CN108774890B - Graphene-based organic PTC (Positive temperature coefficient) self-temperature-control electrothermal fiber and preparation method and application thereof - Google Patents
Graphene-based organic PTC (Positive temperature coefficient) self-temperature-control electrothermal fiber and preparation method and application thereof Download PDFInfo
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
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Abstract
The invention provides an organic PTC temperature self-control electric heating fiber based on graphene and a preparation method and application thereof. The preparation method comprises the following steps: (a) treating the graphene powder with concentrated nitric acid and/or concentrated sulfuric acid, performing ultrasonic treatment, and purifying at high temperature to obtain high-temperature purified graphene; (b) grinding and dispersing the high-temperature purified graphene in a solvent, and performing ultrasonic treatment to obtain graphene high-dispersion slurry; (c) mixing the graphene high-dispersion slurry with a high-thermal-expansion-coefficient polymer resin solution and an auxiliary agent to obtain graphene-based PTC (positive temperature coefficient) electric heating slurry; (d) treating the fiber matrix with a coupling agent and then drying; (e) and coating the dried fiber matrix with graphene-based PTC electric heating slurry, and curing to obtain the graphene-based organic PTC self-temperature-control electric heating fiber. The resistance of the electric heating fiber of the invention rises along with the rise of the temperature, the heating power is reduced, the problem of hidden danger of overheating of the existing electric heating product is solved, and the problem of the bonding force of the fiber matrix and the sizing agent is also solved.
Description
Technical Field
The invention relates to the field of electric heating materials, in particular to an organic PTC (positive temperature coefficient) self-temperature-control electric heating fiber based on graphene and a preparation method and application thereof.
Background
The graphene is composed of a completely-composed SP2A quasi-two-dimensional crystalline material consisting of hybridized carbon atoms and having a thickness of only a single atomic layer or several single atomic layers. Since the first preparation in 2004, graphene has been widely used in various fields, and is known as "the king of new materials" or "black and golden". Due to the excellent performances of high electric conductivity, high strength, high heat conductivity and the like, the stone is made of a high-strength high-conductivity high-strength high-heat-conductivity high-strength highThe graphene has good application prospect in the field of electric heating. The graphene electric heating technology has the advantages of environmental protection, high heat conversion efficiency, far infrared physiotherapy, convenience in paving design and the like, and is widely applied to the fields of modern buildings, heating engineering, decoration and the like.
When the electric heat conduction product made of traditional graphene electric heating materials is used, the characteristics of heating and heat conduction uniformity, flexibility, automatic temperature control (such as a temperature controller) and the like generally need to be controlled by means of external conditions, and meanwhile, potential safety hazards such as fire disasters and the like caused by high current due to disconnection, incapability of electrifying, local overheating or short circuit can exist during use. Therefore, the development of a safe and stable electric heating material is a problem to be solved.
The PTC automatic temperature control principle is a characteristic that a positive coefficient of resistance value increases (so that current is not easily passed) when temperature rises, so that a heating element can reflect the temperature of the heating element, and the PTC automatic temperature control principle has a characteristic of automatically controlling the amount of power-on, and realizes safe and comfortable performance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide an organic PTC self-temperature-control electrothermal fiber based on graphene, which can control heating according to the temperature of a local area. When the temperature is too high due to the shielding of objects and furniture or the irradiation of sunlight, the electric heating fiber can be automatically adjusted, the impedance of the heating body is increased, the heating power is reduced accordingly, the overheating prevention effect is achieved, and therefore the current safety problem of electric heating can be solved.
The second purpose of the invention is to provide a preparation method of the graphene-based organic PTC temperature self-control electrothermal fiber.
The third purpose of the invention is to provide an application of the graphene-based organic PTC temperature self-control electrothermal fiber.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of an organic PTC temperature self-control electric heating fiber based on graphene comprises the following steps:
(a) treating graphene with inorganic acid, performing ultrasonic treatment, and purifying at high temperature to obtain high-temperature purified graphene;
(b) grinding and dispersing high-temperature purified graphene in a solvent, and then carrying out ultrasonic treatment to obtain graphene high-dispersion slurry;
(c) mixing the graphene high-dispersion slurry with a high-thermal-expansion-coefficient polymer resin solution and an auxiliary agent to obtain graphene-based PTC (positive temperature coefficient) electric heating slurry;
(d) treating the fiber matrix with a coupling agent and then drying;
(e) coating the dried fiber matrix with graphene-based PTC electric heating slurry, and then curing to obtain the graphene-based organic PTC self-temperature-control electric heating fiber;
preferably, in the step (a), the graphene is graphene powder; more preferably, the particle size of the graphene powder is 0.5-5 μm;
preferably, in step (a), the acid is a strong inorganic acid; more preferably, the inorganic strong acid is concentrated nitric acid and/or concentrated sulfuric acid.
