CN111393867A - Special composite floor for geothermal and preparation method thereof - Google Patents

Special composite floor for geothermal and preparation method thereof Download PDF

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CN111393867A
CN111393867A CN202010297020.5A CN202010297020A CN111393867A CN 111393867 A CN111393867 A CN 111393867A CN 202010297020 A CN202010297020 A CN 202010297020A CN 111393867 A CN111393867 A CN 111393867A
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parts
powder
graphene
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heating
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雷响
周玉刚
刘玉和
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Anhui Yangzi Flooring Inc Co
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Anhui Yangzi Flooring Inc Co
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00Compositions of lignin-containing materials
    • C08L97/02Lignocellulosic material, e.g. wood, straw or bagasse
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/02Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board the layer being formed of fibres, chips, or particles, e.g. MDF, HDF, OSB, chipboard, particle board, hardboard
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/13Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board all layers being exclusively wood
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/14Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood board or veneer
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04FFINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00Flooring
    • E04F15/02Flooring or floor layers composed of a number of similar elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202Conductive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2471/00Floor coverings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0806Silver
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/001Conductive additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16Fibres; Fibrils

Abstract

The invention discloses a composite floor special for geothermal heating, which comprises a bottom plate, a base plate and a panel, wherein the panel, the base plate and the bottom plate are sequentially bonded from top to bottom; the invention also discloses a preparation method of the special composite floor for geothermal heating; introduce silicon element in the oxidation graphite alkene, make it change and form the individual layer structure, form the fold on its surface, further increase oxidation graphite alkene's specific surface area, and then strengthen its adsorption efficiency, modified graphite alkene makes its structure more loose because the fold on its surface when the gathering moreover, forms the large aperture through-hole, and then strengthens its adsorption efficiency through the large aperture through-hole, makes the base plate have excellent adhesive force moreover.

Description

Special composite floor for geothermal and preparation method thereof
Technical Field
The invention belongs to the technical field of graphene floors, and particularly relates to a composite floor special for geothermal heating and a preparation method thereof.
Background
Floor, i.e. the surface layer of the floor or floor of a house. Made of wood or other material. There are many classifications of floors, classified by structure: solid wood floors, laminate wood floors, three-layer solid wood laminate floors, bamboo and wood floors, anti-corrosion floors, cork floors, and the most popular multilayer solid wood laminate floors at present; classified by use are: household, commercial, antistatic floors, outdoor floors, floors dedicated to stage dancing, floors dedicated to sports stadiums, floors dedicated to track and field, etc.; the environmental protection grades are classified as follows: e0 grade floor, E1 grade floor, F4 grade floor, JAS star standard F4 star floor, and the like. There are many classifications of floors, classified by structure: solid wood floors, laminate wood floors, three-layer solid wood laminate floors, bamboo and wood floors, anti-corrosion floors, cork floors, and the most popular multilayer solid wood laminate floors at present;
the Chinese invention patent CN105352008B discloses a graphene self-heating floor and a low-voltage self-heating floor system, which comprises a plurality of floor blocks which are assembled together, wherein each floor block sequentially comprises a wear-resistant layer, a surface decoration layer, a graphene-based conductive carbon slurry heat-conducting layer, a substrate plate and a heat-insulating layer from top to bottom; the base material board transverse section length is less than surface decoration layer and heat preservation, forms a socket mounting groove, and the base material board all covers with the one deck that graphite alkene base conductive carbon thick liquid heat-generating conduction layer contacted and the both sides that are located the socket mounting groove has the conducting wire. The system comprises the floor, the 220V power supply, the transformer, the temperature controller and the sensor, wherein the sensor is arranged in the floor and is connected with the temperature controller through a lead, and the temperature controller is connected with the 220V power supply through the transformer.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a composite floor special for geothermal energy and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
(1) the existing composite floor special for geothermal energy is often prepared by adopting a preparation method of conductive carbon paste in the preparation process, and the method has slow conductive effect, so that a heating layer of the floor is slow in heating, and the heating effect is not ideal;
(2) the graphene has super van der waals force and conjugate acting force, a three-dimensional structure is easily formed, so that the graphene has poor dispersibility in an organic phase and a water phase solvent, and when the graphene is used as a heating film, the graphene is not ideal in agglomeration effect with other particles, a stable system cannot be formed, and the electric conduction effect is influenced.
