CN113354399A - Low-temperature co-fired composite ceramic material and preparation method thereof - Google Patents
Low-temperature co-fired composite ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of microwave dielectric ceramics, in particular to a low-temperature co-fired composite ceramic material and a preparation method thereof. The invention solves the technical problem of providing the low-temperature co-fired composite ceramic material with low dielectric constant and high quality factor and the preparation method thereof, which have low cost and simple process. The low-temperature co-fired composite ceramic material comprises the following main raw materials in percentage by weight: al (Al)2O330-60%, 0-30% of orthosilicate, 30-60% of low-melting-point glass and 0.1-10% of titanate ceramic. The preparation method comprises the steps of adding water into the raw materials of the low-temperature co-fired composite ceramic material, ball-milling, filtering, drying and dispersing the obtained slurry to obtain low-temperature co-fired composite ceramic powder, and then firing the low-temperature co-fired composite ceramic powderAnd (4) knotting.
Description
Technical Field
The invention relates to the field of microwave dielectric ceramics, in particular to a low-temperature co-fired composite ceramic material and a preparation method thereof.
Background
Low temperature co-fired ceramic (i.e., LTCC) technology was a new material technology developed by houss corporation of america in 1982, and was originally designed to improve the performance associated with large computers. With the subsequent rapid development of wireless communication technology, LTCC has been receiving attention and has been more developed in advanced countries such as the united states, japan, and the like in the fields of mobile communication and high-frequency microwave application.
LTCC technology comprises several aspects: firstly, adding a certain amount of organic additive and solvent into low-temperature sintered ceramic powder, and preparing slurry with proper viscosity and fluidity by a ball milling process; secondly, preparing a green porcelain tape with accurate thickness and compactness by a tape casting process; thirdly, punching, filling holes, printing conductive slurry and other processes on the green porcelain tape to manufacture a required microcircuit pattern; and fourthly, laminating the upper and lower protective layers and a plurality of circuits together, and then co-firing at about 900 ℃ to manufacture the integrated assembly or the functional module embedded with a plurality of passive elements.
The low-temperature co-fired composite ceramic material is one of the keys of the LTCC technology. However, the current mature commercial low-temperature co-fired ceramic powder in China is not widely applied, and the process of the low-temperature co-fired ceramic powder self-developed by enterprises and research institutions in China is relatively complex and has poor repeatability. On the other hand, imported mature commercial low-temperature co-fired ceramic powder is mainly provided by countries such as the United states and Japan, and the import channel is restricted to a certain extent and is expensive. Among them, the low-temperature co-fired ceramic powder with ultrahigh frequency and low loss is limited because of its important application in military electronics.
Disclosure of Invention
In view of the above problems and deficiencies of the prior art, the present invention aims to provide a low-temperature co-fired composite ceramic material and a preparation method thereof, and more particularly to provide a low-dielectric constant high-quality factor low-temperature co-fired composite ceramic material and a preparation method thereof, which have the advantages of low cost and simple process.
The first technical problem to be solved by the invention is to provide a low-temperature co-fired composite ceramic material, which comprises the following main raw materials in percentage by weight: al (Al)2O330-60%, 0-30% of orthosilicate, 30-60% of low-melting-point glass and 0.1-10% of titanate ceramic.
The low-temperature co-fired composite ceramic material comprises the following main raw materials in percentage by weight: al (Al)2O330 to 60% of0-30% of silicate, 30-60% of low-melting-point glass, 0.1-10% of titanate ceramic and 0.1-10% of auxiliary additive.
Preferably, the weight percentage of the auxiliary additive in the low-temperature co-fired composite ceramic material is not higher than 8%.
Wherein the above-mentioned Al2O3The powder is fine-crystal alumina powder, the purity of the powder is more than 96 percent, and the particle size D50 of the powder is less than 1 mu m.
Wherein the orthosilicate is ceramic powder synthesized by a solid phase method, and the powder granularity D50 is less than 1 μm.
Wherein the orthosilicate is at least one of cordierite, wollastonite, recalcitrant limestone, magnesium silicate and zinc silicate.
Wherein, the low-melting-point glass main body is borosilicate glass powder.
