CN115466109A - 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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Abstract
The invention belongs to the technical field of ceramic materials, and provides a calcium-boron-silicon LTCC ceramic material. By designing the low-boron CBS ceramic, the invention reduces the melting volatilization of boron oxide and the precipitation of calcium borate, and reduces the dielectric loss; 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 The introduction of the (B) can also inhibit the precipitation of a high-temperature phase alpha-CaSiO 3 Promote the precipitation of low-temperature phase beta-CaSiO 3 Therefore, 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 6.18, and a dielectric loss tan delta of 1.19X 10 ‑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
A passive device based on a Low Temperature Co-fired Ceramic (LTCC) technology has the advantages of high integration, capability of being Co-fired with high-conductivity metal and the like, and is popular among scientific researchers in a plurality of miniaturized technologies. And the LTCC technology has a millimeter-scale packaging process, so that the passive device can be developed in the direction of miniaturization, high frequency and high performance, and the performance of the passive device is ensured not to be interfered by external factors.
CaO-B, one of the most basic substrate materials for high frequency communication applications 2 O 3 -SiO 2 (CBS) ceramics have a range of excellent performance characteristics, such as: low sintering temperature (C)<900 deg.C), low dielectric constant (ε) r <6.5 Compatible with Au, ag, or Cu), and reduces the delay of high-frequency signals. Thus, CBS ceramics have the potential to become the most suitable high frequency substrates. Meanwhile, with the rapid development of wireless communication, the demand for low dielectric constant materials has also increased greatly. Since the phase delay in wave propagation, which reduces the signal velocity, is proportional to the frequency and the dielectric constant, the use of a substrate material with a low dielectric constant can reduce the signal delay in a high-frequency communication system. B of CBS LTCC ceramic substrate in prior art 2 O 3 The content is usually 30 to 60%, B 2 O 3 Is a glass network former, ensuring B 2 O 3 The dosage of the glass is beneficial to constructing a good glass network and reducing the dielectric loss of the ceramic. However, high content of B 2 O 3 Easy to meltVolatilization, in turn, results in high dielectric loss. Therefore, how to prepare the calboro-silicate LTCC ceramic material with low dielectric constant and low dielectric loss becomes a technical problem which needs to be solved urgently 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 purpose, the invention provides the following technical scheme:
the invention provides a calcium-boron-silicon LTCC ceramic material, which comprises a CBS ceramic component and a rare earth oxide; the CBS ceramic composition comprises: caO 50-60 mol%, B 2 O 3 5 to 15mol%, and SiO 2 35-45 mol%; 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: 51 to 55mol% of CaO, B 2 O 3 5 to 10mol%, and SiO 2 36 to 40mol percent; 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 in the technical scheme, which comprises the following steps:
(1) Mixing CaCO 3 、B 2 O 3 、SiO 2 Mixing with rare earth oxide, melting, and then sequentially quenching and ball-milling to obtain glass powder;
(2) Mixing the glass powder obtained in the step (1) with a binder, granulating, and 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 holding time of the melting is 2-4 h.
Preferably, the quenching mode in the step (1) is water cooling.
Preferably, the rotation 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 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 temperature rise rate is 5-10 ℃/min.
