Silicon carbide reinforced calcium aluminum borosilicate glass composite material and preparation method thereof
By preparing silicon carbide-reinforced calcium aluminum borosilicate glass composites, the limitations of LTCC materials in terms of thermal management and mechanical properties have been overcome, achieving a synergistic breakthrough in high thermal conductivity and high mechanical strength, making them suitable for packaging high power density electronic devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-22
- Publication Date
- 2026-04-14
AI Technical Summary
Existing LTCC materials have significant limitations in terms of thermal management and mechanical properties, making it difficult to meet the needs of high power density scenarios. In particular, their insufficient thermal conductivity and mechanical strength in miniaturized LED packaging lead to increased junction temperature, decreased luminous efficiency, and reduced lifespan.
By using silicon carbide-reinforced calcium aluminum borosilicate glass composite material, and by optimizing the glass composition design and introducing nucleating agents, combined with a reasonable silicon carbide addition ratio and low-temperature sintering process, a material with both high thermal conductivity and high mechanical strength was prepared.
While maintaining low-temperature sintering characteristics and low dielectric properties, the thermal conductivity and mechanical strength of the material are significantly improved, making it suitable for packaging high-power-density electronic devices and providing an ideal packaging substrate material solution.
Smart Images
Figure CN121850361A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of electronic packaging materials and their manufacturing, and relates to a high-strength, high-thermal-conductivity silicon carbide reinforced calcium aluminum borosilicate glass composite material and its preparation method. Background Technology
[0002] With the rapid development of microelectronics technology towards miniaturization and integration, traditional electronic packaging technology has become a key bottleneck restricting industrial upgrading. Against this backdrop, low-temperature co-fired ceramic (LTCC) technology, with its unique advantages, has become an important solution in the field of multilayer electronic packaging. This technology allows for direct co-firing with highly conductive metals such as gold, silver, and copper in an atmospheric environment, significantly reducing process complexity and production costs. It also offers advantages such as flexible wiring and adjustable dielectric properties, providing an ideal platform for the integration of high-performance electronic systems.
[0003] Currently, LTCC materials are mainly divided into two categories: microcrystalline glass systems and glass-ceramic composite systems. Although microcrystalline glass systems can achieve a dense structure, their crystallization process is difficult to control precisely, resulting in problems such as unstable dielectric properties and a narrow process window, which restricts large-scale production and application. In contrast, glass-ceramic composite systems can achieve more stable designability of material properties by adjusting the ratio and type of glass phase and ceramic filler phase.
[0004] After years of research, LTCC technology has matured significantly in developed countries, but research in China is still in its early stages. Current mainstream LTCC materials face significant limitations in thermophysical and mechanical properties, making it difficult to support the stringent operational requirements of high-power-density applications. For example, in miniaturized LED packaging applications, insufficient thermal conductivity directly leads to increased junction temperature, decreased luminous efficiency, and reduced lifespan. Simultaneously, limited mechanical strength under thermal cycling stress easily induces the initiation and propagation of microcracks, posing a potential threat to the long-term reliability of multilayer structures. These performance shortcomings collectively restrict the depth and breadth of application of existing LTCC materials in advanced electronic packaging.
[0005] While high thermal conductivity ceramic materials exhibit excellent thermal conductivity and reinforcing effects in composites sintered at high temperatures (>1400°C), a systematic technical solution remains lacking for effectively introducing these high-performance ceramic fillers into glass matrices within the LTCC process window (below 900°C) to achieve low-temperature densification and synergistic reinforcement. This has resulted in a long-standing bottleneck in the development of LTCC materials in terms of thermal management and mechanical properties.
[0006] Therefore, developing a novel glass-ceramic composite system that significantly improves thermal conductivity and mechanical strength while maintaining the advantages of traditional LTCC materials, such as low-temperature sintering and low dielectric loss, has become an urgent need to drive the development of high-power electronic packaging technology. This invention, against this technological backdrop, aims to overcome the performance limitations of existing LTCC materials through innovative material design and process optimization. Summary of the Invention
[0007] The purpose of this invention is to provide a silicon carbide reinforced calcium aluminum borosilicate glass composite material and its preparation method, so as to meet the current industry demand for high thermal conductivity and high mechanical strength of LTCC materials.
