CN110668795A - Microwave dielectric ceramic material, preparation method and application thereof, microwave dielectric ceramic body, preparation method and application thereof, and microwave device - Google Patents
Microwave dielectric ceramic material, preparation method and application thereof, microwave dielectric ceramic body, preparation method and application thereof, and microwave device Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 106
- 239000000919 ceramic Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 28
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims description 64
- 238000002156 mixing Methods 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 229910052681 coesite Inorganic materials 0.000 claims description 31
- 229910052906 cristobalite Inorganic materials 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 229910052682 stishovite Inorganic materials 0.000 claims description 31
- 229910052905 tridymite Inorganic materials 0.000 claims description 31
- 238000005245 sintering Methods 0.000 claims description 29
- 229910003080 TiO4 Inorganic materials 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 229910010252 TiO3 Inorganic materials 0.000 claims description 16
- 229910017676 MgTiO3 Inorganic materials 0.000 claims description 12
- 229910052634 enstatite Inorganic materials 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 229910002971 CaTiO3 Inorganic materials 0.000 claims description 10
- 229910052839 forsterite Inorganic materials 0.000 claims description 8
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The invention relates to the field of electronic ceramics, and provides a microwave dielectric ceramic material, a preparation method and application thereof, a microwave dielectric ceramic body, a preparation method and application thereof, and a microwave device. The microwave dielectric ceramic material is mainly prepared from a ceramic main material and optional additives: the ceramic main material comprises MgO, CaO and SiO in specific weight percentage2、Nd2O3、Sm2O3And TiO2(ii) a The additive comprises an oxide of R in a specific weight percentage, wherein R comprises at least one of Nb, Zn, Zr, Mn, Y, Ni, Cu, Mo or Al; wherein the sum of the weight percentages of the components is 100 percent. The dielectric constant of the microwave dielectric ceramic material is continuously adjustable between 15 and 30, f x Q at 25 ℃ is more than 45000, and the microwave dielectric ceramic material has good performanceGood temperature characteristic, nearly zero frequency temperature coefficient at minus 40 ℃, 25 ℃ and 110 ℃, and high temperature stability.
Description
Technical Field
The invention relates to the field of electronic ceramics, in particular to a microwave dielectric ceramic material, a preparation method and application thereof, a microwave dielectric ceramic body, a preparation method and application thereof and a microwave device.
Background
With the continuous development of modern communication technology, the requirements for miniaturization, integration and modularization of components are increasingly urgent, higher requirements are put on microwave dielectric materials, and microwave dielectric ceramics become one of the most active research fields of functional ceramics in recent years. The microwave refers to electromagnetic wave with frequency spectrum of 300 MHz-300 GHz, and modern communication technology utilizes the characteristics of wide microwave frequency range, high frequency, strong penetrability and the like, and can carry out large-capacity, high-quality and long-distance transmission.
Over the last three decades, the research on microwave dielectric ceramics has become mature, and many systems have been intensively studied and widely used. In general, the development trend of microwave dielectric ceramics is toward high dielectric constant, high dielectric constant and high quality factor, and low dielectric constant but ultra high quality factor. With the development of communication technology, the requirements for the use of dielectric filters and microwave antennas are higher and higher, and the requirements for microwave dielectric ceramics are more severe, and besides a proper dielectric constant (epsilonr), the requirements must also satisfy high quality factors (Q, Q is inversely proportional to the loss factor tan δ) and a frequency temperature coefficient close to zero. With the higher and higher working frequency of modern communication technology, the miniaturization of microwave devices does not need to rely on high dielectric constant, and the position of medium and low dielectric constant materials (epsilonr 15-30) with high quality factor is increasingly prominent and gradually becomes the focus of research. Among them, magnesium titanate (MgTiO)3) As a conventional microwave dielectric material, ceramic still has excellent microwave dielectric properties such as low dielectric constant and ultra-high quality factor in millimeter wave band, but has a disadvantage of poor temperature stability (τ f ═ 50ppm/° c).
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a microwave dielectric ceramic material which has low dielectric constant, reasonable f x Q value, good dielectric property and good temperature characteristic, the frequency temperature coefficient tau f is close to zero at minus 40 ℃, 25 ℃ and 110 ℃, and the temperature stability is high.
The second purpose of the invention is to provide a preparation method of the microwave dielectric ceramic material.
The third purpose of the invention is to provide an application of the microwave dielectric ceramic material.
It is a fourth object of the present invention to provide a microwave dielectric ceramic body.
The fifth purpose of the invention is to provide a preparation method of the microwave dielectric ceramic body.
The sixth purpose of the invention is to provide the application of the microwave dielectric ceramic body in the preparation of microwave devices.
