CN111763015B - Heating type graphene glass and preparation method thereof - Google Patents
Heating type graphene glass and preparation method thereof Download PDFInfo
- Publication number
- CN111763015B CN111763015B CN202010672196.4A CN202010672196A CN111763015B CN 111763015 B CN111763015 B CN 111763015B CN 202010672196 A CN202010672196 A CN 202010672196A CN 111763015 B CN111763015 B CN 111763015B
- Authority
- CN
- China
- Prior art keywords
- glass
- parts
- graphene
- substrate
- taking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/31—Pre-treatment
Abstract
The invention provides heating graphene glass which is prepared from the following raw materials in parts by weight: 100-200 parts of conductive glass, 10-20 parts of methane, 5-9 parts of superfine alumina, 4-8 parts of silane coupling agent and 1-2 parts of ultraviolet absorbent. According to the invention, high-temperature-resistant quartz glass is used as a substrate, an extremely thin alumina thin layer is deposited on the surface of the glass through a chemical vapor deposition process to form conductive glass, then an ultraviolet absorbent and superfine alumina are connected on the surface through a silane coupling agent to realize surface modification, and further a single-layer graphene is formed on the surface through a high-temperature chemical vapor deposition process by taking methane as a carbon source, so that the preparation of the heating graphene glass is realized.
Description
Technical Field
The invention relates to the technical field of glass manufacturing, in particular to heating graphene glass and a preparation method thereof.
Background
Glass is a long-history, widely used amorphous silicate material, while graphene is a two-dimensional layered material found in recent years consisting of only carbon atoms. Graphene has ultra-high mechanical strength, electrical conductivity, thermal conductivity, and transparency, just complementary to conventional glass. Graphene and glass are combined together, and a novel composite material, namely graphene glass, is developed, so that the advantage of good light transmittance of the glass can be kept, and the glass can be endowed with the characteristics of ultrahigh electrical conductivity, thermal conductivity, surface hydrophobicity and the like of the graphene. Meanwhile, due to the low cost and wide application of the glass, the graphene glass is expected to become a novel material which can be used in daily life.
Glass is a poor conductor of heat and is brittle. When the temperature difference between the inside and the outside of the glass is too large, the glass is cracked due to the inconsistency of the internal stress of the glass caused by the difference of the expansion rates. It is very necessary to solve the problem of glass cracking caused by uneven heating. Graphene is the thinnest and hardest nano material known in the world, single-layer graphene is almost completely transparent and only absorbs 2.3% of light, and the thermal conductivity coefficient of graphene is as high as 5300W/m.K and is higher than that of diamond.
At present, a plurality of technologies for preparing heating glass by using graphene are available: CN108558225A provides graphene glass and a preparation process thereof, quartz sand, borax, boric acid, barite, barium carbonate, limestone and feldspar are taken according to a certain proportioning, fully mixed and stirred, heated at a high temperature, cooled, added with graphene and soda ash and stirred, and then glass forming is carried out; the graphene glass is formed into graphene glass with different shapes or different purposes.
The graphene glass prepared by the graphene glass preparation process has high bending resistance, compression resistance and impact resistance, is soft in material, high in toughness and not easy to damage; however, graphene in the graphene glass prepared by the method is easy to cause the problem of agglomeration, and the graphene is not uniformly distributed in the glass; the heat conduction is also not uniform.
The invention discloses a preparation method of a toughening filler for organic glass, which is a patent number CN201711109005.8, and discloses a preparation method of a toughening filler for organic glass, and the preparation method comprises the following steps: surface pretreatment, (2) primary modification treatment, and (3) secondary modification treatment; the filler particles prepared by the method have special structures, can play a toughening role in organic glass, and improve the use quality of the organic glass.
But the prior art lacks the problem of better applying graphene on the surface of a heating table to solve the problem of glass soaking; in addition, the existing heating glass preparation process is complex, so that a graphene-glass and a preparation method thereof are urgently needed to meet the current requirements.
Disclosure of Invention
The invention aims to provide heating type graphene glass and a preparation method thereof.
