CN101698603A - Method for preparing copper calcium titanate (CCTO) ceramic based on coprecipitation method - Google Patents
Method for preparing copper calcium titanate (CCTO) ceramic based on coprecipitation method Download PDFInfo
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- CN101698603A CN101698603A CN200910218503A CN200910218503A CN101698603A CN 101698603 A CN101698603 A CN 101698603A CN 200910218503 A CN200910218503 A CN 200910218503A CN 200910218503 A CN200910218503 A CN 200910218503A CN 101698603 A CN101698603 A CN 101698603A
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Abstract
The invention discloses a method for preparing CCTO ceramic based on a coprecipitation method. The specific technique is as follows: controlling pH value of titanium oxalate to obtain clarified solution through quantitative reaction of tetrabutyl titanate, oxalic acid and sodium oxalate; and adjusting pH value of mixed solution of calcium and copper through adjusting the proportion of nitrate and acetate, thus being convenient for coprecipitation reaction. Superfine precursor powder with few impurity phase and high purity is obtained by mixing, performing coprecipitation reaction, separating, washing and drying; the precursor powder is calcined for crushing and granulation; and the CCTO ceramic is obtained by sintering the granulated powder at a temperature of 1100 DEG C in the air through conventional dry press forming. The method has the advantages as follows: the technique is simple; pH value is controlled accurately; the repeatability of the result is good; and the method is easy to industrialization. The prepared ceramic has the advantages of high and stable permittivity and low loss.
Description
Technical field
The present invention relates to the preparation method of high dielectric calcium copper titanate ceramics, particularly a kind of method for preparing calcium copper titanate ceramics based on coprecipitation method.
Background technology
In fields such as aviation, military affairs, industry, medical science, all need high electric energy storage system, but passive element, particularly electrical condenser become the principal element that the high electric energy storage system of restriction designs, exploitation high energy storage density electrical condenser becomes a major technology difficult problem.Advantages such as that stupalith has is high temperature resistant, long service life, (Multilayer Ceramic Capacitor, development MLCC) make the application of high-dielectric-constant ceramics in the high energy storage density electrical condenser have more advantage to particularly chip-type laminated electrical condenser.
CaCu 3 Ti 4 O CaCu
3Ti
4O
12Pottery is the huge dielectric constant material of discovered in recent years, compares with other high-dielectric-constant ceramics, and it not only has higher dielectric constant values (at room temperature up to 10
5), and dielectric constant values almost remains unchanged in the temperature range of 100～380K, this characteristic makes the desirable high energy storage density capacitor material that it may become.But, CaCu
3Ti
4O
12The dielectric loss of pottery is bigger, can not satisfy the requirement of capacitor material, presses on the basis that keeps its high-k, reduces its loss.
Existing CaCu
3Ti
4O
12The preparation method of pottery is mainly traditional solid reaction process, because raw material type is more, is difficult for mixing, and also raw material CuO highly volatile in the process of high-temperature calcination, cause the ratio mismatch between each element, make to make CaCu
3Ti
4O
12The dielectric properties of pottery are because very big difference appears in preparation technology's objective variation.For example document 1 (B.A.Bender et al, Materi.Sci.Engin.B, 117 (2005) 339.) has been reported the CaCu of different condition preparation
3Ti
4O
12Pottery, specific inductivity differs 50%.Document 2 (S.Aygun et al, J.Electroceram., 15 (2005) 203) has been reported along with sintering time prolongs, CaCu
3Ti
4O
12Specific inductivity sharply rises under the pottery normal temperature.
Coprecipitation method prepares the polycomponent pottery, can be so that each reaction raw materials contact and reaction in the molecule rank, and it is higher to obtain purity, more uniform ultra-fine forerunner's powder, thus improve microstructure of ceramics, and then improve dielectric properties.
Summary of the invention
The purpose of this invention is to provide and a kind ofly prepare CaCu based on coprecipitation method
3Ti
4O
12The method of pottery can obviously reduce CaCu
3Ti
4O
12The loss of pottery improves the ceramic dielectric performance.
