CN110372217B - Low-temperature co-fired ceramic material and preparation method thereof - Google Patents
Low-temperature co-fired ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-temperature co-fired ceramic material and a preparation method thereof, wherein the low-temperature co-fired ceramic material is prepared from CaO-B 2 O 3 ‑SiO 2 System microcrystalline glass and CaO-B 2 O 3 ‑SiO 2 The system ceramic comprises 72-95 wt% of CBS glass and 5-28 wt% of CBS ceramic. Compared with the existing materials, the raw materials adopted by the invention mainly comprise calcium carbonate, boric acid and silicon dioxide, and the preparation process is simple and the cost is lower. The low-temperature co-fired ceramic material prepared by the invention has low dielectric constant and low loss (less than 0.0017), is sintered compactly at 840-920 ℃, and can be co-fired with gold and silver in a matching way.
Description
Technical Field
The invention relates to a low-temperature co-fired ceramic material and the preparation field thereof, in particular to a method for preparing the low-temperature co-fired ceramic material through solid-liquid phase reaction, and the low-temperature co-fired ceramic material with low dielectric constant and low dielectric loss is obtained by the method.
Background
The existing low-temperature co-fired ceramic material can be divided into two systems: one is a glass-ceramic composite material system, and the other is a microcrystalline glass material system.
The existing low-temperature co-fired ceramic material of a glass-ceramic composite system meets the requirement of low loss, and the phase of the ceramic material is mainly a ceramic phase, such as zirconia, alumina, silicon oxide and the like. Because the sintering temperature of the single ceramic phase is about 1400-1900 ℃, low-melting glass is required to be added for reducing the sintering temperature. The patent application No. 201010582325.7 discloses a low-softening-point glass-ceramic low-temperature co-fired ceramic material, which mainly comprises a low-softening-point glass phase and a ceramic phase, wherein the mass ratio of the glass phase to the ceramic phase is (4.5-2): 3, and a large amount of glass phase is added to influence the dielectric property, especially the dielectric loss is large.
Disclosure of Invention
Aiming at the problems of the existing low-melting-point glass-ceramic low-temperature co-fired ceramic material, the invention provides a microcrystalline glass-ceramic low-temperature co-fired ceramic material which can be sintered at 840-920 ℃ to be compact, has a dielectric constant of 6.0-7.7 and a loss tangent of less than 0.0017, and provides a method for preparing the low-temperature co-fired ceramic material.
In view of the above, the present inventionThe invention provides a low-temperature co-fired ceramic material, which consists of the following components: 72-95 wt% of CaO-B 2 O 3 -SiO 2 Systematic microcrystalline glass (CBS microcrystalline glass), 5-28 wt% CaO-B 2 O 3 -SiO 2 A system ceramic (CBS ceramic), wherein:
the CBS microcrystalline glass consists of CaO and B 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 O、K 2 O、Li 2 And (C) O.
The CBS ceramic consists of CaO and B 2 O 3 、SiO 2 And (4) forming.
The CBS microcrystalline glass and the CBS ceramic are both calcium borosilicate systems, have good wettability with each other, and have low dielectric constant and low dielectric loss.
Preferably, the CBS glass ceramics mainly comprises the following oxides in percentage by mass: 21-24% of CaO; b is 2 O 3 :30～33％；SiO 2 :45～48％；TiO 2 :1～4％；ZrO 2 :1～5％；Na 2 O:0.5～3％；K 2 O:0.5～3％；Li 2 O:0.5～3％。
Preferably, CaO, B in the CBS ceramic 2 O 3 、SiO 2 The molar ratio of (A) is determined according to formula (1):
(1-x-y)CaO-0.5xB 2 O 3 -ySiO 2 (1)；
wherein 0.25< x0.5, 0.12< y < 0.3.
The preparation method of the low-temperature co-fired ceramic material comprises the following steps:
(1) mixing CaCO 3 、H 3 BO 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 CO 3 、K 2 CO 3 、Li 2 CO 3 Wet mixing, drying, sieving, melting the mixed powder into glass liquid (melt), quenching the glass liquid with water to form glass frit, and crushing into glass powder to obtain the CBS glass ceramic powder.