The invention provides a calcium-boron-silicon LTCC ceramic material, which comprises a CBS ceramic component and a rare earth oxide; the CBS ceramic composition comprises: caO 50-60 mol%, B 2 O 3 5 to 15mol%, and SiO 2 35-45 mol%; 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, by designing the low-boron CBS ceramic, 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 The introduction of the (B) can also inhibit the precipitation of a high-temperature phase alpha-CaSiO 3 Promoting the precipitation of low-temperature phase beta-CaSiO 3 Therefore, 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 6.18, and a dielectric loss tan delta of 1.19X 10 -3 (1MHz)。
Drawings
FIG. 1 is an XRD pattern of a CaBorosilicate-based LTCC ceramic material in examples 1 to 5 of the present invention and a CBS ceramic material in comparative example 1;
FIG. 2 is XRD patterns of a CaBorosilicate-based LTCC ceramic material in examples 6 to 10 of the present invention and a CBS ceramic material in comparative example 2;
FIG. 3 is a DSC plot of a CaBsAN-based LTCC ceramic material in examples 1-5 of the present invention and a CBS ceramic material in comparative example 1;
FIG. 4 is a DSC plot of the CaBsAN-based LTCC ceramic materials of examples 6-10 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 of the present invention and comparative example 3;
FIG. 6 is an X-ray diffraction pattern of the ceramic materials in examples 1 to 5 of the present invention and comparative example 1;
FIG. 7 is an X-ray diffraction pattern of the ceramic materials of examples 12, 14, 19, 21, 23 of the present invention and comparative example 4;
FIG. 8 is an X-ray diffraction chart of the ceramic materials 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 of the present invention and comparative example 5;
FIG. 10 is an X-ray diffraction pattern 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 in inventive examples 25, 27, 33, 35, 37 and comparative example 6;
FIG. 12 is an X-ray diffraction chart of the ceramic materials in example 7 and examples 26 to 31 of the present invention;
FIG. 13 shows the dielectric constants ε of the CabSiC LTCC ceramic materials of examples 1 to 5 of the present invention and the CBS ceramic material of comparative example 1 r And a line graph of dielectric loss tan δ.
Detailed Description
The invention provides a calcium-boron-silicon LTCC ceramic material, which comprises a CBS ceramic component and a rare earth oxide; the CBS ceramic composition comprises: caO 50-60 mol%, B 2 O 3 5 to 15mol%, and SiO 2 35-45 mol%; the doping amount of the rare earth oxide is 0 of the CBS ceramic component.5 to 15mol percent; 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 a rare earth oxide. According to the invention, rare earth oxide is doped in the CBS ceramic, so that the glass network structure can be strengthened, the glass viscosity is increased, the dielectric loss of the ceramic material is reduced, and the precipitation of a high-temperature phase alpha-CaSiO can be inhibited 3 Promote the precipitation of low-temperature phase beta-CaSiO 3 Therefore, 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 includes CaO in an amount of 50 to 60mol%, preferably 51 to 55mol%. The CBS ceramic is prepared by taking CaO as a main component. The invention overcomes the defect of high content of B by controlling the dosage of CaO within the range 2 O 3 The disadvantage of (2).
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 reacting with SiO 2 And constructing a glass network structure. The invention is realized by mixing B 2 O 3 The dosage of the boron oxide is controlled within the range, so that the melting volatilization of the boron oxide and the precipitation of the 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 invention 2 For with B 2 O 3 And constructing a glass network structure. The invention is prepared by mixing SiO 2 The amount of the glass powder is controlled within the range, so that 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% based on the CBS ceramic component. According to the invention, the doping amount of the rare earth oxide is controlled within the range, so that the dielectric constant of the ceramic material can be controlled within the range of 5.19-8.92, and the ceramic material with low dielectric loss can be obtained.
In the present inventionIn the invention, the rare earth oxide comprises 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, pressure alkali effect and the like, and can strengthen the glass network structure, increase the viscosity of glass 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, by designing the low-boron CBS ceramic, 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 The introduction of the catalyst can also inhibit the precipitation of high-temperature phase alpha-CaSiO 3 Promote the precipitation of low-temperature phase beta-CaSiO 3 Therefore, 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 in the technical scheme, which comprises the following steps:
(1) Mixing CaCO 3 、B 2 O 3 、SiO 2 Mixing with rare earth oxide, melting, and then sequentially quenching and ball-milling to obtain glass powder;
(2) Mixing the glass powder obtained in the step (1) with a binder, granulating, and 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.
CaCO according to the invention 3 、B 2 O 3 、SiO 2 And mixing with rare earth oxide, melting, and then sequentially quenching and ball-milling to obtain the glass powder.
