CN109133722B - Preparation method of artificial stone containing magnesium aluminate spinel - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/12—Condensation polymers of aldehydes or ketones
- C04B26/122—Phenol-formaldehyde condensation polymers
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/162—Magnesium aluminates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/14—Gas barrier composition
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Abstract
The invention relates to a preparation method of a magnesium aluminate spinel-containing artificial stone, and the nano magnesium aluminate spinel MgAl is prepared by using a magnesium aluminate spinel-containing material2O4Has a special structure, canThe modified carbon is used as a high-quality inorganic nano oxide material and added into talcum powder, phenolic resin or quartz, so that the heat resistance and the strength of the artificial stone are improved, the aging time of the artificial stone is shortened, the artificial stone can be kept from being degraded for a long time under the action of high temperature, a better flame retardant effect can be kept, the carbon residue is increased, and the LOI loss on ignition index is greatly improved.
Description
Technical Field
The invention relates to a preparation method of an artificial stone containing nano magnesia alumina spinel, belonging to the field of building materials.
Background
With the improvement of living standard and living condition of people, the interior decoration industry develops rapidly, and the consumption of decoration building materials is very large, wherein stone is one of the most commonly used and basic building materials, and is widely applied to pavement of ground, wall and table top. The natural stone has high mining cost and large pollution, contains a large amount of natural radioactive substances, and has great harm to human health. With the continuous development of the material field, the performance of the artificial stone is gradually improved, is close to or even exceeds that of the natural stone, is more and more accepted by the market and users, and is widely applied to the decoration of cabinets, bathrooms, floors and wall surfaces. However, the existing artificial stone still has the defects of low strength, poor surface abrasion resistance, poor flame-retardant and heat-resistant performance and poor surface glossiness.
Disclosure of Invention
Aiming at various defects of the existing artificial stone, the invention provides a preparation method of the artificial stone containing magnesium aluminate spinel, which comprises the following steps:
(1) preparation of composite magnesium aluminate spinel MgAl2O4/ZIF-90：
(2) 70-90 parts of talcum powder, 50-60 parts of phenolic resin, 6-10 parts of boron trifluoride, 10-20 parts of white carbon black, 25-30 parts of perlite powder, 5-15 parts of melamine, 5-15 parts of triethyl phosphate, 5-15 parts of hydroxyapatite, 5-15 parts of mica sheet, 50-70 parts of quartz and MgAl obtained in the steps2O410-20 parts of the artificial stone blank and 10-10 parts of the ZIF blank are mixed, poured into a high-speed stirrer, stirred at the speed of 1000 rpm for 30 minutes at room temperature, then stirred at the speed of 3000 rpm for 30 minutes at the temperature of 50 ℃, the uniformly stirred mixed materials are discharged and uniformly spread on a plate-making mould, then the plate-making mould is placed in a vacuum environment for drying, curing and forming, the cured artificial stone blank is taken out of the mould, and the blank is subjected toAnd (5) performing thickness setting, grinding and polishing treatment to obtain the flame-retardant artificial stone.
Wherein, MgAl in the step (1)2O4The preparation method comprises the following steps: 0.02mol Mg (NO) was weighed out separately3)2· 6H2O、0.04molAl(NO3)3 9H2Dissolving O in 50ml deionized water to obtain mixed salt solution, and collecting 0.04mol Na2CO3Dissolving 0.06mol of NaOH in 50ml of deionized water, then quickly stirring, adding an alkali solution into a salt solution to keep the pH value at 9-11, uniformly mixing, filtering a precipitate, washing the precipitate to be neutral by the deionized water, drying the precipitate in an oven at 80-100 ℃ for 8-10h, and then roasting the precipitate in a muffle furnace at 800-1000 ℃ for 4-6 h.
Wherein the preparation method of ZIF-90 in the step (1) comprises the following steps: 2.1mmol of Zn (NO)3)2 6H2Dissolving O and 3.0mmol of imidazole-2-formaldehyde ICA in 30mL of DMF, uniformly stirring, transferring the obtained reaction solution to a reaction kettle with a volume of 40mL and a polytetrafluoroethylene lining, reacting at 100 ℃ for 18h, and naturally cooling to room temperature.
Wherein, the drying, curing and forming temperature in the step (2) is 50-65 ℃, preferably 55-60 ℃.
