products 8g, join in 30g ethanol, stir 30min, then adding the copper nitrate aqueous solution that 8g mass concentration is 20%, lower of agitation condition adds the pH value to 7 that triethylamine regulates solution, then stirs 2h at ambient temperature, filter, the solid product obtained with distilled water and absolute ethanol washing 3 times, is then dried to constant weight in the baking oven of 70 DEG C, obtains modified chitosan copper coordination compound successively; Get 2g modified chitosan copper coordination compound, add 100gN, dinethylformamide, stir and obtain modified chitosan copper coordination compound solution; Described chitosan is dissolved in the acetic acid solution of 1% then to carry out esterification.
Embodiment 2:
Step one, 1.941g Resorcinol is dissolved in 50mL deionized water, after being stirred to solution clarification, add 2.614mL formaldehyde solution, stir 20min, then 0.441mL sodium carbonate solution is added, stir 20min, then supplement 20mL deionized water, obtain reaction soln, under agitation, reaction soln dropwise adds 30mL modified chitosan copper coordination compound solution, continues to stir 30min, obtain mixing solutions; The density 1.066g/mL of described formaldehyde solution, formaldehyde mass percent is 38%; The substance withdrawl syndrome of described sodium carbonate solution is 0.2mol/L; The preparation method of described modified chitosan copper coordination compound solution adopts the method described in embodiment 1;
Step 2, mixing solutions is sealed, and it is positioned in the thermostat container of 80 DEG C gel 30 days, obtain wet gel;
Step 3, the wet gel obtained is placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution carries out acidifying aging 7 days;
Wet gel after step 4, just acidifying burin-in process is placed in the container that fresh acetone is housed and carries out exchange of solvent, and every day changes acetone, continues 5 days;
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extraction instrument, at T=45 DEG C, through CO under P=200bar experiment condition2Supercritical drying obtains aerogel;
Step 6, the aerogel carbonization in tube furnace under flowing argon gas shielded that will obtain, slowly rise to 150 DEG C from room temperature and vacuumize, keep 2h; Then lead to into argon gas with the gas velocity of 50mL/min, slowly rise to 1050 DEG C with 0.6 DEG C/min temperature rise rate from 150 DEG C and keep carbonization 3h, naturally cool to room temperature, obtain carbon aerogels; The density of this carbon aerogels is 40mg/cm3, specific surface area is 997m2/ g, at 400��2000nm ultraviolet-visible-near-infrared band to light reflectance lower than 0.21%, light absorption ratio is greater than 99.79%, and electromicroscopic photograph is shown in Fig. 2.
Embodiment 3:
Step one, 2.588g Resorcinol is dissolved in 50mL deionized water, after being stirred to solution clarification, add 3.485mL formaldehyde solution, stir 20min, then 0.588mL sodium carbonate solution is added, stir 20min, then supplement 20mL deionized water, obtain reaction soln, under agitation, reaction soln dropwise adds 30mL modified chitosan copper coordination compound solution, continues to stir 30min, obtain mixing solutions;The density 1.066g/mL of described formaldehyde solution, formaldehyde mass percent is 38%; The substance withdrawl syndrome of described sodium carbonate solution is 0.2mol/L; The preparation method of described modified chitosan copper coordination compound solution adopts the method described in embodiment 1;
Step 2, mixing solutions is sealed, and it is positioned in the thermostat container of 80 DEG C gel 30 days, obtain wet gel;
Step 3, the wet gel obtained is placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution carries out acidifying aging 7 days;
Wet gel after step 4, just acidifying burin-in process is placed in the container that fresh acetone is housed and carries out exchange of solvent, and every day changes acetone, continues 5 days;
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extraction instrument, at T=45 DEG C, through CO under P=200bar experiment condition2Supercritical drying obtains aerogel;
Step 6, the aerogel carbonization in tube furnace under flowing argon gas shielded that will obtain, slowly rise to 150 DEG C from room temperature and vacuumize, keep 2h; Then lead to into argon gas with the gas velocity of 50mL/min, slowly rise to 1050 DEG C with 0.6 DEG C/min temperature rise rate from 150 DEG C and keep carbonization 3h, naturally cool to room temperature, obtain carbon aerogels; The density of this carbon aerogels is 60mg/cm3, specific surface area is 967m2/ g, at 400��2000nm ultraviolet-visible-near-infrared band to light reflectance lower than 0.19%, light absorption ratio is greater than 99.81%, and electromicroscopic photograph is shown in Fig. 3.
