CN108101531B - Composite spinel material with high infrared emissivity and preparation method thereof - Google Patents
Composite spinel material with high infrared emissivity and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of spinel infrared radiation materials, and discloses a composite spinel material with high infrared emissivity and a preparation method thereof. The method comprises the following steps: (1) dispersing magnesium nitrate, aluminum nitrate and spherical graphite in water, adjusting the pH value to 3-4, adding ethyl orthosilicate, heating and stirring, dripping strong base solution until gel is formed, drying, and performing microwave treatment to obtain primary coated powder; (2) dissolving ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate in water to obtain a mixed solution; dispersing the primary coating powder in water to obtain a dispersion liquid; (3) and uniformly mixing the mixed solution and the dispersion liquid, adding a precipitator, adjusting the pH value to 9-10, filtering, heating the solid by microwave, and performing heat preservation treatment to obtain the composite spinel material. The composite spinel material has a cavity structure, is high in infrared emissivity and is beneficial to spraying; the raw materials are simple and easy to obtain, the cost is low, the preparation process is simple and efficient, and the energy consumption is low.
Description
Technical Field
The invention belongs to the technical field of spinel infrared radiation material preparation, and particularly relates to a composite spinel material with high infrared emissivity and a preparation method thereof.
Background
The infrared radiation material includes low infrared emissivity material, selective infrared radiation material and high efficiency infrared radiation material, including TiO2、SiO2ZnO, cordierite, SiC, transition metal oxide composite materials and the like can be used as infrared radiation materials and are widely applied to the fields of heat insulation materials, stealth materials, heat insulation materials, energy conservation and environmental protection.
At present, spinel infrared radiation materials are synthesized under the traditional process condition, the materials usually need to act for a long time under the high-temperature condition, so that the resources are greatly consumed, toxic and harmful substances or gas are generated in the process, the environment is polluted, the preparation process is complex, the flow is complex, and the prepared materials are usually uneven in component distribution and poor in quality due to the fact that the temperature rise process is uneven. In order to solve the problems, it is necessary to find a simple and efficient synthetic preparation method.
The invention provides a preparation method of a composite spinel material with high infrared emissivity, which utilizes microwave radiation to quickly apply some metal oxides to higher temperature, integrally heats the material, and accelerates the reaction rate of the composite spinel phase, thereby greatly reducing the synthesis temperature and synthesis time of the composite spinel material, improving the uniformity of the prepared material, and preparing the cavity-shaped spinel by designing a spinel macroscopic structure, thereby effectively improving the infrared emissivity.
Disclosure of Invention
In view of the defects of the existing process for preparing the composite spinel material, the invention aims to provide a method for preparing the composite spinel material with high infrared emissivity.
The invention also aims to provide the composite spinel material with high infrared emissivity, which is obtained by the preparation method.
The invention further aims to provide application of the composite spinel material with high infrared emissivity.
The composite spinel material is used for preparing an infrared radiation coating, in particular to an inorganic coating with high infrared emissivity, and the coating is coated on the inner wall of an industrial kiln, so that the energy-saving effect is achieved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a composite spinel material with high infrared emissivity comprises the following steps:
(1) dispersing magnesium nitrate, aluminum nitrate and spherical graphite in water, adjusting the pH value to 3-4, adding ethyl orthosilicate, heating and stirring, dripping strong base solution until gel is formed, drying, and performing microwave treatment to obtain primary coated powder;
(2) dissolving ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate in water to obtain a mixed solution; dispersing the primary coating powder in water to obtain a dispersion liquid;
(3) and uniformly mixing the mixed solution and the dispersion liquid, adding a precipitator, adjusting the pH value to 9-10, filtering, heating the solid to 800-1000 ℃ by microwave, and carrying out heat preservation treatment to obtain the composite spinel material.
