CN116239378B - Low-cost, low-loss and temperature-ultra-stable dielectric material and preparation method thereof - Google Patents
Low-cost, low-loss and temperature-ultra-stable dielectric material and preparation method thereof Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000919 ceramic Substances 0.000 claims abstract description 95
- 239000000843 powder Substances 0.000 claims abstract description 84
- 230000008859 change Effects 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- 239000003292 glue Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims 1
- 229910004762 CaSiO Inorganic materials 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 239000003607 modifier Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 59
- 238000007873 sieving Methods 0.000 description 25
- 239000012071 phase Substances 0.000 description 23
- 229910052709 silver Inorganic materials 0.000 description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 19
- 239000004332 silver Substances 0.000 description 19
- 238000000713 high-energy ball milling Methods 0.000 description 17
- 229910010293 ceramic material Inorganic materials 0.000 description 12
- 238000010304 firing Methods 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention relates to a low-cost, low-loss and temperature-ultra-stable dielectric material and a preparation method thereof, comprising the following steps: 1) BaTiO is mixed with 3 Powder and Y 2 O 3 Mixing, ball milling, drying and presintering the powder to obtain ceramic powder; 2) Adding MgO and CaSiO into ceramic powder 3 And (3) after ball milling, drying, granulating, forming, removing glue and sintering to obtain the temperature-super-stable dielectric material. The medium material meets the temperature change rate of less than or equal to +/-3.3% and the X7D type temperature stability characteristic within the temperature range of-55 ℃ to 125 ℃, wherein the optimal example can meet the temperature change rate of less than or equal to +/-1.97% and the X7C type temperature stability characteristic, and the temperature ultra-stable medium material is successfully prepared; high dielectric constant, dielectric constant at room temperature>1210, a base; the dielectric loss is extremely low, and the dielectric loss is less than or equal to 0.71 percent at room temperature; the system does not contain lead, the modifier has low cost, less doping components and simple process flow, and can be applied to mass production.
Description
Technical Field
The invention belongs to the technical field of electronic information, and particularly relates to a low-cost, low-loss and temperature-ultra-stable dielectric material and a preparation method thereof
Background
With the rapid development of modern electronics and microelectronics technologies, electronic component designs tend to be miniaturized, high-frequency, integrated, and applied in wide temperature range, and ceramic capacitors are required to have higher performanceGood temperature stability and lower dielectric loss. Current multilayer ceramic capacitors (MLCCs) are widely used in various electronic devices such as Personal Computers (PCs), mobile phones, automotive electronics, etc., due to their unique electrical properties. MLCCs currently in use are based on two types, X7R and X8R, with a change in capacitance ΔC/C over a specified use temperature range 25°C Less than or equal to +/-15 percent. With the demands of more precise and high reliability of electronic devices, people pay more attention to the wide temperature stability, that is, the stability and reliability demands in a wide temperature range are gradually increased. The traditional X7R, X R type dielectric material only meets the requirement that the temperature stability under regulation is difficult to meet the application requirement of the advanced precise instrument nowadays. Needs to develop dielectric materials with a temperature change rate of + -10% or lower to meet the requirements of corresponding MLCC, such as X7F type fatter C/C 25°C Less than or equal to + -7.5 percent) and X7E type (fatter C/C) 25°C A dielectric material having a very small rate of change of temperature of not more than + -4.7%). In addition, the X7D type (fatter C/C) is defined in the Electronic Industry Association (EIA) standard 25°C Less than or equal to + -3.3%) and X7C type (fatter C/C) 25°C Less than or equal to + -2.2 percent) of the medium temperature performance of the more precise temperature-super-stable medium material.
Along with the guidance of the green market without lead in China and abroad, the novel development concepts of innovation, coordination, green, openness and sharing are followed, and the lead-free perovskite type BaTiO has the characteristics of high dielectric constant, lower dielectric loss, higher compressive strength and the like 3 Ceramics are widely used as matrix materials for MLCCs. The invention discloses an ultrahigh dielectric constant MLCC medium and a preparation method thereof, wherein the MLCC medium comprises the following ceramic components in percentage by mass: according to BaTiO 3 100 percent of Nb with the addition of 3 to 4 percent 2 O 5 、0.3％～0.5％MgCO 3 MnCO 0.1-0.2% 3 、18％～22％ Ag 2 O, 10-13% of glass powder and 0.2-0.7% of rare earth oxide Y 2 O 3 、Gd 2 O 3 、Ho 2 O 3 One of them. The dielectric constant of the prepared capacitor ceramic can reach tens of thousands, but the dielectric loss is 1.1-1.5%, and the glass powder of the patent contains 20-30％Pb 3 O 4 The current environmental protection requirements are not met.
The invention patent CN102503407A discloses a leadless X8R type multilayer ceramic capacitor medium and a preparation method thereof, wherein the capacitor medium is prepared from barium titanate BaTiO 3 Niobium oxide Nb 2 O 5 Cobalt oxide Co 2 O 3 Neodymium oxide Nd 2 O 3 Manganese dioxide MnO 2 CeO of cerium oxide 2 And bismuth oxide-containing Bi according to the calculated stoichiometric ratio 2 O 3 Tin oxide SnO 2 And titanium dioxide TiO 2 The mass ratio of the raw materials is 100:1-10:5-10:0.25-1:0.5-5:0.25-1:5-15. The capacitor ceramic prepared by the method meets the temperature stability requirement of X8R, but the dielectric constant of the capacitor ceramic is more than 10% from the dielectric constant of the capacitor ceramic at 25 ℃ within the range of-55 ℃ to 125 ℃ and especially at a low temperature section. And dielectric loss exceeds 1%. And the doping agent contains Bi compounds which are easy to volatilize at high temperature and even partially react with the metal electrode, so that the production of the subsequent manufacturing device is not facilitated. As another example, the invention patent CN113831123A discloses a preparation method of dielectric ceramic material for barium titanate-based chip capacitor, which has high dielectric constant and low loss, but in the range of-55-125 ℃, the relative best embodiment only has a temperature change rate of-9.58-11.62%, and the temperature stability can not meet the stability requirement of the precision instrument working in the wide temperature environment at present.
