CN113860748A - Ferrimagnetic foam glass-ceramic and preparation method thereof - Google Patents
Ferrimagnetic foam glass-ceramic and preparation method thereof Download PDFInfo
- Publication number
- CN113860748A CN113860748A CN202111304503.4A CN202111304503A CN113860748A CN 113860748 A CN113860748 A CN 113860748A CN 202111304503 A CN202111304503 A CN 202111304503A CN 113860748 A CN113860748 A CN 113860748A
- Authority
- CN
- China
- Prior art keywords
- ferrimagnetic
- glass
- foam glass
- forming agent
- powder
- 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.)
- Granted
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
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/007—Foam glass, e.g. obtained by incorporating a blowing agent and heating
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0081—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition having a magnetic crystal phase
Abstract
The invention relates to a ferrimagnetic foam glass ceramics and a preparation method thereof, the ferrimagnetic foam glass ceramics is prepared by mixing waste glass powder and a ferrimagnetic crystal forming agent uniformly and then carrying out one-step heat treatment crystallization foaming, the ferrimagnetic crystal forming agent is carbon powder and Fe2O3And (4) forming. And (3) carrying out reduction reaction on the carbon powder and the ferric oxide at the glass softening temperature to generate CO gas to form bubbles in the glass, and reducing the ferric oxide into a ferroferric oxide ferrimagnetic crystal. The ferrimagnetic foam glass ceramics provided by the invention is a novel porous glass functional material, and has double functions of a traditional foam glass heat-insulating material and a novel magnetic wave-absorbing material. The waste glass, the carbon powder and the ferric oxide are adopted as raw materials, the raw materials are easy to obtain, the cost is low, and the high added value recycling of the waste glass is realizedHas double meanings of environmental protection and economy.
Description
Technical Field
The invention relates to ferrimagnetic foam glass ceramics and a preparation method thereof, belonging to the technical field of foam glass production.
Background
Glass has been widely applied to daily life of people as a transparent, safe, pollution-free and high-strength green product, and is increasingly popular with people. Glass is a brittle material, and can be broken inevitably in the using process, so that the using function is lost. Meanwhile, when the glass is used as a packaging container, the glass packaging container loses the preservation value after the packaged articles are consumed. Therefore, most of the glass often loses its use value and becomes waste glass, and one of the characteristics of the glass product as a green product is its recyclability. In the currently implemented household garbage classification list, the first type of recyclable garbage is glass. The recycling of the glass products is of several types, such as a fusing agent for casting, transformation utilization, furnace returning reconstruction, raw material recycling, reutilization and the like. The transformation utilization is a recycling method capable of improving the added value of waste glass, and mainly comprises the steps of taking glass fragments as a doping material for paving a pavement to improve the reflection effect and the internal friction of the pavement; mixing the crushed glass with building materials to prepare building products such as building prefabricated parts, building bricks and the like; waste glass is utilized to manufacture building surface ornaments, reflecting plate materials, industrial art articles and ornaments for clothing; the waste glass is used for manufacturing foam glass and the like. Along with the higher and higher horizontal life of people, the requirements on living environment are higher and higher, such as heat preservation and insulation, low-carbon emission, sound insulation and noise reduction, electromagnetic protection and the like of buildings. Therefore, in the transformation and utilization process of waste glass, the development of the foam glass ceramics with high added value and high performance, which not only has the performance of the traditional foam glass, but also has the advanced electromagnetic function, is urgently needed.
For example, chinese patent document CN107721182A discloses a method for preparing foam glass, which uses graphite powder as a foaming agent, mixes with pretreated glass powder and then fires the mixture to obtain a foam glass product, uses waste glass in daily life as a raw material, cleans and dries the raw material, crushes and ball-mills the raw material into glass powder with a particle size of less than 300 microns, mixes the glass powder and a proper amount of graphite powder, ball-mills the mixture in a ball mill, passes through a 50-mesh sieve, shapes the mixture with a proper amount of mixture under a certain pressure, and then puts the mixture into a stainless steel mold coated with a release agent and fires the mixture under certain process conditions to obtain the foam glass product. US patent US2012176725A1 discloses a process for preparing foam microcrystal glass, which is prepared from borosilicate glass and CaCO3Or SrCO3The foam glass ceramics are prepared for the foaming agent. Chinese patent document CN201210368160.2 discloses a method for preparing foam glass, which is a method for preparing foam glass by using fly ash and waste glass as raw materials and through the processes of mixing, grinding, forming, foaming, annealing and the like. The above-disclosed documents all use waste glass as a main raw material and adopt a foaming agent to prepare foam glass, and the prepared foam glass is traditional heat-insulating material and does not have an electromagnetic protection function.
