CN103833071A - Preparation method and application of nano-CaCu3Ti4O12 ceramic powder - Google Patents

Preparation method and application of nano-CaCu3Ti4O12 ceramic powder Download PDF

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CN103833071A
CN103833071A CN201410045117.1A CN201410045117A CN103833071A CN 103833071 A CN103833071 A CN 103833071A CN 201410045117 A CN201410045117 A CN 201410045117A CN 103833071 A CN103833071 A CN 103833071A
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cacu
ceramic powder
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迟庆国
张昌海
林家齐
刘刚
李晶
孙嘉
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Harbin University of Science and Technology
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Abstract

The invention relates to a hydrothermal preparation method of nano-CaCu3Ti4O12 ceramic powder and application thereof. The method provided by the invention aims to solve the technical problems of high preparation cost, uneven size distribution and uncontrollable shape of existing CaCu3Ti4O12 ceramic powder and poor comprehensive performance of composite materials prepared by taking micrometer CaCu3Ti4O12 ceramic powder as filler particles. The method includes: adding a calcium nitrate solution and a copper sulfate solution into a titanyl sulfate mixed solution, then adding a mixed solution of polyethylene glycol and sodium hydroxide, pouring the obtained solution into a hydrothermal kettle to conduct heat preservation, and carrying out drying, grinding and sintering, thus obtaining the ceramic powder. The nano-CaCu3Ti4O12 ceramic powder is used as filler to prepare a CaCu3Ti4O12/polyimide composite medium. The ceramic powder prepared by the method provided by the invention has uniform size distribution and controllable shape. The composite materials prepared from the powder have excellent comprehensive performance. The invention belongs to the fields of ceramic powder preparation and application.

Description

Nanometer CaCu 3ti 4o 12the preparation method of ceramic powder and application
Technical field
The present invention relates to a kind of hydrothermal method and prepare nanometer CaCu 3ti 4o 12the method of ceramic powder and application.
Background technology
CaCu 3 Ti 4 O-CaCu 3ti 4o 12compound has unusual huge dielectric Changshu and extremely low loss, and particularly within the scope of very wide warm area, dielectric constant values is almost constant, has reflected the high thermal stability of dielectric response.It is likely become and in a series of high-technology fields such as the storage of business's density energy, thin-film device, high dielectric capacitor, obtain application widely.
At present, for the CaCu with huge dielectric constant 3ti 4o 12research in, the experiment specific inductivity that different researchers is reported also exists the difference on the order of magnitude, and the temperature value difference that specific inductivity is undergone mutation is also very large.This has reflected that the each technique of different experimentations, experimental technique and system plays obvious effect to the dielectric properties of material.Current, CaCu 3ti 4o 12powder mainly adopts organic salt preparation, and preparation cost is higher, the production cycle is longer.And, what is more important, the CaCu of current preparation 3ti 4o 12the particle diameter of powder is mostly micron level, grain size skewness; And conventional CaCu 3ti 4o 12powder is prepared sintering temperature higher (being greater than 1000 ℃), consumes the energy serious.Nanometer CaCu 3ti 4o 12because possessing the characteristics such as high reactivity, interfacial effect be obvious, be the important filler of preparing high energy storage density organic matrix/inorganic particle composite material, common micron CaCu 3ti 4o 12powder easily preparation but need very highly doped amount just can obtain desirable performance during as mineral filler, and mechanical property has a greatly reduced quality again, and nanometer CaCu 3ti 4o 12powder can overcome above-mentioned shortcoming because of its special surface property, still, prepare high quality nano level (particularly 50nm) and low cost can be in a large number as the CaCu of filler 3ti 4o 12powder is more difficult, studies rare report in the past.
Summary of the invention
The present invention is in order to solve existing CaCu 3ti 4o 12ceramic powder preparation cost is higher, and distribution of sizes is inhomogeneous, pattern is uncontrollable and micron CaCu 3ti 4o 12when ceramic powder is prepared matrix material as filler particles, the poor technical problem of over-all properties, provides a kind of nanometer CaCu 3ti 4o 12the preparation method of ceramic powder and application.