The invention has the beneficial effects that:
the flame retardant of phosphorus and phosphorus-containing compound is parallel to halogen series and inorganic series as three flame retardant systems. The flame retardant effect of phosphorus compounds such as triethyl phosphate, hydroxyapatite and the like is better, because metaphosphoric acid generated during combustion can be polymerized into a stable polymerized state to become a protective layer of a combustion point, and the contact between a combustible substance and oxygen can be isolated. The generated phosphoric acid and the polymetaphosphoric acid are strong acids, have strong dehydration property, can dehydrate and carbonize the polymer, and form a carbonized layer on the surface of the polymer, thereby achieving the purpose of isolating oxygen and preventing combustion.
The melamine has the advantages of no halogen, low toxicity and low smoke, the nitrogen-containing flame retardant has good flame retardant effect in polyester plastics, especially can form an intumescent flame retardant system by combining with a phosphorus flame retardant, and the flame retardant effect of the phenolic resin ester hydrocarbon artificial stone can be greatly improved by the synergistic effect of the melamine and the phosphorus flame retardant. The melamine, the triethyl phosphate and the hydroxyapatite are combined for use, the proportion of the melamine, the triethyl phosphate and the hydroxyapatite is adjusted, the melamine, the triethyl phosphate and the hydroxyapatite are enabled to play a synergistic effect, an expansion type flame retardant system is formed, and tests show that the optimal mass ratio of the melamine, the triethyl phosphate and the hydroxyapatite is 1:1:1, and the flame retardant effect can be greatly improved. The nano inorganic oxide is a good choice of the flame retardant, for example, nano magnesium oxide, nano zinc oxide and the like can be used as the nano inorganic oxide flame retardant to be added into the phenolic resin ester material. Due to the nano-effect, the polymer/inorganic nanocomposite has incomparable advantages compared with the conventional polymer/filler composite, such as low density, high mechanical strength, air absorption and permeability, and particularly, the heat resistance and flame retardance can be greatly improved. Furthermore, researchers also study the flame retardant properties of clay phyllosilicate nanocomposites such as attapulgite, montmorillonite, etc., and the above inorganic materials all have flame retardant effects of different degrees. The perovskite structure oxide ABO3 has unique optical, electrical and magnetic properties, is widely applied to the aspect of biological agent ceramics, has good thermal stability and low cost, can adsorb oxygen according to the selection of B site, and A, B atoms can adjust the number and activity of lattice oxygen. At present, a nano perovskite material with a more excellent structure or a similar multi-metal composite metal oxide is not adopted as a flame retardant material.
The combustion of high molecular compounds in air is a very violent oxidation reaction, belonging to a chain reaction process. During the combustion process, a large amount of active hydroxyl radicals are multiplied, when the hydroxyl radicals and high molecular compounds meet, hydrocarbon radicals and water are generated, and in the presence of oxygen, the hydrocarbon radicals are decomposed to form new hydroxyl radicals. The circulation is carried out, so that the combustion reaction is continuously continued. The mechanism of action of flame retardants is complex and involves many factors, but primarily through the use of physical or chemical means to retard the combustion cycle.
The magnesium aluminate spinel is used as an inorganic nano flame retardant component for the first time, is compounded with a metal organic framework ZIF and then is added into a high polymer material, and due to the addition of the magnesium aluminate spinel, the transport mode of a current carrier in a medium can be changed, the trap level is reduced, the current carrier is easy to transport along the direction vertical to the thickness direction, the injection of the current carrier along the thickness direction and the accumulation of space charges in the medium are effectively inhibited, an external electric field is weakened to a certain extent by a semi-conducting layer in the thickness direction of a sample, the field strength at the interface of the semi-conducting layer and an insulating layer is weakened, the space charge quantity injected by a cathode is reduced, a small amount of space charges are finally remained in the sample after short circuit, the charge aggregation property is reduced, the electricity saving performance of the material is improved, the ageing resistance and the high temperature resistance of the artificial stone are improved, and the purpose of high-efficiency flame retardance is achieved.
The artificial stone disclosed by the invention adopts the magnesium aluminate spinel material for the first time, utilizes the dominant spatial structure of the material and is compounded with the ZIF material, one part can generate more inorganic nano flame-retardant components, the independent addition of inorganic flame-retardant materials such as inorganic nano magnesium oxide and the like is avoided, the other part can utilize the spatial vacancy and the skeleton structure of the ZIF, the carbonization performance of the polymer material is optimized, the LOI index is improved, and the organic skeleton in the ZIF can be further compounded with the phenolic resin material, so that the comprehensive coverage of the flame-retardant material is facilitated, and the flame-retardant performance is greatly improved. Can greatly reduce the aging and improve the high temperature resistance, the use strength and the flame retardant resistance of the artificial stone.
