CN107141012B - Preparation method of closed-cell graphene oxide-based heat insulation material - Google Patents
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Abstract
A preparation method of a closed-cell graphene oxide-based heat insulation material relates to a preparation method of a heat insulation material. The invention aims to solve the problems of heavy weight, high heat conductivity coefficient, complex forming process and high cost of the existing heat insulating material for the low-temperature storage tank. The preparation method comprises the following steps: firstly, preparing a graphene oxide emulsion; secondly, freeze drying: freezing the graphene oxide emulsion for 0.5-1.5 h at the temperature of-40 ℃ to-60 ℃, then freezing and drying for 5-7 days at the temperature of-60 ℃, and finally drying the freeze-dried graphene oxide block. The method comprises the steps of preparing graphene oxide spherical liquid drops by an emulsion method, and then removing a solvent in the emulsion by freeze drying: and water and paraxylene are used for preparing the graphene oxide heat insulation material with the closed pore structure, so that the heat conductivity coefficient of the graphene oxide heat insulation material is reduced, and the heat insulation performance of the graphene oxide heat insulation material is further improved. The method is suitable for preparing the closed-cell graphene oxide-based heat insulation material.
Description
Technical Field
The invention relates to a preparation method of a closed-cell graphene oxide-based heat insulation material.
Background
The porous heat insulating material has light weight, high porosity and excellent heat insulating performance, and is one of the most widely used and effective materials in heat insulating material system. The traditional organic foam heat-insulating material, glass fiber, asbestos and the like have high heat conductivity coefficient, large practical application volume and large environment pollution, and can achieve the heat-insulating effect only by needing thicker materials; meanwhile, the organic foam material has a large linear expansion coefficient, is easily damaged by temperature change, and cannot be applied to an environment with rapid temperature change.
The low-temperature storage tank in the aerospace field is a main container for storing low-temperature propellant, and the storage tank can effectively control the heat transfer by using a heat insulation material and a heat insulation technology, prevent low-temperature liquid from rapidly evaporating, prevent air from liquefying on the outer wall of the storage tank and achieve the purposes of cold insulation and heat preservation. The design and development of novel light and efficient heat insulation materials are the keys for realizing the weight reduction of the integral structure of the composite material storage box, improving the heat insulation efficiency and realizing the safe storage of low-temperature media. The existing heat insulation materials and heat insulation structures represented by foam, aerogel and vacuum heat insulation interlayers have the disadvantages of heavy weight, high heat conductivity coefficient, complex forming process and high cost, and are difficult to meet the light and efficient heat insulation requirements of the composite material storage box. The characteristic that the organic foam material is easy to absorb moisture seriously affects the heat insulation efficiency; e.g. with SiO2The porous heat-insulating material represented by aerogel has poor molding process; the high vacuum degree of the high vacuum heat insulation sandwich material is difficult to obtain and maintain for a long time, and the high vacuum heat insulation sandwich material is widely applied to metal storage tanks. Therefore, the design and development of the novel light high-efficiency heat insulation material are the keys for realizing the weight reduction of the integral structure of the composite material storage box, improving the heat insulation efficiency and realizing the safe storage of the low-temperature medium.
Disclosure of Invention
The invention provides a preparation method of a closed-pore graphene oxide-based heat insulation material, aiming at solving the problems of heavy weight, high heat conductivity coefficient, complex forming process and high cost of the existing heat insulation material for a low-temperature storage tank.