The technical scheme of the invention is realized as follows:
the invention provides heating graphene glass which is prepared from the following raw materials in parts by weight: 100-200 parts of conductive glass, 10-20 parts of methane, 5-9 parts of superfine alumina, 4-8 parts of silane coupling agent and 1-2 parts of ultraviolet absorbent;
the conductive glass adopts a chemical vapor deposition process, quartz glass is used as a substrate, triisopropyl aluminate is used as a reactant, nitrogen is used as a carrier gas, oxygen and water vapor are used as reaction catalysts, and the deposition is carried out in a chemical vapor deposition furnace, and the process specifically comprises the following steps:
quartz glass is used as a substrate, triisopropyl aluminate serving as a reactant is carried into a reactor of a chemical vapor deposition furnace by a carrier gas in a bubbling mode, the reactant is heated to 100-150 ℃ in an oil bath, the temperature of catalyst oxygen and water vapor is also 100-150 ℃, the catalyst and the reactant begin to be mixed in the reactor, and the mixture is taken out after 1-2h of mixing reaction to obtain conductive glass;
wherein the temperature of the substrate is 300-650 ℃, and the running speed of the substrate is 50-100mm/s.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 120-180 parts of conductive glass, 12-17 parts of methane, 6-8 parts of superfine alumina, 5-7 parts of silane coupling agent and 1.2-1.7 parts of ultraviolet absorbent.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 160 parts of conductive glass, 15 parts of methane, 7 parts of superfine alumina, 6 parts of silane coupling agent and 1.5 parts of ultraviolet absorbent.
As a further improvement of the invention, the ultraviolet absorbent is selected from one or more of phenyl ortho-hydroxybenzoate, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, resorcinol monobenzoate, 2' -thiobis (4-tert-octylphenoxyoxy) nickel, tris (1, 2, 6-pentamethylpiperidinyl) phosphite, 4-benzoyloxy-2, 6-tetramethylpiperidine, 2,4, 6-tris (2 ' -n-butoxyphenyl) -1,3, 5-triazine and hexamethylphosphoric triamide.
As a further improvement of the invention, the silane coupling agent is selected from one or a mixture of several of KH550, KH560, KH570, KH792, KH580, KH561, KH590 and KH 602.
As a further improvement of the invention, the particle size of the ultrafine alumina is less than 100nm.
As a further improvement of the invention, the volume ratio of oxygen to water vapor in the catalyst is 1: (1-5).
The invention further protects a preparation method of the heating graphene glass, which comprises the following steps:
(1) Soaking conductive glass in aqueous solution of silane coupling agent, heating to 30-50 deg.C, treating for 30-50min, and taking out;
(2) Adding an ultraviolet absorbent and superfine alumina into an ethanol solution, uniformly mixing to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 30-60min, and taking out;
(3) Adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling mode, heating to 1000-1100 ℃, mixing and reacting for 2-4h, and taking out to obtain heating graphene glass;
wherein the temperature of the substrate is 1000-1200 ℃, and the running speed of the substrate is 120-150mm/s.
As a further improvement of the invention, the mass fraction of the silane coupling agent in the aqueous solution of the silane coupling agent is 1-2.5%; the mass fraction of ethanol in the ethanol solution is 50-75%.
The invention further protects the application of the heating graphene glass as a glass desktop on a heating table.