The purpose of the invention can be realized by the following technical scheme:
the composite floor board for geothermal heating includes one bottom board, one base board and one panel combined closely from top to bottom;
the substrate is made by the following method:
firstly, weighing the following raw materials in parts by weight: 25-40 parts of modified graphene powder, 5-8 parts of nano carbon powder, 3-5 parts of zinc oxide powder, 30-50 parts of epoxy resin, 10-15 parts of amino resin, 5-15 parts of KH560, 2-6 parts of silver powder, 20-40 parts of dimethylbenzene, 150-200 parts of wood fiber and 10-20 parts of polyacrylamide resin;
secondly, adding epoxy resin and amino resin into dimethylbenzene, adding KH560, heating in a water bath at 45 ℃ and magnetically stirring for 15min, then adding silver powder, stirring for 30-45min at the rotating speed of 450r/min to prepare a mixture, uniformly mixing the modified graphene powder, the zinc oxide powder and the nano carbon powder to prepare a filler, and mixing and stirring the filler and the mixture for 1-2h to prepare the modified graphene adhesive;
thirdly, mixing wood fibers and deionized water according to the weight ratio of 3-5: 100 to prepare slurry, then adjusting the pH until the pH is 3-5, adding polyacrylamide resin and modified graphene glue, dehydrating and pulping to prepare a base plate blank, and then carrying out hot stamping and smouldering on the base plate blank to prepare the base plate.
Secondly, adding epoxy resin and amino resin into dimethylbenzene to prepare conductive adhesive and a filler respectively, then heating at the speed of 0.5-0.8 ℃ in the third step to prevent the solution from being heated too fast due to too high drying temperature and prevent the heating film substrate surface from being dried roughly due to solvent evaporation, wherein the specific surface area of the modified graphene powder is increased through the filler prepared from the modified graphene powder, the zinc oxide powder and the nano carbon powder, so that a stable system can be formed with the zinc oxide powder, the nano carbon powder and the silver powder, the system can form a continuous and complete conductive path in a three-dimensional space, and the silver powder can generate larger resistance due to small contact area, so that when the system is used, the filler and the mixture are mixed and stirred, the modified graphene and the nano carbon powder can be filled between the silver powders, so that the silver powders which are not in contact with each other can generate contact, and the conductive path in the system is, further enhancing the conductivity of the electric heating film and further increasing the heating effect.
Further, the bottom plate and the face plate are both wood floors.
Furthermore, the particle size of the nano carbon powder is 10-500nm, the particle size of the zinc oxide powder is 10-300 mu m, the particle size of the modified graphene powder is 10-200 mu m, and the particle size of the silver powder is 50-500 mu m.
Further, the modified graphene powder is prepared from the following raw materials in parts by weight: 20-30 parts of graphene, 10-15 parts of sodium nitrate, 200-250 parts of 98% concentrated sulfuric acid, 2-4 parts of potassium chlorate, 50-70 parts of 10% aqueous hydrogen peroxide solution, 35-50 parts of ethylene oxide, 5-10 parts of silicon tetrachloride and 15-20 parts of triethylamine.
Further, the modified graphene powder is prepared by the following method:
(1) adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, adding potassium chlorate, continuing to stir for 30min, then heating in a water bath at 40 ℃ for 3h, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, continuing to react for 10min, and preparing a graphene oxide solution;
(2) adding ethylene oxide into the prepared graphene oxide solution, heating to 30-35 ℃, carrying out ultrasonic treatment for 30min at the temperature, then cooling to-8 ℃, adding silicon tetrachloride, stirring at the rotating speed of 120-180r/min for 30-45min, adding triethylamine, heating to 45 ℃, stirring at the rotating speed of 200-240r/min for 10min, then continuously heating and refluxing for 5h, transferring to deionized water, filtering, washing, drying at 80 ℃ for 8-10h, and grinding to obtain the modified graphene powder.