(2) According to the chemical formula (1) of the CBS ceramic, calculating and mixingWeighing CaCO 3 ，H 3 BO 3 And SiO 2 Wet mixing, stoving, sieving, pre-sintering to obtain synthetic CBS ceramic block, (1-x-y) CaO-0.5xB 2 O 3 -ySiO 2 Ceramic powder.
In one embodiment of the invention, in the process of preparing the low-temperature co-fired ceramic material, firstly, the CBS microcrystalline glass powder and the CBS ceramic powder are prepared, then, the glass powder and the ceramic powder are mixed by a wet method, dried and sieved, and the low-temperature co-fired ceramic powder is obtained.
Preferably, the melting temperature of the glass in step (1): 1350-1500 ℃ for 3-6 h (h, the same below).
Preferably, the pre-sintering temperature of the ceramic in the step (2): 810-1050 ℃ for 2-8 h.
The invention provides a low-temperature co-fired ceramic material which comprises the following components: 72-95 wt% of CBS microcrystalline glass and 5-28 wt% of CBS ceramic; the microcrystalline glass is CBS glass, and the ceramic is composed of CaO and B 2 O 3 With SiO 2 The composition is CBS ceramic. Compared with the existing low-temperature co-fired ceramic material, the invention takes the CBS glass ceramics as the low-melting glass, and the crystallization degree is higher;
the invention uses CaO and B 2 O 3 、SiO 2 The component is ceramic material, which has the same kind of main oxide component as CBS microcrystalline glass and well similar compatibility characteristic, and CaO and B in the ceramic material are controlled 2 O 3 With SiO 2 The dielectric constant of the ceramic material can be adjusted, and then the ceramic material is matched and compounded with CBS microcrystalline glass with different proportions, so that the novel low-temperature co-fired ceramic material which is compact in sintering at 840-920 ℃ (see figure 2), has the dielectric constant of 6.0-7.7 and the loss tangent of less than 0.0017 under the condition of 9-13 GHz can be obtained.
The low-temperature co-fired ceramic material obtained by the invention needs to be co-fired with silver and gold electrodes, and the preferred co-firing temperature of the silver and gold electrodes is 830-900 ℃, so that the low-temperature co-fired ceramic material prepared by the invention can be co-fired with the silver and gold electrodes well (see figure 3).
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of a low temperature co-fired ceramic material after sintering according to an embodiment of the present invention;
FIG. 2 is an SEM (scanning electron microscope) spectrum (1000X) of a sintered cross-section of a low-temperature co-fired ceramic material according to an embodiment of the present invention;
FIG. 3 is an SEM image (250X) of a cross section of a low-temperature co-fired ceramic and a silver electrode after co-firing according to an embodiment of the invention.
Detailed Description
For a further understanding of the invention, reference will now be made to specific embodiments of the invention described below in conjunction with certain examples, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention, and not to limit the scope of the claims.
In accordance with one embodiment of the present invention, a low temperature co-fired ceramic material is comprised of: 72-95 wt% of CBS microcrystalline glass and 5-28 wt% of CBS ceramic.
The CBS microcrystalline glass consists of CaO and B 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 O、K 2 O、Li 2 And (C) O.
The CBS ceramic consists of CaO and B 2 O 3 、SiO 2 And (4) forming.
The low-temperature co-fired ceramic is mainly co-fired with silver and gold electrodes, the preferred co-firing temperature of the silver and gold electrodes is 830-900 ℃, and the low-temperature co-fired ceramic material of the existing ceramic-low melting point glass system: the ceramic is taken as the main material, low melting point glass is added for sintering, the sintering temperature of the system is higher, and the dielectric loss is gradually increased along with the addition of the low melting point glass, so that the requirement of co-sintering with silver and gold electrodes in the prior art can not be met. Therefore, the self-crystallization degree is higher, the CBS microcrystalline glass can be used as a sintering-aid material, and the CBS ceramic material used as a framework can meet the requirements of a low-temperature co-fired material.