The invention has the following beneficial effects: according to the invention, a thermal CVD direct growth method is adopted, methane is used as a carbon source, high-quality graphene is grown, and the temperature is usually required to be above 1000 ℃, so that in order to grow the graphene on the surface of glass, high-temperature-resistant glass, namely quartz glass, is selected as a growth substrate, and the graphene is directly grown on the surface of the glass at a high temperature;
from the energy band structure of graphene, it can be known that when the electric field of the single-layer graphene is zero, the concentration of the conductive carrier is zero, which is called "dirac point". At a distance from the dirac point, there is only a single carrier in the graphene. The negative grid voltage enables the graphene to become electron conduction, the resistivity of the device is changed from several kilohms to several hundred ohms finally, current carriers in the graphene are gradually transited from electrons (or holes) to holes (or electrons) near a Dirac point, the Hall coefficient changes the sign (the electrons are positive, the holes are negative) at the position, the concentration of the current carriers is minimum, the resistivity is maximum, and the graphene generates heat after being electrified to generate heat, so that the technical effect of heating is realized;
the invention adopts high-temperature-resistant quartz glass as a substrate, and a very thin alumina thin layer is deposited on the surface of the glass through a chemical vapor deposition process to form conductive glass, and then an ultraviolet absorbent and superfine alumina are connected on the surface through a silane coupling agent to realize surface modification, and the superfine alumina can further form an alumina thin film on the surface of the conductive glass, so that the surface of the glass is ensured to be fully covered by the alumina.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a SEM image of the surface of a heating type graphene glass prepared by the invention;
FIG. 2 is a graph showing the heat generation curves of the respective groups of glasses in test example 2 of the present invention; comparative example 1 is (a); (b) is comparative example 2; (c) comparative example 3; example 5 is (d).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The raw materials comprise the following components in parts by weight: 100 parts of conductive glass, 10 parts of methane, 5 parts of superfine alumina, 4 parts of silane coupling agent KH561, and 1 part of 2,4, 6-tris (2' -n-butoxyphenyl) -1,3, 5-triazine;
the grain size of the superfine alumina is less than 100nm;
preparing conductive glass:
taking quartz glass as a substrate, carrying a reactant triisopropyl aluminate into a chemical vapor deposition furnace reactor by using a carrier gas in a bubbling mode, heating the reactant to 100 ℃ in an oil bath, controlling the temperature of catalyst oxygen and water vapor to be 100 ℃, mixing the catalyst and the reactant in the reactor, and taking out the mixture after the mixture reacts for 1 hour to obtain conductive glass; wherein the temperature of the substrate is 300 ℃ and the running speed of the substrate is 50mm/s.
The preparation method of the heating graphene glass comprises the following steps:
(1) Soaking the conductive glass in an aqueous solution of a silane coupling agent KH561, wherein the mass fraction of the silane coupling agent is 1%, heating to 30 ℃, treating for 30min, and taking out;
(2) Adding 2,4, 6-tri (2' -n-butoxyphenyl) -1,3, 5-triazine and superfine alumina into an ethanol solution, wherein the mass fraction of ethanol is 50%, uniformly mixing to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 30min, and taking out;
(3) And (3) adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling manner, heating to 1000 ℃, mixing and reacting for 2 hours, and taking out to obtain the exothermic graphene glass; wherein the temperature of the substrate is 1000 ℃ and the running speed of the substrate is 120mm/s.
Example 2
The raw materials comprise the following components in parts by weight: 200 parts of conductive glass, 20 parts of methane, 9 parts of superfine alumina, 550 parts of silane coupling agent KH, and 2 parts of 2,2' -thiobis (4-tert-octylphenoloxy) nickel;
the grain size of the superfine alumina is less than 100nm;
preparing conductive glass:
taking quartz glass as a substrate, carrying a reactant triisopropyl aluminate into a chemical vapor deposition furnace reactor by using a carrier gas in a bubbling mode, heating the reactant to 150 ℃ in an oil bath, controlling the temperature of catalyst oxygen and water vapor to be 150 ℃, mixing the catalyst and the reactant in the reactor, and taking out after the mixing reaction is carried out for 2 hours to obtain conductive glass; wherein the temperature of the substrate is 650 ℃ and the running speed of the substrate is 100mm/s.
The preparation method of the heating graphene glass comprises the following steps:
(1) Soaking conductive glass in an aqueous solution of a silane coupling agent KH550, wherein the mass fraction of the silane coupling agent is 2.5%, heating to 50 ℃, treating for 50min, and taking out;
(2) Adding 2,2' -thiobis (4-tert-octylphenoloxy) nickel and superfine alumina into an ethanol solution, uniformly mixing the ethanol solution with the mass fraction of 75% to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 60min, and taking out;
(3) And (3) adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling manner, heating to 1100 ℃, mixing and reacting for 4 hours, and taking out to obtain the exothermic graphene glass; wherein the temperature of the substrate was 1200 ℃ and the running speed of the substrate was 150mm/s.
Example 3
The raw materials comprise the following components in parts by weight: 120 parts of conductive glass, 12 parts of methane, 6 parts of superfine alumina, 792 parts of silane coupling agent KH792, and 1.2 parts of 4-benzoyloxy-2, 6-tetramethylpiperidine;
the grain size of the superfine alumina is less than 100nm;
preparing conductive glass:
taking quartz glass as a substrate, carrying a reactant triisopropyl aluminate into a chemical vapor deposition furnace reactor by using a carrier gas in a bubbling mode, heating the reactant to 110 ℃ in an oil bath, controlling the temperature of catalyst oxygen and water vapor to be 110 ℃, mixing the catalyst and the reactant in the reactor, and taking out the mixture after the mixture reacts for 1 hour to obtain conductive glass; wherein the temperature of the substrate is 350 ℃ and the running speed of the substrate is 60mm/s.
