CN115504769B - Microwave dielectric ceramic material and preparation method and application thereof - Google Patents
Microwave dielectric ceramic material and preparation method and application thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims abstract description 19
- 230000035939 shock Effects 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 73
- 238000000498 ball milling Methods 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 41
- 238000005245 sintering Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- 238000000227 grinding Methods 0.000 claims description 31
- 238000007873 sieving Methods 0.000 claims description 21
- 238000007599 discharging Methods 0.000 claims description 17
- 239000003292 glue Substances 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 9
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 15
- 239000003607 modifier Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 description 28
- 239000000126 substance Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 230000002349 favourable effect Effects 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 9
- 150000002500 ions Chemical group 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/638—Removal thereof
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention provides a microwave dielectric ceramic material, a preparation method and application thereof, and relates to the technical field of ceramic materials, comprising a main material and a modifier, wherein the main material comprises ZnGa 2 O 4 The modifier comprises MnCO 3 And In 2 O 3 Is a composition of (a). The invention solves the problems of ZnGa in the prior art 2 O 4 The technical problems of non-ideal temperature coefficient of resonant frequency and quality factor of the ceramic material can achieve the technical effects that the dielectric constant is about 10, the quality factor is over 130000GHz, the temperature coefficient of resonant frequency is between +/-10 ppm/DEG C, and the thermal shock resistance temperature difference exceeds 160 ℃.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a microwave dielectric ceramic material and a preparation method and application thereof.
Background
The low-dielectric-constant microwave dielectric material has the characteristics of low time delay, low coupling and the like, and is suitable for application in the aspect of microwave substrates. ZnGa 2 O 4 The ceramic is a novel low-dielectric-constant microwave dielectric ceramic alternative material, and has the advantages of low sintering temperature (1400 ℃) and wide sintering range (1300-1500 ℃), dielectric constant of about 9.8 and quality factor of about 83000GHz. However, znGa 2 O 4 The temperature coefficient of the resonance frequency of the ceramic is about-71 ppm/DEG C, which is not beneficial to the stable use of the substrate at different working temperatures; meanwhile, in order to reduce signal attenuation, znGa needs to be lifted 2 O 4 Quality factor of ceramic.
It has been found that in ZnGa 2 O 4 Mn in place of Zn in tetrahedral positions of (2) can be used for temperature-dependent resonance frequencyThe number is adjusted to about-12 ppm/. Degree.C, the quality factor is adjusted to about 181000GHz, and the resonant frequency temperature coefficient is still negative although the performance is excellent; has been reported by scholars to be in ZnGa 2 O 4 The temperature coefficient of the resonant frequency can be adjusted towards the positive direction by replacing Ga with Sc, and the quality factor is improved.
Although ZnGa can be compounded in two phases 2 O 4 The temperature coefficient of the resonance frequency of the ceramic is adjusted to a positive value, but the other phases introduced may damage the ionic order of the octahedral sites in the spinel structure, resulting in a sharp deterioration of the quality factor.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a microwave dielectric ceramic material with excellent performance, which can achieve the effects that the dielectric constant is 9.5-10.5, the quality factor is 130000GHz, the temperature coefficient of resonance frequency is +/-10 ppm/DEG C, and the thermal shock resistance temperature difference exceeds 160 ℃.
The second purpose of the invention is to provide a preparation method of the microwave dielectric ceramic material, which has simple and efficient process and high success rate.
The invention further aims to provide an application of the microwave dielectric ceramic material, which can effectively improve the working performance of the microwave substrate.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, a microwave dielectric ceramic material comprises a main material and a modifier;
the main material comprises ZnGa 2 O 4 ；
The modifier comprises MnCO 3 And In 2 O 3 Is a composition of (a).
Further, the microwave dielectric ceramic material has the following general formula:
Zn 1-x Mn x Ga 2-y In y O 4 ；
preferably, the value range of x is 0.03-0.06;
preferably, y has a value in the range of 0.025 to 0.045.
Further, the dielectric constant of the microwave dielectric ceramic material is 9.5-10.5;
preferably, the quality factor of the microwave dielectric ceramic material is above 130000 GHz;
preferably, the resonant frequency temperature coefficient of the microwave dielectric ceramic material is-10 ppm/DEG C;
preferably, the thermal shock resistance temperature difference of the microwave dielectric ceramic material exceeds 160 ℃.
In a second aspect, a method for preparing a microwave dielectric ceramic material according to any one of the preceding claims, comprising the steps of:
ZnO、Ga 2 O 3 、MnCO 3 in 2 O 3 And mixing in proportion, grinding, presintering, granulating, forming, discharging glue and sintering to obtain the microwave dielectric ceramic material.
