CN115011133A - Heating paper suitable for heating ceramic tile and preparation method thereof - Google Patents
Heating paper suitable for heating ceramic tile and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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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
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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
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
- C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
- C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2493/00—Characterised by the use of natural resins; Derivatives thereof
- C08J2493/04—Rosin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Abstract
The invention discloses heating paper suitable for a heating ceramic tile, which comprises the following raw materials in parts by weight: 10-40 parts of long-cut carbon fiber, 5-10 parts of short-cut carbon fiber, 30-40 parts of plant fiber, 20-30 parts of glass fiber, 10-15 parts of solvent, 1-2 parts of dispersant, 2-5 parts of plasticizer, 0.2-0.4 part of lubricant, 3-5 parts of suspending agent, 0.1-0.5 part of defoaming agent, 3-6 parts of adhesive and 0.5-0.8 part of anion dispersed rosin size, and the preparation method comprises the steps of preparing base slurry, carrying out vacuum degassing on the base slurry, preparing long-cut carbon fiber slurry, preparing conductive slurry and drying. The heating paper prepared by the invention not only ensures the heating power, but also realizes the purposes of uniform and stable heating and long service life.
Description
Technical Field
The invention relates to the technical field of heating paper, in particular to heating paper suitable for a heating ceramic tile and a preparation method thereof.
Background
The heating ceramic tile is a ceramic tile capable of heating by means of an external heating layer, and the heating layer of the heating ceramic tile sold on the market is generally a heating cable or a heating film.
The carbon fiber is a high-performance fiber, has the characteristics of high temperature resistance, friction resistance, electric conduction, heat conduction, corrosion resistance and the like, and can be compounded with the plant fiber to prepare the heating paper with the electric conduction performance. The common conductive paper in the current market has the performances of static electricity prevention and strong aging, can meet the basic heating requirement, but has the problems of uneven heating in use, short service life and the like, so that the use requirement of the heating ceramic tile buried in the wet environment under the ground for a long time is difficult to meet.
Chinese patent CN201911241768 discloses a heating film and a preparation method thereof, and an apparatus and a preparation method using the heating film. This patent adopts the anion, graphite alkene, the synthetic effective ratio of carbon fiber and other materials, filming and preparation etc. can satisfy the demand of generating heat with the membrane base that generates heat that obtains, but follow this patent schematic diagram 2 can know, though it is more even to carbon fiber base material thick liquids activation modification back carbon fiber distribution, nevertheless can see out, the intersection point between each carbon fiber is very much, after the membrane that generates heat lasts the circular telegram, mixed and disorderly inner structure can lead to the intersection point current load too high like this, the easy overload that takes place, take place to puncture electric leakage phenomenon, bring the unstability that generates heat in the use, short service life, potential safety hazard scheduling problem.
Therefore, in order to meet the daily needs of people for the heating ceramic tiles to climb year by year, the development of the heating paper suitable for the heating ceramic tiles and the preparation method thereof are urgently needed.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, a first object of the present invention is to provide a heating paper suitable for a heating tile;
the second purpose of the invention is to provide a preparation method of heating paper suitable for heating ceramic tiles;
the technical scheme adopted by the invention for solving the technical problems is as follows:
the heating paper suitable for the heating ceramic tile comprises the following raw materials in parts by weight: 10-40 parts of long-cut carbon fiber, 5-10 parts of short-cut carbon fiber, 30-40 parts of plant fiber, 20-30 parts of glass fiber, 1-2 parts of dispersing agent, 2-5 parts of plasticizer, 0.2-0.4 part of lubricant, 3-5 parts of suspending agent, 0.1-0.5 part of defoaming agent, 3-6 parts of adhesive and 0.5-0.8 part of anion dispersed rosin size;
further, the plasticizer comprises any one or more of cyclohexane 1, 2-dicarboxylic acid diisononyl ester, polyethylene glycol and butylbenzene phthalate ester; the plasticizer is added, so that the softness of the fiber pulp can be effectively improved, and finally formed heating paper can be cut and folded at will according to the use requirement;
further, the lubricant is one or two of alkylphenol ethoxylates and fatty acid polyoxyethylene esters; adding lubricant to make the conductive slurry flow smoothly on the film carrier;
further, the suspending agent includes propenyl sulfonic acid; the suspending agent is added, so that the suspension property of the fibers in the slurry can be effectively improved, the agglomeration of the fibers is reduced, and the fibers are uniformly distributed;
further, the defoaming agent comprises any one or two of n-butyl alcohol and ethylene glycol; adding a defoaming agent, reducing bubbles in the slurry, improving the quality of the heating paper and ensuring no cross-over points among the carbon fibers;
further, the adhesive comprises any one or two of polyvinyl alcohol and urethane; the adhesive is added to enhance the formability of the heating paper and improve the tensile strength of the heating paper;