The preparation method of the heating graphene glass comprises the following steps:
(1) Soaking conductive glass in an aqueous solution of a silane coupling agent KH792, wherein the mass fraction of the silane coupling agent is 1.5%, heating to 35 ℃, treating for 35min, and taking out;
(2) Adding 4-benzoyloxy-2, 6-tetramethylpiperidine and superfine aluminum oxide into an ethanol solution, wherein the mass fraction of ethanol is 55%, uniformly mixing to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 35min, and taking out;
(3) And (3) adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling mode, heating to 1000 ℃, carrying out mixed reaction for 33 hours, and taking out to obtain the heating graphene glass; wherein the temperature of the substrate is 1000 ℃ and the running speed of the substrate is 125mm/s.
Example 4
The raw materials comprise the following components in parts by weight: 180 parts of conductive glass, 17 parts of methane, 8 parts of superfine alumina, 7 parts of silane coupling agent KH570 and 1.7 parts of hexamethyl phosphoric triamide;
the grain size of the superfine alumina is less than 100nm;
preparing conductive glass:
taking quartz glass as a substrate, carrying a reactant triisopropyl aluminate into a chemical vapor deposition furnace reactor by using a carrier gas in a bubbling mode, heating the reactant to 140 ℃ in an oil bath, controlling the temperature of catalyst oxygen and water vapor to be 140 ℃, mixing the catalyst and the reactant in the reactor, and taking out after the mixing reaction is carried out for 2 hours to obtain conductive glass; wherein the temperature of the substrate is 600 ℃ and the running speed of the substrate is 90mm/s.
The preparation method of the heating graphene glass comprises the following steps:
(1) Soaking conductive glass in an aqueous solution of a silane coupling agent KH570, wherein the mass fraction of the silane coupling agent is 2%, heating to 45 ℃, treating for 45min, and taking out;
(2) Adding hexamethylphosphoric triamide and superfine alumina into an ethanol solution, wherein the mass fraction of ethanol is 70%, uniformly mixing to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 50min, and taking out;
(3) Adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling manner, heating to 1100 ℃, mixing and reacting for 3 hours, and taking out to obtain the exothermic graphene glass; wherein the temperature of the substrate was 1200 ℃ and the running speed of the substrate was 140mm/s.
Example 5
The raw materials comprise the following components in parts by weight: 160 parts of conductive glass, 15 parts of methane, 7 parts of superfine alumina, 6 parts of silane coupling agent KH560 and 1.5 parts of 2-hydroxy-4-methoxybenzophenone;
the grain size of the superfine alumina is less than 100nm;
preparing conductive glass:
taking quartz glass as a substrate, carrying a reactant triisopropyl aluminate into a chemical vapor deposition furnace reactor by using a carrier gas in a bubbling mode, heating the reactant to 125 ℃ in an oil bath, controlling the temperature of catalyst oxygen and water vapor to be 125 ℃, mixing the catalyst and the reactant in the reactor, and taking out the mixture after the mixing reaction is carried out for 1.5 hours to obtain conductive glass; wherein the temperature of the substrate is 450 ℃ and the running speed of the substrate is 75mm/s.
The preparation method of the heating graphene glass comprises the following steps
(1) Soaking conductive glass in an aqueous solution of a silane coupling agent KH560, wherein the mass fraction of the silane coupling agent is 1.8%, heating to 45 ℃, treating for 45min, and taking out;
(2) Adding 2-hydroxy-4-methoxybenzophenone and superfine alumina into an ethanol solution, uniformly mixing the ethanol solution with the mass fraction of 65% to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 45min, and taking out;
(3) Adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling mode, heating to 1050 ℃, mixing and reacting for 3 hours, and taking out to obtain the exothermic graphene glass; wherein the temperature of the substrate is 1050 ℃ and the running speed of the substrate is 135mm/s.
Fig. 1 is a SEM image of the surface of the heat-generating graphene glass prepared in example 5 of the present invention, and it can be seen that a layer of uniform graphene is formed on the surface of the glass.
