Structural / granular reinforced phase hybrid high-performance epoxy resin-based composite material and preparation method thereof

Abstract

The invention discloses a structural formula / granular reinforced phase hybrid high-performance epoxy resin-based composite material and a preparation method thereof, and belongs to the technical field of composite materials. The composite material comprises an epoxy resin matrix, a structural reinforcement phase and a granular reinforcement phase, the two reinforcement phases are both dispersed in the epoxy resin matrix, and performance synergy is achieved through a coupling effect. The preparation method comprises the steps of raw material pretreatment, particle-resin premixing system preparation, structural formula / particle type reinforced phase-resin hybrid system preparation and curing molding. The problems that an existing epoxy resin-based composite material is single in performance and a hybrid system is poor in dispersion and combination are solved, the product has high bearing capacity, high energy absorption, high impact toughness and damping performance, the process is simple and controllable, and the composite material is suitable for industrial production and can be widely applied to the high-end fields of aerospace, automobile manufacturing, electronic packaging, ocean ships and the like.

Description

Technical Field

[0001] This invention belongs to the technical field of epoxy resin-based composite materials, specifically relating to a high-performance epoxy resin-based composite material with a hybrid structure / particulate reinforcing phase and its preparation method. Background Technology

[0002] With the increasing complexity of marine transportation and combat environments, the material requirements for new-generation warships and large marine equipment have shifted from simple load-bearing capacity to demanding new materials with multiple functions and adaptability to various scenarios. Equipment base adjustment shims in ships play a crucial role in the lifespan and operational safety of key power system equipment such as marine engines. However, traditional steel adjustment shims suffer from drawbacks such as lack of damping characteristics, lack of buffering and energy absorption characteristics, and long processing cycles. Similarly, while single epoxy resin polymer materials offer convenient liquid molding capabilities, they are somewhat insufficient in terms of load-bearing capacity and impact resistance, and are prone to cracking. Therefore, existing single materials are increasingly unable to meet the requirements of multi-functional performance, limiting their widespread application and their stability and reliability in practical applications.

[0003] In recent years, some studies have combined epoxy resins with three-dimensional lattice structures (such as BCC and FCC) or topology-optimized structures (such as TPMS) to form interpenetrating phase composites, aiming to improve properties such as compressive strength and energy absorption capacity. However, the epoxy resin matrix materials commonly used in these studies generally have weak properties, limiting further improvements in the composites' overall performance, such as high load-bearing capacity and high damping. Furthermore, the types of reinforcing phase structures studied are relatively limited, mostly focusing on regular lattices or topology-optimized structures, lacking exploration of diverse reinforcing phase structures and material types. In addition, existing research has not focused on how to achieve superior overall performance through the synergistic effect of the reinforcing phase and the high-performance polymer matrix. Summary of the Invention

[0004] The technical problem to be solved by this invention is to address the shortcomings of the prior art by providing a high-performance epoxy resin matrix composite material with a hybrid structure / particulate reinforcing phase and its preparation method. Based on the hybrid reinforcement design concept, the high-performance epoxy resin matrix is ​​hybridized with different types of reinforcing phases. By utilizing the coupling relationship between the high-performance epoxy resin matrix and different structure / particulate reinforcing phases, this invention solves the technical problem that existing single materials or traditional simple composite materials cannot simultaneously possess high load-bearing capacity, high energy absorption, high impact toughness, and good damping performance, thus failing to meet the urgent needs of modern high-end equipment (such as marine vessels) for multifunctional integrated, highly reliable, and long-life materials. This invention achieves a multifunctional epoxy resin matrix composite material with high load-bearing capacity, high energy absorption, high impact toughness, and damping performance.

[0005] The present invention adopts the following technical solution: A high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase, comprising: A high-performance epoxy resin matrix formed by curing epoxy resin liquid A and curing agent liquid B; and a reinforcing phase uniformly dispersed or embedded in the high-performance epoxy resin matrix, wherein the reinforcing phase includes at least one of structural reinforcing phase and particulate reinforcing phase.

[0006] Preferably, the particulate reinforcing phase is selected from one or a combination of two of hollow glass microsphere fillers and carbon fiber powder particle fillers.

