CN108558401A - A kind of sol-gal process preparation Bi2/3Cu2Ta2Ti2O12The method of ceramic powder - Google Patents

A kind of sol-gal process preparation Bi2/3Cu2Ta2Ti2O12The method of ceramic powder Download PDF

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CN108558401A
CN108558401A CN201810472207.7A CN201810472207A CN108558401A CN 108558401 A CN108558401 A CN 108558401A CN 201810472207 A CN201810472207 A CN 201810472207A CN 108558401 A CN108558401 A CN 108558401A
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刘洋
曾杰城
张储君
黎载波
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Shaoguan University
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Abstract

The present invention relates to a kind of sol-gal processes to prepare Bi2/ 3Cu2Ta2Ti2O12The method of ceramic powder, mainly includes the following steps that：Anhydrous potassium carbonate and tantalum pentoxide are weighed, is fitted into cylindrical crucible and melts, obtain milky frit；Milky frit is dissolved in deionized water again, and is gradually dropped nitric acid into solution and generates hydration Ta2O5White precipitate；Separation, washing hydration Ta are filtered again2O5White precipitate is spare, will be hydrated Ta2O5It is added to aqueous citric acid solution, hydrogenperoxide steam generator is added dropwise, forms the aqueous citric acid solution of clarification tantalum；Weigh Bi (NO3)3·5H2O、Cu(NO3)2·3H2O、Ti(C4H9O)4, by Cu (NO3)2·3H2O is dissolved completely in formation solution 1 in the aqueous citric acid solution of tantalum；Ethylene glycol solution is weighed, Ti (C are slowly added dropwise to it4H9O)4, add Bi (NO3)3·5H2O forms solution 2；Solution 1 is added drop-wise in solution 2, ammonium hydroxide formation gel is added dropwise；Through calcining, grinding obtained Bi2/3Cu2Ta2Ti2O12Ceramic powder.Have the characteristics that powder granule grain size fine uniform, synthesis temperature are low, sintering crystal property is good, sintering characteristic is good.

