CN115536376A - Preparation method of low-dielectric low-loss zinc magnesium silicate system microwave dielectric ceramic - Google Patents
Preparation method of low-dielectric low-loss zinc magnesium silicate system microwave dielectric ceramic Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229910052919 magnesium silicate Inorganic materials 0.000 title claims abstract description 6
- 235000019792 magnesium silicate Nutrition 0.000 title claims abstract description 6
- 239000000391 magnesium silicate Substances 0.000 title claims abstract description 6
- 229910004283 SiO 4 Inorganic materials 0.000 claims abstract description 66
- 239000011701 zinc Substances 0.000 claims abstract description 54
- 239000011777 magnesium Substances 0.000 claims abstract description 44
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
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- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 14
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
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- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
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- 238000000643 oven drying Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention relates to a preparation method of low-dielectric-constant low-loss zinc magnesium silicate system microwave dielectric ceramic. The method of the invention uses Zn 2 SiO 4 Ceramic as matrix and Mg 2+ Doping to replace ZnO, mgO and SiO 2 According to formula (Zn) 1‑x Mg x ) 2 SiO 4 Wherein x = 0.6-0.8, and synthesizing Zn by a conventional solid-phase reaction method 2 SiO 4 ‑Mg 2 SiO 4 Two-phase composite microwave dielectric ceramic. The two-phase composition improves the compactness of the sample, so that the prepared (Zn) 1‑x Mg x ) 2 SiO 4 Has low dielectric constant and low dielectric loss, and reduces the sintering temperature of the ceramic sample. The invention can provide an alternative material for microwave communication components such as resonators, filters and the like, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of wireless communication and electronic ceramic materials, and particularly relates to a preparation method of a low-dielectric-constant and low-loss microwave dielectric ceramic.
Background
Discovery of electromagnetic wavesThe development of the microwave band greatly promotes the progress of human society, and the electromagnetic wave in the microwave band makes the connection between people and things more close. The development of mobile communication technology is rapid, a new generation of mobile communication technology is generated every decade, the change of each generation of mobile communication technology enables the frequency of electromagnetic waves to reach a new height, the electromagnetic waves with high frequency can carry a large amount of information, but the defects of poor obstacle bypassing capability, easy attenuation and the like exist, and the frame loss of signals is easily caused in the transmission process. In order to meet the development requirements of 5G/6G communication technology, dielectric ceramics with low dielectric constant, high quality factor and near-zero resonant frequency temperature have attracted wide attention in recent years as key materials of components such as dielectric resonators, dielectric filters, antennas, substrates and the like. The low dielectric constant improves the transmission efficiency of the electric signals, and the high quality factor ensures the frequency selectivity in the signal transmission process. Zn 2 SiO 4 The dielectric material has excellent dielectric properties and a low dielectric constant epsilon r (6.5), high Q-factor Qf (198400 GHz) and relatively negative temperature coefficient of resonance frequency τ f (-41.6 ppm/. Degree. C.). Although the dielectric constant and the quality factor of the material are excellent, the adopted preparation method is complex, and when the material is prepared by adopting a conventional solid phase reaction method, the dielectric loss is increased due to the problems that ZnO volatilizes at high temperature, a second phase of ZnO is generated due to a narrow sintering interval, a sintered sample has more pores and the like, so that the quality factor is seriously reduced; with Zn 2 SiO 4 The sintering temperature of the ceramic sample is high, and the application of the ceramic sample is greatly limited by the two factors. At present, researchers commonly use ion doping method to modify Zn 2 SiO 4 Expanding the sintering space, e.g. (Zn) 1.95 Co 0.05 ) 2 SiO 4 Although the generation of the ZnO second phase is avoided, the sintering temperature is increased, so that the production cost is further increased. Therefore, zn can still be exerted on the basis of enlarging the sintering interval and reducing the sintering temperature 2 SiO 4 The dielectric properties of (a) are in need of further research.
