CN108996902B - Low-temperature co-fired ceramic material and preparation method thereof - Google Patents
Low-temperature co-fired ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN108996902B CN108996902B CN201811097469.6A CN201811097469A CN108996902B CN 108996902 B CN108996902 B CN 108996902B CN 201811097469 A CN201811097469 A CN 201811097469A CN 108996902 B CN108996902 B CN 108996902B
- Authority
- CN
- China
- Prior art keywords
- temperature
- weight
- parts
- low
- fired ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
Abstract
The invention discloses a low-temperature co-fired ceramic material and a preparation method thereof, wherein the low-temperature co-fired ceramic material comprises 30-50 parts by weight of soda borosilicate glass, 50-70 parts by weight of wollastonite microcrystalline glass and 4-10 parts by weight of a high-thermal-conductivity material. The low-temperature co-fired ceramic has the characteristics of low thermal expansion coefficient, high mechanical strength, high thermal conductivity and the like, and can be applied to the field of LTCC substrate materials and other electronic packaging materials.
Description
Technical Field
The invention relates to the field of low-temperature co-fired ceramic, in particular to a low-temperature co-fired ceramic material and a preparation method thereof.
Background
With the rapid development of microelectronic information technology and high-frequency wireless communication technology, the miniaturization, integration and high performance of electronic circuits and electronic components make the requirements of products on electronic packaging technology higher and higher. Low Temperature Co-fired ceramic (LTCC) technology integrates the features of high frequency, Low loss, high integration and high speed transmission, and is a mainstream technology in the field of microelectronic packaging. The LTCC substrate material is one of the most central components in the LTCC technology, and can be sintered to be compact and meet the use requirement under the condition of lower than the sintering temperature of common ceramics.
Because the melting point of the electrode materials mainly adopted by the current electronic device, such as Ag, Au, Cu and the like, is generally lower than 1000 ℃, the sintering temperature of the LTCC substrate material is not higher than 1000 ℃. The ceramic material sintered at the temperature has high internal porosity and cannot meet the use requirement. The microcrystalline glass is a composite material with the characteristics of glass and ceramic, the material has a compact structure, and the mechanical strength, the thermal expansion coefficient and other properties of the material can be adjusted by adjusting the type and the content of a microcrystalline phase in the material, so that the microcrystalline glass can be used as an LTCC material. However, for the preparation of high mechanical strength glass ceramics, when the sintering temperature is below 1000 ℃, the densification and mechanical strength of the material are difficult to satisfy. In addition, a large amount of heat generated in the use process of the electronic device needs to be dissipated in time, the higher the thermal conductivity of the LTCC substrate is, the more beneficial the LTCC substrate is to the process, and the improvement of the thermal conductivity of the LTCC material is necessary.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a low-temperature co-fired ceramic material with high mechanical strength, low thermal expansion coefficient and high thermal conductivity, and correspondingly provide a preparation method of the low-temperature co-fired ceramic material with simple process and low cost.
In order to solve the technical problems, the invention adopts the following technical scheme: the low-temperature co-fired ceramic material comprises 30-50 parts by weight of soda borosilicate glass, 50-70 parts by weight of wollastonite microcrystalline glass and 4-10 parts by weight of a high-thermal-conductivity material.
The soda borosilicate glass as low-melting-point glass can be softened at high temperature to form a large amount of glass melt, the sintering temperature of the wollastonite microcrystalline glass is reduced, and the wollastonite microcrystalline glass can be sintered within 900 ℃ to form a relatively ideal lath staggered crystalline phase structure. The alternate crystal phase structure of the laths in the wollastonite microcrystalline glass is mutually occluded with the glass, so that the mechanical strength of the material is enhanced and the densification is realized. The high-thermal-conductivity material has high thermal conductivity, and is uniformly dispersed in the soda borosilicate glass and the wollastonite microcrystalline glass and well contacted with the soda borosilicate glass and the wollastonite microcrystalline glass to form a network-like thermal-conductivity structure, so that the thermal-conductivity effect of the low-temperature co-fired ceramic material is greatly improved.
In addition, the invention claims a preparation method of the low-temperature co-fired ceramic material, which comprises the following steps:
s1: weighing corresponding components according to the composition formula of the sodium borosilicate glass and the wollastonite microcrystalline glass, respectively mixing, performing ball milling treatment, and drying to respectively obtain a sodium borosilicate glass batch and a wollastonite microcrystalline glass batch;
s2: respectively loading the batch materials into different crucibles, and carrying out melting treatment under the high-temperature condition to obtain molten glass;
s3: directly pouring molten glass liquid into deionized water to obtain glass slag, and performing ball milling to obtain soda borosilicate glass powder and wollastonite microcrystalline glass powder with the average particle size of 1-3 mu m;
s4: mixing 30-50 parts by weight of soda borosilicate glass powder, 50-70 parts by weight of wollastonite microcrystalline glass powder and 4-10 parts by weight of high-thermal-conductivity material to obtain a mixed material, adding a binder, performing ball milling treatment and drying to obtain low-temperature co-fired ceramic powder, and pressing the low-temperature co-fired ceramic powder into a blank;
s5: sintering the blank in an argon atmosphere by adopting a multi-step heating method, and cooling to obtain the low-temperature co-fired ceramic material.