In order to reach above purpose, the present invention takes following technical scheme to be achieved:
A kind ofly prepare the method for calcium copper titanate ceramics, it is characterized in that, comprise the steps: based on coprecipitation method
(1) the oxalic acid aqueous solution 300-500ml that butyl (tetra) titanate ethanolic soln 200-400ml and the pH value of 0.25-0.5mol/L is 1.1-1.5 mixes, and obtains the yellow-white flocks; Add sodium oxalate solution 2000-3000ml again in this solution, wherein, butyl (tetra) titanate, oxalic acid and sodium oxalate such as are at mol ratio; Constantly stir and make resolution of precipitate, obtain clarifying titanous oxalate salts solution and be designated as solution A;
(2) by mass percentage with following component: nitrocalcite 5-12%, lime acetate 12-18%, cupric nitrate 17-35% and venus crystals 42-60% are dissolved in the 2000ml deionized water, are stirred to dissolving fully, make calcium copper mixing solutions and are designated as solution B;
(3) above-mentioned solution A, B are directly mixed, be stirred to and react completely, obtain light blue precipitation, through deionized water wash more than three times and after filtering, drying is removed moisture, obtains forerunner's powder;
(4) forerunner's powder is pulverized granulation, the disk shape green compact that are pressed into then behind 950 ℃ of calcining 8-12h;
(5) with green compact 1100 ℃ of sintering 16-20h under air atmosphere, obtain calcium copper titanate ceramics.
In the such scheme, the pH value among the described titanous oxalate salts solution A is controlled to be 3.The pH value is controlled to be 5-6 among the described calcium copper mixing solutions B.Described intensification and rate of temperature fall are respectively 200 ℃/h and 150 ℃/h.Described drying temperature is not higher than 100 ℃.
Prepared by co-precipitation CaCu provided by the invention
3Ti
4O
12Ceramic methods, preparation process is simple, and is accurate to the control of pH value by calcium salt and mantoquita content, forerunner's powder that available can be stable.CaCu with the conventional solid-state method preparation
3Ti
4O
12The ceramic phase ratio, the CaCu of prepared by co-precipitation of the present invention
3Ti
4O
12Pottery, the microstructure densification, specific inductivity is high and stable, for example acetate and nitrate mass ratio is controlled at 1.2: 1, can significantly reduce calcium copper titanate ceramics dielectric loss (at 100Hz～10kHz tan δ less than 0.06).
Description of drawings
Fig. 1 is the technical process of using coprecipitation method to prepare calcium copper titanate ceramics among the present invention.
Fig. 2 is the XRD figure of the made calcium copper titanate ceramics powder of the embodiment of the invention 1, embodiment 2 and embodiment 3.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Take by weighing the 34.04g butyl (tetra) titanate and dissolve in the 200ml alcohol, obtain the butyl (tetra) titanate ethanolic soln of clear.Take by weighing 12.61g oxalic acid again, be dissolved in the 300ml deionized water, be formulated as the pH value and be 1.1 oxalic acid solution.Above-mentioned two solution are mixed, form the yellow-white flocks.Take by weighing the 13.4g sodium oxalate again, be dissolved in the 2000ml deionized water, be stirred to fully dissolving, adding above-mentionedly has in the sedimentary mixing solutions, is stirred to resolution of precipitate, obtains clear solution.
Take by weighing 1.18g nitrocalcite, the 3.52g lime acetate, 3.62g cupric nitrate and 11.98g venus crystals are dissolved in the 2000ml deionized water, are stirred to dissolving fully, add in the above-mentioned clarification titanous oxalate solution that constantly stirs rapidly, form light blue precipitation.After stirring 4h made it to react completely, filtering-depositing again through 5 washed with de-ionized water, filtered, and at 80 ℃ of oven dry 24h, obtained forerunner's powder.