Embodiment 4:
Step one, 1.941g Resorcinol is dissolved in 50mL deionized water, after being stirred to solution clarification, add 2.614mL formaldehyde solution, stir 30min, then 0.441mL sodium carbonate solution is added, stir 20min, then supplement 30mL deionized water, obtain reaction soln, under agitation, reaction soln dropwise adds 20mL modified chitosan copper coordination compound solution, continues to stir 30min, obtain mixing solutions; The density 1.066g/mL of described formaldehyde solution, formaldehyde mass percent is 38%; The substance withdrawl syndrome of described sodium carbonate solution is 0.2mol/L; The preparation method of described modified chitosan copper coordination compound solution is: gets 6g phthalic anhydride, mixes with 25g acetone, then adds 8g chitosan and the mixing of 4g pyridine, mixture is warming up to 80 DEG C and stirring reaction 10h at this temperature, obtains reacting rear mixture; After mixture after reaction is cooled to room temperature, filtering, filtrate is through dried over mgso, remove and obtain chitosan esterification products after organic solvent again through distillation; Get chitosan esterification products 10g, join in 50g ethanol, stir 20min, then adding the copper nitrate aqueous solution that 7g mass concentration is 20%, lower of agitation condition adds the pH value to 7 that triethylamine regulates solution, then stirs 1h at ambient temperature, filter, the solid product obtained with distilled water and absolute ethanol washing 5 times, is then dried to constant weight in the baking oven of 70 DEG C, obtains modified chitosan copper coordination compound successively; Get 5g modified chitosan copper coordination compound, add 100gN, dinethylformamide, stir and obtain modified chitosan copper coordination compound solution; Described chitosan is dissolved in the acetic acid solution of 1% then to carry out esterification.
Step 2, mixing solutions is sealed, and it is positioned in the thermostat container of 70 DEG C solidifying 45 days, obtain wet gel;
Step 3, the wet gel obtained is placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution carries out acidifying aging 7 days;
Wet gel after step 4, just acidifying burin-in process is placed in the container that fresh acetone is housed and carries out exchange of solvent, and every day changes acetone, continues 5 days;
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extraction instrument, at T=45 DEG C, through CO under P=200bar experiment condition2Supercritical drying obtains aerogel;
Step 6, the aerogel obtained is added in charring furnace, charring furnace is risen to 150 DEG C from room temperature and vacuumizes, insulation 2h, then lead to into nitrogen with the gas velocity of 50mL/min, it is warming up to 200 DEG C with the speed of 0.5 DEG C/min, insulation 25min, then it is warming up to 500 DEG C with the speed of 0.8 DEG C/min, insulation 30min, is then warming up to 900 DEG C with the speed of 0.6 DEG C/min, insulation 2h, then it is warming up to 1100 DEG C with the speed of 0.5 DEG C/min, insulation 1h, naturally cools to room temperature, obtains carbon aerogels; The density of this carbon aerogels is 45mg/cm3, specific surface area is 971m2/ g, this carbon aerogels at 400��2000nm ultraviolet-visible-near-infrared band to light reflectance all lower than 0.08%, light absorption ratio is all greater than 99.92%.
