CN113387676A - Inorganic fiber-carbon nanotube far infrared heating film and preparation method thereof - Google Patents

Inorganic fiber-carbon nanotube far infrared heating film and preparation method thereof Download PDF

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CN113387676A
CN113387676A CN202010172016.6A CN202010172016A CN113387676A CN 113387676 A CN113387676 A CN 113387676A CN 202010172016 A CN202010172016 A CN 202010172016A CN 113387676 A CN113387676 A CN 113387676A
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inorganic fiber
far infrared
infrared heating
carbon nanotube
heating film
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CN113387676B (en
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吴少军
王书杰
蔡晓丽
张要锋
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Henan Kelaiwei Nano Carbon Material Co ltd
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Henan Kelaiwei Nano Carbon Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00Compositions for artificial stone, not containing binders
    • C04B30/02Compositions for artificial stone, not containing binders containing fibrous materials
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/20Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/34Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
    • H05B3/36Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs heating conductor embedded in insulating material

Abstract

The invention belongs to the technical field of far infrared heating, and particularly relates to an inorganic fiber-carbon nanotube far infrared heating film and a preparation method thereof. The inorganic fiber-carbon nanotube far infrared heating film mainly comprises carbon nanotube-inorganic fiber hybrid materials; in the carbon nano tube-inorganic fiber hybrid material, the mass ratio of inorganic fibers to carbon nano tubes is (0.2-0.3): 1; the carbon nano tube is a whisker carbon nano tube with the length of 1-15 mu m; the inorganic fiber is at least one of glass fiber, alumina fiber, rock wool and rock wool. The far infrared heating material provided by the invention has the advantages that inorganic fibers and carbon nano tubes are hybridized together, and the high temperature resistance and the heat conversion efficiency are better.

