Ceramics and Their Preparation Methods and Applications

Abstract

The present invention relates to ceramics and their preparation methods and applications. The chemical formula of the ceramics is Mg 2‑x Ga x Si 1‑x Al x O 4 , where x is the amount of ion substitution, 0 < x ≤ 0.05. When 0 < x ≤ 0.04, the particle size of the ceramics is (10 + 1000x) μm to (15 + 1000x) μm. When 0.04 < x ≤ 0.05, the particle size of the ceramics is 50 μm to 55 μm. By regulating the relationship between the amount of ion substitution x and the particle size in the ceramics, the present invention enables the ceramics to simultaneously have low dielectric loss and high thermal conductivity. Therefore, the circuit board prepared with the ceramics of the present invention can simultaneously have low dielectric loss and high thermal conductivity.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramics, and particularly to ceramics, a preparation method thereof, and an application thereof. Background Art

[0002] When existing ceramics have a high thermal conductivity, their dielectric loss is also high, which cannot meet the requirements for use in high-frequency circuit substrates; while when ceramics have a low dielectric loss, their thermal conductivity is also low, and it is necessary to increase the filling amount of ceramics to improve the thermal conductivity of the circuit substrate. However, an excessive filling amount of ceramics will cause the prepared circuit substrate to be unable to balance low dielectric loss and high thermal conductivity. Summary of the Invention

[0003] Based on this, in view of the above problems, it is necessary to provide a ceramic, a preparation method thereof, and an application thereof. The ceramic can simultaneously have low dielectric loss and high thermal conductivity, and the circuit substrate prepared therefrom can simultaneously have low dielectric loss and high thermal conductivity.

[0004] The present invention provides a ceramic, and the chemical formula of the ceramic is Mg 2-x Ga x Si 1-x Al x O 4 , where x is the ion substitution amount, 0 < x ≤ 0.05, and when 0 < x ≤ 0.04, the particle size of the ceramic is (10 + 1000x) μm to (15 + 1000x) μm, and when 0.04 < x ≤ 0.05, the particle size of the ceramic is 50 μm to 55 μm.

[0005] In one embodiment, the mass fraction of the MgSiO 3 heterophase in the ceramic is less than or equal to 1%.

[0006] In one embodiment, x > 0.02.

[0007] The present invention provides a method for preparing a ceramic, comprising the following steps:

[0008] Mixing MgO, Ga 2 O 3 , Al 2 O 3 , and SiO 2 as raw materials, and the molar ratio of Mg, Ga, Si, and Al in the raw materials is 2 - x : x : 1 - x : x, and 0 < x ≤ 0.05;

[0009] Performing a first ball milling on the raw materials to obtain the powder after the first ball milling;

[0010] Drying, grinding, sieving, and pre-firing the powder after the first ball milling to obtain the pre-fired powder;

[0011] The pre-fired powder is ground and sieved again, and then subjected to a second ball milling to obtain the powder after the second ball milling;

[0012] The powder after the second ball milling is dried, and then subjected to a first sieving, granulation, a second sieving, sintering, crushing and screening to obtain the ceramic.

[0013] In one embodiment, the method for preparing the ceramic satisfies at least one of the following conditions:

[0014] (1) The purity of the raw material is above 99.5% and the particle size is below 20 μm;

[0015] (2) The first ball milling uses ball milling beads with a particle size of 2 mm - 5 mm, and the solvent used includes at least one of deionized water or ethanol;

[0016] (3) The second ball milling uses ball milling beads with a particle size of 2 mm - 5 mm, and the solvent used includes at least one of deionized water or ethanol.

[0017] The present invention also provides a resin composition, comprising a resin and the ceramic.

[0018] In one embodiment, the resin composition satisfies at least one of the following conditions:

[0019] (1) The resin includes at least one of a fluororesin, an epoxy resin, a hydrocarbon resin or a polyphenylene ether resin;

[0020] (2) The mass of the ceramic is 30% - 70% of the total mass of the resin and the ceramic.

[0021] The present invention also provides a prepreg made of the resin composition.

[0022] The present invention also provides a circuit board made of the prepreg.

[0023] The present invention also provides a printed circuit board made of the circuit board.

[0024] By regulating the relationship between the ion substitution amount and the particle size in the ceramic, the present invention improves the grain size and density of the ceramic, thereby enhancing the uniformity of the ceramic microstructure, optimizing the grain boundary structure of the ceramic, simultaneously reducing the interface effect between ceramic particles, reducing scattering and polarization loss, so that the ceramic has both low dielectric loss and high thermal conductivity.