Comparative example 1
Compared with example 5, the common quartz glass is used instead of the conductive glass, and other conditions are not changed.
The raw materials comprise the following components in parts by weight: 160 parts of common quartz glass, 15 parts of methane, 7 parts of superfine alumina, 6 parts of silane coupling agent KH560 and 1.5 parts of 2-hydroxy-4-methoxybenzophenone;
the grain size of the superfine alumina is less than 100nm;
the preparation method of the heating graphene glass comprises the following steps
(1) Soaking common quartz glass in an aqueous solution of a silane coupling agent KH560, wherein the mass fraction of the silane coupling agent is 1.8%, heating to 45 ℃, treating for 45min, and taking out;
(2) Adding 2-hydroxy-4-methoxybenzophenone and superfine alumina into an ethanol solution, uniformly mixing the ethanol solution with the mass fraction of 65% to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 45min, and taking out;
(3) Adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling mode, heating to 1050 ℃, mixing and reacting for 3 hours, and taking out to obtain the exothermic graphene glass; wherein the temperature of the substrate is 1050 deg.C and the running speed of the substrate is 135mm/s.
Comparative example 2
Compared with example 5, no ultrafine alumina was added, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 160 parts of conductive glass, 15 parts of methane, 6 parts of silane coupling agent KH560 and 8.5 parts of 2-hydroxy-4-methoxybenzophenone;
preparing conductive glass:
taking quartz glass as a substrate, carrying a reactant triisopropyl aluminate into a chemical vapor deposition furnace reactor by using a carrier gas in a bubbling mode, heating the reactant to 125 ℃ in an oil bath, controlling the temperature of catalyst oxygen and water vapor to be 125 ℃, mixing the catalyst and the reactant in the reactor, and taking out the mixture after the mixing reaction is carried out for 1.5 hours to obtain conductive glass; wherein the temperature of the substrate is 450 ℃ and the running speed of the substrate is 75mm/s.
The preparation method of the heating graphene glass comprises the following steps:
(1) Soaking the conductive glass in an aqueous solution of a silane coupling agent KH560, wherein the mass fraction of the silane coupling agent is 1.8%, heating to 45 ℃, treating for 45min, and taking out; :
(2) Adding 2-hydroxy-4-methoxybenzophenone into an ethanol solution, uniformly mixing the ethanol solution with the mass fraction of 65% to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 45min, and taking out;
(3) Adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling mode, heating to 1050 ℃, mixing and reacting for 3 hours, and taking out to obtain the exothermic graphene glass; wherein the temperature of the substrate is 1050 ℃ and the running speed of the substrate is 135mm/s.
Comparative example 3
Compared with the example 5, the 2-hydroxy-4-methoxybenzophenone is not added, and other conditions are not changed.
The raw materials comprise the following components in parts by weight: 160 parts of conductive glass, 15 parts of methane, 8.5 parts of superfine alumina and 6 parts of silane coupling agent KH 560;
the grain size of the superfine alumina is less than 100nm;
preparing conductive glass:
taking quartz glass as a substrate, carrying a reactant triisopropyl aluminate into a chemical vapor deposition furnace reactor by using a carrier gas in a bubbling mode, heating the reactant to 125 ℃ in an oil bath, controlling the temperature of catalyst oxygen and water vapor to be 125 ℃, mixing the catalyst and the reactant in the reactor, and taking out the mixture after the mixing reaction is carried out for 1.5 hours to obtain conductive glass; wherein the temperature of the substrate is 450 ℃ and the running speed of the substrate is 75mm/s.
The preparation method of the heating graphene glass comprises the following steps:
(1) Soaking conductive glass in an aqueous solution of a silane coupling agent KH560, wherein the mass fraction of the silane coupling agent is 1.8%, heating to 45 ℃, treating for 45min, and taking out;
(2) Adding superfine alumina into an ethanol solution, uniformly mixing the ethanol solution with the mass fraction of 65% to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 45min, and taking out;
(3) Adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling mode, heating to 1050 ℃, mixing and reacting for 3 hours, and taking out to obtain the exothermic graphene glass; wherein the temperature of the substrate is 1050 ℃ and the running speed of the substrate is 135mm/s.
Test example 1
The glasses prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to the property test, and the results are shown in Table 1.