In one embodiment of the invention, the content of the CBS glass ceramics is 72-95 wt%, preferably 74-94 wt%, because the glass is vitrified at 700-800 ℃, if the glass content is too small, the requirement of sintering temperature is difficult to meet, and if the glass content is too high, the dielectric constant regulation range is too narrow. The CBS ceramic content is 5-28 wt%, preferably 6-26 wt%, if the ceramic content is too high, the requirement of sintering temperature is difficult to meet, and if the ceramic content is too low, the dielectric constant regulation range is too narrow.
In one embodiment of the invention, the CBS microcrystalline glass mainly consists of CaO and B 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 O、K 2 O、Li 2 And (C) O. B is 2 O 3 、SiO 2 The addition of (2) can meet the requirement of low dielectric constant; ZrO (ZrO) 2 、TiO 2 The addition of (2) can promote the crystallization of the glass and reduce the dielectric loss; na (Na) 2 O、K 2 O、Li 2 The addition of O can reduce the viscosity of the molten glass and increase the fluidity of the molten glass.
In one embodiment of the invention, the CBS ceramics only consist of CaO and B 2 O 3 、SiO 2 The three oxides have the same components and similar contents as the main oxides in the CBS microcrystalline glass, have good similar compatibility, have CaO dielectric constant of 11.8, can improve the dielectric constant of the CBS ceramic, have lower SiO2 dielectric constant, can reduce the dielectric constant of the CBS ceramic, and can regulate and control the dielectric constant of the CBS ceramic according to different proportions of the oxides of the CBS ceramic and the CBS microcrystalline glass. The CBS glass is matched with the CBS ceramic, and the dielectric constant and the sintering temperature of the low-temperature co-fired ceramic can be regulated and controlled according to different proportions of the glass and the ceramic. Preferably, the CaO and B are 2 O 3 And SiO 2 According to the expression (1-x-y) CaO-0.5xB 2 O 3 -ySiO 2 And (4) determining.
In one embodiment of the invention, the CBS ceramic is selected, on one hand, due to the high sintering temperature, the CBS ceramic can be matched with low-temperature vitrified CBS glass, and then the sintering temperature of the low-temperature co-fired ceramic is adjusted to a proper range; on the other hand, the main components are CaO and B 2 O 3 、SiO 2 Dielectric of ceramics itselfThe constant can be regulated and controlled in a certain range, the components are the same as those of the CBS glass ceramics, the CBS ceramics and the CBS glass ceramics have better similar compatibility and better wettability, and the reaction is more sufficient when solid-liquid phase reaction occurs.
In another embodiment of the present invention, a method for preparing the low-temperature co-fired ceramic material is further provided, which comprises the following specific steps:
mixing CaCO 3 、H 3 BO 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 CO 3 、K 2 CO 3 、Li 2 CO 3 Wet mixing, drying, melting into glass liquid, water quenching the glass liquid, and crushing into glass powder to obtain the CBS glass ceramic powder.
According to the chemical formula of CBS ceramics ((1-x-y) CaO-0.5 xB) 2 O 3 -ySiO 2 Wherein 0.25<x<0.5，0.12<y<0.3) weighing CaCO 3 、H 3 BO 3 And SiO 2 Wet mixing, stoving, sieving, pre-sintering to obtain ceramic block, crushing and sieving to obtain (1-x-y) CaO-0.5xB 2 O 3 -ySiO 2 Ceramic powder.
And uniformly mixing the CBS microcrystalline glass powder and the optimized CBS ceramic powder by a wet method, drying and sieving to obtain the low-temperature co-fired ceramic powder.
In the implementation process of the invention, the preparation sequence of the glass powder and the ceramic powder is not particularly limited, and the glass powder can be prepared firstly or the ceramic powder can be prepared firstly. In one embodiment of the present invention, the glass frit is prepared as follows:
mixing CaCO 3 、H 3 BO 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 CO 3 、K 2 CO 3 、Li 2 CO 3 Wet mixing, drying, sieving, mixing powder, melting the mixture into glass liquid, quenching the glass liquid with water, and then crushing into glass powder to obtain the CBS glass ceramic powder.