Chinese patent document CN 108503225A discloses electromagnetic shielding foam glass and a preparation method thereof, wherein magnesite, quartz sandstone, pyrophyllite, andalusite, diabase, cordierite, picrite, sodium metavanadate, sodium tetraborate, barium carbonate and composite metal oxide are used as raw materials, and the preparation process comprises the steps of raw material crushing and magnetic separation, low-temperature plasma treatment, melting, molding, annealing and the like. The method adopts various raw materials and complex process, and the prepared electromagnetic shielding foam glass has no magnetic wave absorbing function.
Chinese patent document CN 109020243B discloses a method for preparing microcrystalline foam glass from vanadium-titanium magnet tailings, which comprises the steps of performing acid washing treatment to obtain activated vanadium-titanium magnet tailings, mixing the activated vanadium-titanium magnet tailings with a calibration material, a cosolvent and a foaming agent, performing ball milling, performing compression molding in a cold press, and finally performing melting and crystallization heat treatment in a sintering furnace to obtain the microcrystalline foam glass material. The method needs hydrofluoric acid to carry out acid pickling treatment and other processes on the raw materials, so that environmental pollution can be caused, and the prepared microcrystalline foam glass is only a common heat-insulating material and does not have a magnetic wave-absorbing function.
As the demand for the magnetic function of the foam glass increases, the foam glass having the magnetic function is also widely studied. For example: chinese patent document CN108483928A discloses a method for preparing ferromagnetic foam glass ceramics by using ferromagnetic glass ceramics as main raw material and strontium carbonate as foaming agent, which comprises melting at 1450 ℃ to obtain molten glass, water quenching and grinding the molten glass to obtain ferromagnetic glass ceramics powder, and foaming at 1100 ℃ with strontium carbonate as foaming agent to obtain ferromagnetic foam glass ceramics. The method needs two steps of high temperature processes of melting and foaming, and particularly, the glass melting at 1450 ℃ needs a large amount of energy consumption. KR100877280B1 discloses a foam glass block absorbing electromagnetic waves and a method for manufacturing the same. However, the foam glass block still requires a glass melting step and a foaming step at a relatively high temperature, and has high energy consumption, complicated steps and complicated composition.
Therefore, the simplification of the process steps, the reduction of energy consumption, the preparation of the ferrimagnetic foam glass with simple components and excellent functions become problems to be solved urgently. The invention is therefore proposed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing ferrimagnetic foam glass ceramics by utilizing waste glass. The invention takes waste glass powder as main raw material, and adds proper amount of carbon powder (C) and ferric oxide (Fe)2O3) The formed ferrimagnetic crystal forming agent is prepared by adopting a one-step method for heat treatment crystallization foaming. Reducing carbon powder and ferric oxide at the softening temperature of glass to generate CO gas to form bubbles in the glass, and simultaneously, ferric oxide (Fe)2O3) Is reduced into ferroferric oxide (Fe)3O4) And (4) ferrimagnetic crystals, thereby preparing the ferrimagnetic foam glass ceramics.
The technical scheme of the invention is as follows:
the ferrimagnetic foam glass ceramics comprises the following raw materials:
70.0 to 99.0 percent of waste glass powder
1.0-30.0% of a ferrimagnetic crystal forming agent;
the ferrimagnetic crystal forming agent comprises the following raw materials:
1.0 to 5.0 percent of carbon powder (C)
Iron (Fe) oxide2O3) 95.0～99.0％。
According to the invention, preferably, the ferrimagnetic foam glass ceramics comprises the following raw materials:
80.0-97.0% of waste glass powder
3.0-20.0% of a ferrimagnetic crystal forming agent.
According to the invention, preferably, the ferrimagnetic foam glass ceramics comprises the following raw materials:
80.0-90.0% of waste glass powder
10.0-20.0% of a ferrimagnetic crystal forming agent.
According to the present invention, preferably, the ferrimagnetic crystal former comprises the following raw materials:
2.0 to 4.0 percent of carbon powder (C)
Iron (Fe) oxide2O3) 96.0～98.0％。
According to the invention, the crystal phase of the ferrimagnetic foam glass ceramics is preferably Fe3O4A ferrimagnetic crystal.
