CN110526711A - Magnesium zirconium niobium tin tungsten series microwave dielectric ceramic and preparation method thereof - Google Patents

Magnesium zirconium niobium tin tungsten series microwave dielectric ceramic and preparation method thereof Download PDF

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CN110526711A
CN110526711A CN201910855135.9A CN201910855135A CN110526711A CN 110526711 A CN110526711 A CN 110526711A CN 201910855135 A CN201910855135 A CN 201910855135A CN 110526711 A CN110526711 A CN 110526711A
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肖谧
何苏苏
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Tianjin University
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Abstract

The present invention relates to magnesium zirconium niobium tin tungsten series microwave dielectric ceramics and preparation method thereof.By Nb2O5、SnO2And WO3By metering than ingredient, ball milling, drying, sieving；By powder obtained after 900 DEG C~1000 DEG C pre-burnings, then with MgO and ZrO2Stoichiometrically ingredient, ball milling, is dried again；By mixture after calcining 2~4 hours, additional 6~8% weight percent paraffin is granulated after last ball milling, dry；By powder pressing obtained at green compact, it is sintered at 1260 DEG C~1320 DEG C and ceramic block MgZrNb is made2‑x(Sn1/2W1/2)xO8, wherein 0.03≤x≤0.15；Q × f of ceramics is 78378.4~93346.3GHz, εrFor 23.8042~24.6121, τfIt is -46.78~-50.65ppm/ DEG C.Applied in the microwave communication equipments such as direct broadcasting satellite.

Description

Magnesium zirconium niobium tin tungsten series microwave dielectric ceramic and preparation method thereof
Technical field
The ceramic composition that the invention belongs to a kind of characterized by ingredient is related to a kind of with magnesium zirconium niobium system microwave-medium pottery Based on porcelain, niobium ion is replaced with a small amount of compound ion, to prepare magnesium zirconium niobium tin tungsten series microwave dielectric ceramic and novel preparation Method.
Background technique
The rapid development of present mobile communication, push all kinds of microwave mobile communication terminal devices to miniaturization, lightweight, Multifunction and cost effective direction are fast-developing.Microwave-medium ceramics are modern mobile communication, satellite communication and military thunder Up to the critical material of the microwave devices such as resonator used, filter, medium substrate.Microwave-medium ceramics are smaller for manufacturing Device and the packaging density for improving microwave integrated circuit are highly effective.For making Jie of the devices such as dielectric resonator, filter Matter ceramics, must meet the following conditions: higher relative dielectric constant (εr) to realize the miniaturization of device and improve integrated level, compared with Low-dielectric loss (dielectric loss tangent angle tan δ) to improve selecting frequency characteristic, level off to zero temperature coefficient of resonance frequency (τf) with Improve temperature stability.
By dielectric theory it is found that the dielectric constant and Q × f value of material typically exhibit negative correlativing relation, i.e. dielectric constant Raising be usually associated with the decline of Q × f value, thus there is the material system ten of larger dielectric constant and high quality factor simultaneously Divide and lacks.On the other hand, although microwave current media ceramic has obtained extensive research, a series of new microwave dielectric material It continues to bring out, but about with low-k (20 < εr< 35) and the research of the media ceramic system of high quality factor compared with It is few.The magnesium zirconium niobium system (MgZrNb of wolframite structure2O8) system's ceramics are novel low-loss microwave dielectrics newly developed in recent years Ceramics cause the extensive concern of people with good microwave dielectric property, have miniaturization, high stable, cheap and integrated The advantages that.Since the factors such as ceramic microwave dielectric properties and material structure, micro-structure are closely related and dielectric loss main source In ceramic internal flaw such as crystal boundary, the micro-structures factor such as stomata then contains ceramic microwave dielectric properties by optimizing micro-structure The possibility further improved.For this purpose, the present invention surrounds MgZrNb2O8Ceramic B ion modification regulates and controls its micro-structure and micro-wave dielectric Performance develops a kind of microwave-medium ceramics and preparation method thereof, the results showed that micro compound ion (Sn1/2W1/2)5+Displacement Nb5+Ion can effectively regulate and control MgZrNb2O8The crystallite dimension and microscopic appearance of ceramics, thus in MgZrNb2-x(Sn1/2W1/2)xO8Microwave dielectric property is obtained in material further to be promoted.