Although the presently disclosed invention patent partially meets the temperature stability requirement of X7P, the complex process flow and the excessive cost of raw materials are unavoidable problems, for example, the invention patent CN104609852A discloses a linear high-voltage low-loss capacitor ceramic material and a preparation method thereof, wherein the ceramic capacitor medium comprises 100 parts of BaTiO 3 5-18 parts of ZnNb 2 O 6 Re 1.5-6 parts 2 O 3 0.05 to 0.25 part of MnCO 3 0.5 to 3 parts of BaB 2 O 4 Wherein Re is 2 O 3 Is one or a combination of a plurality of rare earth oxides. Prepared therebyThe capacitor ceramic satisfying the temperature stability of X7P has a dielectric constant of only 810 at the highest, and when the dielectric constant reaches 1000 or more, the temperature stability does not satisfy X7P. And the preparation process is complex, the rare earth oxide in the raw materials is expensive, the production period is long, the cost is high, and the industrial production and the application are not easy.
Also as described in patent CN1102918C, a dielectric ceramic composition with good performance has a high dielectric constant and low dielectric loss of not more than 0.8%, while having good temperature stability. But still has some disadvantages: 1) Although the invention is for cost reduction, Y oxide is selected from Y, dy, ho, tb, gd, eu, and MgO, baO, caO, srO, CR 2 O 3 MgO is selected as the dopant, but the dopant elements of the present invention are excessive, such as MnO, V 2 O 5 , WO 3 And at least one compound as a third subcomponent thereof, (Ba, ca) x SiO 2+x (x=0.8-1.2) is taken as a second auxiliary component and a sixth auxiliary component MnO, so that excessive doping elements are caused, the difficulty of a doping and mixing process is increased, the subsequent performance control difficulty is also increased, and the doping and modification effects of various elements are difficult to accurately control; 2) The invention does not require the grain size refinement, but the refinement of the dielectric material is an important direction because of the trend of thinning and multilayering of the MLCC; 3) The sintering temperature of the patent is 1280-1320 ℃, the sintering temperature is higher, and the heat preservation time is longer than 5 hours. These are unfavorable for the development trend of energy conservation and emission reduction; 4) The invention is aimed at an environment with the applicable temperature direction of more than 80 ℃, particularly 125-150 ℃, and only meets X7P in the range of 55-125 ℃ for example, which can not meet the performance requirement in some application scenes with severe requirements on temperature stability and precision.
In summary, although dielectric materials reported in some patents and papers can meet one or more of the following characteristics of good temperature stability, higher dielectric constant, lower dielectric loss, etc., the following disadvantages still exist: 1) Harmful substances such as lead in the formula do not meet the environmental protection requirements of current electronic components; 2) The preparation method is complex, the raw materials are relatively expensive, and the auxiliary components of the medium material are too many, so that the cost is greatly increased, and the industrial production and application are not facilitated; 3) The characteristics of good temperature stability, higher dielectric constant, lower dielectric loss, low cost and the like cannot be considered; 4) In order to meet the development trend of thinning of MLCC, dielectric ceramic grains are required to be thinned, the average grain size is small, the temperature stability of a finally formed device is easy to be deteriorated, and the temperature stability and the grain refinement of dielectric materials in most of the invention patents are difficult to coexist. 5) Most importantly, under the trend of the MLCC toward more precise development, the medium material with good temperature stability of the existing main stream still has difficulty in meeting the severe ultra-high stability requirement.