[0025] Therefore, when the ceramic of the present invention is applied to a circuit board, a more effective heat conduction path can be constructed, the thermal conductivity of the circuit board can be improved, so that the circuit board can have both low dielectric loss and high thermal conductivity. Detailed Embodiments

[0026] To facilitate the understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. On the contrary, these embodiments or examples are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the description of the present invention herein are only for the purpose of describing specific embodiments or examples and are not intended to limit the present invention. The optional range of the term "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of the related listed items. The any and all combinations include any two related listed items, any more related listed items, or the combination of all related listed items.

[0028] The chemical formula of the ceramic provided by the present invention is Mg 2-x Ga x Si 1-x Al x O 4 , where x is the amount of ionic substitution, 0 < x ≤ 0.05, and when 0 < x ≤ 0.04, the particle size of the ceramic is (10 + 1000x) μm to (15 + 1000x) μm, and when 0.04 < x ≤ 0.05, the particle size of the ceramic is 50 μm to 55 μm.

[0029] For example, when the ionic substitution amount x is 0.01, the particle size of the ceramic is 20 μm - 25 μm, more preferably 20 μm - 22 μm; when the ionic substitution amount x is 0.02, the particle size of the ceramic is 30 μm - 35 μm, more preferably 30 μm - 32 μm; when the ionic substitution amount x is 0.03, the particle size of the ceramic is 40 μm - 45 μm, more preferably 40 μm - 42 μm; when the ionic substitution amount x is 0.04, the particle size of the ceramic is 50 μm - 55 μm, more preferably 50 μm - 52 μm.

[0030] Optionally, in the ceramic of the present invention, MgSiO 3The mass fraction of the miscellaneous phase is less than or equal to 1%. Thereby, the formation of conductive channels with the miscellaneous phase as the medium can be reduced, the influence of impurities on the ceramic crystal structure can be decreased, which helps to form a regular and ordered crystal structure, improve the uniformity and densification of the ceramic, reduce the formation of defects, thereby increasing the thermal conductivity and decreasing the dielectric loss.

[0031] The thermal conductivity and dielectric loss of the ceramic of the present invention are related to the ion substitution amount x and the particle size. For example, as the ion substitution amount x increases, the dielectric loss of the ceramic decreases, and as the ion substitution amount x increases, the optimal particle size also increases. As the particle size increases, the thermal conductivity of the ceramic increases, but the dielectric loss also increases.

[0032] Optionally, it is preferred that the ion substitution amount x > 0.02. Within this range, the thermal conductivity and dielectric loss of the ceramic are relatively better, which is beneficial for preparing a circuit board with excellent thermal conductivity and dielectric loss. Further, when the ion substitution amount is within this range, the content of MgSiO can be further reduced, 3 thereby increasing the thermal conductivity of the ceramic and decreasing the dielectric loss of the ceramic.

[0033] In the ceramic of the present invention, different ion substitution amounts result in different grain sizes and densification degrees of the ceramic. By regulating the relationship between the ion substitution amount x and the particle size in the ceramic, the grain size and densification degree of the ceramic are improved, thereby enhancing the uniformity of the ceramic microstructure, optimizing the grain boundary structure of the ceramic, and at the same time reducing the interface effect between ceramic particles, reducing scattering and polarization losses, enabling the ceramic to have both low dielectric loss and high thermal conductivity. Specifically, the dielectric loss of the ceramic can be as low as 0.5×10 -4 , and the thermal conductivity can be as high as 13 W / m·K.

[0034] The preparation method of the ceramic of the present invention is not particularly limited. As a specific example, the preparation method of the ceramic includes the following steps:

[0035] Mix MgO, Ga 2 O 3 , Al 2 O 3 , SiO 2 as raw materials. The molar ratio of Mg, Ga, Si to Al in the raw materials is 2 - x : x : 1 - x : x, and 0 < x ≤ 0.05; wherein, the purity of the raw materials is preferably above 99.5%, more preferably above 99.99%, and the particle size of the raw materials is preferably below 20 μm. Thus, by selecting the purity and particle size of the raw materials, the generation of miscellaneous phases can be reduced, which is beneficial for increasing the thermal conductivity of the ceramic and decreasing the dielectric loss of the ceramic.

[0036] Then, the raw materials are ball-milled for the first time; wherein, when ball-milling, it is preferred to use ball-milling beads with a particle size of 2 mm - 5 mm, such as ZrO2 Ball milling beads, such as quartz ball milling beads, alumina ball milling beads, etc., and further preferably ZrO ball milling beads with a particle size of 2 mm - 3 mm 2 The ball milling speed is preferably 150 r / min - 250 r / min, and the ball milling time is 20 h - 36 h, which can make the raw materials mix more evenly and is beneficial to reducing the generation of impurity phases. In addition, the solvent during ball milling is not limited, and deionized water, ethanol, etc. are preferred.