Nanometer CaCu 3ti 4o 12the preparation method of ceramic powder carries out according to following steps:
One, titanyl sulfate is dissolved in dilute sulphuric acid, obtains titanyl sulfate mixing solutions, in titanyl sulfate mixing solutions, the concentration of titanyl sulfate is 0.01～80g/L, and the concentration of sulfuric acid is 5～100g/L;
Two, prepare respectively copper-bath and ca nitrate soln, the concentration of copper-bath is 1～10g/L, and the concentration of ca nitrate soln is 0.005～15g/L;
Three, the ratio that is 1:3:4 according to Ca:Cu:Ti mol ratio, adds ca nitrate soln and copper-bath in titanyl sulfate mixing solutions to;
Four, polyoxyethylene glycol being joined to concentration is in 50～100g/L sodium hydroxide solution, obtains mixed solution, and in mixed solution, the concentration of polyoxyethylene glycol is 1～40g/L;
Five, the ratio that is 40～60:1 according to the mol ratio of sodium hydroxide and titanyl sulfate, under the condition stirring, the mixing solutions of step 3 gained is added in the mode of atomization in the mixed solution of step 4 gained, stirring velocity is 300～600r/min, obtains suspension liquid;
Six, the suspension liquid of step 5 gained is poured in water heating kettle, the pH value that adopts nitric acid and sodium hydroxide to adjust mixed solution system in water heating kettle is 10～14, again water heating kettle is put into baking oven, be to be incubated 4～72h under the condition of 120～200 ℃ in temperature, then powder is poured out from water heating kettle, it is 7 that centrifugation is cleaned powder to the pH value of washing lotion with clear water after filtering, and then in 50～80 ℃ of oven dry, after drying, grinds;
Seven, by grind after powder at 600～950 ℃, insulation 30～120min, obtain nanometer CaCu 3ti 4o 12ceramic powder.The model of polyoxyethylene glycol described in step 4 is a kind of of PEG400, PEG1500, PEG2000, PEG10000, PEG20000 and PEG40000 or several mixture wherein.
Nanometer CaCu 3ti 4o 12ceramic powder as filler for the preparation of CaCu 3ti 4o 12/ polyimide complex media.
CaCu 3ti 4o 12the preparation method of/polyimide complex media carries out according to following steps:
One, in N,N-DIMETHYLACETAMIDE, add 4,4'-diaminodiphenyl oxide and nanometer CaCu 3ti 4o 12ceramic powder, after the ultrasonic 1h～2h of frequency with 40kHz～60kHz, under the condition of simultaneously carrying out at ultrasonic electric stirring, add pyromellitic dianhydride or pyromellitic acid anhydride, after all adding, continue to stir, reaction times is 1h～2h, then leave standstill 6h～12h, obtain mixing solutions, wherein the volume of N,N-DIMETHYLACETAMIDE and nanometer CaCu 3ti 4o 12the mass ratio of ceramic powder is 12mL ﹕ 1g, 4,4'-diaminodiphenyl oxide and nanometer CaCu 3ti 4o 12the mass ratio of ceramic powder is 0.39 ﹕ 1, pyromellitic dianhydride or pyromellitic acid anhydride and nanometer CaCu 3ti 4o 12the mass ratio of ceramic powder is 0.43 ﹕ 1;
Two, by the mixing solutions in step 1, be applied on glassly, then put into vacuum drying oven, vacuumize as 100Pa～160Pa, at 70～90 ℃, dry 30min, then at normal pressure, 120～330 ℃, carry out staged hyperthermic treatment in high-temperature test chamber, obtain CaCu 3ti 4o 12/ polyimide complex media, described CaCu 3ti 4o 12nanometer CaCu in/polyimide complex media 3ti 4o 12the volume fraction of ceramic powder is 30%;
The hyperthermic treatment of staged described in step 2 is as follows: at 120 ℃ of constant temperature 30min, then continue heating, at 165 ℃ of constant temperature 30min, at 235 ℃ of constant temperature 30min, at 260 ℃ of constant temperature 1h, at 285 ℃ of constant temperature 1h, at 330 ℃ of constant temperature 1h.