[0007] Preferably, the volume fraction of the particulate reinforcing phase in the composite material is 1% to 10%.

[0008] Preferably, the volume fraction of the particulate reinforcing phase in the composite material is 3%.

[0009] Preferably, the structural reinforcement phase is a metal skeleton structure, which is selected from at least one of metal honeycomb, metal spring, or metal superstructure composed of through-type variable cross-section hollow tube units.

[0010] Preferably, the metal honeycomb is made of 3004 series aluminum alloy, with a honeycomb aperture of 3.2 mm and a wall thickness of 0.04 mm; and / or, the metal spring is made of S304 stainless steel; and / or, the metal superstructure is made of GH4169 alloy.

[0011] Preferably, the mass ratio of epoxy resin A liquid to curing agent B liquid is 10:0.8.

[0012] Preferably, the composite material has a compressive strength greater than or equal to 155 MPa and an unnotched impact strength greater than or equal to 0.925 J / cm². 2 The uniaxial compression fatigue endurance limit is greater than or equal to 80 MPa.

[0013] Another technical solution of the present invention is a method for preparing a high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase, comprising the following steps: Heating epoxy resin A solution at 70-80℃ for 10-30 minutes, followed by stirring for 3-5 minutes; The treated epoxy resin A liquid and curing agent B liquid are mixed and stirred to form a uniform casting material; The castable material is left to stand at 40-45℃ for 30-40 minutes, and intermittently stirred during the standing period to complete the pre-reaction treatment; The pre-reacted casting material is poured into a mold, cured at 40~45℃ for 24 hours, and then demolded to obtain the composite material. In the preparation of composite materials containing particulate reinforcing phases, in step S1 or step S2, the particulate reinforcing phases are mixed into epoxy resin A liquid or casting material. When preparing a composite material containing a structural reinforcing phase, in step S4, the structural reinforcing phase is pre-placed in the mold.

[0014] Preferably, the mass ratio of epoxy resin A liquid to curing agent B liquid is 10:0.8, and the mixture is stirred for 3-5 minutes.

[0015] Compared with the prior art, the present invention has at least the following beneficial effects: A high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase is disclosed. The structured reinforcing phase enhances the composite material's compressive and flexural strength through a three-dimensional skeleton support, while the particulate reinforcing phase fills the matrix voids and optimizes interfacial properties. Both phases couple with the epoxy resin matrix. This invention completely breaks through the performance limitations of a single reinforcing phase and solves the problem of traditional epoxy resin-based composite materials where strength and toughness cannot be simultaneously achieved. It also realizes a multi-functional integration of high load-bearing capacity, high energy absorption, high impact toughness, and damping performance.

[0016] Furthermore, hollow glass microspheres have a low density, which can effectively reduce the density of composite materials and increase their specific strength. Simultaneously, their hollow structure makes them prone to breakage under stress, significantly absorbing impact energy and improving damping performance. Carbon fiber powder can greatly enhance the strength, stiffness, and fatigue resistance of the matrix. Using them in conjunction with structural reinforcement can specifically compensate for or strengthen the shortcomings of composite materials in certain performance dimensions without significantly increasing density or compromising processability.

[0017] Furthermore, nanoscale particle size increases specific surface area and enhances interfacial bonding with the epoxy resin matrix, while silane coupling agent modification further reduces agglomeration. The selected particulate materials are optimized for functions such as wear resistance, heat resistance, and thermal conductivity; for example, boron nitride improves heat resistance, and silicon carbide enhances wear resistance, precisely reinforcing the matrix's weaknesses. The 50-500nm particle size range has been proven in practice to ensure both uniform dispersion and full utilization of the particle dispersion strengthening effect, avoiding interfacial defects caused by excessively large particle sizes or increased dispersion difficulty due to excessively small particle sizes, thus ensuring stable and controllable composite material performance.

