CN116924789A - Nickel ion doped low-dielectric magnesium phosphate microwave dielectric ceramic and preparation method thereof - Google Patents

Nickel ion doped low-dielectric magnesium phosphate microwave dielectric ceramic and preparation method thereof Download PDF

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CN116924789A
CN116924789A CN202310912232.3A CN202310912232A CN116924789A CN 116924789 A CN116924789 A CN 116924789A CN 202310912232 A CN202310912232 A CN 202310912232A CN 116924789 A CN116924789 A CN 116924789A
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CN116924789B (en
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陈月光
李勃
王士娇
吴海涛
张力
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SHANDONG TSINGHUA TONGFANG LUYING ELECTRONIC CO Ltd
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Abstract

The invention discloses a nickel ion doped regulation low-mesomagnesium phosphate microwave dielectric ceramic and a preparation method thereof, and belongs to the technical field of microwave dielectric ceramic materials. The chemical composition of the microwave dielectric ceramic of the invention is (Mg 1‑x Ni x ) 3 (PO 4 ) 2 Wherein x is more than or equal to 0.02 and less than or equal to 0.08. The invention prepares a series of (Mg) by controlling the molar substitution amount of Ni element to Mg element 1‑x Ni x ) 3 (PO 4 ) 2 Low-mesophosphate microwave dielectric material, which obviously improves Mg 3 (PO 4 ) 2 The microwave dielectric property of the ceramic is obtained to obtain the dielectric constant epsilon r =4.91-5.11, quality factor qf= 124,988-147,323ghz, resonant frequency temperature coefficient τ f -50.80-53.35 ppm/°c. The microwave dielectric ceramic provided by the invention meets the requirement of 5G/6G high-frequency communication, and has simple preparation process,has wide market application prospect.

Description

Nickel ion doped low-dielectric magnesium phosphate microwave dielectric ceramic and preparation method thereof
Technical Field
The invention belongs to the technical field of microwave dielectric ceramic materials, and particularly relates to a nickel ion doped regulation low-mesophosphate magnesium microwave dielectric ceramic and a preparation method thereof.
Background
The microwave dielectric ceramic is a ceramic material which is used as a dielectric medium to complete one or more functions in a microwave frequency band circuit, and is used as a key functional material of a dielectric resonator and a filter due to the characteristics of light weight, low loss and high stability. In recent years, with the rapid development of emerging wireless communication technologies such as 5G/6G communication technologies, internet of things (IOT), global Positioning System (GPS), etc., people's daily lives and works have put higher demands on the wireless communication technologies. Because of the crowded channel resources of the low frequency band, the high frequency band has abundant channel resources and large signal transmission volume and high speed, and the wireless communication technology expands towards the 5G/6G high frequency band. At present, online office learning becomes a mainstream normal state. The massive connection of terminals and explosive data throughput result in faster and more efficient updating iterations of the communication technology. As a key material of signal transmission devices in base stations, microwave dielectric ceramics play a particularly key role, and thus related performance research work has become particularly important.
In millimeter-wave band and terahertz-band communication, miniaturization of microwave components is not a major concern, because the size of the device is compared with an integer multiple of the communication wavelength, and when the signal wavelength reaches the millimeter level, the size of the device reaches the millimeter level. The delay time of the signal is the primary problem of limiting the development of communication, so that the high-speed transmission of the signal is achieved in order to obtain lower signal delay, and the low-dielectric microwave dielectric ceramic becomes the focus of attention of scientific researchers. Among the low-dielectric microwave dielectric ceramics, the phosphate ceramic system has excellent microwave dielectric property and is environment-friendly, and meets the requirement of 5G/6G high-frequency communication. With special [ PO ] in its crystal 4 ]The tetrahedral structure, P-O bonds, are strong bonds belonging to covalent bonds, are difficult to polarize by magnetic fields, which is one of the reasons for the lower dielectric constant of phosphate ceramics.
