CN113194556A - Graphene radiation heating film and preparation method thereof - Google Patents
Graphene radiation heating film and preparation method thereof Download PDFInfo
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- CN113194556A CN113194556A CN202110426385.8A CN202110426385A CN113194556A CN 113194556 A CN113194556 A CN 113194556A CN 202110426385 A CN202110426385 A CN 202110426385A CN 113194556 A CN113194556 A CN 113194556A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
Abstract
The invention discloses a graphene radiation heating film and a preparation method thereof. This graphite alkene radiation heating film includes the carrier and will generate heat the layer spraying liquid spraying and be in the layer that generates heat that forms on the carrier, the layer spraying liquid that generates heat includes tin tetrachloride, graphite alkene, the alcohol solution of ferric trichloride. The inventor of the invention applies the nanometer performance, the impedance, the thermal conductivity and the like of graphene, mixes the graphene with stannic chloride, ferric trichloride, 75% alcohol into a block to prepare liquid coating, sprays the liquid coating on a high-temperature resistant planar material (such as a mica plate), and carries out high-temperature film coating to form the heating plate. The heating film is uniform and stable, and the impedance can be adjusted, thereby achieving the purpose of adjusting the power. The produced composite graphene heating film has stable performance, high thermal radiance (more than 0.88), long service life and low cost.
Description
Technical Field
The invention belongs to the field of material engineering, and particularly relates to a graphene radiation heating film and a preparation method thereof.
Background
In the far infrared heating film, the heating methods are generally as follows:
A. the metal wire is embedded in the middle of the heating film, the heating mode is common before, and the heating film has the advantages of simplicity, economy and convenience, and has the defects of linear heating, short service life, poor safety, local high temperature, poor uniformity and comfort, particularly metal conduction and water intolerance, and great potential safety hazard in application;
B. the carbon fiber filaments generate heat. The carbon fiber wire generates heat, the safety performance is better than that of the metal wire, the carbon fiber wire can be made into a flexible film, the flexible film generates heat linearly, local high temperature exists, and the uniformity and the comfort are poor.
C. The carbon crystal plate generates heat. The carbon crystal plate is formed by combining chopped carbon fibers with materials such as resin. The advantage is the face form generates heat, and the shortcoming can only make not light and handy rigid membrane, is fit for the heating field and uses, has very big limitation in the health medicine field, and the cost is also not low.
D. Graphite alkene heating film. The graphene has super-strong electrical conductivity, thermal conductivity and steel toughness, so that the graphene can be made into a thin flexible planar heating film, and has the defects of excellent performance and higher cost.
Disclosure of Invention
The inventors of the present invention have conducted a series of studies on the production of a graphene exothermic film using graphene.
The invention discloses a graphene radiation heating film, which comprises a carrier and a heating layer formed by spraying heating layer spraying liquid on the carrier, wherein the heating layer spraying liquid comprises tin tetrachloride, graphene and ferric chloride alcohol solution.
In some embodiments of the present invention, the heat generating layer spraying liquid comprises the following raw materials in parts by weight:
10-30 parts of stannic chloride, 0.01-0.03 part of graphene, 0.1-0.3 part of ferric trichloride and 40-70 parts of industrial alcohol with the concentration of 70-80% (v/v).
In some preferred embodiments of the present invention, the heat generating layer spraying liquid comprises the following raw materials in parts by weight:
20 parts of tin tetrachloride, 0.021 part of graphene, 0.2 part of ferric trichloride and 50.85 parts of industrial alcohol with the concentration of 75% (v/v).
Graphene has superior electrical conductivity, but it can exhibit resistance under certain mixed materials. The inventor of the invention applies the nanometer performance, the impedance, the thermal conductivity and the like of graphene, mixes the graphene with stannic chloride, ferric trichloride, 75% alcohol into a block to prepare liquid coating, sprays the liquid coating on a high-temperature resistant planar material (such as a mica plate), and carries out high-temperature film coating to form the heating plate. The heating film is uniform and stable, and the impedance can be adjusted, thereby achieving the purpose of adjusting the power. The produced composite graphene heating film has stable performance, high thermal radiance (more than 0.88), long service life and low cost. The preparation method of the graphene heating film is simple and rapid, and excessive loading instruments and equipment are not needed.