According to the invention, the density of the ferrimagnetic foam glass ceramics is preferably 0.3-0.8 g/cm3The specific saturation magnetic moment is 0.5-10.0 emu/g.
According to the invention, the preparation method of the ferrimagnetic foam glass ceramics comprises the following steps:
mixing and forming waste glass powder and a ferrimagnetic crystal forming agent, and then crystallizing and foaming at a glass softening temperature by a one-step method to obtain the material.
According to the present invention, the crystallization foaming temperature is preferably 890-950 ℃, more preferably 900-930 ℃, and most preferably 920 ℃.
According to the invention, the crystallization and foaming time is preferably 10 to 30min, more preferably 15 to 25 min.
According to the present invention, preferably, the crystallization foaming process is performed in a reducing atmosphere or an inert atmosphere, preferably in a nitrogen or rare gas atmosphere, and preferably in a carbon powder atmosphere.
According to the present invention, preferably, the devitrifying foaming conditions are as follows:
crystallization foaming temperature: 900 to 950 ℃,
crystallization foaming time: the time for which is 15 to 25min,
crystallization foaming environment: a reducing atmosphere or an inert atmosphere.
According to the invention, the preparation method of the ferrimagnetic foam glass ceramics comprises the following steps:
(1) crushing, grinding and drying the recovered waste glass to prepare waste glass powder with the granularity of 80-200 meshes;
(2) mixing carbon powder (C) with ferric oxide (Fe)2O3) Uniformly mixing the powder to prepare a ferrimagnetic crystal forming agent;
(3) and (3) mixing the waste glass powder obtained in the step (1) with the ferrimagnetic crystal forming agent obtained in the step (2), grinding and mixing, pressing and forming, performing heat treatment, crystallizing, foaming and cooling to obtain the ferrimagnetic foam glass ceramics.
According to the invention, preferably, the temperature for heat treatment crystallization foaming in the step (3) is 900-930 ℃ and the time is 10-25 minutes;
preferably, the heat treatment foaming process is performed in a reducing atmosphere or an inert atmosphere, and further preferably, the reducing atmosphere is obtained by covering sample carbon powder or the inert atmosphere is obtained by introducing a small amount of nitrogen.
According to the invention, the invention also provides a ferrimagnetic crystal forming agent for preparing the ferrimagnetic foam glass-ceramic by the one-step method, which comprises the following raw materials:
1.0 to 5.0 percent of carbon powder (C)
Iron (Fe) oxide2O3) 95.0～99.0％。
According to the present invention, preferably, the ferrimagnetic crystal former comprises the following raw materials:
2.0 to 4.0 percent of carbon powder (C)
Iron (Fe) oxide2O3) 96.0～98.0％。
The principle of the invention is as follows:
the invention takes waste glass powder as main raw material, and adds proper amount of carbon powder (C) and ferric oxide (Fe)2O3) The formed ferrimagnetic crystal forming agent is subjected to heat treatment crystallization foaming by a one-step method to prepare the ferrimagnetic foam glass ceramics. At the softening temperature of the glass, CO gas generated by the reduction reaction of the carbon powder and the ferric oxide forms bubbles in the glass, and the ferric oxide (Fe) is simultaneously generated2O3) Is reduced into ferroferric oxide (Fe)3O4) And (4) ferrimagnetic crystals, thereby preparing the ferrimagnetic foam glass ceramics.
At high temperature, the carbon powder and ferric oxide can have the following chemical reaction:
C+3Fe2O3＝CO+2Fe3O4 (1)
the mass ratio of the reactants according to the chemical reaction equation (1) was C2.44%, Fe2O397.56%, the reaction products are CO gas and Fe3O4The reaction mass ratio of the ferrimagnetic crystal in the proportion can prepare ferrimagnetic foam glass ceramics.
C+Fe2O3＝CO+2FeO (2)
Mass ratio of the reactant according to the chemical reaction equation (2) was C6.98%, Fe2O393.02 percent, the reaction products are CO gas and FeO nonmagnetic crystals, and the mass ratio of the reactants in the proportion can not prepare the ferrimagnetic foam glass ceramics.
13C+6Fe2O3＝9CO2+4Fe3C (3)
Mass ratio of reactant according to chemical reaction equation (3) is C13.98%, Fe2O386.02%, the reaction product is CO2Gas and Fe3C non-magnetic crystal, the reactant mass ratio of the proportion can not prepare the ferrimagnetic foam glass ceramics.