Further, the preparation method of the microwave dielectric ceramic material comprises the following steps:
(a)ZnO、Ga 2 O 3 、MnCO 3 in 2 O 3 Mixing in proportion to obtain a mixture, and carrying out first grinding to obtain first powder;
(b) The first powder in the step (a) is subjected to first drying and first sieving, and presintering is carried out to obtain presintered powder;
(c) The presintered powder in the step (b) is subjected to second grinding to obtain second powder;
(d) The second powder in the step (c) is subjected to second drying and granulation to obtain granulated powder, and then is subjected to second sieving and molding to obtain a blank;
(e) And (d) performing glue discharging and sintering on the blank body in the step (d) to obtain the microwave dielectric ceramic material.
Further, the first grinding and the second grinding each independently comprise ball milling;
preferably, the ball milling comprises wet ball milling;
preferably, the wet ball milling medium comprises water;
preferably, the ball milling time is 5-7 h, and the rotating speed is 300-350 rpm.
Further, the temperature of the first drying and the second drying are respectively 120-150 ℃;
preferably, the time of the first drying and the second drying is 3-5 h independently;
preferably, the first screen is a 60 mesh screen;
preferably, the second screen is a 100 mesh screen.
Further, the presintering temperature is 1000-1050 ℃, and the presintering time is 2-3 h;
preferably, the temperature rising rate of the presintering is 3 ℃/min;
preferably, the granulated binder comprises at least one of a polyvinyl alcohol solution and paraffin wax;
preferably, the addition amount of the binder is 8-10wt%;
preferably, the polyvinyl alcohol solution comprises 8wt% polyvinyl alcohol solution;
preferably, the method of forming comprises dry press forming;
preferably, the pressure of the dry press molding is 90-110 Mpa.
Further, the temperature of the glue discharging is 550-600 ℃, and the time of the glue discharging is 1.5-2 hours;
preferably, the sintering temperature is 1350-1420 ℃, and the sintering time is 3-4 hours;
preferably, the temperature rise rate of the sintering process is 3 ℃/min.
In a third aspect, a microwave dielectric ceramic material according to any preceding claim for use in a microwave substrate.
Compared with the prior art, the invention has at least the following beneficial effects:
the microwave dielectric ceramic material provided by the invention adopts MnCO 3 And In 2 O 3 The composition of (2) is used as a modifier, the temperature coefficient of the resonant frequency can be adjusted to the positive direction without introducing other temperature compensation materials, the temperature coefficient of the resonant frequency can be adjusted in an ion substitution mode, and the temperature coefficient of the resonant frequency is changedThe quality factor is regulated and controlled by changing the short-range order of octahedral Ga cations, thereby realizing the preparation of ZnGa 2 O 4 The effective adjustment of the temperature coefficient of the resonance frequency and the quality factor of the ceramic material achieves the technical effects that the ceramic material has high quality factor, near-zero temperature coefficient of the resonance frequency and excellent thermal shock resistance, in particular, mn replaces the main material ZnGa 2 O 4 On the premise of Zn tetrahedron position, selecting ion radius, ion polarization rate and Sc 3+ Ion-approximated In 3+ Ions are used for partially replacing the main material ZnGa 2 O 4 By utilizing In at the octahedral Ga site 3+ Partially substituting Ga 3+ To increase the short-range order of cations in the spinel structure and thus the quality factor.
The preparation method of the microwave dielectric ceramic material provided by the invention has the advantages of simple and efficient process and high success rate.
The application of the microwave dielectric ceramic material provided by the invention can effectively improve the working performance of the microwave substrate.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to a first aspect of the present invention, there is provided a microwave dielectric ceramic material comprising a main material and a modifier;
wherein the main material comprises ZnGa 2 O 4 The modifier comprises MnCO 3 And In 2 O 3 Is a composition of (a).
The microwave dielectric ceramic material provided by the invention adopts MnCO 3 And In 2 O 3 The composition of (2) is used as a modifier, the temperature coefficient of the resonant frequency can be adjusted to the positive direction without introducing other temperature compensation materials, the temperature coefficient of the resonant frequency can be adjusted in an ion substitution mode, and the temperature coefficient of the resonant frequency is changedThe quality factor is regulated and controlled by changing the short-range order of octahedral Ga cations, thereby realizing the preparation of ZnGa 2 O 4 The effective adjustment of the temperature coefficient of the resonance frequency and the quality factor of the ceramic material achieves the technical effects that the ceramic material has high quality factor, near-zero temperature coefficient of the resonance frequency and excellent thermal shock resistance, in particular, mn replaces the main material ZnGa 2 O 4 On the premise of Zn tetrahedron position, selecting ion radius, ion polarization rate and Sc 3+ Ion-approximated In 3+ Ions are used for partially replacing the main material ZnGa 2 O 4 By utilizing In at the octahedral Ga site 3+ Partially substituting Ga 3+ To increase the short-range order of cations in the spinel structure and thus the quality factor.