furthermore, the long-cut carbon fibers and the short-cut carbon fibers are obtained by cutting the same type of carbon fibers with single continuity; the length of the long-cut carbon fiber is 10-20 mm, and the length of the short-cut carbon fiber is 0.1-0.5 mm; the same type of carbon fiber with single continuity has the following physical properties: the diameter is 5 to 30 μm, the tensile strength is 1200 to 5000MPa, the elastic modulus is 200 to 400MPa, and the density is 0.10 to 0.40g/cm 3 The thermal expansion coefficient is less than or equal to 0.024, and the thermal shock resistance is 0.2-0.6 MPa;
the carbon fiber mainly comprises carbon elements, has the characteristics of high temperature resistance, friction resistance, electric conduction, heat conduction, corrosion resistance and the like, is fibrous in shape, is soft and can be processed into various fabrics; plant fibers, glass fibers; due to the special multi-level and multi-scale internal structure and the inherent hydrophilic chemical components of the plant fibers, the plant fibers are easy to absorb water and high in water absorption amount in humid air or soaked in water; the glass fiber is an inorganic non-metallic material with excellent performance, has good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but has the defects of brittle performance and poor wear resistance;
in the invention, by adding the plant fiber, the carbon fiber can be well connected because the plant fiber has stronger wrapping property; and the plant fiber has stronger toughness and large tension, and can be mixed with the glass fiber, so that the brittleness of the glass fiber can be integrally reduced, and the heating paper is not easy to tear. In addition, the plant fiber and the glass fiber are used in a composite way, the glass fiber basically does not absorb water, and the water absorption of the heating paper can be reduced.
Preferably, the feeding amount of the long-cut carbon fibers and the short-cut carbon fibers is 2-4:1 in terms of weight ratio. When the ratio of the long-cut carbon fibers to the short-cut carbon fibers in the heating paper is 2-4:1, most of the carbon fibers in the heating paper can be distributed as the long-cut carbon fibers, and a certain amount of the short-cut carbon fibers can play a role of a bridge.
Further, the dispersing agent comprises hydroxyethyl cellulose sodium and anionic polyacrylamide; the chopped carbon fibers have small monofilament diameter and high surface energy, and are easy to agglomerate and deposit under the action of Van der Waals force in the preparation of mixed fiber slurry containing the chopped carbon fibers, the plant fibers and the glass fibers; the hydroxypropyl methyl cellulose is added into the mixed fiber slurry, and the hydroxypropyl methyl cellulose contains more hydroxyl polar groups, so that the hydroxypropyl methyl cellulose is more soluble in water and can form hydrogen bonds with polar groups on the surfaces of the chopped carbon fibers or interact with polar groups on the surfaces of the chopped carbon fibers through van der Waals force, the hydrophilicity and wettability of the chopped carbon fibers are improved, the chopped carbon fibers are in a stable dispersion state, and the phenomena of deposition and agglomeration are not easy to occur;
in the process of preparing the long-cut carbon fiber slurry, the negative charges on the surface of the long-cut carbon fibers can be increased by adding the anionic polyacrylamide, so that the repulsive force among the long-cut carbon fibers, the long-cut carbon fibers and the plant fibers and the long-cut carbon fibers and the glass fibers is increased, and the long-cut carbon fibers are ensured to have dispersibility to a certain extent;
in addition, the anion dispersed rosin size is applied to improve the impermeability of the heating paper to water and liquid, prevent the diffusion and permeation of water-based liquid and ensure that the prepared heating paper can be used in a humid environment for a long time;
in addition, the invention also provides a preparation method of the heating paper suitable for the heating ceramic tile, which comprises the following steps:
s1, preparing basic slurry
Preparing materials according to the parts by weight; mixing short-cut carbon fibers, glass fibers, plant fibers and a proper amount of water to obtain the mixture with the beating degree of 40-45 0 Adding the hydroxyethyl cellulose sodium and the anion dispersed rosin size into the SR mixed fiber slurry, and oscillating for 0.5-1h at room temperature for later use;
mixing a plasticizer, a lubricant, a suspending agent and a proper amount of water, adding the vibrated mixed fiber slurry, adding a binder, and carrying out mixed grinding for 0.5-1h to obtain a base slurry with good stability and fluidity;
s2, vacuum degassing of base slurry
Putting the base slurry prepared in the S1 into a vacuum tank, adding a defoaming agent, stirring for 0.5-1h, sequentially passing through double screens with mesh sizes of 500 mu m and 200 mu m, and then flowing into a hopper of a casting paper machine;
s3, preparing long-cut carbon fiber slurry
Adding long-cut carbon fibers and anionic polyacrylamide into distilled water at the temperature of 37-39 ℃ as a water phase, and stirring for 20min to obtain long-cut carbon fiber slurry;
s4, preparing conductive paste
Transferring the basic slurry flowing out of the lower part of a hopper of a casting paper machine to a movable film carrier, arranging a carbon fiber slurry spraying machine at a position which is 150-200 mm higher than the running position of the film carrier, and arranging a vertical electric field between the movable film carrier and the carbon fiber slurry spraying machine;
the long-cut carbon fiber slurry falls after being sprayed by a carbon fiber slurry spraying machine, and is scattered into the basic slurry on the moving film carrier after being acted by an external electric field to obtain conductive slurry;
s5, drying
And (S4) the conductive paste obtained in the step is moved by a movable film carrier, enters a drying chamber after passing through a slope, and is dried for 70-80 min at the temperature of 75-85 ℃ to obtain the heating paper.