In order to reduce the cost and improve the aging resistance and the corrosion resistance, the inventor of the invention further carries out researches on modification of graphene, addition of zinc chloride, polyurethane and the like.
In some preferred embodiments of the present invention, the graphene is graphene oxide.
In some preferred embodiments of the present invention, the preparation method of the graphene oxide is:
s11, adding graphene powder, sodium nitrate and potassium permanganate into a flask in an ice-water bath, adding concentrated sulfuric acid in a dropwise manner, slowly stirring, adding part of potassium permanganate when part of concentrated sulfuric acid is added, slowly stirring until the liquid is yellowish, heating, and then dropwise adding deionized water for reaction;
s22, adding deionized water, dropwise adding hydrogen peroxide until the liquid is bright yellow, filtering, washing with dilute hydrochloric acid until no sulfate ions are detected, washing with deionized water until the pH of the washing liquid is stable, soaking with a 0.01% (v/v) Tween 80 deionized water solution, centrifuging, and drying to obtain the graphene oxide.
In some preferred embodiments of the present invention, the heat generating layer spraying liquid further includes 0.01 to 0.03 parts of zinc chloride, preferably 0.02 parts.
In some preferred embodiments of the present invention, the heat-generating layer spraying liquid further includes 0.0005 to 0.002 parts of polyurethane, preferably 0.001 parts of polyurethane.
The second aspect of the invention discloses a preparation method of a graphene radiation heating film, which comprises the following steps:
s1, dissolving the crystallized stannic chloride in the alcohol water solution;
s2, dissolving ferric trichloride and zinc chloride in an alcohol water solution;
s3, dissolving thermoplastic polyurethane in N, N-dimethylformamide, adding alcohol, and mixing with the ferric trichloride and zinc chloride solution obtained in the step S2;
s4, mixing the graphene with the tin tetrachloride solution obtained in the S1 step, and then mixing the graphene with the solution obtained in the S3 step;
and S5, spraying the mixed solution obtained in the step S4 on a planar carrier.
In some embodiments of the present invention, the step S22, when soaked in a 0.01% (v/v) tween 80 deionized water solution, further comprises the steps of pre-treatment and ultrasonic treatment:
s31, soaking the fabric by using deionized water, wherein the ultrasonic treatment time under the W1 power is T1;
s32, filtering to remove deionized water, soaking in 0.01% (v/v) Tween 80 deionized water solution under W2 power for T2, and W2 for
T2 is bT 1; wherein a and b are constants, a is 0.10-0.12, and b is 2-3.
In some embodiments of the present invention, the thermal conductivity of the obtained graphene radiation heating film is estimated by the following steps:
s41, preparing 5-10 graphene radiation heating films with different contents of graphene, zinc chloride and polyurethane;
s42, predicting the heat conductivity of the obtained graphene radiation heating film through the following formula:
Rprediction＝K×TP×DC1×EC2×FC3；
Wherein K is a constant, C1Is the content of graphene, C2Is the content of zinc chloride, C3Is the content of polyurethane, D, E, F is the weight;
s43, measuring the heat-conducting property of the obtained graphene radiation heating film, and determining the numerical value ranges of K, D, E, F and the like;
s44, preparing a new graphene radiant heating film which is not within the content range of S41 graphene, zinc chloride and polyurethane, estimating the heat conduction performance of the new graphene radiant heating film by using the formula of S42 and the resin obtained in S43, and comparing the predicted value with the measured value, wherein the condition that the 70% measured value is larger than or equal to the predicted value and larger than or equal to 130% measured value is qualified.