The present application contemplates the inclusion of composite MgAl2O4The ZIF-90 has flame retardant and mechanical properties of the quartz composite material, and is determined by limited oxygen index, vertical combustion and mechanical property experiments, so that the composite material has the advantages of excellent comprehensive properties, stable performance, high oxygen index, good flame retardant effect, lasting effect, low price, no volatilization, little smoke and no toxicity, has the functions of flame retardance, smoke suppression and toxic gas reduction, and has industrial application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1
(1) Preparation of composite magnesium aluminate spinel MgAl2O4/ZIF-90：
(a)MgAl2O4Preparation: 0.02mol Mg (NO) was weighed out separately3)2· 6H2O、0.04molAl(NO3)3 ·9H2Dissolving O in 50ml of deionized water to prepare a mixed salt solution, dissolving 0.04mol of Na2CO3 and 0.06mol of NaOH in 50ml of deionized water, then quickly stirring, adding an alkali solution into the salt solution to keep the pH value at 9-11, uniformly mixing, filtering the precipitate, and washing with deionized water to be neutral. Drying in an oven at 80 ℃ for 8 h. Then roasting for 4-6h in a muffle furnace at 800 ℃.
(b) Preparing ZIF-90: adding Zn (NO)3)2 6H2Dissolving O (2.1mmol) and imidazole-2-formaldehyde ICA (3.0mmol) in 30mL of DMF, uniformly stirring, transferring the obtained reaction solution to a reaction kettle with a volume of 40mL of polytetrafluoroethylene lining, reacting at 100 ℃ for 18h, and naturally cooling to room temperature for later use;
(c) MgAl is added2O4Adding into the reaction kettle, controlling the temperature at 60 ℃, keeping for 30 minutes, and then drying for 30 minutes at 80-100 ℃ to obtain MgAl2O4a/ZIF-90 composite material for standby. Wherein MgAl is controlled2O4ZIF, namely 3: 1.
(2) 70 parts of talcum powder, 50 parts of phenolic resin, 6 parts of boron trifluoride, 10 parts of white carbon black, 25 parts of perlite powder, 5 parts of melamine, 5 parts of triethyl phosphate, 5 parts of hydroxyapatite, 5 parts of mica sheet, 50 parts of quartz and MgAl obtained in the step2O4 10 parts and ZIF-905 parts, mixing, pouring into a high-speed mixer, firstly stirring at the speed of 1000 revolutions per minute for 30 minutes at room temperature, then stirring at the speed of 3000 revolutions per minute for 30 minutes at 50 ℃, discharging the uniformly stirred mixed materials, uniformly spreading the mixed materials on a plate making mould, then placing the plate making mould in a vacuum environment for drying and curing at the temperature of 50 ℃, taking out the cured artificial stone blank from the mould, and carrying out thickness setting, grinding and polishing treatment on the blank to obtain the flame-retardant artificial stone.
Example 2
(1) Preparation of composite magnesium aluminate spinel MgAl2O4/ZIF-90：
(a)MgAl2O4Preparation: 0.02mol Mg (NO3) 26H 2O and 0.04mol Al (NO3) 39H 2O are respectively weighed and dissolved in 50ml deionized water to prepare a mixed salt solution, and 0 is taken out.04mol Na2CO3 and 0.06mol NaOH are dissolved in 50ml deionized water, then the solution is quickly stirred, the salt solution is added into the alkali solution to keep the PH value at 9-11, the mixture is evenly mixed, the precipitate is filtered, and the deionized water is washed to be neutral. Drying in an oven at 100 ℃ for 10 h. Then calcined in a muffle furnace at 800 ℃ for 4 h.
(b) Preparing ZIF-90: adding Zn (NO)3)2· 6H2Dissolving O (2.1mmol) and imidazole-2-formaldehyde ICA (3.0mmol) in 30mL of DMF, uniformly stirring, transferring the obtained reaction solution to a reaction kettle with a volume of 40mL of polytetrafluoroethylene lining, reacting at 100 ℃ for 18h, and naturally cooling to room temperature for later use;
(c) MgAl is added2O4Adding into the reaction kettle, controlling the temperature at 60 ℃, keeping for 30 minutes, and then drying for 30 minutes at 80 ℃ to obtain MgAl2O4a/ZIF-90 composite material for standby. Wherein MgAl is controlled2O4ZIF, wherein the mass ratio of ZIF is 2: 1.