[0037] Then, the powder after the first ball milling is dried, ground, sieved, and pre-fired. Among them, the drying temperature is preferably 70°C - 90°C, the time is preferably 20 h - 36 h, it is preferably sieved through a 120-mesh standard sieve after grinding, the pre-firing temperature is preferably 1100°C - 1200°C, and the time is preferably 3 h - 5 h.

[0038] Then, the powder after pre-firing is ground and sieved again, and the second ball milling is carried out; among them, ball milling beads with a particle size of 2 mm - 5 mm are preferably used during ball milling, such as ZrO 2 Ball milling beads, such as quartz ball milling beads, alumina ball milling beads, etc., and further preferably ZrO ball milling beads with a particle size of 2 mm - 3 mm 2 Ball milling beads can make the raw materials mix more evenly and is beneficial to reducing the generation of impurity phases. The solvent during ball milling is not limited, and deionized water, ethanol, etc. are preferred. In addition, it is preferably sieved through a 120-mesh standard sieve during sieving.

[0039] Then, the powder after the second ball milling is dried, and the first sieving, granulation, second sieving, sintering, crushing, and screening are carried out to obtain the ceramic. Among them, the drying temperature is preferably 70°C - 90°C, the time is preferably 20 h - 36 h, the first sieving is preferably through a 200-mesh standard sieve, granulation is preferably carried out in a PVA solution, the second sieving is preferably through an 80-mesh standard sieve, and the sintering temperature is preferably 1300°C - 1500°C, and the time is preferably 2 h - 4 h.

[0040] By using the preparation method provided by the present invention, ceramics with a relationship between the ion substitution amount x and the particle size can be prepared. In addition, the generation of impurity phases in the ceramics can also be reduced, so that the prepared ceramics can simultaneously have low dielectric loss and high thermal conductivity.

[0041] The present invention also provides a resin composition for preparing a circuit board, wherein the resin composition includes a resin and the ceramic described above.

[0042] The present invention does not particularly limit the selection of the resin in the resin composition, including but not limited to fluororesin, epoxy resin, hydrocarbon resin, polyphenylene ether resin, etc., and is further preferably a fluororesin. The fluororesin includes but not limited to at least one of polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), or ethylene-chlorotrifluoroethylene copolymer (ECTFE), and is more preferably polytetrafluoroethylene (PTFE) with low dielectric loss, so that the obtained circuit board has more excellent dielectric properties.

[0043] Optionally, the mass of the ceramic is 30%-70% of the total mass of the resin and the ceramic. Considering that the agglomeration problem of the ceramic will increase the dielectric loss, further preferably, the mass of the ceramic is 50%-70% of the total mass of the resin and the ceramic, and more preferably 55%-65%, which can make the circuit board have higher thermal conductivity and lower dielectric loss.

[0044] Optionally, the ceramic is treated with a silane coupling agent, which is beneficial to improving the dispersibility of the ceramic in the resin composition, and further beneficial to improving the dielectric loss performance and thermal conductivity of the circuit board. Among them, the silane coupling agent is preferably at least one of a fluorinated silane coupling agent or an amino silane coupling agent, and is further preferably at least one of KH550, Z6124, and F8261.

[0045] The present invention also provides a prepreg made of the above resin composition. The present invention does not limit the specific preparation method of preparing the prepreg from the resin composition. For specific examples, the resin composition is impregnated or coated on a reinforcing material and dried at 120°C - 180°C for 1.5 min - 6 min to obtain an impregnated prepreg or a coated prepreg. Preferably, the reinforcing material is selected from at least one of glass fiber cloth, aramid cloth, PET film, or carbon fiber cloth. Whether to peel the reinforcing material of the coated prepreg can be selected according to actual use requirements.

[0046] The present invention also provides a circuit board made of the above prepreg, including a dielectric layer and a conductive layer disposed on at least one surface of the dielectric layer. Among them, the dielectric layer is pressed by one or at least two laminated prepregs as described above, and the conductive layer is a metal foil layer, preferably a copper foil. Since the ceramic of the present invention can simultaneously have low dielectric loss and high thermal conductivity, the circuit board prepared with the ceramic of the present invention can simultaneously have low dielectric loss and high thermal conductivity.

[0047] The present invention also provides a printed circuit board made of the above circuit board. The printed circuit board is mainly made by processes such as developing, etching, drilling, desmearing, electroless copper plating, electroplating, and lamination of the circuit board.

[0048] Hereinafter, the ceramic, its preparation method and application will be further described by the following specific examples.