Disclosure of Invention
In view of the prior artUnder the circumstances, the invention aims to provide a preparation method of a low-dielectric-constant low-loss zinc magnesium silicate system microwave dielectric ceramic so as to solve the problem of Zn 2 SiO 4 The ceramic sintering temperature is high, and the sintering interval is narrow, so that the dielectric property is deteriorated.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of low-dielectric low-loss zinc magnesium silicate system microwave dielectric ceramic is characterized by comprising the following steps:
(1) Preparing materials: znO, mgO and SiO 2 According to formula (Zn) 1-x Mg x ) 2 SiO 4 Wherein x =0.6 to 0.8, particularly preferably x =0.6;
(2) Mixing materials: well-matched ZnO, mgO and SiO 2 Performing wet ball milling to obtain slurry, wherein the wet ball milling can adopt a polytetrafluoroethylene ball milling tank, zirconia milling balls and a planetary ball mill, the ball milling auxiliary agent is preferably absolute ethyl alcohol, the ball milling time is more than 16h, and in addition, powder materials during ball milling: zirconia grinding balls: absolute ethanol volume ratio = 1;
(3) Drying: pouring out the ball-milled slurry, and placing the ball-milled slurry into an oven to be dried to constant weight to obtain a dried mixture, wherein the drying temperature can be 80-110 ℃;
(4) Pre-burning: sieving and dispersing the mixture, presintering at 1050-1200 ℃ to synthesize (Zn) 1-x Mg x ) 2 SiO 4 The compound powder specifically comprises the steps of firstly screening a constant-weight mixture through a 120-mesh standard sieve, dispersing the mixture, and then placing the mixture into a high-temperature furnace for presintering, wherein the presintering temperature is preferably 1100 ℃;
(5) Ball milling: pre-burning synthesized (Zn) 1-x Mg x ) 2 SiO 4 Compound powder is wet ball milled to form (Zn) 1-x Mg x ) 2 SiO 4 Compound slurry, wet ball milled in the manner as described in step (2) above;
(6) Drying: will (Zn) 1-x Mg x ) 2 SiO 4 Taking out the slurry, and placing the slurry in an oven to dry the slurry to constant weight to obtain (Zn) 1-x Mg x ) 2 SiO 4 Compound powder, wherein the drying temperature can also be 80-110 ℃;
(7) And (3) granulation: after drying (Zn) 1-x Mg x ) 2 SiO 4 Sieving compound powder, adding binder, mixing, and coarse sieving to obtain powder for press molding, wherein the powder may specifically comprise (Zn) obtained after oven drying 1-x Mg x ) 2 SiO 4 The compound powder firstly passes through a 120-mesh standard sieve, then a binder is added, the mixture is ground by an agate mortar to be uniformly mixed with the raw materials, and then the mixture passes through a 40-mesh standard sieve to obtain the raw material for the next step of compression molding, wherein the binder is preferably polyvinyl alcohol (PVA), and the weight ratio of the compound powder to the PVA is preferably 100:9;
(8) And (3) pressing and forming: pressing the powder for press forming into a ceramic green body;
(9) And (3) binder removal and sintering: and (2) putting the pressed green body into a high-temperature furnace, setting the heating rate of the furnace to be 3-5 ℃/min, heating to the temperature of more than 600 ℃ for heat preservation for removing the adhesive, preferably keeping the temperature for 2h, then increasing the temperature according to the same heating rate, setting the sintering range to be 1200-1350 ℃, preferably keeping the temperature for 4h, then reducing the temperature to be less than 400 ℃ at the cooling rate of 2 ℃/min, and then naturally cooling along with the furnace.
The invention provides a method for preparing low-dielectric constant and low-loss microwave dielectric ceramic by using Zn 2 SiO 4 Ceramic as matrix and Mg 2+ Doping substitution, and synthesizing Zn by traditional solid-phase reaction method 2 SiO 4 -Mg 2 SiO 4 Two-phase composite microwave dielectric ceramic. The two-phase compounding improves the compactness of a sample, reduces the sintering temperature of a ceramic sample, and the microwave dielectric ceramic prepared by the method has excellent dielectric property and low loss. The invention can provide an alternative material for microwave communication components such as resonators, filters and the like, and has wide application prospect.
Drawings
FIG. 1 is (Zn) prepared according to examples 1 to 6 of the present invention 1-x Mg x ) 2 SiO 4 XRD pattern of the ceramic.