(2) 80 parts of talcum powder, 55 parts of phenolic resin, 8 parts of boron trifluoride, 15 parts of white carbon black, 28 parts of perlite powder, 10 parts of melamine, 10 parts of triethyl phosphate, 10 parts of hydroxyapatite, 10 parts of mica sheet, 60 parts of quartz and MgAl obtained in the step2O415 parts of the artificial stone and ZIF-908 parts of the artificial stone are mixed, poured into a high-speed mixer, stirred at the speed of 1000 rpm for 30 minutes at room temperature, then stirred at the speed of 3000 rpm for 30 minutes at 50 ℃, the uniformly stirred mixed materials are discharged and uniformly spread on a plate making mould, then the plate making mould is placed in a vacuum environment for drying, curing and forming at the temperature of 55 ℃, the cured artificial stone blank is taken out of the mould, and the blank is subjected to thickness setting, grinding and polishing treatment to obtain the flame-retardant artificial stone.
Example 3
(1) Preparation of composite magnesium aluminate spinel MgAl2O4/ZIF-90：
(a)MgAl2O4Preparation: 0.02mol Mg (NO3) was weighed out separately2 6H2O、0.04molAl(NO3) Dissolving 39H 2O in 50ml deionized water to obtain mixed salt solution, dissolving 0.04mol Na2CO3 and 0.06mol NaOH in 50ml deionized water, rapidly stirring, adding alkali solution into the salt solutionKeeping the pH value at 9-11, mixing uniformly, filtering the precipitate, and washing with deionized water to neutrality. Drying in an oven at 80 ℃ for 10 h. Then calcined in a muffle furnace at 800 ℃ for 6 h.
(b) Preparing ZIF-90: adding Zn (NO)3)2 6H2Dissolving O (2.1mmol) and imidazole-2-formaldehyde ICA (3.0mmol) in 30mL of DMF, uniformly stirring, transferring the obtained reaction solution to a reaction kettle with a volume of 40mL of polytetrafluoroethylene lining, reacting at 100 ℃ for 18h, and naturally cooling to room temperature for later use;
(c) MgAl is added2O4Adding into the reaction kettle, controlling the temperature at 60 ℃, keeping for 30 minutes, and then drying for 30 minutes at 80 ℃ to obtain MgAl2O4a/ZIF-90 composite material for standby. Wherein MgAl is controlled2O4ZIF, wherein the mass ratio of ZIF is 2: 1.
(2) 90 parts of talcum powder, 60 parts of phenolic resin, 10 parts of boron trifluoride, 20 parts of white carbon black, 30 parts of perlite powder, 15 parts of melamine, 15 parts of triethyl phosphate, 15 parts of hydroxyapatite, 15 parts of mica sheet, 70 parts of quartz and MgAl obtained in the step2O420 parts and ZIF-9010 parts, mixing, pouring into a high-speed mixer, stirring at the speed of 1000 rpm for 30 minutes at room temperature, then stirring at the speed of 3000 rpm for 30 minutes at 50 ℃, discharging the uniformly stirred mixed materials, uniformly spreading on a plate making mold, then placing the plate making mold in a vacuum environment for drying and curing at 65 ℃, taking out the cured artificial stone blank from the mold, and carrying out thickness fixing, grinding and polishing treatment on the blank to obtain the flame-retardant artificial stone.
Comparative example 1
The nano magnesium aluminate spinel is not added, and other experimental parameters are the same as those of the example 1.
Comparative example 2
The ZIF-90 material was not added, and the other experimental parameters were the same as those in example 1.
Comparative example 3
The attapulgite is adopted to replace the magnesia-alumina spinel of the invention, and other experimental parameters are the same as those of the example 1.
Comparative example 4
Ordinary molecular sieves were used instead of ZIF-90 of the present invention, and other experimental parameters were the same as in example 1.
Specific detection
The tensile strength (sigma t/MPa) and the elongation at break of the anti-aging artificial stone are detectedδ/%), residual carbon amount, hardness and LOI index, then the anti-aging artificial stone is subjected to hot air aging at 250 ℃ for 30 days, and then the tensile strength retention rate (E) is detected1/%) and retention of elongation at break (E)2/%), the specific results are shown in table 1.
