CN115466109B - Calcium-boron-silicon LTCC ceramic material and preparation method thereof - Google Patents
Calcium-boron-silicon LTCC ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 104
- XCQWHUUYDVTFDE-UHFFFAOYSA-N [Si].[B].[Ca] Chemical compound [Si].[B].[Ca] XCQWHUUYDVTFDE-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 83
- 239000011521 glass Substances 0.000 claims abstract description 51
- 229910004762 CaSiO Inorganic materials 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 31
- 229910052796 boron Inorganic materials 0.000 claims abstract description 25
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 26
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- 238000002156 mixing Methods 0.000 claims description 17
- 235000015895 biscuits Nutrition 0.000 claims description 16
- 238000003825 pressing Methods 0.000 claims description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 11
- 230000000171 quenching effect Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 229910052810 boron oxide Inorganic materials 0.000 abstract description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 4
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 41
- 238000002441 X-ray diffraction Methods 0.000 description 20
- 238000000227 grinding Methods 0.000 description 12
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- 238000010348 incorporation Methods 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000006060 molten glass Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012856 weighed raw material Substances 0.000 description 3
- 238000001238 wet grinding Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910004706 CaSi2 Inorganic materials 0.000 description 1
- GTUNMKRGRHOANR-UHFFFAOYSA-N [B].[Ca] Chemical compound [B].[Ca] GTUNMKRGRHOANR-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000010344 co-firing Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/22—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in calcium oxide, e.g. wollastonite
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract
The present invention belongs to ceramicsThe technical field of materials, and provides a calcium-boron-silicon LTCC ceramic material. According to the invention, through designing the CBS ceramic with low boron, the melting volatilization of boron oxide and the precipitation of calcium borate are reduced, and the dielectric loss is reduced; by introducing rare earth oxides Nb 2 O 5 And/or Ta 2 O 5 Can strengthen the glass network structure, increase the glass viscosity, reduce the dielectric loss of ceramic materials, and simultaneously, the rare earth oxide Nb 2 O 5 And/or Ta 2 O 5 Can also inhibit precipitation of high Wen Xiang-CaSiO 3 Promote precipitation of low-temperature phase beta-CaSiO 3 Thus, the calcium-boron-silicon LTCC ceramic material with low dielectric constant and low dielectric loss can be prepared at low sintering temperature. The results of the examples show that the dielectric constant epsilon of the calcium-boron-silicon LTCC ceramic material provided by the invention r A dielectric loss tan delta of 1.19X10 at 6.18 ‑3 (1MHz)。
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a calcium-boron-silicon LTCC ceramic material and a preparation method thereof.
Background
Passive devices based on low temperature co-fired Ceramic technology (LTCC) have the advantages of high integration, co-firing with high conductivity metals, and the like, and are favored by researchers in numerous miniaturized technologies. And the LTCC technology has a millimeter-scale packaging process, so that the passive device can develop in the directions of miniaturization, high frequency and high performance, and meanwhile, the performance of the passive device is ensured not to be interfered by external factors.
CaO-B as one of the most basic substrate materials applied to the field of high-frequency communication 2 O 3 -SiO 2 The (CBS) ceramic has a range of excellent performance characteristics such as: low sintering temperature<900 ℃ and low dielectric constant (. Epsilon.) r <6.5 Compatible with Au, ag or Cu and reduces the delay of high frequency signals. Therefore, CBS ceramics have the potential to be the most suitable high frequency substrate. Meanwhile, with the rapid development of wireless communication, the demand for low dielectric constant materials is also greatly increasing. Since the phase delay in wave propagation, which reduces the signal velocity, is proportional to the frequency and dielectric constant, the use of a low dielectric constant substrate material can reduce the signal delay in a high frequency communication system. B of CBS LTCC ceramic substrate in the prior art 2 O 3 The content is usually 30 to 60 percent, B 2 O 3 Is a glass network forming agent, ensures B 2 O 3 The amount of the glass is favorable for constructing a good glass network and reducing the dielectric loss of the ceramic. However, a high content of B 2 O 3 Is easily volatilized by melting and leads to high dielectric loss. Therefore, how to prepare a calcium-boron-silicon LTCC ceramic material with low dielectric constant and low dielectric loss is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a calcium-boron-silicon LTCC ceramic material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a calcium-boron-silicon LTCC ceramic material, which comprises a CBS ceramic component and rare earth oxide; the CBS ceramic composition includes: caO 50-60 mol%, B 2 O 3 5 to 15mol% and SiO 2 35 to 45mol%; the doping amount of the rare earth oxide is 0.5-15 mol% of the CBS ceramic component; the rare earth oxide comprises Nb 2 O 5 And/or Ta 2 O 5 。
Preferably, the CBS ceramic composition comprises: caO 51-55 mol%, B 2 O 3 5 to 10mol% and SiO 2 36-40 mol%; the doping amount of the rare earth oxide is 1-8 mol% of the CBS ceramic component.
Preferably, the main crystal phase of the calcium-boron-silicon LTCC ceramic material is beta-CaSiO 3 。
The invention also provides a preparation method of the calcium-boron-silicon LTCC ceramic material, which comprises the following steps:
(1) CaCO is put into 3 、B 2 O 3 、SiO 2 Mixing with rare earth oxide, melting, quenching and ball milling in sequence to obtain glass powder;
(2) Mixing the glass powder obtained in the step (1) with a binder, granulating, and then pressing to obtain a ceramic biscuit;
(3) And (3) sintering the ceramic biscuit obtained in the step (2) to obtain the calcium-boron-silicon LTCC ceramic material.