The sintering of the green body in the preparation method of the low-temperature co-fired ceramic material is sintering in argon atmosphere by adopting a multi-step heating method, and the multi-step heating treatment can enable the microcrystalline glass to generate enough crystal phases under the condition that crystal nuclei are formed, so that the mechanical strength of the low-temperature co-fired ceramic material is improved; and the argon atmosphere sintering can protect the high-heat-conductivity material from being oxidized, thereby ensuring that the material can exert the performance advantage in the material.
Detailed Description
The low-temperature co-fired ceramic material comprises 30-50 parts by weight of soda borosilicate glass, 50-70 parts by weight of wollastonite microcrystalline glass and 4-10 parts by weight of a high-thermal-conductivity material.
The soda borosilicate glass as low-melting-point glass can be softened at high temperature to form a large amount of glass melt, so that the soda lime glass ceramics can be sintered within 900 ℃ to generate a relatively ideal lath staggered crystalline phase structure. Specifically, the sodium borosilicate glass comprises the following oxides in parts by weight: na (Na)225.0 to 35.0 parts by weight of O, B2O335.0 to 45.0 parts by weight of SiO225.0 to 35.0 parts by weight.
The wollastonite microcrystalline glass is used as high-strength microcrystalline glass, and the inner lath staggered crystalline phase structure of the wollastonite is mutually occluded with the glass, so that the densification is realized while the mechanical strength of the material is enhanced. In addition, the crystalline phase structure also has low dielectric loss. The content of crystalline phase in the low-temperature co-fired ceramic material can be increased by increasing the content of the wollastonite microcrystalline glass, so that the dielectric loss of the low-temperature co-fired ceramic material is reduced. In particular, the siliconThe alkali-limestone microcrystalline glass comprises the following oxides in parts by weight: SiO 2245.0 to 60.0 parts by weight of Al2O32.0 to 8.0 parts by weight, 10.0 to 20.0 parts by weight of CaO, CaF210.0 to 20.0 parts by weight of Na2O2.0-15.0 parts by weight, K2O2.0-10.0 parts by weight, ZrO21.0 to 3.0 parts by weight.
The high-thermal-conductivity material has high thermal conductivity, and in the content range, the material is uniformly dispersed in the soda borosilicate glass and the wollastonite microcrystalline glass and is in good contact with the soda borosilicate glass and the wollastonite microcrystalline glass to form a heat-conducting structure similar to a network, so that the heat-conducting effect of the low-temperature co-fired ceramic material is greatly improved. Specifically, the high thermal conductivity material is one or more of graphene, diamond and aluminum nitride. More specifically, the high thermal conductivity material is a mixture including 2 to 5 parts by weight of graphene and 2 to 5 parts by weight of diamond.
The preparation method of the low-temperature co-fired ceramic material mainly comprises the following steps:
s1: weighing corresponding components according to the composition formula of the sodium borosilicate glass and the wollastonite microcrystalline glass, respectively mixing, performing ball milling treatment, and drying to respectively obtain a sodium borosilicate glass batch and a wollastonite microcrystalline glass batch;
s2: respectively loading the batch materials into different crucibles, and carrying out melting treatment under the high-temperature condition to obtain molten glass;
s3: directly pouring molten glass liquid into deionized water to obtain glass slag, and performing ball milling to obtain soda borosilicate glass powder and wollastonite microcrystalline glass powder with the average particle size of 1-3 mu m;
s4: mixing 30-50 parts by weight of soda borosilicate glass powder, 50-70 parts by weight of wollastonite microcrystalline glass powder and 4-10 parts by weight of high-thermal-conductivity material to obtain a mixed material, adding a binder, performing ball milling treatment and drying to obtain low-temperature co-fired ceramic powder, and pressing the low-temperature co-fired ceramic powder into a blank;
s5: sintering the blank in an argon atmosphere by adopting a multi-step heating method, and cooling to obtain the low-temperature co-fired ceramic material.
In the invention, the sodium borosilicate glass mainly comprises 25.0 to 35.0 weight parts of Na2O, 35.0 to 45.0 parts by weight of B2O325.0 to 35.0 parts by weight of SiO2. The wollastonite microcrystalline glass mainly comprises 45.0-60.0 parts by weight of SiO22.0 to 8.0 parts by weight of Al2O310.0 to 20.0 parts by weight of CaO, 10.0 to 20.0 parts by weight of CaF22.0 to 15.0 parts by weight of Na2O, 2.0 to 10.0 parts by weight of K2O, 1.0 to 3.0 parts by weight of ZrO2。
When the batch of the sodium borosilicate glass is prepared, firstly, oxide components in corresponding parts are weighed according to the composition formula of the sodium borosilicate glass, the oxide components in corresponding parts are mixed, then ball milling treatment is carried out, so that the oxide components are uniformly mixed, and then drying is carried out, so as to remove redundant moisture and other volatile impurities, thus obtaining the sodium borosilicate glass batch. The method comprises the steps of preparing a batch of the wollastonite microcrystalline glass by the same method, firstly weighing oxide components in corresponding parts according to a composition formula of the wollastonite microcrystalline glass, mixing the oxide components in corresponding parts, then carrying out ball milling treatment so as to uniformly mix the oxide components, and then drying to remove redundant water and other volatile impurities, thus obtaining the wollastonite microcrystalline glass batch.
