Low-temperature co-fired ceramic / glass composite material and preparation method thereof

Abstract

The invention discloses a low-temperature co-fired ceramic / glass composite material and a preparation method and application thereof, and belongs to the technical field of ceramic materials.According to the low-temperature co-fired ceramic / glass composite material, aluminum oxide (Al2O3) serves as a ceramic phase, CaO-B2O3-SiO2 (CBS) and zinc-boron glass serve as a glass phase, and K2O, CuO and Nb2O5 are added, so that the low-temperature co-fired ceramic / glass composite material is obtained; when the prepared low-temperature co-fired ceramic / glass composite material is used for preparing microelectronic elements, the firing temperature can be reduced to 800-850 DEG C, meanwhile, the dielectric constant is reduced to 7.0-8.5, and the dielectric loss is reduced to 0.3 * 10 <-3 >-0.7 * 10 <-3 > (1MHz).

Description

Technical Field

[0001] The present invention relates to the technical field of organic resins, and particularly relates to a low-temperature co-fired ceramic / glass composite material and a preparation method thereof. Background Art

[0002] With the accelerating development of microelectronic technology, the corresponding electronic packaging has also experienced a rapid development stage. Electronic packaging has multiple functions such as mechanical support, electrical connection, physical protection, external field shielding, stress relaxation, heat dissipation and moisture prevention, size transition, standardization and standardization. An integrated circuit chip without packaging cannot play its huge role. At the same time, the continuous improvement of the performance of bare chips has also put forward higher requirements for electronic packaging.

[0003] The low-temperature co-fired ceramic (LTCC, Low Temperature Cofired Ceramics) technology has become one of the fastest developing and most widely used packaging technologies in recent years. The main reason is that the sintering temperature of the LTCC substrate material is low (<1000 °C), and it can be co-fired with most metal materials with good conductivity, such as Ag, Pd, Au, Cu, etc., which greatly improves the functionality of the packaging. At the same time, thick-film technology process equipment can be used, and the cost is greatly reduced, achieving both high performance and low cost, and meeting the usage requirements in most packaging occasions. For LTCC materials, different performance needs to be pursued according to different application scenarios, but generally, as low a ceramic firing temperature and dielectric loss as possible are required. Dielectric loss is the energy loss caused inside due to the lag effect of medium conductance and medium polarization under the action of an electric field. The lower the dielectric loss of LTCC materials, the lower the attenuation of signal transmission during device operation. And a low sintering temperature is convenient for the material to be co-fired with low-melting-point and high-conductivity metals, such as Ag, Pd, Au, Cu, etc., reducing the process difficulty and production cost.

[0004] However, the existing LTCC firing temperature is generally around 900 °C - 950 °C, and there is still a relatively high dielectric loss. Summary of the Invention

[0005] In view of the above problems, the present invention provides a low-temperature co-fired ceramic / glass composite material, a preparation method and an application thereof, effectively solving the technical problems of high ceramic firing temperature and high dielectric loss existing in the existing low-temperature co-fired ceramic technology. The present invention uses alumina (Al 2 O 3 ) as the ceramic phase, CaO - B 2 O 3 -SiO 2 (CBS) and zinc borate glass as the glass phase, and by adding K 2 O, CuO, Nb 2 O 5, the firing temperature is effectively reduced during the preparation of the low-temperature co-fired ceramic / glass composite material, and the prepared low-temperature co-fired ceramic / glass composite material has lower dielectric loss.

[0006] The first object of the present invention is to provide a low-temperature co-fired ceramic / glass composite material, which is made of the following raw materials in parts by mass: 30-50 parts of CBS glass-ceramics, 3-6 parts of zinc borate glass, 50-70 parts of alumina, Nb 2 O 5 4-6 parts; K 2 O 0.2-0.4 part, 3-5 parts of CuO; the total mass parts of the CBS glass-ceramics and alumina is 100 parts.