The method comprises the following steps that (1) superstrong van der Waals force and conjugate acting force exist among graphene, a three-dimensional structure is easy to form, and the dispersibility of the graphene in an organic phase and an aqueous phase solvent is poor, graphene oxide is prepared from the graphene under the action of potassium chlorate, 10% hydrogen peroxide water solution and the like, the graphene oxide can be dispersed in water and can also be dispersed in the organic solvent, and rich oxygen-containing functional groups are added on the surface of the graphene oxide, so that the graphene oxide is not easy to agglomerate; step (2) is to modify graphene oxide, silicon tetrachloride and graphene oxide are mixed and stirred at-8 ℃, the graphene oxide is modified through silicon tetrachloride, silicon element is introduced into the graphene oxide in the modification process, so that the graphene oxide is easier to form a single-layer structure, folds are formed on the surface of the graphene oxide, the specific surface area of the graphene oxide is further increased, and the adsorption performance of the graphene oxide is further enhanced.
A preparation method of a composite floor special for geothermal comprises the following steps:
the panel, the substrate and the bottom plate are sequentially bonded from top to bottom, the panel is bonded on the upper surface of the substrate, the lower surface of the substrate is fixed on the bottom plate, and the bottom plate, the substrate and the panel are tightly combined with each other.
The invention has the beneficial effects that:
(1) the invention relates to a graphene floor, which comprises a bottom plate, a substrate and a panel, wherein in the preparation process of the substrate, epoxy resin is added into dimethylbenzene to prepare modified graphene glue respectively, then in the third step, the temperature is increased at the speed of 0.5-0.8 ℃, the condition that the solution is heated too fast due to too high drying temperature is prevented, the surface of a heating film base material is rough and dried due to solvent evaporation is avoided, the specific surface area of the modified graphene powder is increased through a filler prepared from the modified graphene powder, zinc oxide powder and nano carbon powder, and then a stable system can be formed with the zinc oxide powder, the nano carbon powder and silver powder, the system can form a continuous and complete conductive path in a three-dimensional space, and the silver powder can generate larger resistance due to small contact area, so when in use, the filler and a mixture are mixed and stirred, and the modified graphene and the nano carbon powder can be filled among the silver powder, the silver powder which is not contacted with each other is contacted, so that a conductive path in a system is increased, the conductivity of the substrate is further enhanced, and the heating effect is further improved; the technical problems that the existing composite floor is often prepared by adopting a preparation method of conductive carbon paste in the preparation process, the method is slow in conductive effect, so that a heating layer of the floor is slow in heating, and the heating effect is not ideal are solved;
(2) according to the invention, the substrate is prepared from raw materials such as modified graphene powder, and the modified graphene powder has super strong van der Waals force and conjugate acting force among graphene in the preparation process, so that a three-dimensional structure is easily formed, and the dispersibility of the modified graphene powder in an organic phase and a water phase solvent is poor, in the step (1), graphene oxide is prepared from the graphene under the action of potassium chlorate, 10% hydrogen peroxide water solution and the like, the graphene oxide can be dispersed in water and can also be dispersed in the organic solvent, and rich oxygen-containing functional groups are added on the surface of the graphene oxide, so that the graphene oxide is not easy to agglomerate; modifying graphene oxide, namely mixing and stirring silicon tetrachloride and graphene oxide at-8 ℃, modifying the graphene oxide by silicon tetrachloride, introducing silicon element into the graphene oxide in the modification process to enable the graphene oxide to easily form a single-layer structure, forming wrinkles on the surface of the graphene oxide, further increasing the specific surface area of the graphene oxide, and further enhancing the adsorption performance of the graphene oxide, wherein the modified graphene has a looser structure due to the wrinkles on the surface of the graphene oxide when being aggregated, so that large-aperture through holes are formed, the adsorption performance of the graphene oxide is enhanced through the large-aperture through holes, and the substrate has excellent adhesion; the method solves the technical problems that the graphene has super van der Waals force and conjugate acting force, a three-dimensional structure is easily formed, the dispersibility of the graphene in an organic phase and a water phase solvent is poor, the agglomeration effect with other particles is not ideal when the graphene is used as a substrate, a stable system cannot be formed, and the electric conduction effect is influenced.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
Fig. 1 is a schematic structural diagram of a graphene floor according to the present invention.