Preferably, the preparation method of the graphene-based organic PTC self-temperature-control electrothermal fiber of the present invention, step (a), comprises the following steps: placing graphene powder in inorganic strong acid; heating, refluxing, washing with water after ultrasonic treatment, and drying; then, performing high-temperature purification treatment in an inert atmosphere to obtain high-temperature purified graphene; more preferably, the heating reflux temperature is 120-150 ℃, and the time is 2-10 h; more preferably, the power of ultrasonic treatment is 1-400 w, and the time is 5-30 min; more preferably, the temperature of the high-temperature purification treatment is 2000-3000 ℃.
Preferably, in the step (b) of the preparation method of the graphene-based organic PTC self-temperature-control electrothermal fiber, the ultrasonic time is 5-30 min; and/or the solvent is one or more of dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
Preferably, the step (c) of the preparation method of the graphene-based organic PTC self-temperature-control electrothermal fiber comprises the following steps: under the condition of heating reflux, dissolving high-thermal-expansion-coefficient high-molecular resin in an organic solvent to obtain a high-thermal-expansion-coefficient high-molecular resin solution; then, adding an auxiliary agent comprising a dispersing agent, a defoaming agent, a leveling agent and a viscosity regulator, and stirring and defoaming to obtain graphene-based PTC (positive temperature coefficient) electric heating slurry; wherein the high thermal expansion coefficient polymer resin comprises: one or more of EVA, PE, PP, PA, POM, PBT, PET, PVDF, PTFE, PPS, or PEEK;
more preferably, the organic solvent includes: one or more of tetrahydronaphthalene, decalin, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isophorone, acetone, ethyl acetate, butyl acetate, dibasic ester and diethylene glycol butyl ether acetate;
more preferably, the solid content of the obtained high-thermal-expansion-coefficient polymer resin solution is 10-50%; further preferably, the solid content of the obtained high-thermal-expansion-coefficient polymer resin solution is 15-30%;
more preferably, the dynamic viscosity of the obtained graphene-based PTC electric heating slurry is 100-5000 mPas.
Preferably, in the step (c) of the preparation method of the graphene-based organic PTC self-temperature-control electrothermal fiber, the use amounts of the raw materials are as follows:
10-20 parts of high-thermal-expansion-coefficient polymer resin, 30-70 parts of organic solvent, 0-1 part of dispersing agent, 0-1 part of defoaming agent, 0-1 part of flatting agent, 0-1 part of viscosity regulator and 1-10 parts of high-temperature purified graphene.
Preferably, in step (d), the preparation method of the graphene-based organic PTC self-temperature-control electrothermal fiber of the present invention includes: one or more of nylon fiber, polyester fiber, acrylic fiber, spandex fiber, polyvinyl chloride fiber or composite fiber; more preferably, the fiber matrix is one or two of nylon fiber or spandex fiber; more preferably, the coupling agent is a silane coupling agent or a titanate coupling agent.
Preferably, the step (d) of the preparation method of the graphene-based organic PTC self-temperature-control electrothermal fiber comprises the following steps: soaking the fiber matrix in ethanol solution of coupling agent at normal temperature, and drying to constant weight; wherein the mass concentration of the ethanol solution of the coupling agent is 0.5-1%; and/or the soaking treatment time at normal temperature is 1-5 h.
Preferably, in the step (e) of the preparation method of the graphene-based organic PTC self-temperature-control electrothermal fiber, coating is performed by adopting a curtain coating, dip coating or atomization spraying manner.
Meanwhile, the invention also provides the graphene-based organic PTC self-temperature-control electrothermal fiber obtained by the method.
Furthermore, the invention also provides the application of the graphene-based organic PTC self-temperature-control electric heating fiber in an electric heating device;
and/or the electric heating device comprises the organic PTC temperature self-control electric heating fiber based on the graphene.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the graphene powder is purified at high temperature, so that the conductivity of the graphene powder is greatly improved, the defect of graphene sheets is fully eliminated, and impurity atoms on the surface of the graphene are removed;
2. according to the invention, the graphene powder subjected to high-temperature purification treatment is pre-dispersed in a suitable organic solvent and then mixed with a polymer matrix, so that the problem of dispersion of graphene in the polymer matrix is solved.