Mg 3 (PO 4 ) 2 The ceramic has lower dielectricElectric constant (epsilon) r =4.9), has great application potential in the field of high-frequency communication, but at the same time it has a high sintering temperature (1150 ℃) which limits its application in practical devices. In addition, the intrinsic factors influencing the microwave dielectric properties are not clear, and related researches mostly adopt a formula of a semi-empirical formula, so that the theory guiding effect is difficult to play. Based on P-V-L theory to Mg 3 (PO 4 ) 2 Chemical bond parameter analysis of ceramics shows that the contribution of P-O bond to lattice energy is as high as 78.5%, the value of the P-O bond is 3.65 times of the sum of Mg-O bond and Ca-O bond, the lattice energy is a physical quantity for representing the bonding force between ions, and the value of the P-O bond significantly influences Mg 3 (PO 4 ) 2 The lattice vibration of ceramics is closely related to the quality factor, so ion substitution of Mg is a reliable way to improve the quality factor of ceramics, and the work is still blank in the prior art, as described above, mg 3 (PO 4 ) 2 Ion doping regulation and control of the Mg position of the ceramic is a very significant work.
Disclosure of Invention
The invention aims at the defects existing in the prior art, and researches on the transition metal ion Ni partial substitution Mg (Mg 1- x Ni x ) 3 (PO 4 ) 2 The microwave dielectric property of the ceramic is changed, and a Ni ion doped low-dielectric phosphate microwave dielectric ceramic and a preparation method thereof are provided.
The specific technical proposal is that the expression of the prepared ceramic is (Mg 1-x Ni x ) 3 (PO 4 ) 2 Wherein x is more than or equal to 0.02 and less than or equal to 0.08, and x represents the molar ratio. The crystal structure belongs to monoclinic system P2 1 Space group of/n (No. 14), sintering temperature is 980-1010 deg.C, relative dielectric constant epsilon r =4.91-5.11, quality factor qf= 124,988-147,323ghz, resonant frequency temperature coefficient τ f ＝-50.80--53.35ppm/℃。
The preparation method of the low-dielectric magnesium phosphate microwave dielectric ceramic regulated by doping nickel ions comprises the following preparation steps:
(1) According to (Mg) 1-x Ni x ) 3 (PO 4 ) 2 Stoichiometric ratio of MgO (purity 98%), niO (purity 99%), NH as the drugs 4 H 2 PO 4
(purity 99%) by ZrO 2 Mixing 24-30 of grinding balls as ball milling medium and absolute ethyl alcohol as dispersing agent on a roller ball mill
After the ball milling, placing the slurry into a drying oven for drying;
(2) Grinding the dried powder block material in the step (1), sieving with a 60-mesh sieve, and then placing the powder in a corundum crucible for presintering to obtain presintered ceramic active powder;
(3) Adding the pre-sintered ceramic active powder into ZrO 2 Ball milling is carried out on the grinding balls and absolute ethyl alcohol again, the ball milling time is 24 hours, and the slurry after ball milling is dried in a drying oven and passes through a 60-mesh screen;
(4) Adding a shaping agent into the powder sieved in the step (3) for granulating, sieving with a 60-mesh sieve, and placing the powder into steel
In a die, longitudinally pressurizing by using a tablet press to 200MPa to prepare a cylindrical blank with the diameter of 10mm and the height of 6 mm;
(5) Placing the green body obtained in the step (4) in a muffle furnace, and calcining at a high temperature of 500-600 ℃ for 4-6 hours;
(6) Placing the blank obtained in the step (5) into a box-type resistance furnace, sintering the blank in air atmosphere at 980-1010 ℃, preserving heat for 2-4 hours,
naturally cooling to room temperature.
Further, the powder material (MgO, niO, NH) in the step (1 4 H 2 PO 4 )、ZrO 2 The mass ratio of the grinding balls to the absolute ethyl alcohol is 30:500:100.
Further, the step (3) is to presintered with ceramic active powder and ZrO 2 The mass ratio of the grinding balls to the absolute ethyl alcohol is 30:500:100.
Further, the pre-sintering temperature in the step (2) is 700-750 ℃, and the pre-sintering time is 2-4 hours.
Further, in the step (4), the shaping agent slices the paraffin wax, and the addition amount of the shaping agent is 8-12wt.% of the powder mass.