In a preferred embodiment, the microwave dielectric ceramic material of the present invention has the general formula:
Zn 1-x Mn x Ga 2-y In y O 4 ；
the value range of x may be 0.03 to 0.06, for example, 0.03, 0.04, 0.05, 0.06, but is not limited thereto; the value of y may be in the range of 0.025 to 0.045, for example, 0.025, 0.03, 0.035, 0.04, and 0.045, but is not limited thereto.
In the present invention, the chemical general formula of the nominal composition of the microwave dielectric ceramic material can be, for example, one of the following:
Zn 0.97 Mn 0.03 Ga 1.975 In 0.025 O 4 、Zn 0.96 Mn 0.04 Ga 1.97 In 0.03 O 4 、Zn 0.95 Mn 0.05 Ga 1.965 In 0.035 O 4 、Zn 0.95 Mn 0.05 Ga 1.96 In 0.04 O 4 、Zn 0.94 Mn 0.06 Ga 1.955 In 0.045 O 4 but is not limited thereto.
The value ranges of x and y in the general formula of the microwave dielectric ceramic are more favorable for improving the performance of the ceramic material, and the dielectric constant of the ceramic material is about 9.5-10.5, the quality factor is over 130000GHz, the temperature coefficient of the resonance frequency is between +/-10 ppm/DEG C, the thermal shock resistance temperature difference exceeds 160 ℃, and the thermal shock resistance is excellent; the value of x is lower than 0.03, which can lead to the temperature coefficient of the resonant frequency still being biased to be negative, or the value of x is higher than 0.06, which can lead to the temperature coefficient of the resonant frequency being excessively biased to be positive, and the quality factor being deteriorated; a value of y below 0.025 will result in a negative temperature coefficient of the resonant frequency, or a value of y above 0.045 will result in a positive temperature coefficient of the resonant frequency, and a deteriorated quality factor.
The dielectric constant of the microwave dielectric ceramic provided by the invention is close to 9.5-10.5, the quality factor exceeds 130000GHz, the temperature coefficient of the resonant frequency is within +/-10 ppm/DEG C, and meanwhile, the microwave dielectric ceramic has no cracking phenomenon under the temperature difference of 160-180 ℃, and has excellent thermal shock resistance.
According to a second aspect of the present invention, there is provided a method of preparing a microwave dielectric ceramic material according to any one of the preceding claims, comprising the steps of:
ZnO、Ga 2 O 3 、MnCO 3 in 2 O 3 Mixing according to a certain proportion, grinding, presintering, granulating, forming, discharging glue and sintering to obtain the microwave dielectric ceramic material.
The preparation method of the microwave dielectric ceramic material provided by the invention has the advantages of simple and efficient process and high success rate.
In a preferred embodiment, the method for preparing the microwave dielectric ceramic material of the present invention comprises the steps of:
(a)ZnO、Ga 2 O 3 、MnCO 3 in 2 O 3 Mixing in proportion to obtain a mixture, and carrying out first grinding to obtain first powder;
(b) The first powder in the step (a) is subjected to first drying and first sieving, and presintering is carried out to obtain presintered powder;
(c) The presintered powder in the step (b) is subjected to second grinding to obtain second powder;
(d) The second powder in the step (c) is subjected to second drying and granulation to obtain granulated powder, and then is subjected to second sieving and molding to obtain a blank;
(e) And (d) performing glue discharging and sintering on the blank body in the step (d) to obtain the microwave dielectric ceramic material.
The preparation method of the microwave dielectric ceramic material provided by the invention has the advantages of simple and efficient process and high product quality.
In the present invention, the first grinding and the second grinding each independently include, but are not limited to, grinding by a ball milling method, wherein the ball milling method includes, but is not limited to, wet ball milling, and is more favorable for fully grinding each raw material, is favorable for subsequent preparation steps, and ensures the performance of the ceramic material, and the medium utilized in the wet ball milling method includes, but is not limited to, water.