3. According to the invention, the fiber matrix is pretreated, so that the adhesion fastness of the slurry and the fiber is improved, and the electric heating performance is more stable.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a schematic structural diagram of a graphene organic PTC temperature self-control electrothermal fiber.
In the figure 1, 1-fiber matrix, 2-fiber matrix surface treatment layer and 3-PTC self-temperature-limiting electric heating layer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In view of the defects of the existing electric heating material in the aspects of service performance, safety and the like, the invention particularly provides an organic PTC temperature self-control electric heating fiber based on graphene, so as to solve the technical problems of the existing material.
Specifically, the preparation method of the graphene-based organic PTC self-temperature-control electrothermal fiber provided by the invention can specifically refer to the following steps:
(a) and (3) graphene purification treatment:
treating graphene with an inorganic acid, wherein the raw material graphene is graphene powder with a particle size of 0.5-5 μm (for example, but not limited to, 1, 1.5, 2, 2.5, 3, 3.5, 4, or 4.5, etc.); meanwhile, the raw material graphene powder can be prepared by a mechanical stripping method or an oxidation reduction method;
then, adding the raw material graphene powder into concentrated nitric acid and/or concentrated sulfuric acid, and heating and refluxing for 2-10 h (for example, but not limited to, 3, 4, 5, 6, 7, 8, or 9h), wherein the refluxing temperature is 120-150 ℃ (for example, but not limited to, 125, 130, 135, 140, or 145 ℃ and the like);
then, after the heating and refluxing treatment, subjecting the graphene powder immersed in the strong acid solution to an ultrasonic treatment, wherein the power of ultrasonic waves used for the ultrasonic treatment is 1-400 w (for example, but not limited to, 10, 30, 50, 70, 90, 100, 150, 200, 250, 300, or 350 w), and the treatment time is 5-30min (for example, but not limited to, 10, 15, 20, or 25 min);
after ultrasonic treatment, taking out the graphene powder from the strong acid solution, then washing with water for 3-10 times, and then drying to constant weight;
then, the dried graphene powder is subjected to a high-temperature purification treatment in an inert atmosphere (preferably in an inert gas high-temperature furnace) at a temperature of 2000 to 3000 ℃ (for example, but not limited to 2100, 2200, 2300, 2500, 2700, 2900 ℃ or the like) to obtain high-temperature purified graphene.
(b) Preparing graphene high-dispersion slurry:
in this step, firstly, the high-temperature purified graphene is ground and dispersed in a solvent. Specifically, the high-temperature purified graphene can be added into one or more of a mixed solvent of dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and then fully ground and dispersed;
and then, carrying out ultrasonic treatment for 5-30min (for example, but not limited to, 10, 15, 20, or 25 min) to obtain the graphene high-dispersion slurry with the solid content of 1-10% (for example, but not limited to, 2, 3, 4, 5, 6, 7, 8, or 9% and the like).