Preferably, the melting temperature in the step (1) is 1400-1450 ℃, and the melting heat preservation time is 2-4 h.
Preferably, the quenching mode in the step (1) is water cooling.
Preferably, the rotating speed of the ball milling in the step (1) is 300-450 rpm, and the ball milling time is 6-12 h.
Preferably, the binder in the step (2) comprises a polyvinyl alcohol solution.
Preferably, the pressing pressure in the step (2) is 70-100 MPa, and the pressing time is 10-20 s.
Preferably, the sintering temperature in the step (3) is 800-900 ℃, the sintering heat preservation time is 15-30 min, and the sintering heating rate is 5-10 ℃/min.
The invention provides a calcium-boron-silicon LTCC ceramic material, which comprises a CBS ceramic component and rare earth oxide; the CBS ceramic composition includes: caO 50-60 mol%, B 2 O 3 5 to 15mol% and SiO 2 35 to 45mol%; the doping amount of the rare earth oxide is 0.5-15 mol% of the CBS ceramic component; the rare earth oxide comprises Nb 2 O 5 And/or Ta 2 O 5 . According to the invention, through designing the CBS ceramic with low boron, the melting volatilization of boron oxide and the precipitation of calcium borate are reduced, and the dielectric loss is reduced; by introducing rare earth oxides Nb 2 O 5 And/or Ta 2 O 5 Can strengthen the glass network structure, increase the glass viscosity, reduce the dielectric loss of ceramic materials, and simultaneously, the rare earth oxide Nb 2 O 5 And/or Ta 2 O 5 Can also inhibit precipitation of high Wen Xiang-CaSiO 3 Promote precipitation of low-temperature phase beta-CaSiO 3 Thus, the calcium-boron-silicon LTCC ceramic material with low dielectric constant and low dielectric loss can be prepared at low sintering temperature. The results of the examples show that the dielectric constant epsilon of the calcium-boron-silicon LTCC ceramic material provided by the invention r A dielectric loss tan delta of 1.19X10 at 6.18 -3 (1MHz)。
Drawings
FIG. 1 is an XRD pattern of a calcium-boron-silicon-based LTCC ceramic material of examples 1 to 5 of the present invention and a CBS ceramic material of comparative example 1;
FIG. 2 is an XRD pattern of the calcium-boron-silicon-based LTCC ceramic materials of examples 6 to 10 and the CBS ceramic material of comparative example 2 according to the present invention;
FIG. 3 is a DSC graph of the calcium-boron-silicon-based LTCC ceramic material of examples 1 to 5 of the present invention and the CBS ceramic material of comparative example 1;
FIG. 4 is a DSC graph of the calcium-boron-silicon-based LTCC ceramic material of examples 6 to 10 of the present invention and the CBS ceramic material of comparative example 2;
FIG. 5 is an X-ray diffraction pattern of the ceramic materials of examples 11, 13, 18, 20, 22 and comparative example 3 of the present invention;
FIG. 6 is an X-ray diffraction chart of the ceramic materials in examples 1 to 5 and comparative example 1 of the present invention;
FIG. 7 is an X-ray diffraction pattern of the ceramic materials of examples 12, 14, 19, 21, 23 and comparative example 4 of the present invention;
FIG. 8 is an X-ray diffraction chart of the ceramic material in example 2 and examples 13 to 17 of the present invention;
FIG. 9 is an X-ray diffraction pattern of the ceramic materials of examples 24, 26, 32, 34, 36 and comparative example 5 of the present invention;
FIG. 10 is an X-ray diffraction chart of the ceramic materials in examples 6 to 10 of the present invention and comparative example 2;
FIG. 11 is an X-ray diffraction pattern of the ceramic materials of examples 25, 27, 33, 35, 37 and comparative example 6 of the present invention;
FIG. 12 is an X-ray diffraction chart of the ceramic material in example 7 and examples 26 to 31 of the present invention;
FIG. 13 shows dielectric constants ε of the calcium-boron-silicon-based LTCC ceramic materials of examples 1 to 5 and the CBS ceramic material of comparative example 1 of the present invention r And a line graph of dielectric loss tan delta.
Detailed Description
The invention provides a calcium-boron-silicon LTCC ceramic material, which comprises a CBS ceramic component and rare earth oxide; the CBS ceramic composition includes: caO 50-60 mol%, B 2 O 3 5 to 15mol% and SiO 2 35 to 45mol%; the doping amount of the rare earth oxide is 0.5-15 mol% of the CBS ceramic component; the rare earth oxide comprises Nb 2 O 5 And/or Ta 2 O 5 。
The calcium-boron-silicon LTCC ceramic material provided by the invention comprises a CBS ceramic component and rare earth oxide. The invention can strengthen the glass network structure, increase the glass viscosity, reduce the dielectric loss of ceramic materials and inhibit the precipitation of high Wen Xiang-CaSiO by doping rare earth oxide into CBS ceramic 3 Promote precipitation of low-temperature phase beta-CaSiO 3 Thus, the calcium-boron-silicon LTCC ceramic material with low dielectric constant and low dielectric loss can be prepared at low sintering temperature.