A seventh object of the present invention is to provide a microwave device.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a microwave dielectric ceramic material, which is mainly prepared from a ceramic main material and an additive:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: 20-40% of MgO, 1-10% of CaO and SiO20-25% and not including 0, Nd2O30.5-15％、Sm2O30-15% and TiO230-65％；
The additive comprises the following components in percentage by weight of the microwave dielectric ceramic material: 0-5% of oxide of R, wherein R comprises at least one of Nb, Zn, Zr, Mn, Y, Ni, Cu, Mo or Al;
wherein the sum of the weight percentages of the components is 100 percent.
As a further preferred technical solution, the ceramic main material includes: 29-36% of MgO, 4-9% of CaO and SiO28-18％、Nd2O35-15％、Sm2O30-10% and TiO232-50％；
Or, the ceramic main material comprises: MgO 24-30%, CaO 4-9%, SiO20.5-9％、Nd2O35-15％、Sm2O30 to 10% andTiO250-65％。
as a further preferable technical scheme, the weight percentage of the oxide of R in the microwave dielectric ceramic material is 1-5%, preferably 1-4%;
preferably, the particle size of each component is 500nm or less.
In a second aspect, the invention provides a preparation method of the microwave dielectric ceramic material, which comprises the following steps: and mixing and dispersing the components, and calcining to obtain the microwave dielectric ceramic material.
As a more preferable means, MgO, CaO, SiO2、Nd2O3、TiO2Optionally Sm2O3And optionally an oxide of R, and then calcining;
or (a) mixing MgO and TiO2Calcining after mixing and dispersing to synthesize MgTiO3And/or Mg2TiO4(b) mixing MgO and SiO2Calcining and synthesizing Mg after mixing and dispersing2SiO4And optionally MgSiO3(c) mixing CaO and TiO2Calcining and synthesizing CaTiO after mixing and dispersing3(d) adding CaO and Nd2O3、TiO2And optionally Sm2O3Calcining and synthesizing Ca after mixing and dispersing(1-x-y)NdxSmyTiO3Wherein x is more than 0 and less than 1, y is more than or equal to 0 and less than 1, and 0 is more than 1-x-y and less than 1; (e) MgTiO is mixed3And/or Mg2TiO4、Mg2SiO4、CaTiO3、Ca(1-x-y)NdxSmyTiO3Additives and optionally MgSiO3Mixing and dispersing;
preferably, the mixing and dispersing comprises: firstly, ball milling and then sanding;
preferably, the calcination temperature in the step (a) is 920-;
preferably, the calcination temperature in the step (b) is 1190-1210 ℃, and the calcination time is 3-4 h;
preferably, the calcination temperature in the step (c) is 1160-1180 ℃, and the calcination time is 2-3 h;
preferably, the calcination temperature in step (d) is 1160-1180 ℃ and the calcination time is 2-3 h.
In a third aspect, the invention provides an application of the microwave dielectric ceramic material or the microwave dielectric ceramic material obtained by the preparation method in preparation of a microwave dielectric ceramic body.
In a fourth aspect, the present invention provides a microwave dielectric ceramic body prepared from the above microwave dielectric ceramic material or the microwave dielectric ceramic material obtained by the above preparation method.
In a fifth aspect, the present invention provides a method for preparing a microwave dielectric ceramic body, comprising: the microwave dielectric ceramic material or the microwave dielectric ceramic material obtained by the preparation method is subjected to granulation, molding and sintering in sequence to obtain a microwave dielectric ceramic body;
preferably, the sintering temperature is 1280-.
In a sixth aspect, the invention provides a use of the microwave dielectric ceramic body or the microwave dielectric ceramic body prepared by the method in the preparation of a microwave device;
preferably, the microwave device comprises a filter, a resonator or an antenna.
In a seventh aspect, the present invention provides a microwave device, comprising the above microwave dielectric ceramic body or the microwave dielectric ceramic body prepared by the above method;
preferably, the microwave device comprises a filter, a resonator or an antenna.
Compared with the prior art, the invention has the beneficial effects that:
the microwave dielectric ceramic material provided by the invention is a magnesium titanate system, and finally comprises MgTiO3And/or Mg2TiO4、Mg2SiO4Optionally MgSiO3、CaTiO3、Ca(1-x-y)NdxSmyTiO3And a ceramic material in which a plurality of stable compounds such as an oxide of R are mixedly dispersed, wherein: MgTiO 23And Mg2TiO4The temperature coefficient of frequency tau f is about-55 ppm/DEG C, fQ is about 120000, MgTiO3Has a dielectric constant of 17, Mg2TiO4Has a dielectric constant of 14; ca(1-x-y)NdxSmyTiO3The temperature coefficient of frequency tau f is 183 ppm/DEG C, f Q is about 15000, and the dielectric constant is about 100; tau f can be neutralized by adjusting the proportion of the two components, and is close to 0, f x Q is more than 50000, and the dielectric constant value is 22-30. Mg (magnesium)2SiO4The temperature coefficient of frequency tau f is-59 ppm/DEG C, f Q is about 160000, the dielectric constant is 7, and Mg is used2SiO4Substituted part of MgTiO3And/or Mg2TiO4Can continuously adjust the dielectric constant between 15 and 30 and adjust Ca simultaneously(1-x-y)NdxSmyTiO3The content of (c) can be adjusted to be about 0, f x Q is more than 45000; CaTiO3The temperature coefficient of frequency tau f is about 800 ppm/DEG C, and the fine adjustment of the ceramic material tau f can be realized.