TABLE 1
Testing the heat conductivity coefficient according to the GB/T3651-2008 standard; the adhesion test is carried out according to the JG/T24-2000 method, and the best grade 0 is grade 1; the conductivity test was carried out in accordance with DIN EN 16813-2017; the aging resistance test is carried out according to the GB/T15750-2008 standard; and other parameters are tested according to the JB/T9226-2008 standard.
As can be seen from Table 1, the heat-generating graphene glasses prepared in examples 1-5 of the present invention have good thermal and electrical conductivity, and the aging resistance, the oven-drying crack resistance, the adhesion and the like of the heat-generating graphene glasses are better than those of the common glasses and comparative examples 1-3.
In comparative example 1, since the common quartz glass was used instead of the conductive glass, the resistivity was remarkably decreased.
In comparative example 2 and comparative example 3, 2-hydroxy-4-methoxybenzophenone or ultrafine alumina is not added respectively, so that the thermal conductivity and the electrical conductivity are reduced, and the addition of 2-hydroxy-4-methoxybenzophenone or ultrafine alumina has a synergistic effect, and in addition, the addition of 2-hydroxy-4-methoxybenzophenone in comparative example 3 obviously reduces the aging resistance of the prepared glass. The addition of the ultraviolet absorbent and the superfine alumina is beneficial to improving the thermal conductivity, high temperature resistance, aging resistance and the like of the glass, so that the performance of the heating graphene glass is further improved.
Test example 2
The glass prepared in example 5 and comparative examples 1 to 3 were tested for heat generation data with reference to the test methods of GB/T7287-2008, JG-T286-2010, with the sample size of 25mm by 25mm. The applied voltage of the sample is 1V to 4V, as can be seen from FIG. 2 (a): comparative example 1 has a small amount of heat generation under the applied voltage, and the surface temperature is only 29 ℃ when the voltage is 4V; as can be seen from fig. 2 (b): in comparative example 2, the heating value under the applied voltage is still smaller than that of the graphene film prepared by the invention, and when the voltage is 4V, the surface temperature is only 30.5 ℃; as can be seen from fig. 2 (c): in the comparative example 3, the heating value under the applied voltage is still smaller than that of the graphene film prepared by the invention, and when the voltage is 4V, the surface temperature is only 32.5 ℃; as can be seen from fig. 2 (d): the surface temperature of example 5 was plotted against heating time. At the initial stage of electrifying, the rising rate of the surface temperature of the heating body is high, the rising rate of the surface temperature of the heating body is gradually reduced along with the increase of the electrifying time, the surface temperature of the heating body does not change after reaching a certain stable temperature, when the voltage is 4V, the stable temperature reached by the sample in the embodiment 1 is 66 ℃, and the requirement of a glass tabletop on a heating table can be met.
Compared with the prior art, the method adopts a thermal CVD direct growth method, takes methane as a carbon source to grow high-quality graphene, and usually the temperature needs to be more than 1000 ℃, so in order to grow the graphene on the surface of glass, high-temperature-resistant glass, namely quartz glass, is selected as a growth substrate, and the graphene is directly grown on the surface of the glass at a high temperature;
from the energy band structure of graphene, it can be known that when the electric field of the single-layer graphene is zero, the concentration of the conductive carrier is zero, which is called "dirac point". At a distance from the dirac point, there is only a single carrier in the graphene. The negative grid voltage enables the graphene to become electron conduction, the resistivity of the device is changed from several kilohms to several hundred ohms finally, current carriers in the graphene are gradually transited from electrons (or holes) to holes (or electrons) near a Dirac point, the Hall coefficient changes the sign (the electrons are positive, the holes are negative) at the position, the concentration of the current carriers is minimum, the resistivity is maximum, and the graphene generates heat after being electrified to generate heat, so that the technical effect of heating is realized;