Description

A kind of sol-gal process preparation Bi2/3Cu2Ta2Ti2O12The method of ceramic powder
Technical field
The invention belongs to ceramic powder fabricating technology fields, are related to a kind of sol-gal process preparation Bi2/ 3Cu2Ta2Ti2O12The method of ceramic powder.
Background technology
Ceramic dielectric material development is swift and violent, has a extensive future.High dielectric ceramic material has high-energy density, dielectric The features such as performance temperature stability is good is the critical material in electronics industry, is concerned.The high-performance prepared as base material using it Ceramic capacitor is to study quite wide electronic component of new generation in recent years, is widely used in necks such as national defence, detection, communications Domain：Multiple-layer sheet ceramic capacitor（MLCC）It is prepared into resistor, PTC and NTC thermistor, demand is growing；Microwave electricity Media ceramic is prepared into resonator, medium wave circuit is widely used in mobile phone mobile communication, satellite receiver etc., scientific research and Engineer application has large development space.
Currently, during the research and development of ceramic capacitor material, the ceramic material of perovskite-like structure is noticeable. Such material sintering temperature is low, and higher dielectric constant and smaller dielectric loss, Er Qie are obtained in wide frequency ranges Dielectric property can be kept stable under different temperatures, ferroelectric phase transition does not occur, distortion of lattice is caused to lead to penalty.Together When, perovskite-like structure material also has many deficiencies：As at ambient temperature, resistance with voltage nonlinear change, sintering when Grain growth speed is too fast, breakdown voltage is less than normal etc..Therefore, in view of the above-mentioned problems, changing preparation process, such material is furtherd investigate Expect the root that high dielectric response generates, effectively reduce dielectric loss and dielectric, nonlinear, improves thermal stability and anti-electrical breakdown is special Property, to research and develop novel perovskite-like ceramic capacitor material, the extensive use for promoting it in field of microelectronics is of great significance.
Invention content
In order to overcome the disadvantages mentioned above of the prior art, the present invention to provide a kind of sol-gal process preparation Bi2/3Cu2Ta2Ti2O12 The method of ceramic powder, with powder granule grain size fine uniform, synthesis temperature is low, sintering crystal property is good, sintering characteristic is good The features such as, while it is extensive to prepare raw material sources, easily operated, free from admixture.
The technical solution adopted by the present invention to solve the technical problems is：A kind of sol-gal process preparation Bi2/ 3Cu2Ta2Ti2O12The method of ceramic powder, mainly includes the following steps that：
（1）According to 4.5 ~ 7:1 molar ratio, precise Anhydrous potassium carbonate and tantalum pentoxide are uniformly mixed, and are packed into cylindrical In crucible, it is placed in 850 ~ 950 DEG C of Muffle furnace and melts 3 ~ 8 hours, obtain milky frit；
（2）By step（1）Milky frit be dissolved in 500mL deionized waters, stand 6 ~ 12 hours, with suction pipe take out upper layer Clear solution, and nitric acid is gradually dropped into solution, it is 2 ~ 3 to adjust its pH value, it is ensured that all generates hydration Ta2O5White precipitate；
（3）Filter separation, washing step（2）Hydration Ta2O5White precipitate is spare, rubs according to citric acid and total metal cation You are than being 1 ~ 4：1 accurate configuration aqueous citric acid solution, then will be hydrated Ta2O5It is added to aqueous citric acid solution, appropriate peroxide is added dropwise Change hydrogen solution, and in heating water bath, stirring, makes hydration Ta2O5It is completely dissolved, forms the aqueous citric acid solution of clarification tantalum；
（4）According to Formula B i2/3Cu2Ta2Ti2O12Stoichiometry weigh Bi (NO respectively3)3·5H2O、Cu(NO3)2·3H2O、 Ti(C4H9O)4, by Cu (NO3)2·3H2O is dissolved completely in the aqueous citric acid solution of tantalum, and heating water bath stirs to clarify, shape At solution 1；
（5）It is 1 ~ 3 according to ethylene glycol and citric acid molar ratio:1 weighs ethylene glycol solution, and Ti (C are slowly added dropwise to it4H9O)4, no It is disconnected to be stirred 30 minutes, add Bi (NO3)3·5H2O continues to be stirred 1 hour, forms solution 2；