The dielectric constant of the microwave dielectric ceramic material is continuously adjustable between 15 and 30, f x Q at 25 ℃ is larger than 45000, the microwave dielectric ceramic material has good temperature characteristic, the frequency temperature coefficient tau f at minus 40 ℃, 25 ℃ and 110 ℃ is close to zero, and the temperature stability is high.
In addition, when the content of the additive is not 0, the microwave performance of the ceramic material can be further adjusted, and meanwhile, the sintering temperature of the ceramic material during sintering into a ceramic (namely sintering into a microwave dielectric ceramic body) is effectively reduced, so that the ceramic material is easy to sinter, and the manufacturing cost is lower.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
According to one aspect of the invention, a microwave dielectric ceramic material is provided, which is mainly prepared from ceramic main materials and additives:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: 20-40% of MgO, 1-10% of CaO and SiO20-25% and not including 0, Nd2O30.5-15％、Sm2O30-15% and TiO230-65％；
The additive comprises the following components in percentage by weight of the microwave dielectric ceramic material: 0-5% of oxide of R, wherein R comprises at least one of Nb, Zn, Zr, Mn, Y, Ni, Cu, Mo or Al;
wherein the sum of the weight percentages of the components is 100 percent.
The microwave dielectric ceramic material is a magnesium titanate system, and finally MgTiO is formed3And/or Mg2TiO4、Mg2SiO4Optionally MgSiO3、CaTiO3、Ca(1-x-y)NdxSmyTiO3And a ceramic material in which a plurality of stable compounds such as an oxide of R are mixedly dispersed, wherein: MgTiO 23And Mg2TiO4The temperature coefficient of frequency tau f is about-55 ppm/DEG C, fQ is about 120000, MgTiO3Has a dielectric constant of 17, Mg2TiO4Has a dielectric constant of 14; ca(1-x-y)NdxSmyTiO3The temperature coefficient of frequency tau f is 183 ppm/DEG C, f Q is about 15000, and the dielectric constant is about 100; tau f can be neutralized by adjusting the proportion of the two components, and is close to 0, f x Q is more than 50000, and the dielectric constant value is 22-30. Mg (magnesium)2SiO4The temperature coefficient of frequency tau f is-59 ppm/DEG C, f Q is about 160000, the dielectric constant is 7, and Mg is used2SiO4Substituted part of MgTiO3And/or Mg2TiO4Can continuously adjust the dielectric constant between 15 and 30 and adjust Ca simultaneously(1-x-y)NdxSmyTiO3The content of (c) can be adjusted to be about 0, f x Q is more than 45000; CaTiO3The temperature coefficient of frequency tau f is about 800 ppm/DEG C, and the fine adjustment of the ceramic material tau f can be realized.
The dielectric constant of the microwave dielectric ceramic material is continuously adjustable between 15 and 30, f x Q at 25 ℃ is larger than 45000, the microwave dielectric ceramic material has good temperature characteristic, the frequency temperature coefficient tau f at minus 40 ℃, 25 ℃ and 110 ℃ is close to zero, and the temperature stability is high.
In addition, when the content of the additive is not 0, the microwave performance of the ceramic material can be further adjusted, and meanwhile, the sintering temperature of the ceramic material during sintering into a ceramic (namely sintering into a microwave dielectric ceramic body) is effectively reduced, so that the ceramic material is easy to sinter, and the manufacturing cost is lower.
In the invention, the weight percentages are as follows: the content of MgO is typically, but not limited to, 20%, 25%, 30%, 35% or 40%; the content of CaO is typically, but not limited to, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%; SiO 22Is typically, but not limited to, 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24% or 25%; nd (neodymium)2O3Is typically, but not limited to, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%; sm2O3Is typically, but not limited to, 0, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14% or 15%; TiO 22Is typically, but not limited to, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64% or 65%; the content of the oxide of R is typically, but not limited to, 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%.