In the step (1), the molar ratio of the magnesium nitrate to the aluminum nitrate to the ethyl orthosilicate is (1-2) to (2-3) to (4-6); the mass ratio of the magnesium nitrate to the spherical graphite is (2-3): (1-2);
completely dissolving the water in the step (1) by using magnesium nitrate and aluminum nitrate;
the substance for adjusting the pH in the step (1) is ammonia water, and the pH in the step (1) is preferably 3;
the heating and stirring temperature in the step (1) is 60-90 ℃, and the heating and stirring time is 30-60 min;
the pH adjustment in the step (1) is carried out at the temperature of 60-90 ℃; stirring for 30-60 min after adjusting the pH; the drying temperature in the step (1) is 60-100 ℃, and the drying time is 3-4 h;
the microwave treatment in the step (1) is microwave heating to 400-600 ℃, and then heat preservation treatment is carried out. The time of the heat preservation treatment is 5-15 min.
And (3) adding ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate into water, and stirring and dissolving at 60-70 ℃ to obtain the mixed solution in the step (2).
The dispersion in the step (2) is ultrasonic dispersion, and the dispersion time is 10-15 min; the mass volume ratio of the primary coating powder to water in the dispersion liquid is (10-15) g (30-50) ml.
The mass ratio of the ferric nitrate in the mixed solution to the primary coating powder in the dispersion liquid in the step (3) is 10: (1-8).
In the step (3), the precipitator is ammonium oxalate, and the ammonium oxalate is added in the form of solution, wherein the concentration of the ammonium oxalate is 0.05-0.1 mol/L; and (4) the substance for adjusting the pH value in the step (3) is ammonia water.
The strong alkali solution in the step (1) is NaOH solution; the concentration of the strong alkali solution is 0.1-0.2 mol/L.
The molar ratio of the ferric nitrate, the manganese nitrate, the cobalt nitrate and the copper nitrate in the step (2) is (2-6): (6-2): 1-2.
In the step (3), the molar ratio of the precipitator to the manganese nitrate is 2: 1.
And (4) keeping the temperature for 10-50 min in the step (3).
The composite spinel material is prepared by the method. The composite spinel material is applied to infrared radiation coatings.
The composite spinel material has higher infrared emissivity, and can reflect more heat under the same condition, thereby achieving the effect of energy conservation.
The principle of the invention is that the wave-absorbing characteristic of the spherical graphite is utilized, the precursor of the required composite spinel material is attached to the surface of the spherical graphite through precipitation, and the spherical graphite inside is oxidized under the action of microwave, so that a cavity structure is formed, and the infrared emissivity of the cavity structure is enhanced. The magnesium-aluminum in the composite spinel material is used as the intermediate layer to ensure that magnesium-aluminum reacts to form a magnesium-aluminum cordierite phase, and then the magnesium-aluminum cordierite phase is used as a wave-absorbing heating carrier to form a spinel phase with iron and manganese; meanwhile, the magnesium-aluminum cordierite is not easy to react with the graphite.
The beneficial effects of the invention compared with the prior art comprise:
1. the composite spinel material with high infrared emissivity is unique in structure, is a secondary coating body with a cavity structure, and has an infrared all-band emissivity of 0.92; the composite spinel material of the invention is nano-scale in size, and is easy to disperse in a solvent, thereby being beneficial to spraying.
2. The invention adopts cheap raw materials and takes the spherical graphite with low cost as the coating body, thereby having lower synthesis temperature and less energy consumption; the spherical graphene is used as a cladding body and also used as a main carrier for absorbing waves and raising temperature.
