A heat-conducting, wave-transparent, waterproof ceramic plastic material

Abstract

The application belongs to the technical field of epoxy cement and particularly relates to a heat-conducting, wave-transparent and waterproof ceramic plastic material. The heat-conducting, wave-transparent and waterproof ceramic plastic material comprises A component and B component. Raw material composition for preparing the A component comprises bisphenol A epoxy resin and filler c composed of boron nitride and nanometer aramid fiber. Raw material composition for preparing the B component comprises phenolic amine curing agent, accelerator and filler d composed of boron nitride. The heat-conducting, wave-transparent and waterproof ceramic plastic material provided by the application forms continuous heat-conducting channels in the resin matrix through the particle size compounding of bimodal boron nitride, greatly improves the heat-conducting performance of the material. The introduction of nanometer aramid fiber forms the reinforcing and toughening effect on the matrix at the microscale, compensating for the brittleness defects caused by the high filling of heat-conducting fillers. The phenolic amine curing agent cooperates with the bisphenol A epoxy resin to give the material the underwater curing ability, and the interface is firmly combined after curing, which can tolerate the humid environment for a long time.

Description

Technical Field

[0001] This invention belongs to the field of epoxy putty technology, and particularly relates to a thermally conductive, wave-transparent, and waterproof ceramic plastic material. Background Technology

[0002] Epoxy resin-based adhesives are widely used in building repair, electronic packaging, aerospace, and other fields due to their high bonding strength, resistance to corrosion, and low curing shrinkage. However, conventional epoxy mortars have significant shortcomings in practical applications: First, when applied in high-humidity or underwater environments, moisture interferes with interfacial bonding, leading to a significant decrease in bond strength or even debonding; second, their poor thermal conductivity makes it difficult to meet the heat dissipation requirements of electronic components; third, their low wave transmittance makes them unsuitable for applications such as radar radomes where signal penetration must be maintained; and fourth, the mechanical strength cannot adequately address the increased brittleness caused by high filler content.

[0003] To address these issues, existing technologies attempt to introduce high thermal conductivity fillers such as boron nitride and alumina into epoxy systems. However, fillers with a single particle size are unlikely to form continuous thermal conductivity pathways, resulting in limited improvement in thermal conductivity. Meanwhile, to improve underwater adhesion, silane coupling agents or hydrophobic modifiers are often added, but this usually comes at the cost of sacrificing curing speed or mechanical properties.

[0004] In summary, how to achieve a synergistic improvement in the thermal conductivity, wave transmission, and mechanical properties of materials while ensuring underwater workability has become a pressing technical challenge in this field. Summary of the Invention

[0005] The main objective of this invention is to provide a thermally conductive, wave-transparent, and waterproof ceramic-plastic material to overcome the shortcomings of the prior art.

[0006] To achieve the aforementioned objectives, the technical solution adopted by this invention includes: According to a first aspect of the present invention, a thermally conductive, wave-transparent, and waterproof ceramic-plastic material is provided, comprising component A and component B; The raw materials used to prepare component A include bisphenol A epoxy resin and filler c composed of boron nitride and nano-aramid fibers; The raw materials used to prepare component B include a phenolic amine curing agent, an accelerator, and a filler d composed of boron nitride; The boron nitride is composed of a combination of micron-sized large-particle boron nitride and micron-sized small-particle boron nitride in a certain proportion; The bisphenol A epoxy resin and the phenolic amine curing agent crosslink to form an organic reinforcing network, and the bimodal compounded boron nitride and nano-aramid fibers form a reinforcing skeleton through multi-scale coupling.

[0007] Furthermore, the mass ratio of large-particle-size boron nitride to small-particle-size boron nitride in the boron nitride is 10:1~5.

[0008] Furthermore, the boron nitride is bimodal compounded using two scales with particle sizes in the range of 20 to 1 micrometer.

[0009] Furthermore, the mass ratio of boron nitride to nano-aramid fiber is 10:1~5.

[0010] Furthermore, the accelerator is one or more of DMP-30, salicylic acid, 2-ethyl-4-methylimidazole, and fluoroboric acid.

[0011] Furthermore, the raw materials for preparing component A, by mass, include: 35-50 parts of bisphenol A epoxy resin and 45-50 parts of filler c.

[0012] Furthermore, the raw material composition for preparing component B, by mass parts, includes: 7-13 parts of phenolic amine curing agent, 5-10 parts of accelerator, and 45-50 parts of filler d.