Further, in the step S5, a scraper is disposed on the movable film carrier, and the thickness of the slurry to be dried is controlled to be 0.1-0.15 mm;
further, in the step S5, an included angle between the slope and the ground is 30-40 degrees; the distribution directivity of the long-cut carbon fibers in the conductive paste can be more definite, so that fewer cross-points are generated.
Further, the strength of the vertical electric field in the step S4 is 1-5 kV/cm, and under the action of the vertical electric field, the long-cut carbon fibers are more easily distributed in the basic slurry in parallel.
The heating paper prepared by the invention is applied to a heating ceramic tile, is used as heating paper, is arranged below a ceramic tile substrate and plays a role in conducting electricity and heating.
The invention has the beneficial effects that:
most of the long-cut carbon fibers in the heating paper prepared by the invention are arranged in a longitudinal parallel manner, the long-cut carbon fibers in a three-dimensional space are basically in a parallel state, the number of crossed joints is small, and the short-cut carbon fibers, the plant fibers and the glass fibers are dispersed among the parallel long-cut carbon fibers after being compounded; the composite fibers are connected with the long-cut carbon fibers distributed in parallel to form a net structure, so that the bridge function of connecting the long-cut carbon fibers distributed in parallel is realized; when the power is supplied, current generally passes through the long-cut carbon fibers distributed in parallel, and even if the joints are disconnected, the current can pass through the short-cut carbon fibers to another long-cut carbon fiber. Therefore, the heating paper prepared by the invention can conduct electricity, ensure the heating power, and realize the purposes of uniform and stable heating and long service life of the heating paper.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a three-dimensional microscopic view of the heat generating paper of the present invention;
FIG. 2 is a schematic view of a three-dimensional structure of the heat generating paper of the present invention;
wherein: 1. plant fibers; 2. glass fibers; 3. short-cut carbon fibers; 4. long-cut carbon fiber
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the present invention.
The carbon fiber in the examples is a carbon fiber having a single continuity, and the physical properties satisfy: the diameter is 5 to 30 μm, the tensile strength is 1200 to 5000MPa, the elastic modulus is 200 to 400MPa, and the density is 0.10 to 0.40g/cm 3 The thermal expansion coefficient is less than or equal to 0.024, and the thermal shock resistance is 0.2-0.6 MPa;
wherein: the long-cut carbon fiber and the short-cut carbon fiber are obtained by cutting the carbon fiber;
wherein: the physical properties of the carbon fiber of example 1 were: diameter of 5 μm, tensile strength of 1200MPa, elastic modulus of 200MPa, and density of 0.10g/cm 3 The thermal expansion coefficient is 0.018, and the thermal shock resistance is 0.2 MPa;
the physical properties of the carbon fiber of example 2 were: the diameter is 30 mu m, the tensile strength is 5000MPa, the elastic modulus is 400MPa, and the density is 0.40g/cm 3 0.015 thermal expansion coefficient and 0.6MPa thermal shock resistance;
the physical properties of the carbon fiber of example 3 were: 15 μm in diameter, 2100MPa in tensile strength, 300MPa in elastic modulus and 0.25g/cm in density 3 The thermal expansion coefficient is less than or equal to 0.024, and the thermal shock resistance is 0.4 MPa;
the physical properties of the carbon fiber of example 4 were: diameter of 10 μm, tensile strength of 3300MPa, elastic modulus of 300MPa, and density of 0.35g/cm 3 The thermal expansion coefficient is less than or equal to 0.024, and the thermal shock resistance is 0.5 MPa;
FIG. 1 is a three-dimensional microscopic structure of the heat generating paper of the present invention, wherein black lines in the figure are long-cut carbon fibers connected to each other as a line.