Summary of the invention
The first purpose of this invention is to provide a kind of novel microwave-medium ceramics.
MgZrNb prepared by the present invention2-x(Sn1/2W1/2)xO8Permittivity ε of the ceramics under microwave frequency bandrFor 23.7~ 24.8, quality factor q × f value is 78378.4~93346.3GHz, resonance frequency temperature system when test frequency is 6~8GHz Number τfIt is -46.7~-50.6ppm/ DEG C, 0.03≤x≤0.15；There is great application in fields such as base station communication, satellite communications Value.
Another object of the present invention is to provide the preparation methods of above-mentioned microwave-medium ceramics.
To achieve the above object, the present invention takes following technical scheme:
(1) by Nb2O5、SnO2、WO3Raw material, by chemical formula MgZrNb2-x(Sn1/2W1/2)xO8, wherein 0.03≤x≤0.15 Ingredient is carried out, in raw material: deionized water: the ratio that zirconia ball mass ratio is 2:16:15~2:18:13 is added in ball grinder, Ball milling 6~8 hours on ball mill, the magma after obtaining ball milling；
(2) magma after step (1) ball milling is placed under the conditions of 100~110 DEG C of temperature and is dried, after to be dried, excessively 40~ 80 meshes obtain evengranular powder；
(3) powder that step (2) are uniformly mixed is fitted into crucible to be placed in high temperature furnace, in 900 DEG C~1000 DEG C pre-burnings 2 ~4 hours, the powder after obtaining pre-burning；
(4) by the powder and MgO, ZrO after step (3) pre-burning2Stoichiometrically ingredient is put into ball grinder, is added Deionized water and zirconia ball, secondary ball milling 6~8 hours on ball mill, the slurries after obtaining ball milling；
(5) slurries after step (4) ball milling are placed in 100~110 DEG C of temperature drying boxes and are dried, 40~80 are crossed after drying Mesh obtains evengranular mixture,；
(6) mixture that step (5) are uniformly mixed is fitted into crucible to be placed in high temperature furnace, is forged at 1000 DEG C~1100 DEG C It burns 2~4 hours, the ceramic crystal after obtaining pre-burning；
(7) ceramic crystal after step (6) pre-burning is put into ball grinder, deionized water and zirconia ball is added, in ball Ball milling 6~8 hours three times on grinding machine, and dried in 100~110 DEG C of temperature drying boxes；It is outer in ceramic powder after drying to add The paraffin of 8% weight percent is granulated, and crosses 40~80 meshes, then be pressed into green body with powder compressing machine；
(8) green body of step (7) is sintered 4~6 hours in 1260 DEG C~1320 DEG C, magnesium zirconium niobium tin tungsten system's microwave is made and is situated between Matter ceramics.
The present invention is in MgZrNb2O8Pass through control compound ion (Sn in ceramics1/2W1/2)5+Replace Nb5+The content of ion, with And control powder forming core is grown up degree during the sintering process, to influence crystallite dimension and microscopic appearance in ceramic microstructures, most Realize that microwave dielectric property regulates and controls improved purpose afterwards.
Before preparation, raw material needs to be ground to certain fineness, when grinding, raw material can be put into ball grinder, oxidation is added Zirconium ball-milling medium and deionized water continuous ball milling 8 hours.
Further, in step (1) step (4), Nb is selected2O5、SnO2、WO3, MgO and ZrO2Purity >=99.99%.
Further, in step (1), step (4) and step (7), ball mill is planetary ball mill.
Further, in step (7), the pressure of powder compressing machine is 4~8Mpa；Green body be diameter 10mm, thickness 1~ The cylindrical body of 5mm.
Further, in step (8), the sintering atmosphere of green compact is air environment, and heating rate is 1~5 DEG C/min, sintering Furnace cooling after the completion.