FIG. 2 is (Zn) prepared according to examples 1 to 6 of the present invention 1-x Mg x ) 2 SiO 4 SEM spectra of the ceramics.
FIG. 3 is (Zn) prepared according to examples 1 to 6 of the present invention 1-x Mg x ) 2 SiO 4 Graph of the actual density of the ceramic.
FIG. 4 is (Zn) prepared according to examples 1 to 6 of the present invention 1-x Mg x ) 2 SiO 4 Graph of dielectric constant of ceramic sample.
FIG. 5 is (Zn) prepared according to examples 1 to 6 of the present invention 1-x Mg x ) 2 SiO 4 Graph of figure of merit for ceramic samples.
FIG. 6 is (Zn) prepared according to examples 1 to 6 of the present invention 1-x Mg x ) 2 SiO 4 Graph of temperature coefficient of resonant frequency for ceramic samples.
Detailed Description
For a clearer understanding of the objects, technical solutions and advantages of the present invention, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments.
The invention provides a preparation method of low-dielectric constant and low-loss microwave dielectric ceramic, which uses Zn 2 SiO 4 Ceramic as matrix and Mg 2+ Doping to replace ZnO, mgO and SiO 2 According to formula (Zn) 1-x Mg x ) 2 SiO 4 Wherein x = 0.6-0.8, and synthesizing Zn by a traditional solid phase reaction method 2 SiO 4 -Mg 2 SiO 4 Two-phase composite microwave dielectric ceramic. The two-phase composition improves the compactness of the sample, so that the prepared (Zn) 1-x Mg x ) 2 SiO 4 Has low dielectric constant and low dielectric loss, and reduces the sintering temperature of the ceramic sample.
Example 1:
preparing materials: znO (99.99%), siO 2 (99.99%) by the formula Zn 2 SiO 4 In a stoichiometric ratio ofIn a certain proportion, i.e., (Zn) 1-x Mg x ) 2 SiO 4 Wherein x =0;
mixing materials: putting the weighed raw materials into a polytetrafluoroethylene ball milling tank, taking zirconium oxide as a grinding ball and absolute ethyl alcohol as a ball milling auxiliary agent, and putting the raw materials into a planetary ball mill for wet ball milling for 16 hours, wherein the raw materials comprise: zirconia grinding balls: anhydrous ethanol in a volume ratio of = 1;
drying: pouring out the ball-milled slurry, and drying in an oven at 80 ℃ to constant weight to obtain a dried mixture;
pre-burning: the constant weight mixture is firstly screened by a 120-mesh standard sieve, and after the mixture is dispersed, the mixture is put into a high temperature furnace for presintering, the presintering temperature is 1100 ℃, and Zn is synthesized 2 SiO 4 A ceramic powder;
ball milling: pre-burning synthesized Zn 2 SiO 4 Adding absolute ethyl alcohol into the compound powder, and placing the mixture into a ball mill for ball milling for 16h to form Zn 2 SiO 4 A compound slurry;
drying: zn is added 2 SiO 4 Taking out the compound slurry, and drying the compound slurry in an oven at 80 ℃ to constant weight to obtain Zn 2 SiO 4 A compound powder;
and (3) granulation: zn after drying 2 SiO 4 The compound powder is firstly sieved by a 120-mesh standard sieve, and then a polyvinyl alcohol (PVA) binding agent is added, wherein the weight ratio of the compound powder to the PVA is 100: grinding by using an agate mortar to uniformly mix the raw materials, and then screening by using a 40-mesh standard sieve to obtain the raw material for the next step of compression molding;
and (3) pressing and forming: weighing a certain amount of powder, pouring the powder into a mold, keeping the powder in a tablet press for 3min under the pressure of 100MPa, and pressing the powder into a ceramic green body with the diameter of 12mm and the height of 7 mm;
and (3) binder removal and sintering: and (2) putting the pressed green body into a high-temperature furnace, setting the heating rate of the furnace to be 3 ℃/min, heating to 650 ℃, keeping for 2h to remove the glue, then increasing to the corresponding temperature according to the same heating rate, wherein the sintering temperature ranges from 1300 ℃ to 1400 ℃ (the specific sintering temperatures are 1300 ℃, 1325 ℃, 1350 ℃, 1375 ℃ and 1400 ℃, and referring to fig. 3), preserving the heat for 4h, then reducing to 400 ℃ at the cooling rate of 2 ℃/min, stopping the procedure, and naturally cooling the furnace.