[0008] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: a silicon carbide reinforced calcium aluminum borosilicate glass composite material, which is composed of a calcium aluminum borosilicate glass matrix and a silicon carbide (SiC) reinforcing phase, wherein the mass percentage of silicon carbide is 15% to 30% of the total mass of the composite material; the composition of the calcium aluminum borosilicate glass, in molar percentage, includes the following components: CaO 10% to 23%, Al2O3 10% to 22%, B2O3 7% to 10%, SiO2 50% to 65%, and a nucleating agent in total of 0.1% to 5%, wherein the nucleating agent is selected from one or more of ZnO, P2O5, and ZrO2.
[0009] The preparation method of the silicon carbide reinforced calcium aluminum borosilicate glass composite material includes the following steps:
[0010] Step 1: Prepare the raw materials CaCO3, Al2O3, B2O3, SiO2, ZnO, P2O5 and ZrO2 according to the formula of molar percentage and mix them evenly;
[0011] Step 2: Place the uniformly mixed powder into a crucible and heat it at 1500-1600℃ for 2-4 hours. Quench the molten glass with water to obtain glass slag. Ball mill the glass slag and dry it to obtain glass powder.
[0012] Step 3: Mix the glass powder and silicon carbide powder obtained in Step 2, wherein the silicon carbide powder accounts for 15-30% of the total mass of the mixed powder; ball mill the mixture and then dry it to obtain a uniform composite powder;
[0013] Step 4: The composite powder obtained in Step 3 is granulated and then dry-pressed to obtain strip-shaped green preforms.
[0014] Step 5: The green embryo obtained in Step 4 is kept at 850-900℃ for 0.5-1 hour to obtain a dense silicon carbide reinforced calcium aluminum borosilicate glass composite material.
[0015] In steps 2 and 3, the ball-to-material ratio in the ball mill is 5:1, and the ball milling medium is deionized water.
[0016] In step 4, the organic binder is acrylic acid, and the amount added is 8-10% of the mass of the composite powder.
[0017] In step 5, the green body is first debonded and then sintered and kept warm.
[0018] The advantages of this invention are: while maintaining the low-temperature sintering characteristics of the material (850-900°C), it achieves a synergistic breakthrough in thermal conductivity and mechanical strength (>220MPa), while maintaining the low dielectric properties (εr=4-5), and is fully compatible with traditional LTCC processes. It can be co-fired with materials such as gold, silver, and copper, providing an ideal packaging substrate material solution for high power density electronic devices. Attached Figure Description
[0019] Figure 1 The X-ray diffraction (XRD) patterns of samples 1 to 4 in Examples of the present invention are shown. Detailed Implementation
[0020] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments.
[0021] Example 1
[0022] In this embodiment of the invention, the molar percentages of each oxide in the calcium aluminum borosilicate glass powder are: CaO 18%, Al2O3 17%, SiO2 50%, B2O3 10%, ZrO2 2%, and P2O5 3%. After calculating the amount of each oxide according to this molar ratio, CaCO3, Al2O3, SiO2, B2O3, ZrO2, and P2O5 are weighed and mixed evenly. After drying, the evenly mixed raw materials are placed in a platinum crucible and kept at 1550℃ for 3 hours. The molten glass is then poured into deionized water for water quenching to obtain transparent glass slag. After ball milling (ball-to-material ratio of 5:1, milling media: zirconium balls and deionized water, milling time 4 hours), it is dried at 110℃ to obtain glass powder. 75% by mass of the above-mentioned glass powder and 25% by mass of purchased silicon carbide were weighed and mixed. After ball milling (ball-to-powder-to-water ratio of 5:1:4, milling media: zirconium balls and deionized water, milling time 12 hours), the mixture was dried at 110°C to obtain a composite powder. The composite powder was granulated (composite powder and 10wt% acrylic acid) and dry-pressed at 15 MPa to obtain strip-shaped green preforms. The strip-shaped green preforms were placed in a muffle furnace and debinded at 450°C for 2 hours, then sintered at 850°C and held for 1 hour. After naturally cooling to room temperature, the preforms were removed, and their properties are shown in Table 1.