In a preferred embodiment, the duration of the wet ball milling may be 5 to 7 hours, for example, may be 5 hours, 6 hours, 7 hours, but is not limited thereto; the rotation speed of wet ball milling can be 300-350 rpm, such as 300rpm, 310rpm, 320rpm, 330rpm, 340rpm and 350rpm, but is not limited to this, and the milling can be conducted every 30min, which is more favorable for the full milling of raw materials.
The grinding step and the technological parameters of the invention are more favorable for fully grinding the raw materials, and ensure the smooth proceeding of the subsequent preparation step and the comprehensive performance of the ceramic material.
In a preferred embodiment, the temperature of the first drying and the second drying in the present invention may be 120 to 150 ℃ independently, for example, 120 ℃, 130 ℃, 140 ℃, 150 ℃, but not limited thereto; the time of the first drying and the second drying may be 3 to 5 hours, for example, 3 hours, 4 hours, 5 hours, independently, but not limited thereto.
The drying temperature and the drying time in the invention are more favorable for fully drying the raw material powder, are favorable for the subsequent preparation process and ensure the performance of the ceramic material.
In a preferred embodiment, the first screen of the invention can be used for screening by a 60-mesh screen, and the second screen can be used for screening by a 100-mesh screen, which is more beneficial to the successful preparation of the ceramic material in the subsequent step and is beneficial to further improving the comprehensive performance of the ceramic material.
In a preferred embodiment, the temperature of the burn-in of the present invention may be 1000 to 1050 ℃, for example, 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃, but not limited thereto; the presintering time can be 2-3 h, for example, 2h, 2.5h and 3h, but is not limited to the above; the temperature rising rate of the burn-in may be 3 deg.c/min, but is not limited thereto.
The presintering temperature, the presintering time and the presintering heating rate are more favorable for fully presintering the raw material powder, so as to ensure the successful preparation of the ceramic material in the subsequent step and further improve the comprehensive performance of the ceramic material.
In a preferred embodiment, the binder used for granulation in the present invention includes, but is not limited to, at least one of a polyvinyl alcohol solution and paraffin wax, and the binder may be added in an amount of 8 to 10wt%, for example, 8wt%, 9wt%, 10wt%, but is not limited thereto, wherein the polyvinyl alcohol solution may be an 8wt% polyvinyl alcohol solution, which is more advantageous in improving the granulation effect and quality.
In a preferred embodiment, the molding method of the present invention includes, but is not limited to, dry press molding, wherein the pressure of the dry press molding may be 90-110 Mpa, for example, 90Mpa, 95Mpa, 100Mpa, 105Mpa, 110Mpa, which is more advantageous for improving the molding effect and quality.
In a preferred embodiment, the temperature of the adhesive discharge in the present invention may be 550 to 600 ℃, for example, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, but not limited thereto; the time for discharging the glue may be 1.5 to 2 hours, for example, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, but is not limited thereto.
The glue discharging temperature and the time of the invention are more favorable for fully discharging glue so as to ensure the comprehensive performance of the ceramic material.
In a preferred embodiment, the sintering temperature in the present invention may be 1350 to 1420 ℃, for example, 1350 ℃, 1360 ℃, 1370 ℃, 1380 ℃, 1390 ℃, 1400 ℃, 1410, 1420 ℃, but not limited thereto; the sintering time may be 3 to 4 hours, for example, 3 hours, 3.5 hours, 4 hours, but is not limited thereto; the temperature rising rate in the sintering process can be 3 ℃/min.
The sintering temperature, time and the temperature rising rate of sintering in the invention are more favorable for full sintering, thereby obtaining ceramic materials with excellent performance.