In the present invention, the CBS ceramic component comprises CaO in an amount of 50 to 60mol%, preferably 51 to 55mol%. The invention takes CaO as a main component to prepare CBS ceramics. The invention overcomes the defect of high content B by controlling the usage amount of CaO within the range 2 O 3 Is not limited to the above-mentioned method.
In the present invention, the CBS ceramic component comprises B 2 O 3 5 to 15mol%, preferably 5 to 10mol%. B in the invention 2 O 3 For use with SiO 2 And constructing a glass network structure. The invention is implemented by using B 2 O 3 The dosage of (2) is controlled within the range, so that the melting volatilization of boron oxide and the precipitation of calcium borate are reduced, and the dielectric loss is reduced.
In the present invention, the CBS ceramic component comprises SiO 2 35 to 45mol%, preferably 36 to 40mol%. SiO in the present invention 2 For use with B 2 O 3 And constructing a glass network structure. The invention is realized by mixing SiO 2 The amount of the glass is controlled within the above range, and the content of the glass body in the ceramic material is ensured.
In the present invention, the rare earth oxide is incorporated in an amount of 0.5 to 15mol%, preferably 1 to 8mol%, more preferably 1 to 6mol% of the CBS ceramic component. By controlling the doping amount of the rare earth oxide in the range, the invention ensures that the dielectric constant of the ceramic material can be controlled within the range of 5.19-8.92, and is beneficial to obtaining the ceramic material with low dielectric loss.
In the present invention, the rare earth oxide includes Nb 2 O 5 And/or Ta 2 O 5 . In the present invention, the Nb 2 O 5 And Ta 2 O 5 The ceramic material has the characteristics of high field intensity, alkali pressing effect and the like, can strengthen the glass network structure, increase the glass viscosity and reduce the dielectric loss of the ceramic material.
In the invention, the main crystal phase of the calcium-boron-silicon LTCC ceramic material is preferably beta-CaSiO 3 . In the present invention, the beta-CaSiO 3 The phase is a low-temperature phase, which is beneficial to reducing the sintering temperature of the ceramic material.
According to the invention, through designing the CBS ceramic with low boron, the melting volatilization of boron oxide and the precipitation of calcium borate are reduced, and the dielectric loss is reduced; by introducing rare earth oxides Nb 2 O 5 And/or Ta 2 O 5 Can strengthen the glass network structure, increase the glass viscosity, reduce the dielectric loss of ceramic materials, and simultaneously, the rare earth oxide Nb 2 O 5 And/or Ta 2 O 5 Can also inhibit precipitation of high Wen Xiang-CaSiO 3 Promote precipitation of low-temperature phase beta-CaSiO 3 Thus, the calcium-boron-silicon LTCC ceramic material with low dielectric constant and low dielectric loss can be prepared at low sintering temperature.
The invention also provides a preparation method of the calcium-boron-silicon LTCC ceramic material, which comprises the following steps:
(1) CaCO is put into 3 、B 2 O 3 、SiO 2 Mixing with rare earth oxide, melting, quenching and ball milling in sequence to obtain glass powder;
(2) Mixing the glass powder obtained in the step (1) with a binder, granulating, and then pressing to obtain a ceramic biscuit;
(3) And (3) sintering the ceramic biscuit obtained in the step (2) to obtain the calcium-boron-silicon LTCC ceramic material.
The invention uses CaCO 3 、B 2 O 3 、SiO 2 And mixing with rare earth oxide, melting, quenching and ball milling in sequence to obtain glass powder.
The invention aims at CaCO 3 、B 2 O 3 、SiO 2 The mode of mixing with the rare earth oxide is not particularly limited, and a mixing mode well known to those skilled in the art may be employed. In the present invention, the mixing time is preferably 60 to 80 minutes; the apparatus used for the mixing is preferably a three-dimensional mixer.
In the present invention, the melting temperature is preferably 1400 to 1450 ℃, more preferably 1400 to 1430 ℃. In the present invention, the holding time for the melting is preferably 2 to 4 hours, more preferably 2 to 3 hours. In the present invention, the heating device for melting is preferably a resistance furnace; the crucible used for the melting is preferably a platinum crucible. In the present invention, the temperature and time of the melting are preferably controlled within the above ranges so that each raw material is sufficiently melted to form a molten glass.
In the present invention, the quenching is preferably performed by water cooling. In the present invention, the water used for the water cooling is preferably deionized water. The present invention forms a molten glass into a glass body by quenching.
In the present invention, the rotational speed of the ball mill is preferably 300 to 450rpm, more preferably 350 to 450rpm. In the present invention, the time of the ball milling is preferably 6 to 12 hours, more preferably 6 to 10 hours. In the present invention, the ball milling medium is preferably deionized water; the grinding balls used for ball milling are preferably zirconium balls; the equipment used for ball milling is preferably a planetary ball mill. The invention pulverizes the glass body by ball milling to prepare powder, which is convenient for subsequent processing.
After ball milling is completed, the ball milling product is preferably screened and dried in sequence to obtain glass powder. The sieving and drying operation is not particularly limited, and the sieving and drying technical scheme well known to those skilled in the art can be adopted. In the present invention, the mesh number of the screen used for the sieving is preferably 500 mesh. In the invention, the temperature of the drying is preferably 80-90 ℃; the drying time is preferably 12-15 hours.