Description

Inorganic fiber-carbon nanotube far infrared heating film and preparation method thereof
Technical Field
The invention belongs to the technical field of far infrared heating, and particularly relates to an inorganic fiber-carbon nanotube far infrared heating film and a preparation method thereof.
Background
At present, far infrared heating materials are widely applied to a plurality of fields such as buildings, agriculture, daily life health care and the like due to the special performance of the far infrared heating materials. Because the existing far infrared heating material has poor thermal stability, low flexibility and low tensile strength, the existing far infrared heating material can not meet the requirements of the fields of decoration, building heating and the like if being used alone. In the prior art, far infrared radiation materials are combined with other materials to prepare multifunctional far infrared heating composite materials. For example, chinese patent application publication No. CN109183513A discloses a polyimide fiber far infrared emitting paper prepared by compounding far infrared radiation material carbon nanotubes with organic fiber polyimide fiber. In the environment with the use temperature of 400-600 ℃, because the high temperature resistance of the organic fiber is poor, the polyimide fiber far infrared transmitting paper is easy to pulverize and is not suitable for long-term use.
Disclosure of Invention
The invention aims to provide an inorganic fiber-carbon nanotube far infrared heating film and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the inorganic fiber-carbon nanotube far infrared heating film is as follows:
an inorganic fiber-carbon nanotube far infrared heating film mainly comprises carbon nanotube-inorganic fiber hybrid materials; in the carbon nano tube-inorganic fiber hybrid material, the mass ratio of inorganic fibers to carbon nano tubes is (0.2-0.3): 1; the carbon nano tube is a whisker carbon nano tube with the length of 1-15 mu m; the inorganic fiber is at least one of glass fiber, alumina fiber, asbestos and rock wool.
The inorganic fiber has the advantages of strong heat resistance, corrosion resistance, mechanical strength and the like; the carbon nano tube has the nano-scale curvature at the tip, can show good field emission characteristic under relatively low voltage, has a wide far infrared radiation wave range, and is a good far infrared emission source.
The inorganic fiber and the carbon nano tube in the inorganic fiber-carbon nano tube far infrared heating material are mutually adsorbed and hybridized together in a winding and overlapping mode, and the inorganic fiber and the carbon nano tube have high bonding degree, so that the inorganic fiber-carbon nano tube far infrared heating material has good high temperature resistance and cannot influence the far infrared radiation performance of the carbon nano tube. The inorganic fiber-carbon nanotube far infrared heating material can bear the high temperature of 600-700 ℃, and the safety performance and the use stability of the far infrared heating material are effectively improved. The inorganic fiber-carbon nano tube far infrared heating material is an electric-heat conversion material, and the influence of the inorganic fiber on the electric conductivity is reduced by adjusting the mass ratio of the inorganic fiber to the carbon nano tube. Therefore, the mass ratio of the inorganic fiber to the carbon nano tube is (0.2-0.3): 1, the far infrared heating material has high temperature resistance and better electrothermal radiation conversion efficiency.
In order to improve the matching property of the inorganic fiber and the carbon nano tube, the length of the inorganic fiber is 0.5-6 mm.
In order to reduce the influence of the agglomeration of the carbon nanotubes on the performance of the far infrared heating material, preferably, the inorganic fiber-carbon nanotube far infrared heating material further comprises a dispersant, and the dispersant is polyvinylpyrrolidone and/or sodium dodecyl sulfate. More preferably, the mass ratio of the dispersant to the carbon nanotubes is (0.008 to 0.01): 1.
The preparation method of the inorganic fiber-carbon nanotube far infrared heating film adopts the technical scheme that:
a preparation method of the inorganic fiber-carbon nanotube far infrared heating film comprises the following steps:
grinding the mixed slurry containing the inorganic fibers and the carbon nano tubes to obtain hybrid slurry; the fineness of the hybrid slurry is below 25 mu m; the hybrid slurry is then made into a film.
In the grinding process, the inorganic fiber and the carbon nano tube are wound and overlapped under the action of external force and are finally adsorbed together. The solvent used in the mixed slurry is water or ethanol.