[0007] The CBS glass-ceramics includes the following raw materials in mass percentage: 35wt%-45wt% CaCO 3 , 20wt%-30wt% H 3 BO 3 , 25wt%-35wt% SiO 2 , and the balance is impurities, totaling 100%.

[0008] The zinc borate glass includes the following raw materials in mass percentage: 40wt%-45wt% ZnO, 40wt%-45wt% B 2 O 3 , 10wt%-15wt% K 2 O, 1wt%-5wt% SiO 2 , totaling 100%.

[0009] As a preferred embodiment, the impurities are 0.5wt%-2wt% MgO, 1wt%-2wt% P 2 O 5 and 0.1wt%-1wt% Na 2 O.

[0010] The second object of the present invention is to provide a preparation method of the above-mentioned low-temperature co-fired ceramic / glass composite material, including the following steps:

[0011] Weigh the raw materials of the CBS glass-ceramics respectively according to the mass percentage, mix them, melt them at 1400-1500 °C to obtain a glass melt, cool and form it, and grind it to obtain CBS glass-ceramics powder.

[0012] Weigh the raw materials of the zinc borate glass according to the mass percentage, mix them, melt them at 1400-1500 °C to obtain a glass melt, cool and form it, and grind it to obtain zinc borate glass powder.

[0013] Using the CBS glass-ceramics powder and zinc borate glass powder as the glass phase, and alumina as the ceramic phase, add Nb2 O 5 ,K 2 O and CuO, and then add anhydrous ethanol, ball mill, and dry to obtain a composite powder.

[0014] Granulate and tablet the composite powder to obtain a green body. Heat the green body to 500 °C for the first time, hold for heat preservation, then heat to 800 °C - 850 °C for the second time, and sinter to obtain a low-temperature co-fired ceramic / glass composite material.

[0015] As a preferred embodiment, the melting time is 4 - 5 h.

[0016] As a preferred embodiment, D10 of the CBS glass-ceramic powder is 0.829 μm, D50 is 2.363 μm, and D90 is 5.428 μm.

[0017] As a preferred embodiment, the heating rate of the first heating is 1 °C / min, and the heat preservation time is 5 - 6 h.

[0018] As a preferred embodiment, the heating rate of the second heating is 2 - 5 °C / min, and the sintering time is 2 - 4 h.

[0019] As a preferred embodiment, add a polyvinyl alcohol solution with a mass concentration of 5% to the composite powder for granulation.

[0020] The third object of the present invention is to provide an application of the above low-temperature co-fired ceramic / glass composite material in electromagnetic shielding.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] The present invention provides a low-temperature co-fired ceramic / glass composite material, using alumina as the ceramic phase, CBS glass-ceramic and zinc borate glass as the glass phase, and through K 2 O, CuO, Nb 2 O 5The addition results in the preparation of a low-temperature co-fired ceramic / glass composite material. In the present invention, CBS glass-ceramics and zinc borate glass play a key role in the densification of ceramic materials. The surface tension of the glass and the wettability of the glass to ceramic particles are very important. The distribution of the glass at the sintering temperature will affect the sintering densification of the material. In this application, CBS glass-ceramics and zinc borate glass are jointly used as the glass phase. As a low-melting-point glass-ceramics, CBS glass-ceramics will introduce new crystal phases during the sintering process, increasing the pores in the sintered body. The precipitated crystal phases will affect the dielectric properties of the material. As a low-melting-point glass, zinc borate glass will not crystallize by itself. It provides a liquid phase to promote the densification of the ceramic / glass composite material, can reduce the sintering temperature to about 800 °C, and has a small impact on the dielectric properties. In the present invention, transition metal oxide Nb 2 O 5 , alkali metal compound K 2 O, and metal oxide CuO are added, improving the dielectric properties and low-temperature sintering performance of the ceramic / glass composite material, reducing the loss in signal transmission, and lowering the production cost. K 2 O reduces the glass softening point, lowers the sintering temperature, and promotes the liquid-phase sintering efficiency. K + ions have a large radius, effectively reducing the ionic migration loss at low frequencies. Trace amounts of K 2 O reduce the dielectric loss of the material; Nb 2 O 5 regulates the precipitated crystal phases to generate calcium niobate at a low sintering temperature. Calcium niobate has a low dielectric loss, thus reducing the dielectric loss of the system; part of the metal oxide CuO enters the glass network to improve the crystallization performance of the glass. In the present invention, the combined action of K 2 O, Nb 2 O 5 and CuO regulates the crystallization process of the glass / ceramic composite material, reduces the sintering temperature, and decreases the dielectric loss. Its firing temperature can be reduced to 800 °C to 850 °C, and at the same time, the dielectric constant is reduced to 7.0 to 8.5, and the dielectric loss is reduced to 0.3×10 -3 to 0.7×10 -3 (1 MHz). BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 FIG. is a schematic process flow diagram for the preparation of the LTCC material in the present invention.