And then, respectively heating and melting the batch materials into molten glass. Specifically, the sodium borosilicate glass batch and the wollastonite microcrystalline glass batch are respectively placed in two different crucibles, the crucibles are respectively sent into a high temperature furnace, and the temperature is raised, so that the batch is heated and melted to obtain glass liquid. In particular, the crucible is preferably an alumina crucible; the heating mode is preferably microwave heating, and the heating method has the advantage of high temperature rise speed and can well improve the preparation efficiency of the material.
More specifically, when the batch is heated and melted into molten glass, the crucible loaded with the sodium borosilicate glass batch is placed in a high-temperature furnace, the temperature of the high-temperature furnace is increased to 1300-1400 ℃ at the temperature increasing rate of 5-15 ℃/min, and the temperature is kept for 2-3 h at the temperature, so that the sodium borosilicate glass liquid is prepared; and (3) placing the batch loaded with the wollastonite microcrystalline glass into a high-temperature furnace, heating the high-temperature furnace to 1550-1600 ℃ at the heating rate of 5-15 ℃/min, and preserving heat for 2-3 hours at the temperature to prepare the wollastonite microcrystalline glass liquid.
Then, the prepared molten glass is further prepared into glass powder. In detail, directly pouring molten sodium borosilicate glass liquid into deionized water to obtain sodium borosilicate glass slag; and carrying out ball milling on the soda borosilicate glass slag to obtain soda borosilicate glass powder with the average particle size of 1-3 mu m. Similarly, directly pouring the molten glauconite microcrystalline glass liquid into deionized water to obtain the glauconite microcrystalline glass slag; and carrying out ball milling on the wollastonite microcrystalline glass slag to obtain the wollastonite microcrystalline glass powder with the average particle size of 1-3 mu m. The ball-milling ball-material ratio is 3: 1, and the ball-milling medium is deionized water.
Then, the soda-borosilicate glass powder, the sillimanite microcrystalline glass powder and the high-thermal-conductivity material are mixed to prepare a mixture. Specifically, the weight parts of soda borosilicate glass powder in the mixture are 30-50, the weight parts of the wollastonite microcrystalline glass are 50-70, and the weight parts of the high-thermal-conductivity material are 4-10. The high thermal conductivity material may be one or more of graphene, diamond and aluminum nitride. Specifically, the high-thermal-conductivity material is a mixture of graphene and diamond, wherein the graphene accounts for 2-5 parts by weight, and the diamond accounts for 2-5 parts by weight. The graphene is used as a material with high thermal conductivity, the thermal conductivity of the graphene can reach 5300W/m.K, and the thermal conductivity of the prepared low-temperature co-fired ceramic can be greatly improved by doping the graphene. The diamond is used as a material with high hardness and thermal conductivity, and the introduction of the diamond is also beneficial to improving the mechanical property and the thermal conductivity of the prepared low-temperature co-fired ceramic.
And further, adding a binder into the mixture, then carrying out ball milling treatment and drying to obtain the low-temperature co-fired ceramic powder. Specifically, the binder is a polyvinyl butyral solution with a volume fraction of 5%, and the usage amount of the polyvinyl butyral solution is 5% of the mass of the mixture.
And further pressing the low-temperature co-fired ceramic powder on a forming machine to form a green body.
And finally, sintering the green body to prepare the low-temperature co-fired ceramic material. Specifically, the green body is placed in a high-temperature furnace, sintered in an argon atmosphere by adopting a multi-step heating method, and cooled to obtain the low-temperature co-fired ceramic material. The multi-step heating treatment can enable the microcrystalline glass to generate enough crystal phases under the condition that crystal nuclei are formed, so that the mechanical strength of the low-temperature co-fired ceramic material is improved; and the argon atmosphere sintering protects the high-heat-conductivity material from being oxidized, thereby ensuring that the high-heat-conductivity material can exert the performance advantage in the substrate material.
More specifically, the multi-step heating method comprises the steps of firstly heating to 450-500 ℃ at a heating rate of 5-15 ℃/min, preserving heat for 1-2 hours, then heating to 600-630 ℃, preserving heat for 1-2 hours, and finally preserving heat for 1-2 hours at 850-900 ℃. The cooling is to naturally cool the mixture to room temperature in a furnace.
The present invention is further described with reference to the following specific examples, which are not intended to limit the invention, and those skilled in the art can make various modifications or improvements based on the basic idea of the invention, but within the scope of the invention, unless they depart from the basic idea of the invention.