The film preparation method comprises the following steps: and coating the hybrid slurry on a filter cloth, rolling to form a film, stripping the filter cloth, and drying to obtain the composite material.
The filter cloth can filter out the solvent. In order to avoid the loss of the carbon nano tube, the aperture size of the preferable filter cloth is 100-150 meshes. And peeling off the substrate, and naturally airing to obtain the far infrared heating material in the form of a film. The preparation method of the invention has simple process by rolling the material. Further preferably, the rolling pressure is 20-22 MPa.
Preferably, the grinding time is 2-3 h.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The glass fibers used in the following examples were obtained from Taishan fibers, Inc., Shandong, under the type G75Y 1/Y2; the alumina fiber used was purchased from energy saving technology ltd, bang yu bang, shandong. The filter cloth is purchased from Henan Predawn Filter Material Co., Ltd, and has a size of 758. The asbestos and rock wool were purchased from mineral products, Inc., Lingshou county. The carbon nano-tube is an electrothermal conversion whisker carbon nano-tube produced by Henan Kelaiwei nano-carbon material GmbH.
First, embodiment of inorganic fiber-carbon nanotube far infrared heating film
Example 1
The inorganic fiber-carbon nanotube far infrared heating film of the embodiment is composed of an inorganic fiber-carbon nanotube hybrid material and a dispersant. Wherein the inorganic fiber is glass fiber with the length of 1-3 mm, the length of the carbon nano tube is 1-15 mu m, and the mass ratio of the glass fiber to the carbon nano tube is 0.28: 1. the dispersant is sodium dodecyl sulfate, and the mass ratio of the dispersant to the carbon nano tube is 0.01: 1.
example 2
The inorganic fiber-carbon nanotube far infrared heating film of the embodiment is composed of an inorganic fiber-carbon nanotube hybrid material and a dispersant. Wherein the inorganic fiber is glass fiber with the length of 1-3 mm, the carbon nano tube has the length of 1-15 mu m, and the mass ratio of the glass fiber to the carbon nano tube is 0.2: 1. the dispersing agent is polyvinylpyrrolidone, and the mass ratio of the dispersing agent to the carbon nano tube is 0.01: 1.
example 3
The inorganic fiber-carbon nanotube far infrared heating film of the embodiment is composed of an inorganic fiber-carbon nanotube hybrid material and a dispersant. Wherein the inorganic fiber is alumina fiber with the length of 0.5-1.5 mm, the length of the carbon nano tube is 1-15 mu m, and the mass ratio of the alumina fiber to the carbon nano tube is 0.3: 1. the dispersant is sodium dodecyl sulfate, and the mass ratio of the dispersant to the carbon nano tube is 0.01: 1.
example 4
The inorganic fiber-carbon nanotube far infrared heating film of the present embodiment is basically the same as the heating film of embodiment 1, except that: the inorganic fiber is asbestos fiber with the length of 1-5 mm, and the mass ratio of the dispersing agent to the carbon nano tube is 0.008: 1.
Example 5
The inorganic fiber-carbon nanotube far infrared heating film of the present embodiment is basically the same as the heating film of embodiment 4, except that: the inorganic fiber is rock wool fiber with the length of 3-6 mm.
Second, example of preparation method of inorganic fiber-carbon nanotube far-infrared heating Material
Example 6
The embodiment is a method for preparing the inorganic fiber-carbon nanotube far infrared heating film in embodiment 1, and specifically includes the following steps:
(1) ultrasonically dispersing 0.42g of glass fiber with the length of 1-3 mm in 50mL of aqueous solution for 40min to obtain dispersion liquid of the glass fiber, putting the dispersion liquid into a stirring kettle, adding 1.5g of carbon nano tubes, and continuously stirring for 30min to obtain mixed slurry;
(2) repeatedly grinding the mixed slurry for 2h by using a mortar to enable the mixed slurry to be a black-gray pasty mixture, and controlling the fineness of the slurry to be below 25 mu m to obtain hybrid slurry with mutual adsorption of glass fibers and carbon nanotubes;
(3) adding 0.015g of sodium dodecyl sulfate into the hybrid slurry, and fully stirring to obtain stable and uniform composite slurry; then uniformly coating the slurry on filter cloth (the aperture is 150 meshes), filtering water, and rolling to form a film by using a roller press (the pressure is 20MPa during rolling); and finally, stripping the filter cloth, and naturally drying the membrane.
Example 7
The embodiment is a method for preparing the inorganic fiber-carbon nanotube far infrared heating film in embodiment 2, which specifically includes the following steps:
(1) putting 0.3g of glass fiber with the length of 1-3 mm into a stirring kettle, adding 50mL of absolute ethyl alcohol, then adding 1.5g of carbon nano tube, and uniformly stirring and mixing to obtain mixed slurry;