The beneficial technical effects of the invention are as follows:
(1) the inventor of the invention applies the nanometer performance, the impedance, the thermal conductivity and the like of graphene, mixes the graphene with stannic chloride, ferric trichloride, 75% alcohol into a block to prepare liquid coating, sprays the liquid coating on a high-temperature resistant planar material (such as a mica plate), and carries out high-temperature film coating to form the heating plate. The heating film is uniform and stable, and the impedance can be adjusted, thereby achieving the purpose of adjusting the power. The produced composite graphene heating film has stable performance, high thermal radiance (more than 0.88), long service life and low cost.
(2) The graphene radiation heating film disclosed by the invention is high in thermal power and good in ageing resistance and corrosion resistance.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The graphene is purchased from Sichuan Jinlu group GmbH, has the thickness of 1-5nm, the number of layers less than 10, the granularity of 0.5-5um, the purity more than 97 percent and the specific surface area of about 45m2The electric conductivity is more than 700S/cm, and the C/O is more than 20.
In the following examples and comparative examples, unless otherwise specified, parallel tests were conducted with the same operating procedures and parameters.
Example 1
A preparation method of a graphene radiation heating film comprises the following steps:
firstly, preparing heating layer spraying liquid, wherein the method comprises the following steps:
the first step is as follows: taking 20Kg of crystallized tin tetrachloride, pouring the crystallized tin tetrachloride into a plastic barrel with the volume of over 100 liters, then adding 50Kg of industrial alcohol with the volume percentage concentration of 75 percent, soaking for 24 hours, and stirring with a plastic rod in the meantime to completely dissolve the tin tetrachloride in the alcohol.
The second step is that: and taking 21g of graphene, and pouring the graphene into the prepared solution in the first step.
The third step: putting 200 g of ferric trichloride into a glass ware with the volume of 2L, adding 1000 ml of 75% industrial alcohol, heating by a heating instrument, magnetically stirring, pouring all dissolved solution into the solution prepared in the first step and the second step after complete dissolution, and mixing and stirring uniformly.
The fourth step: dividing the mixed liquid into three parts, respectively placing the three parts on the front, middle and rear nozzles of a full-automatic film coating machine, and pumping the three parts onto a spray gun for spraying in a negative pressure mode.
The carrier for producing the heating film must be an insulating material resistant to high temperature (above 700 ℃), such as a mica plate. The thicker the spraying, the higher the power; the thinner the spray, the lower the power. The impedance value is adjusted according to the required power during production. The thickness and power of the heat generating layer can be controlled by the time of spraying.
Example 2
A preparation method of a graphene radiation heating film comprises the following steps:
firstly, preparing graphene oxide.
The preparation method of the graphene oxide comprises the steps of adding 1g of graphene powder, 0.5g of sodium nitrate and 1g of potassium permanganate into a flask in an ice water bath, adding 20ml of concentrated sulfuric acid in a dropwise manner, slowly stirring, adding 1g of potassium permanganate when 10ml of concentrated sulfuric acid is added, adding 1g of potassium permanganate when 20ml of concentrated sulfuric acid is added, slowly stirring until the liquid is yellowish, heating to 80 ℃, dropwise adding 50ml of deionized water, and reacting for 1 hour. Then 100ml of deionized water is added, and then 30% of hydrogen peroxide is added dropwise until the liquid is bright yellow. After filtration, the filtrate was washed with 10% dilute hydrochloric acid until no sulfate ion was detected, and then washed with deionized water until the pH of the wash solution stabilized. Soaking the graphene oxide in a 0.01% (v/v) Tween 80 deionized water solution for 30min, centrifuging, drying at 40 ℃ for 10min, and freeze-drying to obtain the graphene oxide.
The obtained graphene oxide is 1415cm-1、3224cm-1The graphene oxide has a strong infrared absorption peak, which shows that the obtained graphene oxide contains more functional groups such as hydroxyl, carboxyl and the like.