Disclosure of Invention
Aiming at the defect of the prior art, the invention provides a low-cost, low-loss and temperature-ultra-stable dielectric material and a preparation method thereof. The invention adopts BaTiO 3 The powder (average particle diameter not more than 300 nm) is used as matrix, and 1.0-2.0 mol% of Y is added 2 O 3 Ball-milling and mixing the powder and presintering to prepare BaTiO 3 The base medium ceramic powder is introduced into CaSiO 3 And MgO as dopant in combination with conventional solid phase method to prepare final BaTiO 3 A base dielectric ceramic material. By adding Y 2 O 3 、CaSiO 3 And MgO, thereby leading to the invention having excellent properties: 1) By presintering to make Y 3+ Ion synergistic partial substitution of Ba in A-position 2+ Ion and Ti in B-position 4+ Ions such that Y 2 O 3 In BaTiO 3 The powder outer layer forms a thin layer of lattice distortion, which is the cubic paraelectric phase. And the thin layer can prevent the subsequent doping of MgO and CaSiO to a certain extent 3 Into BaTiO 3 Inside the crystal, mgO and CaSiO 3 And a thin layer is formed, so that two shell layers are formed, and the proportion of the shell layers is improved overall, so that the temperature stability of the dielectric property is greatly improved, and the effect of fine crystallization is achieved. 2) Y can also be made by presintering 3+ Ba with ion partial substitution A position 2+ Ion and Ti in B-position 4+ Ions, such that the subsequent part of Ca which may be more prone to occupy the A-position 2+ More easily reach the solid solution limit and enter the B site to replace Ti 4+ Finally, a pseudocubic structure with higher symmetry is easier to obtain and dielectric properties can be improved by influencing the oxygen vacancy concentration; 3) By Y 2 O 3 And MgO has a high melting point (2346 ℃ C. And 2852 ℃ C., respectively), so that BaTiO in the present invention 3 The grain growth of the base medium material is greatly blocked in the high-temperature sintering process, so that the fine-grain effect is also achieved; 4) Diffusion rate ratio CaSiO using MgO 3 Low, at and CaSiO 3 At the same time, caSiO can be caused to be mixed together 3 The glass phase is more difficult to diffuse into crystal lattices, and forms a coating layer with higher thickness with MgO in the crystal, and the coating layer has insulativity, is favorable for inhibiting carrier migration, can greatly improve the insulation resistivity and the pressure resistance of the material, and can also greatly reduce leakage conduction loss and dielectric loss; 5) CaSiO (CaSiO) 3 Ca in the medium into the crystal lattice 2+ Replacement of BaTiO 3 Ba of A-position in 2+ Ti in ion or B position 4+ Reduce CaSiO 3 The phase transition temperature from the three phases to the orthogonal phase and from the orthogonal phase to the tetragonal phase is basically unchanged, and the Curie temperature from the tetragonal phase to the cubic phase is basically unchanged, thereby widening the BaTiO 3 The ferroelectric phase stabilizes in a temperature range, and improves temperature stability while maintaining a high dielectric constant. In addition, caSiO 3 The melting point is lower, the sintering temperature can be reduced, the sintering assisting effect is achieved, the sintering densification effect is easier to achieve, and the CaSiO 3 Reacts with other additives and is distributed at grain boundaries, thereby reducing dielectric loss and improving dielectric characteristics.
In conclusion, stable 'core-shell' structure and fine crystallization are obtained by the doping and the process, and the BaTiO is improved 3 Temperature stability of the base dielectric property, reduction of dielectric loss, and improvement of resistivity and voltage resistance. In order to achieve the doping purpose and performance, the invention adopts the following technical scheme:
a low-cost, low-loss and temperature-ultra-stable dielectric material and a preparation method thereof comprise the following steps:
1) By BaTiO 3 Based on 100 moles, addY is added in a molar ratio of 1.0 to 2.0 2 O 3 Y is taken as 2 O 3 With BaTiO 3 Adding deionized water in a proper amount for ball milling and mixing, and pre-sintering after drying to obtain ceramic powder A;
2) The powder is presintered at high temperature, and then ground and sieved to obtain the final uniform particle powder A;
3) Adding BaTiO to powder A 3 MgO in a molar ratio of 0.5% to the raw material, caSiO in a mass ratio of 1.0% 3 Adding deionized water for high-energy ball milling and mixing, and then drying to obtain BaTiO 3 A base ceramic powder B;
4) Adding binder into powder B, granulating, sieving, shaping, removing binder, and sintering to obtain low-loss temperature-ultra-stable BaTiO 3 A base dielectric material.
Wherein as a preferable aspect of the above-mentioned technical scheme, the BaTiO 3 The powder raw material is fine crystal powder (average grain diameter is not more than 300 nm).
As a preferred embodiment of the above method, all analytically pure raw materials are used as the raw materials.
As the optimization of the technical scheme, the ball milling time in the step 1) is 6-9 hours, and the ball milling time in the step 3) is 8-12 hours.
As the preferable technical scheme, the presintering temperature in the step 2) is 1100 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2-4 hours.
As the preferable technical scheme, the sintering temperature in the step 4) is 1200-1250 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2-4 hours.
As the preferable technical scheme, the binder in the step 4) is PVA or PVB, and the addition amount of the binder is 1% -6% of the mass of the ceramic powder, and is preferably 3% -5%.
As the preferable technical scheme, the glue discharging temperature in the step 4) is 600 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2-4 hours.
In summary, the invention has the following advantages:
(1) The invention is realized by introducing Y 2 O 3 、CaSiO 3 The doping of MgO successfully improves BaTiO 3 Temperature stability of ceramic dielectric materials. The material provided by the invention has the advantages that the temperature change rate is less than or equal to +/-3.3% and the X7D characteristic is met within the temperature range of-55-125 ℃, wherein the optimal group meets the temperature change rate of less than or equal to +/-1.97%, and the material has extremely high temperature stability.
(2) The temperature-hyperstable dielectric material provided by the invention has high dielectric constant (> 1210) and low dielectric loss: dielectric loss at room temperature is not more than 0.71%.
(3) BaTiO according to the invention 3 The grain size of the base ceramic is not more than 300nm.
(4) The material system disclosed by the invention is simple in formula, low in cost, free of lead, environment-friendly and good in application prospect; and the preparation process is simple and controllable, and is easy for industrialized mass production and preparation.
Drawings
FIG. 1 shows BaTiO prepared in examples 1 to 3 and comparative examples 1 to 6 3 An X-ray diffraction pattern of the base dielectric material;
FIG. 2 is BaTiO prepared in comparative examples 1, 3, 5 and example 2 3 SEM images of the base dielectric material; wherein figure (a) is SEM of comparative example 1; (b) is SEM of comparative example 3; (c) is SEM of comparative example 5; FIG. (d) is an SEM of example 2;
FIG. 3 shows BaTiO prepared in examples 1 to 3 and comparative examples 1 to 6 3 The change of dielectric constant of the base dielectric material with temperature at 1 kHz;
FIG. 4 shows BaTiO prepared in examples 1 to 3 and comparative examples 1 to 6 3 Dielectric loss of the base dielectric material at 1kHz as a function of temperature;
FIG. 5 shows BaTiO prepared in examples 1 and 2 and comparative examples 4 and 5 3 The rate of change of the capacitance temperature (TCC, based on 25 ℃) of the base dielectric material at 1kHz with temperature.
Detailed Description
In order that the invention may be more readily understood, the invention will be further described with reference to the following examples.
Example 1
A preparation method of a low-cost, low-loss and temperature-ultra-stable dielectric material comprises the following specific steps:
(1) BaTiO in the past 3 2.0mol% of Y is added 2 O 3 Adding deionized water into the powder, performing high-energy ball milling for 6 hours, and then drying and sieving to obtain powder;
(2) The obtained powder is presintered at a high temperature of 1100 ℃ for 2 hours, wherein the heating rate is 5 ℃/min, and then the powder A is obtained by grinding and sieving;
(3) Adding BaTiO to powder A 3 MgO in a molar ratio of 0.5% to the raw material, caSiO in a mass ratio of 1.0% 3 Adding deionized water to perform high-energy ball milling and mixing for 8 hours, and then drying to obtain ceramic powder B;
(4) Adding PVA binder with the mass ratio of 5% into the ceramic powder B, granulating, sieving, forming to obtain ceramic blank with the diameter of 10mm to 1mm, preserving the temperature of the ceramic blank at 600 ℃ for 2 hours, discharging glue, then heating to 1200 ℃ for sintering, and preserving the temperature for 3 hours, wherein the heating rate is 5 ℃/min, thus obtaining BaTiO 3 A base ceramic;
BaTiO is mixed with 3 The upper and lower surfaces of the base ceramic were uniformly coated with silver paste, and electrodes were prepared by firing silver at 550 c, and their electrical properties were tested. Prepared BaTiO 3 The relative density of the base ceramic is 93%, the base ceramic has no mixed phase and pseudo-cubic structure, the crystal grains are fine and uniform, and the average crystal grain size is 182nm; the dielectric constant 1213 and the dielectric loss are 0.69% at room temperature, the capacitance temperature change rate is-2.64% -0.44% within the range of-55 ℃ to 125 ℃, and the X7D characteristic is satisfied.
Example 2
A preparation method of a low-cost, low-loss and temperature-ultra-stable dielectric material comprises the following specific steps:
(1) BaTiO in the past 3 2.0mol% of Y is added 2 O 3 Adding deionized water into the powder, performing high-energy ball milling for 6 hours, and then drying and sieving to obtain powder;
(2) The obtained powder is presintered at a high temperature of 1100 ℃ for 2 hours, wherein the heating rate is 5 ℃/min, and then the powder A is obtained by grinding and sieving;
（3）adding BaTiO to powder A 3 MgO in a molar ratio of 0.5% to the raw material, caSiO in a mass ratio of 1.0% 3 Adding deionized water to perform high-energy ball milling and mixing for 8 hours, and then drying to obtain ceramic powder;
(4) Adding PVA binder with the mass ratio of 5% into the ceramic powder, granulating, sieving, forming to obtain ceramic blank with the diameter of 10mm to 1mm, preserving the temperature of the ceramic blank at 600 ℃ for 2 hours, discharging glue, then heating to 1225 ℃ for sintering, preserving the temperature for 3 hours, wherein the heating rate is 5 ℃/min, and obtaining BaTiO 3 A base ceramic;
BaTiO is mixed with 3 The upper and lower surfaces of the base ceramic were uniformly coated with silver paste, and electrodes were prepared by firing silver at 550 c, and their electrical properties were tested. Prepared BaTiO 3 The relative density of the base ceramic reaches 94%, the base ceramic has no heterogeneous phase and pseudo-cubic structure, the grain size is fine and uniform, and the average grain size is 190nm; the dielectric constant is 1418, the dielectric loss is 0.71% at room temperature, the capacitance temperature change rate is-1.97% -0.89% within the range of-55 ℃ to 125 ℃, and the X7C characteristic is satisfied.
Example 3
A preparation method of a low-cost, low-loss and temperature-ultra-stable dielectric material comprises the following specific steps:
(1) BaTiO in the past 3 2.0mol% of Y is added 2 O 3 Adding deionized water into the powder, performing high-energy ball milling for 6 hours, and then drying and sieving to obtain powder;
(2) The obtained powder is presintered at a high temperature of 1100 ℃ for 2 hours, wherein the heating rate is 5 ℃/min, and then the powder A is obtained by grinding and sieving;
(3) Adding BaTiO to powder A 3 MgO in a molar ratio of 0.5% to the raw material, caSiO in a mass ratio of 1.0% 3 Adding deionized water to perform high-energy ball milling and mixing for 8 hours, and then drying to obtain ceramic powder;
(4) Adding PVA binder with mass ratio of 5% into the ceramic powder, granulating, sieving, forming to obtain ceramic blank with diameter of 10 mm-1 mm, maintaining the ceramic blank at 600deg.C for 2 hr, sintering at 1250 deg.C, and maintaining the temperature for 3 hr, whereinHeating rate is 5 ℃/min, and the BaTiO is obtained 3 A base ceramic;
BaTiO is mixed with 3 The upper and lower surfaces of the base ceramic were uniformly coated with silver paste, and electrodes were prepared by firing silver at 550 c, and their electrical properties were tested. Prepared BaTiO 3 The relative density of the base ceramic reaches 92%, the base ceramic has no heterogeneous phase and pseudo-cubic structure, the grain size is fine and uniform, and the average grain size is 205nm; dielectric constant 1273 and dielectric loss of 0.68% at room temperature, and the temperature change rate of-4.18% -0.55% at-55 ℃ to 125 ℃. Satisfying the X7E characteristic.
Comparative example 1 (pure BaTiO) 3 Ceramic dielectric material
BaTiO 3 The preparation method of the ceramic dielectric material comprises the following specific steps:
(1) Pure BaTiO 3 The powder is presintered at a high temperature of 1100 ℃ for 2 hours, wherein the heating rate is 5 ℃/min, and then the powder A is obtained by grinding and sieving;
(2) Then adding PVA binder with the mass ratio of 5% into the powder A, granulating, sieving and molding to obtain ceramic blank with the diameter of 10mm to 1mm, preserving the temperature of the ceramic blank at 600 ℃ for 2 hours, discharging glue, then heating to 1225 ℃ for sintering, preserving the temperature for 3 hours to obtain a ceramic sample, uniformly coating silver paste on the upper surface and the lower surface of the obtained product after polishing, preparing an electrode by firing silver at 550 ℃ to obtain BaTiO 3 Ceramic material is used as a sample to be measured.
The prepared sample has a tetragonal structure, the relative density is 96%, the average grain size is 307nm, the dielectric constant is 2780 at room temperature, and the dielectric loss is 3.44%. The temperature change rate is-35.97% -137.18% within the range of-55 ℃ to 125 ℃.
Comparative example 2 (CaSiO only) 3 Doping
BaTiO 3 The preparation method of the base ceramic dielectric material comprises the following specific steps:
(1) Pure BaTiO 3 Placing the powder into a ball milling tank, adding deionized water for high-energy ball milling for 6 hours, and then drying and sieving to obtain powder;
(2) The obtained powder is presintered at a high temperature of 1100 ℃ for 2 hours, wherein the heating rate is 5 ℃/min, and then the powder A is obtained by grinding and sieving;
(3) Adding BaTiO to powder A 3 1.0% by mass of CaSiO 3 Adding deionized water to perform high-energy ball milling and mixing for 8 hours, and then drying to obtain ceramic powder;
(4) Adding PVA binder with the mass ratio of 5% into the ceramic powder, granulating, sieving, forming to obtain ceramic blank with the diameter of 10mm to 1mm, preserving the temperature of the ceramic blank at 600 ℃ for 2 hours, discharging glue, then heating to 1225 ℃ for sintering, preserving the temperature for 3 hours, wherein the heating rate is 5 ℃/min, and obtaining BaTiO 3 A base ceramic;
BaTiO is mixed with 3 The upper and lower surfaces of the base ceramic were uniformly coated with silver paste, and electrodes were prepared by firing silver at 550 c, and their electrical properties were tested. Prepared BaTiO 3 The relative density of the base ceramic reaches 97%, the base ceramic has no mixed phase and tetragonal phase structure, and the absolute average grain size is 255nm; the dielectric constant at room temperature was 2176 and the dielectric loss was 2.21%. The temperature change rate is-35.99% -82.86% within the range of-55 ℃ to 125 ℃.
Comparative example 3 (MgO and CaSiO only) 3 Doping
BaTiO 3 The preparation method of the base ceramic dielectric material comprises the following specific steps:
(1) Pure BaTiO 3 Putting the raw materials into a ball milling tank, adding deionized water for high-energy ball milling for 6 hours, and then drying and sieving to obtain powder;
(2) The obtained powder is presintered at a high temperature of 1100 ℃ for 2 hours, wherein the heating rate is 5 ℃/min, and then the powder A is obtained by grinding and sieving;
(3) Adding BaTiO to powder A 3 MgO in a molar ratio of 0.5% to the raw material, caSiO in a mass ratio of 1.0% 3 Adding deionized water to perform high-energy ball milling and mixing for 8 hours, and then drying to obtain ceramic powder;
(4) Adding PVA binder with mass ratio of 5% into the ceramic powder, granulating, sieving, forming to obtain ceramic body with diameter of 10 mm-1 mm, maintaining the ceramic body at 600deg.C for 2 hr, heating to 1225 deg.C, sintering, and maintaining the temperature for 3 hrAt a heating rate of 5 ℃/min to obtain BaTiO 3 A base ceramic;
BaTiO is mixed with 3 The upper and lower surfaces of the base ceramic were uniformly coated with silver paste, and electrodes were prepared by firing silver at 550 c, and their electrical properties were tested. Prepared BaTiO 3 The relative density of the base ceramic reaches 94%, the base ceramic has no heterogeneous phase and pseudo-cubic structure, and the average grain size is 180nm; the dielectric constant at room temperature 2251 and the dielectric loss of 0.72%. The temperature change rate is-10.44% -4.20% within the range of-55 ℃ to 125 ℃.
Comparative example 4 (compared to example 1, Y 2 O 3 Different amounts of (C) are added
A preparation method of a dielectric material with good temperature stability comprises the following specific steps:
(1) BaTiO in the past 3 1.0mol% of Y is added 2 O 3 Adding deionized water into the powder, performing high-energy ball milling for 6 hours, and then drying and sieving to obtain powder;
(2) The obtained powder is presintered at a high temperature of 1100 ℃ for 2 hours, wherein the heating rate is 5 ℃/min, and then the powder A is obtained by grinding and sieving;
(3) Adding BaTiO to powder A 3 MgO in a molar ratio of 0.5% to the raw material, caSiO in a mass ratio of 1.0% 3 Adding deionized water to perform high-energy ball milling and mixing for 8 hours, and then drying to obtain ceramic powder;
(4) Adding PVA binder with the mass ratio of 5% into the ceramic powder, granulating, sieving, forming to obtain ceramic blank with the diameter of 10mm to 1mm, preserving the temperature of the ceramic blank at 600 ℃ for 2 hours, discharging glue, then heating to 1200 ℃ for sintering, preserving the temperature for 3 hours, wherein the heating rate is 5 ℃/min, and obtaining BaTiO 3 A base ceramic;
BaTiO is mixed with 3 The upper and lower surfaces of the base ceramic were uniformly coated with silver paste, and electrodes were prepared by firing silver at 550 c, and their electrical properties were tested. Prepared BaTiO 3 The relative density of the base ceramic reaches 97%, the base ceramic has no heterogeneous phase and pseudo-cubic structure, the grain size is fine and uniform, and the average grain size is 191nm; the dielectric constant at room temperature 1565 and the dielectric loss were 0.77%. The temperature change rate is-5.19% -0.33% within the range of-55 ℃ to 125 ℃.
Comparative example 5 (compared to example 2, Y 2 O 3 Different amounts of (C) are added
A preparation method of a dielectric material with good temperature stability comprises the following specific steps:
(1) BaTiO in the past 3 1.0mol% of Y is added 2 O 3 Adding deionized water into the powder, performing high-energy ball milling for 6 hours, and then drying and sieving to obtain powder;
(2) The obtained powder is presintered at a high temperature of 1100 ℃ for 2 hours, wherein the heating rate is 5 ℃/min, and then the powder is ground and sieved to obtain powder A;
(3) Adding BaTiO to powder A 3 MgO in a molar ratio of 0.5% to the raw material, caSiO in a mass ratio of 1.0% 3 Adding deionized water to perform high-energy ball milling and mixing for 8 hours, and then drying to obtain ceramic powder;
(4) Adding PVA binder with the mass ratio of 5% into the ceramic powder, granulating, sieving, forming to obtain ceramic blank with the diameter of 10mm to 1mm, preserving the temperature of the ceramic blank at 600 ℃ for 2 hours, discharging glue, then heating to 1225 ℃ for sintering, preserving the temperature for 3 hours, wherein the heating rate is 5 ℃/min, and obtaining BaTiO 3 A base ceramic;
BaTiO is mixed with 3 The upper and lower surfaces of the base ceramic were uniformly coated with silver paste, and electrodes were prepared by firing silver at 550 c, and their electrical properties were tested. Prepared BaTiO 3 The relative density of the base ceramic reaches 94%, the base ceramic has no heterogeneous phase and pseudo-cubic structure, the grain size is fine and uniform, and the average grain size is 195nm; the dielectric constant at room temperature was 1509 and the dielectric loss was 0.71%. The temperature change rate is-3.87% -0.31% within the range of-55 ℃ to 125 ℃.
Comparative example 6 (compared to example 3, Y 2 O 3 Different amounts of (C) are added
A preparation method of a dielectric material with good temperature stability comprises the following specific steps:
(1) BaTiO in the past 3 1.0mol% of Y is added 2 O 3 Adding deionized water into the powder, performing high-energy ball milling for 6 hours, and then drying and sieving to obtain powder;
(2) The obtained powder is presintered at a high temperature of 1100 ℃ for 2 hours, wherein the heating rate is 5 ℃/min, and then the powder is ground and sieved to obtain powder A;
(3) Adding BaTiO to powder A 3 MgO in a molar ratio of 0.5% to the raw material, caSiO in a mass ratio of 1.0% 3 Adding deionized water to perform high-energy ball milling and mixing for 8 hours, and then drying to obtain ceramic powder;
(4) Adding PVA binder with the mass ratio of 5% into the ceramic powder, granulating, sieving, forming to obtain ceramic blank with the diameter of 10mm to 1mm, preserving the temperature of the ceramic blank at 600 ℃ for 2 hours, discharging glue, then heating to 1250 ℃ for sintering, preserving the temperature for 3 hours, wherein the heating rate is 5 ℃/min, and obtaining BaTiO 3 A base ceramic;
BaTiO is mixed with 3 The upper and lower surfaces of the base ceramic were uniformly coated with silver paste, and electrodes were prepared by firing silver at 550 c, and their electrical properties were tested. Prepared BaTiO 3 The relative density of the base ceramic reaches 93%, the base ceramic has no heterogeneous phase and pseudo-cubic structure, the grain size is fine and uniform, and the average grain size is 207nm; the dielectric constant 1610 and the dielectric loss were 0.73% at room temperature. The temperature change rate is-4.88% -0.40% within the range of-55 ℃ to 125 ℃.