[0024] Figure 2 FIG. is a cross-sectional SEM image of the sintered low-temperature co-fired ceramic / glass composite material in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] To enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention will be further described below in conjunction with specific embodiments. However, the specific embodiments cited do not limit the present invention. The following test methods and detection methods are all conventional methods unless otherwise specified; the reagents and raw materials are all commercially available unless otherwise specified.

[0026] For low-temperature co-fired ceramic materials, it is generally necessary to have as low a ceramic firing temperature as possible and achieve low dielectric loss of the ceramic material during the preparation process. The lower the dielectric loss of the LTCC material, the lower the attenuation of signal transmission during device operation; the low sintering temperature facilitates co-firing of the material with low-melting-point and high-conductivity metals such as Ag, Pd, Au, Cu, etc., reducing the process difficulty and production cost. However, the firing temperature of existing low-temperature co-fired ceramics is generally around 900°C - 950°C, and there is still a relatively high dielectric loss. In view of the above technical problems, the present invention provides a low-temperature co-fired ceramic / glass composite material, its preparation method and application.

[0027] The technical solution of the present invention will be described in detail below.

[0028] The present invention first provides a low-temperature co-fired ceramic / glass composite material, which is made from the following raw materials in parts by mass: 30 - 50 parts of CBS glass-ceramics, 3 - 6 parts of zinc borate glass, 50 - 70 parts of alumina, Nb 2 O 5 4 - 6 parts; K 2 O0.2 - 0.4 part, 3 - 5 parts of CuO.

[0029] The CBS glass-ceramics include the following raw materials in mass percentage: 35wt% - 45wt% CaCO 3 , 20wt% - 30wt% H 3 BO 3 , 25wt% - 35wt% SiO 2 , and the balance is impurities, totaling 100%.

[0030] The zinc borate glass includes the following raw materials in mass percentage: 40wt% - 45wt% ZnO, 40wt% - 45wt% B 2 O 3 , 10wt% - 15wt% K 2 O, 1wt% - 5wt% SiO 2 , totaling 100%.

[0031] In the above technical solution, alumina (Al 2 O 3 ) is used as the ceramic phase, CaO - B 2 O 3 -SiO2 (CBS) and zinc borate glass are used as the glass phase, and through the addition of K 2 O, CuO, Nb 2 O 5 , when the prepared low-temperature co-fired ceramic / glass composite material is used for preparing microelectronic components, the firing temperature can be reduced to 750 °C to 850 °C, and at the same time, the dielectric constant is reduced to 7.0 to 8.5, and the dielectric loss is reduced to 0.3×10 -3 ~0.7×10 -3 (1 MHz).

[0032] It should be noted that the total mass fraction of the CBS glass-ceramics and alumina is 100 parts.

[0033] In order to further reduce the dielectric loss, the impurities are 0.5 wt% to 2 wt% MgO, 1 wt% to 2 wt% P2O5 and 0.1 wt% to 1 wt% Na2O by mass percentage. MgO and Na 2 O are used as glass network modifiers of the CBS glass-ceramics at the same time, which can break the glass network, destroy the integrity of the glass network, and promote crystallization; P 2 O 5 is used as a nucleating agent for the CBS glass-ceramics, which can promote glass phase separation, thereby promoting crystallization. The glass-ceramics can improve the microwave dielectric properties by promoting its crystallization, thereby reducing the dielectric loss.