A typical preparation method of a microwave dielectric ceramic material comprises the following steps:
(1) In chemically pure ZnO, ga 2 O 3 And analytically pure MnCO 3 、In 2 O 3 As raw material, according to nominal molecular formula Zn 1- x Mn x Ga 2-y In y O 4 Weighing and mixing the raw materials, and then performing first ball milling (wet ball milling) by taking deionized water as a medium to obtain first powder;
wherein the ball milling time is 5-7 h, the rotating speed is 300-350 rpm, and the reversing is carried out once every 30 min;
wherein x is more than or equal to 0.03 and less than or equal to 0.06,0.025, and y is more than or equal to 0.045;
(2) Baking the first powder in the step (1) at 120-150 ℃ for 3-5 hours, grinding, sieving with a 60-mesh sieve, and presintering to obtain presintered powder;
wherein, presintering is to heat up to 1000-1050 ℃ at 3 ℃/min, and preserving heat for 2-3 h;
(3) Performing secondary ball milling (wet ball milling) on the presintered powder in the step (2) to obtain second powder;
wherein the ball milling time is 5-7 h, the rotating speed is 300-350 rpm, and the reversing is carried out once every 30 min;
(4) Drying the second powder in the step (3) at 120-150 ℃ for 3-5 hours, grinding and granulating, wherein the added binder is 8wt% polyvinyl alcohol solution or paraffin accounting for 8-10 wt% of the powder mass, obtaining granulated powder, sieving with a 100-mesh sieve, and then dry-pressing under 90-110 Mpa to obtain a blank;
(5) And (3) preserving heat for 1.5-2 hours at the temperature of 550-600 ℃ for glue discharging, then continuously heating to 1350-1420 ℃ for preserving heat for 3-4 hours for sintering, wherein the heating rate in the sintering process is 3 ℃/min, and then naturally cooling to room temperature to obtain the microwave dielectric ceramic material.
The preparation method of the microwave dielectric ceramic material provided by the invention has the advantages of simple and efficient process, high success rate and excellent rate of products, the dielectric constant of the obtained microwave dielectric ceramic material is close to 10, the quality factor exceeds 130000GHz, the temperature coefficient of the resonant frequency is within +/-10 ppm/DEG C, and the microwave dielectric ceramic material cannot crack under the temperature difference of 160-180 ℃, and has excellent thermal shock resistance.
According to a third aspect of the present invention there is provided the use of a microwave dielectric ceramic material as defined in any one of the preceding claims in a microwave substrate.
The application of the microwave dielectric ceramic material provided by the invention can effectively improve the working performance of the microwave substrate.
The invention is further illustrated by the following examples. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
Example 1
A microwave dielectric ceramic material with nominal component chemical formula of Zn 0.97 Mn 0.03 Ga 1.975 In 0.025 O 4 The preparation method comprises the following steps:
(1) In chemically pure ZnO, ga 2 O 3 And analytically pure MnCO 3 、In 2 O 3 As raw material, according to nominal component chemical formula Zn 0.97 Mn 0.03 Ga 1.975 In 0.025 O 4 Weighing raw materials according to the molar ratio of medium cations, mixing the raw materials, and performing ball milling (wet ball milling) for the first time by taking deionized water as a medium to obtain first powder;
wherein, the ball milling time is 5 hours, the rotating speed is 300rpm, and the reversing is carried out once every 30 minutes;
(2) Baking the first powder in the step (1) for 4 hours at the temperature of 120 ℃, grinding, sieving with a 60-mesh sieve, and presintering to obtain presintered powder;
wherein, presintering is to heat up to 1000 ℃ at 3 ℃/min, and preserving heat for 3 hours;
(3) Performing secondary ball milling (wet ball milling) on the presintered powder in the step (2) to obtain second powder;
wherein, the ball milling time is 5 hours, the rotating speed is 300rpm, and the reversing is carried out once every 30 minutes;
(4) Drying the second powder in the step (3) at 150 ℃ for 4 hours, grinding and granulating, wherein the added binder is 8wt% polyvinyl alcohol solution accounting for 10wt% of the powder to obtain granulated powder, sieving with a 100-mesh sieve, and drying and pressing under 110Mpa to obtain a blank;
(5) And (3) preserving heat for 1.5h at 550 ℃ for discharging glue, and then continuously heating to 1350 ℃ for preserving heat for 3h for sintering, wherein the heating rate in the sintering process is 3 ℃/min, and then naturally cooling to room temperature to obtain the microwave dielectric ceramic material.
Example 2
A microwave dielectric ceramic material with nominal component chemical formula of Zn 0.96 Mn 0.04 Ga 1.97 In 0.03 O 4 The preparation method comprises the following steps:
(1) In chemically pure ZnO, ga 2 O 3 And analytically pure MnCO 3 、In 2 O 3 As raw material, according to nominal component chemical formula Zn 0.96 Mn 0.04 Ga 1.97 In 0.03 O 4 Weighing raw materials according to the molar ratio of medium cations, mixing the raw materials, and performing ball milling (wet ball milling) for the first time by taking deionized water as a medium to obtain first powder;
wherein, the ball milling time is 6 hours, the rotating speed is 320rpm, and the reversing is carried out once every 30 min;
(2) Baking the first powder in the step (1) for 4 hours at the temperature of 150 ℃, grinding, sieving with a 60-mesh sieve, and presintering to obtain presintered powder;
wherein, presintering is to heat up to 1020 ℃ at a speed of 3 ℃/min, and preserving heat for 3h;
(3) Performing secondary ball milling (wet ball milling) on the presintered powder in the step (2) to obtain second powder;
wherein, the ball milling time is 6 hours, the rotating speed is 320rpm, and the reversing is carried out once every 30 min;
(4) Drying the second powder in the step (3) at 150 ℃ for 4 hours, grinding and granulating, wherein the added binder is 8wt% polyvinyl alcohol solution accounting for 10wt% of the powder mass to obtain granulated powder, sieving with a 100-mesh sieve, and drying and pressing under 100Mpa to obtain a blank;
(5) And (3) preserving heat for 1.5h at 570 ℃ for glue discharging, and then continuously heating to 1370 ℃ for 3h for sintering, wherein the heating rate in the sintering process is 3 ℃/min, and then naturally cooling to room temperature to obtain the microwave dielectric ceramic material.