[0049] Example 1

[0050] Take MgO, Ga with a purity of 99.99% and a particle size of 5 μm 2 O 3 , Al 2 O 3 , SiO 2 as raw materials, and prepare them according to the molar ratio of Mg:Ga:Si:Al of 1.99:0.01:0.99:0.01 and put them into a ball mill tank equipped with ZrO 2 ball mill beads. The diameter of the ball mill beads is 3 mm. Add deionized water to the ball mill tank for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h.

[0051] Dry the powder after the first ball milling in a blast drying oven at 80 °C for 24 h, then grind it in a mortar, pass through a standard sieve with 120 meshes, and then pre-sinter it at 1200 °C for 4 h.

[0052] Grind the pre-sintered powder, pass through a standard sieve with 200 meshes, put it into the ball mill tank again, add ZrO with a diameter of 3 mm 2 ball mill beads and deionized water, and conduct the second ball milling. The ball milling speed is 300 r / min and the ball milling time is 12 h.

[0053] Dry the powder after the second ball milling at 80 °C for 24 h, pass through a standard sieve with 200 meshes, put it into a granulator for granulation (with a 1% PVA solution by mass), pass through a standard sieve with 80 meshes, and finally sinter it at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula of Mg 1.99 Ga 0.01 Si 0.99 Al 0.01 O 4 and a particle size of 20 μm - 25 μm are obtained, and the mass fraction of the MgSiO 3 heterophase in the ceramics is 0.5%.

[0054] Example 2

[0055] Take MgO, Ga with a purity of 99.99% and a particle size of 5 μm 2 O 3 , Al 2 O 3 , SiO 2 as raw materials, and prepare them according to the molar ratio of Mg:Ga:Si:Al of 1.98:0.02:0.98:0.02 and put them into a ball mill tank equipped with ZrO2 In a ball milling jar with ball milling beads, where the diameter of the ball milling beads is 3 mm, deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h.

[0056] The powder after the first ball milling is dried in a blast drying oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1200 °C for 4 h.

[0057] The pre-sintered powder is ground, passed through a 200-mesh standard sieve, and put back into the ball milling jar again. ZrO ball milling beads with a diameter of 3 mm and deionized water are added for the second ball milling. The ball milling speed is 300 r / min and the ball milling time is 12 h. 2 The powder after the second ball milling is dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula Mg

[0058] Ga 1.98 Ga 0.02 Si 0.98 Al 0.02 O 4 with a particle size of 30 μm - 35 μm are obtained, and the mass fraction of the MgSiO 3 heterogeneous phase in the ceramics is 0.4%.

[0059] Example 3

[0060] MgO with a purity of 99.99% and a particle size of 5 μm, Ga 2 O 3 Al 2 O 3 SiO 2 are used as raw materials. They are formulated according to the molar ratio of Mg:Ga:Si:Al of 1.97:0.03:0.97:0.03 and put into a ball milling jar with ZrO 2 ball milling beads. The diameter of the ball milling beads is 3 mm. Deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h.

[0061] The powder after the first ball milling is dried in a blast drying oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1200 °C for 4 h.

[0062] The pre-sintered powder is ground, passed through a 200-mesh standard sieve, and put back into the ball milling jar again. 2Ball milling beads and deionized water were used for the second ball milling at a speed of 300 r / min for 12 h.

[0063] The powder after the second ball milling was dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation with a 1% (by mass) PVA solution, passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula Mg 1.97 Ga 0.03 Si 0.97 Al 0.03 O 4 with a particle size of 40 μm - 45 μm were obtained, and the mass fraction of the MgSiO 3 heterophase in the ceramics was 0.3%.

[0064] Example 4

[0065] MgO with a purity of 99.99% and a particle size of 5 μm, Ga 2 O 3 Al 2 O 3 SiO 2 were used as raw materials. They were formulated according to the molar ratio of Mg:Ga:Si:Al of 1.96:0.04:0.96:0.04 and put into a ball milling tank equipped with ZrO 2 ball milling beads with a diameter of 3 mm. Deionized water was added to the ball milling tank for the first low-speed ball milling at a speed of 170 r / min for 24 h.

[0066] The powder after the first ball milling was dried in a blast drying oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1200 °C for 4 h.

[0067] The pre-sintered powder was ground, passed through a 200-mesh standard sieve, and put into the ball milling tank again. ZrO 2 ball milling beads with a diameter of 3 mm and deionized water were added for the second ball milling at a speed of 300 r / min for 12 h.