(c) Mixing the graphene high-dispersion slurry with a high-thermal-expansion-coefficient polymer resin solution and an auxiliary agent to obtain graphene-based PTC (positive temperature coefficient) electric heating slurry;
in this step, firstly, a high thermal expansion coefficient polymer resin solution is prepared, and the preparation steps can be referred to as follows:
a high-thermal-expansion-coefficient polymer resin, comprising: adding one or more resins selected from EVA (ethylene-vinyl acetate copolymer), PE (polyethylene), PP (polypropylene), PA (polyamide), POM (polyoxymethylene), PBT (tetramethyleneterephthalate), PET (polyethylene terephthalate), PVDF (polyvinylidene fluoride), LCP (liquid crystal polymer), PPS (polyphenylene sulfide) and PEEK (polyetheretherketone) into an organic solvent, stirring and refluxing for 5-24 h (for example, 8, 12, 15, 18, 20h and the like) under the condition of 50-100 ℃ (for example, but not limited to 60, 70, 80, or 90 ℃ and the like), and dissolving to obtain a high-thermal-expansion-coefficient polymer resin solution with a solid content of 10-50% (for example, but not limited to 15, 20, 25, 30, 35, 40, or 45%, and the like; preferably 15-30%);
in the dissolving process, the used organic solvent is one or more of tetrahydronaphthalene, decalin, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isophorone, acetone, ethyl acetate, butyl acetate, dibasic ester and diethylene glycol butyl ether acetate;
then, fully mixing the graphene high-dispersion slurry prepared in the step (b) with the high-thermal-expansion-coefficient polymer resin solution prepared as above, optionally adding auxiliary materials such as a dispersing agent, a defoaming agent, a leveling agent, a viscosity regulator and the like, and stirring and defoaming in a full-automatic vacuum defoaming machine for 1-12h (for example, but not limited to 2, 5, 7, 10h and the like) to obtain graphene-based PTC electric heating slurry with the dynamic viscosity of 100-5000mpa · s;
in the above steps, the amounts of the raw materials are as follows: 10-20 parts (for example, but not limited to, 11, 12, 15, 17, or 19 parts) of high-thermal-expansion-coefficient polymer resin; 30-70 parts of organic solvent (used for dissolving the high-thermal-expansion-coefficient polymer resin and enabling the solid content of the high-thermal-expansion-coefficient polymer resin solution to be 10-50%, such as, but not limited to, 35, 40, 45, 50, 55, 60, or 65% and the like); 1-10 parts of graphene high-dispersion slurry (based on the content of high-temperature purified graphene in the graphene high-dispersion slurry; for example, but not limited to, 2, 3, 4, 5, 6, 7, 8, or 9 parts); 0-1 part of a defoaming agent; 0-1 part of a dispersant; 0-1 part of a leveling agent; and 0-1 part of viscosity regulator;
namely, the amount of the high-temperature purified graphene used for preparing the graphene high-dispersion slurry in the step (b) is 1-10 parts (and the obtained product is further used in the step (c)), and the amounts of the other raw materials in the step (c) are as follows: 10-20 parts of high-thermal-expansion-coefficient polymer resin, 30-70 parts of organic solvent, 0-1 part of defoaming agent, 0-1 part of dispersing agent, 0-1 part of flatting agent and 0-1 part of viscosity regulator.
(d) Treating the fiber matrix with a coupling agent and then drying;
in the step, the fiber matrix used as the raw material is one or more of nylon fiber, polyester fiber, polyamide fiber, acrylic fiber, spandex fiber, polyvinyl chloride fiber or composite fiber; preferably one or two of nylon fiber or spandex fiber;
the coupling agent for treating the fiber substrate is preferably an ethanol solution of a silane coupling agent and/or a titanate coupling agent with the solid content of 0.5-1%;
the specific processing method may include: soaking the fiber substrate in a coupling agent ethanol solution at normal temperature for 1-5 h (for example, but not limited to, 2, 3, 4h and the like), and then drying to constant weight.
(e) Coating the surface of the dried fiber substrate with graphene-based PTC electric heating slurry, and then curing to obtain the graphene-based organic PTC self-temperature-control electric heating fiber;
and finally, coating (by adopting a spraying mode, a dip coating mode, an atomizing spraying mode and the like) a layer of graphene-based PTC electric heating slurry prepared in the step (c) on the outer surface of the fiber matrix treated by the coupling agent, and then drying and curing at 10-100 ℃ (for example, but not limited to, 20, 30, 40, 50, 60, 70, 80, or 90 ℃ and the like) to obtain the product of the graphene-based organic PTC self-temperature-control electric heating fiber.
In order to ensure that the prepared product has good electrothermal performance, the types of the solvent used in the step (b), the types and the use amounts of the high-thermal-expansion-coefficient polymer resin and the organic solvent used in the step (c), the types of the fiber matrix and the coupling agent used in the step (d), and the coating manner of the slurry used in the step (e) need to be optimized, and the conditions such as the preferred raw materials and the preferred use amounts of the invention are selected, so that the prepared graphene-based organic PTC self-temperature-control electrothermal fiber has good service performance.
Furthermore, the organic PTC temperature self-control electric heating fiber prepared by the method can be further used for preparing corresponding electric heating devices and used as heating materials, such as heating waistlines, uterus warmers, heating shoulders protectors, electric heating kang, electric heating floors and electric heating paintings, so that the problem of potential overheating hazards of the existing electric heating products is solved, and the use safety of the electric heating devices is improved.