[0034] The present invention also provides a preparation method of the above-mentioned low-temperature co-fired ceramic / glass composite material, including the following steps:

[0035] Weigh the raw materials of the CBS glass-ceramics according to the mass percentage respectively, mix them, melt them at 1400 to 1500 °C for 4 to 5 h to obtain a glass melt, cool and form it, and grind it to obtain CBS glass-ceramic powder.

[0036] Weigh the raw materials of the zinc borate glass according to the mass percentage, mix them, melt them at 1400 to 1500 °C for 4 to 5 h to obtain a glass melt, cool and form it, and grind it to obtain zinc borate glass powder.

[0037] Using the CBS glass-ceramic powder and the zinc borate glass powder as the glass phase, and alumina as the ceramic phase, add Nb 2 O 5 , K 2 O and CuO, and then add anhydrous ethanol, ball mill, and dry to obtain a composite powder.

[0038] Add a polyvinyl alcohol solution with a mass concentration of 5% to the composite powder for granulation and tabletting to obtain a green body. Heat the green body at a rate of 1 °C / min for the first time to 500 °C, hold for 5 - 6 h, then heat at a rate of 2 °C / min - 5 °C / min for the second time to 800 °C - 850 °C, and sinter for 2 - 4 h to obtain a low-temperature co-fired ceramic / glass composite material.

[0039] It should be noted that the D10 of the CBS glass-ceramic powder is 0.829 μm, the D50 is 2.363 μm, and the D90 is 5.428 μm.

[0040] The technical effects of the present invention will be described below with specific examples.

[0041] Example 1

[0042] A low-temperature co-fired ceramic / glass composite material is made from the following raw materials in parts by mass: 35 parts of CBS glass-ceramic, 3 parts of zinc borate glass, 65 parts of alumina, 5 parts of Nb 2 O 5 5 parts; 0.2 part of K 2 O0.2, 4 parts of CuO.

[0043] The CBS glass-ceramic includes the following raw materials in mass percentages: 44 wt% CaCO 3 , 26 wt% H 3 BO 3 , 28 wt% SiO 2 , 1 wt% P 2 O 5 , 0.5 wt% MgO, 0.5 wt% Na 2 O.

[0044] The zinc borate glass includes the following raw materials in mass percentages: 42 wt% ZnO, 42 wt% B 2 O 3 , 13 wt% K 2 O, 3 wt% SiO 2 .

[0045] The preparation method of the above low-temperature co-fired ceramic / glass composite material, as Figure 1 shown, includes the following steps:

[0046] S1. Mix 44 wt% CaCO 3 , 26 wt% H 3 BO 3 , 28 wt% SiO 2 , 1 wt% P 2 O 5 , 0.5 wt% MgO, 0.5 wt% Na 2O, Take a sample and put it into a planetary ball mill. Use a nylon ball milling jar with zirconia balls inside and anhydrous ethanol as the ball milling medium for sufficient mixing. After drying the mixed slurry, then put the powder into a platinum crucible. Place the crucible with the powder inside into a high-temperature furnace and keep it at 1400 °C for 4 h to obtain a high-temperature molten glass liquid.

[0047] S2. Take 42 wt% ZnO, 42 wt% B 2 O 3 , 13 wt% K 2 O, 3 wt% SiO 2 , Take a sample and put it into a planetary ball mill. Use a nylon ball milling jar with zirconia balls inside and anhydrous ethanol as the ball milling medium for sufficient mixing. After drying the mixed slurry, then put the powder into a platinum crucible. Place the crucible with the powder inside into a high-temperature furnace and keep it at 1400 °C for 4 h to obtain a high-temperature molten glass liquid.

[0048] S3. Pour the glass liquids obtained in S1 and S2 into deionized water respectively for cooling quenching to obtain glass blocks with uneven sizes. Crush the obtained glass blocks to get glass powder, thus obtaining CBS glass-ceramic powder and zinc borate glass powder.