3. The preparation method is simple and efficient, consumes less energy and is suitable for industrial production.
Drawings
FIG. 1 is an SEM image of spheroidal graphite;
FIG. 2 is an SEM image of the composite spinel material prepared in example 2 (i.e., spinel secondary-coated spheroidal graphite, composite spinel material F4 incubated at 900 ℃ for 20 min); wherein a: a composite spinel material, namely a spinel secondary cladding spherical graphite pattern; b is a partial enlarged view of a picture a; c, d is a partial enlarged view of the b picture;
FIG. 3 is an XRD pattern of the primary coated powder, composite spinel material prepared in example 2; wherein a is an XRD pattern of the primary coating powder; b is an XRD pattern of the composite spinel material F1 (microwave 900 ℃ without heat preservation); c is an XRD pattern of the composite spinel material F2 (microwave 900 ℃ temperature is kept for 10 min); d is an XRD pattern of the composite spinel material F3 (microwave 900 ℃ and heat preservation for 15 min); f is an XRD pattern of the composite spinel material F4 (microwave 900 ℃ and heat preservation for 20 min);
FIG. 4 is a graph of the IR emissivity of the composite spinel material prepared in example 2 (composite spinel material F4 microwave insulated at 900 ℃ for 20 min); the sol coating-sol preparation of the composite spinel material, the gel coating-gel preparation of the composite spinel material, the sol coating crushing and the gel coating crushing refer to the crushing treatment of the composite material prepared by the sol coating preparation and the gel coating preparation.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Spherical graphite is selected as a wave-absorbing heating carrier, a magnesium aluminum cordierite composite membrane reporting layer is synthesized on the surface of the wave-absorbing heating carrier, a spinel phase coating layer is coated on the carrier coated with the magnesium aluminum cordierite composite membrane through microwave action, and the spherical graphite is oxidized through the microwave high-temperature action to form a cavity; the surfaces of the particles in the composite spinel material prepared by the method are rough surfaces. The SEM image of the spheroidal graphite is shown in fig. 1.
Example 1
(1) Mixing magnesium nitrate and aluminum nitrate according to a molar ratio of 1:2, adding the mixture and spherical graphite (the mass ratio of the magnesium nitrate to the spherical graphite is 2: 1) into deionized water (the deionized water is obtained by completely dissolving the aluminum nitrate and the magnesium nitrate, for example, the dosage relationship of the magnesium nitrate and the deionized water is 1g:20mL), and stirring in a water bath at 60 ℃ for 30 min; adjusting pH to 3 with ammonia water (pH of the original mixed solution is less than 3) in water bath at 80 deg.C, and stirring for 30 min; adding tetraethoxysilane (the molar ratio of tetraethoxysilane to magnesium nitrate is 5:1), stirring in a 90 ℃ water bath for 1h, slowly dropping 0.1mol/L NaOH solution until gel is formed, drying at 80 ℃ for 3h, placing in a microwave oven (the microwave power is 20KW, the frequency is 2450 +/-50 MHz), heating to 500 ℃, and preserving heat for 10min to obtain primary coating powder; the stirring speed is 800 rpm;
(2) adding ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate into deionized water (the dosage of the deionized water is based on the complete dissolution of all substances, and the dosage relationship of the ferric nitrate and the deionized water is 1g:50mL) according to the molar ratio of 6:2:1:1, and stirring in a water bath at 60 ℃ for 30min to obtain a solution A;
(3) adding deionized water into the primary coated powder (the energy consumption ratio of the primary coated powder to the deionized water is 10 g: 40mL), and dispersing for 10min by ultrasonic (the ultrasonic power is 100W, and the frequency is 53KHz) to obtain a solution B; the mass ratio of the primary coated powder in the solution B to the ferric nitrate in the solution A is 1: 10;
(4) adding the solution A into the solution B, uniformly stirring (1500rpm), adding an ammonium oxalate solution (the concentration of the ammonium oxalate solution is 0.05mol/L, the molar ratio of manganese nitrate to ammonium oxalate is 1: 2), adjusting the pH to 9-10 by using ammonia water, stirring for 1h at 1500rpm, filtering, putting the filtered solid into a microwave oven (the microwave power is 20kW, and the frequency is 2450 +/-50 MHz), heating to 900 ℃, and preserving heat for 20min to obtain the composite spinel material.
The infrared all-band emissivity of the composite spinel material prepared by the embodiment is 0.903.