Example 1
1) Carrying out high-temperature purification treatment on graphene to improve conductivity:
the graphene powder is prepared by a mechanical stripping method, the average layer number is 10, and the sheet diameter is 0.5 mu m; the graphene processing method comprises the following steps:
putting graphene powder into concentrated nitric acid, heating and refluxing for 10 hours at 120 ℃, performing ultrasonic treatment for 30min, washing for 10 times, and drying to constant weight;
purifying the graphene powder in an inert gas high-temperature furnace at 2000 ℃ to obtain high-temperature purified graphene powder, and measuring the conductivity of the obtained graphene powder to be 106-107S/m。
2) Preparing graphene high-dispersion slurry: adding high-temperature purified graphene powder into N-methyl pyrrolidone, fully grinding and dispersing, and then carrying out ultrasonic treatment for 5-30min to obtain graphene high-dispersion slurry with the solid content of 5%;
3) preparing graphene-based PTC electric heating slurry: stirring and refluxing EVA resin at 80 ℃ for 10h to dissolve the EVA resin in decalin, and then cooling to normal temperature to obtain a dissolved resin solution; fully mixing the graphene high-dispersion slurry and the obtained resin liquid, adding a dispersing agent, a defoaming leveling agent and a viscosity regulator, and stirring and defoaming in a full-automatic vacuum defoaming machine for 5 hours to obtain graphene-based PTC (positive temperature coefficient) electric heating slurry with the dynamic viscosity of 1000mpa & s;
4) treating a fiber matrix: soaking nylon fiber in 1% titanate coupling agent ethanol solution for 5h, and drying to constant weight;
5) molding: coating a layer of graphene-based PTC electric heating slurry on the fiber substrate treated in the step 4) in an atomization spraying manner, and fully drying and curing at 80 ℃ to obtain the graphene organic PTC electric heating fiber, wherein the structure of the graphene organic PTC electric heating fiber is shown in figure 1 and sequentially comprises the following components from inside to outside: a fiber substrate 1, a fiber substrate surface treatment layer 2 and a PTC self-temperature-limiting electric heating layer 3.
In the graphene-based PTC electrothermal slurry of example 1, the mixture ratio of each material is 25 parts of EVA resin, 2.5 parts of high-temperature purified graphene powder, 25 parts of decalin, 47 parts of N-methylpyrrolidone, 0.01 part of dispersant, and 0.5 part of defoaming and leveling agent.
Example 2
The graphene organic PTC self-temperature-control electrothermal fiber is prepared by the same method as the embodiment 1, and the difference is that: the resin in the step 3) is PE resin.
Example 3
The graphene organic PTC self-temperature-control electrothermal fiber is prepared by the same method as the embodiment 1, and the difference is that: the resin in the step 3) is PVDF resin.
Example 4
1) Carrying out high-temperature purification treatment on graphene to improve conductivity: the graphene powder is prepared by a mechanical stripping method, the average layer number is 10, and the sheet diameter is 0.5 mu m; the graphene processing method comprises the following steps:
putting graphene powder into concentrated nitric acid, heating and refluxing for 10 hours at 120 ℃, performing ultrasonic treatment for 30min, washing for 10 times, and drying to constant weight;
purifying the graphene powder in an inert gas high-temperature furnace at the temperature of 2000-3000 ℃ to obtain high-temperature purified graphene powder, and measuring the electric conductivity of the obtained graphene powder to be 106-107S/m。
2) Preparing graphene high-dispersion slurry: adding high-temperature purified graphene powder into dimethylformamide, fully grinding and dispersing, and then carrying out ultrasonic treatment for 5-30min to obtain graphene high-dispersion slurry with the solid content of 7%;
3) preparing graphene-based PTC electric heating slurry: stirring and refluxing EVA and PE mixed resin at 100 ℃ for 10h to dissolve in decahydronaphthalene, and then cooling to normal temperature to obtain a dissolved resin solution; fully mixing the graphene high-dispersion slurry and the obtained resin liquid, adding a dispersing agent, a defoaming leveling agent and a viscosity regulator, and stirring and defoaming in a full-automatic vacuum defoaming machine for 5 hours to obtain graphene-based PTC (positive temperature coefficient) electric heating slurry with the dynamic viscosity of 1500mpa & s;
4) treating a fiber matrix: soaking nylon fiber in 1% titanate coupling agent ethanol solution for 5 hr, and drying to constant weight;
5) and 4) coating a layer of graphene-based PTC electric heating slurry on the fiber substrate treated in the step 4) in an atomization spraying manner, and fully drying and curing at 100 ℃ to obtain the graphene organic PTC electric heating fiber.