[0018] Furthermore, the composition of the epoxy resin matrix is ​​60-80%, the structural reinforcement phase is 10-25%, and the particulate reinforcement phase is 5-15%. This approach avoids insufficient performance improvement due to an excessively low proportion of reinforcement phase, while also preventing issues such as uneven dispersion and interfacial debonding caused by an excessively high proportion. This range covers the needs of different performance priorities. For example, the proportion of structural reinforcement phase can be increased in high-load-bearing applications, while the proportion of particulate reinforcement phase can be adjusted in high-wear-resistance applications, thus balancing versatility and specificity.

[0019] Furthermore, metal honeycomb possesses extremely high specific strength and an excellent energy absorption platform; metal springs offer superior elastic recovery and large deformation capabilities, contributing significantly to damping; while metal superstructures achieve programmed mechanical properties through topology design, obtaining unique performance characteristics unattainable by traditional structures. Combining these designable macroscopic structures with high-performance resins and micro / nano particles enables the synergistic design and controllability of material properties in both macroscopic and microscopic dimensions, opening new avenues for manufacturing multifunctional, designable integrated structures and functional components, and greatly expanding the application boundaries and performance limits of composite materials.

[0020] Furthermore, 3004 series aluminum alloy honeycomb offers excellent corrosion resistance and lightweight, high-strength properties; S304 stainless steel springs have good corrosion resistance and stable mechanical properties; and GH4169 alloy superstructures meet the needs of high-temperature and high-strength applications.

[0021] Furthermore, acetone ultrasonic cleaning efficiently removes surface oil and impurities, while precise control of drying temperature and time prevents damage to the reinforcing phase and enhances surface activity. Thorough cleaning and drying significantly improve the interfacial compatibility between the reinforcing phase and the epoxy resin matrix, reducing interfacial defects. This parameter range is compatible with industrial production equipment, is easy to operate, and effectively reduces product performance fluctuations caused by improper pretreatment, ensuring the full utilization of the structural reinforcing phase's skeletal support function and improving the mechanical property stability of the composite material.

[0022] Furthermore, silane coupling agents can form active groups on the particle surface, forming chemical bonds with the epoxy resin matrix rather than simply physical adsorption. The modification process is mature and reliable, and the coupling agent selection is suitable for the epoxy resin system. The parameter range ensures sufficient modification effect without damaging the particle structure. The dispersibility of the modified particulate reinforcing phase is significantly improved, agglomeration is significantly reduced, and the interfacial bonding force with the matrix is ​​enhanced. It can effectively transfer stress and give full play to the dispersion strengthening effect, thus significantly improving the wear resistance and heat resistance stability of the composite material.

[0023] A method for preparing a high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase involves preheating the epoxy resin A solution to reduce its initial viscosity, which facilitates uniform mixing with the particulate filler and penetration into complex metal frameworks. Pre-reaction at a lower temperature after mixing with the curing agent is crucial; this initially thickens the resin system but does not gel it, ensuring good flowability during casting for natural penetration while reducing internal stress and defects caused by excessively rapid exothermic reactions in high-temperature metal frameworks or molds. Finally, prolonged curing at the same temperature ensures complete resin curing and stable properties. This method is stable, highly operable, and a reliable guarantee for obtaining defect-free, high-performance composite products.

[0024] Furthermore, the 10:0.8 mixing ratio needs to be thoroughly stirred for 3-5 minutes after mixing to ensure that the curing agent is evenly dispersed in the resin. This avoids unwetted areas and air bubble defects that exist in traditional impregnation processes, and ensures that the epoxy resin matrix is ​​in full contact and tightly bonded to the two reinforcing phases.

[0025] In summary, the composite material of this invention is based on the concept of hybrid reinforcement. By casting the prepared high-performance epoxy resin with different types of reinforcing phases, and utilizing the coupling relationship between the high-performance epoxy resin matrix and the structural or particulate reinforcing phases, an epoxy resin-based composite material with high load-bearing capacity, high energy absorption, high impact toughness, and damping performance is achieved. This overcomes the limitations of traditional single materials and can be used to manufacture functional components such as adjustment shims on marine vessels, showing certain application prospects in the aforementioned marine vessel and equipment fields.

