CN102134068A - Preparation method of graphitic carbon foam with high aperture ratio - Google Patents
Preparation method of graphitic carbon foam with high aperture ratio Download PDFInfo
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- CN102134068A CN102134068A CN 201110102881 CN201110102881A CN102134068A CN 102134068 A CN102134068 A CN 102134068A CN 201110102881 CN201110102881 CN 201110102881 CN 201110102881 A CN201110102881 A CN 201110102881A CN 102134068 A CN102134068 A CN 102134068A
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Abstract
The invention discloses a preparation method of graphitic carbon foam with a high aperture ratio, belonging to the technical filed of inorganic non-metallic carbon material science. In the method, components in asphalt substances, which are soluble in organic solvents, are used as carbon sources of carbon foam, polymer foam is used as a carbon foam template, and a graphitic carbon foam material with high aperture ratio is prepared through dipping, pre-oxidation and carbonization processes. The novel carbon material has both the highly opened foam structure characteristic of solid foam and the structure and property of a graphitic carbon material. The graphitic carbon foam can be applied to multiple fields, such as thermal control materials, reinforced materials, battery substrates, microbial growth stands, fixed bed stuffing and the like.
Description
Technical field
The present invention relates to a kind of preparation method of high opening rate greying Carbon foam, belong to inorganic non-metallic materials science technology branch---carbon material science and technology field.
Background technology
Carbon foam the earliest is the netted glass raw material of wood-charcoal material that W.Ford made by pyrolysis thermosetting phenolic foam in early 1960s.This Carbon foam has high porosity, low density, Heat stability is good, chemical purity advantages of higher, has widely as electrode materials, thermal insulation material, protecting against shock material and support of the catalyst and uses.Yet netted glass raw material of wood-charcoal material is a kind of typical non-graphitized charcoal.And graphite material is because of having the high heat-conductivity conducting performance, and characteristics such as high strength become the target that the carbon material investigator competitively chases.1992, it is that raw material has prepared Carbon foam by making the bubble technology that the Hager of United States Air Force material laboratory adopts mesophase pitch first, its method is that mesophase pitch is under high pressure inflated foaming, carry out pre-oxidation treatment then, charing and greying (Hager J W.Idealized ligament formation and geometry in open-celled foams.Materials Research Society Symposium Proceedings again, California, 1992,270:41.).The researchist Klett success of U.S.'s Oak Ridge National Laboratory is that raw material prepares high graphitization Carbon foam (Klett J by the foaming that volatilizees certainly with the mesophase pitch, Hardy R, Romine E, et al.High-thermal-conductivity, mesophase-pitch-derived carbon foams:effect of precursor on structure and properties.Carbon, 2000,38 (7): 953-973.).The Li Tongqi of University Of Tianjin is with in mesophase pitch or whipping agent and the mesophase pitch adding normal pressure constant volume container, and the temperature more than softening temperature foams then; Obtain greying foam carbon material (CN200410093854.5) through oxidation, charing, graphitization technique again.Carbon foam after the greying has high thermal conductivity, high conductivity and excellent mechanical property, is a kind of ceramic with broad prospect of application.
Though can obtain to have the Carbon foam of high graphitization degree by above-mentioned these methods, resulting Carbon foam percentage of open area is low, makes its application in a lot of fields be subjected to serious restriction.For example, low percentage of open area makes active substance can't enter Carbon foam inside, therefore causes the Carbon foam internal surface not to be utilized effectively, and this is that Carbon foam can not be as a major reason of lead-acid cell substrate.Same low percentage of open area owing to Carbon foam makes Carbon foam internal flow resistance big, causes Carbon foam inside can not form the fluidic forced convection, though therefore the high graphitization carbon material has high thermal, Carbon foam is relatively poor as the heat sink material effect.And people such as Chen Ya are template with polyamine fat vacuole foam, impregnated in foam surface by pitch is mixed back acquisition pulpous state steeping fluid with water and organic additive, obtain to have the asphalt base foam carbon of high opening rate again by oxidation, charing and graphitization technique.But the Carbon foam hole wall that is obtained is formed by the pitch particle sintering and the carbon-coating interlamellar spacing is the 0.3354nm of 0.338nm greater than graphite crystal, confirmation has lower degree of graphitization, and this has caused calorifics, the electrical properties of the Carbon foam that obtained to be subjected to seriously influencing.