In the embodiment, the graphene-based PTC electrothermal slurry comprises 15 parts of EVA resin, 3 parts of PE resin, 4 parts of high-temperature purified graphene powder, 25 parts of decalin, 53 parts of N-methyl pyrrolidone, 0.01 part of dispersing agent and 0.5 part of defoaming and leveling agent.
Comparative example 1
Graphene organic PTC self-temperature-control electrothermal fibers were prepared in the same manner as in example 1, except that the graphene powder was not subjected to a high-temperature purification process (i.e., step 1 was not included)).
Comparative example 2
Graphene organic PTC self-regulating temperature electrothermal fibers were prepared in the same manner as in example 1, except that the nylon fiber matrix was not treated with a coupling agent (i.e., step 4 was not included)).
Comparative example 3
1) Carrying out high-temperature purification treatment on graphene to improve conductivity: the graphene powder is prepared by a mechanical stripping method, the average layer number is 10, and the sheet diameter is 0.5 mu m; the graphene processing method comprises the following steps:
putting graphene powder into concentrated nitric acid, heating and refluxing for 10 hours at 120 ℃, performing ultrasonic treatment for 30min, washing for 10 times, and drying to constant weight;
purifying the graphene powder in an inert gas high-temperature furnace at the temperature of 2000-3000 ℃ to obtain high-temperature purified graphene powder, and measuring the electric conductivity of the graphene powder to be 106-107S/m。
2) Adding high-temperature purified graphene powder into N-methyl pyrrolidone, fully grinding and dispersing, and then carrying out ultrasonic treatment for 5-30min to obtain graphene high-dispersion slurry with the solid content of 5%;
3) dissolving polyurethane in DMF; fully mixing the graphene high-dispersion slurry and the obtained resin liquid, adding a dispersing agent, a defoaming leveling agent and a viscosity regulator, and stirring and defoaming in a full-automatic vacuum defoaming machine for 5 hours to obtain graphene-based electric heating slurry with the dynamic viscosity of 1000mpa & s;
4) soaking nylon fiber in 1% titanate coupling agent ethanol solution for 5 hr, and drying to constant weight;
5) and coating a layer of graphene-based electric heating slurry by an atomization spraying mode, and fully drying and curing at 80 ℃ to obtain the graphene organic electric heating fiber.
In the comparative example, the material ratio of each graphene-based electric heating slurry is 25 parts of polyurethane resin, 2.5 parts of high-temperature purified graphene powder, 25 parts of DMF, 47 parts of N-methyl pyrrolidone, 0.01 part of dispersant and 0.5 part of defoaming and leveling agent.
Experimental example 1
The results of testing the balance temperature, the stable power and the PTC strength of the XPS heat-insulation board covered and the heat-insulation board uncovered under the environment of 220V voltage at room temperature of 25 ℃ are shown in the following table: (sample size length width 30cm)
The electric heating fibers of each embodiment are woven into a heating layer by a loom, two zinc-copper alloy wire current carrying strips are woven into the electric heating fibers at intervals along the weft direction to obtain heating cloth, and the power change at room temperature after the electric heating fibers are kneaded and bent for multiple times is as follows: (sample size length width 30cm)
| Name (R) | Rub for 0 times | Rub the skin 100 times | Rub and rub 1000 times | Rub and knead 5000 times |
| Example 1 | 22.1 | 21.8 | 21.2 | 20 |
| Example 2 | 23.2 | 23.1 | 23 | 22.5 |
| Example 3 | 21 | 20.8 | 20.1 | 19.7 |
| Example 4 | 25 | 24.3 | 23.9 | 23 |
| Comparative example 1 | 17 | 16.5 | 15.5 | 14.8 |
| Comparative example 2 | 21.5 | 19 | 16.2 | 10.5 |
| Comparative example 3 | 22 | 22 | 21.8 | 21.3 |
From the experimental comparison data, the positive resistance coefficient of the heating layer woven by the organic PTC electrothermal fibers prepared by the method is increased and the power is reduced when the temperature is increased, so that the temperature can be automatically controlled, the safety under the covering condition is realized, and the electric energy conservation is realized to a certain extent. When the heating layer prepared by the traditional method is covered, the power cannot be reduced along with the change of the temperature, and the temperature can be gradually increased, so that the danger of overheating and firing can occur.