After the glass powder is obtained, the invention mixes the glass powder and the binder, then carries out granulation and then presses to obtain the ceramic biscuit.
The method of mixing the glass frit and the binder is not particularly limited, and a mixing method well known to those skilled in the art may be adopted.
In the present invention, the binder preferably includes a polyvinyl alcohol solution. In the present invention, the polyvinyl alcohol solution preferably has a mass concentration of 4 to 8%, more preferably 4 to 6%. In the invention, the mass ratio of the glass powder to the binder is preferably 20g:4mL. In the invention, the binder is used for binding glass powder, so that granulation is facilitated; the binder is decomposed during the subsequent sintering process. The source of the polyvinyl alcohol solution is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
The operation of the granulation is not particularly limited, and the granulation method can be adopted by technical schemes well known to those skilled in the art.
After the granulation is completed, the product obtained by the granulation is preferably screened. The sieving operation is not particularly limited in the present invention, and a sieving technique well known to those skilled in the art may be adopted. In the present invention, the mesh number of the screen used for the sieving is preferably 40 mesh.
In the present invention, the pressing pressure is preferably 70 to 100MPa, more preferably 80 to 100MPa; the pressing time is preferably 10 to 20 seconds, more preferably 15 to 20 seconds. In the present invention, the apparatus for pressing is preferably a unidirectional press. The invention presses the powder obtained after granulation into a biscuit with a certain shape by pressing.
In the present invention, the specification of the ceramic greenware is preferably 10mm×10mm×2mm.
After the ceramic biscuit is obtained, the ceramic biscuit is sintered to obtain the calcium-boron-silicon LTCC ceramic material.
In the present invention, the sintering temperature is preferably 800 to 900 ℃, more preferably 850 to 880 ℃. The sintering temperature is preferably controlled within the range, which is favorable for obtaining the main crystal phase beta-CaSiO 3 Is a ceramic material of the ceramic material. In the present invention, the heat-preserving time of the sintering is preferably 15 to 30 minutes, more preferably 15 to 25 minutes; the temperature rise rate of the sintering is preferably 5 to 10 ℃/min, more preferably 5 to 8 ℃/min. In the present invention, the cooling mode after sintering is preferably furnace-following cooling.
The preparation method provided by the invention is simple and convenient to operate, simple in preparation raw materials, low in cost and stable in process, and achieves the conditions of practicality and industrialization.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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.
Example 1
Calcium boron siliconLTCC ceramic material is composed of CBS ceramic component and Nb 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Nb 2 O 5 The incorporation amount of (C) is 1mol% of the CBS ceramic component and is expressed as CBSN 1 ；
The preparation process comprises the following steps:
(1) Weighing CaCO as raw material according to the above composition proportion 3 、B 2 O 3 、SiO 2 And Nb (Nb) 2 O 5 Mixing the weighed raw materials for 60min by a three-dimensional mixer, transferring to a platinum crucible, heating to 1400 ℃ in a resistance furnace, preserving heat for 2h, and pouring molten glass into deionized water for quenching to obtain a glass body; then placing the glass body in a planetary ball mill for wet grinding, wherein the ball grinding medium is deionized water, the grinding balls are zirconium balls, the rotating speed of the ball mill is 450rpm, the ball grinding time is 6 hours, and then, after passing through a 500-mesh sieve, drying the ball-milled material at 80 ℃ for 12 hours to obtain 51mol% CaO-9.6mol% B 2 O 3 -39.4mol％SiO 2 -1mol％Nb 2 O 5 Glass powder;
(2) Weighing 20g of the glass powder obtained in the step (1), adding 4mL of a polyvinyl alcohol solution with the mass concentration of 4%, granulating, sieving the granulated powder with a 40-mesh sieve, and pressing the granulated powder on a unidirectional press for 15s under the pressure of 100MPa to obtain a ceramic biscuit with the mass concentration of 10mm multiplied by 2 mm;
(3) Placing the ceramic biscuit obtained in the step (2) into a resistance furnace, heating to 865 ℃ at a heating rate of 5 ℃/min, preserving heat for 15min, and then cooling along with the furnace to obtain 51mol% CaO-9.6mol% B 2 O 3 -39.4mol％SiO 2 -1mol％Nb 2 O 5 A ceramic material.
Example 2
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Nb 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Nb 2 O 5 The incorporation amount of (C) is 2mol% of the CBS ceramic component and is expressed as CBSN 2 ；
The preparation procedure is as in example 1.
Example 3
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Nb 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Nb 2 O 5 The incorporation amount of (C) is 4mol% of the CBS ceramic component and is expressed as CBSN 4 ；
The preparation procedure is as in example 1.
Example 4
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Nb 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Nb 2 O 5 The incorporation amount of (C) is 6mol% of the CBS ceramic component and is expressed as CBSN 6 ；
The preparation procedure is as in example 1.
Example 5
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Nb 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Nb 2 O 5 The incorporation amount of (C) was 8mol% of the CBS ceramic component, which was referred to as CBSN 8 ；
The preparation procedure is as in example 1.