Example 1
S1: the composition of the soda borosilicate glass is 26.5 parts by weight of Na2O, 44.5 parts by weight of B2O3And 28.9 parts by weight of SiO2(ii) a The composition of the wollastonite microcrystalline glass is 51.1 parts by weight of SiO27.4 parts by weight of Al2O316.5 parts by weight of CaO, 11.9 parts by weight of CaF28.2 parts by weight of Na2O, 2.3 parts by weight of K2O and 2.5 parts by weight of ZrO2. Weighing corresponding raw materials according to the formula, mixing respectively, performing ball milling treatment respectively, and drying.
S2: the mixture was charged into two different alumina crucibles, and the alumina crucibles were fed into a high temperature furnace. Wherein, the temperature of the sodium borosilicate glass is increased to 1350 ℃ at the temperature increasing rate of 10 ℃ per minute when the sodium borosilicate glass is melted, and the temperature is kept for 2 hours at the temperature; when the wollastonite microcrystalline glass is molten, the temperature is increased to 1580 ℃ at the temperature increase rate of 10 ℃ per minute, and the temperature is kept for 3 hours at the temperature, so that the batch materials are heated and molten to obtain glass liquid.
S3: and directly pouring the molten glass liquid into deionized water to obtain glass slag, and performing ball milling to respectively prepare soda borosilicate glass powder and wollastonite microcrystalline glass powder with the average particle size of 1-3 mu m.
S4: mixing 32 parts by weight of soda-borosilicate low-melting-point glass powder, 61 parts by weight of wollastonite microcrystalline glass powder, 3 parts by weight of graphene, 4 parts by weight of diamond powder and 5% by weight of polyvinyl butyral solution with volume fraction of 5% of the mixed materials, performing ball milling treatment, drying to obtain low-temperature co-fired ceramic powder, and pressing to obtain a blank on a forming machine.
S5: and putting the obtained blank into a high-temperature furnace, heating to 500 ℃ at the heating rate of 5 ℃ per minute under the protection of argon, preserving heat for 2h, then heating to 600 ℃ and preserving heat for 1h, finally preserving heat for 2h at 870 ℃, and naturally cooling to room temperature in the furnace to obtain the low-temperature co-fired ceramic material.
Example 2
S1: the composition of the soda borosilicate glass is 30.9 parts by weight of Na2O, 37.3 parts by weight of B2O3And 31.7 parts by weight of SiO2(ii) a The composition of the wollastonite microcrystalline glass is 46.6 parts by weight of SiO25.4 parts by weight of Al2O310.6 parts by weight of CaO, 18.3 parts by weight of CaF212.8 parts by weight of Na2O, 3.6 parts by weight of K2O and 2.7 parts by weight of ZrO2. Weighing corresponding raw materials according to the formula, mixing respectively, performing ball milling treatment respectively, and drying.
S2: the mixture was charged into two different alumina crucibles, and the alumina crucibles were fed into a high temperature furnace. Wherein, the temperature of the sodium borosilicate glass is increased to 1350 ℃ at the temperature increasing rate of 10 ℃ per minute when the sodium borosilicate glass is melted, and the temperature is kept for 2 hours at the temperature; when the wollastonite microcrystalline glass is molten, the temperature is increased to 1580 ℃ at the temperature increase rate of 10 ℃ per minute, and the temperature is kept for 3 hours at the temperature, so that the batch materials are heated and molten to obtain glass liquid.
S3: and directly pouring the molten glass liquid into deionized water to obtain glass slag, and performing ball milling to respectively prepare soda borosilicate glass powder and wollastonite microcrystalline glass powder with the average particle size of 1-3 mu m.
S4: mixing 33 parts by weight of soda-borosilicate low-melting-point glass powder, 57 parts by weight of wollastonite microcrystalline glass powder, 5 parts by weight of graphene, 5 parts by weight of diamond powder and 5% by weight of polyvinyl butyral solution with volume fraction of 5% of the mixed materials, performing ball milling treatment, drying to obtain low-temperature co-fired ceramic powder, and pressing the ceramic powder into a blank on a forming machine.
S5: and putting the obtained blank into a high-temperature furnace, heating to 500 ℃ at the heating rate of 5 ℃ per minute under the protection of argon, preserving heat for 2h, then heating to 600 ℃ and preserving heat for 1h, finally preserving heat for 2h at 870 ℃, and naturally cooling to room temperature in the furnace to obtain the low-temperature co-fired ceramic material.
Example 3
S1: the composition of the soda borosilicate glass is 34.2 parts by weight of Na2O, 39.0 parts by weight of B2O3And 26.9 parts by weight of SiO2(ii) a The composition of the wollastonite microcrystalline glass is 47.3 parts by weight of SiO25.0 parts by weight of Al2O319.5 parts by weight of CaO, 17.2 parts by weight of CaF27.2 parts by weight of Na2O, 2.3 parts by weight of K2O and 1.4 parts by weight of ZrO2. Weighing corresponding raw materials according to the formula, mixing respectively, performing ball milling treatment respectively, and drying.