The present invention prepares nanometer CaCu 3ti 4o 12the inorganic salt raw material cheapness that ceramic powder uses, preparation technology is simple, without main equipment; Sintering temperature is lower, and the nanometer CaCu of preparation 3ti 4o 12even size distribution, the pattern of ceramic powder are controlled, have the energy of saving and can prepare in a large number as mineral filler and the good feature of gained composite material combination property.
Accompanying drawing explanation
Fig. 1 is the CaCu of experiment one preparation 3ti 4o 12stereoscan photograph;
Fig. 2 tests the CaCu of a preparation 3ti 4o 12material phase analysis figure;
Fig. 3 is the CaCu of experiment three preparations 3ti 4o 12/ polyimide (PI) complex media (wherein nanometer CaCu 3ti 4o 12preparation process is shown in experiment one) and a micron CaCu 3ti 4o 12/ PI(is CaCu wherein 3ti 4o 12prepared by traditional solid state reaction sintering process, crystallization temperature is 1050 ℃, and crystallization time is 4h) the specific inductivity comparison diagram of laminated film, in figure-●-represent the CaCu of experiment three preparations 3ti 4o 12the specific inductivity figure of/PI complex media ,-▲-expression micron a CaCu 3ti 4o 12the specific inductivity figure of/PI laminated film.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: nanometer CaCu in present embodiment 3ti 4o 12the preparation method of ceramic powder carries out according to following steps:
One, titanyl sulfate is dissolved in dilute sulphuric acid, obtains titanyl sulfate mixing solutions, in titanyl sulfate mixing solutions, the concentration of titanyl sulfate is 0.01～80g/L, and the concentration of sulfuric acid is 5～100g/L;
Two, prepare respectively copper-bath and ca nitrate soln, the concentration of copper-bath is 1～10g/L, and the concentration of ca nitrate soln is 0.005～15g/L;
Three, the ratio that is 1:3:4 according to Ca:Cu:Ti mol ratio, adds ca nitrate soln and copper-bath in titanyl sulfate mixing solutions to;
Four, polyoxyethylene glycol being joined to concentration is in 50～100g/L sodium hydroxide solution, obtains mixed solution, and in mixed solution, the concentration of polyoxyethylene glycol is 1～40g/L;
Five, the ratio that is 40～60:1 according to the mol ratio of sodium hydroxide and titanyl sulfate, under the condition stirring, the mixing solutions of step 3 gained is added in the mode of atomization in the mixed solution of step 4 gained, stirring velocity is 300～600r/min, obtains suspension liquid;
Six, the suspension liquid of step 5 gained is poured in water heating kettle, the pH value that adopts nitric acid and sodium hydroxide to adjust mixed solution system in water heating kettle is 10～14, again water heating kettle is put into baking oven, be to be incubated 4～72h under the condition of 120～200 ℃ in temperature, then powder is poured out from water heating kettle, it is 7 that centrifugation is cleaned powder to the pH value of washing lotion with clear water after filtering, and then in 50～80 ℃ of oven dry, after drying, grinds;
Seven, by grind after powder at 600～950 ℃, insulation 30～120min, obtain nanometer CaCu 3ti 4o 12ceramic powder.
The model of polyoxyethylene glycol described in step 4 is a kind of of PEG400, PEG1500, PEG2000, PEG10000, PEG20000 and PEG40000 or several mixture wherein.
When polyoxyethylene glycol described in present embodiment is mixture between each composition for arbitrarily than.
Embodiment two: what present embodiment was different from embodiment one is in step 1 in titanyl sulfate mixing solutions, and the concentration of titanyl sulfate is 2g/L, and the concentration of sulfuric acid is 30g/L.Other is identical with embodiment one.
Embodiment three: the concentration of what present embodiment was different from one of embodiment one or two is copper-bath in step 2 is 5g/L, and the concentration of ca nitrate soln is 3g/L.Other is not identical with one of embodiment one or two.
Embodiment four: the concentration of what present embodiment was different from one of embodiment one to three is sodium hydroxide solution in step 4 is 55g/L, and in mixed solution, the concentration of polyoxyethylene glycol is 10g/L.Other is identical with one of embodiment one to three.