[0013] Furthermore, the mass ratio of component A to component B is 1.5 to 2.5:1.

[0014] Furthermore, the bisphenol A epoxy resin is a bisphenol A epoxy resin whose molecular structure contains at least two epoxy groups.

[0015] Furthermore, the cured thermally conductive, wave-transparent, and waterproof ceramic-plastic material has a Shore hardness ≥85, tensile strength ≥33MPa, thermal conductivity ≥1.30W / (m·K), and wave transmittance ≥90%.

[0016] Compared with the prior art, the advantages of the present invention include: This invention provides a thermally conductive, wave-transparent, and waterproof ceramic-plastic material. Through the compounding of bimodal boron nitride particle sizes, a continuous thermally conductive pathway is formed within the resin matrix, significantly improving the material's thermal conductivity. The introduction of nano-aramid fibers reinforces and toughens the matrix at the microscale, compensating for the brittleness caused by highly filled thermally conductive fillers. The combination of phenolic amine curing agent and bisphenol A epoxy resin endows the material with underwater curing capability; after curing, the interface bonding is strong, allowing for long-term tolerance to humid environments. The synergistic effect of the components of this invention enables the material to maintain high thermal conductivity and high wave transmission while possessing good mechanical strength and construction adaptability, making it particularly suitable for radar radomes, marine engineering, and electronic heat dissipation. Attached Figure Description

[0017] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings: Figure 1 This is a schematic diagram of the microstructure of a thermally conductive, wave-transparent, and waterproof ceramic-plastic material in a typical embodiment of the present invention. Detailed Implementation

[0018] In view of the shortcomings of the prior art, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention. The following will further explain and illustrate this technical solution, its implementation process, and its principles.

[0019] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0020] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials used in the following embodiments are commercially available.

[0021] This invention provides a thermally conductive, wave-transparent, and waterproof ceramic-plastic material, comprising component A and component B; The raw materials used to prepare component A include bisphenol A epoxy resin and filler c composed of boron nitride and nano-aramid fibers; The raw materials used to prepare component B include a phenolic amine curing agent, an accelerator, and a filler d composed of boron nitride; The boron nitride is composed of a combination of micron-sized large-particle boron nitride and micron-sized small-particle boron nitride in a certain proportion; The bisphenol A epoxy resin and phenolic amine curing agent crosslink to form an organic reinforcing network, and the bimodal compounded boron nitride and nano-aramid fibers form a reinforcing skeleton through multi-scale coupling.

[0022] Preferably, the mass ratio of large-particle-size boron nitride to small-particle-size boron nitride in the boron nitride is 10:1 to 5. The boron nitride is bimodal compounded using two scales with particle sizes in the range of 20 to 1 micrometer.

[0023] Preferably, the mass ratio of boron nitride to nano-aramid fiber is 10:1~5.

[0024] Preferably, the accelerator is one or more of DMP-30, salicylic acid, 2-ethyl-4-methylimidazole, and fluoroboric acid.

[0025] Preferably, the raw materials for preparing component A, by weight, include: 35-50 parts of bisphenol A epoxy resin and 45-50 parts of filler c. The raw materials for preparing component B include: 7-13 parts of phenolic amine curing agent, 5-10 parts of accelerator, and 45-50 parts of filler d. The mass ratio of component A to component B is 1.5-2.5:1. The bisphenol A epoxy resin is a bisphenol A epoxy resin whose molecular structure contains at least two epoxy groups.

[0026] Preferably, the cured thermally conductive, wave-transparent, and waterproof ceramic-plastic material has a Shore hardness ≥85, tensile strength ≥33MPa, thermal conductivity ≥1.30W / (m·K), and wave transmittance ≥90%.

[0027] To better understand the technical solution of the present invention, a detailed discussion is provided below with reference to specific embodiments. The raw materials used in the following embodiments are all commercially available industrial products, wherein: the bisphenol A epoxy resin selected is a type with an epoxy equivalent of 180~190 g / eq; The phenolic amine curing agent is selected with an amine value of 300~400mgKOH / g; the boron nitride is hexagonal boron nitride, with large-diameter boron nitride particles of 15~20μm and small-diameter boron nitride particles of 1~5μm; the nano-aramid fiber has a diameter of 50~200nm and an aspect ratio ≥100. The accelerator DMP-30 is 2,4,6-tris(dimethylaminomethyl)phenol. Example 1

[0028] This embodiment provides a thermally conductive, wave-transparent, and waterproof ceramic-plastic material, comprising: Preparation of Component A: By mass, take 40 parts of bisphenol A epoxy resin, 45 parts of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2, and 5 parts of nano-aramid fibers. Premix the bimodal boron nitride and nano-aramid fibers evenly, add them to the bisphenol A epoxy resin, and stir in a kneader for 15 minutes until evenly mixed to obtain Component A putty.