In the figure: 1. a base plate; 2. a substrate; 3. a panel.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in fig. 1, a composite floor board specially used for geothermal heating, which is characterized by comprising a bottom board 1, a base board 2 and a panel 3, wherein the panel 3, the base board 2 and the bottom board 1 are tightly combined with each other from top to bottom;
the substrate 2 is made by the following method:
firstly, weighing the following raw materials in parts by weight: 25 parts of modified graphene powder, 5 parts of nano carbon powder, 3 parts of zinc oxide powder, 30 parts of epoxy resin, 10 parts of amino resin, 5 parts of KH560, 2 parts of silver powder, 20 parts of dimethylbenzene, 150 parts of wood fiber and 10 parts of polyacrylamide resin;
secondly, adding epoxy resin and amino resin into dimethylbenzene, adding KH560, heating in a water bath at 45 ℃ and magnetically stirring for 15min, then adding silver powder, stirring for 30min at the rotating speed of 450r/min to prepare a mixture, uniformly mixing the modified graphene powder, zinc oxide powder and nano carbon powder to prepare a filler, and mixing and stirring the filler and the mixture for 1h to prepare the modified graphene adhesive;
thirdly, mixing the wood fiber and the deionized water according to the weight ratio of 3: 100 to prepare slurry, then adjusting the pH until the pH is 3, adding the polyacrylamide resin and the modified graphene glue, dehydrating and pulping to prepare a base plate blank, and then carrying out hot stamping and smouldering on the base plate blank to prepare the base plate 2.
The panel 3, the substrate 2 and the bottom plate 1 are sequentially bonded from top to bottom, the panel 3 is bonded on the upper surface of the substrate 2, the lower surface of the substrate 2 is fixed on the bottom plate 1, and the bottom plate 1, the substrate 2 and the panel 3 are tightly combined with each other.
The modified graphene powder is prepared from the following raw materials in parts by weight: 20 parts of graphene, 10 parts of sodium nitrate, 200 parts of 98% concentrated sulfuric acid, 2 parts of potassium chlorate, 50 parts of 10% aqueous hydrogen peroxide solution, 35 parts of ethylene oxide, 5 parts of silicon tetrachloride and 15 parts of triethylamine.
The modified graphene powder is prepared by the following method:
(1) adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, adding potassium chlorate, continuing to stir for 30min, then heating in a water bath at 40 ℃ for 3h, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, continuing to react for 10min, and preparing a graphene oxide solution;
(2) adding ethylene oxide into the prepared graphene oxide solution, heating to 30-35 ℃, carrying out ultrasonic treatment for 30min at the temperature, then cooling to-8 ℃, adding silicon tetrachloride, stirring for 30min at the rotating speed of 120r/min, adding triethylamine, heating to 45 ℃, stirring for 10min at the rotating speed of 200r/min, then continuously heating and refluxing for 5h, transferring to deionized water, filtering, washing, drying for 8h at the temperature of 80 ℃, and grinding to obtain the modified graphene powder.