A preparation method of a closed-cell graphene oxide-based heat insulation material comprises the following steps:
firstly, preparing a graphene oxide emulsion:
preparing a graphene oxide aqueous dispersion by adopting a Hummers method, stirring and dissolving ethylene oxide-propylene oxide block copolyether into the graphene oxide aqueous dispersion at room temperature under the stirring condition, then adding p-xylene, and finally shearing at a high speed of 8000-16000 r/min for 5-30 min to obtain a graphene oxide emulsion;
the content of graphene oxide in the graphene oxide aqueous dispersion liquid is 7-9 mg/mL; the mass ratio of the graphene oxide to the ethylene oxide-propylene oxide block copolyether in the graphene oxide aqueous dispersion is 1: (0.5 to 4); the volume ratio of the graphene oxide aqueous dispersion to the paraxylene is 5: (5-7); the relative molecular mass of the ethylene oxide-propylene oxide block copolyether is 8530;
secondly, freeze drying:
firstly, freezing the graphene oxide emulsion obtained in the step one for 0.5-1.5 h at the temperature of-40 ℃ to-60 ℃, then carrying out freeze drying for 5-7 days at the temperature of-60 ℃ to obtain a freeze-dried graphene oxide block, and then placing the freeze-dried graphene oxide block in a vacuum drying oven for drying to obtain the closed-cell graphene oxide-based heat insulation material; the drying temperature is 60 ℃, and the drying time is 12-48 h.
The method of the invention has the following beneficial effects:
1. the preparation method comprises the following steps of preparing graphene oxide spherical liquid drops by an emulsion method, and then removing a solvent in the emulsion by freeze drying: the graphene oxide heat insulation material with a closed pore structure is prepared from water and paraxylene, so that the heat conductivity coefficient of the graphene oxide heat insulation material is reduced, and the heat insulation performance of the graphene oxide heat insulation material is further improved;
2. according to the invention, the graphene thermal insulation material is designed into a closed-cell structure, so that the heat convection effect of air in the air holes of the graphene thermal insulation material can be effectively reduced, the thermal insulation performance of the graphene thermal insulation material is further improved, the effective regulation and control and management of heat transfer are realized, and the limitation of traditional thermal insulation materials such as foamed plastics, glass fibers and asbestos is broken through;
3. the graphene thermal insulation material prepared by the invention can be applied to the thermal insulation structure of a composite material low-temperature storage box in the aerospace field, can also be applied to the thermal insulation of thermal pipelines and equipment, and has important scientific value and practical significance for the cold insulation of liquid hydrogen, liquid nitrogen and liquid oxygen conveying pipelines, the storage and transmission of liquefied natural gas and liquefied coal bed gas, the thermal insulation of house buildings, refrigeration equipment and the like.
4. The invention selects ethylene oxide propylene oxide block copolyether (F68) as a high molecular surfactant, can be used for improving the emulsion stability by cooperating with graphene oxide as a stabilizer, and simultaneously F68 is a high molecular polymer with the relative molecular mass of 8530, and plays a supporting role in a closed-cell heat-insulating material.
5. According to the invention, paraxylene is used as an oil phase, the molecular structure of the paraxylene is similar to the hydrophobic end group structure of graphene oxide, the graphene oxide can be directionally arranged on the surfaces of the paraxylene and water, and the mixed solution of the water, the paraxylene and the graphene oxide is sheared at a high speed to form a stable emulsion. According to the invention, the mixed solution of water, p-xylene and graphene oxide adopts p-xylene as an oil phase, and compared with other oil phase materials such as acetophenone, cyclohexane or chloroform, the mixed solution can still keep the stability of the emulsion after being sheared at a high speed of 16000rpm for 10min, and the phenomenon of layering can not occur; the emulsion prepared from acetophenone, cyclohexane or chloroform, etc. can be delaminated and unstable when being sheared at high speed of 16000rpm for 10 min.
6. According to the invention, the graphene oxide emulsion is frozen at-60 ℃, and then freeze-dried, so that the p-xylene oil phase can be recovered in a freeze dryer and can be recycled, and the cost for preparing the closed-cell graphene oxide-based heat insulation material is reduced.
7. The method is environment-friendly, simple, low in cost, repeatable and easy to control.
8. The density of the graphene oxide heat insulation material with the closed-cell structure prepared by the invention is 0.021-0.035 g/cm3The density of the foam is far less than that of common styrene foam (30-40 g/cm)3) The thermal insulation material has the porosity of 95.5-90.2%, the thermal conductivity coefficient of 22.1 mW/(m.K) and less than 55 mW/(m.K), and is a light high-efficiency thermal insulation material.