Therefore, the invention controls the content of carbon powder (C) in the ferrimagnetic crystal forming agent to be 1.0-5.0%, and ferric oxide (Fe)2O3) The content of the reaction product is 95.0-99.0%, and the reaction product is CO gas and Fe under the mixture ratio3O4FerrimagnetAnd (4) forming bubbles in the glass by using the crystal and CO gas, and finally forming the ferrimagnetic foam glass ceramics.
The waste glass used in the invention is a waste glass product recycled by society, carbon powder (C) and ferric oxide (Fe)2O3) Is a mineral raw material or a chemical raw material which is purchased in the market.
The preparation method of the invention is carried out according to the routine operation in the field if not specifically stated.
The technical difficulty of the invention is that:
selecting ferrimagnetic crystal forming agent, foaming gas is from carbon powder (C) and ferric oxide (Fe)2O3) Carbon monoxide (CO) gas produced by a chemical reaction is generated at a high temperature. At the same time, iron sesquioxide (Fe) is present during the foaming process2O3) Is reduced to ferroferric oxide (Fe)3O4) Ferrimagnetic crystals, thereby making the foam glass ferrimagnetic.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts waste glass to prepare the ferrimagnetic functional foam glass ceramics with high added value, and utilizes carbon powder (C) and ferric oxide (Fe)2O3) The foaming gas and the ferrimagnetic crystal are formed in situ by the reduction reaction at the glass softening temperature, so that the foaming and the magnetic crystal forming process are completed at the same time in one step.
2. The ferrimagnetic foam glass ceramics provided by the invention is a novel porous glass functional material, and has double functions of a traditional foam glass heat-insulating material and a novel magnetic wave-absorbing material.
3. The invention adopts the waste glass, the carbon powder and the ferric oxide as raw materials, has easily obtained raw materials and low cost, realizes the high added value recycling of the waste glass, and has double meanings of environmental protection and economy.
4. The invention does not need the preheating process, and the sample formed at room temperature is directly put into a high-temperature furnace with the temperature of 890-950 ℃ for crystallization foaming, and the one-step heat treatment is completed, thereby saving energy and reducing carbon emission.
Drawings
FIG. 1 is a picture of a sample of ferrimagnetic foam glass ceramics obtained in examples 1-2 of the present invention.
Fig. 2 is SEM images of the ferrimagnetic foam glass ceramics prepared in example 1 of the present invention at different magnifications.
Fig. 3 is an XRD chart of the ferrimagnetic foam glass-ceramics obtained in example 1-2 of the present invention.
Fig. 4 shows the hysteresis loops of the ferrimagnetic foam glass-ceramics obtained in examples 1 to 4 of the present invention.
Detailed Description
The present invention will be further described with reference to the following detailed description of embodiments thereof, but not limited thereto, in conjunction with the accompanying drawings.
In the embodiment, the waste glass is recycled waste glass, the carbon powder is processed by anthracite, and the ferric oxide is a commercially available chemical raw material.
Example 1
The ferrimagnetic foamed glass-ceramic has waste glass powder content of 85% and ferrimagnetic crystal forming agent content of 15%. According to the preparation of 10kg, the waste glass powder and the ferrimagnetic crystal forming agent are mixed according to the following mass ratio:
waste glass powder 8.5kg
1.5kg of ferrimagnetic crystal former.
The content of carbon powder (C) in the ferrimagnetic crystal forming agent is 3 percent, and ferric oxide (Fe)2O3) The content was 97%. The ferrimagnetic crystal forming agent is calculated according to the weight percentage of 10kg prepared by the following steps:
0.3kg of carbon powder (C)
Iron (Fe) oxide2O3) 9.7kg。
The preparation steps are as follows:
the recycled waste glass is crushed and ground into powder with a particle size of less than 80 meshes, and the carbon powder and ferric oxide are uniformly mixed according to the mass ratio to prepare the ferrimagnetic crystal forming agent. Weighing 8.5kg of waste glass powder and 1.5kg of ferrimagnetic crystal forming agent, uniformly mixing, directly putting the sample into a high-temperature furnace at 920 ℃ after press forming, and carrying out crystallization and foaming for 20 minutes in a reducing atmosphere to obtain the ferrimagnetic foam glass ceramics.
The ferrimagnetic foam glass ceramics sample prepared in this example is shown in fig. 1 (a). As shown in fig. 1(a), the ferrimagnetic foam glass ceramics prepared in this example contains a large amount of uniformly distributed pores, and is black in color. The reason why the sample appeared black was iron oxide (Fe)2O3) Reduced to black iron oxide (Fe)3O4) A ferrimagnetic crystal.