The microwave dielectric property of microwave-medium ceramics, MgZrNb prepared by the present invention are tested by Network Analyzer2-x (Sn1/2W1/2)xO8Permittivity ε of the ceramics under microwave frequency bandrIt is 23.7~24.8, quality factor q × f value is in test frequency To be 78378.4~93346.3GHz, temperature coefficient of resonance frequency τ when 6~8GHzfIt is -46.7~-50.6ppm/ DEG C.
A kind of application of microwave-medium ceramics in the field of communications.
With the MgZrNb reported in existing literature2O8Ceramic performance compared to (S.D.Ramarao, V.R.K.Murthy.Crystal structure refinement and microwave dielectric properties of new low dielectric loss AZrNb2O8(A:Mn,Zn,Mg and Co)ceramics.Scripta Mater.29 (2013) 274-277), the beneficial effects of the present invention are:
MgZrNb prepared by the present invention2-x(Sn1/2W1/2)xO8Ceramics are only needed through micro compound ion aliquot replacement niobium Ion can obtain extremely excellent microwave dielectric property (εr=23.7~24.8, Q × f=78378.4~ 93346.3GHz).It is analogous to the MgZrNb reported in existing literature2O8Microwave dielectric property (the ε of ceramicsr=9.6, Q × f= 58500GHz), dielectric constant and Q × f value all significantly improve, and can be widely applied to the microwave communications such as the direct broadcasting satellite of f >=8GHz Dielectric resonator device is used as in machine.In addition, preparation process of the present invention is simple, process is pollution-free, is a kind of up-and-coming microwave Dielectric material.
Detailed description of the invention
Fig. 1 is MgZrNb2-x(Sn1/2W1/2)xO8Ceramic powders XRD diffracting spectrum: x=0.03 (embodiment 1)；X=0.06 (embodiment 2)；X=0.09 (embodiment 3)；X=0.12 (embodiment 4)；X=0.15 (embodiment 5).
Fig. 1 explanation: it is analyzed by XRD spectra, all embodiments can be with the standard PDF card of MgZrNb2O8 ceramics (ICDD#48-0329) it is well matched with, and does not detect the second phase, this shows to be formed with the black tungsten of P2/c monoclinic system Mine structure.
Fig. 2 is MgZrNb2-x(Sn1/2W1/2)xO8The SEM image of the sintered surface of ceramics: (b) x=0.03 (embodiment 1)； (c) x=0.06 (embodiment 2)；(d) x=0.09 (embodiment 3)；(e) x=0.12 (embodiment 4)；(f) x=0.15 (embodiment 5)。
Fig. 2 explanation: can find from SEM image, and the crystallite dimension of embodiment does not have significant variation, and free from admixture generates.
Fig. 3 is MgZrNb2-x(Sn1/2W1/2)xO8(0.03≤x≤0.15) ceramics εrWith the variation diagram of substitution amount；
Fig. 3 explanation: with the increase of x value (substitution amount), dielectric constant is gradually reduced.
Fig. 4 is MgZrNb2-x(Sn1/2W1/2)xO8(0.03≤x≤0.15) ceramics Q × f with substitution amount variation diagram；
Fig. 4 explanation: it with the increase of x value (substitution amount), is reduced after Q × f value line increase.
Fig. 5 is MgZrNb2-x(Sn1/2W1/2)xO8(0.03≤x≤0.15) ceramics τfWith the variation diagram of substitution amount；
Fig. 5 explanation: with the increase of x value (substitution amount), τfValue gradually decreases.
Specific embodiment
Following specific embodiments are the further explanations to method provided by the invention and technical solution, but are not construed as Limitation of the present invention.
The present invention is greater than 99.9% chemical raw material Nb using purity2O5、SnO2、WO3、MgO、ZrO2, prepare MgZrNb2-x (Sn1/2W1/2)xO8(x=0.03,0.06,0.09,0.12,0.15) microwave-medium ceramics.Specific embodiment is as follows.