（6）Solution 1 is slowly dropped in solution 2, is thoroughly mixed 20 ~ 30 minutes, is then added dropwise ammonium hydroxide, adjust pH value to 6 ~ 7, and in heating water bath, be stirred to react 6 ~ 10 hours, formed gel；
（7）Gained gel is dried, through calcining, grinding obtained Bi2/3Cu2Ta2Ti2O12Ceramic powder.
Step（3）It is hydrated Ta2O5White precipitate washs 6 ~ 8 times, is 7 ~ 8 through filtered liquid pH.
Step（3）The hydrogenperoxide steam generator is 2 ~ 3 with citric acid molar ratio：1.
Step（3）（4）（6）Water bath heating temperature is 65 ~ 85 DEG C.
Step（7）Drying temperature is 90 ~ 150 DEG C, and drying time is 4 ~ 30 hours；Calcinating system is：By dry sample From room temperature, 500 ~ 800 DEG C are warming up to 2 ~ 4 DEG C/min rates, keeps the temperature 4 ~ 10 hours, furnace cooling.
The positive effect of the present invention is：With anhydrous K2CO3、Ta2O5、Bi(NO3)3·5H2O、Cu(NO3)2·3H2O、Ti (C4H9O)4, citric acid be raw material, select ethylene glycol as solvent, be prepared for epigranular, crystal property using sol-gal process Good Bi2/3Cu2Ta2Ti2O12Ceramic powder is analyzed by XRD diffractometers and sem test, the powder of this method synthesis Grain fine uniform, about 0.5-2 μm of average grain diameter, crystal property is good, and sintering characteristic is good, while it is extensive to prepare raw material sources, is easy to Operation, free from admixture.
Description of the drawings
Fig. 1 is xerogel DSC-TG figures prepared by the present invention.
Fig. 2 is the XRD diagram of xerogel ceramic powder after 500-800 DEG C of calcining prepared by the present invention.
Fig. 3 is the SEM figures of xerogel ceramic powder after 800 DEG C of calcinings prepared by the present invention.
Specific implementation mode
The present invention is further described with reference to the accompanying drawings and embodiments.
Embodiment 1
A kind of sol-gal process preparation Bi2/3Cu2Ta2Ti2O12The method of ceramic powder, includes the following steps：
（1）According to 5:1 molar ratio, precise Anhydrous potassium carbonate and tantalum pentoxide are uniformly mixed, and are packed into cylindrical crucible In, it is placed in 900 DEG C of Muffle furnace and melts 4 hours, obtain milky frit.
（2）By step（1）Milky frit be dissolved in 500mL deionized waters, stand 8 hours, taken out with suction pipe Layer clear solution, and nitric acid is gradually dropped into solution, it is 2 to adjust its pH value, it is ensured that all generates hydration Ta2O5White precipitate.
（3）Filter separation, washing（2）Hydration Ta2O5White precipitate 6 times is spare, is 7 through filtered liquid pH, according to Citric acid is 1.5 with total metal cation molar ratio：1 accurate configuration aqueous citric acid solution, then will be hydrated Ta2O5It is added to lemon Lemon aqueous acid, is added dropwise hydrogenperoxide steam generator, and hydrogenperoxide steam generator is 2 with citric acid molar ratio：1, and in 75 DEG C of heating water baths, Stirring, makes hydration Ta2O5It is completely dissolved, forms the aqueous citric acid solution of clarification tantalum.
（4）According to Formula B i2/3Cu2Ta2Ti2O12Stoichiometry weigh Bi (NO respectively3)3·5H2O、Cu(NO3)2· 3H2O、Ti(C4H9O)4, by Cu (NO3)2·3H2O is dissolved completely in the aqueous citric acid solution of tantalum, 80 DEG C of heating water baths, stirring To clarification, solution 1 is formed.
（5）It is 1.5 according to ethylene glycol and citric acid molar ratio:1 weighs ethylene glycol solution, and Ti is slowly added dropwise to it (C4H9O)4, it is stirred continuously mixing 30 minutes, adds Bi (NO3)3·5H2O continues to be stirred 1 hour, forms solution 2.
（6）Solution 1 is slowly dropped in solution 2, is thoroughly mixed 20 minutes, ammonium hydroxide is then added dropwise, adjusts pH value To 6, and in 80 DEG C of heating water baths, be stirred to react 6 hours, formed gel.
（7）Gained gel is 6 hours dry in 110 DEG C, then dry sample is calcined, with 2 DEG C/min rates 500 DEG C, 600 DEG C, 700 DEG C and 800 DEG C are warming up to, keeps the temperature 8 hours, furnace cooling grinds and Bi is made2/3Cu2Ta2Ti2O12Pottery Porcelain powder.
To the Bi of preparation2/3Cu2Ta2Ti2O12Ceramic powder is tested, and specific test case is as follows：
Using synthesis thermal analyzer（DSC-TG）Heat analysis is carried out to xerogel, as shown in Figure 1, chemical reaction and weight loss are equal It is completed before 500 DEG C；Using XRD diffraction, to xerogel, the ceramic powder after 500-800 DEG C of calcining carries out material phase analysis, by scheming 2 can be seen, and it is Cu that the main object of powder, which is made, mutually3Ta2Ti2O12(JCPDS#70-0610), also include such as TiO2, bismuth titanium oxide etc. A small amount of dephasign, crystal property are good；Using scanning electron microscope（SEM）To preparing xerogel ceramic powder after 800 DEG C of calcinings Pattern observed, Bi as seen from Figure 32/3Cu2Ta2Ti2O12Ceramic powder particle fine uniform, average grain diameter about 0.5- 2 μm, and without apparent agglomeration.