[0029] Preparation of Component B: Take 10 parts by mass of phenolic amine curing agent, 6 parts by mass of accelerator DMP-30, and 44 parts by mass of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2. Slowly add the accelerator to the phenolic amine curing agent while stirring, then add the boron nitride and continue stirring until homogeneous to obtain component B.

[0030] Mix component A and component B at a mass ratio of 2:1 and stir until homogeneous to obtain a thermally conductive, wave-transparent, and waterproof ceramic-plastic material.

[0031] like Figure 1 As shown in the figure, the thermally conductive, wave-transparent, and waterproof ceramic-plastic material prepared in this embodiment forms a multi-scale composite structure. This can be seen from the figure: Large-diameter boron nitride particles of 15-20 μm and small-diameter boron nitride particles of 1-5 μm are distributed in a bimodal pattern in the resin matrix. The large-diameter boron nitride particles form a skeletal support between each other, while the small-diameter boron nitride particles fill the gaps between the large-diameter particles. The two particles are in contact with each other to form a continuous thermal conduction path, as shown by the dashed arrow.

[0032] Nano-aramid fibers (approximately 500 nm in diameter as shown in the figure) are dispersed in the resin matrix and interpenetrate with boron nitride particles to form an inorganic-organic coupled reinforcing framework.

[0033] After crosslinking, bisphenol A epoxy resin and phenolic amine curing agent form an organic enhancement network, which encapsulates the aforementioned inorganic fillers and organic fibers, forming a dense composite material system.

[0034] The 1 μm scale in the figure shows the stacking relationship between boron nitride particles, while the 500 nm scale shows the diameter of the nano-aramid fibers and their interfacial bonding with the surrounding components.

[0035] Through this microstructure design, large-particle boron nitride forms the main heat conduction channels, small-particle boron nitride increases the density of the heat conduction network, and nano-aramid fibers enhance and toughen the resin matrix. At the same time, the dense structure constructed by the three synergistically endows the material with good waterproof and wave-transmitting properties. Example 2

[0036] This embodiment provides a thermally conductive, wave-transparent, and waterproof ceramic-plastic material, comprising: Preparation of Component A: By mass, take 40 parts of bisphenol A epoxy resin, 45 parts of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:1, and 5 parts of nano-aramid fibers. Premix the bimodal boron nitride and nano-aramid fibers evenly, add them to the bisphenol A epoxy resin, and stir in a kneader for 15 minutes until evenly mixed to obtain Component A putty.

[0037] Preparation of Component B: Take 10 parts by mass of phenolic amine curing agent, 6 parts by mass of accelerator DMP-30, and 44 parts by mass of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:1. Slowly add the accelerator to the phenolic amine curing agent while stirring, then add the boron nitride and continue stirring until homogeneous to obtain component B.

[0038] Mix component A and component B at a mass ratio of 2:1 and stir until homogeneous to obtain a thermally conductive, wave-transparent, and waterproof ceramic-plastic material. Example 3

[0039] This embodiment provides a thermally conductive, wave-transparent, and waterproof ceramic-plastic material, comprising: Preparation of Component A: By mass, take 40 parts of bisphenol A epoxy resin, 45 parts of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:5, and 5 parts of nano-aramid fiber. Premix the bimodal boron nitride and nano-aramid fiber evenly, add them to the bisphenol A epoxy resin, and stir in a kneader for 15 minutes until evenly mixed to obtain Component A putty.

[0040] Preparation of Component B: Take 10 parts by mass of phenolic amine curing agent, 6 parts by mass of accelerator DMP-30, and 44 parts by mass of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:5. Slowly add the accelerator to the phenolic amine curing agent while stirring, then add the boron nitride and continue stirring until homogeneous to obtain component B.