When preparing the CBS microcrystalline glass, wet mixing is ball milling by adding deionized water through a ball mill, wherein the ball milling time is as follows: 3-8 h, more preferably 4-7 h, sieving the mixture with a 60-mesh sieve, melting at 1350-1500 ℃, more preferably 1400-1450 ℃, for 3-6 h, more preferably 4-5 h, water quenching the glass liquid into glass blocks, and then ball-milling by a wet method to obtain glass powder. The granularity of the glass powder is 0.5-8 μm, and more preferably 1-7 μm.
In one embodiment of the present invention, in the process of preparing the ceramic powder, the following method is used for preparation: weighing CaCO 3 、H 3 BO 3 And SiO 2 The CBS ceramic powder is prepared by wet mixing, drying, sieving, pre-sintering to obtain a ceramic block, crushing the ceramic block and sieving.
In the process of preparing ceramic powder, CaO and B are added 2 O 3 And SiO 2 The molar ratio of (A) is preferably determined according to formula (1):
(1-x-y)CaO-0.5xB 2 O 3 -ySiO 2 (1)；
wherein 0.25< x <0.5, 0.12< y < 0.3).
The mixing is carried out by water ball milling, the mixture is dried after ball milling, the mixture is sieved by a 60-mesh sieve, then the sieved material is presintered to obtain ceramic powder, namely CBS ceramic powder, and the ceramic powder is further ball milled and crushed. And finally, sieving the crushed ceramic powder with a 120-mesh sieve to obtain the CBS ceramic powder. The ball milling time of the mixed materials is 4-8 h, more preferably 5-7 h, the pre-sintering temperature is 810-1050 ℃, more preferably 830-1000 ℃, and the pre-sintering time is 2-8 h, more preferably 3-7 h. The particle size of the ceramic is 0.5-8 μm, and more preferably 1-7 μm.
After the glass powder and the ceramic powder are respectively prepared, the glass powder and the ceramic powder are mixed according to a certain proportion according to the requirements of sintering temperature and dielectric constant to obtain the low-temperature co-fired ceramic material.
In one embodiment of the invention, a preparation method of a low-temperature co-fired ceramic material is provided, wherein in the preparation process, glass powder and ceramic powder are respectively prepared, and then the glass powder and the ceramic powder are mixed to obtain the low-temperature co-fired ceramic material. Experimental results show that the low-temperature co-fired ceramic material prepared by the invention can be sintered at 840-920 ℃ to be compact, has the dielectric constant of 6.0-7.7 and the loss tangent of less than 0.0017, and can be co-fired with gold and silver electrodes.
For further understanding of the present invention, the present invention will be described in detail with reference to the following examples, which are not to be construed as limiting the scope of the present invention, and the non-essential modifications and adaptations thereof will occur to those skilled in the art. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
High purity CaCO was used in the following examples 3 、H 3 BO 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 CO 3 、K 2 CO 3 、Li 2 CO 3 Preparing CBS glass ceramics by using high-purity CaCO as raw material 3 、H 3 BO 3 、SiO 2 CBS ceramics are prepared as raw materials.
Example 1
Mixing 402g of CaCO 3 、549gH 3 BO 3 、465gSiO 2 、15gTiO 2 、20gZrO 2 、21.2gNa 2 CO 3 、21gK 2 CO 3 、20gLi 2 CO 3 Placing the mixture into a ball milling tank, adding 1000g of deionized water and 3kg of zirconia balls with the diameter of 10mm, ball milling for 5 hours at the rotating speed of 250r/min, filtering out the zirconia balls, then placing the mixed slurry into an oven for drying at 140 ℃, sieving the powder with a 60-mesh sieve, placing the powder into a melting furnace at 1400 ℃, melting for 4 hours, finally quenching the glass liquid into glass blocks, then placing the zirconia balls with the diameter of 2mm into an alumina tank according to the proportion of ball to alcohol of 1:4:2, ball milling for 4 hours at the rotating speed of 250r/min, finally drying the glass slurry, and sieving with a 120-mesh sieve to obtain CBS micro-particles with the particle size of 3-5 mu mAnd (4) crystal glass powder.