Example 6
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Ta 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Ta 2 O 5 The incorporation amount of (C) was 0.5mol% of the CBS ceramic component, which was referred to as CBST 0.5 ；
The preparation process comprises the following steps:
(1) Weighing CaCO as raw material according to the above composition proportion 3 、B 2 O 3 、SiO 2 And Ta 2 O 5 The weighed raw materials are usedAfter mixing materials for 60min by a three-dimensional mixer, transferring the materials to a platinum crucible, heating the materials to 1400 ℃ in a resistance furnace, preserving heat for 2h, and then pouring molten glass into deionized water for quenching to obtain a glass body; then placing the glass body in a planetary ball mill for wet grinding, wherein the ball grinding medium is deionized water, the grinding balls are zirconium balls, the rotating speed of the ball mill is 450rpm, the ball grinding time is 6 hours, and then, after passing through a 500-mesh sieve, drying the ball-milled material at 80 ℃ for 12 hours to obtain 51mol% CaO-9.6mol% B 2 O 3 -39.4mol％SiO 2 -0.5mol％Ta 2 O 5 Glass powder;
(2) Weighing 20g of the glass powder obtained in the step (1), adding 4mL of a polyvinyl alcohol solution with the mass concentration of 4%, granulating, sieving the granulated powder with a 40-mesh sieve, and pressing the granulated powder on a unidirectional press for 15s under the pressure of 100MPa to obtain a ceramic biscuit with the mass concentration of 10mm multiplied by 2 mm;
(3) Placing the ceramic biscuit obtained in the step (2) into a resistance furnace, heating to 875 ℃ at a heating rate of 5 ℃/min, preserving heat for 15min, and then cooling along with the furnace to obtain 51mol% CaO-9.6mol% B 2 O 3 -39.4mol％SiO 2 -0.5mol％Ta 2 O 5 A ceramic material.
Example 7
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Ta 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Ta 2 O 5 The incorporation amount of (C) is 1mol% of the CBS ceramic component, which is referred to as CBST 1 ；
The preparation procedure is as in example 6.
Example 8
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Ta 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Ta 2 O 5 The incorporation amount of (C) is 2mol% of the CBS ceramic component, which is expressed as CBST 2 ；
The preparation procedure is as in example 6.
Example 9
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Ta 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Ta 2 O 5 The incorporation amount of (C) was 4mol% based on the CBS ceramic component, which was designated CBST 4 ；
The preparation procedure is as in example 6.
Example 10
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Ta 2 O 5 The CBS ceramic component consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Ta 2 O 5 The incorporation amount of (C) was 6mol% based on the CBS ceramic component, which was designated CBST 6 ；
The preparation procedure is as in example 6.
Example 11
The difference from example 1 is that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as example 1, denoted as CBSN 11 。
Example 12
The difference from example 1 is that the temperature is raised to 880℃at a temperature rise rate of 5℃per minute in step (3), and the remainder of example 1 is referred to as CBSN 12 。
Example 13
The difference from example 2 is that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as example 2 and designated CBSN 21 。
Example 14
The difference from example 2 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as in example 2 and designated CBSN 22 。
Example 15
The difference from example 2 is that in step (3), the temperature was raised to 805℃at a temperature-raising rate of 5℃per minute, and the remainder was recorded as CBSN in example 2 23 。
Example 16
The difference from example 2 is that in step (3), the temperature was raised to 835℃at a temperature rise rate of 5℃per minute, and the remainder was the same as example 2 and designated CBSN 24 。
Example 17
The difference from example 2 is that the temperature was raised to 850℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as example 2, denoted as CBSN 25 。
Example 18
The difference from example 3 is that in step (3), the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute, and the remainder was the same as example 3, and was designated CBSN 41 。
Example 19
The difference from example 3 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as in example 3 and designated CBSN 42 。
Example 20
The difference from example 4 is that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder of example 4 was designated CBSN 61 。
Example 21
The difference from example 4 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder of example 4 was designated CBSN 62 。
Example 22
The difference from example 5 is that in step (3), the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute, and the remainder was recorded as CBSN in example 5 81 。
Example 23
The difference from example 5 is that the temperature is raised to 880℃at a temperature rise rate of 5℃per minute in step (3), and the remainder of example 5 is referred to as CBSN 82 。
Example 24
The difference from example 6 is that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as in example 6, and was designated CBST 0.51 。
Example 25
The difference from example 6 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as in example 6, and was designated CBST 0.52 。
Example 26
The difference from example 7 is that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as example 7 and designated CBST 11 。
Example 27
The difference from example 7 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as in example 7, and was designated CBST 12 。
Example 28
The difference from example 7 is that the temperature was raised to 800℃at a temperature rise rate of 5℃per minute in step (3), and the remainder was the same as example 7 and designated CBST 13 。
Example 29
The difference from example 7 is that the temperature was raised to 840℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as example 7, and was designated CBST 14 。
Example 30