Wherein the low-melting glass comprises CaO, ZnO, BaO and Li2O or K2At least one of O.
Wherein the initial softening point of the low-melting glass is less than or equal to 750 ℃, and the granularity D50 of the glass powder is less than 3 μm.
Wherein the titanate ceramic is ceramic powder synthesized by a solid phase method, and the powder granularity D50 is less than 1 μm.
Wherein the titanate ceramic comprises at least one of magnesium titanate, calcium titanate, strontium titanate or strontium calcium titanate.
Wherein the auxiliary additive comprises ZrO2、ZnO、CaO、Bi2O3、MnO2、Cr2O3Or MgO.
The second technical problem to be solved by the present invention is to provide a method for preparing the low temperature co-fired composite ceramic material, comprising the following steps: adding water into the raw materials of the low-temperature co-fired composite ceramic material, ball-milling, filtering, drying and dispersing the obtained slurry to obtain low-temperature co-fired composite ceramic powder, and sintering the low-temperature co-fired composite ceramic powder.
In the preparation method of the low-temperature co-fired composite ceramic material, the raw materials are as follows: water: the mass ratio of the balls is 1: 1-1.5: 4.5-5.0.
In the preparation method of the low-temperature co-fired composite ceramic material, the ball milling time is 1-16 hours.
In the preparation method of the low-temperature co-fired composite ceramic material, after ball milling is finished, slurry is filtered and discharged through a gauze with 250 meshes, the slurry is dried at the temperature of 100 ℃, and agglomerated blocky ceramic powder after drying is vibrated or manually dispersed through a stainless steel screen with 80 meshes to obtain the low-temperature co-fired composite ceramic powder.
In the preparation method of the low-temperature co-fired composite ceramic material, the sintering peak temperature is 850-880 ℃, and the heat preservation time is 15-30 minutes.
Has the advantages that: the invention uses Al2O3The invention is different from the prior art that the invention adopts proper ingredients and proportion, can directly carry out the next operation without melting after the ingredients are finished, has simple and convenient operation process and reduces the cost. More preferably, the invention takes the fine crystal alumina and the orthosilicate as the composite base, takes the common commercial commercialized low-melting-point low-expansion glass powder as the main sintering aid, and takes a proper amount of titanate ceramic and auxiliary additives to optimize the high-frequency loss and improve the overall sintering property and the dielectric property. In addition, the ceramic powder takes the fine crystal alumina and the orthosilicate ceramic as a composite main body, the microwave dielectric property is flexible and adjustable, the dielectric loss is low, and the Q multiplied by F value reaches more than 8000 under the test frequency of 10 GHz. Meanwhile, the powder process and the powder characteristic related by the invention have good repeatability and lower cost, and are beneficial to industrial mass production.
Detailed Description
The low-temperature co-fired composite ceramic material comprises the following main raw materials in percentage by weight: al (Al)2O330-60%, 0-30% of orthosilicate, 30-60% of low-melting-point glass and 0.1-10% of titanate ceramic.
Wherein, the low-temperature co-fired composite ceramic material comprises the following main raw materials in percentage by weight：Al2O330-60%, 0-30% of orthosilicate, 30-60% of low-melting-point glass, 0.1-10% of titanate ceramic and 0.1-10% of auxiliary additive.
Preferably, the auxiliary additive is used for reducing loss and optimizing quality factor, and usually has small proportion which affects sintering, so that the weight percentage of the auxiliary additive in the main raw material is not higher than 8%.
Al2O3The microwave high-frequency performance is excellent, and the raw materials are easy to obtain, so that Al is selected from the low-temperature co-fired composite ceramic material2O3More preferably, the above-mentioned Al is used as a base material2O3The powder is fine-crystal alumina powder, the purity of the powder is more than 96 percent, and the particle size D50 of the powder is less than 1 mu m.
Wherein the dielectric constant of the orthosilicate is equal to that of Al2O3The method is close to and can optimize the temperature characteristic and the sintering characteristic, so that the orthosilicate is selected as a composite base in the low-temperature co-fired composite ceramic material. More preferably, the orthosilicate is a ceramic powder synthesized by a solid phase method, and the powder particle size D50 is less than 1 μm.