The difference from example 1 is that in the method of preparing the heat generating layer spray coating liquid, the graphene is graphene oxide. The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Example 3
A preparation method of a graphene radiation heating film comprises the following steps:
the difference from example 2 is that in the method of preparing the heat generating layer spray coating liquid, the amount of graphene oxide used was 0.8 g. The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Comparative example 1
A preparation method of a graphene radiation heating film comprises the following steps:
the difference from example 2 is that in the method of preparing the heat generating layer spray coating liquid, the amount of graphene oxide used was 0.5 g. The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Example 4
A preparation method of a graphene radiation heating film comprises the following steps:
the difference from example 2 lies in the third step in the method for preparing the heat-generating layer spray coating liquid
In the third step:
150 g of ferric trichloride and 20 g of zinc chloride are put into a glass vessel with the volume of 2 liters, 1000 ml of industrial alcohol with the concentration of 75 percent is added, a heating instrument is used for heating, magnetic stirring is carried out, after complete dissolution, all dissolved solution is poured into the solution prepared in the first step and the second step, and the mixture is uniformly mixed and stirred.
The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Example 5
A preparation method of a graphene radiation heating film comprises the following steps:
the difference from example 2 lies in the third step in the method of preparing the heat-generating layer spray liquid.
In the third step:
150 g of ferric trichloride and 10g of zinc chloride are put into a glass vessel with the volume of 2 liters, 1000 ml of industrial alcohol with the concentration of 75 percent is added, a heating instrument is used for heating, magnetic stirring is carried out, after complete dissolution, all dissolved solution is poured into the solution prepared in the first step and the second step, and the mixture is uniformly mixed and stirred.
The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Example 6
A preparation method of a graphene radiation heating film comprises the following steps:
the difference from example 2 lies in the third step in the method of preparing the heat-generating layer spray liquid.
In the third step:
150 g of ferric trichloride and 30g of zinc chloride are put into a glassware with the volume of 2 liters, 1000 ml of industrial alcohol with the concentration of 75 percent is added, a heating instrument is used for heating, magnetic stirring is carried out, after complete dissolution, all dissolved solution is poured into the solution prepared in the first step and the second step, and the mixture is mixed and stirred uniformly.
The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Comparative example 2
A preparation method of a graphene radiation heating film comprises the following steps:
the difference from example 2 lies in the third step in the method of preparing the heat-generating layer spray liquid.
In the third step:
150 g of ferric trichloride and 5g of zinc chloride are put into a glass vessel with the volume of 2 liters, 1000 ml of industrial alcohol with the concentration of 75 percent is added, a heating instrument is used for heating, magnetic stirring is carried out, after complete dissolution, all dissolved solution is poured into the solution prepared in the first step and the second step, and the mixture is uniformly mixed and stirred.
The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Example 7
A preparation method of a graphene radiation heating film comprises the following steps:
the difference from example 4 lies in the third step in the method of preparing the heat-generating layer spraying liquid.
In the third step, a step of adding a polyurethane resin is further included.
In particular, the method comprises the following steps of,
taking 10g of thermoplastic polyurethane with the number average molecular weight of 30000, adding 150ml of N, N-dimethylformamide, heating to 60 ℃, cooling to room temperature after dissolution, and adding 50ml of 75% industrial alcohol for later use;
150 g of ferric trichloride and 20 g of zinc chloride are put into a glassware with the volume of 2 liters, 1000 ml of industrial alcohol with the concentration of 75 percent is added, a heating instrument is used for heating, magnetic stirring is carried out, after the solution is completely dissolved, 20ml of polyurethane resin solution (about 1g of polyurethane resin) is added, ultrasonic treatment is carried out for 30min, all dissolved solution is poured into the solution prepared in the first step and the second step, and the solution is mixed and stirred uniformly.
The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Example 8
A preparation method of a graphene radiation heating film comprises the following steps:
the difference from example 4 lies in the third step in the method of preparing the heat-generating layer spraying liquid.
In the third step, a step of adding a polyurethane resin is further included.
