CN117486609B - Single-phase composite perovskite ceramic powder, microwave dielectric ceramic material and preparation method thereof - Google Patents

Single-phase composite perovskite ceramic powder, microwave dielectric ceramic material and preparation method thereof Download PDF

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CN117486609B
CN117486609B CN202410001980.0A CN202410001980A CN117486609B CN 117486609 B CN117486609 B CN 117486609B CN 202410001980 A CN202410001980 A CN 202410001980A CN 117486609 B CN117486609 B CN 117486609B
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ceramic powder
ball milling
glass
phase
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CN117486609A (en
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林慧兴
姜少虎
任海深
姚晓刚
赵相毓
张奕
彭海益
谢天翼
何飞
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to single-phase composite perovskite ceramic powder, a microwave dielectric ceramic material and a preparation method thereof, belonging to the field of microwave dielectric ceramic material preparation. Aiming at the problem that the performance of the existing microwave dielectric ceramic material is improved to a limited extent, the invention provides single-phase composite perovskite ceramic powder, which consists of (100-m) ABB main phase-m additive AD, wherein the additive AD is dissolved in the ABB main phase in a solid manner; wherein the ABB main phase is Ba (Zn) 1/3 Ta 2/3 )O 3 Or Ba (Co) x Zn 1‑x ) 1/ 3 Nb 2/3 O 3 X=0.58 to 0.63; the additive AD is at least one of glass powder GL and ceramic powder CM, and m=0.05wt% -1.3wt%. The single-phase composite perovskite ceramic powder prepared by the invention has excellent microwave performance, and the process method is simple and feasible, and is suitable for mass industrial production.

Description

Single-phase composite perovskite ceramic powder, microwave dielectric ceramic material and preparation method thereof
Technical Field
The invention belongs to the field of microwave dielectric ceramic material preparation, and particularly relates to single-phase composite perovskite ceramic powder, a microwave dielectric ceramic material and a preparation method thereof.
Background
With the development of microwave devices, the microwave device has high quality factor Q multiplied by f and low dielectric constantThe microwave dielectric ceramic material with the electric loss tg delta and the medium dielectric constant epsilon r is increasingly attracting attention, wherein the microwave dielectric ceramic material with the composite perovskite structure has the optimal comprehensive performance, and is widely applied to microwave radio frequency devices such as microwave capacitors, circulators, diplexers, dielectric filters, microwave antennas and the like. In the microwave medium material with high quality factor, the composite perovskite structure has the composition of Ba (Zn) 1/3 Ta 2/3 )O 3 (hereinafter abbreviated as BZT), ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 The ceramic (BCZN) is a microwave dielectric material with the best comprehensive performance at present. However, due to the factors of high densification temperature, volatile components, difficult control of performance and the like of the series of ceramics, particularly, high-performance single-phase dense ceramics are difficult to obtain, so that the microwave dielectric performance of the material is greatly influenced. Thereby limiting the popularization and application of the series of materials.
To obtain high performance AB' 1/3 B’’ 2/3 O 3 Composite perovskite microwave dielectric ceramic, realizing single-phase preparation of the series of materials and promoting the improvement of B-site ion order degree is key for improving the microwave dielectric property of the materials, wherein single-phase AB' 1/3 B’’ 2/3 O 3 The preparation of the structural powder is the basis for preparing the high-performance material. At present, most researches mainly focus on the adjustment of material structure through doping modification, improvement of material sintering density and the like, so as to realize the regulation and control of the microwave dielectric property of the material, for example, the material is Sr through A, B 2+ 、Zn 2+ And the substitution and addition of sintering aids improve the sintering characteristics of the material, but the performance of the obtained microwave dielectric ceramic material is improved only to a limited extent. Furthermore, single phase AB 'is available' 1/3 B’’ 2/3 O 3 The research of the preparation method of the composite perovskite ceramic in the aspects of batch process stability and the like has serious defects, and the product performance is easy to fluctuate and the product quality is poor. Therefore, a preparation method of the composite perovskite microwave dielectric ceramic with simple preparation, excellent performance and controllability needs to be developed, and the yield and operability of the product are improved.
Disclosure of Invention
Aiming at the problem that the existing microwave dielectric ceramic material has limited performance improvement, the invention provides single-phase composite perovskite ceramic powder, a microwave dielectric ceramic material and a preparation method thereof, and the single-phase composite perovskite ceramic powder and the microwave dielectric ceramic material have the characteristics of stable batch production, good repeatability, excellent performance and the like.
In a first aspect, the invention provides a single-phase composite perovskite ceramic powder, wherein the single-phase composite perovskite ceramic powder comprises (100 wt% -m) ABB main phase-m additive AD, and the additive AD is in solid solution in the ABB main phase; wherein the ABB main phase is Ba (Zn) 1/3 Ta 2/3 )O 3 Or Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 X=0.58 to 0.63; the additive AD is at least one of glass powder GL and ceramic powder CM, and m=0.05wt% -1.3wt%;
the glass powder GL is glass powder containing Ba, sr, ca, B, ti, zr, V and O element components;
the ceramic powder CM is a ceramic powder containing at least three element components of Ba, ca, sr, ti, O.
Preferably, the Ba (Zn) 1/3 Ta 2/3 )O 3 BaO, znO and Ta in 2 O 5 The molar ratio of (59.43-60.02): (19.99-20.78): (19.79 to 19.99);
said Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 BaO, coO, znO and Nb in (V) 2 O 5 The molar ratio of (59.43-60.02): (11.99-12.47): (8.00-8.31): (19.79-19.99).
Preferably, the composition of the glass powder GL includes: baO:40 weight percent to 45 weight percent, caO:6 wt-10 wt%, srO:1 to wt percent to 3 percent by weight, B 2 O 3 ：25 wt%～30wt%，TiO 2 ：15 wt%～18wt%，ZrO 2 :0.5 wt% -2 wt% (preferably 1.1 wt% -2 wt%) V 2 O 5 : 1.1 wt to 3wt% (preferably 2. 2wt to 3 wt%), the sum of the mass percentages of the components being 100. 100wt%;
the composition of the ceramic powder CM comprises: baO:51.02 weight percent 65.75 to wt percent, caO: 0wt% -5.33 wt%, srO: 0.0 wt-4.93-wt%，TiO 2 :34.25 weight percent to 38.72 and wt percent, and the sum of the mass percentages of the components is 100 percent to wt percent;
m=0.1wt%～1.2wt%。
in a second aspect, the invention provides a method for preparing single-phase composite perovskite ceramic powder, which comprises the following steps:
(1) ZnO powder and Ta 2 O 5 Mixing the powder, calcining, and synthesizing ZT calcined material;
(2) CoO powder, znO powder and Nb 2 O 5 Mixing the powder, and calcining to synthesize a CZN calcined material;
(3) Mixing ZT calcined material, ba source and additive AD, and then secondary calcining to obtain single-phase Ba (Zn) 1/ 3 Ta 2/3 )O 3 Ceramic powder; or mixing CZN calcined material, ba source and additive AD, and then performing secondary calcination to obtain single-phase Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 Ceramic powder.
Preferably, in the step (1), the purity of the ZnO powder is more than or equal to 99.5 percent, and the purity of the Ta is more than or equal to 2 O 5 The purity of the powder is more than or equal to 5N; the mixing mode is ball milling mixing, and the parameters of the ball milling mixing comprise: the ball milling medium is deionized water, the ball milling balls are zirconia balls, and the granularity D of the obtained ball milling slurry 50 < 3 μm; the calcination temperature of the ZT calcined material is 1100-1200 ℃, and the heat preservation time is 4-6 hours.
Preferably, in the step (2), the purity of the CoO powder is more than or equal to 99 percent, and the Nb is 2 O 5 The purity of the powder is more than or equal to 99 percent; the mixing mode is ball milling mixing, and the parameters of the ball milling mixing comprise: the ball milling medium is deionized water, and the ball milling balls are zirconia balls; the calcination temperature of the CZN calcination material is 900-1100 ℃, and the heat preservation time is 4-6 hours.
Preferably, in the step (3), the particle size D of the glass powder GL 90 Less than 1 μm; the preparation method of the glass powder GL comprises the following steps: weighing BaCO according to the composition proportion of the glass powder GL 3 、CaCO 3 、SrCO 3 、H 3 BO 3 、TiO 2 、ZrO 2 And V 2 O 5 Raw materials are mixed, molten into glass liquid, and then poured into a sheet rolling machine to prepare glass (for example, the glass is sheet-shaped); filling the obtained glass into a sagger, and carrying out microcrystallization heat treatment in a muffle furnace; ball milling is carried out on the glass subjected to the microcrystallization heat treatment to obtain glass powder GL;
the melting temperature is 1300-1500 ℃, and the melting time is 2-3 hours;
the temperature of the microcrystallization heat treatment is 810-850 ℃, and the microcrystallization heat treatment time is 1-2 hours;
the ball milling treatment parameters comprise: the ball milling medium is deionized water, and the ball milling balls are zirconia balls.
Preferably, in the step (3), the particle size D of the ceramic powder CM 90 ≤1μm；
The preparation method of the ceramic powder CM comprises the following steps: weighing BaCO according to the composition proportion of the ceramic powder CM 3 、CaCO 3 、SrCO 3 Rutile type TiO 2 Mixing the raw materials, calcining, and performing high-energy ball milling to obtain the ceramic powder CM;
the calcining temperature is 1100-1300 ℃, and the heat preservation time is 2-4 h.
Preferably, in the step (3), the Ba source is one of BaO powder or barium carbonate powder;
the single phase Ba (Zn) 1/3 Ta 2/3 )O 3 The secondary calcination temperature of the ceramic powder is 1150-1250 ℃ and the time is 4-6 hours;
said single phase Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 The secondary calcination temperature of the ceramic powder is 1100-1200 ℃ and the time is 4-6 hours.
In a third aspect, the invention provides a method for preparing a microwave dielectric ceramic material, comprising the following steps: and preparing a green body from the single-phase composite perovskite ceramic powder, and sintering to obtain the microwave dielectric ceramic material. Wherein, the forming method of the blank body is dry press forming and the like.
Preferably, the sintering temperature is 1480-1520 ℃; the sintering time is 4-8 hours.
Preferably, the temperature rising rate of the sintering is 3-6 ℃/min; the cooling rate of the sintering is 1-2 ℃/min.
In a fourth aspect, the invention provides a microwave dielectric ceramic material, which is prepared by the preparation method of the microwave dielectric ceramic material. Preferably, the density of the microwave dielectric ceramic material is more than or equal to 99 percent.
The invention has the beneficial effects that:
the invention adopts the method that the adhesive is connected with the substrate AB' 1/3 B’’ 2/3 O 3 The additive AD with similar ceramic components is introduced into perovskite structure nanocrystals, so that the single-phase forming capability of the composite perovskite ceramic is improved, and a good preparation foundation is laid for preparing the high-performance composite perovskite ceramic material. Compared with the prior art, the single-phase composite perovskite ceramic powder prepared by the method has excellent microwave performance, and the process method is simple and feasible and is suitable for mass industrial production.
Drawings
FIG. 1 is an XRD pattern of the glass powder GL of example 1, the ceramic powder CM of example 1 and the glass powder GL of example 7;
FIG. 2 is an XRD pattern of the single-phase composite perovskite ceramic powder obtained in examples 1 to 6;
FIG. 3 is an XRD pattern of the single-phase composite perovskite ceramic powders obtained in examples 7 to 14;
FIG. 4 is an XRD pattern of perovskite ceramic powders prepared in comparative examples 1 to 8.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, the single-phase composite perovskite ceramic powder is single-phase AB' 1/3 B’’ 2/3 O 3 Composite perovskite ceramic powder comprising single-phase Ba (Zn) 1/3 Ta 2/3 )O 3 Ceramic powder or single-phase Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 Ceramic powder. Specifically, single-phase composite calciumThe titanium ore ceramic powder is composed of (100 wt% -m) ABB main phase-m additive AD system. Wherein the ABB main phase is Ba (Zn) 1/3 Ta 2/3 )O 3 、Ba(Co x Zn 1-x ) 1/3 Nb 2/3 O 3 One of the microwave dielectric materials (x=0.58-0.63, preferably 0.60), and the additive AD is one or two of glass powder GL and ceramic powder CM. The glass powder GL has a composition comprising Ba, sr, ca, B, ti, zr, V and O as various element components. The ceramic powder CM is composed of a powder material containing a plurality of element components in Ba, ca, sr, ti, O. Wherein the mass percentage content m of the additive AD is 0.1-1.2 wt%.
In an alternative embodiment, the ABB material composition is: ba (Zn) 1/3 Ta 2/3 )O 3 The system comprises the following components: baO:59.43 mol% -60.02 mol%, znO:19.99 mol% -20.78 mol%, ta 2 O 5 :19.79 mol% -19.99 mol%, the sum of the three composition mole percentages is 100mol%. Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 The system comprises the following components: baO:59.43 mol% -60.02 mol%, coO:11.99 mol% -12.47 mol%, znO:8.00 mol% -8.31 mol%, nb 2 O 5 :19.79 mol% -19.99 mol%, the sum of the four composition mole percentages is 100mol%.
In an alternative embodiment, the composition of additive AD is as follows: the glass powder GL comprises the following components in percentage by weight: baO:40 weight percent to 45 weight percent, caO:6 wt-10 wt%, srO:1 to wt percent to 3 percent by weight, B 2 O 3 ：25 wt%～30wt%，TiO 2 ：15 wt%～18wt%，ZrO 2 ：1 wt%～2wt%，V 2 O 5 : 2-3 wt% of wt, and the sum of the mass percentages of the components is 100wt%. The ceramic powder CM comprises the following components: baO:51.02 weight percent 65.75 to wt percent, caO: 0wt% -5.33 wt%, srO: 0wt% -4.93 wt% TiO 2 :34.25 The weight percent is up to 38.72 and wt percent, and the sum of the mass percent of the components is 100 percent wt percent.
The invention further aims to provide a preparation method of the single-phase composite perovskite ceramic powder. The preparation process of the single-phase composite perovskite ceramic powder is simple, has strong operability and high batch consistency, and is suitable for stable mass production.
The following exemplifies a method for preparing the single-phase composite perovskite ceramic powder.
Weighing raw materials according to the composition ratio of glass powder GL, carrying out dry mixing, melting into glass liquid in a platinum crucible, and pouring into a sheet rolling machine to prepare glass; filling the prepared glass into a sagger, and carrying out microcrystallization heat treatment in a muffle furnace; the treated glass is put into a ball mill, and is ground into glass powder GL with certain granularity by an aqueous medium ball. Specifically, baCO is used as GL raw material of the glass powder 3 、CaCO 3 、SrCO 3 、H 3 BO 3 、TiO 2 、ZrO 2 And V 2 O 5 . The melting temperature of the glass powder GL can be 1300-1500 ℃, and the melting time can be 2-3 h. The temperature of the microcrystallization heat treatment can be 810-850 ℃, and the time of the microcrystallization heat treatment can be 1-2 h. The ball milling medium is deionized water and zirconia balls, ball milling treatment is carried out until the granularity D of the powder is reached 90 ＜1μm。
Weighing raw materials according to the composition ratio of the ceramic powder CM, performing wet ball milling and mixing in a ball mill, drying, and then calcining in an alumina crucible to synthesize the CM powder. And then ball-milling to a certain granularity by high energy, and drying to prepare the ceramic powder CM. Specifically, the ceramic powder CM adopts BaCO as raw material 3 、CaCO 3 、SrCO 3 Rutile type TiO 2 . Wet ball milling, mixing (for example, deionized water as ball milling medium), stoving, calcining to synthesize, and high-energy ball milling to obtain particle size D 90 And less than or equal to 1um. Finally, the ceramic powder CM is prepared by secondary drying. Wherein the calcining temperature can be 1100-1300 ℃, and the heat preservation time can be 2-4 h.
ZnO and Ta 2 O 5 Weighing the raw materials according to the proportion, performing ball milling and mixing, drying, and calcining in an alumina crucible to synthesize a ZT calcined material; coO, znO and Nb 2 O 5 The raw materials are weighed according to the proportion, ball-milled and mixed, dried and calcined in an alumina crucible to synthesize CZN calcined material. Specifically, the raw materials are preferably used for preparing ZnO and chemically pure Nb by an indirect method 2 O 5 High purity 5N grade Ta 2 O 5 . Wherein the ball milling mixed grinding medium is deionized water and zirconia balls, and the ball milling slurry has the granularity D 50 And < 3um. The calcination temperature of the ZT calcined material can be 1100-1200 ℃, and the heat preservation time can be 4-6 h. The calcination temperature of the CZN calcination material is 900-1100 ℃, and the heat preservation time can be 4-6 h.
BaO powder (or BaCO) 3 Powder), ZT calcined material and AD additive powder are weighed according to the proportion, ball milling and mixing are carried out by a ball mill, and after drying, single-phase BZT ceramic powder is synthesized by calcining in an alumina crucible. Wherein, the calcining synthesis temperature of the single-phase BZT ceramic powder can be 1150-1250 ℃, and the heat preservation time can be 4-6 h.
BaO powder (or BaCO) 3 Powder), CZN calcined material and AD additive powder are weighed according to the proportion, ball milling and mixing are carried out by a ball mill, and the mixture is dried and calcined in an alumina crucible, so as to synthesize single-phase BCZN ceramic powder. Wherein, the calcination temperature of the single-phase BCZN ceramic powder can be 1100-1200 ℃, and the heat preservation time can be 4-6 h.
The glass powder GL is microcrystalline glass with crystallization tendency, and is prepared into nano BaTiO after heat treatment and microcrystallization powder preparation 3 、CaTiO 3 、SrTiO 3 Microcrystallized glass powder of seed crystal. Ceramic powder CM is BaTiO synthesized by solid phase method 3 、CaTiO 3 、SrTiO 3 Ceramic powder composed of crystalline phases. Research shows that the nano crystal phase with trace perovskite structure can induce AB' 1/3 B’’ 2/3 O 3 Formation of composite perovskite ceramic crystal phase by addition of additive powder nanocrystalline phase B-site Ti 4+ Ion into AB' 1/3 B’’ 2/3 O 3 The composite perovskite ceramic lattice reduces the potential barrier formed by crystalline phases and promotes the generation of a single-phase ceramic structure.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) Accurately weighing BaCO with purity more than 99.9 percent 3 364.76g、CaCO 3 126.46g、SrCO 3 20.19g of boric acid H 3 BO 3 339.81 g、TiO 2 127.53 g，ZrO 2 7.09 g，V 2 O 5 14.17g, adding the mixture into a three-dimensional mixer, mixing for 1h, melting the mixture in a platinum crucible at 1450 ℃ for 2h, and forming the gadolinium into glass flakes with the thickness less than 2 mm. The glass flakes were placed in a sagger and incubated in a muffle furnace at 810℃for 2h. Cooling, loading into an alumina ball milling tank, and rapidly ball milling to obtain slurry with particle size D 90 Drying the slurry to obtain glass powder GL with the size of 0.9 mu m;
(2) Accurately weighing BaCO with purity more than 99.9 percent 3 543.03 g、CaCO 3 78.69g、SrCO 3 58.04g、TiO 2 320.24g, adding into a nylon ball mill, taking deionized water and zirconia balls as grinding media, ball milling, mixing, drying, loading into an alumina sagger, placing into a muffle furnace, and calcining at 1300 ℃ for 2.5h. Ball milling the calcined synthetic material in a high-energy ball mill to reach the granularity D 90 0.9 mu m, and drying to obtain ceramic powder CM;
(3) Accurately weighing 324.17g of ZnO with purity more than 99 percent, ta 2 O 5 1675.83g, adding all the weighed raw materials into a nylon ball mill, using deionized water and zirconia balls as grinding media, and ball milling to obtain slurry with the granularity D 50 Drying the materials less than 3 mu m, loading the dried materials into an alumina sagger, and calcining the materials in a muffle furnace at 1200 ℃ for 4 hours to obtain ZT calcined materials;
(4) 1057.31g BaCO was weighed accurately 3 Powder, 940.93g ZT synthetic material, 1.76g ceramic powder CM additive; or weighing 1052.17g BaCO 3 Powder, 936.36g ZT synthetic material, 11.47g glass powder GL. Respectively adding the materials into a nylon ball milling tank, using deionized water and zirconia balls as milling media, and ball milling until the slurry granularity is D 50 Drying to 2.0 μm, loading into sagger, and placing into muffle furnace 1250 deg.CPreserving heat for 4 hours to obtain single-phase Ba (Zn) 1/3 Ta 2/3 )O 3 Ceramic powder (single-phase BZT ceramic powder for short). XRD diffraction data of the ceramic powder is shown in figure 2;
(5) The obtained single-phase Ba (Zn) 1/3 Ta 2/3 )O 3 The ceramic powder is molded by adopting an F6mm die and under the pressure of 1-2 MPa, is heated to 1500 ℃ at 5 ℃/min and is preserved for 4 hours, is cooled to 1000 ℃ at 1 ℃/min and is cooled to room temperature along with a furnace, and a microwave dielectric ceramic material sintering sample is obtained.
Example 2
(1) Accurately weighing BaCO with purity more than 99.9 percent 3 390.80g、CaCO 3 75.62g、SrCO 3 30.18g of boric acid H 3 BO 3 376.30 g、TiO 2 105.92 g，ZrO 2 7.06 g，V 2 O 5 14.12g, adding the mixture into a three-dimensional mixer, mixing for 1h, melting the mixture in a platinum crucible at 1500 ℃ for 2.5h, and forming the GL glass sheet with the thickness less than 2mm by gadolinium. The glass flakes were placed in a sagger and incubated in a muffle furnace at 830℃for 1.5h. Cooling, loading into an alumina ball milling tank, and rapidly ball milling to obtain slurry with particle size D 90 Drying the slurry to obtain glass powder GL with the size of 0.7 mu m;
(2) Accurately weighing BaCO with purity more than 99.9 percent 3 660.05 g、CaCO 3 37.20g 、TiO 2 302.75 And g, adding the mixture into a nylon ball mill, taking deionized water and zirconia balls as grinding media, ball milling, mixing, drying, loading into an alumina sagger, placing into a muffle furnace, and calcining at 1200 ℃ for 4 hours. Ball milling the calcined synthetic material in a high-energy ball mill to reach the granularity D 90 0.9 mu m, and drying to obtain ceramic powder CM;
(3) Accurately weighing 316.37 g of ZnO with purity more than 99 percent, ta 2 O 5 1683.63 g, adding all weighed raw materials into a nylon ball mill, using deionized water and zirconia balls as grinding media, and ball milling to obtain slurry with the granularity D 50 Drying the materials less than 3 mu m, loading the dried materials into an alumina sagger, and calcining the materials in a muffle furnace at 1200 ℃ for 6 hours to obtain ZT calcined materials;
(4) 1056.81g BaCO was weighed accurately 3 Powder, 936.13g ZT synthetic material, 7.06g ceramic powder CM, or 1049.32g BaCO 3 Powder, 929.49g ZT synthetic material, 21.19g glass powder GL. Respectively adding the materials into a nylon ball milling tank, using deionized water and zirconia balls as milling media, and ball milling until the slurry granularity is D 50 Drying to 2.5 μm, loading into sagger, and placing into muffle furnace at 1300 deg.C for 4 hr to obtain single-phase Ba (Zn) 1/3 Ta 2/3 )O 3 Ceramic powder. XRD diffraction data of the ceramic powder is shown in figure 2;
(5) The preparation procedure for sintering samples of microwave dielectric ceramic material is described in example 1.
Example 3
(1) Accurately weighing BaCO with purity more than 99.9 percent 3 416.58g、CaCO 3 102.7g、SrCO 3 10.25g of boric acid H 3 BO 3 319.42 g、TiO 2 115.09 g，ZrO 2 14.39 g，V 2 O 5 21.58g, adding the mixture into a three-dimensional mixer, mixing for 1h, melting the mixture in a platinum crucible at 1500 ℃ for 3h, and forming the GL glass sheet with the thickness less than 2mm by gadolinium. The glass flakes were placed in a sagger and incubated in a muffle furnace at 850℃for 2h. Cooling, loading into an alumina ball milling tank, and rapidly ball milling to obtain slurry with particle size D 90 Drying the slurry to obtain glass powder GL with the size of 0.7 mu m;
(2) Accurately weighing BaCO with purity more than 99.9 percent 3 711.89 g、TiO 2 288.11 And g, adding the mixture into a nylon ball mill, taking deionized water and zirconia balls as grinding media, ball milling, mixing, drying, loading into an alumina sagger, placing into a muffle furnace, and calcining at 1100 ℃ for 4 hours. Ball milling the calcined synthetic material in a high-energy ball mill to reach the granularity D 90 0.9 mu m, and drying to obtain ceramic powder CM;
(3) Accurately weighing 311.13 g of ZnO with purity more than 99 percent, ta 2 O 5 1688.87 Adding all weighed raw materials into a nylon ball mill, using deionized water and zirconia balls as grinding media, ball milling until the slurry granularity D50 is less than 3 mu m, drying, loading into an alumina sagger, and calcining in a muffle furnace at 1200 ℃ for 6 hours to obtain a ZT calcined material;
(4) 1061.17g BaCO was weighed accurately 3 Powder, 937.07g ZT synthetic material, 1.76g ceramic powder CM, or 1050.85g BaCO 3 Powder 927.96g ZTbatch, 21.19g of glass powder GL. Respectively adding into nylon ball milling tank, ball milling with deionized water and zirconia balls as milling medium until the slurry particle size D is 50-2.5 μm, oven drying, loading into sagger, and placing into muffle furnace for heat preservation at 1300 deg.C for 4 hr to obtain single-phase Ba (Zn) 1/3 Ta 2/3 )O 3 Ceramic powder. XRD diffraction data of the ceramic powder is shown in figure 2;
(5) The preparation procedure for sintering samples of microwave dielectric ceramic material is described in example 1.
Example 4
(1) Accurately weighing BaCO with purity more than 99.9 percent 3 364.76g、CaCO 3 126.46g、SrCO 3 20.19g of boric acid H 3 BO 3 339.81 g、TiO 2 127.53 g，ZrO 2 7.09 g，V 2 O 5 14.17g, adding the mixture into a three-dimensional mixer, mixing for 1h, melting the mixture in a platinum crucible at 1300 ℃ for 3h, and forming the GL glass sheet with the thickness of less than 2mm by gadolinium. The glass flakes were placed in a sagger and incubated in a muffle furnace at 810℃for 2h. Cooling, loading into an alumina ball milling tank, and rapidly ball milling to obtain slurry with particle size D 90 Drying the slurry to obtain glass powder GL with the size of 0.9 mu m;
(2) Accurately weighing BaCO with purity more than 99.9 percent 3 711.89 g、TiO 2 288.11 And g, adding the mixture into a nylon ball mill, taking deionized water and zirconia balls as grinding media, ball milling, mixing, drying, loading into an alumina sagger, placing into a muffle furnace, and calcining at 1100 ℃ for 4 hours. Ball milling the calcined synthetic material in a high-energy ball mill to reach the granularity D 90 0.9 mu m, and drying to obtain ceramic powder CM;
(3) Accurately weighing CoO 261.9 g,ZnO 189.69g,Nb with purity more than 99 percent 2 O 5 1548.41 g, adding all weighed raw materials into a nylon ball mill, using deionized water and zirconia balls as grinding media, and ball milling to obtain slurry with the granularity D 50 Drying the materials less than 3 mu m, loading the dried materials into an alumina sagger, and calcining the materials in a muffle furnace at 1100 ℃ for 4 hours to obtain CZN calcined materials;
(4) 1258.17g BaCO was weighed accurately 3 Powder, 728.94g CZN composite material, 12.9g ceramic powder CM, or 1265.24g BaCO 3 Powder, 733.04g CZN composite material, 1.72gg glass powder GL. Respectively adding the materials into a nylon ball milling tank, using deionized water and zirconia balls as milling media, and ball milling until the slurry granularity is D 50 Drying to 2.5 μm, loading into sagger, placing into muffle furnace 1100 deg.C, and maintaining for 6 hr to obtain single-phase Ba (Co) 0.6 Zn 0.4 ) 1/3 Nb 2/3 O 3 Ceramic powder (single-phase BCZN ceramic powder for short). XRD diffraction data of the ceramic powder is shown in figure 2;
(5) The obtained single-phase Ba (Co 0.6 Zn 0.4 ) 1/3 Nb 2/3 O 3 And (3) adopting an F6mm die for ceramic powder, carrying out pressure forming under 1-2 MPa, heating to 1500 ℃ at 5 ℃/min, preserving heat for 8 hours, cooling to 1000 ℃ at 1 ℃/min, and cooling to room temperature along with a furnace to obtain the microwave dielectric ceramic material sintering sample.
Example 5
(1) Accurately weighing BaCO with purity more than 99.9 percent 3 390.80g、CaCO 3 75.62g、SrCO 3 30.18g of boric acid H 3 BO 3 376.30 g、TiO 2 105.92 g，ZrO 2 7.06 g，V 2 O 5 14.12g, adding the mixture into a three-dimensional mixer, mixing for 1h, melting the mixture in a platinum crucible at 1450 ℃ for 2.5h, and forming the GL glass flakes with the thickness less than 2mm by gadolinium. The glass flakes were placed in a sagger and incubated in a muffle furnace at 820℃for 2h. Cooling, loading into an alumina ball milling tank, and rapidly ball milling to obtain slurry with particle size D 90 Drying the slurry to obtain glass powder GL with the size of 0.9 mu m;
(2) Accurately weighing BaCO with purity more than 99.9 percent 3 543.03 g、CaCO 3 78.69g、SrCO 3 58.04g、TiO 2 320.24g, adding into a nylon ball mill, taking deionized water and zirconia balls as grinding media, ball milling, mixing, drying, loading into an alumina sagger, placing into a muffle furnace, and calcining at 1250 ℃ for 3h. Ball milling the calcined synthetic material in a high-energy ball mill to reach the granularity D 90 0.9 mu m, and drying to obtain ceramic powder CM;
(3) Accurately weighing CoO 265.94 g,ZnO 192.61g,Nb with purity more than 99 percent 2 O 5 1541.45 g, adding all weighed raw materials into a nylon ball mill, using deionized water and zirconia balls as grinding media, and ball milling untilSize D of slurry 50 Drying the materials less than 3 mu m, loading the dried materials into an alumina sagger, and calcining the materials in a muffle furnace at 1000 ℃ for 6 hours to obtain CZN calcined materials;
(4) 1251.18g BaCO was weighed accurately 3 Powder, 728.17g CZN composite material, 20.65g ceramic powder CM, or 1260.43g BaCO 3 Powder, 733.55g CZN composite, 6.02g glass powder GL. Respectively adding the materials into a nylon ball milling tank, using deionized water and zirconia balls as milling media, and ball milling until the slurry granularity is D 50 Drying to 2.5 μm, loading into sagger, placing into muffle furnace 1100 deg.C, and maintaining for 6 hr to obtain single-phase Ba (Co) 0.6 Zn 0.4 ) 1/3 Nb 2/3 O 3 Ceramic powder. XRD diffraction data of the ceramic powder is shown in figure 2;
(5) The preparation procedure for sintering samples of microwave dielectric ceramic material is described in example 4.
Example 6
(1) Accurately weighing BaCO with purity more than 99.9 percent 3 416.58g、CaCO 3 102.70g、SrCO 3 10.25g of boric acid H 3 BO 3 319.42g、TiO 2 115.09g，ZrO 2 14.39g，V 2 O 5 21.58g, adding the mixture into a three-dimensional mixer, mixing for 1h, melting in a platinum crucible at 1500 ℃ for 2h, and forming the GL glass sheet with the thickness less than 2mm by gadolinium. The glass flakes were placed in a sagger and incubated in a muffle furnace at 850℃for 1h. Cooling, loading into an alumina ball milling tank, and rapidly ball milling to obtain slurry with particle size D 90 Drying the slurry to obtain glass powder GL with the size of 0.7 mu m;
(2) Accurately weighing BaCO with purity more than 99.9 percent 3 660.05g、CaCO 3 37.2g、TiO 2 302.75g, adding into a nylon ball mill, taking deionized water and zirconia balls as grinding media, ball milling, mixing, drying, loading into an alumina sagger, placing into a muffle furnace, and calcining at 1300 ℃ for 2h. Ball milling the calcined synthetic material in a high-energy ball mill to reach the granularity D 90 0.9 mu m, and drying to obtain ceramic powder CM;
(3) Accurately weighing CoO 271.93g,ZnO 196.95g,Nb with purity more than 99 percent 2 O 5 1531.12g, all the weighed materials are added into a nylon ball mill and are removedBall milling is carried out until slurry granularity D by taking sub-water and zirconia balls as grinding media 50 Drying the materials less than 3 mu m, loading the dried materials into an alumina sagger, and calcining the materials in a muffle furnace at 900 ℃ for 6 hours to obtain CZN calcined materials;
(4) 1260.02g BaCO was weighed accurately 3 Powder, 738.26g CZN composite material, 1.72g ceramic powder CM, or 1248.08g BaCO 3 Powder, 731.26g CZN composite, 20.66g glass powder GL. Respectively adding the materials into a nylon ball milling tank, using deionized water and zirconia balls as milling media, and ball milling until the slurry granularity is D 50 Drying to 2.5 μm, loading into sagger, and holding at 1200deg.C for 4 hr to obtain single-phase Ba (Co) 0.6 Zn 0.4 ) 1/3 Nb 2/3 O 3 Ceramic powder. XRD diffraction data of the ceramic powder is shown in figure 2;
(5) The preparation procedure for sintering samples of microwave dielectric ceramic material is described in example 4.
Example 7
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this example 7 is described in example 2, and the only difference is that: the addition amount of the GL glass powder additive is 0.1 weight percent.
Example 8
In this example 8, the preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material is described in example 2, and the difference is only that: the addition amount of the GL glass powder additive is 0.5 weight percent.
Example 9
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this example 9 is described in example 2, and the only difference is that: the addition amount of the GL glass powder additive is 1.0 weight percent.
Example 10
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this embodiment 10 is described in embodiment 1, and the difference is only that: the addition amount of the ceramic powder CM additive was 0.5wt%.
Example 11
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this example 11 is described in example 1, and the only difference is that: the addition amount of the ceramic powder CM additive was 0.9wt%.
Example 12
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this example 12 is described in example 1, and the only difference is that: the addition amount of the ceramic powder CM additive was 1.2wt%.
Example 13
The preparation process of the single-phase BCZN ceramic powder and the microwave dielectric ceramic material in this example 13 is described in example 4, and the difference is only that: the addition amount of the ceramic powder CM additive was 0.1wt%.
Example 14
The preparation process of the single-phase BCZN ceramic powder and the microwave dielectric ceramic material in this example 14 is described in example 4, and the difference is only that: the addition amount of the ceramic powder CM additive was 1.2wt%.
Comparative example 1
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this comparative example 1 is described in example 2, and the only difference is that: the addition amount of the ceramic powder CM or the glass powder GL additive is 0wt%.
Comparative example 2
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this comparative example 2 is described in example 2, and the only difference is that: the addition amount of the glass powder GL additive was 1.5wt%.
Comparative example 3
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this comparative example 3 is described in example 2, and the only difference is that: the addition amount of the ceramic powder CM additive was 1.5wt%.
Comparative example 4
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this comparative example 4 is described in example 2, and the only difference is that: the composition of the glass powder GL is BaO:55wt%, caO:6wt%, srO:3wt%, B 2 O 3 ：20wt%、TiO 2 ：15wt%、ZrO 2 :1wt%; the addition amount of the glass powder GL additive was 0.5wt%.
Comparative example 5
Single-phase BZT ceramic powder and microwave dielectric ceramic material in comparative example 5The preparation of the batch is described in example 2, with the only difference that: the composition of the glass powder GL is BaO:44wt%, caO:6wt%, srO:3wt%, B 2 O 3 ：30wt%、TiO 2 ：15wt%、V 2 O 5 :2wt%; the addition amount of the glass powder GL additive was 0.5wt%.
Comparative example 6
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this comparative example 6 is described in example 2, and the only difference is that: the composition of the glass powder GL is BaO:58wt%, caO:6wt%, srO:3wt%, B 2 O 3 ：30wt%、ZrO 2 ：1wt%、V 2 O 5 :2wt%; the addition amount of the glass powder GL additive was 0.5wt%.
Comparative example 7
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this comparative example 7 is described in example 2, and the only difference is that: the glass powder GL comprises the following components: 46wt%, caO:6wt%, B 2 O 3 ：30wt%、TiO 2 ：15wt%、ZrO 2 ：1wt%、V 2 O 5 :2wt%; the amount of glass powder GL added was 1.0% by weight.
Comparative example 8
The preparation process of the single-phase BZT ceramic powder and the microwave dielectric ceramic material in this comparative example 8 is described in example 2, and the only difference is that: the composition of the glass powder GL is BaO:49wt%, srO:3wt%, B 2 O 3 ：30wt%、TiO 2 ：15wt%、ZrO 2 ：1wt%、V 2 O 5 :2wt%; the addition amount of the glass powder GL additive was 1.0wt%.
Comparative example 9
The preparation process of the single-phase BCZN ceramic powder and the microwave dielectric ceramic material in this comparative example 9 is described in example 4, and the only difference is that: the addition amount of the glass powder GL or the ceramic powder CM additive was 0g.
Table 1 shows the composition of the glass powder GL used in the present invention:
。
table 2 shows typical performance parameters of the single-phase composite perovskite ceramic powder and the fired microwave dielectric ceramic material samples:
。
table 3 is typical performance yield statistics for samples of microwave dielectric ceramic materials prepared in some examples (10 batches per sinter, constant sintering parameters per batch, 1000 samples per batch):
。
in the invention, a TE01 delta mode based on a Hakki-Coleman method is adopted to test Ba (Zn) by a network analyzer Agilent E8362B 1/3 Ta 2/3 )O 3 Performance parameters of microwave dielectric ceramic material: obtained Ba (Zn) 1/3 Ta 2/3 )O 3 The dielectric constant of the microwave dielectric ceramic material is 29.0-31.0; obtained Ba (Zn) 1/3 Ta 2/3 )O 3 The Q multiplied by f value of the microwave dielectric ceramic material is 150500 ～ 170000GHz (the testing frequency ranges from 6GHz to 15 GHz).
In the invention, a TE01 delta mode based on a Hakki-Coleman method is adopted to test Ba (Co) by a network analyzer Agilent E8362B x Zn 1-x ) 1/3 Nb 2/3 O 3 Performance parameters of microwave dielectric ceramic material: obtained Ba (Co) x Zn 1-x ) 1/3 Nb 2/ 3 O 3 The dielectric constant of the microwave dielectric ceramic material is 34.0-36.0; obtained Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 The Q multiplied by f value of the microwave dielectric ceramic material is 82000-88000 GHz (the testing frequency range is 6-15 GHz).
In the invention, the yield of the obtained microwave dielectric ceramic material is more than or equal to 95 percent.
FIG. 1 shows XRD patterns of the glass powder GL of example 1, the ceramic powder CM of example 1 and the glass powder GL of example 7, from which it can be seen that the additives used in the present invention all contain perovskiteBaTiO of structure 3 A crystalline phase in AB' 1/ 3 B’’ 2/3 O 3 The composite perovskite single phase plays a role in inhibiting the formation of mixed phases and promoting the formation of material single phases.
FIGS. 2 to 4 are XRD patterns of the single-phase composite perovskite ceramic powders prepared in examples 1 to 14 and the perovskite ceramic powders prepared in comparative examples 1 to 8, and it is understood from the figures that the ceramic powders prepared by introducing the additive according to the present invention have a significant single-phase property, and that there is a significant impurity phase in the ceramic powders prepared without adding or excessively adding. Because the heterogeneous dielectric loss performance is extremely poor, the quality factor of the material can be seriously reduced, and the material performance is influenced.
In conclusion, the introduction of the additive plays a remarkable role in improving the performance of the fired ceramic sample, and the yield and stability of batches are also greatly improved.

Claims (12)

1. The single-phase composite perovskite ceramic powder is characterized by comprising (100-m) ABB main phase-m additive AD, wherein the additive AD is in solid solution in the ABB main phase;
wherein the ABB main phase is Ba (Zn) 1/3 Ta 2/3 )O 3 Or Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 ，x=0.58～0.63；
The additive AD is at least one of glass powder GL and ceramic powder CM, and m=0.05wt% -1.3wt%;
the glass powder GL is a glass powder containing Ba, sr, ca, B, ti, zr, V and O element components, and comprises the following components: baO:40 wt% -45-wt%, caO:6wt% -10 wt%, srO: 1wt% -3 wt%, B 2 O 3 ：25 wt%～30 wt%，TiO 2 ：15 wt%～18 wt%，ZrO 2 ：0.5 wt%～2wt%，V 2 O 5 :1 to wt weight percent to 3 weight percent, and the sum of the mass percentages of the components is 100 weight percent;
the ceramic powder CM is a ceramic powder containing at least three element components of Ba, ca, sr, ti, O, and the composition thereof comprises: baO:51.02wt%～65.75 wt%，CaO：0 wt%～5.33 wt%，SrO：0 wt%～4.93 wt%，TiO 2 :34.25 weight percent to 38.72 and wt percent, and the sum of the mass percentages of the components is 100 weight percent;
particle size D of the glass powder GL 90 Less than 1 μm; the preparation method of the glass powder GL comprises the following steps: weighing BaCO according to the composition proportion of the glass powder GL 3 、CaCO 3 、SrCO 3 、H 3 BO 3 、TiO 2 、ZrO 2 And V 2 O 5 Raw materials are mixed, molten into glass liquid, and then poured into a sheet rolling machine to prepare glass; filling the obtained glass into a sagger, and carrying out microcrystallization heat treatment in a muffle furnace; ball milling is carried out on the glass subjected to the microcrystallization heat treatment to obtain glass powder GL; the melting temperature is 1300-1500 ℃, and the melting time is 2-3 hours; the temperature of the microcrystallization heat treatment is 810-850 ℃, and the microcrystallization heat treatment time is 1-2 hours;
particle size D of the ceramic powder CM 90 Less than or equal to 1 mu m; the preparation method of the ceramic powder CM comprises the following steps: weighing BaCO according to the composition proportion of the ceramic powder CM 3 、CaCO 3 、SrCO 3 Rutile type TiO 2 Mixing the raw materials, calcining, and performing high-energy ball milling to obtain the ceramic powder CM; the calcining temperature is 1100-1300 ℃, and the heat preservation time is 2-4 h.
2. The single-phase composite perovskite ceramic powder according to claim 1, wherein the Ba (Zn 1/3 Ta 2/3 )O 3 BaO, znO and Ta in 2 O 5 The molar ratio of (59.43-60.02): (19.99-20.78): (19.79 to 19.99);
said Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 BaO, coO, znO and Nb in (V) 2 O 5 The molar ratio of (59.43-60.02): (11.99-12.47): (8.00-8.31): (19.79-19.99).
3. The single-phase composite perovskite ceramic powder according to claim 1 or 2, wherein m = 0.1wt% to 1.2wt%.
4. A method for preparing the single-phase composite perovskite ceramic powder according to any one of claims 1 to 3, comprising the steps of:
(1) ZnO powder and Ta 2 O 5 Mixing the powder, calcining, and synthesizing ZT calcined material;
(2) CoO powder, znO powder and Nb 2 O 5 Mixing the powder, and calcining to synthesize a CZN calcined material;
(3) Mixing ZT calcined material, ba source and additive AD, and then secondary calcining to obtain single-phase Ba (Zn) 1/3 Ta 2/3 )O 3 Ceramic powder; or mixing CZN calcined material, ba source and additive AD, and then performing secondary calcination to obtain single-phase Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 Ceramic powder; particle size D of the glass powder GL 90 Less than 1 μm; the preparation method of the glass powder GL comprises the following steps: weighing BaCO according to the composition proportion of the glass powder GL 3 、CaCO 3 、SrCO 3 、H 3 BO 3 、TiO 2 、ZrO 2 And V 2 O 5 Raw materials are mixed, molten into glass liquid, and then poured into a sheet rolling machine to prepare glass; filling the obtained glass into a sagger, and carrying out microcrystallization heat treatment in a muffle furnace; ball milling is carried out on the glass subjected to the microcrystallization heat treatment to obtain glass powder GL; the melting temperature is 1300-1500 ℃, and the melting time is 2-3 hours; the temperature of the microcrystallization heat treatment is 810-850 ℃, and the microcrystallization heat treatment time is 1-2 hours; particle size D of the ceramic powder CM 90 Less than or equal to 1 mu m; the preparation method of the ceramic powder CM comprises the following steps: weighing BaCO according to the composition proportion of the ceramic powder CM 3 、CaCO 3 、SrCO 3 Rutile type TiO 2 Mixing the raw materials, calcining, and performing high-energy ball milling to obtain the ceramic powder CM; the calcining temperature is 1100-1300 ℃, and the heat preservation time is 2-4 h.
5. The single-phase composite perovskite according to claim 4The preparation method of the mineral ceramic powder is characterized in that in the step (1), the purity of the ZnO powder is more than or equal to 99.5 percent, and the purity of the Ta is more than or equal to 2 O 5 The purity of the powder is more than or equal to 5N; the mixing mode is ball milling mixing, and the parameters of the ball milling mixing comprise: the ball milling medium is deionized water, the ball milling balls are zirconia balls, and the granularity D of the obtained ball milling slurry 50 < 3 μm; the calcination temperature of the ZT calcined material is 1100-1200 ℃, and the heat preservation time is 4-6 hours.
6. The method for producing a single-phase composite perovskite ceramic powder according to claim 4, wherein in the step (2), the purity of the CoO powder is not less than 99%, and the purity of the Nb is not less than 2 O 5 The purity of the powder is more than or equal to 99 percent; the mixing mode is ball milling mixing, and the parameters of the ball milling mixing comprise: the ball milling medium is deionized water, the ball milling balls are zirconia balls, and the granularity D of the obtained ball milling slurry 50 < 3 μm; the calcination temperature of the CZN calcination material is 900-1100 ℃, and the heat preservation time is 4-6 hours.
7. The method for preparing single-phase composite perovskite ceramic powder according to claim 4, wherein in the step (3), the parameters of the ball milling process include: the ball milling medium is deionized water, and the ball milling balls are zirconia balls.
8. The method for producing a single-phase composite perovskite ceramic powder according to any one of claims 4 to 7, wherein in the step (3), the Ba source is one of BaO powder or barium carbonate powder;
the single phase Ba (Zn) 1/3 Ta 2/3 )O 3 The secondary calcination temperature of the ceramic powder is 1150-1250 ℃ and the time is 4-6 hours;
said single phase Ba (Co) x Zn 1-x ) 1/3 Nb 2/3 O 3 The secondary calcination temperature of the ceramic powder is 1100-1200 ℃ and the time is 4-6 hours.
9. The preparation method of the microwave dielectric ceramic material is characterized by comprising the following steps of: preparing a green body from the single-phase composite perovskite ceramic powder according to any one of claims 1-3, and sintering to obtain the microwave dielectric ceramic material.
10. The method of preparing a microwave dielectric ceramic material according to claim 9, wherein the sintering temperature is 1480-1520 ℃; the sintering time is 4-8 hours.
11. The method for preparing a microwave dielectric ceramic material according to claim 9 or 10, wherein the temperature rising rate of sintering is 3-6 ℃/min; the cooling rate of the sintering is 1-2 ℃/min.
12. A microwave dielectric ceramic material characterized by being prepared by the method for preparing the microwave dielectric ceramic material according to any one of claims 9 to 11.
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US2705204A (en) * 1953-02-17 1955-03-29 British Dielectric Res Ltd Ceramic dielectric materials
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CN1518019A (en) * 2003-01-24 2004-08-04 株式会社村田制作所 Dielectric ceramic, method for manufacturing the dielectric ceramic, and monolithic ceramic capacitor
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