The granulation behind 950 ℃ of calcining 12h of forerunner's powder, being pressed into diameter then is the disk shape green compact of 1-2mm for 12.6mm thickness.Green compact are 1100 ℃ of sintering 16h under air atmosphere, and intensification and rate of temperature fall are respectively 200 ℃/h and 150 ℃/h.Concrete technical process as shown in Figure 1.
Take by weighing the 34.04g butyl (tetra) titanate and dissolve in the 400ml alcohol, obtain the butyl (tetra) titanate ethanolic soln of clear.Take by weighing 12.61g oxalic acid again, be dissolved in the 350ml deionized water, be formulated as the pH value and be 1.3 oxalic acid solution.Above-mentioned two solution are mixed, form the yellow-white flocks.Take by weighing the 13.4g sodium oxalate again, be dissolved in the 3000ml deionized water, be stirred to fully dissolving, adding above-mentionedly has in the sedimentary mixing solutions, is stirred to resolution of precipitate, obtains clear solution.
Take by weighing 1.77g nitrocalcite, the 3.08g lime acetate, 5.44g cupric nitrate and 10.48g venus crystals are dissolved in the 2000ml deionized water, are stirred to dissolving fully, add in the above-mentioned clarification titanous oxalate solution that constantly stirs rapidly, form light blue precipitation.After stirring 4h made it to react completely, filtering-depositing again through 3 washed with de-ionized water, filtered, and at 90 ℃ of oven dry 20h, obtained forerunner's powder.
The granulation behind 950 ℃ of calcining 8h of forerunner's powder, being pressed into diameter then is the disk shape green compact of 1-2mm for 12.6mm thickness.Green compact are 1100 ℃ of sintering 18h under air atmosphere, and intensification and rate of temperature fall are respectively 200 ℃/h and 150 ℃/h.Concrete technical process as shown in Figure 1.
Take by weighing the 34.04g butyl (tetra) titanate and dissolve in the 300ml alcohol, obtain the butyl (tetra) titanate ethanolic soln of clear.Take by weighing 12.61g oxalic acid again, be dissolved in the 500ml deionized water, be formulated as the pH value and be 1.5 oxalic acid solution.Above-mentioned two solution are mixed, form the yellow-white flocks.Take by weighing the 13.4g sodium oxalate again, be dissolved in the 2500ml deionized water, be stirred to fully dissolving, adding above-mentionedly has in the sedimentary mixing solutions, is stirred to resolution of precipitate, obtains clear solution.
Take by weighing 2.36g nitrocalcite, the 2.64g lime acetate, 7.25g cupric nitrate and 8.98g venus crystals are dissolved in the 2000ml deionized water, are stirred to dissolving fully, add in the above-mentioned clarification titanous oxalate solution that constantly stirs rapidly, form light blue precipitation.After stirring 4h made it to react completely, filtering-depositing again through 4 washed with de-ionized water, filtered, and at 95 ℃ of oven dry 18h, obtained forerunner's powder.
The granulation behind 950 ℃ of calcining 10h of forerunner's powder, being pressed into diameter then is the disk shape green compact of 1-2mm for 12.6mm thickness.Green compact are 1100 ℃ of sintering 20h under air atmosphere, and intensification and rate of temperature fall are respectively 200 ℃/h and 150 ℃/h.Concrete technical process as shown in Figure 1.
Processing and evaluation method to sample:
Forerunner's powder is made XRD analysis behind 950 ℃ of calcining 10h.The ceramics sample that is used for electrical performance testing, earlier that its surface finish is smooth, the sputter gold electrode.Use Novocontrol wideband dielectric spectrometer test sample-100 ℃～100 ℃, 10
-1～10
6Hz dielectric frequency spectrum.
Be the result who obtains about the analysis of embodiment crystalline phase and dielectric properties evaluation below:
Fig. 2 is the XRD figure of embodiment, warp and CaCu
3Ti
4O
12The contrast of standard spectrogram can be observed CaCu significantly
3Ti
4O
12Diffraction peak illustrates successfully to have prepared CaCu by method provided by the invention
3Ti
4O
12Powder, and dephasign content is less.