[0068] The powder after the second ball milling was dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation with a 1% (by mass) PVA solution, passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula Mg 1.96 Ga 0.04 Si 0.96 Al 0.04 O 4 with a particle size of 50 μm - 55 μm were obtained, and the MgSiO 3The mass fraction of the heterogeneous phase is 0.3%.

[0069] Example 5

[0070] Take MgO, Ga with a purity of 99.99% and a particle size of 5 μm 2 O 3 , Al 2 O 3 , SiO 2 as raw materials, and prepare and put them into a ball mill jar equipped with ZrO 2 ball mill beads with a diameter of 3 mm. Add deionized water to the ball mill jar for the first low-speed ball milling, with a ball milling speed of 170 r / min and a ball milling time of 24 h.

[0071] Dry the powder after the first ball milling in a blast drying oven at 80 °C for 24 h, then grind it in a mortar, pass through a 120-mesh standard sieve, and then pre-burn it at 1200 °C for 4 h.

[0072] Grind the pre-burned powder, pass through a 200-mesh standard sieve, put it back into the ball mill jar, add ZrO 2 ball mill beads with a diameter of 3 mm and deionized water, and conduct the second ball milling with a ball milling speed of 300 r / min and a ball milling time of 12 h.

[0073] Dry the powder after the second ball milling at 80 °C for 24 h, pass through a 200-mesh standard sieve, put it into a granulator for granulation (with a 1% PVA solution by mass), pass through an 80-mesh standard sieve, and finally sinter it at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula Mg 1.95 Ga 0.05 Si 0.95 Al 0.05 O 4 and a particle size of 50 μm - 55 μm are obtained, and the mass fraction of the MgSiO 3 heterogeneous phase in the ceramics is 0.1%.

[0074] Example 6

[0075] Take MgO, Ga with a purity of 99.99% and a particle size of 5 μm 2 O 3 , Al 2 O 3 , SiO 2 as raw materials, and prepare and put them into a ball mill jar equipped with ZrO 2In a ball milling jar with ball milling beads, where the diameter of the ball milling beads is 3 mm, deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h.

[0076] The powder after the first ball milling is dried in a blast drying oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1200 °C for 4 h.

[0077] The pre-sintered powder is ground, passed through a 200-mesh standard sieve, and put back into the ball milling jar again. ZrO ball milling beads with a diameter of 3 mm and deionized water are added for the second ball milling. The ball milling speed is 300 r / min and the ball milling time is 12 h. 2 The powder after the second ball milling is dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula MgGaSiAlO and a particle size of 25 μm - 30 μm are obtained, and the mass fraction of the MgSiO impurity phase in the ceramics is 0.4%.

[0078] The powder after the second ball milling is dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula MgGaSiAlO and a particle size of 25 μm - 30 μm are obtained, and the mass fraction of the MgSiO impurity phase in the ceramics is 0.4%. 1.985 Ga 0.015 Si 0.985 Al 0.015 O 4 Ceramics with a particle size of 25 μm - 30 μm are obtained, and the mass fraction of the MgSiO impurity phase in the ceramics is 0.4%. 3 The powder after the second ball milling is dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula MgGaSiAlO and a particle size of 25 μm - 30 μm are obtained, and the mass fraction of the MgSiO impurity phase in the ceramics is 0.4%.

[0079] Example 7

[0080] MgO, GaO, AlO, and SiO with a purity of 99.99% and a particle size of 5 μm are used as raw materials. They are formulated according to the molar ratio of Mg:Ga:Si:Al of 1.955:0.045:0.955:0.045 and put into a ball milling jar with ZrO ball milling beads. The diameter of the ball milling beads is 3 mm. Deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h. 2 O 3 Al 2 O 3 SiO 2 As raw materials, they are formulated according to the molar ratio of Mg:Ga:Si:Al of 1.955:0.045:0.955:0.045 and put into a ball milling jar with ZrO ball milling beads. The diameter of the ball milling beads is 3 mm. Deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h. 2 In a ball milling jar with ball milling beads, where the diameter of the ball milling beads is 3 mm, deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h.

[0081] The powder after the first ball milling is dried in a blast drying oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1200 °C for 4 h.

[0082] The pre-sintered powder is ground, passed through a 200-mesh standard sieve, and put back into the ball milling jar again. 2Ball milling beads and deionized water were used for the second ball milling at a speed of 300 r / min for 12 h.

[0083] The powder after the second ball milling was dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula Mg 1.955 Ga 0.045 Si 0.955 Al 0.045 O 4 with a particle size of 50 μm - 55 μm were obtained, and the mass fraction of the MgSiO 3 heterophase in the ceramics was 0.1%.