[0023] Example 2
[0024] In this embodiment of the invention, the molar percentages of each oxide in the calcium aluminum borosilicate glass powder are: CaO 23%, Al2O3 12%, SiO2 50%, B2O3 10%, ZrO2 2%, and P2O5 3%. After calculating the amount of each oxide according to this molar ratio, CaCO3, Al2O3, SiO2, B2O3, ZrO2, and P2O5 are weighed and mixed evenly. After drying, the evenly mixed raw materials are placed in a platinum crucible and kept at 1550℃ for 3 hours. The molten glass is then poured into deionized water for water quenching to obtain transparent glass slag. After ball milling (ball-to-material ratio of 5:1, milling media: zirconium balls and deionized water, milling time 4 hours), it is dried at 110℃ to obtain glass powder. 75% by mass of the above-mentioned glass powder and 25% by mass of purchased silicon carbide were weighed and mixed. After ball milling (ball-to-powder-to-water ratio of 5:1:4, milling media: zirconium balls and deionized water, milling time 12 hours), the mixture was dried at 110°C to obtain a composite powder. The composite powder was granulated (composite powder and 10wt% acrylic acid) and dry-pressed at 15 MPa to obtain strip-shaped green preforms. The strip-shaped green preforms were placed in a muffle furnace and debinded at 450°C for 2 hours, then sintered at 850°C and held for 1 hour. After naturally cooling to room temperature, the preforms were removed, and their properties are shown in Table 1.
[0025] Example 3
[0026] In this embodiment of the invention, the molar percentages of each oxide in the calcium aluminum borosilicate glass powder are: CaO 13%, Al2O3 17%, SiO2 55%, B2O3 10%, ZnO 2%, and P2O5 3%. After calculating the amount of each oxide according to this molar ratio, CaCO3, Al2O3, SiO2, B2O3, ZnO, and P2O5 are weighed and mixed evenly. After drying, the evenly mixed raw materials are placed in a platinum crucible and kept at 1550℃ for 3 hours. The molten glass is then poured into deionized water for water quenching to obtain transparent glass slag. After ball milling (ball-to-material ratio of 5:1, milling media: zirconium balls and deionized water, milling time 4 hours), it is dried at 110℃ to obtain glass powder. 85% by mass of the above-mentioned glass powder and 15% by mass of purchased silicon carbide were weighed and mixed. After ball milling (ball-to-powder-to-water ratio of 5:1:4, milling media: zirconium balls and deionized water, milling time 12 hours), the mixture was dried at 110°C to obtain a composite powder. The composite powder was granulated (composite powder and 10wt% acrylic acid) and dry-pressed at 15 MPa to obtain strip-shaped green preforms. The strip-shaped green preforms were placed in a muffle furnace and debinded at 450°C for 2 hours, then heated to 850°C for sintering and held at that temperature for 1 hour. After naturally cooling to room temperature, the preforms were removed, and their properties are shown in Table 1.
[0027] Example 4
[0028] In this embodiment of the invention, the molar percentages of each oxide in the calcium aluminum borosilicate glass powder are: CaO 13%, Al2O3 12%, SiO2 60%, B2O3 10%, ZrO2 2%, and P2O5 3%. After calculating the amount of each oxide according to this molar ratio, CaCO3, Al2O3, SiO2, B2O3, ZrO2, and P2O5 are weighed and mixed evenly. After drying, the evenly mixed raw materials are placed in a platinum crucible and kept at 1550℃ for 3 hours. The molten glass is then poured into deionized water for water quenching to obtain transparent glass slag. After ball milling (ball-to-material ratio of 5:1, milling media: zirconium balls and deionized water, milling time 4 hours), it is dried at 110℃ to obtain glass powder. 75% by mass of the above-mentioned glass powder and 25% by mass of purchased silicon carbide were weighed and mixed. After ball milling (ball-to-powder-to-water ratio of 5:1:4, milling media: zirconium balls and deionized water, milling time 12 hours), the mixture was dried at 110°C to obtain a composite powder. The composite powder was granulated (composite powder and 10wt% acrylic acid) and dry-pressed at 15 MPa to obtain strip-shaped green preforms. The strip-shaped green preforms were placed in a muffle furnace and debinded at 450°C for 2 hours, then sintered at 850°C and held for 1 hour. After naturally cooling to room temperature, the preforms were removed, and their properties are shown in Table 1.