Embodiment five: the ratio that what present embodiment was different from one of embodiment one to four is is 45:1 according to the mol ratio of sodium hydroxide and titanyl sulfate in step 5, the mixing solutions of step 3 gained is added in the mode of atomization in the mixed solution of step 4 gained, stirring velocity is 500r/min.Other is identical with one of embodiment one to four.
Embodiment six: the ratio that what present embodiment was different from one of embodiment one to five is is 45:1 according to the mol ratio of sodium hydroxide and titanyl sulfate in step 5, the mixing solutions of step 3 gained is added in the mode of atomization in the mixed solution of step 4 gained, stirring velocity is 500r/min.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is that the pH value that adopts nitric acid and sodium hydroxide to adjust mixed solution system in water heating kettle in step 6 is 14, again water heating kettle being put into baking oven, is to be incubated 12h under the condition of 140 ℃ in temperature.Other is identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different from one of embodiment one to seven is in step 7 by the powder after grinding at 700～950 ℃, insulation 50min.Other is identical with one of embodiment one to seven.
Embodiment nine: nanometer CaCu in present embodiment 3ti 4o 12ceramic powder as filler for the preparation of CaCu 3ti 4o 12/ polyimide complex media.
Embodiment ten: present embodiment CaCu 3ti 4o 12the preparation method of/polyimide complex media carries out according to following steps:
One, in N,N-DIMETHYLACETAMIDE, the nanometer CaCu that adds 4,4'-diaminodiphenyl oxide and embodiment one to obtain 3ti 4o 12ceramic powder, after the ultrasonic 1h～2h of frequency with 40kHz～60kHz, under the condition of simultaneously carrying out at ultrasonic electric stirring, add pyromellitic dianhydride or pyromellitic acid anhydride, after all adding, continue to stir, reaction times is 1h～2h, then leave standstill 6h～12h, obtain mixing solutions, wherein the volume of N,N-DIMETHYLACETAMIDE and nanometer CaCu 3ti 4o 12the mass ratio of ceramic powder is 12mL ﹕ 1g, 4,4'-diaminodiphenyl oxide and nanometer CaCu 3ti 4o 12the mass ratio of ceramic powder is 0.39 ﹕ 1, pyromellitic dianhydride or pyromellitic acid anhydride and nanometer CaCu 3ti 4o 12the mass ratio of ceramic powder is 0.43 ﹕ 1;
Two, by the mixing solutions in step 1, be applied on glassly, then put into vacuum drying oven, vacuumize as 100Pa～160Pa, at 70～90 ℃, dry 30min, then at normal pressure, 120～330 ℃, carry out staged hyperthermic treatment in high-temperature test chamber, obtain CaCu 3ti 4o 12/ polyimide complex media, described CaCu 3ti 4o 12nanometer CaCu in/polyimide complex media 3ti 4o 12the volume fraction of ceramic powder is 30%;
The hyperthermic treatment of staged described in step 2 is as follows: at 120 ℃ of constant temperature 30min, then continue heating, at 165 ℃ of constant temperature 30min, at 235 ℃ of constant temperature 30min, at 260 ℃ of constant temperature 1h, at 285 ℃ of constant temperature 1h, at 330 ℃ of constant temperature 1h.
Embodiment 11: what present embodiment was different from embodiment ten is in step 2 in vacuum drying oven, vacuumizes as 130Pa, dries 30min at 80 ℃.Other are identical with embodiment ten.