[0084] Example 8

[0085] MgO, Ga 2 O 3 Al 2 O 3 SiO 2 with a purity of 99% and a particle size of 21 μm were used as raw materials. They were formulated according to the molar ratio of Mg:Ga:Si:Al of 1.99:0.01:0.99:0.01 and put into a ball milling tank equipped with ZrO 2 ball milling beads. The diameter of the ball milling beads was 3 mm. Deionized water was added to the ball milling tank for the first low-speed ball milling at a speed of 170 r / min for 24 h.

[0086] The powder after the first ball milling was dried in a blast drying oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1100 °C for 5 h.

[0087] The pre-sintered powder was ground, passed through a 200-mesh standard sieve, and put into the ball milling tank again. ZrO 2 ball milling beads with a diameter of 3 mm and deionized water were added for the second ball milling at a speed of 300 r / min for 12 h.

[0088] The powder after the second ball milling was dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1400 °C for 3 h. After crushing and screening, ceramics with the chemical formula Mg 1.99 Ga 0.01 Si 0.99 Al 0.01 O 4 with a particle size of 20 μm - 25 μm were obtained, and the MgSiO 3The mass fraction of the impurity phase is 1.5%.

[0089] Comparative Example 1

[0090] Using MgO, Ga 2 O 3 、Al 2 O 3 、SiO 2 with a purity of 99.99% and a particle size of 5 μm as raw materials, prepared according to the molar ratio of Mg:Ga:Si:Al of 1.99:0.01:0.99:0.01 and placed in a ball mill jar containing ZrO 2 ball milling beads with a diameter of 3 mm. Deionized water was added to the ball mill jar for the first low-speed ball milling, with a ball milling speed of 170 r / min and a ball milling time of 24 h.

[0091] The powder after the first ball milling was dried in a blast drying oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-fired at 1200 °C for 4 h.

[0092] The pre-fired powder was ground, passed through a 200-mesh standard sieve, and again placed in the ball mill jar. ZrO 2 ball milling beads with a diameter of 3 mm and deionized water were added for the second ball milling, with a ball milling speed of 300 r / min and a ball milling time of 12 h.

[0093] The powder after the second ball milling was dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, placed in a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula Mg 1.99 Ga 0.01 Si 0.99 Al 0.01 O 4 with a particle size of 26 μm - 28 μm were obtained, and the mass fraction of the MgSiO 3 impurity phase in the ceramics was 0.5%.

[0094] Comparative Example 2

[0095] Using MgO, Ga 2 O 3 、Al 2 O 3 、SiO 2 with a purity of 99.99% and a particle size of 5 μm as raw materials, prepared according to the molar ratio of Mg:Ga:Si:Al of 1.99:0.01:0.99:0.01 and placed in a ball mill jar containing ZrO 2In a ball milling jar with ball milling beads, where the diameter of the ball milling beads is 3 mm, deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h.

[0096] The powder after the first ball milling is dried in a forced-air oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1200 °C for 4 h.

[0097] The pre-sintered powder is ground, passed through a 200-mesh standard sieve, and put back into the ball milling jar again. ZrO ball milling beads with a diameter of 3 mm and deionized water are added for the second ball milling. The ball milling speed is 300 r / min and the ball milling time is 12 h. 2 The powder after the second ball milling is dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula MgGaSiAlO and a particle size of 17 μm - 19 μm are obtained, and the mass fraction of the MgSiO heterophase in the ceramics is 0.4%.

[0098] For Comparative Example 3 1.99 Ga 0.01 Si 0.99 Al 0.01 O 4 Using MgO, GaO, AlO, and SiO with a purity of 99.99% and a particle size of 5 μm as raw materials, they are formulated according to the molar ratio of Mg:Ga:Si:Al of 1.955:0.045:0.955:0.045 and put into a ball milling jar with ZrO ball milling beads. The diameter of the ball milling beads is 3 mm. Deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h. 3 The powder after the first ball milling is dried in a forced-air oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1200 °C for 4 h.

[0099] Comparative Example 3

[0100] Using MgO, GaO, AlO, and SiO with a purity of 99.99% and a particle size of 5 μm as raw materials, they are formulated according to the molar ratio of Mg:Ga:Si:Al of 1.955:0.045:0.955:0.045 and put into a ball milling jar with ZrO ball milling beads. The diameter of the ball milling beads is 3 mm. Deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h. 2 O 3 Al 2 O 3 SiO 2 As raw materials, they are formulated according to the molar ratio of Mg:Ga:Si:Al of 1.955:0.045:0.955:0.045 and put into a ball milling jar with ZrO ball milling beads. The diameter of the ball milling beads is 3 mm. Deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h. 2 In a ball milling jar with ball milling beads, where the diameter of the ball milling beads is 3 mm, deionized water is added to the ball milling jar for the first low-speed ball milling. The ball milling speed is 170 r / min and the ball milling time is 24 h.