CaCO of the invention 3 、B 2 O 3 、SiO 2 The manner of mixing with the rare earth oxide is not particularly limited, and a mixing manner known to those skilled in the art may be employed. In the present invention, the mixing time is preferably 60 to 80min; the equipment used for mixing is preferably a three-dimensional blender.
In the present invention, the temperature of the melting 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, and more preferably 2 to 3 hours. In the present invention, the heating apparatus for melting is preferably a resistance furnace; the crucible used for the melting is preferably a platinum crucible. In the present invention, it is preferable to control the melting temperature and time within the above ranges so that each raw material can be sufficiently melted to form 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 molten glass into a vitreous body by quenching.
In the present invention, the rotation speed of the ball mill is preferably 300 to 450rpm, more preferably 350 to 450rpm. In the present invention, the time for the ball milling is preferably 6 to 12 hours, more preferably 6 to 10 hours. In the invention, the ball milling medium is preferably deionized water; the grinding balls used for ball milling are preferably zirconium balls; the ball milling equipment is preferably a planetary ball mill. The invention crushes the vitreous body by ball milling to prepare powder, which is convenient for subsequent processing.
After the ball milling is finished, the ball-milled products are preferably sequentially sieved and dried to obtain the glass powder. The operation of sieving and drying is not particularly limited in the invention, and the technical scheme of sieving and drying known to those skilled in the art can be adopted. In the present invention, the mesh number of the screen used for the screening is preferably 500 meshes. In the invention, the drying temperature is preferably 80-90 ℃; the drying time is preferably 12 to 15 hours.
After the glass powder is obtained, the glass powder and the binder are mixed, granulated and pressed to obtain the ceramic biscuit.
The mixing mode of the glass powder and the binder is not particularly limited in the present invention, and the mixing technical scheme known to those skilled in the art can be adopted.
In the present invention, the binder preferably includes a polyvinyl alcohol solution. In the present invention, the mass concentration of the polyvinyl alcohol solution is preferably 4 to 8%, more preferably 4 to 6%. In the present invention, the ratio of the mass of the glass frit to the volume of the binder is preferably 20g:4mL. In the invention, the binder is used for binding the glass powder, so that granulation is facilitated; the binder decomposes 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 granulation operation is not particularly limited in the present invention, and a granulation technique known to those skilled in the art may be employed.
After the granulation is completed, the present invention preferably screens the product obtained by the granulation. The operation of sieving is not particularly limited in the present invention, and the technical scheme of sieving 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 40 mesh.
In the present invention, the pressure of the pressing is preferably 70 to 100MPa, more preferably 80 to 100MPa; the pressing time is preferably 10 to 20s, more preferably 15 to 20s. In the present invention, the apparatus used for the pressing is preferably a one-way press. The invention presses the powder obtained after granulation into biscuit with a certain shape.
In the present invention, the ceramic biscuit preferably has a specification of 10mm × 10mm × 2mm.
After a ceramic biscuit is obtained, the ceramic biscuit is sintered to obtain the calcium-boron-silicon LTCC ceramic material.