In particular, the method comprises the following steps of,
taking 10g of thermoplastic polyurethane with the number average molecular weight of 30000, adding 150ml of N, N-dimethylformamide, heating to 60 ℃, cooling to room temperature after dissolution, and adding 50ml of 75% industrial alcohol for later use;
150 g of ferric trichloride and 20 g of zinc chloride are put into a glass vessel with the volume of 2 liters, 1000 ml of industrial alcohol with the concentration of 75 percent is added, a heating instrument is used for heating, magnetic stirring is carried out, after the solution is completely dissolved, 10ml of polyurethane resin solution (about 0.5g of polyurethane resin) is added, ultrasonic treatment is carried out for 30min, all dissolved solution is poured into the solution prepared in the first step and the second step, and the solution is mixed and stirred uniformly.
The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Comparative example 3
A preparation method of a graphene radiation heating film comprises the following steps:
the difference from example 4 lies in the third step in the method of preparing the heat-generating layer spraying liquid.
In the third step, a step of adding a polyurethane resin is further included.
In particular, the method comprises the following steps of,
taking 10g of thermoplastic polyurethane with the number average molecular weight of 30000, adding 150ml of N, N-dimethylformamide, heating to 60 ℃, cooling to room temperature after dissolution, and adding 50ml of 75% industrial alcohol for later use;
150 g of ferric trichloride and 20 g of zinc chloride are put into a glass vessel with the volume of 2 liters, 1000 ml of industrial alcohol with the concentration of 75 percent is added, a heating instrument is used for heating, magnetic stirring is carried out, after the solution is completely dissolved, 5ml of polyurethane resin solution (about 0.25g of polyurethane resin) is added, ultrasonic treatment is carried out for 30min, all dissolved solution is poured into the solution prepared in the first step and the second step, and the solution is mixed and stirred uniformly.
The remaining parameters include the amount of mixture consumed, the carrier and the area and time of spraying on the carrier.
Example 9
The difference from the example 2 is that in the step of S22, when soaking the mixture in a 0.01% (v/v) Tween 80 deionized water solution, the method further comprises the steps of pretreatment and ultrasonic treatment:
s31, soaking the fabric by using deionized water, wherein the ultrasonic treatment time under the W1 power is T1;
s32, filtering to remove deionized water, soaking in 0.01% (v/v) Tween 80 deionized water solution under W2 power for T2, and W2 for
T2 is bT 1; wherein a and b are constants, a is 0.10-0.12, and b is 2-3.
Researches show that after high-power ultrasonic treatment is carried out in deionized water, low-power treatment is carried out in an aqueous solution of a surfactant, so that the dispersity can be improved, and the thermal power, the aging resistance and the corrosion resistance of the obtained graphene radiation heating film can be further improved. It is found that the dispersion effect is better when W1 is 300-500W and T1 is 20-30 min.
Example 10
The difference from example 7 is that the thermal conductivity of the obtained graphene radiation heating film is estimated by the following steps:
s41, preparing 5-10 graphene radiation heating films with different contents of graphene, zinc chloride and polyurethane;
s42, predicting the heat conductivity of the obtained graphene radiation heating film through the following formula:
Rprediction＝K×TP×DC1×EC2×FC3；
Wherein K is a constant, C1Is the content of graphene, C2Is the content of zinc chloride, C3Is the content of polyurethane, D, E, F is the weight;
s43, measuring the heat-conducting property of the obtained graphene radiation heating film, and determining the numerical value ranges of K, D, E, F and the like;
s44, preparing a new graphene radiant heating film which is not within the content range of S41 graphene, zinc chloride and polyurethane, estimating the heat conduction performance of the new graphene radiant heating film by using the formula of S42 and the resin obtained in S43, and comparing the predicted value with the measured value, wherein the condition that the 70% measured value is larger than or equal to the predicted value and larger than or equal to 130% measured value is qualified.
The contents of graphene, zinc chloride and polyurethane are key factors influencing the thermal power of the graphene radiation heating film. The method of the embodiment can estimate the heat-conducting property of the obtained graphene radiation heating film, and facilitates design of formulas of graphene radiation heating films with different powers.