Embodiment 1
1. according to microwave-medium ceramics component MgZrNb2-x(Sn1/2W1/2)xO8(x=0.03), claim SnO-0.1267g, WO3- 0.1950g、Nb2O5- 14.6783g ingredient, total 15g；Mixed powder is added in ball grinder, and 120ml deionized water and 112g is added After zirconium ball, ball milling 6 hours on planetary ball mill, the magma after obtaining ball milling；
It is dried 2. the magma after ball milling is placed under the conditions of 100 DEG C of temperature, crosses 40 meshes, obtain evengranular powder；
3. by evengranular powder in 900 DEG C pre-burning 2 hours, obtain pre-burning after powder；
4. according to stoichiometric ratio, powder -12.4134g after weighing pre-burning, separately plus MgO-1.8699, ZrO2- 5.7167g, total 20g is put into ball grinder, deionized water and zirconia ball is added, secondary ball milling 6 hours, are obtained on ball mill Slurries after obtaining ball milling；
5. slurries are dried under the conditions of 100 DEG C of temperature, 40 meshes are crossed, evengranular mixture is obtained；
6. evengranular mixture is calcined 2 hours in 1000 DEG C, the ceramic crystal after obtaining pre-burning；
7. the ceramic crystal after pre-burning is put into ball grinder, deionized water and zirconia ball is added, ball milling 6 is small three times When, it is dried under the conditions of 100 DEG C of temperature after discharging, the paraffin that 8% weight percent is then added is granulated, and crosses 40 mesh Sieve；Diameter is pressed into for 10mm, with a thickness of the green body of 1mm with the pressure of 6Mpa with powder compressing machine again；
8. green body is sintered in 1260 DEG C, 4 hours are kept the temperature, high-performance magnesium zirconium niobium tin tungsten series microwave dielectric ceramic is made.It burns The heating rate for tying technique is 5 DEG C/min, and furnace cooling after the completion of sintering, the XRD diagram of obtained microwave-medium ceramics is referring to figure 1。
Finally, the sample microwave property as obtained by Network Analyzer and the test of dependence test fixture is shown in Table 1.
Embodiment 2
1. according to microwave-medium ceramics component MgZrNb2-x(Sn1/2W1/2)xO8(x=0.06), claim SnO-0.2518g, WO3- 0.3874g、Nb2O5- 14.3608g ingredient, total 15g；Mixed powder is added in ball grinder, and 130ml deionized water and 100g is added After zirconium ball, ball milling 7 hours on planetary ball mill, the magma after obtaining ball milling；
It is dried 2. the magma after ball milling is placed under the conditions of 110 DEG C of temperature, crosses 60 meshes, obtain evengranular powder；
3. by evengranular powder in 1000 DEG C pre-burning 3 hours, obtain pre-burning after powder；
4. according to stoichiometric ratio, powder -12.4441g after weighing pre-burning, separately plus MgO-1.8623, ZrO2- 5.6936g, total 20g is put into ball grinder, deionized water and zirconia ball is added, secondary ball milling 7 hours, are obtained on ball mill Slurries after obtaining ball milling；
5. slurries are dried under the conditions of 110 DEG C of temperature, 60 meshes are crossed, evengranular mixture is obtained；
6. evengranular mixture is calcined 3 hours in 1050 DEG C, the ceramic crystal after obtaining pre-burning；
7. the ceramic crystal after pre-burning is put into ball grinder, deionized water and zirconia ball is added, ball milling 7 is small three times When, it is dried under the conditions of 110 DEG C of temperature after discharging, the paraffin that 8% weight percent is then added is granulated, and crosses 60 mesh Sieve；Diameter is pressed into for 10mm, with a thickness of the green body of 4mm with the pressure of 6Mpa with powder compressing machine again；
8. green body is sintered in 1300 DEG C, 6 hours are kept the temperature, high-performance magnesium zirconium niobium tin tungsten series microwave dielectric ceramic is made.It burns The heating rate for tying technique is 2 DEG C/min, and furnace cooling after the completion of sintering, the XRD diagram of obtained microwave-medium ceramics is referring to figure 1。
Finally, the sample microwave property as obtained by Network Analyzer and the test of dependence test fixture is shown in Table 1.