Embodiment 2
A kind of sol-gal process preparation Bi2/3Cu2Ta2Ti2O12The method of ceramic powder, includes the following steps：
（1）According to 6:1 molar ratio, precise Anhydrous potassium carbonate and tantalum pentoxide are uniformly mixed, and are packed into cylindrical crucible In, it is placed in 920 DEG C of Muffle furnace and melts 6 hours, obtain milky frit.
（2）By step（1）Milky frit be dissolved in 500mL deionized waters, stand 10 hours, taken out with suction pipe Layer clear solution, and nitric acid is gradually dropped into solution, it is 2 to adjust its pH value, it is ensured that all generates hydration Ta2O5White precipitate.
（3）Filter separation, washing（2）Hydration Ta2O5White precipitate 8 times is spare, is 7 through filtered liquid pH, according to Citric acid is 2 with total metal cation molar ratio：1 accurate configuration aqueous citric acid solution, then will be hydrated Ta2O5It is added to lemon Aqueous acid, is added dropwise hydrogenperoxide steam generator, and hydrogenperoxide steam generator is 2.5 with citric acid molar ratio：1, and in 80 DEG C of heating water baths, Stirring, makes hydration Ta2O5It is completely dissolved, forms the aqueous citric acid solution of clarification tantalum.
（4）According to Formula B i2/3Cu2Ta2Ti2O12Stoichiometry weigh Bi (NO respectively3)3·5H2O、Cu(NO3)2· 3H2O、Ti(C4H9O)4, by Cu (NO3)2·3H2O is dissolved completely in the aqueous citric acid solution of tantalum, 85 DEG C of heating water baths, stirring To clarification, solution 1 is formed.
（5）It is 2 according to ethylene glycol and citric acid molar ratio:1 weighs ethylene glycol solution, and Ti (C are slowly added dropwise to it4H9O)4, It is stirred continuously mixing 30 minutes, adds Bi (NO3)3·5H2O continues to be stirred 1 hour, forms solution 2.
（6）Solution 1 is slowly dropped in solution 2, is thoroughly mixed 25 minutes, ammonium hydroxide is then added dropwise, adjusts pH value To 7, and in 80 DEG C of heating water baths, be stirred to react 8 hours, formed gel.
（7）Gained gel is 8 hours dry in 130 DEG C, then dry sample is calcined, with 3 DEG C/min rates 750 DEG C are warming up to, keeps the temperature 8 hours, furnace cooling grinds and Bi is made2/3Cu2Ta2Ti2O12Ceramic powder.
Embodiment 3
A kind of sol-gal process preparation Bi2/3Cu2Ta2Ti2O12The method of ceramic powder, includes the following steps：
（1）According to 7:1 molar ratio, precise Anhydrous potassium carbonate and tantalum pentoxide are uniformly mixed, and are packed into cylindrical crucible In, it is placed in 950 DEG C of Muffle furnace and melts 8 hours, obtain milky frit.
（2）By step（1）Milky frit be dissolved in 500mL deionized waters, stand 12 hours, taken out with suction pipe Layer clear solution, and nitric acid is gradually dropped into solution, it is 3 to adjust its pH value, it is ensured that all generates hydration Ta2O5White precipitate.
（3）Filter separation, washing（2）Hydration Ta2O5White precipitate 8 times is spare, is 8 through filtered liquid pH, according to Citric acid is 4 with total metal cation molar ratio：1 accurate configuration aqueous citric acid solution, then will be hydrated Ta2O5It is added to lemon Aqueous acid, is added dropwise hydrogenperoxide steam generator, and hydrogenperoxide steam generator is 3 with citric acid molar ratio：1, and in 85 DEG C of heating water baths, stir It mixes, makes hydration Ta2O5It is completely dissolved, forms the aqueous citric acid solution of clarification tantalum.
（4）According to Formula B i2/3Cu2Ta2Ti2O12Stoichiometry weigh Bi (NO respectively3)3·5H2O、Cu(NO3)2· 3H2O、Ti(C4H9O)4, by Cu (NO3)2·3H2O is dissolved completely in the aqueous citric acid solution of tantalum, 80 DEG C of heating water baths, stirring To clarification, solution 1 is formed.
（5）It is 3 according to ethylene glycol and citric acid molar ratio:1 weighs ethylene glycol solution, and Ti (C are slowly added dropwise to it4H9O)4, It is stirred continuously mixing 30 minutes, adds Bi (NO3)3·5H2O continues to be stirred 1 hour, forms solution 2.
（6）Solution 1 is slowly dropped in solution 2, is thoroughly mixed 30 minutes, ammonium hydroxide is then added dropwise, adjusts pH value To 7, and in 80 DEG C of heating water baths, be stirred to react 10 hours, formed gel.
（7）Gained gel is 12 hours dry in 150 DEG C, then dry sample is calcined, with 4 DEG C/min rates 650 DEG C are warming up to, keeps the temperature 10 hours, furnace cooling grinds and Bi is made2/3Cu2Ta2Ti2O12Ceramic powder.