TABLE 1 flame-retardant Artificial stone respective test indexes
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| The amount of carbon residue in wt% | 18.5 | 19.5 | 20.1 | 1.19 | 2.1 | 4.3 | 1.5 |
| Hardness, Shore A | 95 | 95 | 97 | 80 | 70 | 75 | 71 |
| Tensile strength, MPa | 51 | 50 | 47 | 40 | 35 | 40 | 40 |
| Elongation at break% | 550 | 510 | 500 | 380 | 391 | 400 | 405 |
| LOI | 39.2 | 37.0 | 39.0 | 19.1 | 20.1 | 25.5 | 27.6 |
| LOI of 30 days at 250 ℃ | 33.1 | 34.1 | 33.1 | 14.3 | 11.7 | 10.5 | 12.6 |
| 250 ℃ X30 days, E1/％ | 97.3 | 95.6 | 97.0 | 77.0 | 72.0 | 73.1 | 80.1 |
| 250 ℃ X30 days, E2/％ | 90.1 | 90.5 | 94.0 | 62.6 | 61.5 | 62.5 | 70.4 |
As can be seen from the above results, the magnesia-alumina spinel MgAl2O4The modified metal organic framework ZIF-90 is favorable for reducing the density of the artificial stone, improving the heat resistance and the strength of the artificial stone, reducing the aging time of the artificial stone, improving the LOI index, having good flame retardance, being capable of keeping the artificial stone from degrading under the action of high temperature for a long time (200 ℃ multiplied by 30 days), and being subjected to the modification treatmentThe flame retardant still has higher LOI index and better flame retardant property for a long time (200 ℃ multiplied by 30 days).
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be made by those skilled in the art without inventive work within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (1)
1. The preparation method of the artificial stone containing the magnesium aluminate spinel is characterized by comprising the following steps:
(1) preparation of composite magnesium aluminate spinel MgAl2O4/ZIF-90：
(2) 90 parts of talcum powder, 60 parts of phenolic resin, 10 parts of boron trifluoride, 20 parts of white carbon black, 30 parts of perlite powder, 15 parts of melamine, 15 parts of triethyl phosphate, 15 parts of hydroxyapatite, 15 parts of mica sheet, 70 parts of quartz and MgAl obtained in the step (1)2O4 20 parts of the mixture and ZIF-9010 parts of the mixture are poured into a high-speed stirrer, the mixture is stirred at the speed of 1000 rpm for 30 minutes at room temperature, then stirred at the speed of 3000 rpm for 30 minutes at 50 ℃, the uniformly stirred mixture is discharged and uniformly spread on a plate making mold, then the plate making mold is placed in a vacuum environment for drying, curing and molding, the cured artificial stone blank is taken out of the mold, and the blank is subjected to thickness setting, polishing and polishing treatment to obtain the flame-retardant artificial stone;
MgAl in the step (1)2O4The preparation method comprises the following steps: 0.02mol Mg (NO) was weighed out separately3)2· 6H2O、0.04molAl(NO3)3 9H2Dissolving O in 50ml deionized water to obtain mixed salt solution, and collecting 0.04mol Na2CO3Dissolving 0.06mol NaOH in 50ml deionized water, rapidly stirring, adding alkaline solution into the salt solution to maintain pH at 9-11, mixing well, filtering the precipitate, washing with deionized water to neutral, oven drying at 80 deg.C for 10 hr, and then placing in 800 deg.C muffle furnaceIntermediate roasting for 6 h;
the preparation method of the ZIF-90 in the step (1) comprises the following steps: 2.1mmol of Zn (NO)3)2 6H2Dissolving O and 3.0mmol of imidazole-2-formaldehyde ICA in 30mL of DMF, uniformly stirring, transferring the obtained reaction solution to a reaction kettle with a volume of 40mL and a polytetrafluoroethylene lining, reacting at 100 ℃ for 18h, and naturally cooling to room temperature;
the drying, curing and forming temperature in the step (2) is 65 ℃.
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| CN105417570A (en) * | 2015-12-14 | 2016-03-23 | 西南化工研究设计院有限公司 | Method for preparing spinel-type complex oxide through co-precipitation, homogenization and spray drying |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044463A (en) * | 2012-12-12 | 2013-04-17 | 中国科学院宁波材料技术与工程研究所 | Method for high-efficiency preparing zeolite imidazole metal organic frame ZIF-90 |
| CN104478289A (en) * | 2014-12-15 | 2015-04-01 | 田忠和 | Fireproof and pressure-resistant artificial quartz stone plate and preparation method thereof |
| CN105417570A (en) * | 2015-12-14 | 2016-03-23 | 西南化工研究设计院有限公司 | Method for preparing spinel-type complex oxide through co-precipitation, homogenization and spray drying |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105949709A (en) | 2016-09-21 |
| CN105949709B (en) | 2018-11-13 |
| CN109133722A (en) | 2019-01-04 |
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