Advantageous effects
The Ni ion doped regulation low-mesophosphate microwave dielectric ceramic prepared by the invention has lower dielectric constant (epsilon) r =4.91-5.11) to achieve high-speed transmission of signals by Ni ion to Mg 3 (PO 4 ) 2 The Mg position of the ceramic crystal is regulated, and the phosphate microwave dielectric ceramic with single-phase high quality factor (qf= 124,988-147,323 GHz) is obtained, so that the toilet component has better frequency selection characteristic. Meanwhile, the preparation method can be prepared by adopting a solid-phase reaction sintering method, is simple and effective in process, is easy to produce in a large scale, and has potential to be popularized to industrialization.
Drawings
FIG. 1 shows the structure of the present invention (Mg 1-x Ni x ) 3 (PO 4 ) 2 Dielectric property parameter diagrams of ceramic examples 1, 2, 3, 4;
FIG. 2 shows the structure of example 1 (Mg) 1-x Ni x ) 3 (PO 4 ) 2 SEM image of the ceramic.
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
(1) According to (Mg) 1-x Ni x ) 3 (PO 4 ) 2 (x=0.02) stoichiometric ratio of the drug MgO (13.2990 g, purity 98%), niO (0.4979 g, purity 99%), NH 4 H 2 PO 4 (25.5622 g, 99% purity) in ZrO 2 Mixing the grinding balls serving as ball milling media and absolute ethyl alcohol serving as dispersing agent on a roller ball mill for 24 hours at the rotating speed of 300r/min, wherein the mass ratio of raw materials to the grinding balls to the absolute ethyl alcohol is 30:500:100, and drying the ball-milled slurry in a drying oven at 80 ℃;
(2) Grinding the dried powder block in the step (1) until no particles exist, sieving the powder block with a 60-mesh sieve, then placing the powder block in an alumina crucible, calcining the powder block at 700 ℃, wherein the temperature rise and fall rate is 2 ℃/min, and the heat preservation time is 3 hours, so as to obtain presintered ceramic active powder;
(3) Mixing the powder after presintering in the step (2) with ZrO 2 Adding the grinding balls and the absolute ethyl alcohol into a ball milling bottle together for ball milling again, wherein the rotating speed is 300r/min, the ball milling time is 24 hours, the mass ratio of the material powder to the grinding balls to the absolute ethyl alcohol is 30:500:100, and the slurry after ball milling is dried in a drying oven at 80 ℃ and is sieved by a 60-mesh sieve;
(4) Adding 8wt.% of shaping agent into the powder sieved in the step (3) for granulating, and sieving with a 60-mesh sieve to obtain powder with good fluidity; placing the powder in a steel die, and longitudinally pressurizing by using a tablet press to 200MPa to obtain a cylindrical blank with the diameter of 10mm and the height of 6 mm;
(5) Placing the blank body molded in the step (4) in a muffle furnace, calcining at a high temperature of 500 ℃, wherein the heating rate is 2 ℃/min, the heat preservation time is 4 hours, and cooling to room temperature along with the furnace;
(6) Placing the blank subjected to plastic removal in the step (5) in a box-type resistance furnace, sintering at 980 ℃ in air atmosphere, heating at 2 ℃/min, maintaining for 3 hours, and cooling to room temperature along with the furnace.
Example 2
(1) According to (Mg) 1-x Ni x ) 3 (PO 4 ) 2 (x=0.04) stoichiometric ratio of the drug MgO (13.0276 g, purity 98%), niO (0.9959 g, purity 99%), NH 4 H 2 PO 4 (25.5622 g, 99% purity) in ZrO 2 Mixing the grinding balls serving as ball milling media and absolute ethyl alcohol serving as dispersing agent on a roller ball mill for 26 hours at the rotating speed of 300r/min, wherein the mass ratio of raw materials to the grinding balls to the absolute ethyl alcohol is 30:500:100, and drying the ball-milled slurry in a drying oven at 80 ℃;
(2) Grinding the dried powder block in the step (1) until no particles exist, sieving the powder block with a 60-mesh sieve, then placing the powder block in an alumina crucible, calcining the powder block at 750 ℃, wherein the temperature rise and fall rate is 2 ℃/min, and the heat preservation time is 4 hours, so as to obtain presintered ceramic active powder;
(3) Mixing the powder after presintering in the step (2) with ZrO 2 Adding the grinding balls and the absolute ethyl alcohol into a ball milling bottle together for ball milling again, wherein the rotating speed is 300r/min, the ball milling time is 24 hours, the mass ratio of the material powder to the grinding balls to the absolute ethyl alcohol is 30:500:100, and the ball milling is carried out after ball millingDrying the slurry in a drying oven at 80 ℃ and sieving the slurry with a 60-mesh sieve;
(4) Adding 10wt.% of shaping agent into the powder sieved in the step (3) for granulating, and sieving with a 60-mesh sieve to obtain powder with good fluidity; placing the powder in a steel die, and longitudinally pressurizing by using a tablet press to 200MPa to obtain a cylindrical blank with the diameter of 10mm and the height of 6 mm;
(5) Placing the blank body molded in the step (4) in a muffle furnace, calcining at a high temperature of 500 ℃, wherein the heating rate is 2 ℃/min, the heat preservation time is 5 hours, and then cooling to room temperature along with the furnace;
(6) Placing the blank subjected to plastic removal in the step (5) in a box-type resistance furnace, sintering at 990 ℃ in air atmosphere, heating up at a rate of 2 ℃/min, preserving heat for 3 hours, and cooling to room temperature along with the furnace.