Example 3
A microwave dielectric ceramic material with nominal component chemical formula of Zn 0.95 Mn 0.05 Ga 1.965 In 0.035 O 4 The preparation method comprises the following steps:
(1) In chemically pure ZnO, ga 2 O 3 And analytically pure MnCO 3 、In 2 O 3 As raw material, according to nominal component chemical formula Zn 0.95 Mn 0.05 Ga 1.965 In 0.035 O 4 Weighing raw materials according to the molar ratio of the medium cations, mixing the raw materials, and performing ball milling (wet ball milling) for the first time by taking deionized water as a medium to obtain first powder;
wherein, the ball milling time is 5 hours, the rotating speed is 350rpm, and the reversing is carried out once every 30 minutes;
(2) Baking the first powder in the step (1) for 4 hours at the temperature of 150 ℃, grinding, sieving with a 60-mesh sieve, and presintering to obtain presintered powder;
wherein, presintering is to heat up to 1030 ℃ at 3 ℃/min, and preserving heat for 2.5h;
(3) Performing secondary ball milling (wet ball milling) on the presintered powder in the step (2) to obtain second powder;
wherein, the ball milling time is 5 hours, the rotating speed is 350rpm, and the reversing is carried out once every 30 minutes;
(4) Drying the second powder in the step (3) at 130 ℃ for 4 hours, grinding and granulating, wherein the added binder is 8wt% polyvinyl alcohol solution accounting for 9wt% of the powder mass, obtaining granulated powder, sieving with a 100-mesh sieve, and performing dry pressing molding under 100Mpa to obtain a blank;
(5) And (3) preserving heat for 2 hours at 600 ℃ for discharging glue, and then continuously heating to 1400 ℃ for preserving heat for 3.5 hours for sintering, wherein the heating rate in the sintering process is 3 ℃/min, and then naturally cooling to room temperature to obtain the microwave dielectric ceramic material.
Example 4
A microwave dielectric ceramic material with nominal component chemical formula of Zn 0.95 Mn 0.05 Ga 1.96 In 0.04 O 4 The preparation method comprises the following steps:
(1) In chemically pure ZnO, ga 2 O 3 And analytically pure MnCO 3 、In 2 O 3 As raw material, according to nominal component chemical formula Zn 0.95 Mn 0.05 Ga 1.96 In 0.04 O 4 Weighing raw materials according to the molar ratio of the medium cations, mixing the raw materials, and performing ball milling (wet ball milling) for the first time by taking deionized water as a medium to obtain first powder;
wherein, the ball milling time is 7 hours, the rotating speed is 350rpm, and the reversing is carried out once every 30 min;
(2) Baking the first powder in the step (1) for 4 hours at the temperature of 140 ℃, grinding, sieving with a 60-mesh sieve, and presintering to obtain presintered powder;
wherein, presintering is to heat up to 1050 ℃ at a speed of 3 ℃/min, and preserving heat for 2h;
(3) Performing secondary ball milling (wet ball milling) on the presintered powder in the step (2) to obtain second powder;
wherein, the ball milling time is 7 hours, the rotating speed is 350rpm, and the reversing is carried out once every 30 min;
(4) Drying the second powder in the step (3) at 130 ℃ for 4 hours, grinding and granulating, wherein the added binder is 8wt% polyvinyl alcohol solution accounting for 9wt% of the powder mass, obtaining granulated powder, sieving with a 100-mesh sieve, and drying and pressing under 110Mpa to obtain a blank;
(5) And (3) preserving heat for 2 hours at 600 ℃ for discharging glue, then continuously heating to 1400 ℃ for preserving heat for 4 hours for sintering, wherein the heating rate in the sintering process is 3 ℃/min, and then naturally cooling to room temperature to obtain the microwave dielectric ceramic material.