As shown in fig. 2, in the schematic three-dimensional structure of the heating paper, most of the long-cut carbon fibers 4 are arranged in a longitudinal parallel manner in the heating paper, the long-cut carbon fibers 4 are basically in a parallel state in a three-dimensional space, the number of cross joints is small, and the short-cut carbon fibers 3, the plant fibers 1 and the glass fibers 2 are dispersed among the parallel long-cut carbon fibers 4 after being compounded; the composite fibers are connected with the long-cut carbon fibers 4 distributed in parallel to form a net structure, and the function of connecting the long-cut carbon fibers 4 distributed in parallel is achieved.
Example 1
The heating paper suitable for the heating ceramic tile comprises the following raw materials in parts by weight: 10 parts of long-cut carbon fiber, 5 parts of short-cut carbon fiber, 30 parts of plant fiber and 20 parts of glass fiber;
0.5 part of hydroxyethyl cellulose sodium, 0.5 part of anionic polyacrylamide, 2 parts of cyclohexane 1, 2-diisononyl phthalate, 0.2 part of alkylphenol polyoxyethylene, 3 parts of propenyl sulfonic acid, 0.1 part of n-butyl alcohol, 3 parts of polyvinyl alcohol and 0.5 part of anionic dispersed rosin size;
a preparation method of heating paper suitable for a heating ceramic tile comprises the following steps:
s1, preparing basic slurry
Preparing materials according to the weight part; mixing short-cut carbon fibers, glass fibers, plant fibers and a proper amount of water to obtain the mixture with the beating degree of 40-45 0 Adding sodium hydroxyethyl cellulose and anion dispersed rosin size into the SR mixed fiber slurry, and oscillating for 0.5h at room temperature for later use;
mixing a plasticizer, a lubricant, a suspending agent and water (1 time of the weight of the chopped carbon fibers), adding the vibrated mixed fiber slurry, adding an adhesive, and carrying out mixed grinding for 0.5h to obtain a base slurry with good stability and fluidity;
s2, vacuum degassing of base slurry
Putting the base slurry prepared in the S1 into a vacuum tank, adding a defoaming agent, stirring for 0.5h, sequentially passing through double screens with mesh sizes of 500 mu m and 200 mu m, and then flowing into a hopper of a tape casting paper machine;
s3, preparing long-cut carbon fiber slurry
Taking distilled water (1 time of the weight of the long-cut carbon fiber slurry) at 37 ℃ as a water phase, adding long-cut carbon fibers and anionic polyacrylamide, and stirring for 20min to obtain long-cut carbon fiber slurry;
s4, preparing conductive paste
Controlling the basic slurry to flow out from the lower part of a hopper of a casting paper machine at a speed of 60g/s to a moving film carrier with a width of 600mm and a moving speed of 800mm/s, arranging a carbon fiber slurry spraying machine with a spraying speed of 3g/s at a position 5-7 mm away from the moving film carrier at the lower part of the hopper of the casting paper machine and 150mm above the running position of the film carrier, and arranging a vertical electric field with an electric field intensity of 1kV/cm between the moving film carrier and the carbon fiber slurry spraying machine;
the long-cut carbon fiber slurry falls after being sprayed by a carbon fiber slurry spraying machine, and is scattered into the basic slurry on the moving film carrier after being acted by an external electric field to obtain conductive slurry;
s5, drying
And (8) operating the conductive slurry obtained in the step (S4) through a movable film carrier, arranging a scraper on the movable film carrier, enabling the thickness of the slurry to be 0.1mm, enabling the plasma slurry treated by the scraper to enter a drying chamber through a slope with an included angle of 30 degrees with the ground, drying for 70min at 75 ℃ to obtain heating paper with the width of 600mm and the thickness of 0.07mm, and winding for later use.
