CN114920462A - Glass brick with magnetic adsorption effect - Google Patents
Glass brick with magnetic adsorption effect Download PDFInfo
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- CN114920462A CN114920462A CN202210411707.6A CN202210411707A CN114920462A CN 114920462 A CN114920462 A CN 114920462A CN 202210411707 A CN202210411707 A CN 202210411707A CN 114920462 A CN114920462 A CN 114920462A
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- 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
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
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- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
Abstract
The invention discloses a glass brick with a magnetic adsorption effect and a preparation method thereof, and relates to the technical field of building decoration materials. The preparation method comprises the following steps of mixing spherical polymethyl methacrylate serving as a template with three-dimensional graphene oxide particles to obtain pretreated particles; sequentially treating the pretreated particles with polyaniline and trichloromethane, and adding hydrazine hydrate for reaction to obtain a three-dimensional graphene hollow sphere; soaking the glass sand in acid, immersing the glass sand in ferric chloride hexahydrate, adding an alkali liquor to deposit a precipitate on the surface of the sand to obtain pretreated glass sand, washing the pretreated glass sand, performing secondary precipitation, roasting to obtain modified glass sand, preparing the modified glass sand into gel, and filling the gel into the three-dimensional graphene hollow spheres to obtain the modified graphene hollow spheres; and (3) the modified graphene hollow spheres are thrown into molten glass, uniformly dispersed, pressed and cooled to obtain the glass brick with the magnetic adsorption effect. The glass brick with the magnetic adsorption effect has the magnetic adsorption effect, excellent pressure resistance and long service life.
Description
Technical Field
The invention relates to the technical field of building decoration materials, in particular to a glass brick with a magnetic adsorption effect.
Background
The glass brick with the magnetic adsorption effect is rapidly cooled when the glass brick is converted from high-temperature molten liquid to solid, the cooling rate is rapidly accelerated, the time of the cooling process is extremely short, atoms in the high-temperature molten liquid are not arranged for a long enough time, a disordered structure in the liquid state is still kept, the crystallinity is inhibited, and finally the glass brick is solidified to form an amorphous body.
The glass brick for decoration circulated in the market at present has defects in mechanical property and pressure resistance, so that the glass brick is easy to crack under heavy pressure or collision, the glass brick is not attractive, and meanwhile potential safety hazards are buried for daily life.
Disclosure of Invention
The invention aims to provide a glass brick with a magnetic adsorption effect and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a glass brick with a magnetic adsorption effect is characterized in that the process flow for preparing the glass brick with the magnetic adsorption effect is as follows:
the preparation method comprises the following steps of preparing three-dimensional reticular graphene oxide sponge, preparing three-dimensional graphene oxide particles, preparing three-dimensional graphene hollow spheres, preparing pretreated glass sand, preparing pre-modified glass sand, preparing modified graphene hollow spheres and preparing glass bricks with magnetic adsorption effects.
Further, the preparation method of the glass brick with the magnetic adsorption effect comprises the following specific steps:
(1) preparing graphene oxide into a graphene dispersion liquid I with the concentration of 20mg/ml, uniformly dispersing by ultrasonic waves, diluting into a dispersion liquid II with the concentration of 10mg/ml, pouring the dispersion liquid II into a freeze-drying mold, firstly adjusting a freeze dryer into a freezing mode, cooling and freezing, then adjusting the freeze dryer into a drying mode, vacuumizing to set the vacuum degree to be 1pa, heating the mold, preserving heat for a period of time, and cooling to obtain three-dimensional reticular graphene oxide sponge;
(2) ball-milling three-dimensional reticular graphene oxide sponge by using a star-shaped ball mill, wherein the ball-to-material ratio is 5:3, and preparing three-dimensional graphene oxide particles; during ball milling, the grinding aid solvent is an acetone solution with the mass fraction of 22%, and the mass ratio of the three-dimensional reticular graphene oxide sponge to the acetone solution is 1: 0.4; the particle size of the three-dimensional graphene oxide particles after ball milling is 700-800 nm;
