CN104909747A - Preparation method for CaCu3Ti4-xZrxO12 ceramic with high dielectric constant and low dielectric loss - Google Patents

Preparation method for CaCu3Ti4-xZrxO12 ceramic with high dielectric constant and low dielectric loss Download PDF

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CN104909747A
CN104909747A CN201510238790.1A CN201510238790A CN104909747A CN 104909747 A CN104909747 A CN 104909747A CN 201510238790 A CN201510238790 A CN 201510238790A CN 104909747 A CN104909747 A CN 104909747A
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dielectric loss
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ceramic
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CN104909747B (en
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孙礼
郝文涛
石永杰
彭华
曹恩思
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Taiyuan University of Technology
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Abstract

The invention discloses a preparation method for a Zr-doping CaCu3Ti4O12 ceramic material with a high dielectric constant and low dielectric loss by utilization of a sol-gel method, and belongs to the dielectric material synthesis technology field. The concrete method is as follows: a sol-gel method is employed, calcium nitrate, cupric nitrate, zirconium oxynitrate and butyl titanate are employed as raw materials, absolute ethyl alcohol is employed as a solvent, nitric acid is employed to adjust the pH of a solution, the raw materials are weighed according to chemical element mol ratios, sol is prepared and placed in a water-bath kettle, stirring is carried out continuously until xerogel is formed, organic matters are removed, CaCu3Ti4-xZrxO12 precursor powder is obtained, then calcining, crushing, grinding, sieving and granulation are carried out, then a ceramic body with a thickness of 1mm and with a diameter of 12mm is prepared, then the ceramic body is placed in a sintering furnace, sintering and thermal insulation are carried out, and finally a CaCu3Ti4-xZrxO12 ceramic sample can be obtained. The method is simple in technology and is easy for industrial production. The prepared ceramic sample has a high density, good particle uniformity and has an enough high dielectric constant and low dielectric loss.

Description

A kind of high-k, low-dielectric loss CaCu 3ti 4-xzr xo 12the preparation method of pottery
Technical field
The invention belongs to dielectric ceramics synthesis technical field, be specifically related to a kind of high-k, low-dielectric loss CaCu 3ti 4-xzr xo 12the preparation method of pottery.
Background technology
The research and development of high dielectric constant ceramic material (ε ' > 1000) make integrated, the miniaturization of the application of large value capacitor and electronic component obtain develop rapidly.CaCu 3 Ti 4 O (CaCu 3ti 4o 12cCTO) be typical case, the representational novel high dielectric material of most be the most found so far 21 century, the specific inductivity of this material is very high, under 1 kHz alternating-electric field effect, specific inductivity can reach 10 more than k, and at 100 K in 400 K temperature ranges, specific inductivity rises and falls little, and its single crystal samples low-frequency dielectric constant even can reach 100 more than k.In addition, CCTO is not leaded, preparation technology is simple, required preparation condition also comparatively " gentleness ", get a good chance of alternative traditional dielectric ceramic material, become high dielectric ceramic material of new generation.
A series of advantage makes CCTO receive rapidly the extensive concern of domestic and international investigator, but, many results of study show, the dielectric loss of CCTO is higher, general more than 0.1 under the dielectric loss room temperature of CCTO polycrystalline ceramics, even more than 0.2 under the dielectric loss room temperature of CCTO film, the loss of single crystal samples is then higher.Too high dielectric loss will inevitably accelerate the rate of ageing of dielectric materials, seriously limits the actual application prospect of CCTO, and therefore ensureing that specific inductivity is sufficiently high while, the dielectric loss how effectively reducing CCTO has great meaning for practical application.
Along with deepening continuously of CCTO Dielectric Properties, although the origin of its dielectric properties does not also form a very definite mechanism, but everybody generally believe the dielectric properties of CCTO material and extrinsic mechanism closely related, as many-sided factors such as semiconduction crystal grain, insulativity crystal boundary, room, impurity, structural disorder, second-phase and electrode contacts.And doping vario-property means can change material microstructure, therefore, the performance of Many researchers to doping CCTO material expands extensive research.2003, Kobayashi seminar first to CCTO carried out A position (Ca, Cu) doping experiment, find Mn doping after dielectric loss without any reduction, specific inductivity lack reduces 2 orders of magnitude.Only have investigator also to carry out substituting of the elements such as Nb, Fe to B position (Ti), find that the specific inductivity of CCTO and loss all start to decline, also have the display of a lot of doping result, while specific inductivity increases, loss does not decline.Afterwards, several seminar is had to attempt adding CaTiO in CCTO 3or ZrO 2under consequently maintaining the prerequisite of the high-k of CCTO, loss can be down to less than 0.05 (50-30 kHz) within the scope of certain frequency, but the specific inductivity of corresponding frequency band only has about 5000 (Appl. Phys. Lett., 2005,87,182911, Eric A. Patterson, Seunghwa Kwon, Chien-Chih Huang and David P. Cann).
In a word, Zr/ZrO 2doping has been proved can play good effect in the dielectric loss reducing CCTO material, can reach the requirement of application, but how to keep higher specific inductivity to be still a problem demanding prompt solution in wider range of frequency.
Summary of the invention
The invention provides a kind of high-k, low-dielectric loss CaCu 3ti 4-xzr xo 12the preparation method of pottery, dielectric loss significantly reduces, and specific inductivity is still in higher level, and gelation time is short, and ceramic plate density is high, uniform crystal particles degree is good.
For reaching above object, the present invention takes following technical scheme to be achieved:
A kind of high-k, low-dielectric loss CaCu 3ti 4-xzr xo 12the preparation method of pottery, comprises the following steps:
(1) ratio being 1:3:4-x:x:9.6 according to calcium, copper, titanium, zirconium, citric acid mol ratio takes the nitrocalcite of respective quality, cupric nitrate, butyl (tetra) titanate, Zircosol ZN and citric acid;
(2) be that nitrocalcite, cupric nitrate, Zircosol ZN and citric acid fully dissolve by solvent with dehydrated alcohol, and by adding nitric acid, adjust ph being 2-3, forming solution A;
(3) in butyl (tetra) titanate, add isopyknic dehydrated alcohol, dilute for B solution;
(4) B solution is slowly added in solution A along glass stick, and keep solution A to be in whipped state, form colloidal sol;
(5) in the colloidal sol formed, add polyoxyethylene glycol, be stirred to and dissolve completely, be positioned in 80 DEG C of water-baths and stir, until form gel;
(6) gel of formation is dried, obtain dry gel powder, be positioned in furnace pot, utilize electric furnace and retort furnace to get rid of organism, obtain CaCu 3ti 4-xzr xo 12precursor powder;
(7) by CaCu 3ti 4-xzr xo 12precursor powder fully grinds in mortar, adds tackiness agent and mixes, so grinding, granulation of sieving, make ceramic body;
(8) by the CaCu of preparation in (7) 3ti 4-xzr xo 12base substrate is placed in sintering oven to carry out sintering, being incubated, and finally obtains CaCu 3ti 4-xzr xo 12ceramics sample.
By the sample surfaces polishing of preparing, polishing, by silver, make electrode, carry out electric performance test.Step (3) described B solution is the butyl (tetra) titanate through dehydrated alcohol dilution, can reduce the possibility of hydrolysis when mixing with solution A.