Wherein, the oxide of R refers to a compound formed by the element R and the element oxygen. R includes, but is not limited to, Nb, Zn, Zr, Mn, Y, Ni, Cu, Mo, Al, a combination of Nb and Zn, a combination of Zr and Mn, a combination of Y and Ni, a combination of Cu and Al, a combination of Cu and Mo, a combination of Nb, Zn and Zr, a combination of Mn, Y and Ni, or a combination of Ni, Cu and Al, and the like. Accordingly, the oxide of R includes, but is not limited to, an oxide of Nb, an oxide of Zn, an oxide of Zr, an oxide of Mn, an oxide of Y, an oxide of Ni, an oxide of Cu, an oxide of Al, a combination of an oxide of Nb and an oxide of Zn, a combination of an oxide of Zr and an oxide of Mn, a combination of an oxide of Y and an oxide of Ni, a combination of an oxide of Cu and an oxide of Al, an oxide of Nb, an oxide of Zn and an oxide of Zr, a combination of an oxide of Mn, an oxide of Y and an oxide of Ni, or a combination of an oxide of Ni, an oxide of Cu and an oxide of Al, and the like.
In a preferred embodiment, the ceramic main material comprises: 29-36% of MgO, 4-9% of CaO and SiO28-18％、Nd2O35-15％、Sm2O30-10% and TiO232-50％；
Or, the ceramic main material comprises: MgO 24-30%, CaO 4-9%, SiO20.5-9％、Nd2O35-15％、Sm2O30-10% and TiO250-65％。
By further optimizing the weight percentage of each component in the ceramic main material, the proportion of each obtained compound can be further optimized, so that the temperature stability of the ceramic material is higher.
In a preferred embodiment, the oxide of R accounts for 1-5% by weight of the microwave dielectric ceramic material, and preferably 1-4% by weight of the microwave dielectric ceramic material. By optimizing the weight percentage of the oxide of R, the sintering temperature and the microwave performance of the ceramic material can be further adjusted by the additive, so that the sintering temperature is further reduced, and the microwave performance is further improved.
In a preferred embodiment, the particle size of each component is 500nm or less. The particle size of each component may be, for example, 500nm, 400nm, 350nm, 200nm, 50nm, 30nm, 10nm, or the like. When the particle size of each component is below 500nm, the sintering temperature of the ceramic material during sintering into ceramic can be reduced to about 1280 ℃.
Therefore, the microwave dielectric ceramic material not only has lower dielectric constant, proper f and Q and high temperature stability, but also has lower sintering temperature (1280 and 1370 ℃) when being sintered into porcelain, can be used for producing microwave devices, has low manufacturing cost, is easy to sinter when preparing ceramic bodies, and has high qualification rate.
Temperature coefficient of frequency τ f: the method has good temperature characteristics, and the resonance frequencies f of-40 ℃, 25 ℃ and 110 ℃ are respectively tested and calculated as follows:
[(f-40℃-f25℃)/f25℃]/(-65)*106(ppm/. degree. C.), denoted τ f (-40 ℃ C.);
[(f110℃-f25℃)/f25℃]/(85)*106(ppm/. degree. C.), denoted τ f (110 ℃ C.);
[(f110℃-f-40℃)/f25℃]/(150)*106(ppm/. degree. C.), mark τ f;
and (3) calculating the result: τ f (-40 ℃), τ f (110 ℃) and τ f are all within-5 to 5 ppm/DEG C.
According to another aspect of the present invention, there is provided a method for preparing the microwave dielectric ceramic material, comprising: and mixing and dispersing the components, and calcining to obtain the microwave dielectric ceramic material. The method is scientific and simple in process and suitable for industrial mass production, and the obtained microwave dielectric ceramic material has a low dielectric constant, a proper f x Q value and high temperature stability.
In a preferred embodiment, MgO, CaO, SiO2、Nd2O3、TiO2Optionally Sm2O3And optionally an oxide of R, and then calcining;
or (a) mixing MgO and TiO2Calcining after mixing and dispersing to synthesize MgTiO3And/or Mg2TiO4(b) mixing MgO and SiO2Calcining and synthesizing Mg after mixing and dispersing2SiO4And optionally MgSiO3(c) mixing CaO and TiO2Calcining and synthesizing CaTiO after mixing and dispersing3(d) adding CaO and Nd2O3、TiO2And optionally Sm2O3Calcining and synthesizing Ca after mixing and dispersing(1-x-y)NdxSmyTiO3Wherein x is more than 0 and less than 1, y is more than or equal to 0 and less than 1, and 0 is more than 1-x-y and less than 1; (e) MgTiO is mixed3And/or Mg2TiO4、Mg2SiO4、CaTiO3、Ca(1-x-y)NdxSmyTiO3Additives and optionally MgSiO3And (4) mixing and dispersing.
It is understood that MgO and TiO2MgTiO can be synthesized by mixing, dispersing and calcining3、Mg2TiO4Or MgTiO3And Mg2TiO4Thus step (e) means that MgTiO is added3、Mg2TiO4Or MgTiO3And Mg2TiO4With Mg2SiO4、CaTiO3、Ca(1-x-y)NdxSmyTiO3Additives and optionally MgSiO3And (4) mixing and dispersing.
In the preferred embodiment, two different ways of calcining the mixture of the raw materials are provided, all the raw materials can be directly mixed and dispersed and then calcined, or a part of the raw materials can be mixed and dispersed first and then calcined to synthesize the corresponding compounds, and then the compounds are mixed and dispersed. This embodiment offers more possibilities for the synthesis of ceramics.