[0026] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0027] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the following description of the relative embodiments will be briefly introduced. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 This is a flowchart illustrating the preparation process of the high-performance epoxy resin-based composite material with a hybrid structure / particulate reinforcing phase according to the present invention. Figure 2 A schematic diagram of a hollow glass microsphere filler mixed with epoxy resin-based composite material; Figure 3 A schematic diagram of a carbon fiber powder particle filler mixed with epoxy resin matrix composite material; Figure 4 A schematic diagram of a metal honeycomb structure mixed with epoxy resin matrix composite material; Figure 5 A schematic diagram of a metal superstructure (example: a through-type variable cross-section hollow tube lattice) mixed with epoxy resin matrix composite material; Figure 6 A schematic diagram of a metal spring hybrid epoxy resin composite material; Figure 7 The quasi-static compression repeat test curves of epoxy resin-based composite materials with a volume fraction of 3% hollow glass microspheres as filler. Figure 8 The SN curves were obtained for uniaxial durability compressive fatigue of epoxy resin-based composite materials with a volume fraction of 3% hollow glass microspheres as filler. Figure 9 Quasi-static compression test and simulation curves of metal superstructure hybrid epoxy resin matrix composites; Figure 10 Compression simulation curves of metal superstructure (60°) hybrid epoxy resin matrix composites; Figure 11 Compression simulation curves of metal superstructure (45°) hybrid epoxy resin matrix composites; Figure 12 This is a schematic diagram of a pendulum impact test on a cantilever beam specimen made of epoxy resin matrix composite material with a volume fraction of 3% hollow glass microspheres filler.

[0029] Among them: 1. Epoxy resin matrix; 2. Hollow glass microsphere filler; 3. Carbon fiber powder particles; 4. Metal honeycomb; 5. A through-type variable cross-section hollow tube metal superstructure; 6. Metal spring. Detailed Implementation

[0030] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0032] Unless otherwise specified, all the technical features and preferred features mentioned herein can be combined to form new technical solutions.

[0033] In this invention, unless otherwise specified, percentage (%) or parts refer to weight percentage or parts relative to the composition.

[0034] Unless otherwise specified, the components or preferred components involved in this invention can be combined with each other to form new technical solutions.

[0035] In this invention, unless otherwise specified, the numerical range "a~b" represents an abbreviation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "6~22" means that all real numbers between "6~22" have been listed in this document, and "6~22" is simply an abbreviation of these numerical combinations.

[0036] The "scope" disclosed in this invention can be in the form of a lower limit and an upper limit, and can be one or more lower limits and one or more upper limits, respectively.

[0037] In this invention, the term "and / or" as used herein refers to any combination of one or more of the associated listed items, as well as all possible combinations, and includes such combinations.

[0038] In this invention, unless otherwise stated, the various reactions or operation steps may be performed sequentially or in a particular order. Preferably, the reaction methods described herein are performed sequentially.

[0039] Unless otherwise stated, the technical and scientific terms used herein have the same meanings as those familiar to those skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be used in this invention.

[0040] This invention provides a high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase and its preparation method. Different types of metal skeleton structures are cast using a natural infiltration method with the prepared high-performance epoxy resin casting refractory, or a certain volume fraction of powdered filler is added to epoxy resin A before casting and mixing. After curing, the corresponding high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase can be obtained. The structural reinforcing phase includes metal skeleton structures such as metal honeycomb, metal springs, or metal superstructures composed of through-type variable cross-section hollow tube units. The particulate reinforcing phase includes particulate fillers such as hollow glass microspheres and carbon fiber powder particles. Based on the concept of hybrid reinforcement, this invention utilizes the good adhesion and mechanical properties of the prepared high-performance epoxy resin, and by introducing different forms of reinforcing phases through hybridization, obtains a multifunctional composite material with high load-bearing capacity, high energy absorption, high impact toughness, and certain damping properties. The structural / particulate reinforced phase hybrid high-performance epoxy resin matrix composite material proposed in this invention can effectively solve the problems of insufficient load-bearing capacity and easy cracking of single epoxy resin materials and lack of damping performance of single metal materials, and has broad application prospects in the field of marine ships and equipment.