[0101] The powder after the first ball milling is dried in a forced-air oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1200 °C for 4 h.

[0102] The pre-sintered powder is ground, passed through a 200-mesh standard sieve, and put back into the ball milling jar again. ZrO ball milling beads with a diameter of 3 mm are added. 2Ball milling beads and deionized water were used for the second ball milling at a speed of 300 r / min for 12 h.

[0103] The powder after the second ball milling was dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula Mg 1.955 Ga 0.045 Si 0.955 Al 0.045 O 4 with a particle size of 56 μm - 58 μm were obtained, and the mass fraction of the MgSiO 3 heterophase in the ceramics was 0.4%.

[0104] Comparative Example 4

[0105] MgO with a purity of 99.99% and a particle size of 5 μm, Ga 2 O 3 Al 2 O 3 SiO 2 were used as raw materials. They were formulated according to the molar ratio of Mg:Ga:Si:Al of 1.94:0.06:0.94:0.06 and put into a ball milling tank equipped with ZrO 2 ball milling beads. The diameter of the ball milling beads was 3 mm. Deionized water was added to the ball milling tank for the first low-speed ball milling at a speed of 170 r / min for 24 h.

[0106] The powder after the first ball milling was dried in a blast drying oven at 80 °C for 24 h, then ground in a mortar, passed through a 120-mesh standard sieve, and then pre-sintered at 1200 °C for 4 h.

[0107] The pre-sintered powder was ground, passed through a 200-mesh standard sieve, and put into the ball milling tank again. ZrO with a diameter of 3 mm 2 ball milling beads and deionized water were added for the second ball milling at a speed of 300 r / min for 12 h.

[0108] The powder after the second ball milling was dried at 80 °C for 24 h, passed through a 200-mesh standard sieve, put into a granulator for granulation (with a 1% PVA solution by mass), passed through an 80-mesh standard sieve, and finally sintered at 1450 °C for 3 h. After crushing and screening, ceramics with the chemical formula Mg 1.94 Ga 0.06 Si 0.94 Al 0.06 O 4 with a particle size of 50 μm - 55 μm were obtained, and in the ceramics, MgSiO 3The mass fraction of the miscellaneous phase is 0.9%.

[0109] Application Example 1

[0110] Use glacial acetic acid to adjust the pH of the ethanol and water (mass ratio 1:9) mixture to 4. At 55 °C, add 60 parts by weight of the ceramic prepared in Example 1 and 1.8 parts by weight of KH550 coupling agent to 120 parts by weight of the mixture, disperse, and dry at 80 °C for 24 h to obtain the modified ceramic.

[0111] Mix the above-mentioned modified ceramic with 40 parts by weight of polytetrafluoroethylene in 80 parts by weight of deionized water solvent to obtain a resin composition.

[0112] Immerse the resin composition on a 106 fiberglass cloth, dry it in an oven at 80 °C for 10 min to obtain a prepreg. Stack 4 prepregs, cover one 1 oz copper foil on each of the upper and lower surfaces, place it in a vacuum hot press, and hot press at a pressure of 6 MPa and a temperature of 390 °C for 8 h to obtain a circuit board.

[0113] Application Example 2

[0114] The difference between Application Example 2 and Application Example 1 is only that the circuit board is prepared using the ceramic prepared in Example 2.

[0115] Application Example 3

[0116] The difference between Application Example 3 and Application Example 1 is only that the circuit board is prepared using the ceramic prepared in Example 3.

[0117] Application Example 4

[0118] The difference between Application Example 4 and Application Example 1 is only that the circuit board is prepared using the ceramic prepared in Example 4.

[0119] Application Example 5

[0120] The difference between Application Example 5 and Application Example 1 is only that the circuit board is prepared using the ceramic prepared in Example 5.

[0121] Application Example 6

[0122] The difference between Application Example 6 and Application Example 1 is only that the circuit board is prepared using the ceramic prepared in Example 6.

[0123] Application Example 7

[0124] The difference between Application Example 7 and Application Example 1 is only that the circuit board is prepared using the ceramic prepared in Example 7.

[0125] Application Example 8

[0126] The difference between Application Example 8 and Application Example 1 is only that the ceramic prepared in Example 8 is used to prepare the circuit board.

[0127] Application Example 9

[0128] The difference between Application Example 9 and Application Example 1 is only that the ceramic is not modified.

[0129] Application Example 10

[0130] The difference between Application Example 10 and Application Example 1 is only that 50 parts by weight of the modified ceramic in Application Example 1 and 50 parts by weight of polytetrafluoroethylene are used.