The difference from example 7 is that the temperature was raised to 860℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was CBST as in example 7 15 。
Example 31
The difference from example 7 is that the temperature was raised to 870℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as in example 7 and designated CBST 16 。
Example 32
The difference from example 8 is that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was recorded as CBST in example 8 21 。
Example 33
The difference from example 8 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder of example 8 was designated CBST 22 。
Example 34
As in example 9Except that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in the step (3), the remainder was the same as in example 9 and was designated CBST 41 。
Example 35
The difference from example 9 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder of example 9 was designated CBST 42 。
Example 36
The difference from example 10 is that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as example 10 and designated CBST 61 。
Example 37
The difference from example 10 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was the same as in example 10 and designated CBST 62 。
Comparative example 1
CBS ceramic material, consisting of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol%, designated CBSN 0 ；
The preparation process comprises the following steps:
(1) Weighing CaCO as the raw material according to the composition proportion 3 、B 2 O 3 And SiO 2 Mixing the weighed raw materials for 60min by a three-dimensional mixer, transferring to a platinum crucible, heating to 1400 ℃ in a resistance furnace, preserving heat for 2h, and pouring molten glass into deionized water for quenching to obtain a glass body; then placing the glass body in a planetary ball mill for wet grinding, wherein the ball grinding medium is deionized water, the grinding balls are zirconium balls, the rotating speed of the ball mill is 450rpm, the ball grinding time is 6 hours, and then sieving the ball grinding material with a 500-mesh sieve and drying the ball grinding material at 80 ℃ for 12 hours to obtain CaO-B 2 O 3 -SiO 2 Glass powder;
(2) Weighing 20g of the glass powder obtained in the step (1), adding 4mL of a polyvinyl alcohol solution with the mass concentration of 4%, granulating, sieving the granulated powder with a 40-mesh sieve, and pressing the granulated powder on a unidirectional press for 15s under the pressure of 100MPa to obtain a ceramic biscuit with the mass concentration of 10mm multiplied by 2 mm;
(3) Will step by stepPlacing the ceramic biscuit obtained in the step (2) into a resistance furnace, heating to 865 ℃ at a heating rate of 5 ℃/min, preserving heat for 15min, and then cooling along with the furnace to obtain 51mol% CaO-9.6mol% B 2 O 3 -39.4mol％SiO 2 A ceramic material.
Comparative example 2
The difference from comparative example 1 is that the temperature was raised to 875℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was recorded as CBST as comparative example 1 0 。
Comparative example 3
The difference from comparative example 1 is that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was recorded as CBSN in comparative example 1 01 。
Comparative example 4
The difference from comparative example 1 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was recorded as CBSN in comparative example 1 02 。
Comparative example 5
The difference from comparative example 1 is that the temperature was raised to 820℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was recorded as CBST as comparative example 1 01 。
Comparative example 6
The difference from comparative example 1 is that the temperature was raised to 880℃at a temperature-raising rate of 5℃per minute in step (3), and the remainder was recorded as CBST as comparative example 1 02 。
TABLE 1 thermal properties of the ceramic materials in comparative examples 1-2 and examples 1-10 at 5 ℃/min
By CBSN 0 Taking the lowest viscosity point temperature of 767 ℃ as a standard point, and sequentially taking CBSN 1 ～CBSN 8 A ceramic material viscosity value; in CBST 0 The minimum point temperature of the viscosity is 774 DEG CQuasi-point, take CBST sequentially 0.5 ～CBST 6 The viscosity values of the ceramic materials are shown in Table 2.
Table 2 viscosity of ceramic materials of comparative examples 1 to 2 and examples 1 to 10
| Sample of | Viscosity (lgPa.S) |
| CBSN 0 | 6.68 |
| CBSN 1 | 6.71 |
| CBSN 2 | 6.76 |
| CBSN 4 | 6.83 |
| CBSN 6 | 6.86 |
| CBSN 8 | 6.89 |
| CBST 0 | 6.68 |
| CBST 0.5 | 6.74 |
| CBST 1 | 6.80 |
| CBST 2 | 6.92 |
| CBST 4 | 7.09 |
| CBST 6 | 7.50 |
As can be seen from Table 2, with Nb 2 O 5 Or Ta 2 O 5 The viscosity value of the ceramic material is increased by increasing the doping amount.
TABLE 3 dielectric Properties at 1MHz of the ceramic materials in comparative examples 1 to 2 and examples 1 to 10
| Sample of | Dielectric constant epsilon r | Dielectric loss tan delta |
| CBSN 0 | 5.93 | 2.39×10 -3 |
| CBSN 1 | 5.66 | 1.59×10 -3 |
| CBSN 2 | 6.42 | 1.05×10 -3 |
| CBSN 4 | 7.14 | 1.15×10 -3 |
| CBSN 6 | 7.45 | 1.28×10 -3 |
| CBSN 8 | 8.66 | 1.55×10 -3 |
| CBST 0 | 5.20 | 51.9×10 -3 |
| CBST 0.5 | 6.19 | 2.38×10 -3 |
| CBST 1 | 6.22 | 1.20×10 -3 |
| CBST 2 | 6.66 | 1.15×10 -3 |
| CBST 4 | 6.07 | 0.82×10 -3 |
| CBST 6 | 8.93 | 0.40×10 -3 |
FIG. 1 shows XRD patterns of the calcium-boron-silicon-based LTCC ceramic materials of examples 1 to 5 and the CBS ceramic material of comparative example 1. FIG. 2 shows XRD patterns of the calcium-boron-silicon-based LTCC ceramic materials of examples 6 to 10 and the CBS ceramic material of comparative example 2. As can be seen from FIGS. 1 and 2, alpha-CaSiO was found in the CBS ceramic materials of comparative examples 1 and 2, which were undoped with rare earth oxides 3 Phase (PDF#31-0300) and CaSi 2 O 5 Phase (PDF# 51-0092), along with Nb 2 O 5 Or Ta 2 O 5 The increase of the content and the evolution of the diffraction peak into a steamed bread peak show that the crystallization of the glass is inhibited, the characterization of the glass is obvious, and the reasons for the phenomena are possibly Nb 5+ And Ta 5+ The ion field intensity is higher.