According to the research, in example 7, when the content of graphene is 10-30g, the content of zinc chloride is 10-30g, and the content of the polyurethane resin solution is 10-20ml, the thermal power of the graphene radiation heating film is approximately in a linear relation with the contents of graphene, zinc chloride and polyurethane. In the weight, E is 3-5 times of D, and F is 1-2 times of D. The difference value between the predicted value and the measured value is not more than 30%, and the heat conduction performance of the obtained graphene radiation heating film can be better estimated.
Experimental example investigation of influence of heating layer spraying liquid on graphene radiation heating film
And (3) taking the graphene radiation heating film obtained in the embodiment and the comparative example, spraying the carrier which is a mica plate in a region of 1cm multiplied by 3cm for 10s, and taking the middle region of 1cm multiplied by 1cm for carrying out thermal power, aging resistance and corrosion resistance tests.
The thermal power test is to connect a direct current power supply and test the current value. The aging resistance test is that the sample is firstly heat-treated in a 90 ℃ oven for 24h, and then the resistance difference before and after treatment is tested by adopting the GB1735-79 method. And in the corrosion resistance test, 1% (w/v) sodium chloride aqueous solution, 3% (w/v) sodium chloride aqueous solution, 5% (w/v) sodium chloride aqueous solution, 10% (w/v) sodium chloride aqueous solution and 15% (w/v) sodium chloride aqueous solution are soaked for 5 hours to observe whether the bubbling phenomenon exists or not.
1 heat power
Compared with the graphene radiation heating film in the embodiment 1, the thermal power of the embodiment 2 is improved by more than 35%, and the thermal power of the embodiment 3 is slightly higher than that of the embodiment 1, which shows that the graphene oxide prepared by the method in the embodiment 2 can obviously improve the thermal conductivity, reduce the dosage of the graphene and greatly reduce the cost. In the comparative example 1, due to the fact that the dosage of the graphene oxide is too low, the thermal power can only reach 60-70% of that of the example 1, the reduction is obvious, and the graphene oxide can not be used instead. In example 1, the thermal power per unit weight was a very gentle parabola in the amount of 10 to 30g of graphene added, and reached the maximum value at the amount of 21g of graphene added.
Compared with the graphene radiation heating film in the embodiment 2, the thermal power of the embodiments 4, 5 and 6 is obviously improved, and the thermal power can be improved by about 12% by taking the embodiment 4 as the best one. Meanwhile, the thermal power improvement of comparative example 2 was not significant, and it is likely that the amount of zinc chloride used therein was low.
Compared with the graphene radiation heating film in the embodiment 4, the thermal power of the embodiments 7 and 8 added with polyurethane is also obviously improved by about 5%. Comparative example 9 increased by 0.5% and was not statistically significant.
2 resistance to aging
The delta R of the examples 1-8 is less than 0.32, and the delta R of the examples 4, 5 and 6 is less than 0.21, which shows the effect of zinc chloride on the aging resistance of the graphene radiant heating film.
3 corrosion resistance
In examples 1 to 8, no bubbling was observed when the treatment was carried out for 5 hours in a 1% (w/v) aqueous solution of sodium chloride. The corrosion resistance properties of example 2 and example 1 were not significantly different. The corrosion resistance of the examples 4, 5 and 6 is obviously better than that of the example 2, and the corrosion resistance of the examples 7 and 8 is obviously better than that of the example 4, which shows the effect of the zinc chloride and the polyurethane on the corrosion resistance of the graphene radiation heating film.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The utility model provides a graphite alkene radiation heating film, its characterized in that includes the carrier and will generate heat the layer spraying liquid spraying and be in the layer that generates heat that forms on the carrier, the layer spraying liquid that generates heat includes tin tetrachloride, graphite alkene, the alcohol solution of ferric trichloride.
