CN1226382C - Short-afterglow zinc-manganese silicate green fluorescent powder and its preparing method - Google Patents
Short-afterglow zinc-manganese silicate green fluorescent powder and its preparing method Download PDFInfo
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- Luminescent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to zinc and manganous silicate green irradiance phosphor powder which is suitable for PDP plasma display with short persistence and a synthetic method thereof. The fluorescent powder of the present invention is synthesized by a metal nitrat-organic combustion method and has the ingredients of Zn2-2xSiO4: 2xMn, and x is 0.0025-0.075. Compared with similar zinc and manganous silicate fluorescent powder synthesized by traditional methods, fluorescent life is reduced to 4 to 8 milliseconds from more than 10 milliseconds, ghost effects of long persistence is eliminated, and the fluorescent powder of the present invention accords with the sensitivity of human eyes to video images. The fluorescent powder of the present invention is suitable for the requirements of using the fluorescent powder, such as plasma display or cathode-ray display, and synthetic processes are simple. The present invention has lower synthesis temperature and faster reaction speed than the products synthesized by traditional high temperature solid phase methods and sol-gel methods and can shorten production processes and reduce energy consumption, and the present invention does not need complicated synthesis devices.
Description
Technical field
The present invention relates to a kind of doped with manganese ionic zinc silicate (silicic acid zinc-manganese) green light-emitting fluorescent powder and preparation method thereof of short persistence of suitable demonstration usefulness.
Background technology
The research of traditional in the past synthetic silicic acid zinc-manganese green light-emitting fluorescent powder has had the history in a lot of years, and its main synthetic method is high temperature solid-state method and sol-gel processing at present.The former uses solid starting material zinc oxide, and manganese oxide and silicon-dioxide directly mix, and add an amount of fusing assistant fluoride amine, and is synthetic at 1200 degrees centigrade of high temperature or above sintering.The latter uses tetraethoxy and zine ion, and mn ion is a raw material, and through colloidal sol, gelation process, zine ion, mn ion are dispersed in the gel network, obtains silicic acid zinc-manganese fluorescent material through suitable about 1,000 celsius temperature sintering.Both have very strong green emitting by method synthetic material, and main glow peak is at 525 nano wave lengths.Though their green emitting is all very strong, but,, show at needs will produce on the display screen of fast-changing video and trail and ghost phenomena generally more than ten milliseconds because its luminous twilight sunset is very long, limited its application, generally it only can be used on the unicolor oscilloscope of some.But because the stability of silicate is very high, luminosity is good, be a kind of fluorescent material that is fit to very much display requirement, particularly in recent years, the development of gas ions technique of display, find that the silicic acid zinc-manganese is fit to the shooting conditions of the fluorescent material of used for plasma display very much, if can be synthetic with suitable method, and its structure of appropriate change, the fluorescence lifetime that also can suitably reduce it under the good condition of its luminosity of reservation about 5 milliseconds, has been eliminated the ghost effect of steady persistence as fluorescence lifetime to suitable degree in fast-changing image shows, identical with human eye to the susceptibility of video image, a kind of exactly fluorescent material of the plasma display that suits the requirements very much.Because these demands are arranged, the someone attempts to improve silicic acid zinc-manganese fluorescent material with several different methods always in recent years, to accelerate its fluorescence decay, reduces fluorescence lifetime.Recently, someone has improved sol-gel processing (Chinese patent: 98813227.3) dwindled the size of particles of silicic acid zinc-manganese fluorescent material, increased the specific surface of fluorescent material, the surface is knitted and is increased the rear surface defective and increase, like this transmission ofenergy speeding up to the surface imperfection center.Fluorescence decay is accelerated like this, and fluorescence lifetime shortens to some extent, but still near 10 milliseconds.But because the size of having reduced fluorescent material, its size is only about one micron, and the size of conventional fluorescent material is three to five microns.Like this, to being used in other colour light emittings of showing usefulness such as red equally, the fluorescent material size of blue-light-emitting is compared just little a lot, like this, just must do bigger change in the technology of display device, is unaccommodated for the manufacture craft of present existing display device.Because plasma display is emerging display mode, arranged development prospect preferably, therefore, very necessary to the continuation research of the short persistence silicic acid zinc-manganese fluorescent material that is suitable for its application needs Zinc, manganese silicate gree luminous fluorescent powder and preparation method thereof of short persistence of the suitable demonstration usefulness of the better performance of exploitation.