the invention adopts high-temperature-resistant quartz glass as a substrate, and a very thin alumina thin layer is deposited on the surface of the glass through a chemical vapor deposition process to form conductive glass, and then an ultraviolet absorbent and superfine alumina are connected on the surface through a silane coupling agent to realize surface modification, and the superfine alumina can further form an alumina thin film on the surface of the conductive glass, so that the surface of the glass is ensured to be fully covered by the alumina.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The preparation method of the heating type graphene glass is characterized in that the heating type graphene glass is prepared from the following raw materials in parts by weight: 100-200 parts of conductive glass, 10-20 parts of methane, 5-9 parts of superfine alumina, 4-8 parts of silane coupling agent and 1-2 parts of ultraviolet absorbent;
the conductive glass adopts a chemical vapor deposition process, quartz glass is used as a substrate, triisopropyl aluminate is used as a reactant, nitrogen is used as a carrier gas, oxygen and water vapor are used as reaction catalysts, and the deposition is carried out in a chemical vapor deposition furnace, and the process specifically comprises the following steps:
quartz glass is used as a substrate, triisopropyl aluminate serving as a reactant is carried into a reactor of a chemical vapor deposition furnace by a carrier gas in a bubbling mode, the reactant is heated to 100-150 ℃ in an oil bath, the temperature of catalyst oxygen and water vapor is also 100-150 ℃, the catalyst and the reactant begin to be mixed in the reactor, and the mixture is taken out after 1-2h of mixing reaction to obtain conductive glass;
wherein the temperature of the substrate is 300-650 ℃, and the running speed of the substrate is 50-100mm/s;
the preparation method comprises the following steps:
(1) Soaking conductive glass in aqueous solution of silane coupling agent, heating to 30-50 deg.C, treating for 30-50min, and taking out;
(2) Adding an ultraviolet absorbent and superfine alumina into an ethanol solution, uniformly mixing to form a suspension, soaking the conductive glass treated in the step (1) in the suspension, treating for 30-60min, and taking out;
(3) Adopting a chemical vapor deposition process, taking the glass treated in the step (2) as a substrate, taking methane as a reactant, taking nitrogen as a carrier gas, taking hydrogen and water vapor as reaction catalysts, and depositing in a chemical vapor deposition furnace, wherein the chemical vapor deposition process specifically comprises the following steps:
taking the glass treated in the step (2) as a substrate, carrying methane into a chemical vapor deposition furnace reactor by using carrier gas in a bubbling manner, heating to 1000-1100 ℃, mixing and reacting for 2-4h, and taking out to obtain the exothermic graphene glass;
wherein the temperature of the substrate is 1000-1200 ℃, and the running speed of the substrate is 120-150mm/s.
2. The preparation method of the exothermic graphene glass according to claim 1, wherein the exothermic graphene glass is prepared from the following raw materials in parts by weight: 120-180 parts of conductive glass, 12-17 parts of methane, 6-8 parts of superfine alumina, 5-7 parts of silane coupling agent and 1.2-1.7 parts of ultraviolet absorbent.
3. The preparation method of the exothermic graphene glass according to claim 2, wherein the exothermic graphene glass is prepared from the following raw materials in parts by weight: 160 parts of conductive glass, 15 parts of methane, 7 parts of superfine alumina, 6 parts of silane coupling agent and 1.5 parts of ultraviolet absorbent.
4. The method for producing a heat-generating graphene glass according to claim 1, wherein the ultraviolet absorber is selected from one or more of phenyl ortho-hydroxybenzoate, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, resorcinol monobenzoate, 2' -thiobis (4-tert-octylphenoxyoxy) nickel, tris (1, 2, 6-pentamethylpiperidinyl) phosphite, 4-benzoyloxy-2, 6-tetramethylpiperidine, 2,4, 6-tris (2 ' -n-butoxyphenyl) -1,3, 5-triazine, and hexamethylphosphoric triamide.
5. The method for preparing heat-generating graphene glass according to claim 1, wherein the silane coupling agent is one or more selected from the group consisting of KH550, KH560, KH570, KH792, KH580, KH561, KH590 and KH 602.
6. The method for producing a heat-generating graphene glass according to claim 1, wherein the ultrafine alumina has a particle size of less than 100nm.
7. The method for preparing heat-generating graphene glass according to claim 1, wherein the volume ratio of oxygen to water vapor in the catalyst is 1: (1-5).
8. The method for preparing the heat-generating graphene glass according to claim 1, wherein the mass fraction of the silane coupling agent in the aqueous solution of the silane coupling agent is 1-2.5%; the mass fraction of ethanol in the ethanol solution is 50-75%.