Example 2
The heating paper suitable for the heating ceramic tile comprises the following raw materials in parts by weight: 40 parts of long-cut carbon fibers, 10 parts of short-cut carbon fibers, 40 parts of plant fibers and 30 parts of glass fibers;
0.3 part of fatty acid polyoxyethylene ester, 4 parts of propenyl sulfonic acid, 0.5 part of ethylene glycol, 6 parts of ethyl carbamate and 0.8 part of anion dispersed rosin size;
a preparation method of heating paper suitable for a heating ceramic tile comprises the following steps:
s1, preparing basic slurry
Preparing materials according to the parts by weight; mixing the short carbon fibers, the glass fibers, the plant fibers and a proper amount of water to obtain the mixture with the beating degree of 40-45 0 Adding sodium hydroxyethyl cellulose and anion dispersed rosin size into the SR mixed fiber slurry, and oscillating for 1h at room temperature for later use;
mixing a plasticizer, a lubricant, a suspending agent and water (1 time of the weight of the chopped carbon fibers), adding the vibrated mixed fiber slurry, adding an adhesive, and mixing and grinding for 1 hour to obtain a base slurry with good stability and fluidity;
s2, vacuum degassing of base slurry
Putting the base slurry prepared in the S1 into a vacuum tank, adding a defoaming agent, stirring for 1h, sequentially passing through double screens with mesh sizes of 500 microns and 200 microns, and then flowing into a hopper of a tape casting paper machine;
s3, preparing long-cut carbon fiber slurry
Taking distilled water (1 time of the weight of the long-cut carbon fiber slurry) with the temperature of 39 ℃ as a water phase, adding long-cut carbon fibers and anionic polyacrylamide, and stirring for 20min to obtain long-cut carbon fiber slurry;
s4, preparing conductive paste
Controlling the basic slurry to flow out of the lower part of a hopper of a casting paper machine at a speed of 75g/s to a moving film carrier with a width of 900mm and a moving speed of 1000mm/s, arranging a carbon fiber slurry spraying machine with a spraying speed of 19g/s at a position 5-7 mm away from the moving film carrier at the lower part of the hopper of the casting paper machine and 200mm above the running position of the film carrier, and arranging a vertical electric field with an electric field intensity of 5kV/cm between the moving film carrier and the carbon fiber slurry spraying machine;
the long-cut carbon fiber slurry falls after being sprayed by a carbon fiber slurry spraying machine, and is scattered into the basic slurry on the moving film carrier after being acted by an external electric field, so that conductive slurry is obtained;
s5, drying
And (4) operating the conductive paste obtained in the step (S4) through a movable film carrier, arranging a scraper on the movable film carrier, enabling the thickness of the paste to be 0.15mm, enabling the plasma material processed by the scraper to enter a drying chamber after passing through a slope with an included angle of 40 degrees with the ground, drying for 80min at 85 ℃ to obtain heating paper with the width of 900mm and the thickness of 0.12mm, and enabling the heating paper to be used for winding.
Example 3
The heating paper suitable for the heating ceramic tile comprises the following raw materials in parts by weight: 24 parts of long-cut carbon fibers, 8 parts of short-cut carbon fibers, 35 parts of plant fibers and 25 parts of glass fibers;
0.8 part of sodium hydroxyethyl cellulose, 0.8 part of anionic polyacrylamide, 4 parts of butylbenzene phthalate ester, 0.3 part of alkylphenol polyoxyethylene, 4 parts of propenyl sulfonic acid, 0.3 part of n-butyl alcohol, 4 parts of polyvinyl alcohol and 0.7 part of anionic dispersed rosin size;
a preparation method of heating paper suitable for a heating ceramic tile comprises the following steps:
s1, preparing base slurry
Preparing materials according to the parts by weight; mixing short-cut carbon fibers, glass fibers, plant fibers and a proper amount of water to obtain the mixture with the beating degree of 40-45 0 Adding sodium hydroxyethyl cellulose and anion dispersed rosin size into the SR mixed fiber slurry, and oscillating for 0.8h at room temperature for later use;
mixing a plasticizer, a lubricant, a suspending agent and water (1 time of the weight of the chopped carbon fibers), adding the vibrated mixed fiber slurry, adding an adhesive, and carrying out mixed grinding for 0.7h to obtain a base slurry with good stability and fluidity;
s2, vacuum degassing of base slurry
Putting the base slurry prepared in the S1 into a vacuum tank, adding a defoaming agent, stirring for 0.7h, sequentially passing through double screens with mesh sizes of 500 mu m and 200 mu m, and then flowing into a hopper of a casting paper machine;
s3, preparing long-cut carbon fiber slurry
Adding long-cut carbon fibers and anionic polyacrylamide into distilled water (1 time of the weight of the long-cut carbon fiber slurry) at 38 ℃ serving as a water phase, and stirring for 20min to obtain long-cut carbon fiber slurry;
s4, preparing conductive paste
Controlling the basic slurry to flow out from the lower part of a hopper of a casting paper machine at a speed of 68g/s to a moving film carrier with a width of 750mm and a moving speed of 900mm/s, wherein the lower part of the hopper of the casting paper machine is 5-7 mm away from the moving film carrier, a carbon fiber slurry spraying machine with a spraying speed of 5g/s is arranged at a position 180mm away from the upper part of the operation position of the film carrier, and a vertical electric field with an electric field intensity of 3kV/cm is additionally arranged between the moving film carrier and the carbon fiber slurry spraying machine;
the long-cut carbon fiber slurry falls after being sprayed by a carbon fiber slurry spraying machine, and is scattered into the basic slurry on the moving film carrier after being acted by an external electric field to obtain conductive slurry;
s5, drying
And (S4) operating the conductive paste obtained in the step (S4) through a movable film carrier, arranging a scraper on the movable film carrier, enabling the thickness of the paste to be 0.13mm, enabling the plasma paste processed by the scraper to enter a drying chamber through a slope with an included angle of 35 degrees with the ground, drying for 75min at 80 ℃ to obtain heating paper with the width of 750mm and the thickness of 0.10mm, and winding for later use.