Summary of the invention
It is short to the purpose of this invention is to provide a kind of luminous twilight sunset, is fit to Zinc, manganese silicate gree luminous fluorescent powder of plasma display (PDP) and negative ray (CRT) display requirement and preparation method thereof.
Green light-emitting fluorescent powder of the present invention, be by with metal nitrate-organic combustion method synthetic product: its composition is Zn
2-2xSiO
4: 2x Mn, x=0.0025～0.075; Its fluorescence lifetime is 4～8 milliseconds.
The preparation method of green light-emitting fluorescent powder of the present invention adopts metal nitrate-organic combustion synthesis method, and concrete steps are
(1). preparation contains the nano silicon of mn ion: (for example can form the silicate class of amorphous silica to the precursor of silicon-dioxide, can be tetraethoxysilane, tetramethoxy-silicane, tetraisopropoxysilan, four butoxy silanes etc.), manganous nitrate, deionized water and alcohol is (for being less than the lower molecular weight Fatty Alcohol(C12-C14 and C12-C18) of 7 carbon atoms, as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, ethylene glycol or glycol ether etc.), perhaps nano silicon, manganous nitrate and deionized water, mixing and stirring; Then at Celsius 60～95 heating in water bath of spending, form colloidal sol, and As time goes on progressively change gel into, gel through 100～150 degrees centigrade of dryings after, pulverize, through 300～700 degrees centigrade of thermal treatments, obtain mn ion uniform distribution nano amorphous earth silicon material (about 5～10 nanometers of granular size usually) therein again; Each composition consumption is: the precursor of silicon-dioxide or silicon-dioxide and manganous nitrate are pressed silicon: manganese=1: 2x (mol ratio), x=0.0025～0.075 (being preferably 0.0025～0.05); The consumption of deionized water is that the abundant hydrolysis of precursor of silicon-dioxide or silicon-dioxide are fully disperseed more than the needed minimum amount; The consumption of alcohol is the precursor of silicon-dioxide: alcohol=1: 1～1: 20 (V/V);
The nano amorphous silicon-dioxide of above-mentioned gained is added deionized water again, and (usually concentration is 10～30%wt) stand-by to be made into finely dispersed suspension;
(2). by zinc: the mol ratio of manganese=1: 0.005～0.5 mixes above-mentioned non-crystal nm silicon dioxide suspension and the zinc nitrate solution that contains mn ion, and wiring solution-forming 1 is stand-by;
The concentration of described zinc nitrate solution is generally 0.05～15 mol, better is in 0.2～5 mol.
(3). in solution 1, add reductive agent (organism fuel), preferably add the combustion reactions auxiliary agent again, make reaction soln 2, this solution 2 leave standstill (be generally 10～120 minutes) more than 10 minutes stand-by;
The add-on of reductive agent is according to the amount of the contained nitric acid acid group (oxygenant) of solution 1, and by oxygenant: reductive agent=0.8～1.2: 1 (is generally 0.9～1.1: reaction equivalent metering 1);
The preferred urea of described reductive agent, also can be carbohydrazide, diformylhydrazine, Regulox, oxalic acid two hydrazines or tetramethyl-triazine, perhaps carboxylic acid (as acetic acid, citric acid, oxalic acid) or their carboxylate salt, perhaps amino acid (as glycine, L-Ala, leucine etc.); The composition of two or more in perhaps above these compounds; Usually, reductive agent is made into the aqueous solution adding of concentration 0.1～1 mol;
Described combustion reactions auxiliary agent can be ammonium nitrate or ammonia chloride, and the compound (as the amine perchlorate, chloric acid amine or potassium perchlorate, sodium chlorate etc.) of oxidation-reduction reaction perhaps self can take place; The add-on of combustion reactions auxiliary agent is generally 3%～30% of original oxygenate content (amount of ie in solution 1 contained nitric acid acid group) mole number, and the aqueous solution that is made into 0.1～1 mol usually adds;
(4). solution 2 heating (being generally 100～300 ℃), most of unnecessary water is removed in evaporation, to becoming collosol state, (is generally 5～30 minutes) more than 5 minutes in 400～800 ℃ of heating again; Obtain the slightly canescent loose powdered shape of white product, be required purpose product.
In the invention described above method, reactant is lighted (zinc nitrate-urea reaction system reaches ignition temperature for about 500 degrees centigrade) by type of heating; The flame of combustion reactions will produce 1300-1600 degree centigrade high temperature, make the zinc-silica composition reaction synthetic silicic acid zinc-manganese fluorescent material of the inside.In the method, contain that the shared mol ratio of mn ion is generally 0.001～0.075 in the earth silicon material of mn ion, be preferably 0.0025～0.05; Manganese ion concentration is crossed low luminosity and is weakened, and as excessive concentration, luminosity also can weaken even also cause the mn ion oxidation; By divalent manganesetion is distributed in the amorphous silica in advance, can prevent the oxidation of divalent manganesetion, mn ion is played a protective role.The ratio of controlled oxidation agent nitrate radical and reductive agent organic-fuel in reaction raw materials (as urea etc.) can obtain the reaction flame of differing temps; Usually, the proportioning of Oxidizing and Reducing Agents can be according to the proportioning of its complete reaction, i.e. oxygenant: the equivalence ratio of reductive agent is 1: 1; Generally under the excessive condition of reductive agent, the reaction flame temperature is lower, and under the excessive slightly situation of oxygenant, the reaction flame temperature is higher, so just can obtain the fluorescent material of different size of particles; Can in combustion flame, obtain higher flame temperature and the more weak atmosphere of oxidisability less than 20% oxygenant is excessive, this is to prevent that divalent manganesetion from the major measure of variation of valence taking place in reaction, but crossing when hanging down, the reductive agent ratio can cause that combustion reactions is insufficient even combustion reactions can not take place, excessive as reductive agent, meeting produces the atmosphere of reductibility in reaction system; General good conditions be the oxygenant equivalent be no more than reductive agent 10%, preferably be no more than 5%.In the methods of the invention, because the silica source of the non-flammability of introducing is disadvantageous to combustion reactions, so also introduce suitable combustion reactions auxiliary agent ammonium nitrate etc., utilize the oxidation-reduction decomposition of its ignition dope self in reaction system to emit the temperature that high heat promotes the generation and the raising reaction of metal-burning urea reaction.Because the time of combustion reactions is very short, so the rate temperature change in the crystal growing process is very big, crystal has a lot of lattice defects in process of growth, has so also formed many luminous defect centers, has accelerated fluorescence decay, reduces luminous twilight sunset.
The present invention is directed to the particular technology requirement of the image video sensitivity of the display mode of display screen and human eye to fluorescent material, with combustion method synthetic silicic acid zinc-manganese fluorescent material, and by being controlled at than lighting under the low starting temperature, under higher flame temperature, finish the condition of building-up reactions, suitably improved the crystalline structure of silicic acid zinc-manganese, keeping its Main physical character (as crystalline structure, size of particles, stability, luminescence peak, luminous intensity) under the constant substantially condition, shortened luminous fluorescence lifetime, made its each main luminosity meet the requirement of plasma display.This fluorescent material not only is fit to plasma display to be used, and is fit to other display modes, as the use of negative ray display mode, has eliminated hangover and ghost phenomena that steady persistence brings.
Combustion method is synthetic to be to burn under the condition of oxidation-reduction reaction with energy incendiary organic substance, and reaction flame provides high temperature, and the reactant in reaction system is synthetic desired material in high temperature.The characteristics of combustion method are that speed of response is fast, the combustion flame temperature height, and needed synthesis device is simple.In the present invention, because initial temperature is low, be about 500 degrees centigrade, and top temperature can reach about 1,600 degree, synthetic silicic acid zinc crystalline material smoothly, and the time of reaction is very short, under very big temperature of reaction variable gradient, the speed of crystal growth is very high, and is like this, just many than what grow with ordinary method at the various lattice defects of products of combustion, increased the luminescence quenching center in the fluor, so just accelerate the speed of quenching of fluorescence, shortened fluorescence lifetime, effectively reduced luminous twilight sunset.Because the synthesis temperature that reaches in the reaction process is very high, the particle diameter and the ordinary method synthetic basically identical of final sintetics.And by the ratio of Oxidizing and Reducing Agents in the change reactant, also the may command flame temperature can obtain different big or small fluorescent material, to be fit to the application and the processing requirement of different occasions, and as lamp phosphor, negative ray demonstration and plasma display etc.
Therefore, the present invention meets the requirement of multiple demonstration purposes with combustion method synthetic silicic acid zinc-manganese fluorescent material.And resultant velocity is fast, and low price has bigger industrial utility value.
Below the invention will be further described by drawings and Examples.
Description of drawings
Fig. 1 is the transmission electron micrograph of fluorescent material of the present invention;
Fig. 2 is the photoluminescence collection of illustrative plates of fluorescent material of the present invention;
Fig. 3 is the photoluminescence extinction curve contrast with sol-gel processing synthetic fluorescent material and fluorescent material of the present invention, and a is the photoluminescence extinction curve of sol-gel processing synthetic fluorescent material, and b is the photoluminescence extinction curve of fluorescent material of the present invention.
Embodiment
Embodiment 1:
At first preparation contains the nano silicon of mn ion: with tetraethoxysilane (tetraethoxy) is starting raw material, according to formula Zn
2-2xSiO
4: the ratio of 2x Mn, silicon composition and manganese components in proportions are 1: the 2x mol ratio, in the present embodiment, x=0.005; Earlier tetraethoxysilane, manganese nitrate solution, the ethanol of deionized water and 95% (V/V) mixes and mixes with stirrer, at the heating in water bath of 60 degree Celsius, form colloidal sol, and As time goes on progressively change gel into then, gel through 100 degrees centigrade of dryings after, pulverize, the dry gel powder that obtains is through 400 degrees centigrade of thermal treatments, obtain about 5 nanometers of granular size, mn ion uniform distribution non-crystal nm silicon dioxide material therein; The deionized water consumption is as the criterion can make the tetraethoxysilane complete hydrolysis, and the consumption of alcohol is a tetraethoxysilane: alcohol is 1: 5 (V/V).The nano amorphous silicon-dioxide that obtains is added deionized water again, and disperse, be made into being uniformly dispersed of 10% weight concentration, the clarifying suspension of appearance transparent is stand-by with the ultra-sonic dispersion machine.
Get the zinc nitrate solution of 1 mol of 20ml, in zinc: the ratio of manganese is that 1: 0.005 mol ratio and the above-mentioned suspension that contains the non-crystal nm silicon dioxide of mn ion mixes, and wiring solution-forming 1 is stand-by.
Urea is made into the aqueous solution of 0.1 mol, the amount (being about 0.04 mole) of the nitrate radical that is contained according to above-mentioned solution 1, by urea: the chemical equivalent metering of nitrate radical complete reaction (is a urea: nitrate radical=3: 5 mol ratios), add urea soln (about 240 milliliters), the amine nitrate solution that adds 20 milliliter of 0.1 mol then is prepared into reaction soln 2; Solution 2 was left standstill 2 hours.
Above-mentioned solution 2 is placed in the porcelain crucible and on common electric furnace heats, most of unnecessary water is removed in evaporation, the solution thickness that progressively becomes along with the minimizing of moisture, and present a kind of collosol state; At moisture under seldom the situation, the box-type furnace of crucible being put into 500 ℃ heats; Take out after half an hour approximately; Get the white slightly loose powdered shape product of ash.Be purpose product Zinc, manganese silicate gree luminous fluorescent powder (Zn
2-2xSiO
4: 2x Mn, x=0.005).
Above-mentioned product is made X-ray diffraction analysis, obtain the data that match fully with international crystal standard diffraction card JCDPS.No.8-492, therefore can judge that product is the crystal of zinc silicate.
With transmission electron microscope product is observed (as Fig. 1), the size of particles of product is about 5 microns as can be seen, and surface ratio is more coarse, has suitably increased surface imperfection.
Photoluminescence spectra with the H-850 of Hitachi type fluorescent spectrophotometer assay product obtains Fig. 2.Show the photoluminescence peak of products therefrom of the present invention and the Zn that obtains with traditional method
2SiO
4: the glow peak of Mn is duplicate.
With wavelength is the ultraviolet excitation sample of 355 nanometers, and the fluorescence lifetime of product is surveyed in 525 nanometers luminous of monitoring product, and its decay of luminescence curve is seen the curve b of Fig. 3, shows that the fluorescence lifetime of product of the present invention is about 6 milliseconds.
Embodiment 2:
With reference to embodiment 1, wherein:
Contain in the preparation of non-crystal nm silicon dioxide suspension of mn ion, silicon composition and manganese components in proportions are 1: 2x mol ratio, x=0.01;
In the preparation of solution 1, the consumption of the suspension of non-crystal nm silicon dioxide, in zinc: the ratio of manganese is 1: 0.01 mol ratio metering;
In the preparation of solution 2, the consumption of aqueous solution of urea is pressed urea: the mol ratio metering (about 200 milliliters) of nitrate radical=2.5: 5;
Other condition is identical with embodiment 1.
Obtain to have the product 2 of light gray black at last.Show that temperature of reaction is too high and oxidisability flame atmosphere is strong excessively, have a spot of mn ion to produce oxidation, valence state changes.
Product 2 is carried out X ray carry out diffraction analysis, obtain with 1 identical result.The product that shows the crystalline structure of having made zinc silicate.
Measure the luminescent spectrum of product 2, identical with Fig. 2 substantially, but the luminosity reduction shows that oxidation has taken place the part mn ion.Product still can be luminous.Measure its fluorescence lifetime and be about 5.5 milliseconds.
Comparative Examples 1: sol-gel processing prepares silicic acid zinc-manganese fluorescent material (Zn
2SiO
4: Mn):
Prepare the aqueous solution of 0.01 mol manganous nitrate, get 20 milliliters of the zinc nitrates of 1 mol, in addition by zinc: manganese=mol ratio was got mn ion solution in 1: 0.005, with zinc, the mixing of mn ion solution, obtained solution 1.
Get 0.001 mole of tetraethoxysilane, add 95% ethanol of 10 ml waters and 100 milliliters, obtain stratified mixed solution, with stirrer mixed solution is mixed, molten fully up to solution is one; Then solution 1 is added, with nitric acid P H value is adjusted to 1, and stirs once more; Put into 60 degrees centigrade water-bath,, progressively obtain colloidal sol by colloidal sol-gelation process, form gel then, gel obtains in gel through 120 degrees centigrade of dryings, after xerogel grinds, put into temperature and be 1100 degrees centigrade box-type furnace heating 3 hours, obtain contrasting the silicic acid zinc-manganese sample of usefulness.
The silicic acid zinc-manganese sample of contrast usefulness obtains the 1 identical result with embodiment through X-ray diffraction analysis.The product that shows the crystalline structure of having made zinc silicate.
With wavelength is the ultraviolet excitation sample of 355 nanometers, and the Zn of sol-gel processing preparation is surveyed in 525 nanometers luminous of monitoring product
2SiO
4: the fluorescence lifetime of Mn obtains its fluorescence decay curve (a).Fig. 3 is seen in the contrast of the fluorescence decay curve (b) of fluorescence decay curve of sol-gel processing sample (a) and combustion method synthetic sample of the present invention, find out obviously that from figure the fluorescence lifetime of the fluorescent material that the inventive method is made far is shorter than the product made from traditional sol-gel processing; The fluorescence lifetime of product of the present invention is about 6 milliseconds, and with the Zn of traditional sol-gel processing method preparation
2SiO
4: the fluorescence lifetime of Mn sample is about 16.5 milliseconds.
Claims (9)
1. the preparation method of a Zinc, manganese silicate gree luminous fluorescent powder is characterized in that adopting metal nitrate-organic compound combustion synthesis method, and concrete steps are:
(1). preparation contains the nano silicon of mn ion: the precursor of silicon-dioxide, manganous nitrate, deionized water be less than the lower molecular weight Fatty Alcohol(C12-C14 and C12-C18) of 7 carbon atoms, perhaps nano silicon, manganous nitrate and deionized water, mixing and stirring; Then at Celsius 60～95 heating in water bath of spending, form colloidal sol, and As time goes on progressively change gel into, gel through 100～150 degrees centigrade of dryings after, pulverize, through 300～700 degrees centigrade of thermal treatments, obtain mn ion uniform distribution nano amorphous earth silicon material therein again; Each composition consumption is: the precursor of silicon-dioxide or silicon-dioxide and manganous nitrate are pressed silicon: manganese=1: 2x mol ratio, x=0.0025～0.075; The consumption of deionized water is that the abundant hydrolysis of precursor of silicon-dioxide or silicon-dioxide are fully disperseed more than the needed minimum amount; The consumption of alcohol is the precursor of silicon-dioxide: alcohol=1: 1～1: 20V/V; The nano amorphous silicon-dioxide of above-mentioned gained is added deionized water again, and it is stand-by to be made into finely dispersed suspension;
(2). by zinc: the mol ratio of manganese=1: 0.0025～0.075 mixes above-mentioned non-crystal nm silicon dioxide suspension and the zinc nitrate solution that contains mn ion, and wiring solution-forming 1 is stand-by;
(3). in solution 1, add reductive agent, make reaction soln 2, leave standstill this solution 2 more than 10 minutes stand-by; The add-on of reductive agent is pressed oxygenant: reductive agent=0.8～1.2 according to the amount of the contained oxygenant nitrate radical of solution 1: 1 reaction equivalent metering; Reductive agent is to be selected from urea, carbohydrazide, diformylhydrazine, Regulox, oxalic acid two hydrazines or tetramethyl-triazine, perhaps acetic acid, citric acid, oxalic acid or their carboxylate salt, perhaps glycine, L-Ala or leucine, the composition of two or more in perhaps above these compounds;
(4). solution 2 heating, most of unnecessary water is removed in evaporation, to becoming collosol state, heats more than 5 minutes in 400～800 ℃ again; Obtain the slightly canescent loose powdered shape of white product, be required purpose product.
2. in accordance with the method for claim 1, it is characterized in that adding the combustion reactions auxiliary agent when step (3) adds reductive agent in solution 1, the add-on of combustion reactions auxiliary agent is 3%～30% of solution 1 original oxygenant mole number, the combustion reactions auxiliary agent is ammonium nitrate or ammonia chloride, perhaps amine perchlorate, chloric acid amine, potassium perchlorate or sodium chlorate.
3. according to claim 1 or 2 described methods, the precursor that it is characterized in that described silicon-dioxide is tetraethoxysilane, tetramethoxy-silicane, tetraisopropoxysilan or four butoxy silanes of silicate class.
4. according to claim 1 or 2 described methods, it is characterized in that described lower molecular weight Fatty Alcohol(C12-C14 and C12-C18) is methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, ethylene glycol or glycol ether.
5. according to claim 1 or 2 described methods, the concentration that it is characterized in that described nano amorphous silica suspension is 10～30%wt.
6. according to claim 1 or 2 described methods, the concentration that it is characterized in that described zinc nitrate solution is 0.05～15 mol.
7. in accordance with the method for claim 6, the concentration that it is characterized in that described zinc nitrate solution is 0.2～5 mol.
8. according to claim 1 or 2 described methods, the add-on that it is characterized in that described reductive agent is pressed oxygenant: reductive agent=0.9～1.1: 1 reaction equivalent metering according to the amount of the contained oxygenant nitric acid acid group of solution 1.
9. according to claim 1 or 2 described methods, it is characterized in that used reductive agent is a urea.
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| CN1325601C (en) * | 2005-02-21 | 2007-07-11 | 东南大学 | Method for preparing small grain size manganese zinc silicate green fluorescent powder |
| CN1294233C (en) * | 2005-02-21 | 2007-01-10 | 东南大学 | Process for preparing silicate green fluorescent powder |
| CN1315984C (en) * | 2005-08-02 | 2007-05-16 | 中国计量学院 | Self-ignite preparation method of spherical nanometer Yttrium europium silicate fluorescent powder |
| US20130075661A1 (en) * | 2010-06-13 | 2013-03-28 | Ocean's King Lighting Science & Technology Co., Ltd. | Silicate luminous material and preparation method thereof |
| CN103773363A (en) * | 2013-12-17 | 2014-05-07 | 中国计量学院 | Green manganese-activated zinc silicate fluorescent powder and preparation method thereof |
| CN104212443B (en) * | 2014-09-29 | 2016-02-03 | 东南大学 | The preparation method of short persistence zinc manganese silicate fluorescent material |
| CN111377722A (en) * | 2018-12-27 | 2020-07-07 | 中国科学院上海硅酸盐研究所 | Microwave dielectric ceramic material, microwave dielectric ceramic antenna and preparation method thereof |
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