(2) repeatedly grinding the mixed slurry for 2.5h by using a mortar to enable the mixed slurry to be a black-gray pasty mixture, and controlling the fineness of the slurry to be below 25 mu m to obtain the hybrid slurry with mutual adsorption of glass fibers and carbon nanotubes;
(3) adding 0.015g of polyvinylpyrrolidone into the hybrid slurry, and fully stirring to obtain stable dispersed slurry; then uniformly coating the dispersed slurry on filter cloth (aperture size is 150 meshes), filtering out ethanol solvent, rolling by using a roller press to form a film (the pressure during rolling is 21MPa), finally peeling off the filter cloth, and naturally drying the film.
Example 8
The embodiment is a method for preparing the inorganic fiber-carbon nanotube far infrared heating film in embodiment 3, which specifically includes the following steps:
(1) putting 0.45g of alumina fiber with the length of 0.5-1.5 mm into a stirring kettle, adding 50mL of water, adding 1.5g of carbon nano tube, and uniformly stirring and mixing to obtain mixed slurry;
(2) repeatedly grinding the mixed slurry for 3h by using a mortar to enable the mixed slurry to be a black-gray pasty mixture, and controlling the fineness of the slurry to be below 25 mu m to obtain hybrid slurry with mutual adsorption of glass fibers and carbon nanotubes;
(3) adding 0.015g of sodium dodecyl sulfate into the hybrid slurry, and fully stirring to obtain stable dispersed slurry; then uniformly coating the dispersed slurry on filter cloth (the aperture size is 150 meshes), filtering water, and rolling to form a film by using a roller press (the pressure is 22MPa during rolling); finally, the filter cloth is peeled off, and the membrane is naturally dried.
Example 9
The embodiment is a method for preparing the inorganic fiber-carbon nanotube far infrared heating film of embodiment 4, which specifically includes the following steps:
(1) tearing and stirring 0.42g of asbestos until the length is 1-5 mm, putting the asbestos into a stirring kettle, adding 50mL of water, then adding 1.5g of carbon nano tubes, and stirring to obtain mixed slurry of the asbestos and the carbon nano tubes;
(2) adding the mixed slurry into a sand mill for grinding, wherein the rotating speed of the sand mill is controlled to be 1000 +/-10 r/min, the grinding time is 50min, so that the mixed slurry is a black-gray pasty mixture, and the fineness of the slurry is controlled to be below 20 mu m, so as to prepare a hybrid slurry with mutually adsorbed carbon nano tubes and asbestos fibers;
(3) adding 0.012g of sodium dodecyl sulfate, fully stirring to obtain stable dispersed slurry, uniformly coating the dispersed slurry on filter cloth (with the aperture size of 150 meshes), filtering to remove water, and rolling by a roller press to form a film, wherein the rolling pressure is 20 MPa; and removing the filter cloth after rolling, and airing to obtain the uniform heating film.
Example 10
This example is a method for preparing the inorganic fiber-carbon nanotube far infrared heating film of example 5, and the specific process is the same as example 9, except that: asbestos is replaced by rock wool, and the rock wool is torn and crushed to 3-6 mm.
Test examples
The far infrared heating materials of examples 1 to 5 were subjected to performance tests, and the test results are shown in table 1.
The performance test method comprises the following steps:
1. maximum withstand temperature
The test was performed in a nitrogen atmosphere using a thermogravimetric analyzer. The results are shown in Table 1.
2. Ductility of the alloy
And (3) at normal temperature, carrying out a tensile test on the far infrared heating material, recording the length change of the material before and after the material is stretched, and testing the ductility of the material. The results are shown in Table 1.
Figure BDA0002409505040000051
3. Conversion efficiency
The conversion efficiency of the far infrared heating film of the present invention was measured according to the measuring method of GB7287.7-87 electric-thermal radiation conversion efficiency, and the results are shown in Table 1
Table 1 results of performance testing
Sample (I) Maximum withstand temperature/. degree.C Ductility of the alloy Conversion efficiency
Example 1 680 108% 82%
Example 2 660 106% 85%
Example 3 770 117% 78%
Example 4 673 112% 80%
Example 5 665 107% 76%
As can be seen from Table 1, the far infrared heating material of the present invention has good high temperature resistance, and the bearing temperature can reach 700 ℃. The inorganic fiber has certain insulating property, so that the far infrared heating material has higher resistance, and part of electric energy is used for overcoming resistance work and influencing the electric energy radiation conversion efficiency, but the electric energy radiation efficiency of the far infrared heating material can still reach over 75 percent.