S2: the mixture was charged into two different alumina crucibles, and the alumina crucibles were fed into a high temperature furnace. Wherein, the temperature of the sodium borosilicate glass is increased to 1350 ℃ at the temperature increasing rate of 10 ℃ per minute when the sodium borosilicate glass is melted, and the temperature is kept for 2 hours at the temperature; when the wollastonite microcrystalline glass is molten, the temperature is increased to 1580 ℃ at the temperature increase rate of 10 ℃ per minute, and the temperature is kept for 3 hours at the temperature, so that the batch materials are heated and molten to obtain glass liquid.
S3: and directly pouring the molten glass liquid into deionized water to obtain glass slag, and performing ball milling to respectively prepare soda borosilicate glass powder and wollastonite microcrystalline glass powder with the average particle size of 1-3 mu m.
S4: mixing 38 parts by weight of soda-borosilicate low-melting-point glass powder, 57 parts by weight of wollastonite microcrystalline glass powder, 3 parts by weight of graphene, 3 parts by weight of diamond powder and 5% by weight of polyvinyl butyral solution with volume fraction of 5% of the mixed materials, performing ball milling treatment, drying to obtain low-temperature co-fired ceramic powder, and pressing to obtain a blank on a forming machine.
S5: and putting the obtained blank into a high-temperature furnace, heating to 500 ℃ at the heating rate of 5 ℃ per minute under the protection of argon, preserving heat for 2h, then heating to 600 ℃ and preserving heat for 1h, finally preserving heat for 2h at 870 ℃, and naturally cooling to room temperature in the furnace to obtain the low-temperature co-fired ceramic material.
Example 4
S1: the composition of the soda borosilicate glass is 32.0 parts by weight of Na2O, 39.6 parts by weight of B2O3And 28.4 parts by weight of SiO2(ii) a The composition of the wollastonite microcrystalline glass is 51.1 parts by weight of SiO26.0 parts by weight of Al2O316.5 parts by weight of CaO, 10.6 parts by weight of CaF24.6 parts by weight of Na2O, 9.7 parts by weight of K2O and 1.5 parts by weight of ZrO2. Weighing corresponding raw materials according to the formula, mixing respectively, performing ball milling treatment respectively, and drying.
S2: the mixture was charged into two different alumina crucibles, and the alumina crucibles were fed into a high temperature furnace. Wherein, the temperature of the sodium borosilicate glass is increased to 1350 ℃ at the temperature increasing rate of 10 ℃ per minute when the sodium borosilicate glass is melted, and the temperature is kept for 2 hours at the temperature; when the wollastonite microcrystalline glass is molten, the temperature is increased to 1580 ℃ at the temperature increase rate of 10 ℃ per minute, and the temperature is kept for 3 hours at the temperature, so that the batch materials are heated and molten to obtain glass liquid.
S3: and directly pouring the molten glass liquid into deionized water to obtain glass slag, and performing ball milling to respectively prepare soda borosilicate glass powder and wollastonite microcrystalline glass powder with the average particle size of 1-3 mu m.
S4: mixing 44 parts by weight of soda-borosilicate low-melting-point glass powder, 50 parts by weight of wollastonite microcrystalline glass powder, 3 parts by weight of graphene, 3 parts by weight of diamond powder and 5% by weight of polyvinyl butyral solution with volume fraction of 5% of the mixed materials, performing ball milling treatment, drying to obtain low-temperature co-fired ceramic powder, and pressing to obtain a blank on a forming machine.
S5: and putting the obtained blank into a high-temperature furnace, heating to 500 ℃ at the heating rate of 5 ℃ per minute under the protection of argon, preserving heat for 2h, then heating to 600 ℃ and preserving heat for 1h, finally preserving heat for 2h at 870 ℃, and naturally cooling to room temperature in the furnace to obtain the low-temperature co-fired ceramic material.
Example 5
S1: the composition of the soda borosilicate glass is 34.3 parts by weight of Na2O, 40.1 parts by weight of B2O3And 25.5 parts by weight of SiO2(ii) a The composition of the wollastonite microcrystalline glass is 51.8 parts by weight of SiO25.8 parts by weight of Al2O317.5 parts by weight of CaO, 13.7 parts by weight of CaF22.8 parts by weight of Na2O, 6.7 parts by weight of K2O and 1.6 parts by weight of ZrO2. Weighing corresponding raw materials according to the formula, mixing respectively, performing ball milling treatment respectively, and drying.
S2: the mixture was charged into two different alumina crucibles, and the alumina crucibles were fed into a high temperature furnace. Wherein, the temperature of the sodium borosilicate glass is increased to 1350 ℃ at the temperature increasing rate of 10 ℃ per minute when the sodium borosilicate glass is melted, and the temperature is kept for 2 hours at the temperature; when the wollastonite microcrystalline glass is molten, the temperature is increased to 1580 ℃ at the temperature increase rate of 10 ℃ per minute, and the temperature is kept for 3 hours at the temperature, so that the batch materials are heated and molten to obtain glass liquid.