Adopt following experimental verification effect of the present invention:
Experiment one:
Nanometer CaCu 3ti 4o 12the preparation method of ceramic powder carries out according to following steps:
One, titanyl sulfate is dissolved in dilute sulphuric acid, obtains titanyl sulfate mixing solutions, in titanyl sulfate mixing solutions, the concentration of titanyl sulfate is 25g/L, and the concentration of sulfuric acid is 40g/L;
Two, prepare respectively copper-bath and ca nitrate soln, the concentration of copper-bath is 10g/L, and the concentration of ca nitrate soln is 5g/L;
Three, the ratio that is 1:3:4 according to Ca:Cu:Ti mol ratio, adds ca nitrate soln and copper-bath in titanyl sulfate mixing solutions to;
Four, PEG2000 being joined to concentration is in 50g/L sodium hydroxide solution, obtains mixed solution, and in mixed solution, the concentration of PEG2000 is 8g/L;
Five, the ratio that is 50:1 according to the mol ratio of sodium hydroxide and titanyl sulfate is added the mixing solutions of step 3 gained in the mixed solution of step 4 gained under the condition stirring in the mode of atomization, stirring velocity is 400r/min, obtains suspension liquid;
Six, the suspension liquid of step 5 gained is poured in water heating kettle, the pH value that adopts nitric acid and sodium hydroxide to adjust mixed solution system in water heating kettle is 11, again water heating kettle is put into baking oven, be to be incubated 8h under the condition of 160 ℃ in temperature, then powder is poured out from water heating kettle, it is 7 that centrifugation is cleaned powder to the pH value of washing lotion with clear water after filtering, and then in 60 ℃ of oven dry, after drying, grinds;
Seven, by grind after powder at 900 ℃, insulation 40min, obtain nanometer CaCu 3ti 4o 12ceramic powder.
As can be seen from Figure 1 prepared CaCu 3ti 4o 12particle size is even, and particle diameter is about 50nm.
As can be seen from Figure 2 the CaCu preparing 3ti 4o 12show pure cubic perovskite structure.
Experiment two:
Nanometer CaCu 3ti 4o 12the preparation method of ceramic powder carries out according to following steps:
One, titanyl sulfate is dissolved in dilute sulphuric acid, obtains titanyl sulfate mixing solutions, in titanyl sulfate mixing solutions, the concentration of titanyl sulfate is 20g/L, and the concentration of sulfuric acid is 20g/L;
Two, prepare respectively copper-bath and ca nitrate soln, the concentration of copper-bath is 10g/L, and the concentration of ca nitrate soln is 15g/L;
Three, the ratio that is 1:3:4 according to Ca:Cu:Ti mol ratio, adds ca nitrate soln and copper-bath in titanyl sulfate mixing solutions to;
Four, polyoxyethylene glycol PEG1500 being joined to concentration is in 60g/L sodium hydroxide solution, obtains mixed solution, and in mixed solution, the concentration of polyoxyethylene glycol PEG1500 is 5g/L;
Five, the ratio that is 60:1 according to the mol ratio of sodium hydroxide and titanyl sulfate is added the mixing solutions of step 3 gained in the mixed solution of step 4 gained in the mode of atomization under the condition stirring, and obtains suspension liquid;
Six, the suspension liquid of step 5 gained is poured in water heating kettle, the pH value that adopts nitric acid and sodium hydroxide to adjust mixed solution system in water heating kettle is 12, again water heating kettle is put into baking oven, be to be incubated 4h under the condition of 140 ℃ in temperature, then powder is poured out from water heating kettle, it is 7 that centrifugation is cleaned powder to the pH value of washing lotion with clear water after filtering, and then in 50 ℃ of oven dry, after drying, grinds;
Seven, by grind after powder at 950 ℃, insulation 30min, obtain nanometer CaCu 3ti 4o 12ceramic powder.
Experiment three:
CaCu 3ti 4o 12the preparation method of/polyimide complex media carries out according to following steps:
One,, in N,N-DIMETHYLACETAMIDE, add 4,4'-diaminodiphenyl oxide and the experiment one nanometer CaCu obtaining 3ti 4o 12ceramic powder, after the ultrasonic 1.5h of frequency with 50kHz, under the condition of simultaneously carrying out at ultrasonic electric stirring, add pyromellitic dianhydride or pyromellitic acid anhydride, after all adding, continue to stir, reaction times is 1.5h, then leaves standstill 10h, obtains mixing solutions, stir speed (S.S.) is 600r/min, wherein the volume of N,N-DIMETHYLACETAMIDE and nanometer CaCu 3ti 4o 12the mass ratio of ceramic powder is 12mL ﹕ 1g, 4,4'-diaminodiphenyl oxide and nanometer CaCu 3ti 4o 12the mass ratio of ceramic powder is 0.39 ﹕ 1, pyromellitic dianhydride or pyromellitic acid anhydride and nanometer CaCu 3ti 4o 12the mass ratio of ceramic powder is 0.43 ﹕ 1;
Two, by the mixing solutions in step 1, be applied on glassly, then put into vacuum drying oven, vacuumize as 160Pa, at 80 ℃, dry 30min, then at normal pressure, 120～330 ℃, carry out staged hyperthermic treatment in high-temperature test chamber, obtain CaCu 3ti 4o 12/ polyimide complex media, described CaCu 3ti 4o 12nanometer CaCu in/polyimide complex media 3ti 4o 12the volume fraction of ceramic powder is 30%;
The hyperthermic treatment of staged described in step 2 is as follows: at 120 ℃ of constant temperature 30min, then continue heating, at 165 ℃ of constant temperature 30min, at 235 ℃ of constant temperature 30min, at 260 ℃ of constant temperature 1h, at 285 ℃ of constant temperature 1h, at 330 ℃ of constant temperature 1h.