(3) dispersing spherical polymethyl methacrylate in deionized water, adding three-dimensional graphene oxide particles, transferring to a magnetic stirrer, stirring for 1-2 h, performing suction filtration, and drying with warm air at 55 ℃ to constant weight to obtain pretreated particles; soaking the pretreated particles by using a polyaniline-methyl pyrrolidone solution with the mass fraction of 37%, and drying by using warm air at 55 ℃ to constant weight to obtain a material a; soaking the material a in a hydrochloric acid solution with the concentration of 3mol/L at 90 ℃, placing the solution on a magnetic stirrer, stirring the solution for 3 to 5min, washing the solution with deionized water until the washing solution is neutral, and drying the solution to obtain a material b; dispersing the material b in deionized water, adding hydrazine hydrate under the condition of magnetic stirring, stirring for reaction until the reaction is finished when the upper layer liquid of a reaction system is clear, cleaning the product by using deionized water until the cleaning liquid is neutral, and freeze-drying at-35 ℃ to obtain the three-dimensional graphene hollow sphere;
(4) screening out 0.5-1 mm of glass sand by using a screen, cleaning the glass sand by using deionized water, soaking the glass sand in a hydrochloric acid solution with the concentration of 1mol/L for 20-24 hours, taking out the glass sand, cleaning the glass sand by using the deionized water until the washing solution is neutral, putting the glass sand into an oven for drying, and naturally cooling the glass sand to room temperature to obtain a material c; soaking the material c into 45% ferric chloride hexahydrate solution, raising the temperature, adding 1.7mol/L sodium hydroxide solution, stirring and reacting for 10-20 min under the condition of keeping the temperature, then carrying out primary precipitation for 3-4 h, taking out the precipitate, washing for three times by using deionized water, and drying to obtain pretreated glass sand;
(5) carrying out secondary precipitation on the pretreated glass sand, washing the pretreated glass sand for three times by using deionized water after the precipitation is finished, and drying the glass sand to obtain the pre-modified glass sand;
(6) placing the pre-modified glass sand into a crucible, then moving the crucible into a muffle furnace for roasting for 2-3 h, and then cooling the product to room temperature to obtain modified glass sand;
(7) crushing the modified glass sand to 0.01-0.05 by using a ball mill to obtain a material d; placing the material d in a flask, adding ethylene glycol monomethyl ether to obtain a mixed solution, stirring for 30-40 min at 60-70 ℃ by using a constant-temperature stirrer, then adding ethanolamine, continuously stirring for 1-2 h to obtain a clear liquid, and aging the clear liquid at room temperature for 20-24 h to obtain glass sand gel; putting the three-dimensional graphene hollow sphere into a mold, pouring glass sand gel, sealing the mold, pressurizing the interior of the mold, filling the three-dimensional graphene hollow sphere to a saturated state under the action of pressure, and curing by hot air at 50 ℃ to obtain a modified graphene hollow sphere;
(8) heating and melting quartz glass, putting the modified graphene hollow spheres into the molten glass, and turning and kneading for multiple times to uniformly disperse the modified graphene hollow spheres to obtain a material e; and pressing, forming, cooling and solidifying the material e to obtain the glass brick with the magnetic adsorption effect.
Further, in the step (1), the temperature is reduced to-45 ℃, and the freezing time is 4-5 hours; controlling the heating rate to be 1 ℃/h, heating to 30 ℃, and keeping the temperature for 24 h.
Further, in the step (3), the mass ratio of the spherical polymethyl methacrylate, the deionized water and the three-dimensional graphene oxide particles is 1: 4: 2.7-1: 4: 3, the speed of the three times of magnetic stirring is 800 r/min; drying time is 20-30 min; the mass ratio of the pretreated particles to the polyaniline-methyl pyrrolidone solution is 1: 4; the mass ratio of the material a to the hydrochloric acid solution is 1: 4; the mass ratio of the material b to the deionized water to the hydrazine hydrate is 1: 3: 0.6.
further, in the step (4), the mass ratio of the glass sand to the hydrochloric acid solution is 1: 3; the drying temperature is 100-110 ℃; the mass ratio of the material c, ferric chloride hexahydrate and sodium hydroxide solution is 1: 2.4: 0.7, raising the temperature to 80 ℃, and stirring at the speed of 800 r/min; the drying method is drying with warm air at 45 ℃ for 1-2 h.
Further, in the step (5), during the secondary precipitation, the mass ratio of the pretreated glass sand to the ferric chloride hexahydrate solution to the sodium hydroxide solution is 1: 2: 0.5, the precipitation conditions are the same as those in the initial precipitation.
Further, in the step (6), the temperature is 450-500 ℃ during roasting; the cooling method is a quenching method, and ethanol solution with the temperature of 30 ℃ below zero is used as cooling liquid.
Further, in the step (7), the mass ratio of the material d, ethylene glycol monomethyl ether and ethanolamine is 1.5: 1.2: 1.2; the stirring speed is 500 r/min; the mass ratio of the three-dimensional graphene hollow spheres to the glass sand gel is 1: 2.3 and the pressure is 2 MPa.