Sample post-treatment and test: the sintered sample is ground to 3000 meshes by using sand paper and subjected to surface polishing treatment, and then ultrasonic cleaning treatment is carried out.
Example 2:
according to formula (Zn) 0.8 Mg 0.2 ) 2 SiO 4 ZnO (99.99%), siO were weighed 2 (99.99%) and MgO (99.99%), drying at 110 deg.C, heating to 600 deg.C at a rate of 5 deg.C/min, and the same procedure as in example 1.
Example 3:
according to formula (Zn) 0.6 Mg 0.4 ) 2 SiO 4 ZnO (99.99%), siO were weighed 2 (99.99%) and MgO (99.99%), the rest being the same as in example 1.
Example 4:
according to formula (Zn) 0.4 Mg 0.6 ) 2 SiO 4 ZnO (99.99%), siO were weighed 2 (99.99%) and MgO (99.99%), the sintering temperature ranges from 1200 ℃ to 1300 ℃ (the specific sintering temperatures are 1200 ℃, 1225 ℃, 1250 ℃, 1275 ℃ and 1300 ℃, respectively, see FIG. 3), otherwise the same as example 2. In addition, in this case (x = 0.6), the sintering temperature can reach up to 1350 ℃ above which burning out of the final product can occur.
Example 5:
according to formula (Zn) 0.2 Mg 0.8 ) 2 SiO 4 ZnO (99.99%) and SiO were weighed 2 (99.99%) and MgO (99.99%), the sintering temperature ranges from 1200 ℃ to 1300 ℃ (the specific sintering temperatures are 1200 ℃, 1225 ℃, 1250 ℃, 1275 ℃ and 1300 ℃, respectively, see FIG. 3), otherwise the same as example 2. Likewise, in this case (x = 0.8), the sintering temperature can reach up to 1350 ℃, above which burning out of the final product can occur.
Example 6:
according to the formula Mg 2 SiO 4 Weighing SiO 2 (99.99%) and MgO (99.99%), i.e., (Zn) 1 -xMg x ) 2 SiO 4 Wherein x =1, the sintering temperature is 1300 ℃ to 1400 ℃, and the other steps are the same as those of example 1.
FIG. 1 is an XRD pattern of examples 1 to 6, by XRD analysis, zn was obtained at x =0.6 and x =0.8 2 SiO 4 And Mg 2 SiO 4 Two-phase coexisting ceramic samples, when combined with FIG. 2 (SEM spectra of examples 1-6) and FIG. 3 (relative density data of examples 1-6), can be obtained in Zn 2 SiO 4 And Mg 2 SiO 4 When two phases coexist, the sample has good compactness, uniform and smaller grain distribution and lower sintering temperature, compared with Zn 2 SiO 4 And Mg 2 SiO 4 The sintering temperature is reduced by 100 ℃. At the same time in (Zn) 1 -xMg x ) 2 SiO 4 In the system, the sample still has good dielectric properties, the dielectric constant of the sample is less than 10 and is adjustable, the adjustable range is 5.12-7.37 (see figure 4), and the quality factor is excellent (Qxf = 94570-148859 GHz) (see figure 5). Has a relatively negative temperature coefficient of resonance frequency (-71 ppm/DEG C ≦ tau) while having a relatively low dielectric constant f ≦ -51 ppm/. Degree.C.) (see FIG. 6). In addition, as can be seen from the trends in relative densities shown in FIG. 3, the samples of examples 1-3 and 6 (i.e., x is outside of 0.6-0.8) have lower relative densities at 1200-1300 ℃ and are not densified, and higher relative densities at 1300-1400 ℃ indicating that higher temperatures are conducive to densification of the samples for these components.