Embodiment 5:
Step one, 2.588g Resorcinol is dissolved in 50mL deionized water, it is stirred to after solution clarifies, adds 3.485mL formaldehyde solution, stir 20min, then add 0.588mL sodium carbonate solution, stir 20min, then supplement 20mL deionized water, obtain reaction soln, under agitation, reaction soln dropwise adds 30mL modified chitosan copper coordination compound solution, then solution is placed in the ultrasonic 50min of ultrasonic wave separating apparatus, ultrasonic power is 1200W, and ultrasonic frequency is at 28KHz; Complete ultrasonic after, continue stir 30min, obtain mixing solutions; The density 1.066g/mL of described formaldehyde solution, formaldehyde mass percent is 38%; The substance withdrawl syndrome of described sodium carbonate solution is 0.2mol/L; The preparation method of described modified chitosan copper coordination compound solution adopts the method described in embodiment 4;
Step 2, mixing solutions is sealed, and it is positioned in the thermostat container of 80 DEG C gel 30 days, obtain wet gel;
Step 3, the wet gel obtained is placed in trifluoroacetic acid (3vol.%)/acetone (97vol.%) solution carries out acidifying aging 7 days;
Wet gel after step 4, just acidifying burin-in process is placed in the container that fresh acetone is housed and carries out exchange of solvent, and every day changes acetone, continues 5 days;
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extraction instrument, at T=45 DEG C, through CO under P=200bar experiment condition2Supercritical drying obtains aerogel;
Step 6, the aerogel obtained is added in charring furnace, charring furnace is risen to 150 DEG C from room temperature and vacuumizes, insulation 2h, then lead to into nitrogen with the gas velocity of 50mL/min, it is warming up to 200 DEG C with the speed of 0.5 DEG C/min, insulation 25min, then it is warming up to 500 DEG C with the speed of 0.8 DEG C/min, insulation 30min, is then warming up to 900 DEG C with the speed of 0.6 DEG C/min, insulation 2h, then it is warming up to 1100 DEG C with the speed of 0.5 DEG C/min, insulation 1h, naturally cools to room temperature, obtains carbon aerogels; The density of this carbon aerogels is 58mg/cm3, specific surface area is 980m2/ g, this carbon aerogels at 400��2000nm ultraviolet-visible-near-infrared band to light reflectance all lower than 0.06%, light absorption ratio is all greater than 99.94%.
The present invention is by control reaction parameter and condition, hydrogel is made through crosslinking reaction by Resorcinol, formaldehyde and modified chitosan copper coordination compound, then the carbon aerogels with wide spectrum dimmer reflecting structure can be prepared through supercritical drying, high temperature cabonization, the raw material adopted in the process of preparation is in ratio of the present invention, each parameter is in described scope, and the carbon aerogels density of preparation is lower than 60mg/cm3, specific surface area is greater than 950m2/ g, gained carbon aerogels at 400��2000nm ultraviolet-visible-near-infrared band to light reflectance lower than 0.3%, light absorption ratio is greater than 99.7%, and the existence due to modified chitosan copper coordination compound, there is interaction of hydrogen bond in amino and the Resorcinol of modified chitosan copper coordination compound molecular surface, and formaldehyde can react with modified chitosan copper coordination compound, promote the crosslinked of modified chitosan copper coordination compound, methylol group can be formed again with Resorcinol, thus further phenol and formaldehyde molecule are adsorbed on around the skeleton of chitosan, the stability being cross-linked is strengthened, the carbon aerogels that simultaneously aerogel obtains through carbonization comprises nano oxidized steel structure, the application of carbon aerogels can be expanded, can be used as the super black-materials of a kind of novelty, sensor is detected in aerospace, solar energy photothermal converter, the fields such as national defence stealthy technique have potential using value widely.In addition, adopt and ultrasonic mixing solutions is processed, ultrasonic energy discharges huge energy, localized hyperthermia's hyperbaric environment of generation and the microjet with strong impacts, it is easy to realize each phase Homogeneous phase mixing, elimination partial concn is uneven, improve speed of response, stimulate the formation of cenotype, and reunion can also be played shearing action, be conducive to the formation of nanocluster, and existence that can be stable. And in the process of carbonization, adopt temperature programming, temperature programming can play the greatest benefit of each temperature section, reduce the medial temperature of whole process, reduce total power loss, improving overall capacity usage ratio, meanwhile, temperature programming decreases the heating unit working hour at high temperature, thus reduce the requirement to heating unit high-temperature stability, it is to increase the rate of utilization of heating installation and reliability.
Although embodiment of the present invention are open as above, but listed application that it is not restricted in specification sheets and enforcement mode, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore claim is not being deviated from and under general concept that equivalency range limits, the present invention is not limited to specific details and illustrates and the legend described here.