Further, in the step (8), the heating temperature of the quartz glass is 1600 ℃; the mass ratio of the modified graphene hollow spheres to the quartz glass is 1: 1.2; the cooling method adopts an air cooling method, and the refrigerating capacity is 770 kW.
Further, the glass brick with the magnetic adsorption effect prepared by the preparation method of the glass brick with the magnetic adsorption effect comprises the following raw materials in parts by weight: 100-150 parts of three-dimensional graphene hollow spheres, 70-90 parts of modified graphene hollow spheres and 84-108 parts of quartz glass; the three-dimensional graphene hollow sphere is prepared by processing three-dimensional reticular graphene oxide sponge and spherical polymethyl methacrylate; the modified graphene hollow sphere is prepared from a three-dimensional graphene hollow sphere and glass sand through technological treatment.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method comprises the steps of preparing three-dimensional mesh graphene oxide sponge by using a freeze drying method, and crushing to obtain three-dimensional graphene oxide particles; using spherical polymethyl methacrylate as a template, mixing the spherical polymethyl methacrylate with three-dimensional graphene oxide particles, and coating the three-dimensional graphene oxide particles on the surface of the polymethyl methacrylate to obtain pretreated particles; after sequentially treating the pretreated particles by using polyaniline and trichloromethane, adding hydrazine hydrate to reduce graphene oxide into graphene, and preparing a three-dimensional graphene hollow sphere; the three-dimensional graphene oxide hollow microspheres are prepared from the three-dimensional graphene oxide, the three-dimensional graphene oxide is more stable in structure, and meanwhile, the specific surface area of the three-dimensional graphene oxide is large, so that the three-dimensional graphene oxide hollow microspheres are more fully contacted with a filler, and the mechanical property and the compression resistance of a glass brick are favorably improved; after the spherical polymethyl methacrylate and the three-dimensional graphene oxide particles are mixed, the positively charged polymethyl methacrylate and the negatively charged three-dimensional graphene oxide particles are adsorbed together, so that the dispersibility of the polymethyl methacrylate and the three-dimensional graphene oxide particles in a system is effectively improved; the polyaniline treatment enables the three-dimensional graphene oxide to be self-adhered, the appearance of the three-dimensional graphene oxide is maintained, and the chloroform etches the polymethyl methacrylate to form a three-dimensional graphene oxide hollow sphere; the hollow three-dimensional graphene ball can increase the mechanical property of the glass brick in a glass brick system, effectively share the pressure and shearing force of the glass brick in service, distribute the excessive pressure on the surface of the hollow ball and weaken the hollow ball, and increase the service life and compressive capacity of the glass brick.
Performing surface treatment on glass sand by using hydrochloric acid, then immersing the glass sand into a ferric chloride hexahydrate solution, heating, adding alkali liquor, stirring for reaction, standing, and performing primary precipitation to precipitate iron oxide on the surface of sand grains to obtain pretreated glass sand; taking out the pretreated glass sand, washing with deionized water, and performing secondary precipitation to obtain pre-modified glass sand; placing the pre-modified glass sand into a muffle furnace for roasting to obtain modified glass sand; crushing the modified glass sand to prepare gel, and filling the gel into the three-dimensional graphene hollow sphere to obtain a modified graphene hollow sphere; putting the modified graphene hollow spheres into molten glass, uniformly dispersing, pressing, and cooling to obtain a glass brick with a magnetic adsorption effect; the chemical activity of the surface of the glass sand is enhanced by hydrochloric acid leaching, after the glass sand is immersed in ferric chloride hexahydrate, iron falls off by concentrated alkali and is deposited on the surface of the glass sand, and the iron content is increased by secondary precipitation; the modified glass sand is filled in the three-dimensional graphene hollow sphere, the modified graphene hollow sphere is put into molten glass, the glass sand in the modified graphene hollow sphere is melted, softened and adhered together at high temperature to form a large-particle glass sand sphere, and the large-particle glass sand sphere can bear stress and shearing force borne by a glass brick while supporting the spherical shape of the graphene hollow sphere, so that the service life and the pressure resistance of the glass brick are prolonged; the ferric hydroxide is heated to become ferric oxide, and the ferric oxide is melted by high temperature and mutually connected in the hollow microsphere, so that an iron hollow sphere is formed along the supporting point of the three-dimensional graphene sphere; a large amount of hollow microspheres are close each other in the same place, can change the successive layer when successive layer transmits with the pressure and the shearing force that the glass brick received and solve, prevent that the glass brick is broken when receiving pressure to iron element's existence makes the glass brick have magnetic force adsorption effect, increases the life and the compressive capacity of glass brick simultaneously.