In a preferred embodiment, the mixing and dispersing comprises: ball milling is carried out firstly, and then sanding is carried out. After ball milling and sand milling, the particle size of each component can be controlled below 500nm, thereby reducing the calcination temperature. The above-mentioned "mixed dispersion" means mixed dispersion between the respective components, for example, MgO, CaO, SiO2、Nd2O3、TiO2Optionally Sm2O3And optionally, mixed dispersion of oxides of R, MgO and TiO2Mixed dispersion of MgO and SiO2Mixed dispersion, CaO and TiO between2Mixing and dispersing of CaO and Nd2O3、TiO2And optionally Sm2O3Mixed dispersion of them, or MgTiO3And/or Mg2TiO4、Mg2SiO4、CaTiO3、Ca(1-x-y)NdxSmyTiO3Additives and optionally MgSiO3The mixing and dispersing between the two.
In a preferred embodiment, the calcination temperature in step (a) is 920-. The calcination temperature may be, for example, 920, 925, 930, 935 or 940 ℃; the calcination time may be, for example, 2, 2.5 or 3 hours.
Preferably, the calcination temperature in step (b) is 1190-1210 ℃, and the calcination time is 3-4 h. The calcination temperature may be, for example, 1190, 1195, 1200, 1205 or 1210 ℃; the calcination time may be, for example, 3, 3.5 or 4 hours.
Preferably, the calcination temperature in step (c) is 1160-1180 ℃ and the calcination time is 2-3 h. The calcination temperature may be 1160, 1165, 1170, 1175 or 1180 ℃, for example; the calcination time may be, for example, 2, 2.5 or 3 hours.
Preferably, the calcination temperature in step (d) is 1160-1180 ℃ and the calcination time is 2-3 h. The calcination temperature may be 1160, 1165, 1170, 1175 or 1180 ℃, for example; the calcination time may be, for example, 2, 2.5 or 3 hours.
The calcination temperature should not be too high or too low, too low the desired compound cannot be synthesized, too high the activity of the compound is reduced, and the sintering temperature of the material during sintering into porcelain is not reduced.
The number of the above calcination may be one or more.
According to another aspect of the present invention, there is provided a use of the above microwave dielectric ceramic material in the preparation of a microwave dielectric ceramic body. The microwave dielectric ceramic material is applied to the preparation of the microwave dielectric ceramic body, so that the sintering temperature of the microwave dielectric ceramic body can be effectively reduced, the preparation cost is reduced, and the good dielectric property of the microwave dielectric ceramic body is ensured.
According to another aspect of the present invention, there is provided a microwave dielectric ceramic body manufactured using the above microwave dielectric ceramic material. The microwave dielectric ceramic body is prepared from the microwave dielectric ceramic material, so that the microwave dielectric ceramic body has the advantages of dielectric property, low sintering temperature and low cost.
According to another aspect of the present invention, there is provided a method for preparing a microwave dielectric ceramic body, comprising: and (3) granulating, molding and sintering the microwave dielectric ceramic material in sequence to obtain the microwave dielectric ceramic body. The method has simple and reasonable process, and can prepare the microwave dielectric ceramic body with good dielectric property, lower sintering temperature and preparation cost.
Preferably, the sintering temperature is 1280-. The sintering temperature may be 1280, 1290, 1300, 1310, 1320, 1330, 1340, 1350, 1360, or 1370 ℃, for example. Compared with the traditional magnesium titanate system ceramic body, the sintering temperature is higher than 1450 ℃, the sintering temperature is lower, the required microwave dielectric ceramic body can be obtained at the sintering temperature, the energy is saved, and the preparation cost is lower.
The steps of granulating and shaping in the preparation process of the microwave dielectric ceramic body are not particularly limited as long as the desired ceramic body can be made. For example, spray granulation may be used for granulation.
According to another aspect of the present invention, there is provided a use of the above-described microwave dielectric ceramic body in the manufacture of a microwave device. The microwave dielectric ceramic body is applied to the preparation of microwave devices, and the microwave dielectric property and the temperature stability of the microwave devices can be effectively improved.
Preferably, the microwave device comprises a filter, a resonator or an antenna.
According to another aspect of the present invention, there is provided a microwave device comprising the microwave dielectric ceramic material described above. The microwave device comprises the microwave dielectric ceramic body, so that the microwave dielectric ceramic body has the advantages of good microwave dielectric property and high temperature stability.
Preferably, the microwave device comprises a filter, a resonator or an antenna.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
A microwave dielectric ceramic material is prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO 30%, CaO5.5%, SiO210％、Nd2O37.5% and TiO247％；
The particle size of each component was 550 nm.
Example 2
A microwave dielectric ceramic material is mainly prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO 33%, CaO4.5%, SiO210％、Nd2O35.5% and TiO247％；
The particle size of each component was 550 nm.
