CN103601486A - Medium-temperature sintered multiplayer ceramic capacitor dielectric material and preparation method thereof - Google Patents

Medium-temperature sintered multiplayer ceramic capacitor dielectric material and preparation method thereof Download PDF

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CN103601486A
CN103601486A CN201310578515.5A CN201310578515A CN103601486A CN 103601486 A CN103601486 A CN 103601486A CN 201310578515 A CN201310578515 A CN 201310578515A CN 103601486 A CN103601486 A CN 103601486A
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dielectric material
ceramic capacitor
ball milling
mixing
synthetic
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李玲霞
王鸣婧
付瑞雪
柳亚然
陈俊晓
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Tianjin University
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Tianjin University
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Abstract

The invention discloses a medium-temperature sintered multiplayer ceramic capacitor dielectric material and a preparation method thereof. The preparation method of the dielectric material is as follows: based on BaTiO3, 0.8-1.5% by mass Ni1-xNbxO1+1.5x, 0.2-0.5% by mass of Mn1-yNbyO1+1.5y, 0.2-1.5% by mass of CaZrO3 and 4-7% by mass of a glass fluxing agent are added, and then subjected to burdening, ball milling, drying, sieving, calcining, pelleting, compression moulding and the like, and finally sintered at the temperature of 1120-1150 DEG C, wherein x is 0.6-0.8, and Ni1-xNbxO1+1.5x is synthesized from NiO and Nb2O5 in the mol ratio of (1-x): (x/2); y is 0.4-0.6, and Mn1-yNbyO1+1.5y is synthesized from MnCO3 and Nb2O5 in the mole ratio of (1-y): (y/2); CaZrO3 is synthesized from CaCO3 and ZrO2 in the mole ratio of 1:1; the glass fluxing agent is synthesized from 17wt% of BaO, 34wt% of B2O3, 12wt% of ZnO and 37wt% of Bi2O3. Between the temperature interval of minus 55 DEG C-150 DEG C, the medium-temperature sintered multiplayer ceramic capacitor dielectric material has the capacitance change rate of minus15%-15%, higher room temperature dielectric constant (3000) and lower loss (tan delta is less than 1.5%), and is capable of realizing medium-temperature sintering below 1150 DEG C and suitable for commercialized application.

Description

Medium temp sintered multilayer ceramic capacitor dielectric material and preparation method thereof
Technical field
The present invention relates to a kind of ceramic composition that composition is feature of take, be specifically related to a kind of X8R type medium material for multilayer ceramic capacitors with temperature stability and preparation method thereof
Background technology
Chip multilayer ceramic capacitor (Multilayer Ceramic Capacitor, be called for short MLCC) as base electronic components and parts, except generally using, in industries such as the Military Electronic Equipment such as aerospace, tank electronics, military mobile communication, the control of weapon bullet and military signal monitoring and petroleum prospectings, all there is application quite widely in the products for civilian use such as smart mobile phone, panel computer, broadcast television, mobile communication, home computer, household electrical appliance, surveying instrument, medical facilities and consumer electronics.Barium titanate (BaTiO 3) base temperature-stable MLCC because of its environmental sound, is the focus of research with dielectric material always, using at present maximum is EIA X7R(-55 ℃～125 ℃, Δ C/C 20 ℃≤ ± 15%) dielectric material.Develop rapidly along with MLCC, to MLCC with researching and proposing of dielectric material higher requirement, in higher temperature environment, still keep stable dielectric properties, as in summer, temperature in automobile engine nacelle can reach more than 130 ℃, now, X7R type dielectric material is just difficult to meet actual needs.Therefore, X8R(-55 ℃～150 ℃, Δ C/C 20 ℃≤ ± 15%) development of dielectric material for type MLCC, has very important practical significance.