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 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.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe the method in detail, and the method for testing each index of the glass block having magnetic adsorption effect manufactured in the following examples is as follows:
impact resistance: the impact resistance of the glass blocks having a magnetic force adsorption effect obtained by the components of example 1, example 2 and comparative example 1 was tested, and the glass blocks having a magnetic force adsorption effect obtained by vertically and positively impacting elastomer pellets having a diameter of 6cm against the components of example 1, example 2 and comparative example 1 at a speed of 100m/s were calculated to find that the lower the breakage degree, the better the impact resistance of the glass blocks having a magnetic force adsorption effect.
Magnetic attraction performance: the magnetic chips are placed on a horizontal desktop, the glass bricks with the magnetic adsorption effect obtained by the components of the example 1, the example 2 and the comparative example 2 are suspended, and the glass bricks are swung, so that the glass stands 3cm above the magnetic chips when swinging, if the magnetic chips are adsorbed on the glass bricks, the glass bricks have the magnetic adsorption effect, otherwise, the glass bricks do not have the magnetic adsorption effect.
Example 1
A glass brick with magnetic adsorption effect mainly comprises the following components in parts by weight: 100 parts of three-dimensional graphene hollow spheres, 70 parts of modified graphene hollow spheres and 84 parts of quartz glass.
A preparation method of a glass brick with a magnetic adsorption effect comprises the following steps:
(1) preparing graphene oxide into a graphene dispersion liquid I with the concentration of 20mg/ml, uniformly dispersing by ultrasonic waves, diluting into a dispersion liquid II with the concentration of 10mg/ml, pouring the dispersion liquid II into a freeze-drying mold, firstly adjusting a freeze dryer into a freezing mode, cooling and freezing, then adjusting the freeze dryer into a drying mode, vacuumizing to set the vacuum degree to be 1pa, heating the mold, preserving heat for a period of time, and cooling to obtain three-dimensional reticular graphene oxide sponge; wherein the temperature is reduced to-45 ℃ and the freezing time is 4 h; controlling the heating rate to be 1 ℃/h, heating to 30 ℃, and keeping the temperature for 24 h;
(2) ball-milling three-dimensional reticular graphene oxide sponge by using a star-shaped ball mill, wherein the ball-to-material ratio is 5:3, and preparing three-dimensional graphene oxide particles; the grinding-aid solvent is acetone solution with the mass fraction of 22% during ball milling, and the mass ratio of the three-dimensional reticular graphene oxide sponge to the acetone solution is 1: 0.4 of the total weight of the mixture; the particle size of the three-dimensional graphene oxide particles after ball milling is 700 nm;
(3) dispersing spherical polymethyl methacrylate in deionized water, adding three-dimensional graphene oxide particles, transferring to a magnetic stirrer, stirring for 1h, performing suction filtration, and drying with warm air at 55 ℃ to constant weight to obtain pretreated particles; soaking the pretreated particles by using a polyaniline-methyl pyrrolidone solution with the mass fraction of 37%, and drying the pretreated particles by using warm air at the temperature of 55 ℃ to constant weight to obtain a material a; soaking the material a in a hydrochloric acid solution with the concentration of 3mol/L at 90 ℃, placing the solution on a magnetic stirrer, stirring the solution for 3min, washing the solution by using deionized water until the washing solution is neutral, and drying the solution to obtain a material b; dispersing the material b in deionized water, adding hydrazine hydrate under the condition of magnetic stirring, stirring for reaction until the reaction is finished when the upper layer liquid of a reaction system is clear, cleaning the product by using deionized water until the cleaning liquid is neutral, and freeze-drying at-35 ℃ to obtain the three-dimensional graphene hollow sphere; wherein the mass ratio of the spherical polymethyl methacrylate to the deionized water to the three-dimensional graphene oxide particles is 1: 4: 2.7, the speed of the three times of magnetic stirring is 800 r/min; drying for 20 min; the mass ratio of the pretreated particles to the polyaniline-methyl pyrrolidone solution is 1: 4; the mass ratio of the material a to the hydrochloric acid solution is 1: 4; the mass ratio of the material b to the deionized water to the hydrazine hydrate is 1: 3: 0.6;