2. The heating film according to claim 1, wherein the heating layer spraying liquid comprises the following raw materials in parts by weight:
10-30 parts of stannic chloride, 0.01-0.03 part of graphene, 0.1-0.3 part of ferric trichloride and 40-70 parts of industrial alcohol with the concentration of 70-80% (v/v).
3. The heating film according to claim 1, wherein the heating layer spraying liquid comprises the following raw materials in parts by weight:
20 parts of tin tetrachloride, 0.021 part of graphene, 0.2 part of ferric trichloride and 50.85 parts of industrial alcohol with the concentration of 75% (v/v).
4. A heating film according to any one of claims 1 to 3, wherein the graphene is graphene oxide.
5. The heat generation film according to claim 4, wherein the graphene oxide is prepared by:
s11, adding graphene powder, sodium nitrate and potassium permanganate into a flask in an ice-water bath, adding concentrated sulfuric acid in a dropwise manner, slowly stirring, adding part of potassium permanganate when part of concentrated sulfuric acid is added, slowly stirring until the liquid is yellowish, heating, and then dropwise adding deionized water for reaction;
s22, adding deionized water, dropwise adding hydrogen peroxide until the liquid is bright yellow, filtering, washing with dilute hydrochloric acid until no sulfate ions are detected, washing with deionized water until the pH of the washing liquid is stable, soaking with a 0.01% (v/v) Tween 80 deionized water solution, centrifuging, and drying to obtain the graphene oxide.
6. A heating film according to any one of claims 1 to 5, wherein said heating layer spraying solution further comprises zinc chloride in an amount of 0.01 to 0.03 parts, preferably 0.02 parts.
7. A heating film according to any one of claims 1 to 7, wherein the heat generating layer spraying liquid further contains 0.0005 to 0.002 parts, preferably 0.001 parts, of polyurethane.
8. A preparation method of a graphene radiation heating film is characterized by comprising the following steps:
s1, dissolving the crystallized stannic chloride in the alcohol water solution;
s2, dissolving ferric trichloride and zinc chloride in an alcohol water solution;
s3, dissolving thermoplastic polyurethane in N, N-dimethylformamide, adding alcohol, and mixing with the ferric trichloride and zinc chloride solution obtained in the step S2;
s4, mixing the graphene with the tin tetrachloride solution obtained in the S1 step, and then mixing the graphene with the solution obtained in the S3 step;
and S5, spraying the mixed solution obtained in the step S4 on a planar carrier.
9. The method according to claim 5, wherein the step of S22, when soaking in 0.01% (v/v) Tween 80 in deionized water, further comprises the steps of pre-treatment and ultrasonic treatment:
s31, soaking the fabric by using deionized water, wherein the ultrasonic treatment time under the W1 power is T1;
s32, filtering to remove deionized water, soaking in 0.01% (v/v) Tween 80 deionized water solution under W2 power for T2, and W2 for
T2 is bT 1; wherein a and b are constants, a is 0.10-0.12, and b is 2-3.
10. The method according to claim 8, wherein the thermal conductivity of the obtained graphene radiation heating film is estimated by the following steps:
s41, preparing 5-10 graphene radiation heating films with different contents of graphene, zinc chloride and polyurethane;
s42, predicting the heat conductivity of the obtained graphene radiation heating film through the following formula:
Rprediction＝K×TP×DC1×EC2×FC3；
Wherein K is a constant, C1Is the content of graphene, C2Is the content of zinc chloride, C3Is the content of polyurethane, D, E, F is the weight;
s43, measuring the heat-conducting property of the obtained graphene radiation heating film, and determining the numerical value ranges of K, D, E, F and the like;
s44, preparing a new graphene radiant heating film which is not within the content range of S41 graphene, zinc chloride and polyurethane, estimating the heat conduction performance of the new graphene radiant heating film by using the formula of S42 and the resin obtained in S43, and comparing the predicted value with the measured value, wherein the condition that the 70% measured value is larger than or equal to the predicted value and larger than or equal to 130% measured value is qualified.
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