[0049] S4. Ball mill the obtained CBS glass-ceramic powder, zinc borate glass powder, alumina ceramic powder, alkali metal oxide potassium oxide, transition metal oxide niobium pentoxide, and metal oxide copper oxide in anhydrous ethanol at a rotation speed of 280 r / min for 6 h to obtain a mixed slurry. Dry it to obtain a composite powder. Add a 5% polyvinyl alcohol solution by mass to the composite powder for granulation and tabletting to obtain a green body. Heat the green body at a rate of 1 °C / min for the first time to 500 °C and keep it warm for 5 - 6 h. Then heat it at a rate of 5 °C / min for the second time to 800 °C and sinter for 2 h to obtain a low-temperature co-fired ceramic / glass composite material.

[0050] Test: Silver the two sides of the sintered ceramic chip. Finally, use an impedance analyzer 4291A to test the performance of the wafer as follows: dielectric constant 8.00, dielectric loss 0.4×10 -3 (1 MHz).

[0051] Example 2

[0052] A low-temperature co-fired ceramic / glass composite material is made from the following raw materials in parts by mass: 35 parts of CBS glass-ceramic, 3 parts of zinc borate glass, 65 parts of alumina, Nb 2 O 5 5 parts; K 2 O 0.2 parts, 4 parts of CuO.

[0053] The CBS glass-ceramic comprises the following raw materials in percentage by weight: 44wt% CaCO 3 , 26wt%H 3 BO 3 , 28wt%SiO 2 , 1wt%P 2 O 5 , 0.5wt%MgO, 0.5wt%Na 2 O.

[0054] The zinc-boron glass comprises the following raw materials in percentage by weight: 42 wt % ZnO, 42 wt % B 2 O 3 , 13wt%K 2 O, 3wt%SiO 2 .

[0055] The preparation method of the above-mentioned low temperature co-fired ceramic / glass composite material is as follows: Figure 1 As shown, the following steps are included:

[0056] S1. 44wt% CaCO 3 , 26wt%H 3 BO 3 , 28wt%SiO 2 , 1wt%P 2 O 5 , 0.5wt%MgO, 0.5wt%Na 2 O, take a sample and put it into a planetary ball mill, use a nylon ball mill with built-in zirconium balls, use anhydrous ethanol as the ball milling medium, mix it thoroughly, dry the mixed slurry, and then put the powder into a platinum crucible, put the crucible with the built-in powder into a high-temperature furnace, and keep it warm at 1400°C for 4 hours to obtain a high-temperature molten glass liquid.

[0057] S2. 42wt% ZnO, 42wt% B 2 O 3 , 13wt%K 2 O, 3wt%SiO 2 , take a sample and put it into a planetary ball mill, use a nylon ball mill with built-in zirconium balls, use anhydrous ethanol as the ball milling medium, mix it thoroughly, dry the mixed slurry, and then put the powder into a platinum crucible, put the crucible with the built-in powder into a high-temperature furnace, and keep it warm at 1400℃ for 4h to obtain high-temperature molten glass liquid.

[0058] S3. Pour the glass liquids obtained from S1 and S2 into deionized water respectively for cooling and quenching to obtain glass blocks of uneven sizes. The obtained glass blocks are crushed to obtain glass powder, thereby obtaining CBS microcrystalline glass powder and zinc-boron glass powder.

[0059] S4. The obtained CBS glass-ceramic powder, zinc borate glass powder, alumina ceramic powder, alkali metal oxide potassium oxide, transition metal oxide niobium pentoxide, and metal oxide copper oxide are ball-milled in absolute ethanol at a rotation speed of 280 r / min for 6 h to obtain a mixed slurry, which is dried to obtain a composite powder. A polyvinyl alcohol solution with a mass concentration of 5% is added to the composite powder for granulation and tabletting to obtain a green body. The green body is first heated to 500 °C at a rate of 1 °C / min and held for 5 - 6 h, and then heated to 850 °C at a rate of 5 °C / min and sintered for 2 h to obtain a low-temperature co-fired ceramic / glass composite material.