[0041] Mix component A and component B at a mass ratio of 2:1 and stir until homogeneous to obtain a thermally conductive, wave-transparent, and waterproof ceramic-plastic material. Example 4

[0042] This embodiment provides a thermally conductive, wave-transparent, and waterproof ceramic-plastic material, comprising: Preparation of Component A: By mass, take 40 parts of bisphenol A epoxy resin, 45 parts of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2, and 4.5 parts of nano-aramid fiber. Premix the bimodal boron nitride and nano-aramid fiber evenly, add them to the bisphenol A epoxy resin, and stir in a kneader for 15 minutes until evenly mixed to obtain Component A putty.

[0043] Preparation of Component B: Take 10 parts by mass of phenolic amine curing agent, 6 parts by mass of accelerator DMP-30, and 44 parts by mass of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2. Slowly add the accelerator to the phenolic amine curing agent while stirring, then add the boron nitride and continue stirring until homogeneous to obtain component B.

[0044] Mix component A and component B at a mass ratio of 2:1 and stir until homogeneous to obtain a thermally conductive, wave-transparent, and waterproof ceramic-plastic material. Example 5 This embodiment provides a thermally conductive, wave-transparent, and waterproof ceramic-plastic material, comprising: Preparation of Component A: By mass, take 40 parts of bisphenol A epoxy resin, 45 parts of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2, and 22.5 parts of nano-aramid fibers. Premix the bimodal boron nitride and nano-aramid fibers evenly, add them to the bisphenol A epoxy resin, and stir in a kneader for 15 minutes until evenly mixed to obtain Component A putty.

[0045] Preparation of Component B: Take 10 parts by mass of phenolic amine curing agent, 6 parts by mass of accelerator DMP-30, and 44 parts by mass of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2. Slowly add the accelerator to the phenolic amine curing agent while stirring, then add the boron nitride and continue stirring until homogeneous to obtain component B.

[0046] Mix component A and component B at a mass ratio of 2:1 and stir until homogeneous to obtain a thermally conductive, wave-transparent, and waterproof ceramic-plastic material. Example 6

[0047] This embodiment provides a thermally conductive, wave-transparent, and waterproof ceramic-plastic material, comprising: Preparation of Component A: By mass, take 35 parts of bisphenol A epoxy resin, 45 parts of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2, and 5 parts of nano-aramid fiber. Premix the bimodal boron nitride and nano-aramid fiber evenly, add them to the bisphenol A epoxy resin, and stir in a kneader for 15 minutes until evenly mixed to obtain Component A putty.

[0048] Preparation of Component B: Take 7 parts by mass of phenolic amine curing agent, 5 parts by mass of accelerator DMP-30, and 50 parts by mass of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2. Slowly add the accelerator to the phenolic amine curing agent while stirring, then add the boron nitride and continue stirring until homogeneous to obtain component B.

[0049] Mix component A and component B at a mass ratio of 1.5:1 and stir until homogeneous to obtain a thermally conductive, wave-transparent, and waterproof ceramic-plastic material. Example 7

[0050] This embodiment provides a thermally conductive, wave-transparent, and waterproof ceramic-plastic material, comprising: Preparation of Component A: By mass, take 50 parts of bisphenol A epoxy resin, 40.5 parts of bimodal boron nitride (composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2), and 4.5 parts of nano-aramid fibers. Premix the bimodal boron nitride and nano-aramid fibers evenly, add them to the bisphenol A epoxy resin, and stir in a kneader for 15 minutes until evenly mixed to obtain Component A putty.

[0051] Preparation of Component B: By mass, take 13 parts of phenolic amine curing agent, 10 parts of accelerator DMP-30, and 45 parts of bimodal boron nitride composed of large-particle boron nitride and small-particle boron nitride in a mass ratio of 10:2. Slowly add the accelerator to the phenolic amine curing agent while stirring, then add the boron nitride and continue stirring until homogeneous to obtain Component B.

[0052] Mix component A and component B at a mass ratio of 2.5:1 and stir until homogeneous to obtain a thermally conductive, wave-transparent, and waterproof ceramic-plastic material.

[0053] Comparative Example 1 The difference between this comparative example and Example 1 is that boron nitride uses a single particle size, with its particle size distribution concentrated at D50=18μm, and no bimodal compounding is performed. The other raw material ratios and preparation methods are the same.

[0054] Comparative Example 2 The difference between this comparative example and Example 1 is that: no nano-aramid fibers are added, the amount of boron nitride in filler c is increased accordingly to keep the total number of fillers unchanged, and the proportions of other raw materials and preparation methods are the same.