Adding 3mol CaCO 3 Powder, 2molH 3 BO 3 Powder, 2mol SiO 2 Placing the powder in a ball milling tank, and mixing the following materials: mixing materials according to the water ratio of 2:2:1, carrying out ball milling for 4h, drying the mixture, sieving with a 60-mesh sieve, presintering the sieved materials for 4h at 1000 ℃ to obtain ceramic powder, then putting zirconia balls with the diameter of 2mm into an alumina tank according to the ball-to-alcohol ratio of 1:4:2, carrying out ball milling for 4h at the rotating speed of 250r/min, finally drying the ceramic slurry, and sieving with a 120-mesh sieve to obtain CBS ceramic powder with the particle size of 3-5 mu m.
Mixing 94 wt% of CBS microcrystalline glass powder and 6 wt% of CBS ceramic powder in a ball mill for 1h, drying and sieving to obtain the low-temperature co-fired ceramic powder. And adding PVB with the mass fraction of 3% into the sieved powder as a binder for granulation, pressing the mixture into a cylindrical blank, removing the binder at 450 ℃ for 1h, and sintering the cylindrical blank at 850 ℃ for 30min to obtain a sintered compact ceramic sample, wherein the microwave dielectric property test shows that the dielectric constant of the sample is 7.51(@10.63GHz) and the dielectric loss is 7.9 multiplied by 10 < -4 >.
Mixing 88 wt% of CBS microcrystalline glass powder and 12 wt% of CBS ceramic powder in a ball mill for 1h, drying and sieving to obtain the low-temperature co-fired ceramic powder. And adding PVB with the mass fraction of 3% into the sieved powder as a binder for granulation, pressing the mixture into a cylindrical blank, discharging the binder at 450 ℃ for 1h, and sintering the blank at 910 ℃ for 30min to obtain a sintered compact ceramic sample, wherein the microwave dielectric property test shows that the dielectric constant of the sample is 7.23(@10.99GHz) and the dielectric loss is 1.1 x 10 < -3 >.
Example 2
Mixing 402g of CaCO 3 、549gH 3 BO 3 、465gSiO 2 、15gTiO 2 、20gZrO 2 、21.2gNa 2 CO 3 、21gK 2 CO 3 、20gLi 2 CO 3 Placing the mixture into a ball milling tank, adding 1000g of deionized water and 3kg of zirconia balls with the diameter of 10mm, ball milling for 5 hours at the rotating speed of 250r/min, filtering out the zirconia balls, then placing the mixed slurry into an oven for drying at 140 ℃, sieving the powder with a 60-mesh sieve, placing the powder into a melting furnace at 1400 ℃, melting for 4 hours, finally quenching the glass liquid into glass blocks, and then mixing the glass blocks according to the ratio of ball to alcohol of 1:4:2Proportionally, putting zirconia balls with the diameter of 2mm into an alumina tank, ball-milling for 4 hours at the rotating speed of 250r/min, finally drying the glass slurry, and sieving by a 120-mesh sieve to obtain the CBS glass-ceramic powder with the granularity of 3-5 microns.
2mol CaCO 3 Powder, 2molH 3 BO 3 Powder, 1mol SiO 2 Putting the powder into a ball milling tank, mixing the materials according to the reference ratio of ball to water of 2:2:1, ball milling for 4h, drying the mixture, sieving by a 60-mesh sieve, pre-sintering the sieved material at 950 ℃ for 4h to obtain ceramic powder, and then: ball: and (3) putting zirconia balls with the diameter of 2mm into an alumina pot at the alcohol ratio of 1:4:2, ball-milling for 4h at the rotating speed of 250r/min, drying the ceramic slurry, and sieving with a 120-mesh sieve to obtain the CBS ceramic powder with the particle size of 3-5 microns.