[0060] Testing: The sintered ceramic sheet is silvered on both sides, and finally the performance of the wafer is measured by an impedance analyzer 4291A as follows: dielectric constant 7.00, dielectric loss 0.7×10 -3 (1 MHz).

[0061] Compared with Example 1, in Example 2, only the sintering temperature is increased from 800 °C to 850 °C. The dielectric constant of the low-temperature co-fired ceramic / glass composite material decreases from 8.00 to 7.00, and the dielectric loss increases from 0.4×10 -3 (1 MHz) to 0.7×10 -3 (1 MHz). Therefore, the increase in the sintering temperature will lead to a decrease in the dielectric constant and an increase in the dielectric loss of the material.

[0062] Example 3

[0063] A low-temperature co-fired ceramic / glass composite material is made from the following raw materials in parts by mass: 35 parts of CBS glass-ceramic, 3 parts of zinc borate glass, 65 parts of alumina, Nb 2 O 5 5 parts; K 2 O 0.2 part, 4 parts of CuO.

[0064] The CBS glass-ceramic includes the following raw materials in mass percentages: 45 wt% CaCO 3 , 26 wt% H 3 BO 3 , 25 wt% SiO 2 , 1.5 wt% P 2 O 5 , 1.5 wt% MgO, 1 wt% Na 2 O.

[0065] The zinc borate glass includes the following raw materials in mass percentages: 41 wt% ZnO, 42 wt% B 2 O 3 , 13 wt% K 2 O, 4 wt% SiO 2 .

[0066] The preparation method of the above low-temperature co-fired ceramic / glass composite material comprises the following steps:

[0067] S1. Take 45wt% CaCO 3 , 26wt% H 3 BO 3 , 25wt% SiO 2 , 1.5wt% P 2 O 5 , 1.5wt% MgO, 1wt% Na 2 O, sample and put it into a planetary ball mill. Use a nylon ball milling pot with zirconia balls inside, and use absolute ethanol as the ball milling medium to mix thoroughly. After drying the mixed slurry, then put the powder into a platinum crucible, put the crucible with the powder inside into a high-temperature furnace, and keep it at 1400 °C for 4 h to obtain a high-temperature molten glass liquid.

[0068] S2. Take 41wt% ZnO, 42wt% B 2 O 3 , 13wt% K 2 O, 4wt% SiO 2 , sample and put it into a planetary ball mill. Use a nylon ball milling pot with zirconia balls inside, and use absolute ethanol as the ball milling medium to mix thoroughly. After drying the mixed slurry, then put the powder into a platinum crucible, put the crucible with the powder inside into a high-temperature furnace, and keep it at 1400 °C for 4 h to obtain a high-temperature molten glass liquid.

[0069] S3. Pour the glass liquids obtained in S1 and S2 into deionized water respectively for cooling and quenching to obtain glass blocks with uneven sizes. Crush the obtained glass blocks to obtain glass powder, thereby obtaining CBS glass-ceramic powder and zinc borate glass powder.

[0070] S4. Put the obtained CBS glass-ceramic powder, zinc borate glass powder, alumina ceramic powder, alkali metal oxide potassium oxide, transition metal oxide niobium pentoxide and metal oxide copper oxide into absolute ethanol, and ball mill at a speed of 280 r / min for 6 h to obtain a mixed slurry. Dry it to obtain a composite powder. Add a 5% by mass concentration of polyvinyl alcohol solution to the composite powder for granulation operation. Next, dry press through a mold to form a round green body with a diameter of 12 mm and a thickness of about 1 mm. Next, put it into a muffle furnace for debinding and sintering. The debinding process is at 1 °C / min, first heating to 500 °C and holding for 5 h, and then heating to 800 °C at 2 °C / min and holding for 3 h for sintering to obtain a low-temperature co-fired ceramic / glass composite material.