Traditional B aTiO 3based dielectric material need to be in the air higher than 1300 ℃ sintering, thereby can only select the precious metals such as Pt, Pd as inner electrode.Along with the increase of MLCC demand, electrode cost in an urgent demand reduces.At present, can be by adding the method for glass fusing assistant, by BaTiO 3the sintering temperature of based dielectric material drops to below 1150 ℃, usings and realizes the Ag-Pd alloy (as Ag70-Pd30) of high Ag as the preparation technology of interior electrode.
Summary of the invention
Object of the present invention, is to provide a kind of intermediate sintering temperature (1150 ℃ following) and has X8R type medium material for multilayer ceramic capacitors of high dielectric constant and preparation method thereof.
The present invention is achieved by following technical solution.
A medium temp sintered multilayer ceramic capacitor dielectric material, with BaTiO 3for base-material, at BaTiO 3on basis, the Ni that additional mass percentage content is 0.8～1.5% 1-xnb xo 1+1.5x, wherein x=0.6～0.8,0.2～0.5% Mn 1-ynb yo 1+1.5y, wherein y=0.4～0.6,0.2～1.5% CaZrO 3form with 4～7% glass fusing assistant;
Described Ni 1-xnb xo 1+1.5xwherein x=0.6～0.8 compound is by NiO and Nb 2o 5(1-x) in molar ratio: (x/2) synthetic; Described Mn 1-ynb yo 1+1.5ywherein y=0.4～0.6 compound is by MnCO 3and Nb 2o 5(1-y) in molar ratio: (y/2) synthetic;
Described CaZrO 3by CaCO 3and ZrO 21:1 is synthetic in molar ratio;
The raw material of described glass fusing assistant forms and mass percentage content is: 17% BaO, 34% B 2o 3, 12% ZnO and 37%Bi 2o 3;
The preparation method of above-mentioned medium temp sintered multilayer ceramic capacitor dielectric material, step is as follows:
(1) Ni 1-xnb xo 1+1.5xwherein x=0.6～0.8 compound is synthetic: by NiO, Nb 2o 5(1-x) in molar ratio: (x/2) batching, 4 hours post-dryings of mixing and ball milling, sieve, in 800～1000 ℃ of calcinings, obtain;
(2) Mn 1-ynb yo 1+1.5ywherein y=0.4～0.6 compound is synthetic: by MnCO 3, Nb 2o 5(1-y) in molar ratio: (y/2) batching, 4 hours post-dryings of mixing and ball milling, sieve, in 800～1000 ℃ of calcinings, obtain;
(3) CaZrO 3synthetic: CaCO 3, ZrO 21:1 batching in molar ratio, 4 hours post-dryings of mixing and ball milling, sieves, and in 1000 ℃ of calcinings, obtains;
(4) glass fusing assistant is synthetic: by mass percentage, and by 17% BaO, 34% B 2o 3, 12% ZnO and 37%Bi 2o 3fully mixing, melt quenching, levigate, make after sieving;
(5) with BaTiO 3as base-material, the Ni that additional mass percentage content is 0.8～1.5% 1-xnb xo 1+1.5xwherein x=0.6～0.8,0.2～0.5% Mn 1-ynb yo 1+1.5ywherein y=0.4～0.6,0.2～1.5% CaZrO 3with 4～7% glass fusing assistant, institute join raw material mixes with deionized water after ball milling 4～12 hours, the binding agent that after oven dry, additional mass percent is 5～8% granulation of sieving;
(6) the granulation powder of step (5) is pressed into green compact, in 1120 ℃～1150 ℃ sintering, is incubated 1～3 hour, make medium temp sintered multilayer ceramic capacitor dielectric material.
The binding agent of described step (5) is paraffin.
The preferred sintering temperature of described step (6) is 1150 ℃.
Beneficial effect of the present invention is as follows:
1. medium material for multilayer ceramic capacitors disclosed by the invention has good dielectric properties: in-55 ℃～150 ℃ warm areas, rate of change of capacitance, in ± 15%, and has higher room temperature dielectric constant (～3000) and compared with low-loss (tan δ <1.5%);
2. medium material for multilayer ceramic capacitors disclosed by the invention, by the interpolation of glass fusing assistant, can be realized 1150 ℃ of following intermediate sintering temperatures, is applicable to commercial applications.
Embodiment
The present invention is raw materials used is commercially available chemically pure reagent, and below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1
By 2.9877gNiO and 7.9743gNb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain Ni 0.4nb 0.6o 1.9compound; By 4.5979gMnCO 3and 7.9743gNb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain Mn 0.4nb 0.6o 1.9compound; By 22.329g CaCO 3with 27.5114g ZrO 24 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain CaZrO 3; By 17g BaO, 34g B 2o 3, 12g ZnO and g Bi 2o 3fully mixing, melt quenching, levigate, make glass fusing assistant after sieving; By 20g BaTiO 3, 0.2g Ni 0.4nb 0.6o 1.9, 0.06g Mn 0.4nb 0.6o 1.9, 0.1g CaZrO 3ball milling 6 hours after mixing with deionized water with 1.2g glass fusing assistant, after oven dry, adding mass percent is the granulation of sieving of 7% paraffin; Powder pressing after granulation is become to disk green compact, be warming up to 550 ℃ of de-waxings through 3.5 hours, 1.5h rises to 1130 ℃ of sintering, is incubated 1 hour, makes medium material for multilayer ceramic capacitors.
The upper and lower surface of gained medium material for multilayer ceramic capacitors is evenly applied to silver slurry, through 850 ℃ of burning infiltrations, prepare electrode, make laminated ceramic capacitor.The main dielectric properties of embodiment 1 refer to table 1.
Embodiment 2
By 2.9877g NiO and 7.9743g Nb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain Ni 0.4nb 0.6o 1.9compound; By 4.5979g MnCO 3with 7.9743g Nb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain Mn 0.4nb 0.6o 1.9compound; By 22.329g CaCO 3with 27.5114g ZrO 24 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain CaZrO 3; By 17g BaO, 34g B 2o 3, 12g ZnO and g Bi 2o 3fully mixing, melt quenching, levigate, make glass fusing assistant after sieving; By 20g BaTiO 3, 0.22g Ni 0.4nb 0.6o 1.9, 0.04g Mn 0.4nb 0.6o 1.9, 0.2g CaZrO 3ball milling 6 hours after mixing with deionized water with 1.1g glass fusing assistant, after oven dry, adding mass percent is the granulation of sieving of 7% paraffin; Powder pressing after granulation is become to disk green compact, be warming up to 550 ℃ of de-waxings through 3.5 hours, 1.5h rises to 1140 ℃ of sintering, is incubated 1 hour, makes medium material for multilayer ceramic capacitors.
The upper and lower surface of gained medium material for multilayer ceramic capacitors is evenly applied to silver slurry, through 850 ℃ of burning infiltrations, prepare electrode, make laminated ceramic capacitor.The main dielectric properties of embodiment 2 refer to table 1.
Embodiment 3
By 2.2408g NiO and 9.3034g Nb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Ni 0.3nb 0.7o 2.05compound; By 5.7473gMnCO 3and 6.6452gNb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Mn 0.5nb 0.5o 1.75compound; By 22.329g CaCO 3with 27.5114g ZrO 24 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain CaZrO 3; By 17g BaO, 34g B 2o 3, 12g ZnO and g Bi 2o 3fully mixing, melt quenching, levigate, make glass fusing assistant after sieving; By 50g BaTiO 3, 0.4g Ni 0.3nb 0.7o 2.05, 0.2g Mn 0.5nb 0.5o 1.75, 0.5g CaZrO 3ball milling 8 hours after mixing with deionized water with 2.5g glass fusing assistant, after oven dry, adding mass percent is the granulation of sieving of 7% paraffin; Powder pressing after granulation is become to disk green compact, be warming up to 550 ℃ of de-waxings through 3.5 hours, 1.5h rises to 1150 ℃ of sintering, is incubated 2 hours, makes medium material for multilayer ceramic capacitors.
The upper and lower surface of gained medium material for multilayer ceramic capacitors is evenly applied to silver slurry, through 850 ℃ of burning infiltrations, prepare electrode, make medium material for multilayer ceramic capacitors.The main dielectric properties of embodiment 3 refer to table 1.
Embodiment 4
By 2.2408g NiO and 9.3034g Nb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Ni 0.3nb 0.7o 2.05compound; By 5.7473gMnCO 3and 6.6452gNb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Mn 0.5nb 0.5o 1.75compound; By 22.329g CaCO 3with 27.5114g ZrO 24 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain CaZrO 3; By 17g BaO, 34g B 2o 3, 12g ZnO and g Bi 2o 3fully mixing, melt quenching, levigate, make glass fusing assistant after sieving; By 50g BaTiO 3, 0.45g Ni 0.3nb 0.7o 2.05, 0.1g Mn 0.5nb 0.5o 1.75, 0.125g CaZrO 3ball milling 8 hours after mixing with deionized water with 3.5g glass fusing assistant, after oven dry, adding mass percent is the granulation of sieving of 7% paraffin; Powder pressing after granulation is become to disk green compact, be warming up to 550 ℃ of de-waxings through 3.5 hours, 1.5h rises to 1120 ℃ of sintering, is incubated 1 hour, makes medium material for multilayer ceramic capacitors.
The upper and lower surface of gained medium material for multilayer ceramic capacitors is evenly applied to silver slurry, through 850 ℃ of burning infiltrations, prepare electrode, make laminated ceramic capacitor.The main dielectric properties of embodiment 3 refer to table 1.
Embodiment 5
By 1.4939g NiO and 10.6324g Nb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Ni 0.2nb 0.8o 2.2compound; By 6.8968gMnCO 3and 5.3162gNb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Mn 0.6nb 0.4o 1.6compound; By 22.329g CaCO 3with 27.5114g ZrO 24 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain CaZrO 3; By 17g BaO, 34g B 2o 3, 12g ZnO and g Bi 2o 3fully mixing, melt quenching, levigate, make glass fusing assistant after sieving; By 50g BaTiO 3, 0.5g Ni 0.2nb 0.8o 2.2, 0.15gMn 0.6nb 0.4o 1.6, 0.75g CaZrO 3ball milling 10 hours after mixing with deionized water with 3g glass fusing assistant, after oven dry, adding mass percent is the granulation of sieving of 7% paraffin; Powder pressing after granulation is become to disk green compact, be warming up to 550 ℃ of de-waxings through 3.5 hours, 1.5h rises to 1130 ℃ of sintering, is incubated 3 hours, makes medium material for multilayer ceramic capacitors.
The upper and lower surface of gained medium material for multilayer ceramic capacitors is evenly applied to silver slurry, through 850 ℃ of burning infiltrations, prepare electrode, make laminated ceramic capacitor.The main dielectric properties of embodiment 5 refer to table 1.
Embodiment 6
By 1.4939g NiO and 10.6324g Nb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Ni 0.2nb 0.8o 2.2compound; By 6.8968gMnCO 3and 5.3162gNb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Mn 0.6nb 0.4o 1.6compound; By 22.329g CaCO 3with 27.5114g ZrO 24 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain CaZrO 3; By 17g BaO, 34g B 2o 3, 12g ZnO and g Bi 2o 3fully mixing, melt quenching, levigate, make glass fusing assistant after sieving; By 50g BaTiO 3, 0.75g Ni 0.2nb 0.8o 2.2, 0.1g Mn 0.6nb 0.4o 1.6, 0.5g CaZrO 3ball milling 12 hours after mixing with deionized water with 2.25g glass fusing assistant, after oven dry, adding mass percent is the granulation of sieving of 7% paraffin; Powder pressing after granulation is become to disk green compact, be warming up to 550 ℃ of de-waxings through 3.5 hours, 1.5h rises to 1130 ℃ of sintering, is incubated 1 hour, makes medium material for multilayer ceramic capacitors.