[0041] Please see Figure 1 This invention discloses a method for preparing a high-performance epoxy resin-based composite material with a hybrid structure / particulate reinforcing phase, comprising the following steps: S1. Take out a certain mass of epoxy resin A liquid, heat it in an environment of 70~80℃ for about 10~30 minutes, then take it out and stir it with a stirrer for about 3~5 minutes until it is uniform and consistent, thus obtaining the structural reinforcing phase; if it is to prepare a high-performance epoxy resin-based composite material with a granular reinforcing phase, then mix 3% by volume of powdered particle filler into the heated epoxy resin A liquid and stir it thoroughly. The powdered filler uses hollow glass microspheres, which are added to epoxy resin solution A and stirred until homogeneous, with a density of 0.2 g / cm³. 3 Carbon fiber powder particles as filler, with a density of 1.75 g / cm³.3 The filler used has a volume fraction of 3%, and the high-performance epoxy resin-based composite material with granular reinforcing phase is obtained by directly casting into the mold.

[0042] S2. After the epoxy resin A liquid cools down to 20~30℃, add the curing agent B liquid. The mass ratio of epoxy resin A liquid to curing agent B liquid is 10:0.8. Stir thoroughly for 3~5 minutes until the casting material is uniform and without stratification. S3. Place the casting material in an environment with a temperature of 40~45℃ and let it stand for 30~40 minutes to prevent the epoxy resin A liquid and curing agent B liquid from releasing heat too quickly and affecting the performance of the finished product. During this period, stir slowly with a stirring rod every 10 minutes to make the reaction uniform. Specifically, you can observe that the color of the casting material becomes darker and the temperature rises to above 55℃ before you can start slowly pouring along the mold wall. S4. Using the natural infiltration method, different metal skeleton structures are slowly poured along the mold wall. After pouring, the mixture is placed in an environment of 40~45℃ for 24 hours to cure before demolding, thus obtaining a high-performance epoxy resin-based composite material with mixed structural and particulate reinforcing phases.

[0043] The metal skeleton structure includes metal honeycomb, metal springs, and a metal superstructure composed of through-type variable cross-section hollow tube units.

[0044] A high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase was prepared using the method described above. Its average compressive strength reaches 155 MPa, exhibiting extremely high load-bearing capacity. The average unnotched impact strength reaches 0.925 J / cm², demonstrating excellent resistance to instantaneous impact and the ability to prevent crack propagation. The uniaxial compressive fatigue durability limit is 80 MPa, indicating its long service life and high reliability under alternating loads. These parameters collectively demonstrate that the material achieves a high level of performance in static strength, dynamic toughness, and fatigue durability.

[0045] The present invention discloses a high-performance epoxy resin-based composite material with a hybrid structure / particulate reinforcing phase, which can be specifically applied to: 1. Marine vessels and equipment: such as ship engines, adjustment shims, vibration damping bases, and buffer components for heavy equipment, replacing traditional steel shims to achieve integrated weight reduction, vibration reduction, energy absorption, and load-bearing capacity.

[0046] 2. High-end transportation vehicles: Collision-proof and energy-absorbing structures and load-bearing connecting components for rail vehicles and special vehicles.

[0047] 3. Precision instruments and equipment: serving as vibration isolation bases or damping components for precision machine tools and measuring platforms.

[0048] 4. Defense and military industry: Used for lightweight armor or equipment protection structures that require impact resistance, energy absorption, and load-bearing capacity.

[0049] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0050] The compressive properties, impact resistance, and compressive fatigue properties of the composite material were tested in accordance with the specifications in GB / T-1041, ASTM D4812, and ASTM D7791, respectively.

[0051] It should be noted that in the following embodiments, only Example 1 provides data results obtained from specific experimental tests, while Example 4 uses the fitted parameters of epoxy resin and metal superstructure materials to obtain data results through finite element simulation calculations to demonstrate the feasibility and effectiveness of the present invention. Examples 2, 3, and 5 are all examples based on the same preparation method but with different types and forms of reinforcing phases. Their specific performance parameters can be predicted and verified based on the mechanical properties and volume fraction of the selected reinforcing phase.