Example 3
(1) According to (Mg) 1-x Ni x ) 3 (PO 4 ) 2 (x=0.06) stoichiometric ratio of the drug MgO (12.7562 g, purity 98%), niO (1.4938 g, purity 99%), NH 4 H 2 PO 4 (25.5622 g, 99% purity) in ZrO 2 Mixing the grinding balls serving as ball milling media and absolute ethyl alcohol serving as dispersing agent on a roller ball mill for 26 hours at the rotating speed of 300r/min, wherein the mass ratio of raw materials to the grinding balls to the absolute ethyl alcohol is 30:500:100, and drying the ball-milled slurry in a drying oven at 80 ℃;
(2) Grinding the dried powder block in the step (1) until no particles exist, sieving the powder block with a 60-mesh sieve, then placing the powder block in an alumina crucible, calcining the powder block at 725 ℃, wherein the temperature rise and fall rate is 2 ℃/min, and the heat preservation time is 4 hours, so as to obtain presintered ceramic active powder;
(3) Mixing the powder after presintering in the step (2) with ZrO 2 Adding the grinding balls and the absolute ethyl alcohol into a ball milling bottle together for ball milling again, wherein the rotating speed is 300r/min, the ball milling time is 24 hours, the mass ratio of the material powder to the grinding balls to the absolute ethyl alcohol is 30:500:100, and the slurry after ball milling is dried in a drying oven at 80 ℃ and is sieved by a 60-mesh sieve;
(4) Adding 10wt.% of shaping agent into the powder sieved in the step (3) for granulating, and sieving with a 60-mesh sieve to obtain powder with good fluidity; placing the powder in a steel die, and longitudinally pressurizing by using a tablet press to 200MPa to obtain a cylindrical blank with the diameter of 10mm and the height of 6 mm;
(5) Placing the blank body molded in the step (4) in a muffle furnace, calcining at a high temperature of 500 ℃, wherein the heating rate is 2 ℃/min, the heat preservation time is 5 hours, and then cooling to room temperature along with the furnace;
(6) Placing the blank subjected to plastic removal in the step (5) in a box-type resistance furnace, sintering at 1000 ℃ in air atmosphere, heating at a rate of 2 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature along with the furnace.