[0029] Example 5
[0030] In this embodiment of the invention, the molar percentages of each oxide in the calcium aluminum borosilicate glass powder are: CaO 10%, Al2O3 10%, SiO2 65%, B2O3 10%, ZrO2 2%, and P2O5 3%. After calculating the amount of each oxide according to this molar ratio, CaCO3, Al2O3, SiO2, B2O3, ZrO2, and P2O5 are weighed and mixed evenly. After drying, the evenly mixed raw materials are placed in a platinum crucible and kept at 1550℃ for 4 hours. The molten glass is then poured into deionized water for water quenching to obtain transparent glass slag. After ball milling (ball-to-material ratio of 5:1, milling media: zirconium balls and deionized water, milling time 4 hours), it is dried at 110℃ to obtain glass powder. 70% by mass of the above-mentioned glass powder and 30% by mass of purchased silicon carbide were weighed and mixed. After ball milling (ball-to-powder-to-water ratio of 5:1:4, ball milling media: zirconium balls and deionized water, ball milling time 12 hours), the mixture was dried at 110°C to obtain a composite powder. The composite powder was granulated (composite powder and 10wt% acrylic acid) and dry-pressed at 15 MPa to obtain strip-shaped green preforms. The strip-shaped green preforms were placed in a muffle furnace and debinded at 450°C for 2 hours, then heated to 880°C for sintering and held at that temperature for 1 hour. After naturally cooling to room temperature, the preforms were removed, and their properties are shown in Table 1.
[0031] Example 6
[0032] In this embodiment of the invention, the molar percentages of each oxide in the calcium aluminum borosilicate glass powder are: CaO 15%, Al2O3 15%, SiO2 60%, B2O3 8%, and ZnO 2%. After calculating the amount of each oxide according to this molar ratio, CaCO3, Al2O3, SiO2, B2O3, and ZnO are weighed and mixed evenly. After drying, the evenly mixed raw materials are placed in a platinum crucible and kept at 1550℃ for 4 hours. The molten glass is then poured into deionized water for water quenching to obtain transparent glass slag. After ball milling (ball-to-material ratio of 5:1, milling media being zirconium balls and deionized water, milling time 4 hours), it is dried at 110℃ to obtain glass powder. 80% by mass of the above-mentioned glass powder and 20% by mass of purchased silicon carbide were weighed and mixed. After ball milling (ball-to-powder-to-water ratio of 5:1:4, milling media: zirconium balls and deionized water, milling time 12 hours), the mixture was dried at 110°C to obtain a composite powder. The composite powder was granulated (composite powder and 10wt% acrylic acid) and dry-pressed at 15 MPa to obtain strip-shaped green preforms. The strip-shaped green preforms were placed in a muffle furnace at 450°C for 2 hours to remove the binder, then heated to 900°C for sintering and held at that temperature for 1 hour. After naturally cooling to room temperature, the preforms were removed, and their properties are shown in Table 1.