The upper and lower surface of gained medium material for multilayer ceramic capacitors is evenly applied to silver slurry, through 850 ℃ of burning infiltrations, prepare electrode, make laminated ceramic capacitor.The main dielectric properties of embodiment 6 refer to table 1.
Embodiment 7
By 2.2408g NiO and 9.3034g Nb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Ni 0.3nb 0.7o 2.05compound; By 5.7473gMnCO 3and 6.6452gNb 2o 54 hours post-dryings of mixing and ball milling, sieve, in 900 ℃ of calcinings, obtain Mn 0.5nb 0.5o 1.75compound; By 22.329g CaCO 3with 27.5114g ZrO 24 hours post-dryings of mixing and ball milling, sieve, in 1000 ℃ of calcinings, obtain CaZrO 3; By 17g BaO, 34g B 2o 3, 12g ZnO and g Bi 2o 3fully mixing, melt quenching, levigate, make glass fusing assistant after sieving; By 50g BaTiO 3, 0.45g Ni 0.3nb 0.7o 2.05, 0.25g Mn 0.5nb 0.5o 1.75, 0.6g CaZrO 3ball milling 4 hours after mixing with deionized water with 2.25g glass fusing assistant, after oven dry, adding mass percent is the granulation of sieving of 7% paraffin; Powder pressing after granulation is become to disk green compact, be warming up to 550 ℃ of de-waxings through 3.5 hours, 1.5h rises to 1150 ℃ of sintering, is incubated 2 hours, makes medium material for multilayer ceramic capacitors.
The upper and lower surface of gained medium material for multilayer ceramic capacitors is evenly applied to silver slurry, through 850 ℃ of burning infiltrations, prepare electrode, make laminated ceramic capacitor.The main dielectric properties of embodiment 7 refer to table 1.
Testing method of the present invention and test set are as follows:
(1) dielectric properties tests (AC test signals: frequency is 1kHz, voltage is 1V)
Use electrical capacity C and the loss tan δ of HEWLETT PACKARD4278A type capacitance tester specimen, and calculate the specific inductivity of sample, calculation formula is:
s = 14.4 &times; c &times; d D 2
(2) TC characteristic test
Utilize GZ-ESPEK high-low temperature chamber, HM27002 type electrical condenser C-T/V characteristic dedicated tester and HEWLETTPACKARD4278A to test.The electrical capacity of measure sample in warm area-55 ℃～150 ℃, adopts following formula to calculate rate of change of capacitance: Δ C/C 20 ℃=(C-C 20 ℃)/C20 ℃* 100%.
Table 1
The present invention is not limited to above-described embodiment, and the variation of a lot of details is possible, but therefore this do not run counter to scope and spirit of the present invention.

Claims (3)

1. a medium temp sintered multilayer ceramic capacitor dielectric material, with BaTiO 3for base-material, at BaTiO 3on basis, the Ni that additional mass percentage content is 0.8～1.5% 1-xnb xo 1+1.5x, wherein x=0.6～0.8,0.2～0.5% Mn 1-ynb yo 1+1.5y, wherein y=0.4～0.6,0.2～1.5% CaZrO 3form with 4～7% glass fusing assistant;
Described Ni 1-xnb xo 1+1.5xwherein x=0.6～0.8 compound is by NiO and Nb 2o 5(1-x) in molar ratio: (x/2) synthetic; Described Mn 1-ynb yo 1+1.5ywherein y=0.4～0.6 compound is by MnCO 3and Nb 2o 5(1-y) in molar ratio: (y/2) synthetic;
Described CaZrO 3by CaCO 3and ZrO 21:1 is synthetic in molar ratio;
The raw material of described glass fusing assistant forms and mass percentage content is: 17% BaO, 34% B 2o 3, 12% ZnO and 37%Bi 2o 3;
The preparation method of above-mentioned medium temp sintered multilayer ceramic capacitor dielectric material, step is as follows:
(1) Ni 1-xnb xo 1+1.5xwherein x=0.6～0.8 compound is synthetic: by NiO, Nb 2o 5(1-x) in molar ratio: (x/2) batching, 4 hours post-dryings of mixing and ball milling, sieve, in 800～1000 ℃ of calcinings, obtain;
(2) Mn 1-ynb yo 1+1.5ywherein y=0.4～0.6 compound is synthetic: by MnCO 3, Nb 2o 5(1-y) in molar ratio: (y/2) batching, 4 hours post-dryings of mixing and ball milling, sieve, in 800～1000 ℃ of calcinings, obtain;
(3) CaZrO 3synthetic: CaCO 3, ZrO 21:1 batching in molar ratio, 4 hours post-dryings of mixing and ball milling, sieves, and in 1000 ℃ of calcinings, obtains;
(4) glass fusing assistant is synthetic: by mass percentage, and by 17% BaO, 34% B 2o 3, 12% ZnO and 37%Bi 2o 3fully mixing, melt quenching, levigate, make after sieving;
(5) with BaTiO 3as base-material, the Ni that additional mass percentage content is 0.8～1.5% 1-xnb xo 1+1.5xwherein x=0.6～0.8,0.2～0.5% Mn 1-ynb yo 1+1.5ywherein y=0.4～0.6,0.2～1.5% CaZrO 3with 4～7% glass fusing assistant, institute join raw material mixes with deionized water after ball milling 4～12 hours, the binding agent that after oven dry, additional mass percent is 5～8% granulation of sieving;
(6) the granulation powder of step (5) is pressed into green compact, in 1120 ℃～1150 ℃ sintering, is incubated 1～3 hour, make medium temp sintered multilayer ceramic capacitor dielectric material.
2. a kind of medium temp sintered multilayer ceramic capacitor dielectric material according to claim 1, is characterized in that, the binding agent of described step (5) is paraffin.
3. a kind of medium temp sintered multilayer ceramic capacitor dielectric material according to claim 1, is characterized in that, the preferred sintering temperature of described step (6) is 1150 ℃.
CN201310578515.5A 2013-11-14 2013-11-14 Medium-temperature sintered multiplayer ceramic capacitor dielectric material and preparation method thereof Pending CN103601486A (en)

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CN104045341A (en) * 2014-06-24 2014-09-17 天津大学 Lead-free high-dielectric-constant multilayer ceramic capacitor dielectric material and preparation method thereof
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CN104761258A (en) * 2015-03-18 2015-07-08 河南科技大学 Method of low-temperature sintering calcium zirconate microwave dielectric ceramic

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103864416A (en) * 2014-02-27 2014-06-18 天津大学 Method for preparing barium titanate ceramic capacitor medium at low sintering temperature
CN103922732A (en) * 2014-03-18 2014-07-16 天津大学 High voltage resistance multilayer ceramic capacitor dielectric material and preparation method thereof
CN103992106A (en) * 2014-04-28 2014-08-20 天津大学 Medium temperature sintered multilayer ceramic capacitor dielectric material
CN103992107A (en) * 2014-04-28 2014-08-20 天津大学 Low-loss multilayer ceramic capacitor dielectric material
CN103992107B (en) * 2014-04-28 2015-12-02 天津大学 A kind of low-loss medium material for multilayer ceramic capacitors
CN104030677A (en) * 2014-06-24 2014-09-10 天津大学 Low-loss multilayer ceramic capacitor dielectric material and preparation method thereof
CN104045341A (en) * 2014-06-24 2014-09-17 天津大学 Lead-free high-dielectric-constant multilayer ceramic capacitor dielectric material and preparation method thereof
CN104692808A (en) * 2015-02-06 2015-06-10 佛山市三水新华雄陶瓷有限公司 Additive and method for lowering ceramic firing temperature
CN104761258A (en) * 2015-03-18 2015-07-08 河南科技大学 Method of low-temperature sintering calcium zirconate microwave dielectric ceramic
CN104761258B (en) * 2015-03-18 2017-06-20 河南科技大学 A kind of method of low-temperature sintering calcium zirconate microwave-medium ceramics

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Application publication date: 20140226