Wherein the orthosilicate is at least one of cordierite, wollastonite, recalcitrant limestone, magnesium silicate and zinc silicate.
Wherein, the low-melting glass is used for sintering assistance and reduces the sintering temperature, so the low-melting glass is also added into the low-temperature co-fired composite ceramic material. More specifically, the low-melting-point glass body is borosilicate glass frit.
Wherein the low-melting glass comprises CaO, ZnO, BaO and Li2O or K2At least one of O.
Wherein, the finished ceramic powder is sintered at 900 ℃ or below, so the initial softening point of the low-melting glass is required to be less than or equal to 750 ℃, and the granularity D50 of the glass powder is required to be less than 3 μm.
Wherein, the electronic ceramics require submicron particles, the titanate ceramics are ceramic powder synthesized by a solid phase method, and the electrical property can be optimized when the powder granularity D50 is less than 1 μm.
Wherein the titanate ceramic comprises at least one of magnesium titanate, calcium titanate, strontium titanate or strontium calcium titanate.
Wherein the auxiliary additive comprises ZrO2、ZnO、CaO、Bi2O3、MnO2、Cr2O3Or MgO.
The invention also provides a preparation method of the low-temperature co-fired composite ceramic material, which comprises the following steps: adding water into the raw materials of the low-temperature co-fired composite ceramic material, ball-milling for 1-16 hours, filtering and discharging slurry through a 250-mesh gauze, drying at 100 ℃, vibrating or manually dispersing the dried agglomerated massive ceramic powder through an 80-mesh stainless steel screen to obtain low-temperature co-fired composite ceramic powder, and sintering the low-temperature co-fired composite ceramic powder. Wherein the raw materials are as follows: water: the mass ratio of the balls is 1: 1-1.5: 4.5-5.0.
Before sintering the low-temperature co-fired composite ceramic powder, in order to bond the powder and then sinter without influencing the performance and quality of the powder, the low-temperature co-fired composite ceramic powder is mixed with a PVA solution and then uniformly granulated to prepare a low-temperature co-fired ceramic cylindrical blank, and then sintering is carried out. The addition amount of the PVA solution is 10 wt% of the powder. The PVA solution concentration was 10 wt%.
The low-temperature co-fired composite ceramic material is required to be co-fired with metal silver paste during final use, generally the temperature is lower than 900 ℃, the cracking is easy to occur when the temperature is too high, the ceramic strength is insufficient when the temperature is too low, therefore, the sintering peak temperature is 850-880 ℃, and the heat preservation time is 15-30 minutes.
Wherein, the test result after sintering the low-temperature co-fired composite ceramic material is that the microwave dielectric constant is as follows: 7.0 to 7.9, QXF value: 8000@10GHz, frequency temperature drift coefficient (25 ℃ -85 ℃): 10 ppm/DEG C.
Example 1
First, 950 g of phi 3 zirconium balls were weighed with an electronic scale, and a one-liter planetary nylon jar was used as a ball-milling jar. Next, the ingredients were weighed as in table 1. Then, a ball milling process is formulated according to the table 2, wherein the dispersing agent is used for better dispersing, and the quality of the low-temperature co-fired ceramic is not influenced by a small amount of the dispersing agent. After the ball milling was completed, the slurry was filtered through a 250 mesh gauze and dried at 100 ℃. Taking a small amount of dry powder, adding PVA solution (with the concentration of 10%) accounting for 10% of the weight of the powder, uniformly granulating, and pressing under 20MPa to prepare a low-temperature co-fired ceramic cylindrical blank with the diameter phi of 10 and the height of 4.5 mm. And (3) putting the cylindrical blank into a sintering furnace, heating to 875 ℃ at the speed of 2 ℃/min, preserving heat for 30 min, and cooling to room temperature along with the furnace. Sintering the compact low-temperature co-fired ceramic cylindrical ceramic body, testing the microwave dielectric constant by using a vector network analyzer (Dekocht N5227A) and a parallel metal plate method, and testing the Q multiplied by F value by using the vector network analyzer and a closed metal cavity. The tests are shown in Table 3.