[0131] Application Example 11

[0132] The difference between Application Example 11 and Application Example 1 is only that 40 parts by weight of the modified ceramic in Application Example 1 and 60 parts by weight of polytetrafluoroethylene are used.

[0133] Application Example 12

[0134] The difference between Application Example 12 and Application Example 1 is only that 30 parts by weight of the modified ceramic in Application Example 1 and 70 parts by weight of polytetrafluoroethylene are used.

[0135] Application Comparative Example 1

[0136] The difference between Application Example 1 and Application Example 1 is only that the ceramic prepared in Comparative Example 1 is used to prepare the circuit board.

[0137] Application Comparative Example 2

[0138] The difference between Application Example 2 and Application Example 1 is only that the ceramic prepared in Comparative Example 2 is used to prepare the circuit board.

[0139] Application Comparative Example 3

[0140] The difference between Application Example 3 and Application Example 1 is only that the ceramic prepared in Comparative Example 3 is used to prepare the circuit board.

[0141] Application Comparative Example 4

[0142] The difference between Application Example 4 and Application Example 1 is only that the ceramic prepared in Comparative Example 4 is used to prepare the circuit board.

[0143] The performance tests were respectively carried out on the ceramics prepared in Examples 1 to 8 and Comparative Examples 1 to 4, and the test results are shown in Table 1. Among them, the specific test methods are as follows:

[0144] Dielectric loss: Measured using the metal cavity resonance method at a frequency of 10 GHz;

[0145] Thermal conductivity: Measured using ASTM-D5470;

[0146] Table 1

[0147]

[0148] Performance tests were respectively carried out on the circuit boards prepared in Application Examples 1 to 12 and Application Comparative Examples 1 to 4. The test results are shown in Table 2. Among them, the specific test methods are as follows:

[0149] Dielectric loss: Measured using IPC-TM-650 2.5.5.5;

[0150] Thermal conductivity: Measured using ASTM-D5470.

[0151] Table 2

[0152]

[0153] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0154] The above-described embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it cannot be understood as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A ceramic used for preparing a circuit substrate, characterized in that: The circuit substrate is prepared by using a resin composition containing the ceramic, and the chemical formula of the ceramic is Mg 2-x Ga x Si 1-x Al x O4, wherein x is the amount of ion substitution, 0<x≤0.05, and when 0<x≤0.04, the particle size of the ceramic is (10+1000x)μm to (15+1000x)μm, and when 0.04<x≤0.05, the particle size of the ceramic is 50μm to 55μm.

2. The ceramic according to claim 1, characterized in that The mass fraction of the MgSiO3 impurity phase in the ceramic is less than or equal to 1%.

3. The ceramic according to claim 1, characterized in that x＞0.02。 4. A method for preparing a ceramic according to any one of claims 1 to 3, characterized in that: The following steps are involved: MgO, Ga2O3, Al2O3 and SiO2 are mixed as raw materials, wherein the molar ratio of Mg, Ga, Si and Al in the raw materials is 2-x:x:1-x:x, and 0<x≤0.05; The raw material is subjected to a first ball milling to obtain a first ball milled powder; Drying, grinding, sieving and pre-calcining the powder after the first ball milling to obtain a pre-calcined powder; Grinding and sieving the pre-sintered powder again, and ball milling the powder for a second time to obtain a second ball milled powder; The powder after the second ball milling is dried, and subjected to the first screening, granulation, the second screening, sintering, crushing and screening to obtain the ceramic.

5. The method for preparing ceramics according to claim 4, characterized in that: The method for preparing the ceramic satisfies at least one of the following conditions: (1) The purity of the raw materials is above 99.5% and the particle size is below 20 μm; (2) The first ball milling uses ball milling beads with a particle size of 2 mm to 5 mm, and the solvent used includes at least one of deionized water or ethanol; (3) The second ball milling uses ball milling beads with a particle size of 2 mm-5 mm, and the solvent used includes at least one of deionized water or ethanol.

6. A resin composition, characterized in that The method comprises a resin and the ceramic according to any one of claims 1 to 3.

7. The resin composition according to claim 6, characterized in that The resin composition satisfies at least one of the following conditions: (1) The resin includes at least one of fluorine-containing resin, epoxy resin, hydrocarbon resin or polyphenylene ether resin; (2) The mass of the ceramic is 30%-70% of the total mass of the resin and the ceramic.

8. A prepreg made from the resin composition according to any one of claim 6 or claim 7.

9. A circuit substrate made of the prepreg as claimed in claim 8.

10. A printed circuit board made using the circuit substrate as claimed in claim 9.

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