Example 4
The heating paper suitable for the heating ceramic tile comprises the following raw materials in parts by weight: 18 parts of long-cut carbon fibers, 5 parts of short-cut carbon fibers, 31 parts of plant fibers and 29 parts of glass fibers;
0.7 part of hydroxyethyl cellulose sodium, 0.9 part of anionic polyacrylamide, 4 parts of butylbenzene phthalate ester, 0.28 part of alkylphenol polyoxyethylene, 3.5 parts of propenyl sulfonic acid, 0.4 part of ethylene glycol, 5 parts of ethyl carbamate and 0.7 part of anionic dispersed rosin size;
a preparation method of heating paper suitable for a heating ceramic tile comprises the following steps:
s1, preparing basic slurry
Preparing materials according to the parts by weight; mixing short-cut carbon fibers, glass fibers, plant fibers and a proper amount of water to obtain the mixture with the beating degree of 40-45 0 Adding sodium hydroxyethyl cellulose and anion dispersed rosin size into the SR mixed fiber slurry, and oscillating for 0.6h at room temperature for later use;
mixing a plasticizer, a lubricant, a suspending agent and water (1 time of the weight of the chopped carbon fibers), adding the vibrated mixed fiber slurry, adding an adhesive, and carrying out mixed grinding for 0.9h to obtain a base slurry with good stability and fluidity;
s2, vacuum degassing of base slurry
Putting the base slurry prepared in the S1 into a vacuum tank, adding a defoaming agent, stirring for 0.8h, sequentially passing through double screens with mesh sizes of 500 mu m and 200 mu m, and then flowing into a hopper of a tape casting paper machine;
s3, preparing long-cut carbon fiber slurry
Adding long-cut carbon fibers and anionic polyacrylamide into distilled water (1 time of the weight of the long-cut carbon fiber slurry) at 39 ℃ serving as a water phase, and stirring for 20min to obtain long-cut carbon fiber slurry;
s4, preparing conductive paste
Controlling the basic slurry to flow out from the lower part of a hopper of a casting paper machine at a speed of 65g/s to a moving film carrier with a width of 800mm and a moving speed of 800mm/s, wherein the lower part of the hopper of the casting paper machine is 6mm away from the moving film carrier, a carbon fiber slurry spraying machine with a spraying speed of 15g/s is arranged at a position 180mm away from the upper part of the operation position of the film carrier, and a vertical electric field with an electric field intensity of 4kV/cm is additionally arranged between the moving film carrier and the carbon fiber slurry spraying machine;
the long-cut carbon fiber slurry falls after being sprayed by a carbon fiber slurry spraying machine, and is scattered into the basic slurry on the moving film carrier after being acted by an external electric field to obtain conductive slurry;
s5, drying
And (4) operating the conductive paste obtained in the step (S4) through a movable film carrier, arranging a scraper on the movable film carrier, enabling the thickness of the paste to be 0.14mm, enabling the plasma material processed by the scraper to enter a drying chamber after passing through a slope with an included angle of 37 degrees with the ground, drying for 78min at 79 ℃ to obtain heating paper with the width of 850mm and the thickness of 0.09mm, and winding for later use.
Comparative example 1
The electric field is not applied, and the rest conditions are the same as those of the example 1;
comparative example 2
The long-cut carbon fibers were not added, the amount of the short-cut carbon fibers in comparative example 2 added was the total amount of the short-cut carbon fibers and the long-cut carbon fibers added in example 1, and the remaining conditions were the same as in example 1;
comparative example 3
The anionic dispersed rosin size was not added, and the remaining conditions were the same as in example 1;
and (3) performance testing:
the prepared heating paper is compounded on the back of a ceramic tile with the specification of 600 x 900mm, and a performance application test is carried out under the power supply of a 36V direct current power supply in a humid environment.