(4) screening out 0.5mm of glass sand by using a screen, cleaning the glass sand by using deionized water, soaking the glass sand in a hydrochloric acid solution with the concentration of 1mol/L for 20 hours, taking out the glass sand, cleaning the glass sand by using the deionized water until the washing solution is neutral, putting the glass sand into an oven for drying, and naturally cooling the glass sand to room temperature to obtain a material c; soaking the material c into 45% ferric chloride hexahydrate solution, raising the temperature, adding 1.7mol/L sodium hydroxide solution, stirring and reacting for 10min under the condition of keeping the temperature, then carrying out primary precipitation for 3h, taking out the precipitate, washing for three times by using deionized water, and drying to obtain pretreated glass sand; wherein the mass ratio of the glass sand to the hydrochloric acid solution is 1: 3; the drying temperature is 100 ℃; the mass ratio of the material c, ferric chloride hexahydrate and sodium hydroxide solution is 1: 2.4: 0.7, raising the temperature to 80 ℃, and stirring at the speed of 800 r/min; the drying method is drying with warm air at 45 deg.C for 1 h;
(5) carrying out secondary precipitation on the pretreated glass sand, washing the pretreated glass sand for three times by using deionized water after the precipitation is finished, and drying the glass sand to obtain the pre-modified glass sand; during secondary precipitation, the mass ratio of the pretreated glass sand to the ferric chloride hexahydrate solution to the sodium hydroxide solution is 1: 2: 0.5, the precipitation conditions are consistent with those of the primary precipitation;
(6) putting the pre-modified glass sand into a crucible, then moving the crucible into a muffle furnace for roasting for 2 hours, and then cooling the product to room temperature to obtain modified glass sand; wherein the roasting temperature is 450 deg.C, the cooling method is quenching method, and ethanol solution of-30 deg.C is used as cooling liquid
(7) Crushing the modified glass sand to 0.01 by using a ball mill to obtain a material d; placing the material d in a flask, adding ethylene glycol monomethyl ether to obtain a mixed solution, stirring for 30min at 60 ℃ by using a constant-temperature stirrer, then adding ethanolamine, continuously stirring for 1h to obtain a clear solution, and aging the clear solution at room temperature for 20h to obtain glass sand gel; putting the three-dimensional graphene hollow sphere into a mold, pouring glass sand gel, sealing the mold, pressurizing the interior of the mold, filling the three-dimensional graphene hollow sphere to a saturated state under the action of pressure, and curing by hot air at 50 ℃ to obtain a modified graphene hollow sphere; wherein the mass ratio of the material d, ethylene glycol monomethyl ether and ethanolamine is 1.5: 1.2: 1.2; the stirring speed is 500 r/min; the mass ratio of the three-dimensional graphene hollow spheres to the glass sand gel is 1: 2.3, the pressure is 2 MPa;
(8) heating and melting quartz glass, putting the modified graphene hollow spheres into the molten glass, and turning and kneading for multiple times to uniformly disperse the modified graphene hollow spheres to obtain a material e; pressing, forming, cooling and solidifying the material e to obtain the glass brick with the magnetic adsorption effect; wherein the heating temperature of the quartz glass is 1600 ℃; the mass ratio of the modified graphene hollow spheres to the quartz glass is 1: 1.2; the cooling method adopts an air cooling method, and the refrigerating capacity is 770 kW.
Example 2
A glass brick with a magnetic adsorption effect mainly comprises the following components in parts by weight: 150 parts of three-dimensional graphene hollow spheres, 90 parts of modified graphene hollow spheres and 108 parts of quartz glass.