Claims (5)

1. a kind of sol-gal process prepares Bi2/3Cu2Ta2Ti2O12The method of ceramic powder, it is characterised in that include mainly following step Suddenly：
（1）According to 4.5 ~ 7:1 molar ratio, precise Anhydrous potassium carbonate and tantalum pentoxide are uniformly mixed, and are packed into cylindrical In crucible, it is placed in 850 ~ 950 DEG C of Muffle furnace and melts 3 ~ 8 hours, obtain milky frit；
（2）By step（1）Milky frit be dissolved in 500mL deionized waters, stand 6 ~ 12 hours, with suction pipe take out upper layer Clear solution, and nitric acid is gradually dropped into solution, it is 2 ~ 3 to adjust its pH value, it is ensured that all generates hydration Ta2O5White precipitate；
（3）Filter separation, washing step（2）Hydration Ta2O5White precipitate is spare, rubs according to citric acid and total metal cation You are than being 1 ~ 4：1 accurate configuration aqueous citric acid solution, then will be hydrated Ta2O5It is added to aqueous citric acid solution, appropriate peroxide is added dropwise Change hydrogen solution, and in heating water bath, stirring, makes hydration Ta2O5It is completely dissolved, forms the aqueous citric acid solution of clarification tantalum；
（4）According to Formula B i2/3Cu2Ta2Ti2O12Stoichiometry weigh Bi (NO respectively3)3·5H2O、Cu(NO3)2·3H2O、Ti (C4H9O)4, by Cu (NO3)2·3H2O is dissolved completely in the aqueous citric acid solution of tantalum, and heating water bath stirs to clarify, and is formed Solution 1；
（5）It is 1 ~ 3 according to ethylene glycol and citric acid molar ratio:1 weighs ethylene glycol solution, and Ti (C are slowly added dropwise to it4H9O)4, no It is disconnected to be stirred 30 minutes, add Bi (NO3)3·5H2O continues to be stirred 1 hour, forms solution 2；
（6）Solution 1 is slowly dropped in solution 2, is thoroughly mixed 20 ~ 30 minutes, is then added dropwise ammonium hydroxide, adjust pH value to 6 ~ 7, and in heating water bath, be stirred to react 6 ~ 10 hours, formed gel；
（7）Gained gel is dried, through calcining, grinding obtained Bi2/3Cu2Ta2Ti2O12Ceramic powder.
2. sol-gal process as described in claim 1 prepares Bi2/3Cu2Ta2Ti2O12The method of ceramic powder, it is characterised in that：Step Suddenly（3）It is hydrated Ta2O5White precipitate washs 6 ~ 8 times, is 7 ~ 8 through filtered liquid pH.
3. sol-gal process as described in claim 1 prepares Bi2/3Cu2Ta2Ti2O12The method of ceramic powder, it is characterised in that：Step Suddenly（3）The hydrogenperoxide steam generator is 2 ~ 3 with citric acid molar ratio：1.
4. sol-gal process as described in claim 1 prepares Bi2/3Cu2Ta2Ti2O12The method of ceramic powder, it is characterised in that：Step Suddenly（3）（4）（6）Water bath heating temperature is 65 ~ 85 DEG C.
5. sol-gal process as described in claim 1 prepares Bi2/3Cu2Ta2Ti2O12The method of ceramic powder, it is characterised in that：Step Suddenly（7）Drying temperature is 90 ~ 150 DEG C, and drying time is 4 ~ 30 hours；Calcinating system is：By dry sample from room temperature, with 2 ~ 4 DEG C/min rates are warming up to 500 ~ 800 DEG C, keep the temperature 4 ~ 10 hours, furnace cooling.
CN201810472207.7A 2018-05-17 2018-05-17 Preparation of Bi by sol-gel method2/3Cu2Ta2Ti2O12Method for producing ceramic powder Active CN108558401B (en)

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CN116477947A (en) * 2023-05-18 2023-07-25 韶关学院 Method for improving dielectric property of copper tantalate ceramic material

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