The shapes of scanning electron microscopes with different magnifications of the ferrimagnetic foam glass ceramics prepared by the embodiment are shown in fig. 2. As can be seen from fig. 2(a), the maximum diameter of the pores in the ferrimagnetic foam glass ceramics prepared in this example is about 400 μm; as shown in FIG. 2(b), Fe having a size of about 5 μm is distributed on the inner surface of the pores of the foam glass3O4And (4) crystals.
The XRD pattern of the ferrimagnetic foam glass ceramics obtained in this example is shown in fig. 3 (a). As can be seen from FIG. 3(a), the crystal phase of the ferrimagnetic foam glass ceramics obtained in this example (foaming at 920 ℃ for 20min) is Fe3O4A magnetic crystal.
The hysteresis loop of the ferrimagnetic foam glass ceramics prepared in this example is shown in fig. 4, and the content of the ferrimagnetic crystal forming agent is 15%. As can be seen from FIG. 4, the specific saturation magnetic moment of the ferrimagnetic foamed glass-ceramics obtained in this example (foaming at 920 ℃ C. for 20min) is about 3.3 A.m2/kg。
Example 2
The ferrimagnetic foamed glass-ceramic has waste glass powder content of 90% and ferrimagnetic crystal forming agent content of 10%. According to the preparation of 10kg, the waste glass powder and the ferrimagnetic crystal forming agent are mixed according to the following mass ratio:
9.0kg of waste glass powder
Ferrimagnetic Crystal-Forming agent 1.0kg
The content of carbon powder (C) in the ferrimagnetic crystal forming agent is 3 percent, and ferric oxide (Fe)2O3) The content was 97%. The ferrimagnetic crystal forming agent was as follows, in terms of 10kg of preparationThe mass percentage is as follows:
0.3kg of carbon powder (C)
Iron (Fe) oxide2O3) 9.7kg。
The preparation steps are as follows:
the recycled waste glass is crushed and ground into powder with a particle size of less than 80 meshes, and the carbon powder and ferric oxide are uniformly mixed according to the mass ratio to prepare the ferrimagnetic crystal forming agent. Weighing 9.0kg of waste glass powder and 1.0kg of ferrimagnetic crystal forming agent, uniformly mixing, directly putting the sample into a high-temperature furnace at 920 ℃ after press forming, and carrying out crystallization and foaming for 20 minutes in a reducing atmosphere to obtain the ferrimagnetic foam glass ceramics.
The ferrimagnetic foam glass ceramics sample prepared in this example is shown in fig. 1 (b). As can be seen from fig. 1(b), the ferrimagnetic foam glass ceramics prepared in this example contains a large amount of uniformly distributed pores, and is black in color. The reason why the sample appeared black was iron oxide (Fe)2O3) Reduced to black iron oxide (Fe)3O4) A ferrimagnetic crystal.
The XRD pattern of the ferrimagnetic foam glass ceramics obtained in this example is shown in fig. 3 (b). As can be seen from FIG. 3(b), the crystal phase of the ferrimagnetic foam glass ceramics obtained in this example (foaming at 920 ℃ for 20min) is Fe3O4A magnetic crystal.