Example 3
A microwave dielectric ceramic material is prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO 28%, CaO5.5%, SiO24.8％、Nd2O36.7% and TiO255％；
The particle size of each component was 550 nm.
Example 4
A microwave dielectric ceramic material is prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO 25%, CaO4.8%, SiO23.2％、Nd2O36% and TiO261％；
The particle size of each component was 550 nm.
Example 5
A microwave dielectric ceramic material is prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO 24.5%, CaO4.7%, SiO23.1％、Nd2O35.9％、Sm2O31.8% and TiO260％；
The particle size of each component was 550 nm.
Unlike embodiment 4, the present embodiment further includes Sm2O3。
Example 6
A microwave dielectric ceramic material is prepared from ceramic main materials and additives:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO24.5%, CaO4.7%, SiO23.1％、Nd2O35.9％、Sm2O31.8% and TiO260％；
The additive comprises the following components in percentage by weight of the microwave dielectric ceramic material: 1% of ZnO;
the particle size of each component was 550 nm.
Unlike example 5, this example also included an additive ZnO.
Example 7
A microwave dielectric ceramic material is prepared from ceramic main materials and additives:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO24.5%, CaO4.7%, SiO23.1％、Nd2O35.9％、Sm2O31.8% and TiO260％；
The additive comprises the following components in percentage by weight of the microwave dielectric ceramic material: y is2O30.5% and ZnO0.5%;
the particle size of each component was 550 nm.
Unlike example 6, the present example was different in the kind and content of the additive.
Example 8
A microwave dielectric ceramic material is prepared from ceramic main materials and additives:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO24.5%, CaO4.7%, SiO23.1％、Nd2O35.9％、Sm2O31.8% and TiO260％；
The additive comprises the following components in percentage by weight of the microwave dielectric ceramic material: MoO30.5% and ZnO0.5%;
the particle size of each component was 550 nm.
Unlike example 6, the present example was different in the kind and content of the additive.
Examples 9 to 10
A microwave dielectric ceramic material is different from that in example 8 in that the particle sizes of the components in examples 9 to 10 are 500nm and 300nm respectively.
The particle size of the components of examples 9-10 are within the preferred range of the present invention.
The preparation method of the microwave dielectric ceramic material in the above embodiments comprises: the components were mixed and dispersed throughout, and then calcined at 1170 ℃.
Example 11
A microwave dielectric ceramic material, which is different from the embodiment 10, in the embodiment, the preparation method of the microwave dielectric ceramic material includes: (a) mixing MgO and TiO2Calcining after mixing and dispersing to synthesize MgTiO3And/or Mg2TiO4The calcination temperature is 930 ℃, and the calcination time is 2.5 h; (b) mixing MgO and SiO2Calcining and synthesizing Mg after mixing and dispersing2SiO4And optionally MgSiO3The calcination temperature is 1200 ℃, and the calcination time is 3.5 h; (c) mixing CaO and TiO2Calcining and synthesizing CaTiO after mixing and dispersing3The calcination temperature is 1170 ℃, and the calcination time is 2.5 h; (d) CaO, Nd2O3、TiO2And optionally Sm2O3Calcining and synthesizing Ca after mixing and dispersing(1-x-y)NdxSmyTiO3Wherein x is more than 0 and less than 1, y is more than or equal to 0 and less than 1, and 0 is more than 1-x-y and less than 1; the calcining temperature is 1170 ℃, and the calcining time is 2.5 h; (e) MgTiO is mixed3And/or Mg2TiO4、Mg2SiO4、CaTiO3、Ca(1-x-y)NdxSmyTiO3Additives and optionally MgSiO3And (4) mixing and dispersing.
This example uses the preferred method of the present invention to prepare ceramic materials.
Comparative example 1
A microwave dielectric ceramic material is prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: 19.5% of MgO, 4.8% of CaO8% of SiO23.2％、Nd2O36% and TiO266.5％；
The particle size of each component was 550 nm.
Unlike example 4, in this comparative example, MgO and TiO are used2In amounts not provided for by the present inventionWithin the range of (1). The preparation method is the same as that of example 1.
Comparative example 2
A microwave dielectric ceramic material is prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO 25%, CaO4.8%, SiO23.2% and TiO267％；
The particle size of each component was 550 nm.
Unlike example 4, this comparative example contained no Nd2O3And TiO is2The content of (a) is different from that of example 4. The preparation method is the same as that of example 1.
Comparative example 3
A microwave dielectric ceramic material is prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO 33%, SiO22% and TiO265％；
The particle size of each component was 550 nm.
Unlike example 4, this comparative example contained no CaO and Nd2O3And MgO and TiO2The content of (a) is different from that of example 4. The preparation method is the same as that of example 1.