S3: and directly pouring the molten glass liquid into deionized water to obtain glass slag, and performing ball milling to respectively prepare soda borosilicate glass powder and wollastonite microcrystalline glass powder with the average particle size of 1-3 mu m.
S4: mixing 34 parts by weight of soda-borosilicate low-melting-point glass powder, 57 parts by weight of wollastonite microcrystalline glass powder, 5 parts by weight of graphene, 4 parts by weight of diamond powder and 5% by weight of polyvinyl butyral solution with volume fraction of 5% of the mixed materials, performing ball milling treatment, drying to obtain low-temperature co-fired ceramic powder, and pressing to obtain a blank on a forming machine.
S5: and putting the obtained blank into a high-temperature furnace, heating to 500 ℃ at the heating rate of 5 ℃ per minute under the protection of argon, preserving heat for 2h, then heating to 600 ℃ and preserving heat for 1h, finally preserving heat for 2h at 870 ℃, and naturally cooling to room temperature in the furnace to obtain the low-temperature co-fired ceramic material.
Example 6
Example 6 as a comparison to example 1, a low temperature co-fired ceramic material was prepared using 100 wt% soda borosilicate glass under the same heat treatment conditions as example 1.
Example 7
Example 7 as a comparison to example 1, a low temperature co-fired ceramic material was prepared using 100 wt% canasite microcrystalline glass under the same heat treatment conditions as example 1.
Example 8
Example 8 as a comparison to example 2, a low temperature co-fired ceramic material was prepared using 100 wt% soda borosilicate glass under the same heat treatment conditions as example 2.
Example 9
Example 9 as a comparison to example 2, a low temperature co-fired ceramic material was prepared using 100 wt% canasite microcrystalline glass under the same heat treatment conditions as example 2.
Example 10
Example 10 as a comparison to example 3, a low temperature co-fired ceramic material was prepared using 100 wt% soda borosilicate glass under the same heat treatment conditions as example 3.
Example 11
Example 11 as a comparison to example 3, a low temperature co-fired ceramic material was prepared using 100 wt% canasite microcrystalline glass under the same heat treatment conditions as example 3.
Example 12
Example 12 is a comparison of example 4, which is a low temperature co-fired ceramic material prepared using 100 wt% soda borosilicate glass under the same heat treatment conditions as example 4.
Example 13
Example 13 as a comparison to example 4, a low temperature co-fired ceramic material was prepared using 100 wt% canasite microcrystalline glass under the same heat treatment conditions as example 4.
Performance testing
Table 1: test results of electrical property, mechanical property and thermal property of low-temperature co-fired ceramic material
As can be seen from table 1, compared with a low-temperature co-fired ceramic material prepared from only a wollastonite microcrystalline glass or a soda borosilicate glass, the low-temperature co-fired ceramic material is prepared by adding soda borosilicate low-melting-point glass, graphene and diamond powder into the wollastonite microcrystalline glass and performing multi-step heat treatment under an argon protection condition, and has not only higher mechanical strength, but also lower thermal expansion coefficient and higher thermal conductivity. The low-temperature co-fired ceramic has the characteristics of low thermal expansion coefficient, high mechanical strength, high thermal conductivity and the like, and can be applied to the field of LTCC substrate materials and other electronic packaging materials.
Claims (7)
1. The low-temperature co-fired ceramic material is characterized by comprising 30-50 parts by weight of soda borosilicate glass, 50-70 parts by weight of wollastonite microcrystalline glass and 4-10 parts by weight of high-thermal-conductivity material;
the sodium borosilicate glass comprises the following oxides in parts by weight:
Na225.0 to 35.0 parts by weight of O,
B2O335.0 to 45.0 parts by weight,
SiO225.0 to 35.0 parts by weight;
the high-thermal-conductivity material is one or more of graphene, diamond and aluminum nitride;
the wollastonite microcrystalline glass comprises the following oxides in parts by weight:
2. the low-temperature co-fired ceramic material according to claim 1, wherein the high thermal conductivity material is a mixture of 2 to 5 parts by weight of graphene and 2 to 5 parts by weight of diamond.
3. The preparation method of the low-temperature co-fired ceramic material according to any one of claims 1 to 2, characterized by comprising the following steps:
s1: weighing corresponding components according to the composition formula of the sodium borosilicate glass and the wollastonite microcrystalline glass, respectively mixing, performing ball milling treatment, and drying to respectively obtain a sodium borosilicate glass batch and a wollastonite microcrystalline glass batch;
s2: respectively loading the batch materials into different crucibles, and carrying out melting treatment under the high-temperature condition to obtain molten glass;
s3: directly pouring molten glass liquid into deionized water to obtain glass slag, and performing ball milling to obtain soda borosilicate glass powder and wollastonite microcrystalline glass powder with the average particle size of 1-3 mu m;
s4: mixing soda borosilicate glass powder, wollastonite microcrystalline glass powder and a high-thermal-conductivity material to obtain a mixed material, adding a binder, performing ball milling treatment, drying to obtain low-temperature co-fired ceramic powder, and pressing the low-temperature co-fired ceramic powder into a green body;
s5: sintering the blank in an argon atmosphere by adopting a multi-step heating method, and cooling to obtain the low-temperature co-fired ceramic material.