The hysteresis loop of the ferrimagnetic foam glass ceramics prepared in this example is shown in fig. 4, and the content of the ferrimagnetic crystal forming agent is 10%. As can be seen from FIG. 4, the specific saturation magnetic moment of the ferrimagnetic foamed glass-ceramics obtained in this example (foaming at 920 ℃ C. for 20min) is about 1.9 A.m2/kg。
Example 3
The ferrimagnetic foam glass ceramics has waste glass powder content of 95% and ferrimagnetic crystal forming agent content of 5%. According to the preparation of 10kg, the waste glass powder and the ferrimagnetic crystal forming agent are mixed according to the following mass ratio:
9.5kg of waste glass powder
Ferrimagnetic Crystal-Forming agent 0.5kg
The content of carbon powder (C) in the ferrimagnetic crystal forming agent is 3 percent, and ferric oxide (Fe)2O3) The content was 97%. The ferrimagnetic crystal forming agent is calculated according to the weight percentage of 10kg prepared by the following steps:
0.3kg of carbon powder (C)
Iron (Fe) oxide2O3) 9.7kg。
The preparation steps are the same as example 1, the hysteresis loop of the ferrimagnetic foam glass ceramics prepared by the present example is shown in fig. 4, and the content of the ferrimagnetic crystal forming agent is 5%. As can be seen from FIG. 4, the specific saturation magnetic moment of the ferrimagnetic foamed glass-ceramics obtained in this example (crystallization foaming at 920 ℃ C. for 20min) is about 0.3 A.m2/kg。
Example 4
The ferrimagnetic foamed glass-ceramic has waste glass powder content of 80% and ferrimagnetic crystal forming agent content of 20%. According to the preparation of 10kg, the waste glass powder and the ferrimagnetic crystal forming agent are mixed according to the following mass ratio:
waste glass powder 8.0kg
Ferrimagnetic Crystal-Forming agent 2.0kg
The content of carbon powder (C) in the ferrimagnetic crystal forming agent is 3 percent, and ferric oxide (Fe)2O3) The content was 97%. The ferrimagnetic crystal forming agent is calculated according to the weight percentage of 10kg prepared by the following steps:
0.3kg of carbon powder (C)
Iron (Fe) oxide2O3) 9.7kg。
The preparation steps are the same as example 1, the hysteresis loop of the ferrimagnetic foam glass ceramics prepared by the present example is shown in fig. 4, and the content of the ferrimagnetic crystal forming agent is 20%. As can be seen from FIG. 4, the specific saturation magnetic moment of the ferrimagnetic foamed glass-ceramics obtained in this example (crystallization foaming at 920 ℃ C. for 20min) is about 4.9 A.m2/kg。
Example 5
As described in example 1, except that:
in the preparation steps, the crystallization foaming temperature is 900 ℃, and the heat preservation time is 10 minutes.
Example 6
As described in example 1, except that:
in the preparation steps, the crystallization foaming temperature is 910 ℃, and the heat preservation time is 30 minutes.
Example 7
As described in example 1, except that:
in the preparation steps, the crystallization foaming temperature is 900 ℃, and the heat preservation time is 25 minutes.
Example 8
As described in example 1, except that:
in the preparation steps, the crystallization foaming temperature is 940 ℃, and the heat preservation time is 20 minutes.
Example 9
As described in example 1, except that:
in the preparation step, the content of carbon powder (C) in the ferrimagnetic crystal forming agent is 2 percent, and ferric oxide (Fe)2O3) The content was 98%. The ferrimagnetic crystal forming agent is calculated according to the weight percentage of 10kg prepared by the following steps:
0.2kg of carbon powder (C)
Iron (Fe) oxide2O3) 9.8kg。
Example 10
As described in example 1, except that:
in the preparation step, the content of carbon powder (C) in the ferrimagnetic crystal forming agent is 4 percent, and ferric oxide (Fe)2O3) The content is 96%. The ferrimagnetic crystal forming agent is calculated according to the weight percentage of 10kg prepared by the following steps:
0.4kg of carbon powder (C)
Iron (Fe) oxide2O3) 9.6kg。
Example 11
As described in example 1, except that:
in the preparation step, the content of carbon powder (C) in the ferrimagnetic crystal forming agent is1% of ferric oxide (Fe)2O3) The content is 99%. The ferrimagnetic crystal forming agent is calculated according to the weight percentage of 10kg prepared by the following steps:
0.1kg of carbon powder (C)
Iron (Fe) oxide2O3) 9.9kg。
Example 12
As described in example 1, except that:
in the preparation step, the content of carbon powder (C) in the ferrimagnetic crystal forming agent is 5 percent, and ferric oxide (Fe)2O3) The content was 95%. The ferrimagnetic crystal forming agent is calculated according to the weight percentage of 10kg prepared by the following steps:
0.5kg of carbon powder (C)
Iron (Fe) oxide2O3) 9.5kg。
Comparative example 1
As described in example 1, except that the foam was devitrified at 920 ℃ for 5 min. Because the crystal generated in short foaming time is ferrous oxide (FeO) without ferrimagnetism, and ferroferric oxide (Fe) is not generated3O4) Ferrimagnetic crystal, as shown in fig. 3 (a). Although foam glass can be obtained, the foam glass has no magnetism, so that ferrimagnetic foam glass ceramics cannot be obtained.
Comparative example 2
As described in example 1, except that the glass was devitrified and foamed at 870 ℃ for 20 minutes, the foam glass could not be obtained because the glass did not soften and could not be foamed at that temperature.