FIG. 3 is a DSC graph of the calcium-boron-silicon-based LTCC ceramic material of examples 1 to 5 and the CBS ceramic material of comparative example 1. As can be seen from FIG. 3 and Table 1, most of the ceramic samples had significant softening points (T g ) Crystallization onset temperature (T) c1 And T c2 ) And exothermic crystallization peak temperature (T) p1 And T p2 )。T p1 And T p2 Possibly with CaSiO 3 And Canb 2 O 6 The formation of crystals is relevant. With Nb 2 O 5 The content is increased from 1mol% to 8mol%, T g The value increased from 697℃to 761℃T p1 The peak intensity of (c) starts to increase and become sharp, and the peak temperature is increased from CBSN 1 777℃of sample moves to CBSN 8 833 ℃. T (T) g 、T c And T p The values all shift to high values, indicating that with Nb 2 O 5 The increase in content suppresses crystallization.
FIG. 4 shows the calcium-boron-silicon-based LTCC ceramic materials and the comparison of examples 6 to 10DSC profile of CBS ceramic material in example 2. As can be seen from FIG. 4 and Table 1, most of the ceramic samples had significant softening points (T g ) Crystallization onset temperature (T) c1 And Tc 2 ) And exothermic crystallization peak temperature (T) p1 And T p2 )。Tp 1 And Tp 2 Possibly with CaSiO 3 And Ca 2 Ta 2 O 7 The formation of crystals is relevant. With Ta 2 O 5 The content was increased from 0.5mol% to 6mol%, T g The value increased from 698℃to 766℃T p1 The peak intensity of (2) starts to increase and becomes sharp, the peak from CBST 0.5 The sample was moved to CBST at 794 ℃ 6 887 ℃. T (T) g 、T c And T p The values all move to the high value, indicating that with Ta 2 O 5 The increase in content suppresses crystallization.
Fig. 5 is an X-ray diffraction pattern of the ceramic materials in examples 11, 13, 18, 20, 22 and comparative example 3. As can be seen from FIG. 5, CBSN is obtained when the sintering temperature is 820 DEG C 01 In the sample there is a large amount of alpha-CaSiO 3 Phase (PDF#31-0300) and small amounts of beta-CaSiO 3 Phase (PDF# 42-0547), along with Nb 2 O 5 Is added with alpha-CaSiO 3 Phase sharply decreases, beta-CaSiO 3 Phase rapidly increases, CBSN 81 The sample remained glassy, a phenomenon that suggests that with Nb 2 O 5 The doped amount is increased, the glass phase content of the CBSN ceramic material is increased, and the crystallization behavior is inhibited.
Fig. 6 is an X-ray diffraction chart of the ceramic materials in examples 1 to 5 and comparative example 1. As can be seen from FIG. 6, the ceramic sample is mainly beta-CaSiO present when the sintering temperature is 865 DEG C 3 And (3) phase (C). With Nb 2 O 5 Is added with (A) and (B) CaNb 2 O 6 The diffraction peak of the (PDF # 39-1392) phase is gradually sharp.
Fig. 7 is an X-ray diffraction pattern of the ceramic materials in examples 12, 14, 19, 21, 23 and comparative example 4. As can be seen from FIG. 7, when the sintering temperature is 880 ℃, the sintering temperature is equal to or higher than the sintering temperature, wherein for CBSN 82 Sample, main phase has been formed from beta-CaSiO 3 Conversion to Canb 2 O 6 。
From FIG. 5As can be seen from fig. 7, as the sintering temperature increases, the ceramic material gradually crystallizes, reaching full crystallization at 865 ℃; more importantly, the main crystal phase precipitated at this time is beta-CaSiO 3 。
Fig. 8 is an X-ray diffraction chart of the ceramic material in example 2 and examples 13 to 17. In the figure, beta-CaSiO 3 Is the main crystal phase, and in addition, in a sample with higher doping content, caNb 2 O 6 Exists as an additional crystal phase, ca 2 Nb 2 O 7 The relative intensity of the diffraction peaks increases gradually as the sintering temperature increases from 805 ℃ to 880 ℃.
Fig. 9 is an X-ray diffraction pattern of the ceramic materials of examples 24, 26, 32, 34, 36 and comparative example 5. As can be seen from FIG. 9, CBST is obtained when the sintering temperature is 820 DEG C 01 In the sample there is a large amount of alpha-CaSiO 3 Phase (PDF#31-0300) and small amounts of beta-CaSiO 3 Phase (PDF# 42-0547), with Ta 2 O 5 Is added with alpha-CaSiO 3 Phase sharply decreases, beta-CaSiO 3 The phase increases rapidly. CBST 61 The sample remained glassy, a phenomenon that suggests that with Ta 2 O 5 The doped amount is increased, the glass phase content of the CBST ceramic material is increased, and the crystallization behavior is inhibited.