4. The preparation method of the low-temperature co-fired ceramic material according to claim 3, wherein in S2, the temperature of the sodium borosilicate glass batch is raised to 1300-1400 ℃ at a temperature raising rate of 5-15 ℃/min, and the temperature is kept for 2-3 h; the temperature of the wollastonite microcrystalline glass batch is increased to 1550-1600 ℃ at the heating rate of 5-15 ℃/min, and the temperature is kept for 2-3 h at the temperature.
5. The preparation method of the low-temperature co-fired ceramic material according to claim 3, wherein in S5, the multi-step heating method comprises heating to 450-500 ℃ at a heating rate of 5-15 ℃/min, preserving heat for 1-2 h, heating to 600-630 ℃, preserving heat for 1-2 h, and finally preserving heat for 1-2 h at 850-900 ℃.
6. The method according to claim 3, wherein in S2, the melting process is performed by microwave heating.
7. The method for preparing the low-temperature co-fired ceramic material as claimed in claim 3, wherein in S4, the binder is 5% by volume polyvinyl butyral solution, and the amount of the binder is 5% by mass of the mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811097469.6A CN108996902B (en) | 2018-09-19 | 2018-09-19 | Low-temperature co-fired ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811097469.6A CN108996902B (en) | 2018-09-19 | 2018-09-19 | Low-temperature co-fired ceramic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108996902A CN108996902A (en) | 2018-12-14 |
| CN108996902B true CN108996902B (en) | 2021-10-26 |
Family
ID=64591796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811097469.6A Active CN108996902B (en) | 2018-09-19 | 2018-09-19 | Low-temperature co-fired ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108996902B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5468694A (en) * | 1992-11-21 | 1995-11-21 | Yamamura Glass Co. Ltd. | Composition for producing low temperature co-fired substrate |
| CN1483689A (en) * | 2002-09-18 | 2004-03-24 | 深圳南虹电子陶瓷有限公司 | Low temp cofired low specific inductive capacity glass ceramic material |
| WO2005042426A2 (en) * | 2003-10-28 | 2005-05-12 | Inocermic Gesellschaft für innovative Keramik mbH | Glass-ceramic (ltcc) capable of being assembled with silicon by anodic bonding |
| CN1796322A (en) * | 2004-12-30 | 2006-07-05 | 电子科技大学 | Formula of a glass ceramic material and preparation method |
| KR100638888B1 (en) * | 2005-09-05 | 2006-10-27 | 삼성전기주식회사 | Low temperature co-fired ceramics having high quality factor and low dielectric constant |
| CN102503137A (en) * | 2011-10-13 | 2012-06-20 | 天津大学 | Calcium-aluminum-boron-silicon glass and fused quartz low-temperature co-fired ceramic material and preparation method thereof |
| CN102898145A (en) * | 2012-10-09 | 2013-01-30 | 天津大学 | Li2O-Al2O3-SiO2-B2O3, CaO-Al2O3-SiO2-B2O3 crystallizable glass low-temperature co-fired composite material and preparation method thereof |
| CN103819089A (en) * | 2014-03-08 | 2014-05-28 | 曹小松 | Method for preparing glass ceramics through melting and glass ceramics with high flatness |
| CN104445953A (en) * | 2014-11-21 | 2015-03-25 | 柳州创宇科技有限公司 | Calcium aluminum silicon glass base low-temperature cofiring ceramic material and preparation method thereof |
| CN105619266A (en) * | 2015-12-23 | 2016-06-01 | 郑州磨料磨具磨削研究所有限公司 | Low-temperature sintering ceramic binding agent, grinding wheel and preparation method thereof |
| CN106514499A (en) * | 2016-12-29 | 2017-03-22 | 富耐克超硬材料股份有限公司 | Microcrystalline glass binder, preparation method thereof, superhard material grinding tool and preparation method thereof |
| CN107473717A (en) * | 2017-07-26 | 2017-12-15 | 广东风华高新科技股份有限公司 | Boroaluminosilicate mineral material, LTCC composite, LTCC, composite base plate and preparation method thereof |
-
2018
- 2018-09-19 CN CN201811097469.6A patent/CN108996902B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5468694A (en) * | 1992-11-21 | 1995-11-21 | Yamamura Glass Co. Ltd. | Composition for producing low temperature co-fired substrate |
| CN1483689A (en) * | 2002-09-18 | 2004-03-24 | 深圳南虹电子陶瓷有限公司 | Low temp cofired low specific inductive capacity glass ceramic material |
| WO2005042426A2 (en) * | 2003-10-28 | 2005-05-12 | Inocermic Gesellschaft für innovative Keramik mbH | Glass-ceramic (ltcc) capable of being assembled with silicon by anodic bonding |
| CN1796322A (en) * | 2004-12-30 | 2006-07-05 | 电子科技大学 | Formula of a glass ceramic material and preparation method |
| KR100638888B1 (en) * | 2005-09-05 | 2006-10-27 | 삼성전기주식회사 | Low temperature co-fired ceramics having high quality factor and low dielectric constant |