Summary of the invention
In order to overcome above-mentioned problems of the prior art, the invention provides a kind of preparation method of high opening rate greying Carbon foam.This procedure is simple, and Carbon foam has the greying of the hole bubble structure and the height of high opening, the shape of while Carbon foam, and size is easily controlled.
The technical solution used in the present invention is: a kind of preparation method's of high opening rate greying Carbon foam concrete steps are as follows: the 1-5 organic solvent doubly with bitumen weight extracts the acquisition extraction liquid to bitumen, to in above-mentioned extraction liquid, flood 2-10min as the superpolymer foam of template, take out the template foam after flooding, squeeze out excessive extraction liquid and obtain the mixture foam, with the dry 5-300min under 0-150 ℃ of the mixture foam after the extruding, with dried mixture foam under air or oxygen atmosphere, with 0.5-5 ℃/min temperature programming to 200-350 ℃, oxide treatment 20-120min is cooled to the mixture foam that obtains after the room temperature after the oxidation; Mixture foam after the oxidation under protection of inert gas, is obtained Carbon foam with 0.01-50 ℃/min temperature programming to 700-1500 ℃; With the gained Carbon foam with 1-50 ℃/min temperature programming to 2800-3000 ℃, obtain high opening rate greying Carbon foam.
Described organic solvent is selected from the mixture of tetrahydrofuran (THF), pyridine, quinoline and above-mentioned two or more solvent.
Described bitumen is selected from carbobitumen, oil is that pitch or naphthalene are mesophase pitch, and the organic solvent solvend surpasses 30%.
Described template foam is selected from polyurethane foam or phenolic resin foam.
The present invention compared with prior art has following advantage:
(1) Carbon foam that obtains has the hole bubble structure of high graphitization and high opening concurrently.
(2) the present invention can regulate pore structure, density and the intensity of Carbon foam easily, and Carbon foam hole bubble structure is even.
(3) preparation process is simple, not high to equipment requirements, and parameter is controlled easily, processing ease, is easy to amplify.
Embodiment
The invention will be further described below by embodiment.
Embodiment one
Is that 142 ℃ petroleum pitch extracts the solution that obtains the tetrahydrofuran (THF) solvend with the tetrahydrofuran (THF) of 1 times of pitch weight to softening temperature, to in above-mentioned extraction liquid, flood 2min as the polyamine fat vacuole foam of template, take out the polyamine fat vacuole foam after flooding, squeeze out excessive extraction liquid and obtain the mixture foam, with the dry 5min under 0 ℃ of the mixture foam after the extruding, with dried mixture foam under air atmosphere, with 0.5 ℃/min temperature programming to 200 ℃, oxide treatment 1h is cooled to the mixture foam that obtains after the room temperature after the oxidation; Mixture foam after the oxidation under protection of inert gas, ℃ is obtained Carbon foam with 0.01 ℃/min temperature programming to 700.The above-mentioned Carbon foam of gained with 1 ℃/min temperature programming to 2800 ℃, is obtained high opening rate greying Carbon foam.
Gained Carbon foam aperture is 500 microns, and percentage of open area reaches 100%, and the carbon-coating interlamellar spacing is 0.3356 nanometer.Hole bubble structure and high graphitization structure with high opening.
Embodiment two
Is that 193 ℃ coal-tar pitch extracts the solution that obtains the quinoline solvend with the quinoline of 4 times of pitch weight to softening temperature, to in above-mentioned extraction liquid, flood 5min as the phenolic resin foam of template, take out the phenolic resin foam after flooding, squeeze out excessive extraction liquid and obtain the mixture foam, with the dry 20min under 150 ℃ of the mixture foam after the extruding, with dried mixture foam under air atmosphere, with 5 ℃/min temperature programming to 300 ℃, oxide treatment 1h is cooled to the mixture foam that obtains after the room temperature after the oxidation; Mixture foam after the oxidation under protection of inert gas, ℃ is obtained Carbon foam with 5 ℃/min temperature programming to 1500.The above-mentioned Carbon foam of gained with 5 ℃/min temperature programming to 3000 ℃, is obtained high opening rate greying Carbon foam.