Example 2
(1) Mixing magnesium nitrate and aluminum nitrate according to a molar ratio of 1:2, adding the mixture and spherical graphite (the mass ratio of the magnesium nitrate to the spherical graphite is 3: 1) into deionized water (the deionized water is obtained by completely dissolving the aluminum nitrate and the magnesium nitrate, for example, the dosage relationship of the magnesium nitrate and the deionized water is 1g:20mL), and stirring in a 70 ℃ water bath for 30 min; adjusting pH to 3 with ammonia water (pH of the original mixed solution is less than 3) in water bath at 80 deg.C, and stirring for 30 min; adding tetraethoxysilane (the molar ratio of tetraethoxysilane to magnesium nitrate is 5:1), stirring in a 90 ℃ water bath for 1h, slowly dropping 0.15mol/L NaOH solution until gel is formed, drying at 100 ℃ for 3h, placing in a microwave oven (the microwave power is 20KW, the frequency is 2450 +/-50 MHz), heating to 500 ℃, and preserving heat for 10min to obtain primary coating powder; the stirring speed is 800 rpm;
(2) adding ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate into deionized water (the dosage of the deionized water is based on the complete dissolution of all substances, and the dosage relationship of the ferric nitrate and the deionized water is 1g:50mL) according to the molar ratio of 6:2:1:1, and stirring in a 70 ℃ water bath for 30min to obtain a solution A;
(3) adding deionized water into the primary coated powder (the energy consumption ratio of the primary coated powder to the deionized water is 10 g: 40mL), and dispersing for 10min by ultrasonic (the ultrasonic power is 100W, and the frequency is 53KHz) to obtain a solution B; the mass ratio of the primary coated powder in the solution B to the ferric nitrate in the solution A is 3: 10;
(4) adding the solution A into the solution B, uniformly stirring (1000rpm), adding an ammonium oxalate solution (the concentration of the ammonium oxalate solution is 0.05mol/L, the molar ratio of manganese nitrate to ammonium oxalate is 1: 2), adjusting the pH to 9-10 by using ammonia water, stirring for 1h at 1500rpm, filtering, putting the filtered solid into a microwave oven (the microwave power is 20kW, and the frequency is 2450 +/-50 MHz), heating to 900 ℃, and respectively carrying out the following treatments: and (4) keeping the temperature for 10min without heat preservation, keeping the temperature for 15min, and keeping the temperature for 20min to respectively obtain the composite spinel materials F1 (without heat preservation), F2 (with heat preservation for 10min), F3 (with heat preservation for 15min), and F4 (with heat preservation for 20 min).
The infrared all-band emissivity of the composite spinel material prepared by the embodiment is 0.924.
FIG. 2 is an SEM image of the composite spinel material prepared in example 2 (i.e., spinel secondary-coated spheroidal graphite, composite spinel material F4 incubated at 900 ℃ for 20 min); wherein a: a composite spinel material, namely a spinel secondary cladding spherical graphite pattern; b is a partial enlarged view of a picture a; c and d are partial enlarged views of the b picture. From the graph a of FIG. 2, it can be seen that the particle size of the powder sample is greatly increased relative to that of graphite, and some particles reach 100 μm, and in the enlarged graph b, it can be seen that the surface layer of the particles is coated with a layer of coarse particles, and some small particles are attached near the large particles, and the particles can be better coated. Of course, in the further enlargement of c, d, it was found that in some local areas there was an incomplete coating, in the c-picture there appeared to be a damage from which it was clearly seen that a single layer of granular spinel grains was present in the form of spherical 5SiO2-2Al2O3-2MgO composite membrane surface layer. From the d-diagram, it can be seen that a small ball is partially exposed and in a completely uncoated stateIt is not caused by external force damage, because no fracture is found at the place where the small ball is linked with the large granule, but a layer of spinel can be seen to have an upward climbing coating state at the contact place. The phenomenon is that some small balls are formed before secondary coating is carried out, spherical graphite is not coated in the small balls, when secondary coating experiments are carried out, the wave absorbing and temperature rising performances of the carriers without coating the spherical graphite are poor, and the small balls cannot stimulate the absorption and synthesis of spinel on the surface of the carriers.