Embodiment 3
1. according to microwave-medium ceramics component MgZrNb2-x(Sn1/2W1/2)xO8(x=0.09), claim SnO-0.3753g, WO3- 0.5774g、Nb2O5- 14.0474g ingredient, total 15g；Mixed powder is added in ball grinder, and 125ml deionized water and 100g is added After zirconium ball, ball milling 8 hours on planetary ball mill, the magma after obtaining ball milling；
It is dried 2. the magma after ball milling is placed under the conditions of 110 DEG C of temperature, crosses 80 meshes, obtain evengranular powder；
3. by evengranular powder in 950 DEG C pre-burning 3 hours, obtain pre-burning after powder；
4. according to stoichiometric ratio, powder -12.4745g after weighing pre-burning, separately plus MgO-1.8548, ZrO2- 5.6707g, total 20g is put into ball grinder, deionized water and zirconia ball is added, secondary ball milling 8 hours, are obtained on ball mill Slurries after obtaining ball milling；
5. slurries are dried under the conditions of 110 DEG C of temperature, 40 meshes are crossed, evengranular mixture is obtained；
6. evengranular mixture is calcined 3 hours in 1050 DEG C, the ceramic crystal after obtaining pre-burning；
7. the ceramic crystal after pre-burning is put into ball grinder, deionized water and zirconia ball is added, ball milling 8 is small three times When, it is dried under the conditions of 110 DEG C of temperature after discharging, the paraffin that 8% weight percent is then added is granulated, and crosses 60 mesh Sieve；Diameter is pressed into for 10mm, with a thickness of the green body of 5mm with the pressure of 8Mpa with powder compressing machine again；
8. green body is sintered in 1320 DEG C, 6 hours are kept the temperature, high-performance magnesium zirconium niobium tin tungsten series microwave dielectric ceramic is made.It burns The heating rate for tying technique is 4 DEG C/min, and furnace cooling after the completion of sintering, the XRD diagram of obtained microwave-medium ceramics is referring to figure 1。
Finally, the sample microwave property as obtained by Network Analyzer and the test of dependence test fixture is shown in Table 1.
Embodiment 4
1. according to microwave-medium ceramics component MgZrNb2-x(Sn1/2W1/2)xO8(x=0.12), claim SnO-0.4972g, WO3- 0.7649g、Nb2O5- 13.7380g ingredient, total 15g；Mixed powder is added in ball grinder, and 125ml deionized water and 105g is added After zirconium ball, ball milling 6 hours on planetary ball mill, the magma after obtaining ball milling；
It is dried 2. the magma after ball milling is placed under the conditions of 105 DEG C of temperature, crosses 40 meshes, obtain evengranular powder；
3. by evengranular powder in 1000 DEG C pre-burning 3 hours, obtain pre-burning after powder；
4. according to stoichiometric ratio, powder -12.5047g after weighing pre-burning, separately plus MgO-1.8474, ZrO2- 5.6479g, total 20g is put into ball grinder, deionized water and zirconia ball is added, secondary ball milling 8 hours, are obtained on ball mill Slurries after obtaining ball milling；
5. slurries are dried under the conditions of 105 DEG C of temperature, 80 meshes are crossed, evengranular mixture is obtained；
6. evengranular mixture is calcined 3 hours in 1050 DEG C, the ceramic crystal after obtaining pre-burning；
7. the ceramic crystal after pre-burning is put into ball grinder, deionized water and zirconia ball is added, ball milling 8 is small three times When, it is dried under the conditions of 105 DEG C of temperature after discharging, the paraffin that 8% weight percent is then added is granulated, and crosses 80 mesh Sieve；Diameter is pressed into for 10mm, with a thickness of the green body of 5mm with the pressure of 7Mpa with powder compressing machine again；
8. green body is sintered in 1280 DEG C, 6 hours are kept the temperature, high-performance magnesium zirconium niobium tin tungsten series microwave dielectric ceramic is made.It burns The heating rate for tying technique is 4 DEG C/min, and furnace cooling after the completion of sintering, the XRD diagram of obtained microwave-medium ceramics is referring to figure 1。
Finally, the sample microwave property as obtained by Network Analyzer and the test of dependence test fixture is shown in Table 1.