Description of the drawings:
FIG. 1 is a photograph of a real object of the graphene oxide-based heat insulating material prepared in example 1;
FIG. 2 is a photograph of a real object of the graphene oxide-based heat insulating material prepared in example 2;
FIG. 3 is a photograph of an actual object of the graphene oxide-based heat insulating material prepared in example 3;
FIG. 4 is a photograph of an actual object of the graphene oxide-based heat insulating material prepared in example 4;
FIG. 5 is an optical micrograph of a graphene oxide emulsion prepared according to example 4, wherein the scale is 20 μm;
FIG. 6 is a photograph of a real object of the graphene oxide-based heat insulating material prepared in example 5;
FIG. 7 is an optical micrograph of a graphene oxide emulsion prepared according to example 5, wherein the scale is 20 μm;
FIG. 8 is a scanning electron microscope image of the graphene oxide-based heat insulating material prepared in example 5.
The specific implementation mode is as follows:
the technical scheme of the invention is not limited to the specific embodiments listed below, and any reasonable combination of the specific embodiments is included.
The first embodiment is as follows: the preparation method of the closed-cell graphene oxide-based heat insulation material comprises the following steps:
firstly, preparing a graphene oxide emulsion:
preparing a graphene oxide aqueous dispersion by adopting a Hummers method, stirring and dissolving ethylene oxide-propylene oxide block copolyether into the graphene oxide aqueous dispersion at room temperature under the stirring condition, then adding p-xylene, and finally shearing at a high speed of 8000-16000 r/min for 5-30 min to obtain a graphene oxide emulsion;
secondly, freeze drying:
firstly, freezing the graphene oxide emulsion obtained in the step one for 0.5-1.5 h at the temperature of-40 ℃ to-60 ℃, then carrying out freeze drying for 5-7 days at the temperature of-60 ℃ to obtain a freeze-dried graphene oxide block, and then placing the freeze-dried graphene oxide block in a vacuum drying oven for drying to obtain the closed-cell graphene oxide-based heat insulation material.
The embodiment has the following beneficial effects:
1. in the embodiment, the graphene oxide spherical liquid drop is prepared by an emulsion method, and then the solvent in the emulsion is removed by freeze drying: the graphene oxide heat insulation material with a closed pore structure is prepared from water and paraxylene, so that the heat conductivity coefficient of the graphene oxide heat insulation material is reduced, and the heat insulation performance of the graphene oxide heat insulation material is further improved;
2. according to the embodiment, the graphene thermal insulation material is designed into a closed-cell structure, so that the heat convection effect of air in the air holes of the graphene thermal insulation material can be effectively reduced, the thermal insulation performance of the graphene thermal insulation material is further improved, the effective regulation and control and management of heat transfer are realized, and the limitation of traditional thermal insulation materials such as foamed plastics, glass fibers and asbestos is broken through;
3. the graphene thermal insulation material prepared by the embodiment can be applied to the thermal insulation structure of the composite material low-temperature storage box in the aerospace field, can also be applied to the thermal insulation of thermal pipelines and equipment, and has important scientific value and practical significance for the cold insulation of liquid hydrogen, liquid nitrogen and liquid oxygen conveying pipelines, the storage and transmission of liquefied natural gas and liquefied coal bed gas, the thermal insulation of house buildings, freezing and refrigerating equipment and the like.
4. In the embodiment, ethylene oxide-propylene oxide block copolyether (F68) is selected as a high molecular surfactant, can be used as a stabilizer in cooperation with graphene oxide to improve the emulsion stability, and meanwhile, F68 is a high molecular polymer with the relative molecular mass of 8530 and plays a supporting role in a closed-cell heat-insulating material.