Claims (10)
1. one kind has the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure, it is characterised in that, comprise the following steps:
Step one, Resorcinol is dissolved in deionized water, after being stirred to solution clarification, add formaldehyde solution, stir 10��30min, then sodium carbonate is added, stir 10��30min, then supplement deionized water, obtain reaction soln, under agitation, reaction soln dropwise adds modified chitosan copper coordination compound solution, continues stirring 10��30min, obtain mixing solutions;
Step 2, mixing solutions is sealed, and it is positioned in the thermostat container of 60��80 DEG C and carries out gelation, obtain wet gel;
Step 3, that the wet gel obtained is placed in trifluoroacetic acid/acetone soln carries out acidifying is aging;
Step 4, the wet gel after acidifying is placed in acetone soln carries out exchange of solvent;
Step 5, the wet gel after exchange of solvent is put into supercritical carbon dioxide extraction instrument, carry out CO 2 supercritical drying, obtain aerogel;
Step 6, the aerogel obtained is put into temperature programmed control charring furnace, carries out sintering under protection of inert gas, carbonization, obtain carbon aerogels.
2. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterized in that, the preparation method of described modified chitosan copper coordination compound solution is: by weight, get 5��8 parts of phthalic anhydrides, mix with 20��30 parts of acetone, add chitosan and the mixing of 1��5 part of pyridine of 3��10 parts again, mixture is warming up to 75��85 DEG C and stirring reaction 5��10h at this temperature, obtains reacting rear mixture; After mixture after reaction is cooled to room temperature, filtering, filtrate is through dried over mgso, remove and obtain chitosan esterification products after organic solvent again through distillation; Get chitosan esterification products 5��10 parts, join in 20��60 parts of ethanol, stir 10��30min, then adding 5��10 parts of mass concentrations is the copper nitrate aqueous solution of 20%, and lower of agitation condition adds triethylamine and regulates the pH value of solution to 7-8, then stirs 1��2h at ambient temperature, filter, the solid product obtained with distilled water and absolute ethanol washing 3��5 times, is then dried to constant weight in the baking oven of 50��70 DEG C, obtains modified chitosan copper coordination compound successively;Get 1��5 part of modified chitosan copper coordination compound, add 100 parts of N, dinethylformamide, stir and obtain modified chitosan copper coordination compound solution.
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, in the reaction soln that described step one obtains, the total mass mark of Resorcinol and formaldehyde is 1wt%��4wt%; In described step one, the mass ratio of Resorcinol and sodium carbonate is 100��200:1; In described step one, the mass ratio of Resorcinol and modified chitosan copper coordination compound is 1:0.5��2.
4. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterized in that, after described step one dropwise adds modified chitosan copper coordination compound solution in reaction soln, solution is placed in the ultrasonic 30��60min of ultrasonic wave separating apparatus, the regulation range of ultrasonic power is at 500��1500W, and ultrasonic frequency is at 20��40KHz.
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, in described step 2, gelation time is 15 days��45 days.
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, the described rare gas element in step 6 is the one in helium, argon gas, nitrogen.
7. there is the preparation method of the carbon aerogels of wide spectrum dimmer reflecting structure as described in claim 1, it is characterized in that, in described step 6, the process of temperature programmed control is: from room temperature, charring furnace is risen to 150 DEG C and vacuumizes, insulation 2h, then lead to into rare gas element with the gas velocity of 50mL/min, it is warming up to 200��400 DEG C with the speed of 0.5 DEG C/min, insulation 25��35min, then it is warming up to 500��700 DEG C with the speed of 0.8 DEG C/min, insulation 30��60min, then it is warming up to 800��900 DEG C with the speed of 0.6 DEG C/min, insulation 1��2h, then it is warming up to 1000��1100 DEG C with the speed of 0.5 DEG C/min, insulation 1��3h, naturally cool to room temperature, obtain carbon aerogels.
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 carbonization process temperature rise rate in described step 6 is 0.5 DEG C/min��1 DEG C/min; Described carbonization process sintering temperature is 900 DEG C��1100 DEG C.
9. 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 of supercritical drying 45 DEG C, pressure 200bar in described step 5.
10. 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 density of described carbon aerogels is 20��60mg/cm3, specific surface area is 1783��967m2/ g, described carbon aerogels at 400��2000nm ultraviolet-visible-near-infrared band to light reflectance all lower than 0.3%, light absorption ratio is all greater than 99.7%.
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