Comparative example 3
As described in example 1, except that the glass was devitrified and foamed at 1060 ℃ for 20 minutes, the gas formed was rapidly discharged due to the flattening of the glass melt at the temperature, and no bubble was present in the glass, so that a foam glass could not be obtained.
Comparative example 4
As described in example 2, except that the mass percentage of the carbon powder (C) in the foaming gas and the ferrimagnetic crystal former was 7%, the carbon powder was highly reactive with iron oxide (Fe)2O3) FeO is completely generated in the reaction, and ferroferric oxide (Fe) cannot be formed3O4) A ferrimagnetic crystal.
Comparative example 5
As described in example 2, except that the mass percentage of the carbon powder (C) in the foaming gas and the ferrimagnetic crystal former is 15%, the carbon powder content is high and the iron oxide (Fe) is high2O3) React to generate Fe3C, inability to form iron oxide (Fe)3O4) A ferrimagnetic crystal.
Comparative example 6
As described in example 2, except that the waste glass powder was 60% by mass and the ferrimagnetic crystal former was 40% by mass, the sample could not be softened due to the decrease in the content of the waste glass powder, and the foam glass could not be produced.
Claims (10)
1. The ferrimagnetic foam glass ceramics is characterized by comprising the following raw materials:
70.0 to 99.0 percent of waste glass powder
1.0-30.0% of a ferrimagnetic crystal forming agent;
the ferrimagnetic crystal forming agent comprises the following raw materials:
1.0 to 5.0 percent of carbon powder (C)
Iron (Fe) oxide2O3) 95.0～99.0％。
2. The ferrimagnetic foam glass-ceramic according to claim 1, wherein the ferrimagnetic foam glass-ceramic comprises the following raw materials:
80.0-97.0% of waste glass powder
3.0-20.0% of a ferrimagnetic crystal forming agent.
3. The ferrimagnetic foam glass-ceramic according to claim 1, wherein the ferrimagnetic foam glass-ceramic comprises the following raw materials:
80.0-90.0% of waste glass powder
10.0-20.0% of a ferrimagnetic crystal forming agent.
4. The ferrimagnetic foam glass-ceramic according to claim 1, wherein the ferrimagnetic crystal former comprises the following raw materials:
2.0 to 4.0 percent of carbon powder (C)
Iron (Fe) oxide2O3) 96.0～98.0％。
5. The ferrimagnetic foam glass-ceramic as claimed in claim 1, wherein the crystal phase of the ferrimagnetic foam glass-ceramic is Fe3O4A ferrimagnetic crystal.
6. The ferrimagnetic foam glass-ceramic according to claim 1, wherein the density of the ferrimagnetic foam glass-ceramic is 0.3-0.8 g/cm3The specific saturation magnetic moment is 0.5-10.0 emu/g.
7. The preparation method of the ferrimagnetic foam glass-ceramic as claimed in claim 1, comprising the steps of:
mixing the waste glass powder and the ferrimagnetic crystal forming agent, and crystallizing and foaming at the glass softening temperature by a one-step method to obtain the material.
8. The method for preparing the ferrimagnetic foam glass-ceramic according to claim 7, wherein the crystallization foaming temperature is 890-950 ℃, preferably 900-930 ℃.
9. The preparation method of the ferrimagnetic foam glass-ceramic according to claim 7, characterized in that the devitrification foaming time is 10-30min, preferably 15-25 min.