Embodiment 5
1. according to microwave-medium ceramics component MgZrNb2-x(Sn1/2W1/2)xO8(x=0.15), claim SnO-0.6175g, WO3- 0.9500g、Nb2O5- 13.4325g ingredient, total 15g；Mixed powder is added in ball grinder, and 135ml deionized water and 97g zirconium is added After ball, ball milling 8 hours on planetary ball mill, the magma after obtaining ball milling；
It is dried 2. the magma after ball milling is placed under the conditions of 110 DEG C of temperature, crosses 60 meshes, obtain evengranular powder；
3. by evengranular powder in 1000 DEG C pre-burning 4 hours, obtain pre-burning after powder；
4. according to stoichiometric ratio, powder -12.5347g after weighing pre-burning, separately plus MgO-1.8400, ZrO2- 5.6253g, total 20g is put into ball grinder, deionized water and zirconia ball is added, secondary ball milling 8 hours, are obtained on ball mill Slurries after obtaining ball milling；
5. slurries are dried under the conditions of 110 DEG C of temperature, 60 meshes are crossed, evengranular mixture is obtained；
6. evengranular mixture is calcined 4 hours in 1100 DEG C, the ceramic crystal after obtaining pre-burning；
7. the ceramic crystal after pre-burning is put into ball grinder, deionized water and zirconia ball is added, ball milling 8 is small three times When, it is dried under the conditions of 110 DEG C of temperature after discharging, the paraffin that 8% weight percent is then added is granulated, and crosses 60 mesh Sieve；Diameter is pressed into for 10mm, with a thickness of the green body of 5mm with the pressure of 8Mpa with powder compressing machine again；
8. green body is sintered in 1320 DEG C, 6 hours are kept the temperature, high-performance magnesium zirconium niobium tin tungsten series microwave dielectric ceramic is made.It burns The heating rate for tying technique is 2 DEG C/min, and furnace cooling after the completion of sintering, the XRD diagram of obtained microwave-medium ceramics is referring to figure 1。
Finally, the sample microwave property as obtained by Network Analyzer and the test of dependence test fixture is shown in Table 1.
The detection method of the specific embodiment of the invention is as follows:
1. the diameter and thickness of sample is measured using micrometer.
2. by Agilent 8720ES Network Analyzer, prepared cylindrical ceramic is measured using starting to rob parallel plate method Test fixture is put into ESPEC MC-710F type high/low temperature circulation incubator and carries out resonance frequency temperature system by the dielectric constant of material Several measurements, temperature range are 25-85 DEG C of test frequency within the scope of 6-8GHz.It is measured using enclosed cell method prepared cylindrical The quality factor of ceramics sample, test frequency is within the scope of 6-8GHz；Every key parameter of the specific embodiment of the invention and Jie See Table 1 for details for electrical property testing result.
3. the cylindrical dielectric ceramic surface that Examples 1 to 5 is prepared is sprayed Jin Houyong scanning electron microscope Sample surfaces and section crystallite dimension and microscopic appearance are observed, referring to fig. 2.It can be found from SEM image, the crystallite dimension of embodiment There is no significant variation, and free from admixture generates.
4. the figure that gained performance changes with substitution amount is referring to Fig. 3,4 and 5.Fig. 3 explanation: with the increase of x value (substitution amount), Dielectric constant is gradually reduced.Fig. 4 explanation: it with the increase of x value (substitution amount), is reduced after Q × f value line increase.Fig. 5 explanation: with The increase of x value (substitution amount), τfValue gradually decreases.
5. the present invention is not limited to the above embodiment, the variation of many details is possible, but therefore this does not violate this The scope and spirit of invention.
Table 1
As shown in Table 1, in MgZrNb2-x(Sn1/2W1/2)xO8Compound ion (Sn is adjusted in ceramics1/2W1/2)5Content can Its microwave dielectric property is influenced significantly, and dielectric properties are substantially better than in other documents and report MgZrNb2O8Ceramics.Meanwhile phase Than in traditional ceramic preparation, this experiment additionally increases the treatment process to raw material, i.e., by carrying out part raw material Pre-burning come increase ceramics performance.The excellent ceramics of preparation can be widely applied to the microwave communication equipments such as the direct broadcasting satellite of f >=8GHz It is middle to be used as dielectric resonator device.