9. Use of the exothermic graphene glass of claim 1 as a glass tabletop on a heating table.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010672196.4A CN111763015B (en) | 2020-07-14 | 2020-07-14 | Heating type graphene glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010672196.4A CN111763015B (en) | 2020-07-14 | 2020-07-14 | Heating type graphene glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111763015A CN111763015A (en) | 2020-10-13 |
| CN111763015B true CN111763015B (en) | 2022-12-27 |
Family
ID=72726422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010672196.4A Active CN111763015B (en) | 2020-07-14 | 2020-07-14 | Heating type graphene glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111763015B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112266182A (en) * | 2020-11-05 | 2021-01-26 | 北京石墨烯研究院 | Graphene glass and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7160578B2 (en) * | 2004-03-10 | 2007-01-09 | Pilkington North America | Method for depositing aluminum oxide coatings on flat glass |
| CN105295319A (en) * | 2015-12-04 | 2016-02-03 | 太仓陶氏电气有限公司 | Multifunctional heat dissipation device |
| CN105957646A (en) * | 2016-06-24 | 2016-09-21 | 成都天航智虹企业管理咨询有限公司 | Preparation method for conductive thin film |
| CN107311466A (en) * | 2017-05-11 | 2017-11-03 | 北京大学 | A kind of in-situ preparation method of Graphene glass |
| CN110255915B (en) * | 2019-07-03 | 2020-07-31 | 湖南步升取暖科技有限公司 | Heating type graphene glass and preparation method thereof |
-
2020
- 2020-07-14 CN CN202010672196.4A patent/CN111763015B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111763015A (en) | 2020-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20130243682A1 (en) | METHOD FOR MANUFACTURING SiC POWDERS WITH HIGH PURITY | |
| CN106882926B (en) | The method for preparing transparent graphene conductive film | |
| CN111763015B (en) | Heating type graphene glass and preparation method thereof | |
| CN108342716A (en) | Plasma enhanced chemical vapor deposition prepares the system and method for two-dimensional material | |
| JP2007294422A (en) | Sico-li based composite and its manufacturing method, as well as negative electrode material for nonaqueous electrolyte secondary battery | |
| CN103046166A (en) | Chemical gas-phase crosslinking method of polycarbosilane fibers | |
| CN110028058A (en) | A kind of nitrogen mixes grapheme material and preparation method thereof | |
| CN110562983B (en) | Efficient preparation device and preparation method of high-performance wave-absorbing material | |
| CN103214274A (en) | Graphene supported porous ceramic conductive material and preparation method thereof | |
| CN111205097A (en) | Fiber preform with double-wave-transparent ceramic coating and preparation method thereof | |
| CN101906616A (en) | Coating process for silicon solar cells | |
| CN106916311B (en) | Preparation method of beryllium-containing ceramic precursor | |
| CN105525277A (en) | Silicon carbide ceramic boat for plasma enhanced chemical vapor deposition and preparation method thereof | |
| CN110042653B (en) | Carbon fiber with multi-scale SiC-SiOC ceramic coating on surface and preparation method thereof | |
| WO2009002635A2 (en) | Method for the preparation of high purity silicon | |
| CN102557730B (en) | Surface modification method for silicon carbide ceramic | |
| JPS62287513A (en) | Transparent conducting film and manufacture thereof | |
| CN115124838A (en) | Polysulfone/modified filler composite dielectric film material and preparation method thereof | |
| CN1304638C (en) | Process for preparing graphite surface anti oxidation coating material silicon carbide for nuclear reactor | |
| CN113788697A (en) | Ceramic precursor slurry applicable to winding process and preparation method thereof | |
| CN1636870A (en) | Nanometer SiC powder preparing process | |
| CN112010571A (en) | Graphene glass and preparation method and application thereof | |
| CN108376780B (en) | Preparation method of three-dimensional porous silicon-doped titanium source and carbon composite negative electrode material | |
| Ramachandran et al. | Novel Two-Dimensional Siloxene Material for Electrochemical Energy Storage and Sensor Applications | |
| CN112028067A (en) | Silicon-carbon negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221205 Address after: Floor 1 and 5, Building A, Phase III Standard Plant, Jizhuang Cluster, Jishou Economic Development Zone, Xiangxi Tujia and Miao Autonomous Prefecture, Hunan Province 416000 Applicant after: Hunan Ruiying Photoelectric Technology Co.,Ltd. Address before: 410205 room 4125, 4th floor, main building, No. 15, Lutian Road, Changsha high tech Development Zone, Changsha, Hunan Applicant before: Changsha Luqiao Technology Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |