CN115304367A - Preparation method and product of microwave dielectric ceramic - Google Patents
Preparation method and product of microwave dielectric ceramic Download PDFInfo
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- CN115304367A CN115304367A CN202210856172.3A CN202210856172A CN115304367A CN 115304367 A CN115304367 A CN 115304367A CN 202210856172 A CN202210856172 A CN 202210856172A CN 115304367 A CN115304367 A CN 115304367A
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Abstract
The invention belongs to the technical field of microwave dielectric ceramics, and particularly relates to a preparation method and a product of microwave dielectric ceramics. The preparation method comprises the following steps: (1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 2 The powder is taken as a raw material; (2) According to the structural formula (Mg) （1‑a‑b） La a Nd b ）（Ti 1‑x‑ y Nb x Ta y ）O 3 Wherein a is 0.001 to 0.01, b is 0.001 to 0.01; x is 0.02 to 0.03; y is 0.02 to 0.03, weighing raw materials, performing wet ball milling with absolute ethyl alcohol as a ball milling medium, and performing ball milling; (3) drying and pre-calcining the ball-milled powder; (4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; (5) Drying the powder after the secondary ball milling, adding the powder into a ceramic mortar, and adding 5wt% of PVAAnd uniformly mixing the solution, granulating, pressing under 30 to 60MPa to form an embryo, discharging the gel from the embryo, sintering at 1270 to 1330 ℃ for 3 to 6 hours, and naturally cooling to room temperature to obtain the microwave dielectric ceramic. A dielectric constant of the microwave dielectric ceramic of 603 r 18.72 to 19.95, and a quality factor Qxf of 2.12 × 10 5 ~2.25×10 5 GHz with temperature coefficient τ f The concentration is-49.1 to-43.3 ppm/DEG C.
Description
Technical Field
The present invention belongs to the field of microwave dielectric ceramic technology. And more particularly, to a method of preparing a microwave dielectric ceramic and a product.
Background
In recent years, with the rapid development of wireless communication systems, microwave dielectric ceramics are receiving more and more attention of researchers as a material widely used in the fields of satellite communication, intelligent systems, internet of things and the like. The rapid development of 5G communication technology also makes higher requirements on the performance of microwave dielectric ceramics. High quality factor (Qf) can reduce signal loss, improve signal selectivity, and have a large dielectric constant (εr) can realize miniaturization of the device and near-zero temperature coefficient of resonance frequency (cτ f ) Stability of the frequency with temperature variation can be ensured. Thus having a high Qf, is suitableε r And near zeroτ f Microwave dielectric ceramics have become a research hotspot in the field of electronic information materials.
MgTiO 3 The ceramic has good microwave dielectric properties (Qf =160000GHz,ε r =17，τ f =-5.0×10 -5 ℃ -1 ) And the cost of raw materials is low, which makes the microwave dielectric material widely attract attention in the field of microwave dielectric materials. MgTiO reduction by addition of low melting point materials 3 The sintering temperature of the ceramic is an effective mode, and low-melting-point substances are easy to form a liquid phase in the sintering process, so that the densification and sintering of the ceramic can be promoted.
CN111763083A discloses a low-temperature sintered microwave dielectric ceramic, a preparation method and an application thereof, wherein the method comprises the following steps: mixing the main crystal phase material and the doping material, adding water, ball-milling, drying to prepare premixed powder, mixing the premixed powder with a binder and acetic acid, pouring the premixed powder into a heatable mould, and carrying out temperature programming and sintering under the pressurization condition to prepare the material; controlling the pressure under the pressurizing condition to be 300-400MPa, and carrying out temperature programming to comprise the following stages: heating from room temperature to 150-250 deg.c at certain speed and maintaining; then heating to 450-500 ℃, and preserving heat; the microwave dielectric ceramic prepared by the method and the application thereof in preparing microwave communication devices; the method can prepare the microwave dielectric ceramic material at extremely low sintering temperature, greatly reduces the production cost and difficulty, and ensures that the prepared material has excellent Qf value, proper dielectric constant and near-zero temperature coefficient of resonance frequency, thereby meeting the application under microwave condition.
CN111763083B discloses a low-temperature sintered microwave dielectric ceramic, a preparation method and an application thereof, wherein the method comprises the following steps: mixing the main crystal phase material and the doping material, adding water, ball-milling, drying to prepare premixed powder, mixing the premixed powder with a binder and acetic acid, pouring the premixed powder into a heatable mould, and carrying out temperature programming and sintering under the pressurization condition to prepare the material; controlling the pressure under the pressurizing condition to be 300-400MPa, and carrying out temperature programming to comprise the following stages: heating from room temperature to 150-250 deg.c at certain speed and maintaining; then heating to 450-500 ℃, and preserving heat; the microwave dielectric ceramic prepared by the method and the application thereof in preparing microwave communication devices; the method can prepare the microwave dielectric ceramic material at extremely low sintering temperature, greatly reduces the production cost and the difficulty, and ensures that the prepared material has excellent Q' f value, proper dielectric constant and near-zero temperature coefficient of resonance frequency, thereby meeting the application under the microwave condition.
TWI334147B discloses a process for producing MgTiO by mixing, baking, grinding, direct compression molding and sintering various starting powders without calcination 3 、MgTiO 3 -CaTiO 3 And MgTiO 3 -SrTiO 3 A method for producing a microwave dielectric ceramic body. Manufacture of MgTiO 3 Using Mg (OH) 2 With TiO 2 Preparing MgTiO from raw material powder 3 -CaTiO 3 Using Mg (OH) 2 ，TiO 2 With CaCO 3 Raw material powder, mgTiO production 3 -SrTiO 3 Using Mg (OH) 2 ，TiO 2 With SrCO 3 Is raw material powder. Since the manufacturing method of the present invention directly molds and sinters the mixed raw material powder without sintering, it is a simpler and time-saving manufacturing method compared with the conventional solid state reaction powder manufacturing method.
However, the prior art has been on MgTiO 3 The modification of the dielectric ceramic can improve the dielectric constant and the quality factor, but the temperature coefficient cannot be guaranteed, so that the development of a new microwave dielectric ceramic for improving the dielectric ceramic under the premise of guaranteeing the temperature coefficient is urgently neededDielectric constant and quality factor of the porcelain.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method and a product of microwave dielectric ceramic. The preparation method comprises the following steps: (1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 The powder is taken as a raw material; (2) According to the structural formula (Mg) （1-a-b） La a Nd b ）（Ti 1-x- y Nb x Ta y ）O 3 Wherein a is 0.001 to 0.01, b is 0.001 to 0.01; x is 0.02 to 0.03; y is 0.02 to 0.03, weighing the raw materials, and performing wet ball milling by using absolute ethyl alcohol as a ball milling medium; (3) drying and pre-calcining the ball-milled powder; (4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; (5) And drying the powder subjected to secondary ball milling, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, uniformly mixing, granulating, pressing into a blank under the pressure of 30-60MPa, discharging the glue from the blank, sintering at the temperature of 1270-1330 ℃ for 3-6h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic. A dielectric constant of the microwave dielectric ceramic of 603 r 18.72 to 19.95, and a quality factor Qxf of 2.12 × 10 5 ~2.25×10 5 GHz, temperature coefficient of τ f The temperature is-49.1 to-43.3 ppm/DEG C.
The invention aims to provide a preparation method of microwave dielectric ceramic.
It is another object of the present invention to provide a microwave dielectric ceramic.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a microwave dielectric ceramic comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 The powder is used as a raw material;
(2) According to the structural formula (Mg) （1-a-b） La a Nd b ）（Ti 1-x-y Nb x Ta y ）O 3 Wherein a is 0.001 to 0.01, b is 0.001 to 0.01; x is 0.02 to 0.03; y is 0.02 to 0.03, weighing raw materials, performing wet ball milling with absolute ethyl alcohol as a ball milling medium, and performing ball milling;
(3) Drying and pre-calcining the ball-milled powder;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling;
(5) And drying the powder subjected to secondary ball milling, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, uniformly mixing, granulating, pressing into a blank under the pressure of 30-60MPa, discharging the glue from the blank, sintering at the temperature of 1270-1330 ℃ for 3-6h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Preferably, in the step (1), the raw materials are dried for 14 to 24 hours at 120 to 140 ℃ before being prepared.
Preferably, in the step (2), the ball milling time is 15 to 25h, and the rotating speed is 300 to 400 r/min.
Preferably, in the step (3), the drying temperature is 90 to 120 ℃, and the drying time is 6 to 10 hours.
Preferably, in the step (3), the precalcination is performed under the condition of being performed for 3 to 6h at 950 to 1050 ℃, and the heating rate is 1 to 3 ℃/min.
Preferably, in the step (4), the ball milling time is 8 to 12h, and the rotating speed is 300 to 400 r/min.
Preferably, in the step (5), the drying temperature is 110 to 130 ℃, and the mixing time is 30 to 50min.
Preferably, in the step (5), the rubber discharging is carried out at 400 to 500 ℃ for 3 to 5 hours.
Preferably, in the step (5), the blank is subjected to glue discharging at 400 to 500 ℃ for 3 to 5h, then is sintered at 1270 to 1330 ℃ for 3 to 6h, specifically, the temperature is increased from room temperature to 400 to 500 ℃ at 1 to 3 ℃/min, glue discharging is carried out for 3 to 5h, and then the temperature is increased to 1270 to 1330 ℃ at 4 to 7 ℃/min, and then is sintered for 3 to 6h.
Preparation method of microwave dielectric ceramic based on aboveThe microwave dielectric ceramic of (2), characterized in that: a dielectric constant of the microwave dielectric ceramic of 603 r 18.72 to 19.95, and a quality factor Qxf of 2.12 × 10 5 ~2.25×10 5 GHz, temperature coefficient of τ f The temperature is-49.1 to-43.3 ppm/DEG C.
The invention has the following beneficial effects:
(1) The dielectric constant and quality factors are obviously improved on the premise of improving the temperature coefficient of the microwave dielectric ceramic by modifying the metal elements, and the applicant finds that the modified metal elements have a mutual synergistic effect; the performance of the microwave dielectric ceramic is significantly improved by the mutual cooperation of the components.
(2) The invention adopts the traditional process for preparation, has simple preparation process and low preparation cost, and is beneficial to industrial production.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 The powder is taken as a raw material; drying the raw materials at 130 ℃ for 20h before proportioning;
(2) According to the structural formula (Mg) 0.99 La 0.005 Nd 0.005 ）（Ti 0.95 Nb 0.025 Ta 0.025 ）O 3 Weighing raw materials, and performing ball milling by a wet method, wherein a ball milling medium is absolute ethyl alcohol; the ball milling time is 20h, and the rotating speed is 350 r/min;
(3) Drying the ball-milled powder at 110 ℃ for 8h, and then heating to 1000 ℃ at the speed of 2 ℃/min to pre-calcine for 5h;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; the ball milling time is 10h, and the rotating speed is 350 r/min.
(5) And drying the powder subjected to secondary ball milling at 120 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 40min, uniformly mixing, granulating, pressing under 45MPa to obtain a blank, heating the blank to 450 ℃ at the speed of 2 ℃/min, discharging glue for 4h, heating to 1300 ℃ at the speed of 6 ℃/min, sintering for 4.5h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Example 2
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 2 The powder is used as a raw material; drying the raw materials for 14-24 h at 120-140 ℃ before proportioning;
(2) According to the structural formula (Mg) 0.989 La 0.001 Nd 0.01 ）（Ti 0.95 Nb 0.03 Ta 0.02 ）O 3 Weighing raw materials, and performing ball milling by a wet method, wherein a ball milling medium is absolute ethyl alcohol; the ball milling time is 25h, and the rotating speed is 300 r/min;
(3) Drying the ball-milled powder at 120 ℃ for 6h, and then heating to 1050 ℃ at 3 ℃/min for precalcination for 3h;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; the ball milling time is 12h, and the rotating speed is 300 r/min.
(5) And drying the powder subjected to secondary ball milling at 130 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 30min, uniformly mixing, granulating, pressing into a blank under 60MPa, heating the blank to 500 ℃ at 3 ℃, discharging glue for 3h, heating to 1330 ℃ at 7 ℃/min, sintering for 3h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Example 3
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 The powder is used as a raw material; drying the raw materials at 120 deg.C for 24 hr before compounding;
(2) According to the structural formula (Mg) 0.989 La 0.01 Nd 0.001 ）（Ti 0.95 Nb 0.03 Ta 0.02 ）O 3 Weighing raw materials, ball-milling by a wet method, wherein a ball-milling medium is absolute ethyl alcohol, and ball-milling; the ball milling time is 15h, and the rotating speed is 400 r/min;
(3) Drying the ball-milled powder at 90 ℃ for 10h, and then heating to 950 ℃ at 1 ℃/min for pre-calcining for 6h;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; the ball milling time is 8h, and the rotating speed is 400 r/min.
(5) And drying the powder subjected to secondary ball milling at 110 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 50min, uniformly mixing, granulating, pressing under 30MPa to obtain a blank, heating the blank to 400 ℃ at 1 ℃/min, discharging for 5h, sintering at 1270 ℃ at 4 ℃/min for 6h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Comparative example 1
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 The powder is taken as a raw material; drying the raw materials at 130 ℃ for 20h before proportioning;
(2) According to the structural formula (Mg) 0.99 La 0.01 ）（Ti 0.95 Nb 0.025 Ta 0.025 ）O 3 Weighing raw materials, and performing ball milling by a wet method, wherein a ball milling medium is absolute ethyl alcohol; the ball milling time is 20h, and the rotating speed is 350 r/min;
(3) Drying the ball-milled powder at 110 ℃ for 8h, and then heating to 1000 ℃ at the speed of 2 ℃/min to pre-calcine for 5h;
(4) Putting the presintered powder into an agate mortar, and performing secondary ball milling; the ball milling time is 10h, and the rotating speed is 350 r/min.
(5) And drying the powder subjected to secondary ball milling at 120 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 40min, uniformly mixing, granulating, pressing under 45MPa to obtain a blank, heating the blank to 450 ℃ at the speed of 2 ℃/min, discharging glue for 4h, heating to 1300 ℃ at the speed of 6 ℃/min, sintering for 4.5h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Comparative example 2
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、Nd 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 2 The powder is taken as a raw material; drying the raw materials at 130 ℃ for 20h before proportioning;
(2) According to the structural formula (Mg) 0.99 Nd 0.01 ）（Ti 0.95 Nb 0.025 Ta 0.025 ）O 3 Weighing raw materials, ball-milling by a wet method, wherein a ball-milling medium is absolute ethyl alcohol, and ball-milling; the ball milling time is 20h, and the rotating speed is 350 r/min;
(3) Drying the ball-milled powder at 110 ℃ for 8h, and then heating to 1000 ℃ at the speed of 2 ℃/min to pre-calcine for 5h;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; the ball milling time is 10h, and the rotating speed is 350 r/min.
(5) And drying the powder subjected to secondary ball milling at 120 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 40min, uniformly mixing, granulating, pressing under 45MPa to obtain a blank, heating the blank to 450 ℃ at the speed of 2 ℃/min, discharging glue for 4h, heating to 1300 ℃ at the speed of 6 ℃/min, sintering for 4.5h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Comparative example 3
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Ta 2 O 5 And TiO 2 The powder is used as a raw material; drying the raw materials at 130 ℃ for 20h before proportioning;
(2) According to the structural formula (Mg) 0.99 La 0.005 Nd 0.005 ）（Ti 0.95 Ta 0.05 ）O 3 Weighing raw materials, ball-milling by a wet method, wherein a ball-milling medium is absolute ethyl alcohol, and ball-milling; the ball milling time is 20h, and the rotating speed is 350 r/min;
(3) Drying the ball-milled powder at 110 ℃ for 8h, and then heating to 1000 ℃ at the speed of 2 ℃/min to pre-calcine for 5h;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; the ball milling time is 10h, and the rotating speed is 350 r/min.
(5) And drying the powder subjected to secondary ball milling at 120 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 40min, uniformly mixing, granulating, pressing under 45MPa to obtain a blank, heating the blank to 450 ℃ at the speed of 2 ℃/min, discharging glue for 4h, heating to 1300 ℃ at the speed of 6 ℃/min, sintering for 4.5h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Comparative example 4
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Nb 2 O 5 And TiO 2 The powder is taken as a raw material; drying the raw materials at 130 ℃ for 20h before proportioning;
(2) According to the structural formula (Mg) 0.99 La 0.005 Nd 0.005 ）（Ti 0.95 Nb 0.05 ）O 3 Weighing raw materials, and performing ball milling by a wet method, wherein a ball milling medium is absolute ethyl alcohol; the ball milling time is 20h, and the rotating speed is 350 r/min;
(3) Drying the ball-milled powder at 110 ℃ for 8h, and then heating to 1000 ℃ at the speed of 2 ℃/min to pre-calcine for 5h;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; the ball milling time is 10h, and the rotating speed is 350 r/min.
(5) And drying the powder subjected to secondary ball milling at 120 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 40min, uniformly mixing, granulating, pressing under 45MPa to obtain a blank, heating the blank to 450 ℃ at the speed of 2 ℃/min for glue discharging for 4h, heating to 1300 ℃ at the speed of 6 ℃/min for sintering for 4.5h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Comparative example 5
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Ta 2 O 5 And TiO 2 2 The powder is used as a raw material; drying the raw materials at 130 ℃ for 20h before proportioning;
(2) According to the structural formula (Mg) 0.965 La 0.03 Nd 0.005 ）（Ti 0.975 Ta 0.025 ）O 3 Weighing raw materials, and performing ball milling by a wet method, wherein a ball milling medium is absolute ethyl alcohol; the ball milling time is 20h, and the rotating speed is 350 r/min;
(3) Drying the ball-milled powder at 110 ℃ for 8h, and then heating to 1000 ℃ at the speed of 2 ℃/min to pre-calcine for 5h;
(4) Putting the presintered powder into an agate mortar, and performing secondary ball milling; the ball milling time is 10h, and the rotating speed is 350 r/min.
(5) And drying the powder subjected to secondary ball milling at 120 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 40min, uniformly mixing, granulating, pressing under 45MPa to obtain a blank, heating the blank to 450 ℃ at the speed of 2 ℃/min, discharging glue for 4h, heating to 1300 ℃ at the speed of 6 ℃/min, sintering for 4.5h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Comparative example 6
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、Nd 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 2 The powder is used as a raw material; drying the raw materials at 130 ℃ for 20h before proportioning;
(2) According to the structural formula (Mg) 0.995 Nd 0.005 ）（Ti 0.945 Nb 0.03 Ta 0.025 ）O 3 Weighing raw materials, and performing ball milling by a wet method, wherein a ball milling medium is absolute ethyl alcohol; the ball milling time is 20h, and the rotating speed is 350 r/min;
(3) Drying the ball-milled powder at 110 ℃ for 8h, and then heating to 1000 ℃ at the speed of 2 ℃/min to pre-calcine for 5h;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; the ball milling time is 10h, and the rotating speed is 350 r/min.
(5) And drying the powder subjected to secondary ball milling at 120 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 40min, uniformly mixing, granulating, pressing under 45MPa to obtain a blank, heating the blank to 450 ℃ at the speed of 2 ℃/min for glue discharging for 4h, heating to 1300 ℃ at the speed of 6 ℃/min for sintering for 4.5h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Comparative example 7
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Nb 2 O 5 And TiO 2 The powder is used as a raw material; drying the raw materials at 130 ℃ for 20h before proportioning;
(2) According to the structural formula (Mg) 0.965 La 0.005 Nd 0.03 ）（Ti 0.975 Nb 0.025 ）O 3 Weighing raw materials, and performing ball milling by a wet method, wherein a ball milling medium is absolute ethyl alcohol; the ball milling time is 20h, and the rotating speed is 350 r/min;
(3) Drying the ball-milled powder at 110 ℃ for 8h, and then heating to 1000 ℃ at the speed of 2 ℃/min to pre-calcine for 5h;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; the ball milling time is 10h, and the rotating speed is 350 r/min.
(5) And drying the powder subjected to secondary ball milling at 120 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 40min, uniformly mixing, granulating, pressing under 45MPa to obtain a blank, heating the blank to 450 ℃ at the speed of 2 ℃/min, discharging glue for 4h, heating to 1300 ℃ at the speed of 6 ℃/min, sintering for 4.5h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Comparative example 8
A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 The powder is taken as a raw material; drying the raw materials at 130 ℃ for 20h before proportioning;
(2) According to the structural formula (Mg) 0.995 La 0.005 ）（Ti 0.945 Nb 0.025 Ta 0.03 ）O 3 Weighing raw materials, and performing ball milling by a wet method, wherein a ball milling medium is absolute ethyl alcohol; the ball milling time is 20h, and the rotating speed is 350 r/min;
(3) Drying the ball-milled powder at 110 ℃ for 8h, and then heating to 1000 ℃ at the speed of 2 ℃/min to pre-calcine for 5h;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling; the ball milling time is 10h, and the rotating speed is 350 r/min.
(5) And drying the powder subjected to secondary ball milling at 120 ℃, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, mixing for 40min, uniformly mixing, granulating, pressing under 45MPa to obtain a blank, heating the blank to 450 ℃ at the speed of 2 ℃/min for glue discharging for 4h, heating to 1300 ℃ at the speed of 6 ℃/min for sintering for 4.5h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
Grinding and polishing the microwave dielectric ceramic obtained in the above examples 1 to 3 to obtain a ceramic finished product with a flat and smooth surface, and testing the cylindrical ceramic by using a Keysight E5232B vector network analyzerThe microwave dielectric properties at resonant frequency are shown in Table 1 (dielectric constant test System (dielectric resonator method)) by connecting a test fixture to a vector network analyzer by a cable, placing the test fixture in a high-low temperature box, performing resonance frequency, qxf value and dielectric constant test at normal temperature, heating the test fixture, raising the temperature of the sample to 85 deg.C, and testing the resonance frequency, and calculating the temperature coefficient of resonance frequency tau f )。
Table 1:
| ɛ r | Q×f （GHz） | τ f （ppm/℃） | |
| example 1 | 19.95 | 2.25×10 5 | -43.3 |
| Example 2 | 18.72 | 2.12×10 5 | -49.1 |
| Example 3 | 19.13 | 2.18×10 5 | -45.5 |
Grinding and polishing the microwave dielectric ceramics obtained in the comparative examples 1 to 8 to obtain ceramic finished products with flat and smooth surfaces, and testing the microwave dielectric properties of the cylindrical ceramics under the resonance frequency by adopting a Keysight E5232B vector network analyzer as shown in the following table 1 (dielectric constant testing system (dielectric resonator method)), wherein a testing clamp is connected to the vector network analyzer by a cable, the testing clamp is placed in a high-low temperature box, and the resonance frequency, the Qxf value and the dielectric constant of normal temperature are tested at normal temperature, the specific testing conditions are completely the same as the examples 1 to 3, and the specific testing results are shown in the table 2:
TABLE 2
| ɛ r | Q×f （GHz） | |
| Comparative example 1 | 18.12 | 1.83×10 5 |
| Comparative example 2 | 18.31 | 2.03×10 5 |
| Comparative example 3 | 18.05 | 1.77×10 5 |
| Comparative example 4 | 18.15 | 1.87×10 5 |
| Comparative example 5 | 18.08 | 1.79×10 5 |
| Comparative example 6 | 18.21 | 1.94×10 5 |
| Comparative example 7 | 18.01 | 1.73×10 5 |
| Comparative example 8 | 18.19 | 1.91×10 5 |
As can be seen from the comparison of the table 1 and the table 2, the dielectric constant of the microwave dielectric ceramic is 603due to the mutual synergistic effect of the components by adopting the La, nd, nb and Ta for modification r 19.95, the optimal quality factor Qxf is 2.25 × 10 5 GHz and temperature coefficient τ f Reaches-43.3 ppm/DEG C. Therefore, the microwave dielectric ceramic prepared by the method has excellent microwave performance and is suitable for practical production and application.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of microwave dielectric ceramics is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) MgCO with the purity of 99.9 percent 3 、La 2 O 3 、Nd 2 O 3 、Nb 2 O 5 、Ta 2 O 5 And TiO 2 The powder is taken as a raw material;
(2) According to the structural formula (Mg) （1-a-b） La a Nd b ）（Ti 1-x-y Nb x Ta y ）O 3 Wherein a is 0.001 to 0.01, b is 0.001 to 0.01; x is 0.02 to 0.03; y is 0.02 to 0.03, weighing the raw materials, and performing wet ball milling by using absolute ethyl alcohol as a ball milling medium;
(3) Drying and pre-calcining the ball-milled powder;
(4) Putting the pre-sintered powder into an agate mortar, and carrying out secondary ball milling;
(5) And drying the powder subjected to secondary ball milling, adding the powder into a ceramic mortar, adding 5wt% of PVA solution, uniformly mixing, granulating, pressing into a blank under the pressure of 30-60MPa, discharging the glue from the blank, sintering at the temperature of 1270-1330 ℃ for 3-6h, and naturally cooling to room temperature to obtain the microwave dielectric ceramic.
2. A method of preparing a microwave dielectric ceramic according to claim 1, wherein: in the step (1), the raw materials are dried for 14 to 24 hours at the temperature of 120 to 140 ℃ before proportioning.
3. A method of preparing a microwave dielectric ceramic according to claim 1, wherein: in the step (2), the ball milling time is 15 to 25h, and the rotating speed is 300 to 400 r/min.
4. A method of preparing a microwave dielectric ceramic according to claim 1, wherein: in the step (3), the drying temperature is 90-120 ℃, and the drying time is 6-10 h.
5. A method of preparing a microwave dielectric ceramic according to claim 1 or 4, wherein: in the step (3), the precalcination is carried out for 3 to 6 hours at 950 to 1050 ℃, and the heating rate is 1 to 3 ℃/min.
6. A method of preparing a microwave dielectric ceramic according to claim 1, wherein: in the step (4), the ball milling time is 8 to 12h, and the rotating speed is 300 to 400 r/min.
7. A method of preparing a microwave dielectric ceramic according to claim 1, wherein: in the step (5), the drying temperature is 110 to 130 ℃, and the mixing time is 30 to 50min.
8. A method of preparing a microwave dielectric ceramic according to claim 1, wherein: in the step (5), the glue discharging is carried out at 400 to 500 ℃ for 3 to 5 hours.
9. A method of preparing a microwave dielectric ceramic according to claim 8, wherein: in the step (5), the blank is subjected to glue discharging at 400 to 500 ℃ for 3 to 5 hours, then is sintered at 1270 to 1330 ℃ for 3 to 6 hours, specifically, the temperature is increased from room temperature to 400 to 500 ℃ at 1 to 3 ℃/min, glue discharging is carried out for 3 to 5 hours, and then the temperature is increased to 1270 to 1330 ℃ at 4 to 7 ℃/min, and then is sintered for 6 hours.
10. A microwave dielectric ceramic produced by the production method of a microwave dielectric ceramic according to any one of claims 1 to 9, wherein: a dielectric constant of the microwave dielectric ceramic of 603 r 18.72 to 19.95, and a quality factor Qxf of 2.12 x 10 5 ~2.25×10 5 GHz, temperature coefficient of τ f The concentration is-49.1 to-43.3 ppm/DEG C.
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