Mixing 92 wt% of CBS microcrystalline glass powder and 8wt% of CBS ceramic powder in a ball mill for 1h, drying and sieving to obtain the low-temperature co-fired ceramic powder. Adding PVB with the mass fraction of 3% into the sieved powder as a binder for granulation, pressing the mixture into a cylindrical blank, removing glue at 450 ℃ for 1h, sintering the blank at 850 ℃ for 30min to obtain a sintered compact ceramic sample, and testing the microwave dielectric property to show that the sample has the dielectric constant of 7.31(@9.52GHz) and the dielectric loss of 9.7 multiplied by 10 -4 。
Mixing 84 wt% of CBS microcrystalline glass powder and 16 wt% of CBS ceramic powder in a ball mill for 1h, drying and sieving to obtain the low-temperature co-fired ceramic powder. Adding PVB with the mass fraction of 3% into the sieved powder as a binder for granulation, pressing the mixture into a cylindrical blank, discharging the binder at 450 ℃ for 1h, sintering the blank at 910 ℃ for 30min to obtain a sintered compact ceramic sample, and testing the microwave dielectric property to show that the sample has the dielectric constant of 7.11(@9.21GHz) and the dielectric loss of 1.3 multiplied by 10 -3 。
Example 3
402g of CaCO 3 、549gH 3 BO 3 、465gSiO 2 、15gTiO 2 、20gZrO 2 、21.2gNa 2 CO 3 、21gK 2 CO 3 、20gLi 2 CO 3 Placing in a ball milling tank, adding 1000g deionized water and 3kg zirconia balls with diameter of 10mm, ball milling at 250r/min for 5h, filtering to remove oxidationAnd (2) putting the mixed slurry into a 140 ℃ oven for drying, sieving the powder with a 60-mesh sieve, putting the powder into a 1400 ℃ melting furnace for melting for 4 hours, finally quenching the glass liquid into a glass block, putting the zirconia balls with the diameter of 2mm into an alumina pot according to the proportion of ball to alcohol of 1:4:2, ball-milling for 4 hours at the rotating speed of 250r/min, drying the glass slurry, and sieving with a 120-mesh sieve to obtain the CBS microcrystalline glass powder with the granularity of 3-5 mu m.
Adding 3mol CaCO 3 Powder, 4molH 3 BO 3 Powder, 1mol SiO 2 Placing the powder in a ball milling tank, and mixing the following materials: mixing materials according to the water ratio of 2:2:1, carrying out ball milling for 4h, drying the mixture, sieving with a 60-mesh sieve, presintering the sieved materials at 900 ℃ for 4h to obtain ceramic powder, then putting zirconia balls with the diameter of 2mm into an alumina pot according to the ball-to-alcohol ratio of 1:4:2, carrying out ball milling for 4h at the rotating speed of 250r/min, finally sieving with a 120-mesh sieve, and drying to obtain CBS ceramic powder with the particle size of 3-5 mu m.