TABLE 1
| Al2O3Powder | Low-melting-point glass powder | SrTiO3 | ZnO | Bi2O3 | ZrO2 |
| 100 g | 85 g | 2.50 g | 3.50 g | 3.50 g | 1.00 g |
TABLE 2
| Ball milling method | Ionic water | Dispersing agent | Speed of rotation/rpm | Time/h |
| Planet mill | 200 g | 0.96 g | 350 | 2.0 |
TABLE 3
| Sintering conditions | Dielectric constant | Q x F value @10GHz | Density of porcelain body |
| 880 deg.C/20 min | 7.26 | 8660 | 2.95g/cm3 |
Example 2
First, about 950 g of Φ 3 zirconium balls were weighed with an electronic scale, and a one-liter planetary nylon jar was used as a ball mill jar. Next, the ingredients were weighed as in table 4. Then, a ball milling process is formulated according to the table 5, wherein the dispersing agent is used for better dispersing, and the quality of the low-temperature co-fired ceramic is not influenced by a small amount of the dispersing agent. After the ball milling was completed, the slurry was filtered through a 250 mesh gauze and dried at 100 ℃. Taking a small amount of dry powder, adding PVA solution (with the concentration of 10%) accounting for 10% of the weight of the powder, uniformly granulating, and pressing under 20MPa to obtain a low-temperature co-fired ceramic cylindrical blank with the diameter phi of 10 and the height of about 4.5 mm. And (3) putting the cylindrical blank into a sintering furnace, heating to 875 ℃ at the speed of 2 ℃/min, preserving heat for 30 min, and cooling to room temperature along with the furnace. Sintering the compact low-temperature co-fired ceramic cylindrical ceramic body, testing the microwave dielectric constant by using a vector network analyzer (Dekocht N5227A) and a parallel metal plate method, and testing the Q multiplied by F value by using the vector network analyzer and a closed metal cavity. The tests are shown in Table 6.
TABLE 4
| Al2O3Powder | Zn2SiO4 | Low-melting-point glass powder | SrTiO3 | CaO | Cr2O3 |
| 70 g | 30 g | 90 g | 4.00 g | 3.60 g | 1.50 g |
TABLE 5
| Ball milling method | Ionic water | Dispersing agent | Speed of rotation/rpm | Time/h |
| Planet mill | 200 g | 0.96 g | 350 | 2.0 |
TABLE 6
| Sintering conditions | Dielectric constant | Q x F value @10GHz | Density of porcelain body |
| 875 ℃/30 minutes | 7.45 | 8580 | 2.98g/cm3 |
Example 3
First, about 950 g of Φ 3 zirconium balls were weighed with an electronic scale, and a one-liter planetary nylon jar was used as a ball mill jar. Next, the ingredients were weighed as in Table 7. Then, a ball milling process is formulated according to the table 8, wherein the dispersing agent is used for better dispersing, and the quality of the low-temperature co-fired ceramic is not affected by a small amount of the dispersing agent. After the ball milling was completed, the slurry was filtered through a 250 mesh gauze and dried at 100 ℃. Taking a small amount of dry powder, adding PVA solution (with the concentration of 10%) accounting for 10% of the weight of the powder, uniformly granulating, and pressing under 20MPa to obtain a low-temperature co-fired ceramic cylindrical blank with the diameter phi of 10 and the height of about 4.5 mm. And (3) putting the cylindrical blank into a sintering furnace, heating to 875 ℃ at the speed of 2 ℃/min, preserving heat for 30 min, and cooling to room temperature along with the furnace. Sintering the compact low-temperature co-fired ceramic cylindrical ceramic body, testing the microwave dielectric constant by using a vector network analyzer (Dekocht N5227A) and a parallel metal plate method, and testing the Q multiplied by F value by using the vector network analyzer and a closed metal cavity. The tests are shown in Table 9.