5. In the embodiment, the p-xylene is used as an oil phase, the molecular structure of the p-xylene is similar to the hydrophobic end group structure of the graphene oxide, the graphene oxide can be directionally arranged on the surfaces of the p-xylene and water, and the mixed solution of the water, the p-xylene and the graphene oxide is sheared at a high speed to form a stable emulsion. In the embodiment, the mixed solution of water, paraxylene and graphene oxide adopts paraxylene as an oil phase, and compared with other oil phase materials such as acetophenone, cyclohexane or chloroform and the like, the mixed solution can still keep the stability of the emulsion after being sheared at a high speed of 16000rpm for 10min, and the layering phenomenon can not occur; the emulsion prepared from acetophenone, cyclohexane or chloroform, etc. can be delaminated and unstable when being sheared at high speed of 16000rpm for 10 min.
6. According to the embodiment, the graphene oxide emulsion is frozen at-60 ℃, and then freeze-dried, so that the p-xylene oil phase can be recovered in a freeze dryer and can be recycled, and the cost for preparing the closed-cell graphene oxide-based heat insulation material is reduced.
7. The method of the embodiment is environment-friendly, simple, low in cost, repeatable and easy to control.
8. The density of the graphene oxide heat insulation material with the closed-cell structure prepared by the embodiment is 0.021-0.035 g/cm3The density of the foam is far less than that of common styrene foam (30-40 g/cm)3) The thermal insulation material has the porosity of 95.5-90.2%, the thermal conductivity coefficient of 22.1 mW/(m.K) and less than 55 mW/(m.K), and is a light high-efficiency thermal insulation material.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, the content of graphene oxide in the graphene oxide aqueous dispersion is 7-9 mg/mL. Other steps and parameters are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: step one, the mass ratio of the graphene oxide to the ethylene oxide-propylene oxide block copolyether in the graphene oxide aqueous dispersion is 1: (0.5 to 4). Other steps and parameters are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: step one, the volume ratio of the graphene oxide aqueous dispersion to the paraxylene is 5: (5-7). Other steps and parameters are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: step one the ethylene oxide propylene oxide block copolyether has a relative molecular mass of 8530. Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and the drying temperature in the second step is 60 ℃, and the drying time is 12-48 h. Other steps and parameters are the same as in one of the first to fifth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1:
a preparation method of a closed-cell graphene oxide-based heat insulation material comprises the following steps:
firstly, preparing a graphene oxide emulsion:
preparing a graphene oxide aqueous dispersion by adopting a Hummers method, stirring and dissolving ethylene oxide-propylene oxide block copolyether into the graphene oxide aqueous dispersion at room temperature under the stirring condition, then adding p-xylene, and finally shearing at a high speed of 16000 for 10min to obtain a graphene oxide emulsion;
the content of graphene oxide in the graphene oxide aqueous dispersion liquid is 8 mg/mL; the mass ratio of the graphene oxide to the ethylene oxide-propylene oxide block copolyether in the graphene oxide aqueous dispersion is 1: 0.5; the volume ratio of the graphene oxide aqueous dispersion to the paraxylene is 5: 7; the relative molecular mass of the ethylene oxide-propylene oxide block copolyether is 8530;
secondly, freeze drying:
firstly, freezing the graphene oxide emulsion obtained in the step one for 0.5h at the temperature of-60 ℃, then freezing and drying for 5 days at the temperature of-60 ℃ to obtain a freeze-dried graphene oxide block, and then drying the freeze-dried graphene oxide block in a vacuum drying oven to obtain the closed-cell graphene oxide-based heat insulation material; the drying temperature is 60 ℃, and the drying time is 24 hours; a photograph of the graphene oxide-based heat insulating material prepared in example 1 is shown in fig. 1;
example 2:
this example differs from example 1 in that: step one, the mass ratio of the graphene oxide to the ethylene oxide-propylene oxide block copolyether in the graphene oxide aqueous dispersion is 1: 1; the rest is the same as the embodiment 1; a photograph of the graphene oxide-based heat insulating material prepared in example 2 is shown in fig. 2;
example 3:
this example differs from example 1 in that: step one, the mass ratio of the graphene oxide to the ethylene oxide-propylene oxide block copolyether in the graphene oxide aqueous dispersion is 1: 2; the rest is the same as the embodiment 1;
a photograph of the graphene oxide-based heat insulating material prepared in example 3 is shown in fig. 3; the comparison of fig. 1, 2 and 3 shows that in the graphene oxide closed-cell thermal insulation materials prepared with different F68 contents, when the mass ratio of graphene oxide to F68 is 1:2, the shape of the sample obtained by freeze drying is better maintained, and further, the F68 can play a role in supporting the thermal insulation material structure.