For the doping vario-property means of CCTO material, select suitable moulding process extremely important, control dose is than crucial too.The present invention utilizes sol-gel method to prepare Zr doping CCTO ceramic powder, by the control to pilot processs such as Zr doping content, solution ph, gelling temperature, stirring velocity, pre-burning condition, body preparation pressure, finally achieve that density is high, good uniformity, and there is the CaCu of low-dielectric loss (2 k-40 kHz range of frequency internal losses are lower than 0.05), high-k 3ti 4-xzr xo 12(CCTZO) ceramics sample (, between 23 k to 24 k, frequency stability is stronger for 2 k-40 kHz range of frequency specific inductivity); In addition, dielectric characteristics shows with the characteristic test of temperature, and when measuring at some frequencies (during as 200 kHz), specific inductivity can show extraordinary temperature stability (20 DEG C-180 DEG C, specific inductivity is increased to about 26 k from about 22 k) equally.
Further, CaCu 3ti 4-xzr xo 12precursor powder crosses 80 order-120 mesh sieves, under 500 MPa pressure, make base substrate.
The powder size adopted in body preparation process and pressure ensure that final product has lower dielectric loss and higher specific inductivity, and simultaneously the density of product and homogeneity have also been obtained effective raising.
The present invention adopts the advantage of technique scheme to be: (1) nitrocalcite, cupric nitrate, Zircosol ZN cheap, and raw materials cost is low; (2) sol gel reaction process component is controlled, prevents dephasign; (3) gelation time is about 4-6 hour, reduces time cost; (4) preparation technology is simple, and the ceramics sample better crystallinity degree obtained, uniformity coefficient are high; (5) dielectric loss of CCTZO ceramics sample significantly reduces, and specific inductivity is still higher.
Accompanying drawing explanation
Fig. 1 is CaCu in embodiment 1 3ti 3.95zr 0.05o 12the X-ray diffractogram of ceramics sample.
Fig. 2 is CaCu in embodiment 1 3ti 3.95zr 0.05o 12the scanning electron microscope (SEM) photograph of ceramics sample.
Fig. 3 is CaCu in embodiment 1 3ti 3.95zr 0.05o 12ceramics sample dielectric and magnetic figure (ε '-f and tan δ-f curve).
Fig. 4 is CaCu in embodiment 1 3ti 3.95zr 0.05o 12the dielectric thermogram of ceramics sample (ε '-T curve).
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described, but never limit the scope of the invention.
Embodiment 1:
(1) 8.349 g nitrocalcite, 25.624 g cupric nitrates, 0.407g Zircosol ZN and 64.876 g citric acids are taken, adopt dehydrated alcohol as solvent, four kinds of raw materials are dissolved completely, then utilizes nitric acid, adjust ph is 2-3, finally obtains blue-tinted transparent mixed solution A (x=0.05);
(2) measure 47.771 mL butyl (tetra) titanates, and add the dehydrated alcohol of equivalent, be stirred to and mix completely, obtain faint yellow mixing solutions B;
(3) solution A is placed in magnetic stirring apparatus, keeps whipped state, then B solution is slowly added in solution A and (prevent butyl (tetra) titanate be hydrolyzed), until form transparent mixed solution, then add 2 g polyoxyethylene glycol promotion plastics;
(4) mixing solutions obtained final in above-mentioned steps (3) is placed in water-bath, regulate temperature to be 80 DEG C, stir speed (S.S.) is 200 rpm, until form blue xerogel;
(5) the blue xerogel obtained is placed in furnace pot, furnace temperature is regulated to be 500 DEG C, organic preliminary eliminating is carried out in ventilating kitchen, grey powder can be obtained, then grinding evenly, is placed in retort furnace, is incubated 2 h at 650 DEG C, organism is got rid of further, finally can obtain grey CaCu 3ti 3.95zr 0.05o 12precursor powder;
(6) to CaCu 3ti 3.95zr 0.05o 12add polyvinyl alcohol, glycerine in precursor powder as tackiness agent, mix, fully grind, under 200 MPa pressure, make thickness about 5 mm, the disk of diameter 25 mm, be then placed in mortar and grind, cross 80 order-120 mesh sieves;
(7) powder in selecting step (6) between 80 mesh sieves and 120 mesh sieves carries out CaCu 3ti 3.95zr 0.05o 12the making of ceramic body, pressure is 500 MPa, base substrate thickness about 1 mm, diameter 12 mm;
(8) base substrate made is placed in retort furnace to sinter, sintering temperature is 1100 DEG C, and temperature rise rate is 300 DEG C/h, soaking time 16h, carries out Programmed freezing according to 600 DEG C/h afterwards, final acquisition CCTZO ceramics sample, it is Emission in Cubic that Fig. 1 shows this sample, occurs without dephasign; The grain-size that Fig. 2 shows this embodiment sample is not from 2 μm to tens of μm etc.
(9) by ceramics sample surface finish, polishing, by silver, make electrode, carry out electric performance test.Fig. 3 shows this in 2 k-40 kHz range of frequency, and sample ε ' is between 23 k to 24 k, and frequency stability is stronger, and in said frequencies section, tan δ is all lower than 0.05, and near 10 kHz, tan δ is minimum is down to 0.026; When Fig. 4 is presented at 200 kHz, ε ' presents extraordinary temperature stability in useful range, and from 20 DEG C to 180 DEG C, ε ' is only increased to about 26 k from about 22 k, and in other two frequency bands (20 kHz, 2 MHz) ε ' big rise and fall.
In order to study the impact of the dopant dose comparison dielectric properties of Zr, have also been devised following two embodiments:
Embodiment 2:
The difference of the present embodiment and embodiment 1 is, the doping difference (CaCu of Zr 3ti 4-xzr xo 12, x=0.1), find through dielectric properties test, compare embodiment 1, the grain-size of sample reduces, and ε ' has and declines by a relatively large margin; Tan δ is overall higher than embodiment 1, and minimum tan δ is 0.039, appears near 10 kHz.
Embodiment 3:
The difference of the present embodiment and embodiment 1 is, the doping difference (CaCu of Zr 3ti 4-xzr xo 12, x=0.2), find through dielectric properties test, compare embodiment 1 and 2, the grain-size of sample reduces further, and ε ' entirety continues to decline; Tan δ is higher than embodiment 1 and 2, and Schwellenwert is 0.058, appears at equally near 10 kHz.

Claims (5)

1. a high-k, low-dielectric loss CaCu 3ti 4-xzr xo 12the preparation method of pottery, is characterized in that comprising the following steps:
(1) ratio being 1:3:4-x:x:9.6 according to calcium, copper, titanium, zirconium, citric acid mol ratio takes the nitrocalcite of respective quality, cupric nitrate, butyl (tetra) titanate, Zircosol ZN and citric acid;
(2) be that nitrocalcite, cupric nitrate, Zircosol ZN and citric acid fully dissolve by solvent with dehydrated alcohol, and by adding nitric acid, adjust ph being 2-3, forming solution A;
(3) in butyl (tetra) titanate, add isopyknic dehydrated alcohol, dilute for B solution;
(4) B solution is slowly added in solution A along glass stick, and keep solution A to be in whipped state, form colloidal sol;
(5) in the colloidal sol formed, add polyoxyethylene glycol, be stirred to and dissolve completely, be positioned in 80 DEG C of water-baths and stir, until form gel;
(6) gel of formation is dried, obtain dry gel powder, be positioned in furnace pot, utilize electric furnace and retort furnace to get rid of organism, obtain CaCu 3ti 4-xzr xo 12precursor powder;
(7) by CaCu 3ti 4-xzr xo 12precursor powder fully grinds in mortar, adds tackiness agent and mixes, so grinding, granulation of sieving, make ceramic body;
(8) by the CaCu of preparation in (7) 3ti 4-xzr xo 12base substrate is placed in sintering oven to carry out sintering, being incubated, and finally obtains CaCu 3ti 4-xzr xo 12ceramics sample.
2. a kind of high-k according to claim 1, low-dielectric loss CaCu 3ti 4-xzr xo 12the preparation method of pottery, is characterized in that, the stir speed (S.S.) in step (5) in water-bath is 200 rpm.
3. a kind of high-k according to claim 1 and 2, low-dielectric loss CaCu 3ti 4-xzr xo 12the preparation method of pottery, is characterized in that, CaCu 3ti 4-xzr xo 12precursor powder crosses 80 order-120 mesh sieves, under 500 MPa pressure, make base substrate.
4. a kind of high-k according to claim 1 and 2, low-dielectric loss CaCu 3ti 4-xzr xo 12the preparation method of pottery, is characterized in that, in step (7), tackiness agent adopts polyvinyl alcohol and glycerine.
5. a kind of high-k according to claim 1 and 2, low-dielectric loss CaCu 3ti 4-xzr xo 12the preparation method of pottery, is characterized in that, in step (8), the sintering temperature of ceramic body is 1100 DEG C, and soaking time is 16 h.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997684A (en) * 2018-08-29 2018-12-14 西安科技大学 High dielectric ceramic/PVDF composite material and preparation method
CN109627049A (en) * 2017-10-09 2019-04-16 湖北大学 A method of improving energy storage ceramic material dielectric constant
CN115650722A (en) * 2022-05-09 2023-01-31 西南科技大学 Gel and application thereof in circulator composite substrate
CN115849898A (en) * 2021-09-24 2023-03-28 华为技术有限公司 Thermal sensitive ceramic material, preparation method thereof and thermistor

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SU YANLI ET AL.,: "Dielectric Properties and Electrical Conductivity of CaCu3Ti4O12 Ceramics Doped with Zr4+", 《JOURNAL OF WUHAN UNIVERSITY OF TECHNOLOGY-MATER.SCI.ED.》 *
王茂华 等: "溶胶-凝胶法制备CaCu3Ti4O12粉体及其电性能", 《中国粉体技术》 *
赵艳会: "共沉淀法制备钛酸铜钙及介电性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109627049A (en) * 2017-10-09 2019-04-16 湖北大学 A method of improving energy storage ceramic material dielectric constant
CN108997684A (en) * 2018-08-29 2018-12-14 西安科技大学 High dielectric ceramic/PVDF composite material and preparation method
CN108997684B (en) * 2018-08-29 2021-07-02 西安科技大学 High dielectric ceramic/PVDF composite material and preparation method thereof
CN115849898A (en) * 2021-09-24 2023-03-28 华为技术有限公司 Thermal sensitive ceramic material, preparation method thereof and thermistor
CN115650722A (en) * 2022-05-09 2023-01-31 西南科技大学 Gel and application thereof in circulator composite substrate

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