In the present invention, the temperature of the sintering is preferably 800 to 900 ℃, more preferably 850 to 880 ℃. The invention preferably controls the sintering temperature within the range, which is favorable for obtaining the beta-CaSiO crystal phase as the main crystal phase 3 Of a ceramic material. In the invention, the heat preservation time of the sintering is preferably 15-30 min, and more preferably 15-25 min; the heating rate of the sintering is preferably 5 to 10 ℃/min, more preferably 5 to 8 ℃/min. In the present invention, the cooling means after sintering is preferably furnace 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 practical and industrial conditions.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The calcium-boron-silicon LTCC ceramic material consists of CBS ceramic component and Nb 2 O 5 The CBS ceramic component consists of: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Nb 2 O 5 The amount of incorporation of (A) is 1mol% of the CBS ceramic component, and is designated as CBSN 1 ；
The preparation process comprises the following steps:
(1) Weighing CaCO as raw material 3 、B 2 O 3 、SiO 2 And Nb 2 O 5 Mixing the weighed raw materials by a three-dimensional mixer for 60min, transferring the mixture to a platinum crucible, heating the mixture to 1400 ℃ in a resistance furnace, preserving the heat for 2h, and then pouring molten glass liquid into deionized water for quenching to obtain a glass body; then placing the vitreous body in a planetary ball mill for wet milling, wherein the ball milling medium is deionized water, the milling balls are zirconium balls, the rotating speed of the ball mill is 450rpm, the ball milling time is 6h, then sieving the ball milling material with a 500-mesh sieve, drying the ball milling material at 80 ℃ for 12h to obtain the content of 51mol percent CaO-9.6mol percent 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 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 one-way press under the pressure of 100MPa for 15s to obtain a ceramic biscuit with the thickness of 10mm multiplied by 2 mm;
(3) Placing the ceramic biscuit obtained in the step (2) in a resistance furnace, heating to 865 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 15min, and then cooling along with the furnace to obtain the content of 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: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Nb 2 O 5 The amount of incorporation of (A) is 2mol% of the CBS ceramic component, and is designated as CBSN 2 ；
The 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 amount of incorporation of (A) is 4mol% of the CBS ceramic component, and is designated as CBSN 4 ；
The 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 amount of incorporation of (A) is 6mol% of the CBS ceramic component, and is designated as CBSN 6 ；
The 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: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Nb 2 O 5 In an amount of 8mol% based on the CBS ceramic component, and is designated as CBSN 8 ；
The 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 Is added in an amount of 0.5mol% of the CBS ceramic component, and is designated as CBST 0.5 ；
The preparation process comprises the following steps:
(1) Weighing the raw materials CaCO according to the composition proportion 3 、B 2 O 3 、SiO 2 And Ta 2 O 5 Mixing the weighed raw materials by a three-dimensional mixer for 60min, transferring the mixture to a platinum crucible, heating the mixture to 1400 ℃ in a resistance furnace, preserving the heat for 2h, and then pouring molten glass liquid into deionized water for quenching to obtain a glass body; subsequently subjecting the vitreous body to wet milling in a planetary ball mill with a milling medium of deionized water, milling balls of zirconium, a mill speed of 450rpm and a milling time of 6h, after which the ball milled material is passed through a 500 mesh sieve and dried at 80 ℃ for 12h, obtaining 51mol% of CaO-9.6mol% of 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 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 one-way press under the pressure of 100MPa for 15s to obtain a ceramic biscuit with the thickness of 10mm multiplied by 2 mm;
(3) Placing the ceramic biscuit obtained in the step (2) in a resistance furnace, heating to 875 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 15min, and then cooling along with the furnace to obtain the ceramic biscuit with the content of 51mol% CaO-9.6mol% 2 O 3 -39.4mol％SiO 2 -0.5mol％Ta 2 O 5 A ceramic material.
Example 7
The calcofilicon LTCC ceramic material is composed of CBS ceramic component and Ta 2 O 5 The CBS ceramic component consists of: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Ta 2 O 5 Is 1mol% of the CBS ceramic component and is denoted as CBST 1 ；
The 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: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Ta 2 O 5 Is 2mol% of the CBS ceramic component and is designated as CBST 2 ；
The procedure was 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: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol％，Ta 2 O 5 Is 4mol% of the CBS ceramic component and is denoted as CBST 4 ；
The procedure was 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 Is 6mol% of the CBS ceramic component and is designated as CBST 6 ；
The procedure was as in example 6.