Example 4:
this example differs from example 1 in that: step one, the mass ratio of the graphene oxide to the ethylene oxide-propylene oxide block copolyether in the graphene oxide aqueous dispersion is 1: 4; the rest is the same as in example 1. A photograph of the graphene oxide-based heat insulating material prepared in example 4 is shown in fig. 4; the optical micrograph of the graphene oxide emulsion prepared in example 4 is shown in fig. 5, wherein the scale in the micrograph is 20 μm, and it can be seen from fig. 5 that the droplet diameter of the graphene oxide microemulsion is 6.5 ± 3.8 μm;
example 5:
this example differs from example 1 in that: step (2) no ethylene oxide propylene oxide block copolyether is added into the graphene oxide aqueous dispersion; the rest is the same as in example 1.
A photograph of the graphene oxide-based heat insulating material prepared in example 5 is shown in fig. 6; as can be seen from comparison between fig. 4 and 6, the graphene oxide closed-cell thermal insulation material containing F68 can maintain the shape during freeze drying, and plays a role in structural support;
the optical micrograph of the graphene oxide emulsion prepared in example 5 is shown in FIG. 7, wherein the scale is 20 μm; as can be seen from the figure, the diameter of the graphene oxide microemulsion liquid drop is 15.9 +/-7.3 μm; as can be seen from fig. 7 and 5, F68 can reduce the diameter of emulsion droplets, which is beneficial to improving the stability of the emulsion;
FIG. 8 is a scanning electron micrograph of the graphene oxide-based heat insulating material prepared in example 5; as can be seen from fig. 8, the graphene oxide emulsion can form a spherical closed cell structure after freeze-drying, and the pore size after freeze-drying is similar to the diameter of the droplets in the emulsion.
Claims (2)
1. A preparation method of a closed-cell graphene oxide-based heat insulation material is characterized by comprising the following steps: the method comprises the following steps;
firstly, preparing a graphene oxide emulsion:
preparing a graphene oxide aqueous dispersion by adopting a Hummers method, stirring and dissolving ethylene oxide-propylene oxide block copolyether into the graphene oxide aqueous dispersion at room temperature under the stirring condition, then adding p-xylene, and finally shearing at a high speed of 8000-16000 r/min for 5-30 min to obtain a graphene oxide emulsion;
step one, the content of graphene oxide in the graphene oxide aqueous dispersion liquid is 7-9 mg/mL;
step one, the mass ratio of the graphene oxide to the ethylene oxide-propylene oxide block copolyether in the graphene oxide aqueous dispersion is 1: (0.5 to 4);
step one, the volume ratio of the graphene oxide aqueous dispersion to the paraxylene is 5: (5-7);
step one, the relative molecular mass of the ethylene oxide-propylene oxide block copolyether is 8530;
secondly, freeze drying:
firstly, freezing the graphene oxide emulsion obtained in the step one for 0.5-1.5 h at the temperature of-40 ℃ to-60 ℃, then carrying out freeze drying for 5-7 days at the temperature of-60 ℃ to obtain a freeze-dried graphene oxide block, and then placing the freeze-dried graphene oxide block in a vacuum drying oven for drying to obtain the closed-cell graphene oxide-based heat insulation material.
2. The method of preparing a closed-cell graphene oxide-based thermal insulation material according to claim 1, wherein: and the drying temperature in the second step is 60 ℃, and the drying time is 12-48 h.
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