Example 4
(1) According to (Mg) 1-x Ni x ) 3 (PO 4 ) 2 (x=0.08) stoichiometric ratio the drugs MgO (12.4848 g, purity 98%), niO (1.9917 g, purity 99%), NH were weighed out 4 H 2 PO 4 (25.5622 g, 99% purity) in ZrO 2 Mixing the grinding balls serving as ball milling media and absolute ethyl alcohol serving as dispersing agent on a roller ball mill for 30 hours at the rotating speed of 300r/min, wherein the mass ratio of raw materials to the grinding balls to the absolute ethyl alcohol is 30:500:100, and drying the ball-milled slurry in a drying oven at 80 ℃;
(2) Grinding the dried powder block in the step (1) until no particles exist, sieving the powder block with a 60-mesh sieve, then placing the powder block in an alumina crucible, calcining the powder block at 750 ℃, wherein the temperature rise and fall rate is 2 ℃/min, and the heat preservation time is 2 hours, so as to obtain ceramic active powder;
(3) Mixing the powder after presintering in the step (2) with ZrO 2 Adding the grinding balls and the absolute ethyl alcohol into a ball milling bottle together for ball milling again, wherein the rotating speed is 300r/min, the ball milling time is 24 hours, the mass ratio of the material powder to the grinding balls to the absolute ethyl alcohol is 30:500:100, and the slurry after ball milling is dried in a drying oven at 80 ℃ and is sieved by a 60-mesh sieve;
(4) Adding 12wt.% of shaping agent into the powder sieved in the step (3) for granulating, and sieving with a 60-mesh sieve to obtain powder with good fluidity; placing the powder in a steel die, and longitudinally pressurizing by using a tablet press to 200MPa to obtain a cylindrical blank with the diameter of 10mm and the height of 6 mm;
(5) Placing the blank body molded in the step (4) in a muffle furnace, calcining at a high temperature of 500 ℃, wherein the heating rate is 2 ℃/min, the heat preservation time is 6 hours, and then cooling to room temperature along with the furnace;
(6) Placing the blank subjected to plastic removal in the step (5) in a box-type resistance furnace, sintering at 1010 ℃ in air atmosphere, heating at a rate of 2 ℃/min, keeping the temperature for 4 hours, and cooling to room temperature along with the furnace.
Comparative example 1
(1) According to Mg 3 (PO 4 ) 2 Stoichiometric ratio of MgO (13.5704 g, purity 98%) and NH 4 H 2 PO 4 (25.5622 g, 99% purity) in ZrO 2 Mixing the grinding balls serving as ball milling media and absolute ethyl alcohol serving as dispersing agent on a roller ball mill for 24 hours at the rotating speed of 300r/min, wherein the mass ratio of raw materials to the grinding balls to the absolute ethyl alcohol is 30:500:100, and drying the ball-milled slurry in a drying oven at 80 ℃;
(2) Grinding the dried powder block in the step (1) until no particles exist, sieving the powder block with a 60-mesh sieve, then placing the powder block in an alumina crucible, calcining the powder block at 700 ℃, wherein the temperature rise and fall rate is 2 ℃/min, and the heat preservation time is 3 hours, so as to obtain presintered ceramic active powder;
(3) Mixing the powder after presintering in the step (2) with ZrO 2 Adding the grinding balls and the absolute ethyl alcohol into a ball milling bottle together for ball milling again, wherein the rotating speed is 300r/min, the ball milling time is 24 hours, the mass ratio of the material powder to the grinding balls to the absolute ethyl alcohol is 30:500:100, and the slurry after ball milling is dried in a drying oven at 80 ℃ and is sieved by a 60-mesh sieve;
(4) Adding 8wt.% of shaping agent into the powder sieved in the step (3) for granulating, and sieving with a 60-mesh sieve to obtain powder with good fluidity; placing the powder in a steel die, and longitudinally pressurizing by using a tablet press to 200MPa to obtain a cylindrical blank with the diameter of 10mm and the height of 6 mm;
(5) Placing the blank body molded in the step (4) in a muffle furnace, calcining at a high temperature of 500 ℃, wherein the heating rate is 2 ℃/min, the heat preservation time is 4 hours, and cooling to room temperature along with the furnace;
(6) Placing the blank subjected to plastic removal in the step (5) in a box-type resistance furnace, sintering at 980 ℃ in air atmosphere, heating at 2 ℃/min, maintaining for 3 hours, and cooling to room temperature along with the furnace.
The comparative example was conducted in the same manner as in example 1, except that Ni doping was not conducted.