[0071] Test: The sintered ceramic chips were subjected to silvering on both sides, and finally, the performance of the wafers was measured by an impedance analyzer 4291A as follows: dielectric constant 7.72, dielectric loss 0.3×10 -3 (1 MHz).

[0072] Figure 2 This is the SEM cross-sectional view of the low-temperature co-fired ceramic / glass composite material prepared in Example 3 of the present invention. As can be seen from Figure 2 it, the microstructure of the low-temperature co-fired ceramic / glass composite material of the present invention is relatively dense, and no large pores appear.

[0073] Example 4

[0074] A low-temperature co-fired ceramic / glass composite material is made from the following raw materials in parts by mass: 35 parts of CBS glass-ceramics, 3 parts of zinc borate glass, 65 parts of alumina, Nb 2 O 5 5 parts; K 2 O 0.2 part, 4 parts of CuO.

[0075] The CBS glass-ceramics include the following raw materials in mass percentages: 40 wt% CaCO 3 , 28 wt% H 3 BO 3 , 30 wt% SiO 2 , 1.0 wt% P 2 O 5 , 0.5 wt% MgO, 0.5 wt% Na 2 O.

[0076] The zinc borate glass includes the following raw materials in mass percentages: 41 wt% ZnO, 42 wt% B 2 O 3 , 13 wt% K 2 O, 4 wt% SiO 2 .

[0077] The preparation method of the above low-temperature co-fired ceramic / glass composite material includes the following steps:

[0078] S1. Mix 40 wt% CaCO 3 , 28 wt% H 3 BO 3 , 30 wt% SiO 2 , 1.0 wt% P 2 O 5 , 0.5 wt% MgO, 0.5 wt% Na 2Take a sample and place it in a planetary ball mill. Use a nylon ball milling jar with zirconium balls inside and anhydrous ethanol as the ball milling medium to mix thoroughly. After drying the mixed slurry, then put the powder into a platinum crucible, place the crucible with the powder inside into a high-temperature furnace, and keep it at 1400 °C for 4 h to obtain a high-temperature molten glass liquid.

[0079] S2. Take 41 wt% ZnO, 42 wt% B 2 O 3 , 13 wt% K 2 O, 4 wt% SiO 2 Take a sample and place it in a planetary ball mill. Use a nylon ball milling jar with zirconium balls inside and anhydrous ethanol as the ball milling medium to mix thoroughly. After drying the mixed slurry, then put the powder into a platinum crucible, place the crucible with the powder inside into a high-temperature furnace, and keep it at 1400 °C for 4 h to obtain a high-temperature molten glass liquid.

[0080] S3. Pour the glass liquids obtained in S1 and S2 into deionized water respectively for cooling quenching to obtain glass blocks with uneven sizes. Crush the obtained glass blocks to get glass powder, and thus obtain CBS glass-ceramic powder and zinc borate glass powder.

[0081] S4. Put the obtained CBS glass-ceramic powder, zinc borate glass powder, alumina ceramic powder, alkali metal oxide potassium oxide, transition metal oxide niobium pentoxide, and metal oxide copper oxide into anhydrous ethanol, and ball mill them at a speed of 280 r / min for 6 h to obtain a mixed slurry. Dry it to obtain a composite powder. Add a polyvinyl alcohol solution with a mass concentration of 5% to the composite powder for granulation operation. Next, dry press it through a mold into a disc-shaped green body with a diameter of 12 mm and a thickness of about 1 mm. Then put it into a muffle furnace for debinding and sintering. During the debinding process, heat it at 1 °C / min, first raise the temperature to 500 °C and keep it for 5 h. Next, heat it at 2 °C / min, and secondarily raise the temperature to 825 °C and keep it for 4 h for sintering to obtain a low-temperature co-fired ceramic / glass composite material.

[0082] Test: Perform silver plating on both sides of the sintered ceramic chip. Finally, use an impedance analyzer 4291A to test the performance of the disc as follows: dielectric constant 8.07, dielectric loss 0.7×10 -3 (1 MHz).