FIG. 3 is an XRD pattern of the primary coated powder, composite spinel material prepared in example 2; wherein a is an XRD pattern of the primary coating powder; b is an XRD pattern of the composite spinel material F1 (microwave 900 ℃ without heat preservation); c is an XRD pattern of the composite spinel material F2 (microwave 900 ℃ temperature is kept for 10 min); d is an XRD pattern of the composite spinel material F3 (microwave 900 ℃ and heat preservation for 15 min); f is the XRD pattern of the composite spinel material F4 (microwave 900 ℃ temperature is kept for 20 min). In the graph a of FIG. 3, only the graphite peak is observed, and no other hetero peak is observed, but in the graph a, an amorphous peak is observed at a 2 θ of 20 to 30 degrees, which indicates that the first layer 5SiO2-2Al2O3The MgO coating is present in the state of an amorphous material. In the b diagram, besides the graphite peak, Co is present3Fe7And spinel phase peaks, during which mainly CoFe occurs2O4+C→Co3Fe7+CO2The microwave heating promotes the spinel phase in the material to be quickly formed, and the formed iron spinel phase reacts with graphite under the condition of microwave heating to generate Co3Fe7Phase, and Co3Fe7Has good wave absorbing performance. With the microwave heat preservation effect at high temperature for a period of time, the graphite is completely oxidized in the c diagram, and Co3Fe7The phases are also oxidized in air to complex spinel phase species, SiO appearing in the c diagram2Crystalline phase peaks, but SiO with continued microwaving for a period of time2The crystalline phase peak gradually disappears again; no graphite peak is found in the c, d and f images, which proves that the spinel phase continues to absorb the wave and increase the temperature in the later heat preservation process, so that the temperature is increased at high temperatureSiO at room temperature2Disappearance of crystalline phase peak.
FIG. 4 is a graph of the IR emissivity of the composite spinel material prepared in example 2 (composite spinel material F4 microwave insulated at 900 ℃ for 20 min); the sol coating and gel coating crushing refers to crushing of the composite material prepared by sol coating and gel coating. FIG. 4 shows IR emissivity measurements for IR composites prepared in sol and wet gel states and broken and added to coatings. From the figure, it is found that the infrared emissivity of the composite materials prepared by different methods is not very different, and the composite materials prepared in the sol state are slightly better than those prepared in the wet gel state. It was found that when it was crushed, a significant reduction in its infrared properties occurred, which of course could be related to the space occupancy of the material, since when it was crushed, the material lost its cavity structure, which inevitably reduced the occupancy.
Example 3
(1) Mixing magnesium nitrate and aluminum nitrate according to a molar ratio of 1:2, adding the mixture and spherical graphite (the mass ratio of the magnesium nitrate to the spherical graphite is 3: 1) into deionized water (the deionized water is obtained by completely dissolving the aluminum nitrate and the magnesium nitrate, for example, the dosage relationship of the magnesium nitrate and the deionized water is 1g:20mL), and stirring in a 70 ℃ water bath for 30 min; adjusting pH to 3 with ammonia water (pH of the original mixed solution is less than 3) in water bath at 80 deg.C, and stirring for 30 min; adding tetraethoxysilane (the molar ratio of tetraethoxysilane to magnesium nitrate is 5:1), stirring in a 90 ℃ water bath for 1h, slowly dropping 0.15mol/L NaOH solution until gel is formed, drying at 100 ℃ for 3h, placing in a microwave oven (the microwave power is 20KW, the frequency is 2450 +/-50 MHz), heating to 500 ℃, and preserving heat for 10min to obtain primary coating powder; the stirring speed is 800 rpm;
(2) adding ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate into deionized water (the dosage of the deionized water is based on the complete dissolution of all substances, and the dosage relationship of the ferric nitrate and the deionized water is 1g:50mL) according to the molar ratio of 6:2:1:1, and stirring in a 70 ℃ water bath for 30min to obtain a solution A;
(3) adding deionized water into the primary coated powder (the energy consumption ratio of the primary coated powder to the deionized water is 10 g: 40mL), and dispersing for 10min by ultrasonic (the ultrasonic power is 100W, and the frequency is 53KHz) to obtain a solution B; the mass ratio of the primary coated powder in the solution B to the ferric nitrate in the solution A is 8: 10;
(4) adding the solution A into the solution B, uniformly stirring (1500rpm), adding an ammonium oxalate solution (the concentration of the ammonium oxalate solution is 0.05mol/L, the molar ratio of manganese nitrate to ammonium oxalate is 1: 2), adjusting the pH to 9-10 by using ammonia water, stirring for 1h at 1500rpm, filtering, putting the filtered solid into a microwave oven (the microwave power is 20kW, and the frequency is 2450 +/-50 MHz), heating to 900 ℃, and preserving heat for 20min to obtain the composite spinel material.
The performance test data of the composite spinel material prepared by the embodiment is that the infrared all-band emissivity is 0.913.