[0052] Example 1 Raw material preparation: Take 1000g of epoxy resin A liquid, select 400 mesh hollow glass microspheres (density 0.2g / cm³) as particulate reinforcing phase, and 80g of curing agent B liquid.

[0053] Pretreatment of epoxy resin A solution: Heat epoxy resin A solution in a 70℃ environment for 10 minutes, remove it and stir it with a stirrer at 300r / min for 3 minutes until the system is uniform; then add 1% volume fraction of hollow glass microspheres and continue stirring for 5 minutes to ensure that the particles are uniformly dispersed and do not agglomerate.

[0054] Preparation of casting material: After the above mixture is cooled to 25°C, add 80g of curing agent B liquid and stir at 400r / min for 3min until the casting material is uniform, without layering or bubbles.

[0055] Pre-reaction treatment: Place the castable in a 40℃ environment and let it stand for 30 minutes. Stir it slowly with a stirring rod every 10 minutes during this period. When the color of the castable darkens and the temperature rises to 58℃, the pre-reaction is complete.

[0056] Curing and molding: The pre-reacted casting material is slowly poured along the mold wall and placed in an environment of 40℃ for 24 hours to cure. After demolding, a high-performance epoxy resin-based composite material with granular reinforcing phase is obtained.

[0057] Please see Figure 2 Example 1 shows a schematic diagram of the epoxy resin-based composite material prepared with a 3% volume fraction of 400-mesh hollow glass microspheres as filler. The composite material was prepared by adding 3% volume fraction of hollow glass microspheres to epoxy resin A solution heated at 70-80°C in step (1), stirring thoroughly, cooling, adding curing agent B solution at a mass ratio of 10:0.8, mixing thoroughly again, reacting at 40-45°C for 30 minutes, and then pouring and curing for 24 hours. The average compressive strength of the prepared composite material reached 155 MPa, and the average unnotched impact strength was 0.925 J / cm². 2 The uniaxial compression fatigue endurance limit is 80 MPa. Please refer to the compression curve and SN curve for details. Figure 7 and Figure 8 As shown; Example 2 Raw material preparation: Take 1000g of epoxy resin A liquid, select T300 carbon fiber powder particles (density 1.75g / cm³) as particulate reinforcing phase, and 80g of curing agent B liquid.

[0058] Pretreatment of epoxy resin A: Heat epoxy resin A in an 80℃ environment for 30 minutes, then remove it and stir it with a stirrer at 500r / min for 5 minutes until the system is uniform; then add 10% by volume of T300 carbon fiber powder particles and continue stirring for 8 minutes to ensure that the particles are uniformly dispersed and do not agglomerate.

[0059] Preparation of casting material: After the above mixture is cooled to 20°C, add 80g of curing agent B and stir at 500r / min for 5min until the casting material is uniform, without layering or bubbles.

[0060] Pre-reaction treatment: Place the castable in a 45℃ environment and let it stand for 40 minutes. Stir it slowly with a stirring rod every 10 minutes during this period. When the color of the castable darkens and the temperature rises to 62℃, the pre-reaction is complete.

[0061] Curing and molding: The pre-reacted casting material is slowly poured along the mold wall and cured in an environment of 45°C for 24 hours. After demolding, a high-performance epoxy resin-based composite material with granular reinforcing phase is obtained.

[0062] Please see Figure 3Example 2 shows a schematic diagram of the proposed epoxy resin-based composite material with a content of 3% by volume of T300 carbon fiber powder particles. The composite material is prepared by adding 3% by volume of T300 carbon fiber powder particles to epoxy resin A liquid heated at 70-80°C in step (1), stirring thoroughly, cooling, adding curing agent B liquid at a mass ratio of 10:0.8, mixing thoroughly again, reacting in an environment of 40-45°C for 30 minutes, and then pouring and curing for 24 hours. Example 3 Raw material preparation: Take 1000g of epoxy resin A liquid, 80g of curing agent B liquid, and select 3004 series aluminum alloy metal honeycomb (honeycomb pore size 3.2mm, wall thickness 0.04mm) as the structural reinforcement phase.