Fig. 3 is the CaCu of this experiment preparation 3ti 4o 12/ polyimide complex media (wherein nanometer CaCu 3ti 4o 12preparation process is shown in experiment one) with common micron CaCu 3ti 4o 12/ PI(is CaCu wherein 3ti 4o 12prepared by traditional solid state reaction sintering process, crystallization temperature is 1050 ℃, and crystallization time is 4h) the specific inductivity comparison diagram of laminated film, as can be seen from the figure, with respect to conventional 40vol% micron CaCu 3ti 4o 12/ PI film, the nanometer CaCu that this experiment prepares 3ti 4o 12/ PI film, (30vol%CaCu under lower ceramic powder is filled 3ti 4o 12), realize specific inductivity and significantly improved.And, the micron CaCu preparing with respect to routine 3ti 4o 12powder, the nanometer CaCu that this experiment prepares 3ti 4o 12tc is low, and crystallization time is short, saves mass energy.

Claims (9)

1. nanometer CaCu 3ti 4o 12the preparation method of ceramic powder, is characterized in that nanometer CaCu 3ti 4o 12the preparation method of ceramic powder carries out according to following steps:
One, titanyl sulfate is dissolved in dilute sulphuric acid, obtains titanyl sulfate mixing solutions, in titanyl sulfate mixing solutions, the concentration of titanyl sulfate is 0.01～80g/L, and the concentration of sulfuric acid is 5～100g/L;
Two, prepare respectively copper-bath and ca nitrate soln, the concentration of copper-bath is 1～10g/L, and the concentration of ca nitrate soln is 0.005～15g/L;
Three, the ratio that is 1:3:4 according to Ca:Cu:Ti mol ratio, adds ca nitrate soln and copper-bath in titanyl sulfate mixing solutions to;
Four, polyoxyethylene glycol being joined to concentration is in 50～100g/L sodium hydroxide solution, obtains mixed solution, and in mixed solution, the concentration of polyoxyethylene glycol is 1～40g/L;
Five, the ratio that is 40～60:1 according to the mol ratio of sodium hydroxide and titanyl sulfate, under the condition stirring, the mixing solutions of step 3 gained is added in the mode of atomization in the mixed solution of step 4 gained, stirring velocity is 300～600r/min, obtains suspension liquid;
Six, the suspension liquid of step 5 gained is poured in water heating kettle, the pH value that adopts nitric acid and sodium hydroxide to adjust mixed solution system in water heating kettle is 10～14, again water heating kettle is put into baking oven, be to be incubated 4～72h under the condition of 120～200 ℃ in temperature, then powder is poured out from water heating kettle, it is 7 that centrifugation is cleaned powder to the pH value of washing lotion with clear water after filtering, and then in 50～80 ℃ of oven dry, after drying, grinds;
Seven, by grind after powder at 600～950 ℃, insulation 30～120min, obtain nanometer CaCu 3ti 4o 12ceramic powder;
The model of polyoxyethylene glycol described in step 4 is a kind of of PEG400, PEG1500, PEG2000, PEG10000, PEG20000 and PEG40000 or several mixture wherein.
2. nanometer CaCu according to claim 1 3ti 4o 12the preparation method of ceramic powder, is characterized in that in step 1 in titanyl sulfate mixing solutions that the concentration of titanyl sulfate is 2g/L, and the concentration of sulfuric acid is 30g/L.