[0083] In summary, using the low-temperature co-fired ceramic / glass composite material provided by the present invention, the sintering temperature of this microwave dielectric ceramic material is significantly lower than the 1500 °C required for alumina ceramic materials, with less energy consumption. And compared with the dielectric constant of 6.26 and dielectric loss of 1.00×10 -3(1 MHz), the dielectric properties have been significantly improved, with excellent dielectric properties: the dielectric constant is 7.0 - 8.5, and the dielectric loss is 0.3×10 -3 ~0.7×10 -3 (1 MHz). It has a wide range of applications, stable performance, and can be used to manufacture microwave components such as resonators, filters, and dielectric ceramic substrates. The preparation process is simple and industrialized mass production can be achieved.

[0084] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these changes and modifications.

Claims

1. A low temperature co-fired ceramic / glass composite material, characterized in that: Made of the following raw materials in parts by weight: 30-50 parts of CBS glass-ceramics, 3-6 parts of zinc-boron glass, 50-70 parts of aluminum oxide, 4-6 parts of Nb2O5, 0.2-0.4 parts of K2O, and 3-5 parts of CuO; the total parts by weight of the CBS glass-ceramics and aluminum oxide is 100 parts; The CBS glass-ceramics comprises the following raw materials in percentage by weight: 35wt% to 45wt% CaCO3, 20wt% to 30wt% H3BO3, 25wt% to 35wt% SiO2, and the remainder is impurities, which totals 100%; The zinc-boron glass comprises the following raw materials in percentage by weight: 40wt% to 45wt% ZnO, 40wt% to 45wt% B2O3, 10wt% to 15wt% K2O, and 1wt% to 5wt% SiO2, which totals 100%.

2. The low temperature co-fired ceramic / glass composite material according to claim 1, characterized in that: The impurities are 0.5wt% to 2wt% MgO, 1wt% to 2wt% P2O5 and 0.1wt% to 1wt% Na2O in mass percentage.

3. A method for preparing the low temperature co-fired ceramic / glass composite material according to claim 1 or 2, characterized in that: The following steps are involved: Weigh the raw materials of CBS glass-ceramics according to mass percentage, mix them, melt them at 1400° C. to 1500° C. to obtain glass liquid, cool them into shape, grind them, and obtain CBS glass-ceramics powder; Weigh the raw materials of zinc-boro glass according to mass percentage, mix them, melt them at 1400-1500° C. to obtain glass liquid, cool them into shape, grind them, and obtain zinc-boro glass powder; The CBS microcrystalline glass powder and zinc-boron glass powder are used as the glass phase, alumina is used as the ceramic phase, Nb2O5, K2O and CuO are added, and then anhydrous ethanol is added, ball milled, and dried to obtain a composite powder; The composite powder is granulated and tableted to obtain a green body, the green body is heated to 500°C for the first time, kept warm, and heated to 800°C to 850°C for the second time, sintered to obtain a low temperature co-fired ceramic / glass composite material.

4. The method for preparing the low temperature co-fired ceramic / glass composite material according to claim 3, characterized in that: The melting time is 4h to 5h.

5. The method for preparing the low temperature co-fired ceramic / glass composite material according to claim 3, characterized in that: The CBS glass-ceramic powder has a D10 of 0.829 μm, a D50 of 2.363 μm, and a D90 of 5.428 μm.

6. The method for preparing the low temperature co-fired ceramic / glass composite material according to claim 3, characterized in that: The first heating rate is 1°C / min, and the insulation time is 5h to 6h.

7. The method for preparing the low temperature co-fired ceramic / glass composite material according to claim 3, characterized in that: The second heating rate is 2°C / min to 5°C / min, and the sintering time is 2h to 4h.

8. The method for preparing the low temperature co-fired ceramic / glass composite material according to claim 3, characterized in that: A polyvinyl alcohol solution with a mass concentration of 5% is added to the composite powder for granulation.

9. Use of the low temperature co-fired ceramic / glass composite material according to claim 1 or 2 in electromagnetic shielding.

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