Gained Carbon foam aperture is 300 microns, and percentage of open area reaches 100%, and the carbon-coating interlamellar spacing is 0.3355 nanometer.Hole bubble structure and high graphitization structure with high opening.
Embodiment three
Is that 89 ℃ coal-tar pitch extracts the solution that obtains the pyridine solvend with the pyridine of 2 times of pitch weight to softening temperature, to in above-mentioned extraction liquid, flood 3min as the polyamine fat vacuole foam of template, take out the polyamine fat vacuole foam after flooding, squeeze out excessive extraction liquid and obtain the mixture foam, with the dry 500min under 100 ℃ of the mixture foam after the extruding, with dried mixture foam under oxygen atmosphere, with 5 ℃/min temperature programming to 300 ℃, oxide treatment 20min is cooled to the mixture foam that obtains after the room temperature after the oxidation; Mixture foam after the oxidation under protection of inert gas, ℃ is obtained Carbon foam with 5 ℃/min temperature programming to 1200.The above-mentioned Carbon foam of gained with 50 ℃/min temperature programming to 2800 ℃, is obtained high opening rate greying Carbon foam.
Gained Carbon foam aperture is 750 microns, and percentage of open area reaches 100%, and the carbon-coating interlamellar spacing is 0.3356 nanometer.Hole bubble structure and high graphitization structure with high opening.
Embodiment four
Is that 89 ℃ coal-tar pitch extracts the solution that obtains the pyridine solvend with the pyridine of 5 times of pitch weight to softening temperature, to in above-mentioned extraction liquid, flood 10min as the polyamine fat vacuole foam of template, take out the polyamine fat vacuole foam after flooding, squeeze out excessive extraction liquid and obtain the mixture foam, with the dry 500min under 80 ℃ of the mixture foam after the extruding, with dried mixture foam under air atmosphere, with 1 ℃/min temperature programming to 300 ℃, oxide treatment 60min is cooled to the mixture foam that obtains after the room temperature after the oxidation; Mixture foam after the oxidation under protection of inert gas, ℃ is obtained Carbon foam with 50 ℃/min temperature programming to 800.The above-mentioned Carbon foam of gained with 50 ℃/min temperature programming to 2800 ℃, is obtained high opening rate greying Carbon foam.
Gained Carbon foam aperture is 500 microns, and percentage of open area reaches 100%, and the carbon-coating interlamellar spacing is 0.3356 nanometer.Hole bubble structure and high graphitization structure with high opening.
Claims (4)
1. the preparation method of a high opening rate greying Carbon foam, it is characterized in that: the concrete steps of this method are as follows:
1-5 organic solvent doubly with bitumen weight extracts the acquisition extraction liquid to bitumen, to in above-mentioned extraction liquid, flood 2-10min as the superpolymer foam of template, take out the template foam after flooding, squeeze out excessive extraction liquid and obtain the mixture foam, with the dry 5-300min under 0-150 ℃ of the mixture foam after the extruding, with dried mixture foam under air or oxygen atmosphere, with 0.5-5 ℃/min temperature programming to 200-350 ℃, oxide treatment 20-120min is cooled to the mixture foam that obtains after the room temperature after the oxidation; Mixture foam after the oxidation under protection of inert gas, is obtained Carbon foam with 0.01-50 ℃/min temperature programming to 700-1500 ℃; With the gained Carbon foam with 1-50 ℃/min temperature programming to 2800-3000 ℃, obtain high opening rate greying Carbon foam.
2. the preparation method of a kind of high opening rate greying Carbon foam according to claim 1 is characterized in that: described organic solvent is selected from the mixture of tetrahydrofuran (THF), pyridine, quinoline and above-mentioned two or more solvent.