Mixing 80 wt% of CBS microcrystalline glass powder and 20 wt% of CBS ceramic powder in a ball mill for 1h, drying and sieving to obtain the low-temperature co-fired ceramic powder. Adding PVB with the mass fraction of 3% into the sieved powder as a binder for granulation, pressing the mixture into a cylindrical blank, discharging the binder at 450 ℃ for 1h, sintering the blank at 850 ℃ for 30min to obtain a sintered compact ceramic sample, and testing the microwave dielectric property, wherein the dielectric constant of the sample is 6.78(@11.93GHz), the dielectric loss is 1.2 multiplied by 10 -3 。
Mixing 74 wt% of CBS microcrystalline glass powder and 26 wt% of CBS ceramic powder in a ball mill for 1h, drying and sieving to obtain the low-temperature co-fired ceramic powder. Adding PVB with the mass fraction of 3% into the sieved powder as a binder for granulation, pressing the mixture into a cylindrical blank, removing glue at 450 ℃ for 1h, sintering the blank at 900 ℃ for 30min to obtain a sintered compact ceramic sample, and testing the microwave dielectric property to show that the sample has the dielectric constant of 6.54(@11.02GHz) and the dielectric loss of 1.4 multiplied by 10 -3 。
Example 4
402g of CaCO 3 、549gH 3 BO 3 、465gSiO 2 、15gTiO 2 、20gZrO 2 、21.2gNa 2 CO 3 、21gK 2 CO 3 、20gLi 2 CO 3 Placing the mixture into a ball milling tank, adding 1000g of deionized water and 3kg of zirconia balls with the diameter of 10mm, ball milling for 5 hours at the rotating speed of 250r/min, filtering out the zirconia balls, then placing the mixed slurry into an oven for drying at 140 ℃, sieving the powder by a 60-mesh sieve, placing the powder into a melting furnace at 1400 ℃, melting for 4 hours, finally quenching the glass liquid into glass blocks, then placing the zirconia balls with the diameter of 2mm into an alumina tank according to the proportion of ball to alcohol of 1:4:2, ball milling for 4 hours at the rotating speed of 250r/min, finally drying the glass slurry, and sieving by a 120-mesh sieve to obtain the CBS glass ceramic powder with the particle size of 3-5 mu m.
1mol CaCO 3 Powder, 2molH 3 BO 3 Powder, 1mol SiO 2 Placing the powder in a ball milling tank, and mixing the following materials: mixing materials according to the water ratio of 2:2:1, carrying out ball milling for 4h, drying the mixture, sieving with a 60-mesh sieve, presintering the sieved materials for 4h at 850 ℃ to obtain ceramic powder, then putting zirconia balls with the diameter of 2mm into an alumina pot according to the ball-to-alcohol ratio of 1:4:2, carrying out ball milling for 4h at the rotating speed of 250r/min, finally drying the ceramic slurry, and sieving with a 120-mesh sieve to obtain CBS ceramic powder with the particle size of 3-5 mu m.
Mixing 80 wt% of CBS microcrystalline glass powder and 20 wt% of CBS ceramic powder in a ball mill for 1h, drying and sieving to obtain the low-temperature co-fired ceramic powder. Adding PVB with the mass fraction of 3% into the sieved powder as a binder for granulation, pressing the mixture into a cylindrical blank, discharging the binder at 450 ℃ for 1h, sintering the blank at 830 ℃ for 30min to obtain a sintered compact ceramic sample, and testing the microwave dielectric property to show that the sample has the dielectric constant of 6.32(@10.46GHz) and the dielectric loss of 1.3 multiplied by 10 -3 。
Mixing 75 wt% of CBS microcrystalline glass powder and 25 wt% of CBS ceramic powder in a ball mill for 1h, drying and sieving to obtain the low-temperature co-fired ceramic powder. Adding PVB with the mass fraction of 3% into the sieved powder as a binder for granulation, pressing the mixture into a cylindrical blank, discharging the binder at 450 ℃ for 1h, sintering the blank at 890 ℃ for 30min to obtain a sintered compact ceramic sample, and testing the microwave dielectric property to show that the sample has the dielectric constant of 6.1(@10.91GHz) and the dielectric loss of 1.5 multiplied by 10 -3 。
Claims (7)
1. A low-temperature co-fired ceramic material comprises the following components:
72-95 wt% of CBS microcrystalline glass and 5-28 wt% of CBS ceramic, wherein: the CBS microcrystalline glass consists of CaO and B 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 O、K 2 O、Li 2 O, the CBS ceramic consists of CaO and B 2 O 3 、SiO 2 Composition is carried out; the CBS microcrystalline glass consists of 21-24 wt% of CaO; 30 to 33 wt% of B 2 O 3 ；45～48wt％SiO 2 ；1～4wt％TiO 2 ；1～5wt％ZrO 2 ；0.5～3wt％Na 2 O；0.5～3wt％K 2 O；0.5～3wt％Li 2 And (C) O.