Example 5
Microwave dielectric ceramicPorcelain material with nominal component chemical formula of Zn 0.94 Mn 0.06 Ga 1.955 In 0.045 O 4 The preparation method comprises the following steps:
(1) In chemically pure ZnO, ga 2 O 3 And analytically pure MnCO 3 、In 2 O 3 As raw material, according to nominal component chemical formula Zn 0.94 Mn 0.06 Ga 1.955 In 0.045 O 4 Weighing raw materials according to the molar ratio of the medium cations, mixing the raw materials, and performing ball milling (wet ball milling) for the first time by taking deionized water as a medium to obtain first powder;
wherein, the ball milling time is 6 hours, the rotating speed is 350rpm, and the reversing is carried out once every 30 min;
(2) Baking the first powder in the step (1) for 4 hours at the temperature of 140 ℃, grinding, sieving with a 60-mesh sieve, and presintering to obtain presintered powder;
wherein, presintering is to heat up to 1050 ℃ at a speed of 3 ℃/min, and preserving heat for 2h;
(3) Performing secondary ball milling (wet ball milling) on the presintered powder in the step (2) to obtain second powder;
wherein, the ball milling time is 6 hours, the rotating speed is 350rpm, and the reversing is carried out once every 30 min; the method comprises the steps of carrying out a first treatment on the surface of the
(4) Drying the second powder in the step (3) at 130 ℃ for 4 hours, grinding and granulating, wherein the added binder is 8wt% polyvinyl alcohol solution accounting for 9wt% of the powder mass, obtaining granulated powder, sieving with a 100-mesh sieve, and drying and pressing under 110Mpa to obtain a blank;
(5) And (3) preserving heat for 2 hours at the temperature of 580 ℃ for discharging glue, and then continuously heating to 1420 ℃ for preserving heat for 3 hours for sintering, wherein the heating rate in the sintering process is 3 ℃/min, and then naturally cooling to room temperature to obtain the microwave dielectric ceramic material.
Example 6
The difference between this example and example 1 is that the nominal composition chemical formula of the microwave dielectric ceramic material in this example is Zn 0.98 Mn 0.02 Ga 1.975 In 0.025 O 4 The preparation method is the same as in example 1 to obtain a microA wave dielectric ceramic material.
Example 7
The difference between this example and example 1 is that the nominal composition chemical formula of the microwave dielectric ceramic material in this example is Zn 0.93 Mn 0.07 Ga 1.975 In 0.025 O 4 The preparation method is the same as in example 1, and a microwave dielectric ceramic material is obtained.
Example 8
The difference between this example and example 1 is that the nominal composition chemical formula of the microwave dielectric ceramic material in this example is Zn 0.97 Mn 0.03 Ga 1.98 In 0.02 O 4 The preparation method is the same as in example 1, and a microwave dielectric ceramic material is obtained.
Example 9
The difference between this example and example 1 is that the nominal composition chemical formula of the microwave dielectric ceramic material in this example is Zn 0.97 Mn 0.03 Ga 1.95 In 0.05 O 4 The preparation method is the same as in example 1, and a microwave dielectric ceramic material is obtained.
Comparative example 1
The difference between this comparative example and example 1 is that the raw material of this comparative example does not contain modifier MnCO 3 And In 2 O 3 The other raw materials are the same as in example 1, and the preparation method is the same as in example 1, so as to obtain the microwave dielectric ceramic material.
Comparative example 2
The difference between this comparative example and example 1 is that the raw material of this comparative example does not contain modifier MnCO 3 The other raw materials are the same as in example 1, and the preparation method is the same as in example 1, so as to obtain the microwave dielectric ceramic material.
Comparative example 3
The difference between this comparative example and example 1 is that the raw material of this comparative example does not contain modifier In 2 O 3 The other raw materials are the same as in example 1, and the preparation method is the same as in example 1, so as to obtain the microwave dielectric ceramic material.
Test example 1
The properties and test results of the microwave dielectric ceramic materials of examples 1 to 9 and comparative examples 1 to 3 are shown in Table 1.