Example 11
The difference from example 1 is that in step (3) the temperature is increased to 820 ℃ at a rate of 5 ℃/min, and the temperature is recorded as CBSN in example 1 11 。
Example 12
The difference from example 1 is that in step (3), the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as example 1 and is denoted as CBSN 12 。
Example 13
The difference from example 2 is that in step (3), the temperature is raised to 820 ℃ at a rate of 5 ℃/min, which is otherwise the same as example 2 and is denoted as CBSN 21 。
Example 14
The difference from example 2 is that in step (3), the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as example 2 and is denoted as CBSN 22 。
Example 15
The difference from example 2 is that in step (3), the temperature is raised to 805 ℃ at a rate of 5 ℃/min, and the temperature is recorded as CBSN in example 2 23 。
Example 16
The difference from example 2 is that in step (3), the temperature is raised to 835 ℃ at a rate of 5 ℃/min, and the temperature is recorded as CBSN in example 2 24 。
Example 17
The difference from example 2 is that in step (3) the temperature is raised to 850 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 2 and is denoted as CBSN 25 。
Example 18
The difference from example 3 is that in step (3) the temperature is increased to 820 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 3 and is denoted as CBSN 41 。
Example 19
The difference from example 3 is that in step (3) the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 3 and is designated CBSN 42 。
Example 20
The difference from example 4 is that in step (3) the temperature is increased to 820 ℃ at a rate of 5 ℃/min, and the rest is the same as example 4 and is marked CBSN 61 。
Example 21
The difference from example 4 is that in step (3), the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as example 4 and is denoted as CBSN 62 。
Example 22
The difference from example 5 is that in step (3), the temperature is raised to 820 ℃ at a rate of 5 ℃/min, which is otherwise the same as example 5, and is denoted as CBSN 81 。
Example 23
The difference from example 5 is that in step (3) the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 5 and is denoted as CBSN 82 。
Example 24
The difference from example 6 is that in step (3) the temperature is increased to 820 ℃ at a rate of 5 ℃/min, and the remainder is the same as example 6, and is denoted CBST 0.51 。
Example 25
The difference from example 6 is that in step (3) the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 6 and is denoted CBST 0.52 。
Example 26
The difference from example 7 is that in step (3), the temperature is raised to 820 ℃ at a rate of 5 ℃/min, which is otherwise the same as example 7, and is denoted as CBST 11 。
Example 27
The difference from example 7 is that in step (3) the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 7 and is denoted CBST 12 。
Example 28
The difference from example 7 is that in step (3) the temperature was raised to 800 ℃ at a rate of 5 ℃/min, and the remainder of the example is the same as example 7 and is denoted CBST 13 。
Example 29
The difference from example 7 is that in step (3) the temperature is raised to 840 ℃ at a rate of 5 ℃/min, as in example 7, where CBST is noted 14 。
Example 30
The difference from example 7 is that in step (3) the temperature was raised to 860 ℃ at a rate of 5 ℃/min, as in example 7, which is denoted CBST 15 。
Example 31
The difference from example 7 is that in step (3) the temperature is raised to 870 ℃ at a rate of 5 ℃/min, and the remainder is the same as example 7, denoted CBST 16 。
Example 32
The difference from example 8 is that the temperature in step (3) is increased to 820 ℃ at a rate of 5 ℃/min, which is otherwise the same as example 8 and is denoted as CBST 21 。
Example 33
The difference from example 8 is that in step (3) the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 8 and is denoted CBST 22 。
Example 34
The difference from example 9 is that in step (3) the temperature is increased to 820 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 9 and is denoted CBST 41 。
Example 35
The difference from example 9 is that in step (3) the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 9 and is denoted CBST 42 。
Example 36
The difference from example 10 is that in step (3) the temperature is increased to 820 ℃ at a rate of 5 ℃/min, and the remainder is the same as example 10, and is denoted CBST 61 。
Example 37
The difference from example 10 is that in step (3) the temperature is raised to 880 ℃ at a rate of 5 ℃/min, which is otherwise the same as in example 10 and is denoted CBST 62 。