1. Temperature rise efficiency: continuously electrifying to detect the temperature of the brick surface under the environment with ideal heat preservation and no air circulation, wherein the first 10min is more than or equal to 0.6 ℃/min at any temperature;
2. overvoltage test and nominal working life test: according to the method for estimating the service life in the GB/T7287-;
| nominal working life | Test time |
| 3000 | 36 |
| 4000 | 48 |
| 5000 | 60 |
| ... | ... |
| 10000 | 120 |
3. And (3) testing the heating uniformity: and under the environment of ideal heat preservation, rest and no air circulation, the temperature of the surface of the brick is continuously electrified and detected. Equally dividing the brick surface into 6 areas, measuring the brick surface temperature in each area, and calculating the maximum temperature difference;
4. and (3) testing the heating stability: and (3) fully covering a plurality of layers of insulation boards on the surface and below the ceramic tile, measuring the highest temperature and power of the surface of the ceramic tile, and judging the safety of the heating ceramic tile when covered by an article. The thickness of the heat preservation plate is 3cm, the number of the heat preservation plate is the bottom layer and the top layer, the measuring points are 6 random points of the brick surface, the highest temperature point of the brick surface and power data are continuously recorded within 120 days, whether the power is attenuated or not is judged, and the data are recorded in the following table 1.
As can be seen from Table 1, the heat-generating paper prepared in examples 1-4 has a temperature rise efficiency of 1.3-1.5, a nominal service life of 84000-92000h, a maximum temperature difference of 0.3-0.6 ℃, no power attenuation, high heat-conducting property and no power attenuation under the condition of long service life;
in contrast to comparative example 1, the obtained heating paper has a temperature rise efficiency of 1.0, a nominal working life of 48000 hours, a maximum temperature difference of 1.9 ℃ and a power attenuation of 0.6%, which indicates that under the condition of no electric field, long-cut carbon fibers cannot be well distributed in parallel, so that the distribution of the long-cut fibers in the heating paper is unbalanced, and therefore, when the heating paper is heated, the temperature difference is too large, the temperature rise efficiency is low, the service life is also influenced, and the power attenuation is 0.6%.
Comparative example 2, the obtained heating paper has the temperature rise efficiency of 0.5, the nominal working life of 45000h, the maximum temperature difference value of 2.4 ℃ and the power attenuation of 1.5 percent; the fact that long-cut carbon fibers are not added is shown, and under the condition that the added carbon fibers are all short-cut carbon fibers, the short-cut carbon fibers are large in amount and easy to agglomerate, which is shown in the fact that more nodes exist in the heating paper, so that high temperature difference is easy to exist, the breakdown phenomenon can occur, the nominal working life is influenced, and the power is attenuated by 1.5%;
comparative example 3, the obtained heating paper has the temperature rise efficiency of 0.2, the nominal working life of 21000h, the maximum temperature difference of 0.8 ℃ and the power attenuation of 10 percent; under the condition of not adding anion dispersed rosin size, the impermeability of the heating paper to water and liquid is reduced, and when the heating paper works in a humid environment, the phenomena of water quality and liquid diffusion and permeation occur, so that the nominal working life and the temperature rise efficiency are seriously influenced, and the power attenuation is 10 percent.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. The heating paper suitable for the heating ceramic tile is characterized by comprising the following raw materials in parts by weight: 10-40 parts of long-cut carbon fiber, 5-10 parts of short-cut carbon fiber, 30-40 parts of plant fiber, 20-30 parts of glass fiber, 1-2 parts of dispersing agent, 2-5 parts of plasticizer, 0.2-0.4 part of lubricant, 3-5 parts of suspending agent, 0.1-0.5 part of defoaming agent, 3-6 parts of adhesive and 0.5-0.8 part of anion dispersed rosin size;
the long-cut carbon fibers and the short-cut carbon fibers are the same carbon fibers with single continuity; the length of the long-cut carbon fiber is 10-20 mm, and the length of the short-cut carbon fiber is 0.1-0.5 mm; the long-cut carbon fibers in the three-dimensional space of the heating paper are basically in a parallel state, the number of cross joints is small, and the short-cut carbon fibers, the plant fibers and the glass fibers are dispersed among the parallel long-cut carbon fibers after being compounded.
2. A heating paper suitable for a heating ceramic tile according to claim 1, wherein the dispersant comprises sodium hydroxyethyl cellulose, anionic polyacrylamide.