Table 1 shows the preparation of BaTiO for examples 1-3 and comparative examples 1-6 3 Dielectric properties of the base ceramic samples comparative:
the dielectric constants and dielectric losses at 25℃at 1kHz were 1213 and 0.69% (example 1), 1418 and 0.71% (example 2), 1273 and 0.68% (example 3), 2780 and 3.44% (comparative example 1), 2176 and 2.21% (comparative example 2), 2251 and 0.72% (comparative example 3), 1565 and 0.77% (comparative example 4), 1509 and 0.71% (comparative example 5), 1610 and 0.73% (comparative example 6), respectively. As is clear from table 1, the effect of comparative example 2 was not obvious although the dielectric properties were improved as compared with comparative example 1. But only CaSiO is added 3 Comparative example 3, which is comparable to MgO, only satisfies the X7R type temperature stabilizing property, although the temperature stability is improved to some extent compared with comparative examples 1 and 2. BaTiO prepared in examples 1 to 3 and comparative examples 4 to 6 except comparative example 1 and comparative example 2 3 The dielectric constant and dielectric loss of the base ceramic are reduced, and the dielectric property is warmThe stability is obviously improved, the temperature stability is good within the temperature range of-55-125 ℃, and all the components meet the specification of the X7F type fatter C/C 25°C Less than or equal to + -7.5 percent) of medium material, which proves that Y 2 O 3 MgO and CaSiO 3 Is effective. Wherein BaTiO prepared in examples 1-3 3 The temperature stability of the base ceramic material is further improved, namely Y, as compared with comparative examples 4 to 6 2 O 3 At levels up to 2.0mol%, the best performance under this synthesis process can be achieved, where example 1, example 2 both satisfy the X7D type (.sup.C/C) 25°C The temperature change rate of the most preferred embodiment example 2 is less than or equal to 3.3 percent and less than or equal to 1.97 percent, and can meet the requirement of X7C type (C/C) 25°C Less than or equal to +/-2.2 percent) to obtain the temperature-ultra-stable dielectric material.
BaTiO prepared in examples 1 to 3 and comparative examples 1 to 6 3 XRD testing of the base ceramic material is carried out, the XRD pattern is shown in figure 1, and analysis shows that: all ceramic samples were of a single perovskite phase. And observing diffraction peaks (002) and (200) at about 45 degrees, it can be seen that the diffraction peaks of comparative example 1 and comparative example 2 have obvious peak separation, which indicates that the diffraction peaks are still tetragonal phase and only doped with Ca 2+ The diffraction peak of comparative example 2 of (2) is significantly shifted to a high angle compared to that of comparative example 1, illustrating Ca 2+ At this time, the lattice is contracted by entering the a-site. Whereas XRD of comparative example 3 showed a shift of diffraction peaks toward a low angle, it was found that there was little Ca due to the presence of MgO 2+ The B-site was entered, and at this time, the (002), (200) diffraction peaks were not significantly split. Furthermore, the doping Y can be obtained from XRDs of comparative examples 4 to 6 and examples 1 to 3 2 O 3 MgO and CaSiO 3 So that the BaTiO 3-based ceramic is converted from tetragonal phase to pseudocubic phase, and Y 2 O 3 At a doping level of 1mol%, Y 3+ Mainly into BaTiO 3 Ba in unit cell 2+ The bit, a bit, causes lattice contraction, the characteristic peak shifts to high angles; with Y 2 O 3 Increased content, part Y 3+ Gradually start to occupy BaTiO 3 Ti in unit cell 4+ The B-bit, which is also the characteristic peak of examples 1 to 3, tends to shift toward a lower angle than comparative examples 4 to 6, respectively.
Comparative example 1, comparative example 3, comparative example 5 and BaTiO prepared in example 2 3 SEM scanning is carried out on the base ceramic material, and an SEM image, a corresponding particle size distribution diagram and calculated average particle size are respectively shown in figures (a) - (d) of figure 2. Wherein (a) is BaTiO prepared in comparative example 1 3 The average grain size of the base ceramic material is 307nm; (b) BaTiO prepared in comparative example 3 shown 3 The average grain size of the base ceramic material is 180nm; (c) BaTiO prepared in comparative example 5 shown 3 The average grain size of the base ceramic material is 195nm; (d) BaTiO prepared in example 2 shown 3 The average grain size of the base ceramic material is 190nm; thus, it can be seen that BaTiO obtained by doping modification 3 The grain size of the base dielectric material is far smaller than that of pure BaTiO subjected to the same process 3 Ceramic materials, the grain size of which is not more than 200nm, i.e. doped with Y 2 O 3 MgO and CaSiO 3 Plays a role of refining grains, and finally obtains the quasi-nano BaTiO 3 A base dielectric material.
The prepared BaTiO 3 The dielectric property test is carried out after polishing the base dielectric material sample to prepare the silver electrode, and the change of dielectric constant and dielectric loss along with temperature at 1kHz (TCC, based on 25 ℃ C.) is shown in figures 3-5 respectively: 1) As can be seen from FIG. 3, comparative example 1 and comparative example 2 have sharp dielectric peaks around 125℃and thus have poor dielectric constant temperature stability, failing to meet the isothermal stability requirement of X7R, X R, but comparative example 2 has Ca 2+ Doping into the a-site relatively broadens some of the dielectric peaks, but not significantly. Comparative example 3 has greatly improved temperature stability due to the formation of the core-shell structure, and because of part of Ca 2+ Entering the B-site causes the dielectric peak to begin to move significantly toward the low temperature end. In addition, the dielectric peaks of the doped and modified examples 1-3 and comparative examples 4-6 are further reduced, and the dielectric peaks are moved to the low temperature end compared with the comparative examples 1 and 2, so that the dielectric constant change in the temperature range of-55 ℃ to 125 ℃ is obviously reduced. As can be seen from the enlarged view of the temperature of-55 ℃ to 125 ℃ in FIG. 3, the dielectric constant of examples 1 to 3 is smoother than that of comparative examples 4 to 6The number is also relatively reduced, but still above 1200; 2) As can be seen from fig. 4, the dielectric loss of comparative example 2 was slightly reduced but still higher than that of comparative example 1, while that of comparative example 3 was already significantly reduced as compared with the beginning, and in addition, the dielectric loss of examples 1 to 3 and comparative examples 4 to 6 after doping modification was significantly reduced as compared with comparative examples 1 and 2, and the dielectric loss was also more stable with temperature change. Wherein the dielectric loss at room temperature of examples 1-3 is also substantially lower than that of comparative examples 4-6, and the most preferred example is example 3, wherein the dielectric loss at room temperature is only 0.68%; 3) Wherein FIG. 5 shows that examples 1-2 and comparative examples 3-4, which were both doped and modified, achieved very good temperature stability, wherein examples 1-2 met X7D (fatter C/C) 25°C Less than or equal to + -3.3%) and especially example 2, and more particularly X7C (.sup.C/C) 25°C Less than or equal to + -2.2%) of the performance requirements of such temperature-hyperstable dielectric materials (as shown in solid line boxes).
Table 1 shows the dielectric constants, dielectric losses, and rates of change of capacitance at 1kHz (TCC, based on 25 ℃) for the dielectric materials of examples 1-3 and comparative examples 1-6 at room temperature (25 ℃)
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. The preparation method of the low-cost, low-loss and temperature-ultra-stable dielectric material is characterized by comprising the following steps of:
1) By BaTiO 3 The powder is mainly composed of BaTiO 3 Y is calculated as 100 moles 2 O 3 According to the mole ratio of 1.0-2.0, baTiO 3 Mixing, adding deionized water for ball milling, and pre-sintering after drying to obtain ceramic powder A;
2) Adding BaTiO to ceramic powder A 3 0.5 mol% of raw materialMgO in molar proportion, caSiO in mass proportion of 1.0% 3 Adding deionized water for ball milling and mixing, drying the mixed powder, adding a binder for granulating, then forming, discharging glue, and sintering to obtain the low-cost, low-loss and temperature-ultra-stable BaTiO 3 A base dielectric material;
the BaTiO 3 The grain size of the base dielectric material is not more than 300nm;
the presintering temperature in the step 1) is 1000-1150 ℃, the heating rate is 3-8 ℃/min, and the heat preservation time is 1-4 hours;
the sintering temperature in the step 2) is 1100-1300 ℃, the heating rate is 3-8 ℃/min, and the heat preservation time is 2-6 hours.
2. The method of manufacturing according to claim 1, characterized in that: the binder is PVA or PVB, and the addition amount of the binder is 1% -6% of the mass of the ceramic powder.
3. The method of manufacturing according to claim 1, characterized in that: the ball milling time in the step 1) is 3-24 hours, and the ball milling time in the step 2) is 6-24 hours.
4. The method of manufacturing according to claim 1, characterized in that: the glue discharging temperature in the step 2) is 500-600 ℃, the heating rate is 3-8 ℃/min, and the heat preservation time is 2-4 hours.
5. The method of manufacturing according to claim 1, characterized in that: baTiO 3 The average particle size of the powder raw material is not more than 300nm.
6. The method of manufacturing according to claim 1, characterized in that: the preparation raw materials are all analytically pure raw materials.
7. The temperature-hyperstable dielectric material produced by the production method according to any one of claims 1 to 6, characterized in that: the temperature ultra-stable dielectric material meets the condition that the temperature change rate is less than or equal to +/-3.3% and meets the X7D characteristic within the range of-55-125 ℃; at room temperature, the dielectric constant is 1210-1610, and the dielectric loss is not more than 0.71%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005294290A (en) * | 2004-03-31 | 2005-10-20 | Tdk Corp | Multilayered ceramic capacitor |
| CN101298385A (en) * | 2007-03-29 | 2008-11-05 | Tdk株式会社 | Manufacturing methods of dielectric ceramic composition and electronic component |
| CN102190492A (en) * | 2010-02-09 | 2011-09-21 | Tdk株式会社 | Dielectric ceramic composition and electronic device |
| CN102381876A (en) * | 2010-08-31 | 2012-03-21 | Tdk株式会社 | Dielectric ceramic composition and ceramic electronic device |
| CN113582683A (en) * | 2021-09-02 | 2021-11-02 | 福州大学 | BaTiO for X8R MLCC3Preparation method of base ceramic material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005294290A (en) * | 2004-03-31 | 2005-10-20 | Tdk Corp | Multilayered ceramic capacitor |
| CN101298385A (en) * | 2007-03-29 | 2008-11-05 | Tdk株式会社 | Manufacturing methods of dielectric ceramic composition and electronic component |
| CN102190492A (en) * | 2010-02-09 | 2011-09-21 | Tdk株式会社 | Dielectric ceramic composition and electronic device |
| CN102381876A (en) * | 2010-08-31 | 2012-03-21 | Tdk株式会社 | Dielectric ceramic composition and ceramic electronic device |
| CN113582683A (en) * | 2021-09-02 | 2021-11-02 | 福州大学 | BaTiO for X8R MLCC3Preparation method of base ceramic material |
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| BaTiO_3基陶瓷介电材料的研究进展;杨公安;蒲永平;王瑾菲;庄永勇;;中国陶瓷(11);全文 * |
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