3. the preparation method of a kind of high opening rate greying Carbon foam according to claim 1 is characterized in that: described bitumen is selected from carbobitumen, oil is that pitch or naphthalene are mesophase pitch, and the organic solvent solvend surpasses 30%.
4. the preparation method of a kind of high opening rate greying Carbon foam according to claim 1 is characterized in that: described template foam is selected from polyurethane foam or phenolic resin foam.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613096A (en) * | 2013-12-06 | 2014-03-05 | 福州大学 | Low-cost method for preparing graphene macroform |
| CN103803529A (en) * | 2014-02-28 | 2014-05-21 | 东北林业大学 | Method for preparing honeycomb-type multiporous foam carbon with high specific surface area from larix gmelini sawdust |
| CN103950917A (en) * | 2014-05-07 | 2014-07-30 | 北京理工大学 | Method for preparing porous carbon material |
| CN106582260A (en) * | 2016-11-02 | 2017-04-26 | 广西大学 | Apparatus for purifying hydrophobic organic waste gas and purifying method therefor |
| CN107055527A (en) * | 2017-06-26 | 2017-08-18 | 俞惠英 | A kind of preparation method of graphitizable foams charcoal |
| CN107244665A (en) * | 2017-06-27 | 2017-10-13 | 常州市协旺纺织品有限公司 | A kind of preparation method of phenolic resin based foam carbon |
| CN110407203A (en) * | 2019-06-06 | 2019-11-05 | 湖南中科星城石墨有限公司 | A kind of highly conductive graphite foam and preparation method thereof |
| CN114956040A (en) * | 2022-06-10 | 2022-08-30 | 四川大学 | Nitrogen-oxygen doped graded porous carbon material, preparation method and application |
Citations (2)
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| CN101434388A (en) * | 2008-12-05 | 2009-05-20 | 华东理工大学 | Preparation of small pore diameter carbon foam |
| CN101693533A (en) * | 2009-10-23 | 2010-04-14 | 大连理工大学 | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials |
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2011
- 2011-04-24 CN CN 201110102881 patent/CN102134068A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434388A (en) * | 2008-12-05 | 2009-05-20 | 华东理工大学 | Preparation of small pore diameter carbon foam |
| CN101693533A (en) * | 2009-10-23 | 2010-04-14 | 大连理工大学 | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613096A (en) * | 2013-12-06 | 2014-03-05 | 福州大学 | Low-cost method for preparing graphene macroform |
| CN103803529A (en) * | 2014-02-28 | 2014-05-21 | 东北林业大学 | Method for preparing honeycomb-type multiporous foam carbon with high specific surface area from larix gmelini sawdust |
| CN103950917A (en) * | 2014-05-07 | 2014-07-30 | 北京理工大学 | Method for preparing porous carbon material |
| CN106582260A (en) * | 2016-11-02 | 2017-04-26 | 广西大学 | Apparatus for purifying hydrophobic organic waste gas and purifying method therefor |
| CN107055527A (en) * | 2017-06-26 | 2017-08-18 | 俞惠英 | A kind of preparation method of graphitizable foams charcoal |
| CN107244665A (en) * | 2017-06-27 | 2017-10-13 | 常州市协旺纺织品有限公司 | A kind of preparation method of phenolic resin based foam carbon |
| CN107244665B (en) * | 2017-06-27 | 2019-12-17 | 福州市岩下亭农业综合开发有限公司 | Preparation method of phenolic resin based foam carbon |
| CN110407203A (en) * | 2019-06-06 | 2019-11-05 | 湖南中科星城石墨有限公司 | A kind of highly conductive graphite foam and preparation method thereof |
| CN114956040A (en) * | 2022-06-10 | 2022-08-30 | 四川大学 | Nitrogen-oxygen doped graded porous carbon material, preparation method and application |
| CN114956040B (en) * | 2022-06-10 | 2023-06-02 | 四川大学 | Nitrogen-oxygen doped hierarchical porous carbon material, preparation method and application |
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Application publication date: 20110727 |