Comparative example 4
A microwave dielectric ceramic material is prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: 19.5% of MgO, 4.8% of CaO8% of SiO23.2％、Nb2O56% and TiO266.5％；
The particle size of each component was 550 nm.
Unlike comparative example 1, in this comparative example Nd was used2O3Is replaced by Nb2O5. The preparation method was the same as in comparative example 1.
Comparative example 5
A microwave dielectric ceramic material is prepared from ceramic main materials:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: MgO 25%, CaO3.5%, SiO21.5％、Al2O313.5% and TiO256.5％。
The microwave dielectric ceramic materials in the above embodiments and the comparative examples are respectively made into microwave dielectric ceramic bodies, and the preparation method comprises the following steps: and (3) granulating, forming and sintering the microwave dielectric ceramic materials in sequence to obtain a microwave dielectric ceramic body, wherein the sintering temperature is 1300 ℃. The dielectric properties of each microwave dielectric ceramic body were then tested and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the comprehensive dielectric properties of the microwave dielectric ceramic body prepared by the embodiments are superior to those of each proportion, so that the microwave dielectric ceramic material provided by the invention is scientifically and reasonably matched and can effectively improve the dielectric properties of the microwave dielectric ceramic body.
Further analysis shows that the examples 1-4 are examples with different dielectric constants, data show that the dielectric constant of the material can be adjusted by adjusting the components, and other microwave properties all reach better levels; example 5 by addition of Sm2O3The negative temperature frequency temperature coefficient is improved; examples 6-8 can be adjusted properly by the addition of additives and examples 9-10 can be optimized for microwave performance by adjusting the dimensions of the material, mainly because the addition of additives and size optimization contribute to the sintering of the material; example 11 material properties were further optimized by process tuning.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. A microwave dielectric ceramic material is characterized by being mainly prepared from ceramic main materials and additives:
according to the weight percentage of each component in the microwave dielectric ceramic material, the ceramic main material comprises: 20-40% of MgO, 1-10% of CaO and SiO20-25% and not including 0, Nd2O30.5-15％、Sm2O30-15% and TiO230-65％；
The additive comprises the following components in percentage by weight of the microwave dielectric ceramic material: 0-5% of oxide of R, wherein R comprises at least one of Nb, Zn, Zr, Mn, Y, Ni, Cu, Mo or Al;
wherein the sum of the weight percentages of the components is 100 percent.
2. A microwave dielectric ceramic material as claimed in claim 1, wherein the ceramic main material comprises: 29-36% of MgO, 4-9% of CaO and SiO28-18％、Nd2O35-15％、Sm2O30-10% and TiO232-50％；
Or, the ceramic main material comprises: MgO 24-30%, CaO 4-9%, SiO20.5-9％、Nd2O35-15％、Sm2O30-10% and TiO250-65％。
3. A microwave dielectric ceramic material according to claim 1 or 2, wherein the oxide of R is 1-5%, preferably 1-4% by weight of the microwave dielectric ceramic material;
preferably, the particle size of each component is 500nm or less.
4. A process for the preparation of a microwave dielectric ceramic material according to any one of claims 1 to 3, comprising: and mixing and dispersing the components, and calcining to obtain the microwave dielectric ceramic material.
5. The method according to claim 4, wherein MgO, CaO, SiO2、Nd2O3、TiO2Optionally Sm2O3And optionally an oxide of R, and then calcining;
or (a) mixing MgO and TiO2Calcining after mixing and dispersing to synthesize MgTiO3And/or Mg2TiO4(b) mixing MgO and SiO2Calcining and synthesizing Mg after mixing and dispersing2SiO4And optionally MgSiO3(c) mixing CaO and TiO2Calcining and synthesizing CaTiO after mixing and dispersing3(d) adding CaO and Nd2O3、TiO2And optionally Sm2O3Calcining and synthesizing Ca after mixing and dispersing(1-x-y)NdxSmyTiO3Wherein x is more than 0 and less than 1, y is more than or equal to 0 and less than 1, and 0 is more than 1-x-y and less than 1; (e) MgTiO is mixed3And/or Mg2TiO4、Mg2SiO4、CaTiO3、Ca(1-x-y)NdxSmyTiO3Additives and optionally MgSiO3Mixing and dispersing;
preferably, the mixing and dispersing comprises: firstly, ball milling and then sanding;
preferably, the calcination temperature in the step (a) is 920-;
preferably, the calcination temperature in the step (b) is 1190-1210 ℃, and the calcination time is 3-4 h;
preferably, the calcination temperature in the step (c) is 1160-1180 ℃, and the calcination time is 2-3 h;
preferably, the calcination temperature in step (d) is 1160-1180 ℃ and the calcination time is 2-3 h.
6. Use of the microwave dielectric ceramic material according to any one of claims 1 to 3 or obtained by the preparation method according to claim 4 or 5 in the preparation of a microwave dielectric ceramic body.