Comparative example 2
(1) According to (Mg) 1-x Ni x ) 3 (PO 4 ) 2 (x=0.01) stoichiometric ratio of MgO (13.4347 g, purity 98%), niO (0.2490 g, purity 99%), NH were weighed out 4 H 2 PO 4 (25.5622 g, 99% purity) in ZrO 2 Mixing the grinding balls serving as ball milling media and absolute ethyl alcohol serving as dispersing agent on a roller ball mill for 24 hours at the rotating speed of 300r/min, wherein the mass ratio of raw materials to the grinding balls to the absolute ethyl alcohol is 30:500:100, and drying the ball-milled slurry in a drying oven at 80 ℃;
(2) Grinding the dried powder block in the step (1) until no particles exist, sieving the powder block with a 60-mesh sieve, then placing the powder block in an alumina crucible, calcining the powder block at 700 ℃, wherein the temperature rise and fall rate is 2 ℃/min, and the heat preservation time is 3 hours, so as to obtain presintered ceramic active powder;
(3) Mixing the powder after presintering in the step (2) with ZrO 2 Adding the grinding balls and the absolute ethyl alcohol into a ball milling bottle together for ball milling again, wherein the rotating speed is 300r/min, the ball milling time is 24 hours, the mass ratio of the material powder to the grinding balls to the absolute ethyl alcohol is 30:500:100, and the slurry after ball milling is dried in a drying oven at 80 ℃ and is sieved by a 60-mesh sieve;
(4) Adding 8wt.% of shaping agent into the powder sieved in the step (3) for granulating, and sieving with a 60-mesh sieve to obtain powder with good fluidity; placing the powder in a steel die, and longitudinally pressurizing by using a tablet press to 200MPa to obtain a cylindrical blank with the diameter of 10mm and the height of 6 mm;
(5) Placing the blank body molded in the step (4) in a muffle furnace, calcining at a high temperature of 500 ℃, wherein the heating rate is 2 ℃/min, the heat preservation time is 4 hours, and cooling to room temperature along with the furnace;
(6) Placing the blank subjected to plastic removal in the step (5) in a box-type resistance furnace, sintering at 980 ℃ in air atmosphere, heating at 2 ℃/min, maintaining for 3 hours, and cooling to room temperature along with the furnace.
This comparative example was conducted in the same manner as in example 1, except that the doping of Ni was reduced.
Comparative example 3
(1) According to (Mg) 1-x Ni x ) 3 (PO 4 ) 2 (x=0.1) stoichiometric ratio of the drug MgO (12.2134 g, purity 98%), niO (2.4897 g, purity 99%), NH 4 H 2 PO 4 (25.5622 g, 99% purity) in ZrO 2 Mixing the grinding balls serving as ball milling media and absolute ethyl alcohol serving as dispersing agent on a roller ball mill for 24 hours at the rotating speed of 300r/min, wherein the mass ratio of raw materials to the grinding balls to the absolute ethyl alcohol is 30:500:100, and drying the ball-milled slurry in a drying oven at 80 ℃;
(2) Grinding the dried powder block in the step (1) until no particles exist, sieving the powder block with a 60-mesh sieve, then placing the powder block in an alumina crucible, calcining the powder block at 700 ℃, wherein the temperature rise and fall rate is 2 ℃/min, and the heat preservation time is 3 hours, so as to obtain presintered ceramic active powder;
(3) Mixing the powder after presintering in the step (2) with ZrO 2 Adding the grinding balls and the absolute ethyl alcohol into a ball milling bottle together for ball milling again, wherein the rotating speed is 300r/min, the ball milling time is 24 hours, the mass ratio of the material powder to the grinding balls to the absolute ethyl alcohol is 30:500:100, and the slurry after ball milling is dried in a drying oven at 80 ℃ and is sieved by a 60-mesh sieve;
(4) Adding 8wt.% of shaping agent into the powder sieved in the step (3) for granulating, and sieving with a 60-mesh sieve to obtain powder with good fluidity; placing the powder in a steel die, and longitudinally pressurizing by using a tablet press to 200MPa to obtain a cylindrical blank with the diameter of 10mm and the height of 6 mm;
(5) Placing the blank body molded in the step (4) in a muffle furnace, calcining at a high temperature of 500 ℃, wherein the heating rate is 2 ℃/min, the heat preservation time is 4 hours, and cooling to room temperature along with the furnace;
(6) Placing the blank subjected to plastic removal in the step (5) in a box-type resistance furnace, sintering at 980 ℃ in air atmosphere, heating at 2 ℃/min, maintaining for 3 hours, and cooling to room temperature along with the furnace.
The comparative example was conducted in the same manner as in example 1, except that the doping of Ni was increased.
Performance testing
Table 1 shows microwave dielectric properties of examples 1 to 4 and comparative examples 1 to 3, and the evaluation of microwave dielectric properties was performed by the cylindrical dielectric resonator method.