Meanwhile, the graphene can be purified at high temperature to effectively improve the conductivity, and the fiber substrate is subjected to surface treatment to improve the adhesion between the heating layer and the fiber substrate, so that the bending resistance and the kneading resistance of the heating layer are effectively improved.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (4)
1. A preparation method of an organic PTC temperature self-control electric heating fiber based on graphene is characterized by comprising the following steps:
1) carrying out high-temperature purification treatment on graphene powder to improve conductivity:
the graphene powder is prepared by a mechanical stripping method, the average layer number is 10, and the sheet diameter is 0.5 mu m; the graphene powder processing method comprises the following steps:
putting graphene powder into concentrated nitric acid, heating and refluxing for 10 hours at 120 ℃, performing ultrasonic treatment for 30min, washing for 10 times, and drying to constant weight;
② the above graphene powderPurifying the graphene oxide powder in an inert gas high-temperature furnace at 2000 deg.C to obtain high-temperature purified graphene powder, and measuring the electric conductivity of the obtained graphene powder to 106-107S/m；
2) Preparing graphene high-dispersion slurry: adding high-temperature purified graphene powder into N-methyl pyrrolidone, fully grinding and dispersing, and then carrying out ultrasonic treatment for 5-30min to obtain graphene high-dispersion slurry with the solid content of 5%;
3) preparing graphene-based PTC electric heating slurry: stirring and refluxing PE resin at 80 ℃ for 10h to dissolve the PE resin in decalin, and then cooling to normal temperature to obtain a dissolved resin solution; fully mixing the graphene high-dispersion slurry and the obtained resin solution, adding a dispersing agent, a defoaming leveling agent and a viscosity regulator, and stirring and defoaming in a full-automatic vacuum defoaming machine for 5 hours to obtain graphene-based PTC (positive temperature coefficient) electric heating slurry with the dynamic viscosity of 1000mpa & s;
4) treating a fiber matrix: soaking nylon fiber in 1% titanate coupling agent ethanol solution for 5h, and drying to constant weight;
5) molding: coating a layer of graphene-based PTC electric heating slurry on the fiber substrate treated in the step 4) in an atomization spraying manner, and fully drying and curing at 80 ℃ to obtain graphene organic PTC electric heating fibers;
in the graphene-based PTC electric heating slurry, the material ratio is 25 parts of PE resin, 2.5 parts of high-temperature purified graphene powder, 25 parts of decalin, 47 parts of N-methyl pyrrolidone, 0.01 part of dispersing agent and 0.5 part of defoaming and leveling agent.
2. A graphene-based organic PTC self-regulating temperature electrothermal fiber prepared by the method of claim 1.
3. Use of the graphene-based organic PTC self-regulating temperature electrical heating fiber of claim 2 in an electrical heating device.
4. An electrothermal heating device comprising the graphene-based organic PTC self-temperature-controlling electrothermal fiber according to claim 2.
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| CN109930388A (en) * | 2019-03-04 | 2019-06-25 | 华中科技大学鄂州工业技术研究院 | A kind of preparation method of carbon fiber Wesy modified polyether ether ketone resin base sizing agent |
| CN110022623B (en) * | 2019-04-04 | 2020-01-10 | 碳翁(北京)科技有限公司 | Preparation and application of high-temperature-resistant electric heating fiber |
| CN111287003B (en) * | 2020-03-30 | 2022-09-09 | 新材料与产业技术北京研究院 | Water-based graphene PTC conductive dye, preparation method thereof and conductive fiber treated by dye |
| CN111411533B (en) * | 2020-04-17 | 2021-03-23 | 维珍妮内衣(深圳)有限公司 | Method for preparing graphene heating non-woven fabric through roll-to-roll printing |
| GB2596293A (en) * | 2020-06-22 | 2021-12-29 | Univ Cranfield | A method and system for forming a fibre composite and a composite |
| CN112593415A (en) * | 2020-12-01 | 2021-04-02 | 肃宁县中原纺织有限责任公司 | Water-based graphene flame-retardant PTC conductive paste, preparation method thereof and flexible conductive heating cloth |
| CN114181563B (en) * | 2021-12-20 | 2023-06-09 | 深圳清华大学研究院 | High-magnification self-temperature-control graphene powder, self-temperature-control ink and graphene self-temperature-control heating coating |
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