Table 1 is the room temperature dielectric constant ε ' of embodiment under several representative frequencies and the evaluation result of dielectric loss tan δ.As shown in table 1, embodiment 1 and embodiment 2, particularly the specific inductivity of embodiment 3 is all 10
4More than, and the loss of embodiment 3 is very little, at 100Hz～10kHz less than 0.06.
The specific inductivity of table 1 embodiment and dielectric loss
Claims (5)
1. one kind prepares the method for calcium copper titanate ceramics based on coprecipitation method, it is characterized in that, comprises the steps:
(1) the oxalic acid aqueous solution 300-500ml that butyl (tetra) titanate ethanolic soln 200-400ml and the pH value of 0.25-0.5mol/L is 1.1-1.5 mixes, and obtains the yellow-white flocks; Add sodium oxalate solution 2000-3000ml again in this solution, wherein, butyl (tetra) titanate, oxalic acid and sodium oxalate such as are at mol ratio; Constantly stir and make resolution of precipitate, obtain clarifying titanous oxalate salts solution and be designated as solution A;
(2) by mass percentage with following component: nitrocalcite 5-12%, lime acetate 12-18%, cupric nitrate 17-35% and venus crystals 42-60% are dissolved in the 2000ml deionized water, are stirred to dissolving fully, make calcium copper mixing solutions and are designated as solution B;
(3) above-mentioned solution A, B are directly mixed, be stirred to and react completely, obtain light blue precipitation, through deionized water wash more than three times and after filtering, drying is removed moisture, obtains forerunner's powder;
(4) forerunner's powder is pulverized granulation, the disk shape green compact that are pressed into then behind 950 ℃ of calcining 8-12h;
(5) with green compact 1100 ℃ of sintering 16-20h under air atmosphere, obtain calcium copper titanate ceramics.
2. as claimed in claim 1ly prepare the method for calcium copper titanate ceramics, it is characterized in that the pH value among the described titanous oxalate salts solution A is controlled to be 3 based on coprecipitation method.
3. as claimed in claim 1ly prepare the method for calcium copper titanate ceramics, it is characterized in that the pH value is controlled to be 5-6 among the described calcium copper mixing solutions B based on coprecipitation method.
4. as claimed in claim 1ly prepare the method for calcium copper titanate ceramics, it is characterized in that described intensification and rate of temperature fall are respectively 200 ℃/h and 150 ℃/h based on coprecipitation method.
5. as claimed in claim 1ly prepare the method for calcium copper titanate ceramics, it is characterized in that described drying temperature is not higher than 100 ℃ based on coprecipitation method.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515744A (en) * | 2011-12-12 | 2012-06-27 | 苏州大学 | CaCu3Ti4O12 micro nano sized fiber and its preparation method |
| CN102815936A (en) * | 2012-07-12 | 2012-12-12 | 西安交通大学 | Preparation method for copper calcium titanate multiphase ceramic with high potential gradient |
| CN103482974A (en) * | 2013-09-29 | 2014-01-01 | 哈尔滨理工大学 | Preparation method of CaCu3Ti4O12 ceramic powder |
-
2009
- 2009-10-23 CN CN200910218503A patent/CN101698603A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515744A (en) * | 2011-12-12 | 2012-06-27 | 苏州大学 | CaCu3Ti4O12 micro nano sized fiber and its preparation method |
| CN102515744B (en) * | 2011-12-12 | 2013-07-24 | 苏州大学 | CaCu3Ti4O12 micro nano sized fiber and its preparation method |
| CN102815936A (en) * | 2012-07-12 | 2012-12-12 | 西安交通大学 | Preparation method for copper calcium titanate multiphase ceramic with high potential gradient |
| CN103482974A (en) * | 2013-09-29 | 2014-01-01 | 哈尔滨理工大学 | Preparation method of CaCu3Ti4O12 ceramic powder |
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Application publication date: 20100428 |