A preparation method of a glass brick with a magnetic adsorption effect comprises the following steps:
(1) preparing graphene oxide into a first graphene dispersion liquid with the concentration of 20mg/ml, uniformly dispersing by ultrasonic waves, diluting into a second graphene dispersion liquid with the concentration of 10mg/ml, pouring the second graphene dispersion liquid into a freeze-drying mold, firstly adjusting a freeze dryer into a freezing mode, cooling and freezing, then adjusting the freeze dryer into a drying mode, vacuumizing to set the vacuum degree to be 1pa, heating the mold, preserving heat for a period of time, and cooling to obtain a three-dimensional reticular graphene oxide sponge; wherein the temperature is reduced to-45 ℃, and the freezing time is 5 h; controlling the heating rate to be 1 ℃/h, heating to 30 ℃, and keeping the temperature for 24 h;
(2) ball-milling three-dimensional reticular graphene oxide sponge by using a star-shaped ball mill, wherein the ball-to-material ratio is 5:3, and preparing three-dimensional graphene oxide particles; the grinding-aid solvent is acetone solution with the mass fraction of 22% during ball milling, and the mass ratio of the three-dimensional reticular graphene oxide sponge to the acetone solution is 1: 0.4; the particle size of the three-dimensional graphene oxide particles after ball milling is 800 nm;
(3) dispersing spherical polymethyl methacrylate in deionized water, adding three-dimensional graphene oxide particles, transferring to a magnetic stirrer, stirring for 2 hours, performing suction filtration, and drying with warm air at 55 ℃ to constant weight to obtain pretreated particles; soaking the pretreated particles by using a polyaniline-methyl pyrrolidone solution with the mass fraction of 37%, and drying by using warm air at 55 ℃ to constant weight to obtain a material a; soaking the material a in a hydrochloric acid solution with the concentration of 3mol/L at 90 ℃, placing the solution on a magnetic stirrer, stirring the solution for 5min, washing the solution by using deionized water until the washing solution is neutral, and drying the solution to obtain a material b; dispersing the material b in deionized water, adding hydrazine hydrate under the condition of magnetic stirring, stirring for reaction until the reaction is finished when the supernatant of a reaction system is clear, washing the product by using deionized water until the washing liquid is neutral, and freeze-drying at-35 ℃ to obtain the three-dimensional graphene hollow sphere; wherein the mass ratio of the spherical polymethyl methacrylate to the deionized water to the three-dimensional graphene oxide particles is 1: 4: 3, the speed of the three times of magnetic stirring is 800 r/min; drying for 30 min; the mass ratio of the pretreated particles to the polyaniline-methyl pyrrolidone solution is 1: 4; the mass ratio of the material a to the hydrochloric acid solution is 1: 4; the mass ratio of the material b to the deionized water to the hydrazine hydrate is 1: 3: 0.6;
(4) screening out 1mm of glass sand by using a screen, cleaning the glass sand by using deionized water, soaking the glass sand in a hydrochloric acid solution with the concentration of 1mol/L for 24 hours, taking out the glass sand, cleaning the glass sand by using the deionized water until the washing solution is neutral, putting the glass sand into an oven for drying, and naturally cooling the glass sand to room temperature to obtain a material c; soaking the material c into 45% ferric chloride hexahydrate solution, raising the temperature, adding 1.7mol/L sodium hydroxide solution, stirring and reacting for 20min under the condition of keeping the temperature, then carrying out primary precipitation for 4h, taking out the precipitate, washing for three times by using deionized water, and drying to obtain pretreated glass sand; wherein the mass ratio of the glass sand to the hydrochloric acid solution is 1: 3; the drying temperature is 110 ℃; the mass ratio of the material c, ferric chloride hexahydrate and sodium hydroxide solution is 1: 2.4: 0.7, raising the temperature to 80 ℃, and stirring at the speed of 800 r/min; the drying method is drying with warm air at 45 ℃ for 2 h;
(5) carrying out secondary precipitation on the pretreated glass sand, washing the pretreated glass sand for three times by using deionized water after the precipitation is finished, and drying the pretreated glass sand to obtain pre-modified glass sand; during secondary precipitation, the mass ratio of the pretreated glass sand to the ferric chloride hexahydrate solution to the sodium hydroxide solution is 1: 2: 0.5, the precipitation conditions are consistent with those of the primary precipitation;
(6) placing the pre-modified glass sand into a crucible, moving the crucible into a muffle furnace for roasting for 3 hours, and cooling a product to room temperature to obtain modified glass sand; wherein the roasting temperature is 500 deg.C, the cooling method is quenching method, and ethanol solution of-30 deg.C is used as cooling liquid
(7) Crushing the modified glass sand to 0.05 by using a ball mill to obtain a material d; placing the material d in a flask, adding ethylene glycol monomethyl ether to obtain a mixed solution, stirring for 40min at 70 ℃ by using a constant-temperature stirrer, then adding ethanolamine, continuously stirring for 2h to obtain a clear solution, and aging the clear solution at room temperature for 24h to obtain glass sand gel; putting the three-dimensional graphene hollow sphere into a mold, pouring glass sand gel, sealing the mold, pressurizing the interior of the mold, filling the three-dimensional graphene hollow sphere to a saturated state under the action of pressure, and curing by hot air at 50 ℃ to obtain a modified graphene hollow sphere; wherein the mass ratio of the material d, the ethylene glycol monomethyl ether and the ethanolamine is 1.5: 1.2: 1.2; the stirring speed is 500 r/min; the mass ratio of the three-dimensional graphene hollow spheres to the glass sand gel is 1: 2.3, the pressure is 2 MPa;
(8) heating and melting quartz glass, putting the modified graphene hollow spheres into the molten glass, and turning and kneading for multiple times to uniformly disperse the modified graphene hollow spheres to obtain a material e; pressing, forming, cooling and solidifying the material e to obtain the glass brick with the magnetic adsorption effect; wherein the heating temperature of the quartz glass is 1600 ℃; the mass ratio of the modified graphene hollow spheres to the quartz glass is 1: 1.2; the cooling method adopts an air cooling method, and the refrigerating capacity is 770 kW.