Comparative example 1
The CBS ceramic material consists of the following components: caO 51mol%, B 2 O 3 9.6mol% and SiO 2 39.4mol% is designated as CBSN 0 ；
The preparation process comprises the following steps:
(1) According to the aboveComposition proportioning weighing raw material CaCO 3 、B 2 O 3 And SiO 2 Mixing the weighed raw materials for 60min by using a three-dimensional mixer, transferring the mixture to a platinum crucible, heating the mixture to 1400 ℃ in a resistance furnace, preserving the heat for 2h, and then pouring molten glass liquid into deionized water for quenching to obtain a glass body; then putting the glass body into a planetary ball mill for wet milling, wherein the ball milling medium is deionized water, the milling ball is a zirconium ball, the rotating speed of the ball mill is 450rpm, the ball milling time is 6h, then, sieving the ball milling material by a 500-mesh sieve, and drying the ball milling material at 80 ℃ for 12h 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 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 one-way press under the pressure of 100MPa for 15s to obtain a ceramic biscuit with the thickness of 10mm multiplied by 2 mm;
(3) Placing the ceramic biscuit obtained in the step (2) in a resistance furnace, heating to 865 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 15min, and then cooling along with the furnace to obtain the content of 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 in step (3) is raised to 875 ℃ at a rate of 5 ℃/min, and the remainder is recorded as CBST in the same manner as in comparative example 1 0 。
Comparative example 3
The difference from comparative example 1 is that in step (3) the temperature is raised to 820 ℃ at a rate of 5 ℃/min, and the remainder is recorded as CBSN as in comparative example 1 01 。
Comparative example 4
The difference from comparative example 1 is that in step (3) the temperature is raised to 880 ℃ at a rate of 5 ℃/min, and the remainder is recorded as CBSN in the same manner as in comparative example 1 02 。
Comparative example 5
The difference from comparative example 1 is that in step (3) the temperature is raised to 820 ℃ at a rate of 5 ℃/min, and the remainder is similar to comparative example 1 and is denoted as CBST 01 。
Comparative example 6
The difference from comparative example 1 is that in step (3) the temperature is raised to 880 ℃ at a rate of 5 ℃/min, and the remainder is recorded as CBST, as in comparative example 1 02 。
TABLE 1 thermal behavior at 5 deg.C/min for the ceramic materials of comparative examples 1-2 and examples 1-10
With CBSN 0 The temperature of the lowest point of viscosity is 767 ℃ as a standard point, and sequentially taking CBSN 1 ～CBSN 8 A ceramic material viscosity value; by CBST 0 The temperature of the lowest viscosity point is 774 ℃ is taken as a standard point, and CBST is sequentially taken 0.5 ～CBST 6 The viscosity values of the ceramic materials, the results are shown in Table 2.
TABLE 2 viscosity of ceramic materials of comparative examples 1 to 2 and examples 1 to 10
| Sample(s) | 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 number of the ceramic material is improved 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 (I) | Dielectric constant ε 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 is XRD patterns of the calboro-silicate-based LTCC ceramic materials of examples 1 to 5 and the CBS ceramic material of comparative example 1. FIG. 2 is an XRD pattern of the CabSiC LTCC ceramic materials of examples 6-10 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 are not doped with rare earth oxides 3 Phase (PDF # 31-0300) and CaSi 2 O 5 Phase (PDF # 51-0092), with Nb 2 O 5 Or Ta 2 O 5 The content is increased, the diffraction peak is transformed into a steamed bread peak, which shows that the crystallization of the glass is inhibited, the glass is obviously characterized, and the reason for the phenomena is probably Nb 5+ And Ta 5+ The ionic field strength is higher.
FIG. 3 is a DSC plot of the calboro-silicon LTCC ceramic materials of examples 1-5 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 a distinct softening point (T) g ) Crystallization initiation 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 Begins to increase in intensity and becomes sharp, the peak temperature is shifted from CBSN 1 777 ℃ shift of the sample to CBSN 8 833 ℃. T is g 、T c And T p The values are all shifted to high values, illustrating that with Nb 2 O 5 The crystallization is inhibited by the increase of the content.