TABLE 7
| Al2O3Powder | Mg2SiO4 | Low-melting-point glass powder | SrCaTiO3 | CaO | ZnO |
| 80 g | 20 g | 95 g | 5.50 g | 1.00 g | 3.50 g |
TABLE 8
| Ball milling method | Ionic water | Dispersing agent | Speed of rotation/rpm | Time/h |
| Planet mill | 200 g | 0.96 g | 350 | 2.0 |
TABLE 9
| Sintering conditions | Dielectric constant | Q x F value @10GHz | Density of porcelain body |
| 870 ℃ for 30 minutes | 7.58 | 8800 | 3.03g/cm3 |
Claims (10)
1. The low-temperature co-fired composite ceramic material is characterized in that: the main raw materials comprise the following components in percentage by weight: al (Al)2O330-60%, 0-30% of orthosilicate, 30-60% of low-melting-point glass and 0.1-10% of titanate ceramic.
2. The low temperature co-fired composite ceramic material of claim 1, wherein: the main raw materials comprise the following components in percentage by weight: al (Al)2O330-60%, 0-30% of orthosilicate, 30-60% of low-melting-point glass, 0.1-10% of titanate ceramic and 0.1-10% of auxiliary additive.
3. The low-temperature co-fired composite ceramic material according to claim 1 or 2, characterized in that: the orthosilicate is at least one of cordierite, wollastonite, recalcitrant limestone, magnesium silicate or zinc silicate.
4. The low-temperature co-fired composite ceramic material according to any one of claims 1 to 3, characterized in that: the low melting point glass satisfies at least one of the following:
the main body is borosilicate glass powder;
the components of CaO, ZnO, BaO and Li2O or K2At least one of O;
the initial softening point is less than or equal to 750 ℃, and the granularity D50 of the glass powder is less than 3 μm.
5. The low-temperature co-fired composite ceramic material according to any one of claims 1 to 4, wherein: the titanate ceramic comprises at least one of magnesium titanate, calcium titanate, strontium titanate or strontium calcium titanate.
6. The low-temperature co-fired composite ceramic material according to any one of claims 1 to 5, wherein: the auxiliary additive component is ZrO2、ZnO、CaO、Bi2O3、MnO2、Cr2O3Or MgO.
7. The preparation method of the low-temperature co-fired composite ceramic material as claimed in any one of claims 1 to 6, characterized in that: the method comprises the following steps: adding water into the raw materials of the low-temperature co-fired composite ceramic material according to any one of claims 1 to 6, ball-milling, filtering, drying and dispersing the obtained slurry to obtain low-temperature co-fired composite ceramic powder, and sintering the low-temperature co-fired composite ceramic powder.
8. The method for preparing a low-temperature co-fired composite ceramic material according to claim 7, wherein the method comprises the following steps: the raw materials are as follows: water: the mass ratio of the balls is 1: 1-1.5: 4.5-5.0.
9. The method for preparing a low-temperature co-fired composite ceramic material according to claim 7 or 8, characterized in that: and the ball milling time is 1-16 hours, after the ball milling is finished, the slurry is filtered and discharged through a gauze with 250 meshes, the slurry is dried at 100 ℃, and the agglomerated blocky ceramic powder after the drying is vibrated or manually dispersed through a stainless steel screen with 80 meshes to obtain the low-temperature co-fired composite ceramic powder.
10. The preparation method of the low-temperature co-fired composite ceramic material according to any one of claims 7 to 9, characterized in that: the sintering peak temperature is 850-880 ℃, and the heat preservation time is 15-30 minutes.
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| CN111995383A (en) * | 2020-09-08 | 2020-11-27 | 中物院成都科学技术发展中心 | Mg2-xMxSiO4-CaTiO3Composite microwave dielectric ceramic and preparation method thereof |
| CN114573333A (en) * | 2022-02-28 | 2022-06-03 | 嘉兴佳利电子有限公司 | Low-dielectric wollastonite low-temperature co-fired ceramic material and preparation method thereof |
| CN115073007A (en) * | 2022-07-26 | 2022-09-20 | 宜宾红星电子有限公司 | Low-temperature co-fired glass ceramic composite material and preparation method thereof |
| CN115141007A (en) * | 2022-07-26 | 2022-10-04 | 冷水江市汇鑫电子陶瓷有限公司 | Composite special ceramic material and preparation method thereof |
| CN115959895A (en) * | 2022-12-12 | 2023-04-14 | 大富科技(安徽)股份有限公司 | Microwave dielectric ceramic material, preparation method thereof and microwave dielectric ceramic device |
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