[0033] Table 1 Performance of sintered samples in each embodiment Width (mm) Height (mm) <![CDATA[Dielectric constant ε r > Thermal conductivity (W / m / K) Three-point bending strength (MPa) Example 1 5.31 2.09 4.22 5.2 251.31 Example 2 5.27 2.23 4.27 4.9 238.22 Example 3 5.33 2.12 4.15 4.2 240.37 Example 4 5.30 2.14 4.67 4.8 167.46 Example 5 5.32 2.17 4.53 5.3 153.51 Example 6 5.31 2.21 4.82 4.7 164.74
[0034] Figure 1 The X-ray diffraction (XRD) patterns of the glass-ceramic materials of the present invention after sintering at 850°C for 4 hours are shown, corresponding to Examples 1 to 4 respectively. Figure 1 It can be seen that the main crystalline phase in Examples 1-3 is CaAl2Si2O8, and the main crystalline phase in Example 4 is CaAl2SiO6. The CaAl2Si2O8 grains have a plate-like structure and are dense. In addition, the data analysis in Table 1 shows that the more CaAl2Si2O8 crystals there are, the higher the mechanical strength of the glass-ceramic material.
[0035] In summary, this invention provides a calcium aluminum borosilicate glass / silicon carbide composite material with excellent thermal conductivity and mechanical properties, and its preparation method. By optimizing the glass composition design and introducing a specific nucleating agent, combined with a reasonable silicon carbide addition ratio and a low-temperature sintering process, the thermal conductivity (4-6 W / m / K) and mechanical strength (>220 MPa) of the material are significantly improved while maintaining a low dielectric constant (4-5). The material preparation process is compatible with the traditional LTCC process and can achieve densification sintering at 850-900℃, making it suitable for packaging and substrate applications of high power density electronic devices.
[0036] Although the present invention has been described in detail above with reference to specific embodiments, the present invention is not limited to the disclosed embodiments. Those skilled in the art can easily adjust or make equivalent substitutions to the described material composition range and process parameters. All equivalent improvements or substitutions based on the core technology of the present invention should be included within the protection scope of the present invention.
Claims
1. A silicon carbide reinforced calcium aluminum borosilicate glass composite material, characterized in that, The composite material is composed of a calcium aluminum borosilicate glass matrix and a silicon carbide (SiC) reinforcing phase, wherein the mass percentage of silicon carbide is 15% to 30% of the total mass of the composite material; the composition of the calcium aluminum borosilicate glass, by molar percentage, includes the following components: CaO 10% to 23%, Al2O3 10% to 22%, B2O3 7% to 10%, SiO2 50% to 65%, and a nucleating agent in total of 0.1% to 5%, wherein the nucleating agent is selected from one or more of ZnO, P2O5, and ZrO2.
2. A method for preparing a silicon carbide reinforced calcium aluminum borosilicate glass composite material as described in claim 1, characterized in that, Includes the following steps: Step 1: Prepare the raw materials CaCO3, Al2O3, B2O3, SiO2, ZnO, P2O5 and ZrO2 according to the formula of molar percentage and mix them evenly; Step 2: Place the above-mentioned uniformly mixed powder into a crucible and keep it at 1500-1600℃ for 2-4 hours. Quench the molten glass liquid with water to obtain glass slag. After ball milling and drying the glass slag, obtain glass powder. Step 3: Mix the glass powder and silicon carbide powder obtained in Step 2, wherein the silicon carbide powder accounts for 15-30% of the total mass of the mixed powder; ball mill the mixture and then dry it to obtain a uniform composite powder; Step 4: The composite powder obtained in Step 3 is granulated and then dry-pressed to obtain strip-shaped green embryos; Step 5: The green embryo obtained in Step 4 is kept at 850-900℃ for 0.5-1 hour to obtain a dense silicon carbide reinforced calcium aluminum borosilicate glass composite material.
3. The method for preparing the silicon carbide reinforced calcium aluminum borosilicate glass composite material as described in claim 2, characterized in that: In steps 2 and 3, the ball-to-material ratio in the ball mill is 5:1, and the ball milling medium is deionized water.
4. The method for preparing the silicon carbide reinforced calcium aluminum borosilicate glass composite material as described in claim 2, characterized in that: In step 4, the organic binder is acrylic acid, and the amount added is 8-10% of the mass of the composite powder.
5. The method for preparing the silicon carbide reinforced calcium aluminum borosilicate glass composite material as described in claim 2, characterized in that: In step 5, the green body is first debonded and then sintered and kept warm.