2. The low temperature co-fired ceramic material of claim 1, wherein the CBS ceramic contains CaO, B 2 O 3 、SiO 2 The molar ratio of (A) is determined according to the following formula: (1-x-y) CaO-0.5xB 2 O 3 -ySiO 2 Wherein 0.25<x<0.5，0.12<y<0.3。
3. A method of preparing a low temperature co-fired ceramic material as claimed in any one of claims 1-2, comprising the steps of:
weighing raw material CaCO 3 、H 3 BO 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 CO 3 、K 2 CO 3 、Li 2 CO 3 Carrying out wet mixing treatment, drying, melting into glass melt, carrying out water quenching on the glass melt to obtain glass frit, drying the glass frit, and crushing into glass powder to obtain CBS glass ceramic powder;
weighing raw material CaCO 3 ，H 3 BO 3 And SiO 2 Performing wet mixing treatment, drying, sieving, pre-sintering to obtain ceramic blocks, and pulverizing and sieving the ceramic blocks to obtain CBS ceramic powder;
and uniformly mixing the CBS microcrystalline glass powder and the CBS ceramic by a wet method, drying and sieving to obtain the low-temperature co-fired ceramic powder.
4. The method for preparing low-temperature co-fired ceramic material according to claim 3, wherein the CBS ceramic powder is prepared from CaO and B 2 O 3 、SiO 2 Composition of the CaO and B 2 O 3 、SiO 2 The molar ratio of (A) is determined according to the following formula: (1-x-y) CaO-0.5xB 2 O 3 -ySiO 2 Wherein 0.25<x<0.5，0.12<y<0.3。
5. The preparation method of the low-temperature co-fired ceramic material according to claim 3, wherein in the step of preparing the CBS glass-ceramic powder, the material mixing time is 3-8 hours, the melting temperature is 1350-1500 ℃, the melting time is 3-6 hours, and the granularity of the CBS glass-ceramic powder is 1-7 μm.
6. The preparation method of the low-temperature co-fired ceramic material as claimed in claim 3, wherein in the step of preparing the CBS ceramic powder, the mixture is water ball milling mixture, the ball milling time is 4-8 h, the pre-sintering temperature is 810-1050 ℃, the pre-sintering time is 2-8 h, and the granularity of the CBS ceramic powder is 1-7 μm.
7. The method for preparing the low-temperature co-fired ceramic material as claimed in claim 3, wherein the CaO, B in the CBS ceramic is controlled 2 O 3 With SiO 2 The dielectric constant of the CBS ceramic is adjusted, and the low-temperature co-fired ceramic material is obtained by matching with CBS glass ceramics with different proportions.
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| CN113372103B (en) * | 2021-07-13 | 2023-01-20 | 中国振华集团云科电子有限公司 | Low-dielectric low-high-frequency-loss LTCC ceramic material and preparation method thereof |
| CN113716870B (en) * | 2021-09-03 | 2023-03-07 | 中国人民解放军国防科技大学 | LTCC substrate material suitable for high frequency and preparation method thereof |
| CN115806390A (en) * | 2021-09-15 | 2023-03-17 | 浙江矽瓷科技有限公司 | Low-temperature co-fired ceramic powder and preparation method and application thereof |
| CN113754409B (en) * | 2021-09-17 | 2022-10-28 | 深圳陶陶科技有限公司 | Low-temperature sintered glass ceramic powder and preparation method and application thereof |
| CN114315334B (en) * | 2021-12-30 | 2023-05-23 | 西安宏星电子浆料科技股份有限公司 | LTCC material and preparation method thereof |
| WO2024050660A1 (en) * | 2022-09-05 | 2024-03-14 | 中国科学院深圳先进技术研究院 | Glass/ceramic composite material for low-temperature co-fired ceramic, preparation method therefor and use thereof |
| CN115572073B (en) * | 2022-11-08 | 2024-02-20 | 昆明贵研新材料科技有限公司 | Controllable strong crystallization high-frequency low-loss LTCC substrate material and preparation method thereof |
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