Comparative example 1
The formulation of comparative example 1 was the same as example 1. The preparation method of the glass brick with the magnetic adsorption effect is different from that of the example 1 only in that the preparation process of the three-dimensional graphene hollow sphere is not carried out, the ferric hydroxide precipitate and the modified glass sand are directly added into the fused quartz glass, and the other preparation steps are the same as those of the example 1.
Comparative example 2
The formulation of comparative example 2 was the same as example 1. The preparation method of the glass brick with the magnetic adsorption effect is different from that of the example 1 only in that the glass sand is not modified, and the other preparation steps are the same as those of the example 1.
Effect example 1
The following table 1 shows the results of impact resistance analysis of the glass blocks having magnetic force adsorption effect obtained by using the components of example 1, example 2 and comparative example 1 according to the present invention.
TABLE 1
| Example 1 | Example 2 | Comparative example 1 | |
| Degree of damage | 8% | 9% | 27% |
As can be seen from the above table, the glass brick with magnetic adsorption effect prepared from the components in example 1 has more excellent impact resistance compared with example 2 and comparative example 1, which shows that the hollow three-dimensional graphene spheres can increase the mechanical properties of the glass brick in a glass brick system, effectively share the pressure and shear force applied to the glass brick in service, and distribute the excessive pressure applied to the surface of the hollow spheres to weaken the surface of the hollow spheres, thereby increasing the service life and compressive capacity of the glass brick.
Effect example 2
The following table 2 shows the analysis results of the magnetic attraction performance of the glass bricks with magnetic attraction effect obtained by using the components of example 1, example 2 and comparative example 2 of the present invention.
TABLE 2
| With no magnetism | |
| Example 1 | Is provided with |
| Example 2 | Is provided with |
| Comparative example 2 | Is free of |
The glass brick with the magnetic adsorption effect increases the original mechanical property of the glass brick, endows the glass brick with magnetic adsorption property, shows that iron elements in ferric chloride are deposited on the surface of glass sand, are melted at high temperature and are connected with each other in the hollow microspheres to form an iron hollow sphere along the supporting point of the three-dimensional graphene sphere, and the service life and the pressure resistance of the glass brick are increased while the glass brick is ensured to have the magnetic adsorption effect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (1)
1. The utility model provides a glass brick with magnetic force adsorbs effect which characterized in that: mainly comprises the following components in parts by weight: 100 parts of three-dimensional graphene hollow spheres, 70 parts of modified graphene hollow spheres and 84 parts of quartz glass;
the preparation method of the glass brick with the magnetic adsorption effect comprises the following steps:
(1) preparing graphene oxide into a first graphene dispersion liquid with the concentration of 20mg/ml, uniformly dispersing by ultrasonic waves, diluting into a second graphene dispersion liquid with the concentration of 10mg/ml, pouring the second graphene dispersion liquid into a freeze-drying mold, firstly adjusting a freeze dryer into a freezing mode, cooling and freezing, then adjusting the freeze dryer into a drying mode, vacuumizing to set the vacuum degree to be 1pa, heating the mold, preserving heat for a period of time, and cooling to obtain a three-dimensional reticular graphene oxide sponge; wherein the temperature is reduced to-45 ℃ and the freezing time is 4 h; controlling the heating rate to be 1 ℃/h, heating to 30 ℃, and keeping the temperature for 24 h;
(2) ball-milling three-dimensional reticular graphene oxide sponge by using a star-shaped ball mill, wherein the ball-to-material ratio is 5:3, and preparing three-dimensional graphene oxide particles; the grinding-aid solvent is acetone solution with the mass fraction of 22% during ball milling, and the mass ratio of the three-dimensional reticular graphene oxide sponge to the acetone solution is 1: 0.4 of the total weight of the mixture; the particle size of the three-dimensional graphene oxide particles after ball milling is 700 nm;