FIG. 10 is an X-ray diffraction chart of the ceramic materials in examples 6 to 10 and comparative example 2. As can be seen from FIG. 10, the ceramic sample is mainly beta-CaSiO present 3 Phase with Ta 2 O 5 Is added with Ca 2 Ta 2 O 7 The diffraction peaks of the (PDF # 74-1355) phases are gradually sharp.
FIG. 11 is an X-ray diffraction pattern of the ceramic materials of examples 25, 27, 33, 35, 37 and comparative example 6. As can be seen from FIG. 11, when the sintering temperature is 880 ℃, the temperature is lower than that of CBST 62 Sample, main phase has been formed from beta-CaSiO 3 Conversion to Ca 2 Ta 2 O 7 。
As can be seen from fig. 9 to 11, the ceramic material gradually crystallizes with increasing sintering temperature, reaching complete crystallization at 875 ℃; more importantly, the main crystal phase precipitated at this time is beta-CaSiO 3 。
Fig. 12 is an X-ray diffraction chart of the ceramic material in example 7 and examples 26 to 31. In the figure, beta-CaSiO 3 Is a main crystal phase, and in addition, in a sample with higher doping content, ca 2 Ta 2 O 7 Exists as an additional crystal phase, ca 2 Ta 2 O 7 The relative intensity of the diffraction peaks increases gradually as the sintering temperature increases from 800 ℃ to 880 ℃.
FIG. 13 shows the dielectric constants ε of the calcium-boron-silicon-based LTCC ceramic materials of examples 1-5 and the CBS ceramic material of comparative example 1 r And a line graph of dielectric loss tan delta. As can be seen from fig. 13, with Nb 2 O 5 Is added with epsilon r The curve increases continuously, which is mainly related to the morphology change of the particles and the devitrification behavior of the glass. The reasons for this situation may be: first, the increase of fine particles results in an increase of grain boundaries and defects; next, nb 2 O 5 May form Canb by addition of (C) 2 O 6 A phase having a dielectric constant (. Epsilon.) r And ≡ 15) is larger than CBS ceramics. Nb (Nb) 2 O 5 The tan delta value is greatly reduced and then increased, which is probably caused by alkali pressing effect. Adding Nb to CBS glass 2 O 5 In this case, the inhibition effect is particularly remarkable. Due to Nb 5+ The high ion field intensity has a plurality of binding sites, can consolidate the structure of the relaxation alkali glass, and reduces the relaxation polarization, so that the tan delta is reduced. Wherein, contains 2mol% of Nb 2 O 5 The CBSN ceramic of (C) has excellent dielectric property and epsilon after being sintered for 15min at 865 DEG C r ＝6.42，tanδ＝1.049×10 -3 (1MHz)。
As can be seen from the above examples, the calcium-boron-silicon LTCC ceramic material provided by the invention has low dielectric constant and low dielectric loss, and dielectric constant epsilon r A dielectric loss tan delta of 1.19X10 at 6.18 -3 (1MHz)。
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A calcium boron silicon LTCC ceramic material comprises a CBS ceramic component and rare earth oxide; the CBS ceramic composition includes: caO 50-60 mol%, B 2 O 3 5 to 15mol% and SiO 2 35 to 45mol%; the doping amount of the rare earth oxide is 4-6 mol% of the CBS ceramic component; the rare earth oxide is Ta 2 O 5 。
2. The calcium-boron-silicon-based LTCC ceramic material of claim 1, wherein the CBS ceramic composition comprises: caO 51-55 mol%, B 2 O 3 5 to 10mol% and SiO 2 36-40 mol%; the doping amount of the rare earth oxide is 4-6mol% of the CBS ceramic component.
3. The calcium-boron-silicon-based LTCC ceramic material according to claim 1 or 2, wherein the main crystal phase of the calcium-boron-silicon-based LTCC ceramic material is β -CaSiO 3 。
4. A method for preparing the calcium-boron-silicon-based LTCC ceramic material as claimed in any one of claims 1 to 3, comprising the steps of:
(1) CaCO is put into 3 、B 2 O 3 、SiO 2 Mixing with rare earth oxide, melting, quenching and ball milling in sequence to obtain glass powder;
(2) Mixing the glass powder obtained in the step (1) with a binder, granulating, and then pressing to obtain a ceramic biscuit;
(3) And (3) sintering the ceramic biscuit obtained in the step (2) to obtain the calcium-boron-silicon LTCC ceramic material.
5. The method according to claim 4, wherein the melting temperature in the step (1) is 1400 to 1450 ℃, and the melting holding time is 2 to 4 hours.
6. The method according to claim 4, wherein the quenching in the step (1) is performed by water cooling.
7. The method according to claim 4, wherein the rotational speed of the ball milling in the step (1) is 300 to 450rpm, and the time of the ball milling is 6 to 12 hours.
8. The method according to claim 4, wherein the binder in the step (2) comprises a polyvinyl alcohol solution.
9. The method according to claim 4, wherein the pressing pressure in the step (2) is 70 to 100MPa and the pressing time is 10 to 20s.
10. The method according to claim 4, wherein the sintering temperature in the step (3) is 800-900 ℃, the sintering heat-preserving time is 15-30 min, and the sintering temperature-rising rate is 5-10 ℃/min.
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