FIG. 4 is a DSC plot of the CaBsASi-based LTCC ceramic materials of examples 6-10 and the CBS ceramic material of comparative example 2. As can be seen from FIG. 4 and Table 1, most of the ceramic samples had a distinct softening point (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 is increased from 0.5mol% to 6mol%, T g The value increases from 698 ℃ to 766 ℃ T p1 Begins to increase in intensity and becomes sharp, with the peak from CBST 0.5 794 ℃ shift of samples to CBST 6 887 deg.C. T is g 、T c And T p The values are all shifted to high values, indicating that with Ta 2 O 5 The crystallization is inhibited by the increase of the content.
FIG. 5 is an X-ray diffraction pattern of the ceramic materials of examples 11, 13, 18, 20, 22 and comparative example 3. As can be seen from FIG. 5, when the sintering temperature is 820 deg.C, CBSN 01 The samples had a large amount of alpha-CaSiO 3 Phase (PDF # 31-0300) and small amount of beta-CaSiO 3 Phase (PDF # 42-0547), with Nb 2 O 5 Addition of alpha-CaSiO 3 Sharp decrease of phase, beta-CaSiO 3 Phase increase rapidly, CBSN 81 The sample remained in the glassy state, which is shown to follow Nb 2 O 5 The doping 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 pattern of the ceramic materials in examples 1 to 5 and comparative example 1. As can be seen from FIG. 6, when the sintering temperature is 865 deg.C, β -CaSiO is mainly present in the ceramic sample 3 And (4) phase(s). With Nb 2 O 5 Addition of CaNb 2 O 6 The diffraction peaks of the (PDF # 39-1392) phases were gradually sharp.
FIG. 7 is an X-ray diffraction pattern of the ceramic materials of examples 12, 14, 19, 21, 23 and comparative example 4. It can be seen from FIG. 7 that when the sintering temperature is 880 deg.C, where for CBSN 82 Sample, the main phase has been formed from beta-CaSiO 3 Conversion to CaNb 2 O 6 。
As can be seen from FIGS. 5 to 7, the ceramic material gradually crystallizes with the increase of the sintering temperature, and the ceramic material is completely crystallized at 865 ℃; more importantly, the main crystal phase precipitated at the time is beta-CaSiO 3 。
FIG. 8 is an X-ray diffraction chart of the ceramic materials in example 2 and examples 13 to 17. In the figure, beta-CaSiO 3 Is a main crystal phase, and in addition, in the sample with higher doping content, caNb 2 O 6 Present as an additional crystalline phase, ca 2 Nb 2 O 7 The relative intensity of the diffraction peaks gradually increased as the sintering temperature increased from 805 ℃ to 880 ℃.
FIG. 9 is an X-ray diffraction pattern of the ceramic materials in examples 24, 26, 32, 34, 36 and comparative example 5. As can be seen in FIG. 9, CBST exhibited a sintering temperature of 820 deg.C 01 The samples had a large amount of alpha-CaSiO 3 Phase (PDF # 31-0300) and a small amount of beta-CaSiO 3 Phase (PDF # 42-0547) with Ta 2 O 5 Addition of alpha-CaSiO 3 Sharp phase reduction, beta-CaSiO 3 The phase increases rapidly. CBST 61 The sample remained glassy, a phenomenon that is shown with Ta 2 O 5 Increased doping of CBST ceramic materialsThe content of the glass phase of (2) is increased and the devitrification behavior is suppressed.
FIG. 10 is an X-ray diffraction pattern of the ceramic materials in examples 6 to 10 and comparative example 2. As can be seen in FIG. 10, β -CaSiO is predominantly present in the ceramic sample 3 Phase with Ta 2 O 5 Addition of (2), ca 2 Ta 2 O 7 The diffraction peak of the (PDF # 74-1355) phase was gradually sharp.