Claims (8)

1. An inorganic fiber-carbon nanotube far infrared heating film is characterized by mainly comprising carbon nanotube-inorganic fiber hybrid materials; in the carbon nano tube-inorganic fiber hybrid material, the mass ratio of inorganic fibers to carbon nano tubes is (0.2-0.3): 1; the carbon nano tube is a whisker carbon nano tube with the length of 1-15 mu m; the inorganic fiber is one of glass fiber, alumina fiber, rock wool and asbestos.
2. The inorganic fiber-carbon nanotube far infrared heating film according to claim 1, wherein the length of the inorganic fiber is 0.5 to 6 mm.
3. The inorganic fiber-carbon nanotube far infrared heating film according to claim 1 or 2, wherein the inorganic fiber-carbon nanotube far infrared heating material further comprises a dispersant, and the dispersant is polyvinylpyrrolidone and/or sodium dodecyl sulfate.
4. The inorganic fiber-carbon nanotube far infrared heating film according to claim 3, wherein a mass ratio of the dispersant to the carbon nanotubes is (0.008 to 0.01): 1.
5. A preparation method of the inorganic fiber-carbon nanotube far infrared heating film as claimed in any one of claims 1 to 4, characterized by comprising the following steps: grinding the mixed slurry containing the inorganic fibers and the carbon nano tubes to obtain hybrid slurry; the fineness of the hybrid slurry is below 25 mu m; the hybrid slurry is then made into a film.
6. The method for preparing the inorganic fiber-carbon nanotube far infrared heating film according to claim 5, wherein the method for preparing the film comprises the following steps: and coating the hybrid slurry on a filter cloth, rolling to form a film, stripping the filter cloth, and drying to obtain the composite material.
7. The method for preparing the inorganic fiber-carbon nanotube far infrared heating film according to claim 6, wherein the rolling pressure is 20 to 22 MPa.
8. The method for preparing the inorganic fiber-carbon nanotube far infrared heating film according to any one of claims 5 to 7, wherein the grinding time is 2 to 3 hours.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013082610A (en) * 2011-09-29 2013-05-09 Kj Specialty Paper Co Ltd Carbon nanotube aqueous dispersion and composite sheet obtained by using the same
CN107079746A (en) * 2017-05-31 2017-08-22 北京绿能嘉业新能源有限公司 For agricultural greenhouse graphene Far-infrared Heating anion light wave plate and preparation method
CN108824086A (en) * 2018-07-06 2018-11-16 江西克莱威纳米碳材料有限公司 Carbon nanotube-aramid far-infrared paper and preparation method thereof, and carbon nanotube far-infrared physiotherapy shoe sole lining
CN109183513A (en) * 2018-09-10 2019-01-11 江西克莱威纳米碳材料有限公司 A kind of polyimide fiber far infrared transmission paper and preparation method thereof
CN109183280A (en) * 2018-09-03 2019-01-11 河南克莱威纳米碳材料有限公司 A kind of fire-proof high-temperature resistant far infrared transmission non-woven fabrics and preparation method thereof
CN109367516A (en) * 2018-12-07 2019-02-22 江西克莱威纳米碳材料有限公司 A kind of automobile rearview mirror Far-infrared Heating eliminates spray device and preparation method thereof
CN109467335A (en) * 2019-01-16 2019-03-15 刘丽荣 Far infrared heater material and preparation method thereof
CN110016803A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of high temperature resistant fibre electroheating and its application

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013082610A (en) * 2011-09-29 2013-05-09 Kj Specialty Paper Co Ltd Carbon nanotube aqueous dispersion and composite sheet obtained by using the same
CN107079746A (en) * 2017-05-31 2017-08-22 北京绿能嘉业新能源有限公司 For agricultural greenhouse graphene Far-infrared Heating anion light wave plate and preparation method
CN108824086A (en) * 2018-07-06 2018-11-16 江西克莱威纳米碳材料有限公司 Carbon nanotube-aramid far-infrared paper and preparation method thereof, and carbon nanotube far-infrared physiotherapy shoe sole lining
CN109183280A (en) * 2018-09-03 2019-01-11 河南克莱威纳米碳材料有限公司 A kind of fire-proof high-temperature resistant far infrared transmission non-woven fabrics and preparation method thereof
CN109183513A (en) * 2018-09-10 2019-01-11 江西克莱威纳米碳材料有限公司 A kind of polyimide fiber far infrared transmission paper and preparation method thereof
CN109367516A (en) * 2018-12-07 2019-02-22 江西克莱威纳米碳材料有限公司 A kind of automobile rearview mirror Far-infrared Heating eliminates spray device and preparation method thereof
CN109467335A (en) * 2019-01-16 2019-03-15 刘丽荣 Far infrared heater material and preparation method thereof
CN110016803A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of high temperature resistant fibre electroheating and its application

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