[0055] Performance testing The materials obtained in the above examples and comparative examples were cured under standard conditions (23℃±2℃, relative humidity 50%±5%) for 24 hours, and then their performance was tested. Some samples were cured underwater (water depth 1m) and their underwater adhesion performance was tested. The test methods are as follows: (1) Initial curing time: determined according to GB / T 13477.5-2002; (2) Shore hardness: determined according to GB / T 2411-2008; (3) Tensile strength: determined according to GB / T 2567-2008; (4) Thermal conductivity: determined according to ASTM D5470; (5) Transmittance: Measured using the waveguide method at a frequency of 10 GHz; (6) Underwater bonding performance: The material is coated on the surface of cement mortar substrate and cured underwater for 24 hours. The tensile bond strength is tested according to GB / T12954-91.

[0056] The test results are shown in Table 1.

[0057] Table 1 Performance test results of the examples and comparative examples

[0058] As can be seen from the data in Table 1, the thermal conductivity of the example using bimodal boron nitride compound is significantly higher than that of Comparative Example 1 with a single particle size; the tensile strength and underwater bonding strength of the example with added nano-aramid fibers are both superior to those of Comparative Example 2 without addition. This indicates that the present invention achieves a synergistic improvement in thermal conductivity, mechanical properties, and underwater bonding properties through the multi-scale coupling design of bimodal boron nitride and nano-aramid fibers.

[0059] The above descriptions are merely some embodiments of the present invention. It should be noted that those skilled in the art can make other modifications and improvements without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A thermally conductive, wave-transparent, and waterproof ceramic-plastic material, characterized in that, Includes component A and component B; The raw materials used to prepare component A include bisphenol A epoxy resin and filler c composed of boron nitride and nano-aramid fibers; The raw materials used to prepare component B include a phenolic amine curing agent, an accelerator, and a filler d composed of boron nitride; The boron nitride is composed of a combination of micron-sized large-particle boron nitride and micron-sized small-particle boron nitride in a certain proportion; The bisphenol A epoxy resin and the phenolic amine curing agent crosslink to form an organic reinforcing network, and the bimodal compounded boron nitride and nano-aramid fibers form a reinforcing skeleton through multi-scale coupling.

2. The thermally conductive, wave-transparent, and waterproof ceramic-plastic material according to claim 1, characterized in that, The mass ratio of large-particle-size boron nitride to small-particle-size boron nitride in the boron nitride is 10:1~5.

3. The thermally conductive, wave-transparent, and waterproof ceramic-plastic material according to claim 1, characterized in that, The boron nitride is bimodal compounded using two scales with particle sizes in the range of 20 to 1 micrometer.

4. The thermally conductive, wave-transparent, and waterproof ceramic-plastic material according to claim 1, characterized in that, The mass ratio of boron nitride to nano-aramid fiber is 10:1~5.

5. The thermally conductive, wave-transparent, and waterproof ceramic-plastic material according to claim 1, characterized in that, The accelerator is one or more of DMP-30, salicylic acid, 2-ethyl-4-methylimidazole, and fluoroboric acid.

6. The thermally conductive, wave-transparent, and waterproof ceramic-plastic material according to claim 1, characterized in that, The raw materials for preparing component A, by mass, include: 35-50 parts of bisphenol A epoxy resin and 45-50 parts of filler c.

7. The thermally conductive, wave-transparent, and waterproof ceramic-plastic material according to claim 1, characterized in that, The raw materials used to prepare component B, by mass, include: 7-13 parts of phenolic amine curing agent, 5-10 parts of accelerator, and 45-50 parts of filler d.

8. The thermally conductive, wave-transparent, and waterproof ceramic-plastic material according to claim 1, characterized in that, The mass ratio of component A to component B is 1.5~2.5:

1.

9. The thermally conductive, wave-transparent, and waterproof ceramic-plastic material according to claim 1, characterized in that, The bisphenol A epoxy resin is a bisphenol A epoxy resin whose molecular structure contains at least two epoxy groups.

10. The thermally conductive, wave-transparent, and waterproof ceramic-plastic material according to claim 1, characterized in that, The cured thermally conductive, wave-transparent, and waterproof ceramic-plastic material has a Shore hardness ≥85, tensile strength ≥33MPa, thermal conductivity ≥1.30W / (m·K), and wave transmittance ≥90%.

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