Example 2
The special composite floor for geothermal heating is characterized by comprising a bottom plate 1, a base plate 2 and a panel 3, wherein the panel 3, the base plate 2 and the bottom plate 1 are tightly combined with each other from top to bottom;
the substrate 2 is made by the following method:
firstly, weighing the following raw materials in parts by weight: 30 parts of modified graphene powder, 6 parts of nano carbon powder, 4 parts of zinc oxide powder, 35 parts of epoxy resin, 12 parts of amino resin, 10 parts of KH560, 4 parts of silver powder, 25 parts of xylene, 160 parts of wood fiber and 14 parts of polyacrylamide resin;
secondly, adding epoxy resin and amino resin into dimethylbenzene, adding KH560, heating in a water bath at 45 ℃ and magnetically stirring for 15min, then adding silver powder, stirring for 30min at the rotating speed of 450r/min to prepare a mixture, uniformly mixing the modified graphene powder, zinc oxide powder and nano carbon powder to prepare a filler, and mixing and stirring the filler and the mixture for 1h to prepare the modified graphene adhesive;
thirdly, mixing the wood fiber and the deionized water according to the weight ratio of 3: 100 to prepare slurry, then adjusting the pH until the pH is 3, adding the polyacrylamide resin and the modified graphene glue, dehydrating and pulping to prepare a base plate blank, and then carrying out hot stamping and smouldering on the base plate blank to prepare the base plate 2.
The rest is the same as example 1.
Example 3
The special composite floor for geothermal heating is characterized by comprising a bottom plate 1, a base plate 2 and a panel 3, wherein the panel 3, the base plate 2 and the bottom plate 1 are tightly combined with each other from top to bottom;
the substrate 2 is made by the following method:
firstly, weighing the following raw materials in parts by weight: 35 parts of modified graphene powder, 7 parts of nano carbon powder, 4 parts of zinc oxide powder, 45 parts of epoxy resin, 14 parts of amino resin, 13 parts of KH560, 5 parts of silver powder, 35 parts of xylene, 180 parts of wood fiber and 18 parts of polyacrylamide resin;
secondly, adding epoxy resin and amino resin into dimethylbenzene, adding KH560, heating in a water bath at 45 ℃ and magnetically stirring for 15min, then adding silver powder, stirring for 30min at the rotating speed of 450r/min to prepare a mixture, uniformly mixing the modified graphene powder, zinc oxide powder and nano carbon powder to prepare a filler, and mixing and stirring the filler and the mixture for 1h to prepare the modified graphene adhesive;
thirdly, mixing the wood fiber and the deionized water according to the weight ratio of 3: 100 to prepare slurry, then adjusting the pH until the pH is 3, adding the polyacrylamide resin and the modified graphene glue, dehydrating and pulping to prepare a base plate blank, and then carrying out hot stamping and smouldering on the base plate blank to prepare the base plate 2.
The rest is the same as example 1.
Example 4
The special composite floor for geothermal heating is characterized by comprising a bottom plate 1, a base plate 2 and a panel 3, wherein the panel 3, the base plate 2 and the bottom plate 1 are tightly combined with each other from top to bottom;
the substrate 2 is made by the following method:
firstly, weighing the following raw materials in parts by weight: 40 parts of modified graphene powder, 8 parts of nano carbon powder, 5 parts of zinc oxide powder, 50 parts of epoxy resin, 15 parts of amino resin, 15 parts of KH560, 2-6 parts of silver powder, 40 parts of xylene, 200 parts of wood fiber and 20 parts of polyacrylamide resin;
secondly, adding epoxy resin and amino resin into dimethylbenzene, adding KH560, heating in a water bath at 45 ℃ and magnetically stirring for 15min, then adding silver powder, stirring for 30min at the rotating speed of 450r/min to prepare a mixture, uniformly mixing the modified graphene powder, zinc oxide powder and nano carbon powder to prepare a filler, and mixing and stirring the filler and the mixture for 1h to prepare the modified graphene adhesive;
thirdly, mixing the wood fiber and the deionized water according to the weight ratio of 3: 100 to prepare slurry, then adjusting the pH until the pH is 3, adding the polyacrylamide resin and the modified graphene glue, dehydrating and pulping to prepare a base plate blank, and then carrying out hot stamping and smouldering on the base plate blank to prepare the base plate 2.