The method of the present invention that the above embodiments are only used to help understand and its core concept.It should be pointed out that for For those skilled in the art, without departing from the principle of the present invention, if can also be carried out to the present invention Dry improvement and modification, these improvement and modification are also fallen into the claims in the present invention protection scope.

Claims (7)

1. magnesium zirconium niobium tin tungsten series microwave dielectric ceramic, chemical expression are as follows: MgZrNb2-x(Sn1/2W1/2)xO8, wherein 0.03≤x ≤ 0.15, the ceramics are under microwave frequency band, permittivity εrIt is 23.8~24.7, quality factor q × f value is in test frequency It is 78378~93346.3GHz, temperature coefficient of resonance frequency τ when 6~8GHzfIt is -46.7~-50.6ppm/ DEG C.
2. the preparation method of the magnesium zirconium niobium tin tungsten series microwave dielectric ceramic of claim 1, it is characterized in that the following steps are included:
(1) by Nb2O5、SnO2、WO3Raw material, by chemical formula MgZrNb2-x(Sn1/2W1/2)xO8(0.03≤x≤0.15) is matched Material, in raw material: deionized water: the ratio that zirconia ball mass ratio is 2:16:15~2:18:13 is added in ball grinder, in ball milling Ball milling 6~8 hours on machine, the magma after obtaining ball milling；
(2) magma after step (1) ball milling is placed in 100~110 DEG C of temperature drying boxes and is dried, 40~80 mesh are crossed after drying Sieve, obtains evengranular powder；
(3) powder that step (2) are uniformly mixed is fitted into crucible to be placed in high temperature furnace, in 900 DEG C~1000 DEG C pre-burnings 2~4 Hour, the powder after obtaining pre-burning；
(4) by the powder and MgO, ZrO after step (3) pre-burning2Stoichiometrically ingredient is put into ball grinder, and deionization is added Water and zirconia ball, secondary ball milling 6~8 hours on ball mill, the slurries after obtaining ball milling；
(5) slurries after step (4) ball milling are placed in 100~110 DEG C of temperature drying boxes and are dried, 40~80 mesh are crossed after drying Sieve, obtains evengranular mixture；
(6) mixture that step (5) are uniformly mixed is fitted into crucible to be placed in high temperature furnace, calcines 2 at 1000 DEG C~1100 DEG C ~4 hours, the ceramic crystal after obtaining pre-burning；
(7) ceramic crystal after step (6) pre-burning is put into ball grinder, deionized water and zirconia ball is added, in ball mill On ball milling 6~8 hours three times, and dried in 100~110 DEG C of temperature drying boxes；It is outer in ceramic crystal after drying to add 8% weight The paraffin of amount percentage is granulated, and crosses 40~80 meshes, then be pressed into green body with tablet press machine；
(8) green body of step (7) is sintered 4~6 hours in 1260 DEG C~1320 DEG C, magnesium zirconium niobium tin tungsten series microwave dielectric pottery is made Porcelain.
3. according to the method described in claim 2, it is characterized in that, the Nb of the step (1)2O5、SnO2、WO3, MgO or ZrO2 The purity of raw material is greater than 99.9%.
4. according to the method described in claim 2, it is characterized in that, the ball mill of the step (1), step (4) is planetary Ball mill.
5. according to the method described in claim 2, it is characterized in that, the pressure of the tablet press machine of the step (4) is 4~8Mpa.
6. according to the method described in claim 2, it is characterized in that, the green body of the step (4) be diameter 10mm, thickness 1~ The cylindrical body of 5mm.
7. according to the method described in claim 2, it is characterized in that, the sintering atmosphere of green compact is air ring in the step (8) Border, heating rate are 1~5 DEG C/min, furnace cooling after the completion of sintering.
CN201910855135.9A 2019-09-10 2019-09-10 Magnesium zirconium niobium tin tungsten series microwave dielectric ceramic and preparation method thereof Pending CN110526711A (en)

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JPS55128283A (en) * 1979-03-27 1980-10-03 Mitsubishi Mining & Cement Co Surge absorbing element
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