| CN102503137A (en) * | 2011-10-13 | 2012-06-20 | 天津大学 | Calcium-aluminum-boron-silicon glass and fused quartz low-temperature co-fired ceramic material and preparation method thereof |
| CN102898145A (en) * | 2012-10-09 | 2013-01-30 | 天津大学 | Li2O-Al2O3-SiO2-B2O3, CaO-Al2O3-SiO2-B2O3 crystallizable glass low-temperature co-fired composite material and preparation method thereof |
| CN103819089A (en) * | 2014-03-08 | 2014-05-28 | 曹小松 | Method for preparing glass ceramics through melting and glass ceramics with high flatness |
| CN104445953A (en) * | 2014-11-21 | 2015-03-25 | 柳州创宇科技有限公司 | Calcium aluminum silicon glass base low-temperature cofiring ceramic material and preparation method thereof |
| CN105619266A (en) * | 2015-12-23 | 2016-06-01 | 郑州磨料磨具磨削研究所有限公司 | Low-temperature sintering ceramic binding agent, grinding wheel and preparation method thereof |
| CN106514499A (en) * | 2016-12-29 | 2017-03-22 | 富耐克超硬材料股份有限公司 | Microcrystalline glass binder, preparation method thereof, superhard material grinding tool and preparation method thereof |
| CN107473717A (en) * | 2017-07-26 | 2017-12-15 | 广东风华高新科技股份有限公司 | Boroaluminosilicate mineral material, LTCC composite, LTCC, composite base plate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "LTCC基板制造及控制技术";何健锋;《电子工艺技术》;20050331(第2期);第75-81页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108996902A (en) | 2018-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111410524B (en) | LTCC microwave dielectric material and preparation method thereof | |
| CN104774005B (en) | Low-temperature sintered lead-free microwave dielectric ceramic and preparation method thereof | |
| CN109836141B (en) | High-thermal-conductivity low-temperature co-fired ceramic material and preparation method thereof | |
| CN102531392B (en) | Low-temperature co-fired ceramic material and preparation method thereof | |
| CN109608050B (en) | High-frequency low-dielectric low-loss microcrystalline glass/ceramic LTCC substrate material and preparation method thereof | |
| CN109250920A (en) | A kind of low-temperature co-burning ceramic material and preparation method thereof | |
| CN109721340A (en) | A kind of high intensity low-loss LTCC material and preparation method thereof | |
| WO2022188220A1 (en) | Sio2-series high-frequency low-dielectric low-temperature co-fired ceramic material and preparation method therefor | |
| CN103553559A (en) | CaO-B2O3-SiO2 glass and aluminum nitride ceramic composite material and preparation method thereof | |
| CN102173587A (en) | Glass ceramic material for electronic substrate and preparation method thereof | |
| CN104230329A (en) | Low-temperature sintered microwave ceramic material and preparation method thereof | |
| CN108395102B (en) | LTCC substrate material with low thermal expansion coefficient and preparation method thereof | |
| CN102531396A (en) | Low-temperature co-fired glass ceramic composites and preparation method thereof | |
| CN106673446B (en) | A kind of low Jie's high frequency devitrified glass LTCC material and preparation method thereof | |
| CN112299825A (en) | Preparation method of low dielectric low temperature co-fired ceramic material | |
| CN108218406A (en) | Low-temperature co-burning ceramic material of low dielectric constant and low loss and preparation method thereof | |
| JP3737773B2 (en) | Dielectric ceramic composition | |
| CN109180006A (en) | A kind of low-temperature co-burning ceramic material and preparation method thereof | |
| CN109180173A (en) | A kind of low temperature sintering microwave ceramic material and preparation method thereof | |
| JP3096136B2 (en) | Glass composition for low-temperature fired substrate and substrate obtained therefrom | |
| CN108996902B (en) | Low-temperature co-fired ceramic material and preparation method thereof | |
| CN110407579A (en) | One kind having ultrahigh Q-value microwave dielectric material and preparation method thereof | |
| CN109251021A (en) | A kind of low-temperature co-burning ceramic material and preparation method thereof | |
| TWI784286B (en) | Glass powder, dielectric material, sintered body, and high-frequency circuit components | |
| CN111574213B (en) | Low-dielectric-constant LTCC material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211027 Address after: 251900 20m north of the intersection of Kaifa 2nd Road and Xinghu 2nd Road, Wudi County Economic Development Zone, Binzhou City, Shandong Province Patentee after: Wudi Yurou Ceramics Co.,Ltd. Address before: 518000 1st floor, building A3, Junfeng Industrial Zone, Heping community, Fuyong street, Bao'an District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN JINGTE SMART MANUFACTURING TECHNOLOGY Co.,Ltd. |