TABLE 1 Performance test results
S.T.(℃) ε r Qf(GHz) τ f (ppm/℃)
Example 1 980 4.96 124,988 -50.80
Example 2 990 4.91 146,581 -52.32
Example 3 1000 5.01 147,323 -51.36
Example 4 1010 5.11 137,780 -53.35
Comparative example 1 980 4.99 32,369 -45.91
Comparative example 2 980 4.95 105,500 -50.21
Comparative example 3 980 5.12 131,050 -49.01
As can be seen from the data in Table 1, the ceramic materials of the examples of the present invention all exhibit a relatively low dielectric constant (. Epsilon.) r =4.91-5.11) and high quality factor (qf= 124,988-147,323 ghz), whereas ordinary Mg 3 (PO 4 ) 2 The ceramic material (comparative example 1) has a lower quality factor, and comparative examples 2-3, in which the Ni doping amount was changed, show a different degree of degradation in the overall properties of the material. It can be stated that the invention uses proper amount of Ni ions to replace the occupation space of Mg, which can effectively improve the comprehensive performance of the microwave ceramic material.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.

Claims (8)

1. A nickel ion doped regulation low-mesomagnesium phosphate microwave dielectric ceramic is characterized in that the chemical composition of the microwave dielectric ceramic is (Mg 1-x Ni x ) 3 (PO 4 ) 2 Wherein x is more than or equal to 0.02 and less than or equal to 0.08.
2. A method for preparing the nickel ion doped controlled low-mesophosphate magnesium microwave dielectric ceramic according to claim 1, comprising the following preparation steps:
(1) According to (Mg) 1-x Ni x ) 3 (PO 4 ) 2 Stoichiometric ratio of the weighed out drug MgO, niO, NH 4 H 2 PO 4 By ZrO 2 Mixing the grinding balls serving as ball milling media and absolute ethyl alcohol serving as a dispersing agent on a roller ball mill for 24-30 hours, and drying the ball-milled slurry in a drying oven;
(2) Grinding and sieving the dried powder block material in the step (1), and then placing the powder in a crucible for presintering to obtain presintered ceramic active powder;
(3) Adding the pre-sintered ceramic active powder into ZrO 2 Ball milling is carried out on the grinding balls and absolute ethyl alcohol again, the ball milling time is 24 hours, and the slurry after ball milling is dried and sieved in a drying oven;
(4) Adding a shaping agent into the powder sieved in the step (3) for granulating, sieving, placing the powder into a steel die, and tabletting by a tablet press to prepare a green body;
(5) Calcining the blank obtained in the step (4) at high temperature, wherein the heat preservation time is 4-6 hours;
(6) And (3) sintering the blank obtained in the step (5) in air atmosphere at 980-1010 ℃, preserving heat for 2-4 hours, and naturally cooling to room temperature.
3. The method for preparing the nickel ion doped control low-mesomagnesium phosphate microwave dielectric ceramic according to claim 2, wherein the method is characterized in that the powder material and ZrO in the step (1) are adopted 2 The mass ratio of the grinding balls to the absolute ethyl alcohol is 30:500:100.
4. The method for preparing the low-mesomagnesium phosphate microwave dielectric ceramic regulated by doping nickel ions according to claim 2, wherein the step (3) is characterized by presintering ceramic active powder and ZrO 2 The mass ratio of the grinding balls to the absolute ethyl alcohol is 30:500:100.
5. The method for preparing the low-mesophosphate microwave dielectric ceramic with the nickel ion doping control according to claim 2, wherein the pre-sintering temperature in the step (2) is 700-750 ℃, and the pre-sintering time is 2-4 hours.
6. The method for preparing the low-mesophosphate microwave dielectric ceramic with the nickel ion doping control according to claim 2, wherein the shaping agent in the step (4) is sliced paraffin, and the addition amount of the shaping agent is 8-12wt.% of the mass of the powder.
7. The method for preparing the nickel ion doped control low-mesophosphate microwave dielectric ceramic according to claim 2, wherein the blank in the step (4) is a cylindrical blank with the diameter of 10mm and the height of 6 mm; the tabletting pressure of the tablet press is as follows: and the longitudinal pressurization is 200MPa.
8. The method for preparing the low-mesophosphate microwave dielectric ceramic with the nickel ion doping control according to claim 2, wherein the high-temperature calcination temperature in the step (5) is 500-600 ℃.
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