3. according to nanometer CaCu described in claim 1 or 2 3ti 4o 12the preparation method of ceramic powder, the concentration that it is characterized in that copper-bath in step 2 is 5g/L, the concentration of ca nitrate soln is 3g/L.
4. according to nanometer CaCu described in claim 1 or 2 3ti 4o 12the preparation method of ceramic powder, is characterized in that the concentration of sodium hydroxide solution in step 4 is 55g/L, and in mixed solution, the concentration of polyoxyethylene glycol is 10g/L.
5. according to nanometer CaCu described in claim 1 or 2 3ti 4o 12the preparation method of ceramic powder, it is characterized in that the ratio that is 45:1 according to the mol ratio of sodium hydroxide and titanyl sulfate in step 5, the mixing solutions of step 3 gained is added in the mode of atomization in the mixed solution of step 4 gained, stirring velocity is 500r/min.
6. according to nanometer CaCu described in claim 1 or 2 3ti 4o 12the preparation method of ceramic powder, is characterized in that the pH value that adopts nitric acid and sodium hydroxide to adjust mixed solution system in water heating kettle in step 6 is 12, then water heating kettle is put into baking oven, is to be incubated 8h under the condition of 160 ℃ in temperature.
7. according to nanometer CaCu described in claim 1 or 2 3ti 4o 12the preparation method of ceramic powder, is characterized in that the pH value that adopts nitric acid and sodium hydroxide to adjust mixed solution system in water heating kettle in step 6 is 14, then water heating kettle is put into baking oven, is to be incubated 12h under the condition of 140 ℃ in temperature.
8. according to nanometer CaCu described in claim 1 or 2 3ti 4o 12the preparation method of ceramic powder, is characterized in that in step 7 by the powder after grinding at 700～950 ℃ insulation 50min.
9. nanometer CaCu 3ti 4o 12the application of ceramic powder, is characterized in that nanometer CaCu 3ti 4o 12ceramic powder as filler for the preparation of CaCu 3ti 4o 12/ polyimide complex media.
CN201410045117.1A 2014-02-07 2014-02-07 Preparation method and application of nano-CaCu3Ti4O12 ceramic powder Pending CN103833071A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104945645A (en) * 2015-06-23 2015-09-30 绥化学院 Preparation method of polyethylene composite material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05163022A (en) * 1991-12-11 1993-06-29 Ishihara Sangyo Kaisha Ltd Spherical anatase titanium oxide and its production
CN102070333A (en) * 2010-11-19 2011-05-25 西安交通大学 Method for preparing copper calcium titanate ceramic
CN102432062A (en) * 2011-09-26 2012-05-02 常州大学 Preparation method of perovskite-like varistor ceramic material CaCu3Ti4O12 with high dielectric constant
CN102924920A (en) * 2012-11-23 2013-02-13 哈尔滨理工大学 Amorphous calcium-copper-titanium-oxygen ceramic/polyimide composite film and preparation method thereof
CN103482974A (en) * 2013-09-29 2014-01-01 哈尔滨理工大学 Preparation method of CaCu3Ti4O12 ceramic powder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05163022A (en) * 1991-12-11 1993-06-29 Ishihara Sangyo Kaisha Ltd Spherical anatase titanium oxide and its production
CN102070333A (en) * 2010-11-19 2011-05-25 西安交通大学 Method for preparing copper calcium titanate ceramic
CN102432062A (en) * 2011-09-26 2012-05-02 常州大学 Preparation method of perovskite-like varistor ceramic material CaCu3Ti4O12 with high dielectric constant
CN102924920A (en) * 2012-11-23 2013-02-13 哈尔滨理工大学 Amorphous calcium-copper-titanium-oxygen ceramic/polyimide composite film and preparation method thereof
CN103482974A (en) * 2013-09-29 2014-01-01 哈尔滨理工大学 Preparation method of CaCu3Ti4O12 ceramic powder

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104945645A (en) * 2015-06-23 2015-09-30 绥化学院 Preparation method of polyethylene composite material
CN104945645B (en) * 2015-06-23 2018-02-09 绥化学院 The preparation method of composite polyethylene material

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Application publication date: 20140604