The rest is the same as example 1.
Comparative example 1
Compared with example 1, the preparation method of the comparative example, which replaces the modified graphene powder with the graphene powder, is as follows:
firstly, weighing the following raw materials in parts by weight: 25 parts of graphene powder, 5 parts of nano carbon powder, 3 parts of zinc oxide powder, 30 parts of epoxy resin, 10 parts of amino resin, 5 parts of KH560, 2 parts of silver powder, 20 parts of dimethylbenzene, 150 parts of wood fiber and 10 parts of polyacrylamide resin;
secondly, adding epoxy resin and amino resin into dimethylbenzene, adding KH560, heating in a water bath at 45 ℃ and magnetically stirring for 15min, then adding silver powder, stirring for 30min at the rotating speed of 450r/min to prepare a mixture, uniformly mixing graphene powder, zinc oxide powder and nano carbon powder to prepare a filler, and mixing and stirring the filler and the mixture for 1h to prepare the modified graphene adhesive;
thirdly, mixing the wood fiber and the deionized water according to the weight ratio of 3: 100 to prepare slurry, then adjusting the pH until the pH is 3, adding the polyacrylamide resin and the modified graphene glue, dehydrating and pulping to prepare a base plate blank, and then carrying out hot stamping and smouldering on the base plate blank to prepare the base plate 2.
Comparative example 2
Compared with example 1, the preparation method of the comparative example, which replaces the modified graphene glue with the conductive carbon paste, is as follows:
coating the conductive carbon paste on the surface of a glass plate, controlling the coating thickness to be 1.5mm, then transferring the glass plate to a drying box, heating at the speed of 0.5 ℃ until the temperature is 250 ℃, preserving the heat for 2h at the temperature to obtain a heating film substrate, and then compounding the heating film substrate and the plate to obtain the composite floor special for geothermal energy.
Comparative example 3
The comparative example is a composite floor special for geothermal heating in the market.
The adhesion, the sheet resistance and the sum of the results of the adhesion of the electric heating films of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table;
adhesion force: the adhesion test was carried out according to the requirements of JB/T8554-1997 scratch test method for adhesion of vapor deposited films to substrates. The WS-2005 type coating adhesive force automatic scratch tester is adopted for testing, and the testing method comprises the following steps: and (5) testing an acoustic emission measurement mode. The loading rate was 5N/min and the scratch rate was 2 mm/min.
Rate of change of resistance: resistance change rate after 2500 hours of operation.
Adhesive force N Square resistance omega Rate of change in resistance (%)
Example 1 128 42 3.01
Example 2 129 40 3.18
Example 3 132 38 3.20
Example 4 134 38 3.20
Comparative example 1 110 66 5.78
Comparative example 2 85 78 8.80
Comparative example 3 88 80 11.21
As can be seen from the above table, the adhesion of examples 1-4 is 128-134N, the sheet resistance is 38-42 Ω, the rate of change in resistance is 3.01-3.20%, the adhesion of comparative examples 1-3 is 85-110N, the sheet resistance is 66-80 Ω, and the rate of change in resistance is 5.78-11.21%; therefore, silicon element is introduced into the graphene oxide in the modification process, so that the graphene oxide is easier to form a single-layer structure, folds are formed on the surface of the graphene oxide, the specific surface area of the graphene oxide is further increased, the adsorption performance of the graphene oxide is further enhanced, the structure of the modified graphene is looser due to the folds on the surface of the modified graphene when the modified graphene is gathered, a large-aperture through hole is formed, the adsorption performance of the modified graphene is enhanced through the large-aperture through hole, and the electrothermal film has excellent adhesion; the technical problems that the graphene has super van der Waals force and conjugate acting force, a three-dimensional structure is easily formed, the dispersibility of the graphene in an organic phase and a water phase solvent is poor, the agglomeration effect with other particles is not ideal when the graphene is used as a heating film, a stable system cannot be formed, and the electric conduction effect is influenced are solved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims (6)