It is emphasized that, although the above-described embodiments have been disclosed above, they are not limited to the above-described examples, but are not to be construed as limiting the embodiments. And that it may be readily modified in many ways by those skilled in the art to which it pertains, and that embodiments of this invention are not limited. Any similar design considerations and obvious changes or modifications are within the scope of the invention as it is conceived.
Claims (10)
1. A preparation method of a composite spinel material with high infrared emissivity is characterized by comprising the following steps: comprises the following steps:
(1) dispersing magnesium nitrate, aluminum nitrate and spherical graphite in water, adjusting the pH value to 3-4, adding ethyl orthosilicate, heating and stirring, dripping strong base solution until gel is formed, drying, and performing microwave treatment to obtain primary coated powder;
(2) dissolving ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate in water to obtain a mixed solution; dispersing the primary coating powder in water to obtain a dispersion liquid;
(3) and uniformly mixing the mixed solution and the dispersion liquid, adding a precipitator, adjusting the pH value to 9-10, filtering, heating the solid to 800-1000 ℃ by microwave, and carrying out heat preservation treatment to obtain the composite spinel material.
2. The method for preparing the high infrared emissivity composite spinel material of claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of the magnesium nitrate to the aluminum nitrate to the ethyl orthosilicate is (1-2) to (2-3) to (4-6);
the microwave treatment in the step (1) is microwave heating to 400-600 ℃, and then heat preservation treatment is carried out;
the mass ratio of the ferric nitrate in the mixed solution to the primary coating powder in the dispersion liquid in the step (3) is 10: (1-8).
3. The method for preparing the high infrared emissivity composite spinel material of claim 2, wherein the method comprises the following steps: in the step (1), the heat preservation treatment time is 5-15 min.
4. The method for preparing the high infrared emissivity composite spinel material of claim 1, wherein the method comprises the following steps: the heat preservation treatment time in the step (3) is 10-50 min;
the molar ratio of the ferric nitrate, the manganese nitrate, the cobalt nitrate and the copper nitrate in the step (2) is (2-6): (6-2): 1-2.
5. The method for preparing the high infrared emissivity composite spinel material of claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of the magnesium nitrate to the spherical graphite is (2-3): (1-2); the substance for adjusting the pH in the step (1) is ammonia water, and the pH is 3;
in the step (1), the strong alkali solution is NaOH solution.
6. The method for preparing the high infrared emissivity composite spinel material of claim 1, wherein the method comprises the following steps: the heating and stirring temperature in the step (1) is 60-90 ℃, and the heating and stirring time is 30-60 min;
in the step (3), the precipitator is ammonium oxalate; the substance for adjusting the pH value in the step (3) is ammonia water;
in the step (2), the mass-to-volume ratio of the primary coating powder to water in the dispersion liquid is (10-15) g: (30-50) ml; in the step (1), the concentration of the strong alkali solution is 0.1-0.2 mol/L.
7. The method for preparing the high infrared emissivity composite spinel material of claim 6, wherein the method comprises the steps of: the ammonium oxalate is added in the form of solution, and the concentration is 0.05-0.1 mol/L.
8. The method for preparing the high infrared emissivity composite spinel material of claim 1, wherein the method comprises the following steps: the pH adjustment in the step (1) is carried out at the temperature of 60-90 ℃, and stirring is carried out for 30-60 min after the pH adjustment;
adding ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate into water, and stirring and dissolving at 60-70 ℃ to obtain the mixed solution in the step (2);
the dispersion in the step (2) is ultrasonic dispersion, and the dispersion time is 10-15 min.
9. A composite spinel material with high infrared emissivity obtained by the preparation method of any one of claims 1-8.
10. Use of a high ir-emissivity composite spinel material according to claim 9, wherein: the composite spinel material is applied to infrared radiation paint.
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| CN105198394A (en) * | 2015-09-30 | 2015-12-30 | 盐城工学院 | High-infrared-emitting-ability cordierite-spinel ceramic material and preparation method thereof |
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| CN105198394A (en) * | 2015-09-30 | 2015-12-30 | 盐城工学院 | High-infrared-emitting-ability cordierite-spinel ceramic material and preparation method thereof |
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