The test method of dielectric constant/quality factor/resonant frequency temperature coefficient comprises the following steps:
the pelleting powder generated in the case is sintered into a sample with the diameter of 12.9mm and the height of 6.3mm by dry pressing, and the electrical properties such as dielectric constant, quality factor, resonant frequency temperature coefficient and the like of the product are tested by adopting a microwave resonant cavity method;
the method for testing the thermal shock temperature difference comprises the following steps:
the test of thermal shock is carried out by adopting a sample of 3mm x 4mm x 36mm sintered by dry pressing of the granulated powder, and the test of thermal shock is carried out by adopting a single thermal shock method by adopting a water quenching method (the thermal shock temperature delta T=the highest non-cracking temperature of the medium-water temperature).
TABLE 1
As can be seen from Table 1, the ZnGa according to the present invention 2 O 4 The modified microwave dielectric ceramic material has excellent performance, dielectric constant of about 9.5-10.5, quality factor value exceeding 130000GHz, resonant frequency temperature coefficient within +/-10 ppm/DEG C, thermal shock temperature difference of 160-180 ℃ and excellent thermal shock resistance. The microwave dielectric ceramic material provided by the invention has a small temperature coefficient of resonance frequency, is spinel type low-dielectric-constant microwave dielectric ceramic with excellent comprehensive performance, has a large application potential, is suitable for being applied to a microwave substrate, and can effectively improve the working performance of the microwave substrate.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (17)
1. A microwave dielectric ceramic material characterized by having the general formula:
Zn 1-x Mn x Ga 2-y In y O 4 ；
the value range of x is 0.03-0.06;
the value range of y is 0.025-0.045.
2. The microwave dielectric ceramic material according to claim 1, wherein the dielectric constant of the microwave dielectric ceramic material is 9.5 to 10.5;
the quality factor of the microwave dielectric ceramic material is above 130000 GHz;
the temperature coefficient of the resonant frequency of the microwave dielectric ceramic material is-10 ppm/DEG C;
the thermal shock resistance temperature difference of the microwave dielectric ceramic material exceeds 160 ℃.
3. A method for preparing the microwave dielectric ceramic material according to claim 1 or 2, comprising the following steps:
ZnO、Ga 2 O 3 、MnCO 3 in 2 O 3 And mixing in proportion, grinding, presintering, granulating, forming, discharging glue and sintering to obtain the microwave dielectric ceramic material.
4. A method of preparing a microwave dielectric ceramic material according to claim 3, comprising the steps of:
(a)ZnO、Ga 2 O 3 、MnCO 3 in 2 O 3 Mixing in proportion to obtain a mixture, and carrying out first grinding to obtain first powder;
(b) The first powder in the step (a) is subjected to first drying and first sieving, and presintering is carried out to obtain presintered powder;
(c) The presintered powder in the step (b) is subjected to second grinding to obtain second powder;
(d) The second powder in the step (c) is subjected to second drying and granulation to obtain granulated powder, and then is subjected to second sieving and molding to obtain a blank;
(e) And (d) performing glue discharging and sintering on the blank body in the step (d) to obtain the microwave dielectric ceramic material.
5. The method of preparing according to claim 4, wherein the first grinding and the second grinding each independently comprise ball milling;
the ball milling comprises wet ball milling.
6. The method of claim 5, wherein the wet ball milling medium comprises water.
7. The method according to claim 5, wherein the ball milling is performed for 5 to 7 hours at a rotational speed of 300 to 350rpm.
8. The method according to claim 4, wherein the first drying and the second drying are each independently carried out at a temperature of 120 to 150 ℃.
9. The method of claim 8, wherein the first drying and the second drying are each independently performed for a period of 3 to 5 hours.
10. The method of claim 4, wherein the first sieving is a 60 mesh sieve;
the second sieving is a 100-mesh sieving.
11. The method according to claim 4, wherein the pre-firing temperature is 1000 to 1050 ℃ and the pre-firing time is 2 to 3 hours.
12. The method of claim 11, wherein the pre-firing is at a ramp rate of 3 ℃/min.
13. The method of claim 4, wherein the granulated binder comprises at least one of a polyvinyl alcohol solution and paraffin wax;
the addition amount of the binder is 8-10wt%;
the polyvinyl alcohol solution comprises 8wt% polyvinyl alcohol solution.
14. The method of claim 4, wherein the forming comprises dry press forming;
the pressure of the dry pressing molding is 90-110 Mpa.
15. The preparation method according to claim 4, wherein the temperature of the adhesive is 550-600 ℃ and the adhesive removing time is 1.5-2 h.
16. The method according to claim 4, wherein the sintering temperature is 1350-1420 ℃ and the sintering time is 3-4 hours;
the temperature rising rate in the sintering process is 3 ℃/min.
17. Use of a microwave dielectric ceramic material according to claim 1 or 2 in a microwave substrate.
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