3. A heating paper suitable for a heating ceramic tile according to claim 1, wherein the plasticizer comprises any one or more of cyclohexane 1, 2-dicarboxylic acid diisononyl ester, polyethylene glycol, and styrene-butadiene phthalate.
4. A heat-generating paper suitable for a heat-generating tile according to claim 1, wherein the lubricant is either one or both of alkylphenol ethoxylate and fatty acid polyoxyethylene ester.
5. A heat generating paper suitable for a heat generating ceramic tile according to claim 1, wherein the suspending agent comprises acryl sulfone.
6. A heating paper suitable for a heating tile according to claim 1, wherein the antifoaming agent comprises either or both of n-butanol and ethylene glycol.
7. A heat generating paper suitable for a heat generating tile according to claim 1, wherein the binder comprises either or both of polyvinyl alcohol and urethane.
8. A method for preparing a heat generating paper suitable for a heat generating tile according to any one of claims 1 to 7, comprising the steps of:
s1, preparing basic slurry
Preparing materials according to the parts by weight; mixing short-cut carbon fibers, glass fibers, plant fibers and a proper amount of water to prepare mixed fiber slurry with a beating degree of 40-45 DEG SR, adding sodium hydroxyethyl cellulose and anion dispersed rosin size, and shaking for 0.5-1h at room temperature for later use;
mixing a plasticizer, a lubricant, a suspending agent and a solvent, adding the vibrated mixed fiber slurry, adding an adhesive, and carrying out mixed grinding for 0.5-1h to obtain a base slurry with good stability and fluidity;
s2, vacuum degassing of base slurry
Putting the base slurry prepared in the S1 into a vacuum tank, adding a defoaming agent, stirring for 0.5-1h, sequentially passing through double screens with mesh sizes of 500 mu m and 200 mu m, and then flowing into a casting paper machine hopper;
s3, preparing long-cut carbon fiber slurry
Adding long-cut carbon fibers and anionic polyacrylamide into distilled water at the temperature of 37-39 ℃ as a water phase, and stirring for 20min to obtain long-cut carbon fiber slurry;
s4, preparing conductive paste
Transferring the basic slurry flowing out of the lower part of a hopper of a casting paper machine to a movable film carrier, arranging a carbon fiber slurry spraying machine at a position which is 150-200 mm higher than the running position of the film carrier, and arranging a vertical electric field between the movable film carrier and the carbon fiber slurry spraying machine;
the long-cut carbon fiber slurry falls after being sprayed by a carbon fiber slurry spraying machine, and is scattered into the basic slurry on the moving film carrier after being acted by an external electric field to obtain conductive slurry;
s5, drying
And (S4) the conductive paste obtained in the step is moved by a movable film carrier, enters a drying chamber after passing through a slope, and is dried for 70-80 min at the temperature of 75-85 ℃ to obtain the heating paper.
9. A method for preparing heat generating paper suitable for a heat generating ceramic tile according to claim 8, wherein in the step S5, the included angle between the slope and the ground is 30-40 °.
10. The method of claim 8, wherein the intensity of the vertical electric field in the step S4 is 1-5 kV/cm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2063024A1 (en) * | 2007-11-22 | 2009-05-27 | Ching-Ling Pan | Nano carbon crystal material and method of manufacturing electrothermal board by using the same |
| WO2014081002A1 (en) * | 2012-11-26 | 2014-05-30 | 三菱レイヨン株式会社 | Chopped carbon fiber bundles and method for producing chopped carbon fiber bundles |
| CN108660864A (en) * | 2018-06-28 | 2018-10-16 | 南京柯普新材料科技有限公司 | A kind of method that glass fibre compounding carbon fiber prepares conductive felt |
| CN113699824A (en) * | 2021-08-25 | 2021-11-26 | 上海骏珲新材料科技有限公司 | Carbon fiber composite conductive paper and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2063024A1 (en) * | 2007-11-22 | 2009-05-27 | Ching-Ling Pan | Nano carbon crystal material and method of manufacturing electrothermal board by using the same |
| WO2014081002A1 (en) * | 2012-11-26 | 2014-05-30 | 三菱レイヨン株式会社 | Chopped carbon fiber bundles and method for producing chopped carbon fiber bundles |
| CN108660864A (en) * | 2018-06-28 | 2018-10-16 | 南京柯普新材料科技有限公司 | A kind of method that glass fibre compounding carbon fiber prepares conductive felt |
| CN113699824A (en) * | 2021-08-25 | 2021-11-26 | 上海骏珲新材料科技有限公司 | Carbon fiber composite conductive paper and preparation method thereof |
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