1. The composite floor special for geothermal is characterized by comprising a bottom plate (1), a base plate (2) and a panel (3), wherein the panel (3), the base plate (2) and the bottom plate (1) are tightly combined with each other from top to bottom;
the substrate (2) is made by the following method:
firstly, weighing the following raw materials in parts by weight: 25-40 parts of modified graphene powder, 5-8 parts of nano carbon powder, 3-5 parts of zinc oxide powder, 30-50 parts of epoxy resin, 10-15 parts of amino resin, 5-15 parts of KH560, 2-6 parts of silver powder, 20-40 parts of dimethylbenzene, 150-200 parts of wood fiber and 10-20 parts of polyacrylamide resin;
secondly, adding epoxy resin and amino resin into dimethylbenzene, adding KH560, heating in a water bath at 45 ℃ and magnetically stirring for 15min, then adding silver powder, stirring for 30-45min at the rotating speed of 450r/min to prepare a mixture, uniformly mixing the modified graphene powder, the zinc oxide powder and the nano carbon powder to prepare a filler, and mixing and stirring the filler and the mixture for 1-2h to prepare the modified graphene adhesive;
and thirdly, mixing wood fibers and deionized water according to the weight ratio of 3-5: 100 to prepare slurry, then adjusting the pH until the pH is 3-5, adding polyacrylamide resin and modified graphene glue, dehydrating and pulping to prepare a base plate blank, and then carrying out hot stamping and smouldering on the base plate blank to prepare the base plate (2).
2. The graphene floor according to claim 1, wherein the bottom plate (1) and the face plate (3) are both wood floor.
3. The graphene floor according to claim 1, wherein the nano carbon powder has a particle size of 10-500nm, the zinc oxide powder has a particle size of 10-300 μm, the modified graphene powder has a particle size of 10-200 μm, and the silver powder has a particle size of 50-500 μm.
4. The graphene floor according to claim 1, wherein the modified graphene powder is prepared from the following raw materials in parts by weight: 20-30 parts of graphene, 10-15 parts of sodium nitrate, 200-250 parts of 98% concentrated sulfuric acid, 2-4 parts of potassium chlorate, 50-70 parts of 10% aqueous hydrogen peroxide solution, 35-50 parts of ethylene oxide, 5-10 parts of silicon tetrachloride and 15-20 parts of triethylamine.
5. The graphene floor according to claim 1, wherein the modified graphene powder is prepared by the following method:
(1) adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, adding potassium chlorate, continuing to stir for 30min, then heating in a water bath at 40 ℃ for 3h, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, continuing to react for 10min, and preparing a graphene oxide solution;
(2) adding ethylene oxide into the prepared graphene oxide solution, heating to 30-35 ℃, carrying out ultrasonic treatment for 30min at the temperature, then cooling to-8 ℃, adding silicon tetrachloride, stirring at the rotating speed of 120-180r/min for 30-45min, adding triethylamine, heating to 45 ℃, stirring at the rotating speed of 200-240r/min for 10min, then continuously heating and refluxing for 5h, transferring to deionized water, filtering, washing, drying at 80 ℃ for 8-10h, and grinding to obtain the modified graphene powder.
6. The preparation method of the composite floor special for geothermal is characterized by comprising the following steps:
the panel (3), the substrate (2) and the bottom plate (1) are sequentially bonded from top to bottom, the panel (3) is bonded on the upper surface of the substrate (2), the lower surface of the substrate (2) is fixed on the bottom plate (1), and the bottom plate (1), the substrate (2) and the panel (3) are tightly combined with each other.
CN202010297020.5A 2020-04-15 2020-04-15 Special composite floor for geothermal and preparation method thereof Pending CN111393867A (en)

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