FIG. 11 is an X-ray diffraction pattern of the ceramic materials in examples 25, 27, 33, 35, 37 and comparative example 6. As can be seen in FIG. 11, when the sintering temperature is 880 deg.C, where for CBST 62 Sample, the 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, as the sintering temperature increases, the ceramic material gradually crystallizes, and reaches complete crystallization at 875 ℃; more importantly, the main crystal phase precipitated at the time is beta-CaSiO 3 。
FIG. 12 is an X-ray diffraction chart of the ceramic materials in example 7 and examples 26 to 31. In the figure, beta-CaSiO 3 Is a main crystal phase, and in addition, ca is contained in a sample with a high doping content 2 Ta 2 O 7 Present as an additional crystalline phase, ca 2 Ta 2 O 7 The relative intensities of the diffraction peaks gradually increased as the sintering temperature increased from 800 ℃ to 880 ℃.
FIG. 13 shows the dielectric constants ε of the CabSiC LTCC ceramic materials of examples 1 to 5 and the CBS ceramic material of comparative example 1 r And a line graph of dielectric loss tan δ. As can be seen from FIG. 13, with Nb 2 O 5 Addition of ε r The curve increases continuously, which is mainly related to the change of the particle morphology and the devitrification behavior of the glass. The reasons for this situation may be: first, the increase in fine particles leads to an increase in grain boundaries and defects; second, nb 2 O 5 May form CaNb 2 O 6 Phase, dielectric constant (. Epsilon.) of the phase r 15) is larger than the CBS ceramic. Nb 2 O 5 The tan delta value increases after a large decrease, which may be caused by the alkali-pressing effect. Addition of Nb to CBS glasses 2 O 5 The inhibition effect is particularly obvious. Since Nb 5+ The high ionic field strength and the plurality of binding sites can consolidate the structure of the relaxed alkali glass and reduce the relaxation polarization, so that the tan delta is reduced. Wherein 2mol% of Nb 2 O 5 The CBSN ceramic has excellent dielectric property after being sintered for 15min at 865 ℃, and epsilon 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 the dielectric constant epsilon r 6.18, and a dielectric loss tan delta of 1.19X 10 -3 (1MHz)。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A calcium boron silicon LTCC ceramic material comprises a CBS ceramic component and a rare earth oxide; the CBS ceramic composition comprises: caO 50-60 mol%, B 2 O 3 5 to 15mol%, and SiO 2 35-45 mol%; 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 。
2. The calceii-based LTCC ceramic material of claim 1, wherein the CBS ceramic composition comprises: 51 to 55mol% of CaO, B 2 O 3 5 to 10mol%, and SiO 2 36 to 40mol percent; the doping amount of the rare earth oxide is 1-8 mol% of the CBS ceramic component.
3. The calc-borosilicate-based LTCC ceramic material of claim 1 or 2, wherein the calc-borosilicate-based LTCC ceramic material has a main crystalline phase of β -CaSiO 3 。
4. A process for the preparation of a calcelosilicate LTCC ceramic material according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing CaCO 3 、B 2 O 3 、SiO 2 Mixing with rare earth oxide, melting, and then sequentially quenching and ball-milling to obtain glass powder;
(2) Mixing the glass powder obtained in the step (1) with a binder, granulating, and 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 preparation method according to claim 4, wherein the melting temperature in the step (1) is 1400-1450 ℃, and the holding time for melting is 2-4 h.
6. The method of claim 4, wherein the quenching in step (1) is water cooling.
7. The preparation method of claim 4, wherein the rotation speed of the ball milling in the step (1) is 300-450 rpm, and the ball milling time is 6-12 h.
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 preparation method according to claim 4, wherein the sintering temperature in the step (3) is 800-900 ℃, the sintering holding time is 15-30 min, and the sintering temperature rise rate is 5-10 ℃/min.
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