7. A microwave dielectric ceramic body obtained by using the microwave dielectric ceramic material according to any one of claims 1 to 3 or the microwave dielectric ceramic material obtained by the production method according to claim 4 or 5.
8. A method for preparing a microwave dielectric ceramic body is characterized by comprising the following steps: sequentially granulating, molding and sintering the microwave dielectric ceramic material according to any one of claims 1 to 3 or the microwave dielectric ceramic material obtained by the preparation method according to claim 4 or 5 to obtain a microwave dielectric ceramic body;
preferably, the sintering temperature is 1280-.
9. Use of the microwave dielectric ceramic body according to claim 7 or the microwave dielectric ceramic body produced by the method according to claim 8 for producing a microwave device;
preferably, the microwave device comprises a filter, a resonator or an antenna.
10. A microwave device comprising the microwave dielectric ceramic body according to claim 7 or the microwave dielectric ceramic body produced by the method according to claim 8;
preferably, the microwave device comprises a filter, a resonator or an antenna.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111276778A (en) * | 2020-02-12 | 2020-06-12 | 广东国华新材料科技股份有限公司 | Medium resonant disk and medium filter |
| CN112759383A (en) * | 2021-02-18 | 2021-05-07 | 山东国瓷功能材料股份有限公司 | Microwave dielectric ceramic with medium dielectric constant and preparation method thereof |
| CN112919894A (en) * | 2021-03-10 | 2021-06-08 | 嘉兴佳利电子有限公司 | Frequency-stable low-dielectric microwave dielectric ceramic material and preparation method thereof |
| CN112939596A (en) * | 2021-04-06 | 2021-06-11 | 无锡市高宇晟新材料科技有限公司 | Microwave dielectric ceramic and preparation method thereof |
| CN113105231A (en) * | 2021-04-12 | 2021-07-13 | 无锡市高宇晟新材料科技有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN113336539A (en) * | 2021-07-01 | 2021-09-03 | 无锡市高宇晟新材料科技有限公司 | Microwave dielectric ceramic material, preparation method and application |
| CN113563061A (en) * | 2021-09-26 | 2021-10-29 | 广东康荣高科新材料股份有限公司 | Low dielectric constant dielectric material for single-cavity filter and preparation method thereof |
| CN116606142A (en) * | 2023-05-29 | 2023-08-18 | 绵阳市维奇电子技术有限公司 | A kind of microwave dielectric ceramic and its preparation method and application |
| TWI815177B (en) * | 2021-01-28 | 2023-09-11 | 大陸商山東國瓷功能材料股份有限公司 | A low-temperature co-fired ceramic material and slurry, green ceramic tape, microwave dielectric ceramic device and use for preparing microwave dielectric ceramic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111276778A (en) * | 2020-02-12 | 2020-06-12 | 广东国华新材料科技股份有限公司 | Medium resonant disk and medium filter |
| TWI815177B (en) * | 2021-01-28 | 2023-09-11 | 大陸商山東國瓷功能材料股份有限公司 | A low-temperature co-fired ceramic material and slurry, green ceramic tape, microwave dielectric ceramic device and use for preparing microwave dielectric ceramic device |
| CN112759383A (en) * | 2021-02-18 | 2021-05-07 | 山东国瓷功能材料股份有限公司 | Microwave dielectric ceramic with medium dielectric constant and preparation method thereof |
| CN112919894A (en) * | 2021-03-10 | 2021-06-08 | 嘉兴佳利电子有限公司 | Frequency-stable low-dielectric microwave dielectric ceramic material and preparation method thereof |
| CN112939596A (en) * | 2021-04-06 | 2021-06-11 | 无锡市高宇晟新材料科技有限公司 | Microwave dielectric ceramic and preparation method thereof |
| CN113105231A (en) * | 2021-04-12 | 2021-07-13 | 无锡市高宇晟新材料科技有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN113105231B (en) * | 2021-04-12 | 2023-01-13 | 无锡市高宇晟新材料科技有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN113336539A (en) * | 2021-07-01 | 2021-09-03 | 无锡市高宇晟新材料科技有限公司 | Microwave dielectric ceramic material, preparation method and application |
| CN113563061A (en) * | 2021-09-26 | 2021-10-29 | 广东康荣高科新材料股份有限公司 | Low dielectric constant dielectric material for single-cavity filter and preparation method thereof |
| CN113563061B (en) * | 2021-09-26 | 2021-12-21 | 广东康荣高科新材料股份有限公司 | Low dielectric constant dielectric material for single-cavity filter and preparation method thereof |
| CN116606142A (en) * | 2023-05-29 | 2023-08-18 | 绵阳市维奇电子技术有限公司 | A kind of microwave dielectric ceramic and its preparation method and application |
| CN116606142B (en) * | 2023-05-29 | 2024-11-19 | 绵阳市维奇电子技术有限公司 | A microwave dielectric ceramic and its preparation method and application |
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