10. A ferrimagnetic crystal forming agent for preparing ferrimagnetic foam glass-ceramic by a one-step method comprises the following raw materials:
1.0 to 5.0 percent of carbon powder (C)
Iron (Fe) oxide2O3) 95.0～99.0％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111304503.4A CN113860748B (en) | 2021-11-05 | 2021-11-05 | Ferrimagnetic foam microcrystalline glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111304503.4A CN113860748B (en) | 2021-11-05 | 2021-11-05 | Ferrimagnetic foam microcrystalline glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113860748A true CN113860748A (en) | 2021-12-31 |
| CN113860748B CN113860748B (en) | 2023-06-09 |
Family
ID=78987253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111304503.4A Active CN113860748B (en) | 2021-11-05 | 2021-11-05 | Ferrimagnetic foam microcrystalline glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113860748B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB959406A (en) * | 1960-08-24 | 1964-06-03 | Siemens Ag | Improvements in or relating to ferromagnetic materials and processes for producing the same |
| WO2012020017A1 (en) * | 2010-08-12 | 2012-02-16 | Dennert Poraver Gmbh | Process for producing magnetic granular expanded glass and granular expanded glass produced thereby |
| RU2540754C1 (en) * | 2013-12-05 | 2015-02-10 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт химии силикатов им. И.В. Гребенщикова Российской академии наук (ИХС РАН) | Method of producing high-silica porous glass with magnetic properties |
| EP2966044A1 (en) * | 2014-07-07 | 2016-01-13 | A/S Graasten Teglværk | A method to produce foam glasses |
| CN107586040A (en) * | 2017-09-11 | 2018-01-16 | 河南科技大学 | A kind of preparation method of high heat production than magnetic bioactive glass-ceramics |
| JP2018162177A (en) * | 2017-03-24 | 2018-10-18 | 新日鉄住金化学株式会社 | Porous carbon material, and method of producing the same |
-
2021
- 2021-11-05 CN CN202111304503.4A patent/CN113860748B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB959406A (en) * | 1960-08-24 | 1964-06-03 | Siemens Ag | Improvements in or relating to ferromagnetic materials and processes for producing the same |
| WO2012020017A1 (en) * | 2010-08-12 | 2012-02-16 | Dennert Poraver Gmbh | Process for producing magnetic granular expanded glass and granular expanded glass produced thereby |
| RU2540754C1 (en) * | 2013-12-05 | 2015-02-10 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт химии силикатов им. И.В. Гребенщикова Российской академии наук (ИХС РАН) | Method of producing high-silica porous glass with magnetic properties |
| EP2966044A1 (en) * | 2014-07-07 | 2016-01-13 | A/S Graasten Teglværk | A method to produce foam glasses |
| JP2018162177A (en) * | 2017-03-24 | 2018-10-18 | 新日鉄住金化学株式会社 | Porous carbon material, and method of producing the same |
| CN107586040A (en) * | 2017-09-11 | 2018-01-16 | 河南科技大学 | A kind of preparation method of high heat production than magnetic bioactive glass-ceramics |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113860748B (en) | 2023-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shang et al. | Production of glass-ceramics from metallurgical slags | |
| CN100551857C (en) | Utilize iron ore tailings to prepare the method for porose glass composite material | |
| Meng et al. | The recycling of leaded glass in cathode ray tube (CRT) | |
| CN103602804B (en) | A kind of high performance pellet binder | |
| CN102515553A (en) | Method for producing microcrystalline foam thermal-insulation sheet material through utilizing industrial lithium tailings | |
| CN104891815B (en) | A kind of method that utilization high-temperature liquid state metallurgical cinder prepares foam glass | |
| CN110316984B (en) | Composite alkali-excited solid waste type high-shearing-force high-temperature-resistant inorganic adhesive and preparation method thereof | |
| CN104513898A (en) | High-reducibility pellet and preparation method thereof | |
| WO2011057537A1 (en) | Composition used to produce igneous rock crystal glass material, igneous rock crystal glass material and production method thereof | |
| CN110330242B (en) | Composite alkali-activated solid waste type high-performance inorganic adhesive and preparation method thereof | |
| CN103710536A (en) | Preparation method of pellet binder with high performance | |
| CN102633426A (en) | Method for producing microcrystal foam heat-insulation plate by aid of industrial red mud | |
| CN1329328C (en) | Method for preparing micro crystal glass plate for building using waste glass | |
| CN113860748A (en) | Ferrimagnetic foam glass-ceramic and preparation method thereof | |
| CN103332853B (en) | A kind of method of temperature production foam glass product | |
| CN108483928A (en) | A kind of ferromagnetism foam pyroceram and the preparation method and application thereof | |
| CN114763582A (en) | Method for producing magnesium pellets by using oriented silicon steel magnesium oxide waste | |
| CN109320089B (en) | Functional microcrystalline glass using asbestos tailings as raw material | |
| CN111377615A (en) | Basalt ferromagnetic glass fiber and preparation method and application thereof | |
| CN116002998A (en) | Method for preparing composite mineral admixture from water quenched converter slag | |
| CN103482874B (en) | Utilize the method for cullet low-firing crystallizing glass sheet material | |
| CN103332860A (en) | Method for manufacturing glass ceramic plate used for architectural decoration by utilizing coal gangue | |
| CN110204312A (en) | A kind of preparation method of ferronickel dregs porcelain granule | |
| CN103667683B (en) | Compound flux of high-MgO sinter ore, and preparation method and application of the compound flux | |
| CN102557454A (en) | Method for producing microcrystalline foamed heat-insulation board with dolomite |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |