CN103708835A - Method for fine synthesis of ternary manganese-tantalum mine structure ZnTiTa2O8 microwave dielectric ceramic by using sol-gel method - Google Patents
Method for fine synthesis of ternary manganese-tantalum mine structure ZnTiTa2O8 microwave dielectric ceramic by using sol-gel method Download PDFInfo
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Abstract
The invention belongs to the technical field of electronic ceramic preparation and application, and particularly relates to a method for fine synthesis of a ternary ZnO-Ta2O5-TiO2 system microwave dielectric ceramic by using a sol-gel method. The technical scheme comprises adopting a sol-gel method to finely synthesize a ternary ZnO-Ta2O5-TiO2 system microwave dielectric ceramic, and specifically comprises: 1) preparing a citric acid aqueous solution of Zn ions; 2) preparing a citric acid aqueous solution of Ti ions and Ta ions; and 3) synthesizing a ternary ZnO-Ta2O5-TiO2 system microwave dielectric ceramic nanometer precursor, and preparing the ceramic. The ternary ZnO-Ta2O5-TiO2 system microwave dielectric ceramic has significant advantages of low synthesis temperature, uniform ceramic particles, good ceramic particle dispersity, pure phase, nano-scale powder (particle size of less than 50 nm), high specific surface energy, high activity and the like. In addition, compared with the conventional solid-phase method, the method of the present invention has the following characteristics that: the sintering temperature can be significantly reduced by 100-200 DEG C so as to achieve low temperature sintering, maintain the good microwave dielectric property, and meet the LTCC application requirements.
Description
Technical field
The invention belongs to electronic ceramic preparation and applied technical field, relate in particular to a kind of meticulous synthesis of ternary ixiolite of sol-gel method structure ZnTiTa that utilizes
2o
8microwave-medium ceramics method.
Background technology
LTCC LTCC Technology is the type material technology of being developed by Hughes Electronics in nineteen eighty-two, it adopts thick-film material, according to the structure designing in advance, by electrode materials, substrate, electron devices etc. are disposable to be burnt till, a kind ofly can realize high integration, the technology of high performance circuit encapsulation, its main application fields has: high frequency field of wireless communication is (as mobile telephone, Global Positioning System and Bluetooth technology etc.), aerospace industry and military field are (as communications satellite, detection and tracking radar system etc.), MEMS (micro electro mechanical system) and sensing technology, automotive electronics etc.
LTCC technology is a kind of low temperature co-fired technology of multilayer wiring, and the microwave dielectric ceramic materials of selecting should possess sintering temperature and be less than 1000 ℃.ZnTiTa
2o
8pottery, due to its specific crystalline structure, presents good sintering characteristic and good microwave property.At present about this architectural study, units such as the Central China University of Science and Technology, Taiwan success university and University Of Tianjin, all take conventional solid-state method technique as main, sintering ZnTiTa both at home and abroad
2o
8pottery temperature range remains on 1150-1200 ℃, and microwave dielectric property is
ε r~ 36-41, Q ~ 46,000-65,000GHz.In order to realize LTCC application demand, numerous researchists attempt preparing sosoloid or adding second-phase glass as fusing assistant by implement Material cladding thinking in this system, reduce sintering temperature, complex process is difficult to control, and often take and sacrifice its microwave dielectric property as cost.At present about this ternary system ZnTiTa
2o
8microwave dielectric ceramics pottery adopts wet chemical technology to carry out the meticulous synthetic report that always there is not yet both at home and abroad.
Summary of the invention
The object of the invention is the LTCC Technology application demand based on following LTCC (Low Temperature Co-fired Ceramic), overcome traditional solid phase synthesis powder temperature drift, synthetic powder granularity is larger, is unfavorable for the shortcoming of follow-up ceramic post sintering; A kind of meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes is provided
2o
5-TiO
2system microwave-medium ceramics method, adopts the meticulous synthetic ZnTiTa of sol-gel method
2o
8ceramic powder, have that synthesis temperature is low, ceramic particle evenly, mutually pure, the powder of good dispersity, thing has nano particle size and has high-ratio surface energy, presents the significant advantages such as greater activity, can realize low-temperature sintering, and keep its good microwave dielectric property, meet LTCC application demand.
For solving the problems of the technologies described above, technical scheme of the present invention is:
Utilize the meticulous synthesis of ternary ZnO-Ta of sol-gel method
2o
5-TiO
2system microwave-medium ceramics method, comprises the following steps:
1) aqueous citric acid solution of preparation Zn ion;
2) aqueous citric acid solution of preparation Ti and Ta ion;
3) ternary ZnO-Ta
2o
5-TiO
2synthetic and the pottery preparation of system microwave-medium ceramics nanometer presoma;
(a) the Zn aqueous citric acid solution of being prepared by step (1), (2), Ti mix with Ta ion aqueous citric acid solution, then add polyoxyethylene glycol to carry out esterification, and the 4-6 that the molar weight that polyoxyethylene glycol adds is citric acid doubly; Heating
,stir, obtain Zn-Ti-Ta precursor sol;
(b) the Zn-Ti-Ta precursor solution of being prepared by step (a) is placed in drying in oven, shrinks and forms xerogel;
(c) xerogel of step (b) is placed in to High Temperature Furnaces Heating Apparatus 750-950 ℃ calcination processing, can obtains evengranular nano level ZnTiTa
2o
8powder;
(d) by above-mentioned ZnTiTa
2o
8powder is fried wax, is sieved, granulation, moulding; Realize its low-temperature sintering and test its microwave property.
2, the meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes according to claim 1
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: the aqueous citric acid solution of described step 1) preparation Zn ion comprises the following steps:
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, adjusts ZnO/TiO
2/ Ta
2o
5mole proportioning is 1+x/1/1, and wherein x is: 0<x<0.05; First take zinc nitrate, be dissolved in appropriate amount of deionized water, or weigh corresponding stoichiometric ratio zinc oxide as raw material, add nitric acid to dissolve, form colourless transparent solution;
(b) take citric acid, the mol ratio of citric acid be zinc nitrate or zinc oxide 4-6 doubly, add in above-mentioned solution, impel citric acid and Zn ion forming complex, make water white transparency Zn ion aqueous citric acid solution.
3, the meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes according to claim 1
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: the described step 2) aqueous citric acid solution of preparation Ti and Ta ion, comprises the following steps:
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, takes titanium dioxide and tantalum oxide, is placed in ceramic dielectic reactor, seals after adding hydrofluoric acid, then utilizes baking oven to carry out pyroprocessing 1-3 hour, and accelerate dissolution forms the common molten HF acid solution of water white transparency Ti and Ta ion
;
(b), in the HF acid solution of above-mentioned Ti and Ta ion, adding ammoniacal liquor to adjust pH value is 8-10, impels Ti and Ta ion to complete precipitation with the form of metatitanic acid and tantalic acid;
(c) filter above-mentioned precipitation, repeatedly clean to be placed on for several times in lemon aqueous acid and carry out magnetic agitation, form the white citric acid suspension liquid that is uniformly dispersed, wherein adding citric acid molar weight is metal ion total amount 4-8 times;
(d) above-mentioned white citric acid suspension liquid is placed in to the sealing of ceramic dielectic autoclave, then utilize baking oven to carry out pyroprocessing 3-6 hour, impel and react, impel citric acid and Ti and Ta ion to carry out reacting forming complex dissolving, finally form the aqueous citric acid solution that mixes of water white transparency Ti and Ta ion.
4, the meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes according to claim 3
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: described step (a) and (d) in the temperature of baking oven pyroprocessing be 100-150 ℃.
5, the meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes according to claim 1
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: described step 3) ternary ZnO-Ta
2o
5-TiO
2synthetic and the pottery preparation of system microwave-medium ceramics nanometer presoma comprises the following steps:
(a) the Zn aqueous citric acid solution of being prepared by step (1), (2), Ti mix with Ta ion aqueous citric acid solution, then add polyoxyethylene glycol to carry out esterification, and the molar weight that polyoxyethylene glycol adds is 4-6 times of Citric Acid Dosage total amount; By water-bath 60-90 ℃ of heating 8-20 hour, and constantly stir, guarantee evenly, to obtain Zn-Ti-Ta precursor sol;
(b) the Zn-Ti-Ta precursor solution of step (3) (a) being prepared is placed in drying in oven, shrinks and forms xerogel;
(c) step (3) xerogel (b) is placed in to retort furnace in 750-950 ℃ of calcining 1-2 hour, can obtains evengranular nano level ZnTiTa
2o
8powder;
(d) by above-mentioned ZnTiTa
2o
8powder is fried wax, is sieved, granulation, moulding, and wherein frying paraffin add-on weight percent in wax link is 10-15%, sieves as 60-80 mesh standard sieve, and forming pressure is 4-10MPa; In employing, warm retort furnace, with heat-up rate 3-10/min, can be realized it for 2-6 hour in 950-1050 ℃ of insulation and sinter porcelain into.
The invention has the beneficial effects as follows: the present invention adopts cheap zinc oxide, tantalum oxide, titanium dioxide is as raw material, substitute expensive metallorganics alkoxide, with mineral acid, carry out dissolution process, based on collosol and gel principle, in conjunction with the advantage of hydro-thermal technique, realize the ternary ZnTiTa of very low temperature synthesis of nano yardstick
2o
8ceramic powder.The synthetic microwave ceramic powder particle of this technology is tiny, even, and synthesis temperature is low, forms ZnTiTa
2o
8ceramic powder has good sintering characteristic, can realize sintering in 1000 ℃, has good microwave dielectric property simultaneously, can meet LTCC field microwave-medium ceramics application demand.
Utilize the nano level ternary that sol gel process is prepared at a lower temperature to stablize ZnTiTa
2o
8ceramic systems powder.The synthetic microwave ceramic powder particle of this technology is tiny, even, and good dispersity has the yardstick of Nano grade, have good sintering characteristic, thing phase purity is high, without any impurity, easy-sintering also has good microwave dielectric property, is expected to become the candidate material of LTCC application.
Adopt raw material to be inorganic, metal oxide or nitrate, cheap, can effectively substitute expensive organism and metal alkoxide; The metering of sol gel process process chemistry is more accurate than controlling, and technique is simple, reproducible; Synthesis of ternary ZnTiTa
2o
8media ceramic thing is stablized single mutually, without dephasign, disturbs; Synthesis of ternary ZnTiTa
2o
8dielectric ceramic powder is nanoscale, has high-specific surface area, high-ratio surface energy, and active high, easy-sintering, can meet LTCC application demand.
Accompanying drawing explanation
Fig. 1 is that sol gel process of the present invention is prepared ZnTiTa
2o
8ceramic process schema,
Fig. 2 is XRD result after Zn-Ti-Ta differing temps calcining of the present invention,
Fig. 3 is TEM shape appearance figure after 750 ℃ of calcinings of xerogel of the present invention,
Fig. 4 (a-c) is ZnTiTa of the present invention
2o
8pottery micro-structure diagram under 950-1050 ℃ of sintering condition,
Fig. 5 is ZnTiTa of the present invention
2o
8pottery XRD result under 950-1050 ℃ of sintering condition.
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
Embodiment
embodiment 1
According to Fig. 1 sol gel process, prepare ZnTiTa
2o
8ceramic process schema, has following steps:
1) aqueous citric acid solution of preparation Zn ion
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, adjusts ZnO(or Zn (NO
3)
2.6H
2o)/TiO
2/ Ta
2o
5mole proportioning is 1+x/1/1 (0<x<0.05); First precision balance takes Zn (NO
3)
2.6H
2totally 8.925 grams of O, are dissolved in 100ml ionized water, and magnetic agitation forms colourless transparent solution;
(b) take 85 grams of citric acids, add in above-mentioned solution and stir, impel citric acid and Zn ion forming complex, make water white transparency Zn ion aqueous citric acid solution;
2) aqueous citric acid solution of preparation Ti and Ta ion
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, take respectively 13.257 grams of 2.396 grams of titanium dioxide and tantalum oxide, be placed in ceramic dielectic reactor, after adding 100ml hydrofluoric acid, seal, then utilize baking oven to carry out 1 hour accelerate dissolution of 150 ℃ of hydrothermal treatment consists of high temperature, form the common molten HF acid solution of water white transparency Ti and Ta ion
;
(b), in the HF acid solution of above-mentioned Ti and Ta ion, adding ammoniacal liquor 250ml to adjust pH value is 10, impels Ti and Ta ion to complete precipitation with the form of metatitanic acid and tantalic acid;
(c) filter above-mentioned precipitation, repeatedly clean to be placed on for several times in lemon aqueous acid and carry out magnetic agitation, form the white citric acid suspension liquid that is uniformly dispersed, wherein adding citric acid molar weight is 230 grams;
(d) above-mentioned white citric acid suspension liquid is placed in to the sealing of ceramic dielectic autoclave, then utilize baking oven to carry out 150 ℃ of processing of high temperature and within 3 hours, impel reaction, impel citric acid and Ti and Ta ion to carry out reacting forming complex dissolving, finally form the aqueous citric acid solution that mixes of water white transparency Ti and Ta ion;
3) ternary ZnO-Ta
2o
5-TiO
2synthetic and the pottery preparation of system microwave-medium ceramics nanometer presoma
(a) the Zn aqueous citric acid solution of being prepared by step (1), (2), Ti mix with Ta ion aqueous citric acid solution, then add polyoxyethylene glycol to carry out esterification, and polyoxyethylene glycol dosage is 100g; By 90 ℃ of heating of water-bath 10 hours, and constantly stir, guarantee evenly, to obtain Zn-Ti-Ta precursor sol;
(b) the Zn-Ti-Ta precursor solution of step (3) (a) being prepared is placed in 150 ℃ of drying in oven, shrinks and forms xerogel;
(c) step (3) xerogel (b) is placed in to retort furnace in 750 ℃ of calcinings 1 hour, can obtains evengranular nano level ZnTiTa
2o
8powder; See that Fig. 2 is XRD result after Zn-Ti-Ta differing temps calcining of the present invention: accompanying drawing 3 is TEM shape appearance figure after 750 ℃ of calcinings of xerogel of the present invention.
(d) by above-mentioned ZnTiTa
2o
8precursor powder is fried wax, is sieved, granulation, moulding, and wherein frying paraffin add-on weight percent in wax link is 15%, and 80 orders that sieve carry out granulation, and forming pressure is 10MPa; In employing, warm retort furnace, with heat-up rate 10/min, can be realized it for 6 hours in 950 ℃ of insulations and sinter porcelain into; Its microwave property is after tested
ε r=38.1,
qf=53,200GHz; Accompanying drawing 4 is SEM shape appearance figure after 6 hours sintering of 950 ℃ of insulations of the present invention; Accompanying drawing 5 is ceramic crystallization XRD figure after 6 hours sintering of 950 ℃ of insulations of the present invention.
According to Fig. 1 sol gel process, prepare ZnTiTa
2o
8ceramic process schema, has following steps:
1) aqueous citric acid solution of preparation Zn ion
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, adjusts ZnO/TiO
2/ Ta
2o
5mole proportioning is 1+x/1/1 (0<x<0.05); First precision balance takes Zn (NO
3)
2.6H
2totally 11.9 grams of O, are dissolved in 100ml ionized water, and magnetic agitation forms colourless transparent solution;
(b) take 95 grams of citric acids, add in above-mentioned solution and stir, impel citric acid and Zn ion forming complex, make water white transparency Zn ion aqueous citric acid solution;
2) aqueous citric acid solution of preparation Ti and Ta ion
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, take respectively 17.676 grams of 3.195 grams of titanium dioxide and tantalum oxide, be placed in ceramic dielectic reactor, after adding 90ml hydrofluoric acid, seal, then utilize baking oven to carry out 3 hours accelerate dissolution of 100 ℃ of hydrothermal treatment consists of high temperature, form the common molten HF acid solution of water white transparency Ti and Ta ion
;
(b), in the HF acid solution of above-mentioned Ti and Ta ion, adding ammoniacal liquor 200ml to adjust pH value is 8, impels Ti and Ta ion to complete precipitation with the form of metatitanic acid and tantalic acid;
(c) filter above-mentioned precipitation, repeatedly clean to be placed on for several times in lemon aqueous acid and carry out magnetic agitation, form the white citric acid suspension liquid that is uniformly dispersed, wherein adding citric acid molar weight is 280 grams;
(d) above-mentioned white citric acid suspension liquid is placed in to the sealing of ceramic dielectic autoclave, then utilizing baking oven to carry out 100 ℃ of high temperature processes to impel for 6 hours and reacts, impel citric acid and Ti and Ta ion to carry out reacting forming complex dissolving, finally form the aqueous citric acid solution that mixes of water white transparency Ti and Ta ion;
3) ternary ZnO-Ta
2o
5-TiO
2synthetic and the pottery preparation of system microwave-medium ceramics nanometer presoma
(a) the Zn aqueous citric acid solution of being prepared by step (1), (2), Ti mix with Ta ion aqueous citric acid solution, then add polyoxyethylene glycol to carry out esterification, and polyoxyethylene glycol dosage is 120g; By 60 ℃ of heating of water-bath 15 hours, and constantly stir, guarantee evenly, to obtain Zn-Ti-Ta precursor sol;
(b) the Zn-Ti-Ta precursor solution of step (3) (a) being prepared is placed in 100 ℃ of drying in oven, shrinks and forms xerogel;
(c) step (3) xerogel (b) is placed in to retort furnace in 850 ℃ of calcinings 1 hour, can obtains evengranular nano level ZnTiTa
2o
8powder; Fig. 2 is XRD result after Zn-Ti-Ta differing temps calcining of the present invention.
(d) by above-mentioned ZnTiTa
2o
8precursor powder is fried wax, is sieved, granulation, moulding, and wherein frying paraffin add-on weight percent in wax link is 12%, and 60 orders that sieve carry out granulation, and forming pressure is 5MPa; In employing, warm retort furnace, with heat-up rate 3/min, can be realized it for 4 hours in 1000 ℃ of insulations and sinter porcelain into; Its microwave property is after tested
ε r=39.8, Qf=57,800GHz; Accompanying drawing 4 is SEM shape appearance figure after 4 hours sintering of 1000 ℃ of insulations of the present invention; Accompanying drawing 5 is ceramic crystallization XRD figure after 4 hours sintering of 1000 ℃ of insulations of the present invention.
embodiment 3
According to Fig. 1 sol gel process, prepare ZnTiTa
2o
8ceramic process schema, has following steps:
1) aqueous citric acid solution of preparation Zn ion
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, adjusts ZnO/TiO
2/ Ta
2o
5mole proportioning is 1+x/1/1 (0<x<0.05); First precision balance takes Zn (NO
3)
2.6H
2totally 5.95 grams of O, are dissolved in 100ml ionized water, and magnetic agitation forms colourless transparent solution;
(b) take 100 grams of citric acids, add in above-mentioned solution and stir, impel citric acid and Zn ion forming complex, make water white transparency Zn ion aqueous citric acid solution;
2) aqueous citric acid solution of preparation Ti and Ta ion
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, take respectively 8.838 grams of 1.598 grams of titanium dioxide and tantalum oxide, be placed in ceramic dielectic reactor, after adding 80ml hydrofluoric acid, seal, then utilize baking oven to carry out 2 hours accelerate dissolution of 130 ℃ of hydrothermal treatment consists of high temperature, form the common molten HF acid solution of water white transparency Ti and Ta ion
;
(b), in the HF acid solution of above-mentioned Ti and Ta ion, adding ammoniacal liquor 190ml to adjust pH value is 9, impels Ti and Ta ion to complete precipitation with the form of metatitanic acid and tantalic acid;
(c) filter above-mentioned precipitation, repeatedly clean to be placed on for several times in lemon aqueous acid and carry out magnetic agitation, form the white citric acid suspension liquid that is uniformly dispersed, wherein adding citric acid molar weight is 300 grams;
(d) above-mentioned white citric acid suspension liquid is placed in to the sealing of ceramic dielectic autoclave, then utilize baking oven to carry out 130 ℃ of processing of high temperature and within 4 hours, impel generation hydro-thermal reaction, impel citric acid and Ti and Ta ion to carry out reacting forming complex dissolving, finally form the aqueous citric acid solution that mixes of water white transparency Ti and Ta ion;
3) ternary ZnO-Ta
2o
5-TiO
2synthetic and the pottery preparation of system microwave-medium ceramics nanometer presoma
(a) the Zn aqueous citric acid solution of being prepared by step (1), (2), Ti mix with Ta ion aqueous citric acid solution, then add polyoxyethylene glycol to carry out esterification, and polyoxyethylene glycol dosage is 150g; By 80 ℃ of heating of water-bath 12 hours, and constantly stir, guarantee evenly, to obtain Zn-Ti-Ta precursor sol;
(b) the Zn-Ti-Ta precursor solution of step (3) (a) being prepared is placed in 120 ℃ of drying in oven, shrinks and forms xerogel;
(c) step (3) xerogel (b) is placed in to retort furnace in 950 ℃ of calcinings 1 hour, can obtains evengranular nano level ZnTiTa
2o
8powder; See that Fig. 2 is XRD result after Zn-Ti-Ta differing temps calcining of the present invention.
(d) by above-mentioned ZnTiTa
2o
8precursor powder is fried wax, is sieved, granulation, moulding, and wherein frying paraffin add-on weight percent in wax link is 13%, and 60 orders that sieve carry out granulation, and forming pressure is 4MPa; In employing, warm retort furnace, with heat-up rate 5/min, can be realized it for 2 hours in 1050 ℃ of insulations and sinter porcelain into; Its microwave property after tested
for ε r=40.5, Qf=60,080GHz; Accompanying drawing 4 is SEM shape appearance figure after 2 hours sintering of 1050 ℃ of insulations of the present invention; Accompanying drawing 5 is ceramic crystallization XRD figure after 2 hours sintering of 1050 ℃ of insulations of the present invention.
Claims (6)
1. utilize the meticulous synthesis of ternary ZnO-Ta of water-soluble sol gel process
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: comprise the following steps:
(1) aqueous citric acid solution of preparation Zn ion;
(2) aqueous citric acid solution of preparation Ti and Ta ion;
(3) ternary ZnO-Ta
2o
5-TiO
2synthetic and the pottery preparation of system microwave-medium ceramics nanometer presoma;
(a) the Zn aqueous citric acid solution of being prepared by step (1), (2), Ti mix with Ta ion aqueous citric acid solution, then add polyoxyethylene glycol to carry out esterification, and the 4-6 that the molar weight that polyoxyethylene glycol adds is citric acid doubly; Heating
,stir, obtain Zn-Ti-Ta precursor sol;
(b) the Zn-Ti-Ta precursor solution of being prepared by step (a) is placed in drying in oven, shrinks and forms xerogel;
(c) xerogel of step (b) is placed in to High Temperature Furnaces Heating Apparatus 750-950 ℃ calcination processing, can obtains evengranular nano level ZnTiTa
2o
8powder;
(d) by above-mentioned ZnTiTa
2o
8powder is fried wax, is sieved, granulation, moulding; Realize its low-temperature sintering and test its microwave property.
2. the meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes according to claim 1
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: the aqueous citric acid solution of described step 1) preparation Zn ion comprises the following steps:
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, adjusts ZnO/TiO
2/ Ta
2o
5mole proportioning is 1+x/1/1, and wherein x is: 0<x<0.05; First take zinc nitrate, be dissolved in appropriate amount of deionized water, or weigh corresponding stoichiometric ratio zinc oxide as raw material, add nitric acid to dissolve, form colourless transparent solution;
(b) take citric acid, the mol ratio of citric acid be zinc nitrate or zinc oxide 4-6 doubly, add in above-mentioned solution, impel citric acid and Zn ion forming complex, make water white transparency Zn ion aqueous citric acid solution.
3. the meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes according to claim 1
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: described step 2) aqueous citric acid solution of preparation Ti and Ta ion comprises the following steps:
(a) according to ZnTiTa
2o
8the stoichiometric ratio of microwave ceramics thing phase, takes titanium dioxide and tantalum oxide, is placed in ceramic dielectic reactor, seals after adding hydrofluoric acid, then utilizes baking oven to carry out pyroprocessing 1-3 hour, and accelerate dissolution forms the common molten HF acid solution of water white transparency Ti and Ta ion
;
(b), in the HF acid solution of above-mentioned Ti and Ta ion, adding ammoniacal liquor to adjust pH value is 8-10, impels Ti and Ta ion to complete precipitation with the form of metatitanic acid and tantalic acid;
(c) filter above-mentioned precipitation, repeatedly clean to be placed on for several times in lemon aqueous acid and carry out magnetic agitation, form the white citric acid suspension liquid that is uniformly dispersed, wherein adding citric acid molar weight is metal ion total amount 4-8 times;
(d) above-mentioned white citric acid suspension liquid is placed in to the sealing of ceramic dielectic autoclave, then utilize baking oven to carry out pyroprocessing 3-6 hour, impel and react, impel citric acid and Ti and Ta ion to carry out reacting forming complex dissolving, finally form the aqueous citric acid solution that mixes of water white transparency Ti and Ta ion.
4. the meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes according to claim 3
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: described step (a) and (d) in the temperature of baking oven pyroprocessing be 100-150 ℃.
5. the meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes according to claim 1
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: described step 3) ternary ZnO-Ta
2o
5-TiO
2synthetic and the pottery preparation of system microwave-medium ceramics nanometer presoma comprises the following steps:
(a) the Zn aqueous citric acid solution of being prepared by step (1), (2), Ti mix with Ta ion aqueous citric acid solution, then add polyoxyethylene glycol to carry out esterification, and the molar weight that polyoxyethylene glycol adds is 4-6 times of Citric Acid Dosage total amount; By water-bath 60-90 ℃ of heating 8-20 hour, and constantly stir, guarantee evenly, to obtain Zn-Ti-Ta precursor sol;
(b) the Zn-Ti-Ta precursor solution of step (3) (a) being prepared is placed in drying in oven, shrinks and forms xerogel;
(c) step (3) xerogel (b) is placed in to retort furnace in 750-950 ℃ of calcining 1-2 hour, can obtains evengranular nano level ZnTiTa
2o
8powder;
(d) by above-mentioned ZnTiTa
2o
8powder is fried wax, is sieved, granulation, moulding, and wherein frying paraffin add-on weight percent in wax link is 10-15%, sieves as 60-80 mesh standard sieve, and forming pressure is 4-10MPa; In employing, warm retort furnace, with heat-up rate 3-10/min, can be realized it for 2-6 hour in 950-1050 ℃ of insulation and sinter porcelain into.
6. the meticulous synthesis of ternary ZnO-Ta of sol-gel method that utilizes according to claim 5
2o
5-TiO
2system microwave-medium ceramics method, is characterized in that: the temperature of the baking oven hyperthermia drying in described step (b) is 100-150 ℃.
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| CN201310195331.0A CN103708835A (en) | 2013-05-24 | 2013-05-24 | Method for fine synthesis of ternary manganese-tantalum mine structure ZnTiTa2O8 microwave dielectric ceramic by using sol-gel method |
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| CN201310195331.0A CN103708835A (en) | 2013-05-24 | 2013-05-24 | Method for fine synthesis of ternary manganese-tantalum mine structure ZnTiTa2O8 microwave dielectric ceramic by using sol-gel method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531528A (en) * | 2009-04-13 | 2009-09-16 | 天津大学 | Method for preparing magnesium niobate microwave ceramic powder on the basis of sol-gel technique |
| CN102093053A (en) * | 2011-01-14 | 2011-06-15 | 天津大学 | New microwave medium ceramic material prepared through middle-temperature sintering |
| CN102775141A (en) * | 2012-08-16 | 2012-11-14 | 济南大学 | Method for finely synthesizing ternary ZnO-Nb2O5-TiO2 microwave dielectric ceramics by wet chemical process |
-
2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531528A (en) * | 2009-04-13 | 2009-09-16 | 天津大学 | Method for preparing magnesium niobate microwave ceramic powder on the basis of sol-gel technique |
| CN102093053A (en) * | 2011-01-14 | 2011-06-15 | 天津大学 | New microwave medium ceramic material prepared through middle-temperature sintering |
| CN102775141A (en) * | 2012-08-16 | 2012-11-14 | 济南大学 | Method for finely synthesizing ternary ZnO-Nb2O5-TiO2 microwave dielectric ceramics by wet chemical process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484170A (en) * | 2018-05-11 | 2018-09-04 | 李冰雪 | A kind of laser chemistry microwave ceramics preparation method |
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