The preparation method of the invention adopts Zn 2 SiO 4 Ceramic as matrix and Mg 2+ Doping substitution, changing phase composition and phase content, and synthesizing Zn by traditional solid phase reaction method 2 SiO 4 -Mg 2 SiO 4 The two-phase composite microwave dielectric ceramic reduces the sintering temperature of a ceramic sample. The two-phase composition improves the compactness of the sample, so that the prepared (Zn) 1-x Mg x ) 2 SiO 4 Has low dielectric constant and low dielectric loss, wherein (Zn) is 0.4 Mg 0.6 ) 2 SiO 4 The ceramic sample shows excellent dielectric property and dielectric constant epsilon r =6.8, is typically lowDielectric microwave dielectric ceramic, qf is as high as 148900GHz, tau f = 58 ppm/DEG C, the sintering temperature is 1250 ℃, and good dielectric property is still maintained on the basis of the reduced sintering temperature of 100 ℃. The invention can provide an alternative material for microwave communication components such as resonators, filters and the like, and has wide application prospect.
Claims (10)
1. A preparation method of low-dielectric low-loss zinc magnesium silicate system microwave dielectric ceramic is characterized by comprising the following steps:
(1) Preparing materials: znO, mgO and SiO 2 According to formula (Zn) 1-x Mg x ) 2 SiO 4 The stoichiometric ratio of (1), wherein x = 0.6-0.8;
(2) Mixing materials: well-matched ZnO, mgO and SiO 2 Performing wet ball milling to obtain slurry;
(3) Drying: drying the slurry to constant weight to obtain a dry mixture;
(4) Pre-burning: dispersing the mixture, presintering at 1050-1200 ℃ to synthesize (Zn) 1-x Mg x ) 2 SiO 4 A compound powder;
(5) Ball milling: pre-burning synthesized (Zn) 1-x Mg x ) 2 SiO 4 Compound powder is wet ball milled to form (Zn) 1-x Mg x ) 2 SiO 4 A compound slurry;
(6) Drying: will (Zn) 1-x Mg x ) 2 SiO 4 Drying the compound slurry to constant weight to obtain (Zn) 1-x Mg x ) 2 SiO 4 A compound powder;
(7) And (3) granulation: after drying (Zn) 1-x Mg x ) 2 SiO 4 Fine screening the compound powder, adding an adhesive, uniformly mixing, and coarse screening to obtain powder for press molding;
(8) And (3) pressing and forming: pressing the powder for press forming into a ceramic green body;
(9) And (3) binder removal and sintering: heating the ceramic green body to over 600 ℃, preserving heat to remove the adhesive, then heating to 1200-1350 ℃ for sintering, then cooling to below 400 ℃ and furnace cooling.
2. The method of claim 1, wherein x =0.6.
3. The method according to claim 1, wherein the sintering temperature in step (9) is 1200 to 1300 ℃.
4. The method of claim 1, wherein ZnO, mgO, siO 2 The purity of (2) was 99.99%.
5. The method according to claim 1, wherein the binder in the step (7) is polyvinyl alcohol, and the weight ratio of the compound powder to the polyvinyl alcohol is 100:9, adopting a 120-mesh standard sieve for the fine sieve and adopting a 40-mesh standard sieve for the coarse sieve.
6. The method according to claim 1, wherein the wet ball milling adopts a polytetrafluoroethylene ball milling pot, zirconia milling balls and a planetary ball mill, wherein the ball milling auxiliary agent is absolute ethyl alcohol, and the ball milling time is more than 16 h.
7. The method of claim 6, wherein the powder: zirconia grinding balls: volume ratio of anhydrous ethanol = 1.
8. The method according to claim 1, wherein the drying temperature in the step (3) and the step (6) is 80 ℃ to 110 ℃.
9. The method of claim 1, wherein the sintering time in step (9) is 4 hours and the hold time to exclude the binder is 2 hours.
10. The method according to claim 1, wherein the temperature rising rate in the step (9) is 3 to 5 ℃/min and the temperature falling rate is 2 ℃/min.
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| SONG等: "Microwave dielectric characteristics of ceramics in Mg2SiO4-Zn2SiO4 system" * |
| 宋开新: "(Mg1-xZnx)2SiO4（0≤ｘ≤1）陶瓷微波介电性能研究" * |
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