(3) dispersing spherical polymethyl methacrylate in deionized water, adding three-dimensional graphene oxide particles, transferring the mixture to a magnetic stirrer, stirring for 1 hour, performing suction filtration, and drying the mixture with warm air at 55 ℃ to constant weight to obtain pretreated particles; soaking the pretreated particles by using a polyaniline-methyl pyrrolidone solution with the mass fraction of 37%, and drying by using warm air at 55 ℃ to constant weight to obtain a material a; soaking the material a in a hydrochloric acid solution with the concentration of 3mol/L at 90 ℃, placing the solution on a magnetic stirrer, stirring the solution for 3min, washing the solution with deionized water until the washing solution is neutral, and drying the solution to obtain a material b; dispersing the material b in deionized water, adding hydrazine hydrate under the condition of magnetic stirring, stirring for reaction until the reaction is finished when the supernatant of a reaction system is clear, washing the product by using deionized water until the washing liquid is neutral, and freeze-drying at-35 ℃ to obtain the three-dimensional graphene hollow sphere; wherein the mass ratio of the spherical polymethyl methacrylate to the deionized water to the three-dimensional graphene oxide particles is 1: 4: 2.7, the speed of the three times of magnetic stirring is 800 r/min; drying for 20 min; the mass ratio of the pretreated particles to the polyaniline-methyl pyrrolidone solution is 1: 4; the mass ratio of the material a to the hydrochloric acid solution is 1: 4; the mass ratio of the material b to the deionized water to the hydrazine hydrate is 1: 3: 0.6;
(4) screening out 0.5mm of glass sand by using a screen, cleaning the glass sand by using deionized water, soaking the glass sand in a hydrochloric acid solution with the concentration of 1mol/L for 20 hours, taking out the glass sand, cleaning the glass sand by using the deionized water until the washing solution is neutral, putting the glass sand into an oven for drying, and naturally cooling the glass sand to room temperature to obtain a material c; soaking the material c into 45 mass percent ferric chloride hexahydrate solution, raising the temperature, adding 1.7mol/L sodium hydroxide solution, stirring and reacting for 10min under the condition of keeping the temperature, then carrying out primary precipitation for 3h, taking out the precipitate, washing for three times by using deionized water, and drying to obtain pretreated glass sand; wherein the mass ratio of the glass sand to the hydrochloric acid solution is 1: 3; the drying temperature is 100 ℃; the mass ratio of the material c, ferric chloride hexahydrate and sodium hydroxide solution is 1: 2.4: 0.7, raising the temperature to 80 ℃, and stirring at the speed of 800 r/min; the drying method is drying with warm air at 45 ℃ for 1 h;
(5) carrying out secondary precipitation on the pretreated glass sand, washing the pretreated glass sand for three times by using deionized water after the precipitation is finished, and drying the glass sand to obtain the pre-modified glass sand; during secondary precipitation, the mass ratio of the pretreated glass sand to the ferric chloride hexahydrate solution to the sodium hydroxide solution is 1: 2: 0.5, the precipitation conditions are consistent with those of the primary precipitation;
(6) putting the pre-modified glass sand into a crucible, then moving the crucible into a muffle furnace for roasting for 2 hours, and then cooling the product to room temperature to obtain modified glass sand; wherein the roasting temperature is 450 deg.C, the cooling method is quenching method, and ethanol solution of-30 deg.C is used as cooling liquid
(7) Crushing the modified glass sand to 0.01 by using a ball mill to obtain a material d; placing the material d in a flask, adding ethylene glycol monomethyl ether to obtain a mixed solution, stirring for 30min at 60 ℃ by using a constant-temperature stirrer, then adding ethanolamine, continuously stirring for 1h to obtain a clear solution, and aging the clear solution at room temperature for 20h to obtain glass sand gel; putting the three-dimensional graphene hollow spheres into a mold, pouring glass sand gel, closing the mold, pressurizing the interior of the mold, filling the three-dimensional graphene hollow spheres to a saturated state under the action of pressure, and curing by hot air at 50 ℃ to obtain modified graphene hollow spheres; wherein the mass ratio of the material d, ethylene glycol monomethyl ether and ethanolamine is 1.5: 1.2: 1.2; the stirring speed is 500 r/min; the mass ratio of the three-dimensional graphene hollow spheres to the glass sand gel is 1: 2.3, the pressure is 2 MPa;
(8) heating and melting quartz glass, putting the modified graphene hollow spheres into the molten glass, and turning and kneading for multiple times to uniformly disperse the modified graphene hollow spheres to obtain a material e; pressing, forming, cooling and solidifying the material e to obtain the glass brick with the magnetic adsorption effect; wherein the heating temperature of the quartz glass is 1600 ℃; the mass ratio of the modified graphene hollow spheres to the quartz glass is 1: 1.2; the cooling method adopts an air cooling method, and the refrigerating capacity is 770 kW.
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