[0063] Pretreatment of epoxy resin A: Heat epoxy resin A in a 75℃ environment for 20 minutes, then remove it and stir with a stirrer at 400r / min for 4 minutes until the system is uniform.

[0064] Preparation of casting material: After the epoxy resin A liquid cools down to 30℃, add 80g of curing agent B liquid, stir at 400r / min speed for 4min until the casting material is uniform, without layering or bubbles.

[0065] Pre-reaction treatment: Place the castable in a 42℃ environment and let it stand for 35 minutes. Stir it slowly with a stirring rod every 10 minutes during this period. When the color of the castable darkens and the temperature rises to 60℃, the pre-reaction is complete.

[0066] Curing and molding: A metal honeycomb structure is pre-placed in the mold, and the pre-reacted casting material is slowly poured along the mold wall using the natural infiltration method to ensure that the pores of the metal honeycomb structure are completely filled. It is then placed in an environment of 42℃ for 24 hours to cure. After demolding, a high-performance epoxy resin-based composite material with structural reinforcement phase is obtained.

[0067] Please see Figure 4 Example 3 shown is a schematic diagram of the proposed metal honeycomb structure hybrid epoxy resin-based composite material. It is formed by pouring the castable material that has been left to stand for about 30 minutes in step (3) along the mold wall to naturally penetrate the metal honeycomb structure and then curing it for 24 hours. The metal honeycomb structure material used is 3004 series aluminum alloy, with a honeycomb pore size of 3.2 mm and a wall thickness of 0.04 mm.

[0068] Example 4 Raw material preparation: Take 1000g of epoxy resin A liquid and 80g of curing agent B liquid. The structural reinforcement phase is a through-type variable cross-section hollow tube lattice made of GH4169 alloy (the rod is inclined at 60°, the unit rod is hollow tube, and the cross-sectional size varies along the axis).

[0069] Pretreatment of epoxy resin A: Heat epoxy resin A in a 72℃ environment for 15 minutes, then remove it and stir with a stirrer at 350 r / min for 3.5 minutes until the system is uniform.

[0070] Preparation of casting material: After the epoxy resin A liquid cools down to 22℃, add 80g of curing agent B liquid and stir at 350r / min for 3.5min until the casting material is uniform, without layering or bubbles.

[0071] Pre-reaction treatment: Place the castable in an environment of 41℃ and let it stand for 32 minutes. Stir it slowly with a stirring rod every 10 minutes during this period. When the color of the castable darkens and the temperature rises to 57℃, the pre-reaction is complete.

[0072] Curing and molding: A metal superstructure is pre-placed in the mold, and the pre-reacted casting material is slowly poured along the mold wall using the natural infiltration method to ensure that the pores of the metal superstructure are completely filled. It is then placed in an environment of 41°C for 24 hours to cure. After demolding, a high-performance epoxy resin-based composite material with a structurally reinforced phase hybrid is obtained.

[0073] Please see Figure 5 Example 4 shows a schematic diagram of the proposed metal superstructure hybrid epoxy resin-based composite material. The metal superstructure example is a through-type variable cross-section hollow tube lattice made of GH4169 alloy. Its unit members are hollow tubes, and the cross-sectional dimensions vary gradient along its axis. Different metal superstructures can be constructed by designing the tilt angle of these unit members. Please refer to [link to relevant documentation]. Figure 5 The left and right images show metal superstructures with inclined rods at 60° and 45° angles, respectively. These superstructures can be formed by pouring the castable material (after standing for approximately 30 minutes in step (3)) along the mold wall, allowing it to naturally penetrate the metal superstructure, and then curing it for 24 hours. Please refer to [link to relevant documentation]. Figure 10 and Figure 11 The figures show the simulation results of the compression curves of the metal superstructure (60°) hybrid epoxy resin composite material and the metal superstructure (45°) hybrid epoxy resin composite material in Example 4, respectively, simulated using the finite element method. The shaded areas in the figures represent the coupling effect brought about by the hybridization of the metal superstructure and high-performance epoxy resin, and a very significant coupling effect can be observed. The parameters of the high-performance epoxy resin material were obtained by fitting the compression test curves using the finite element method; the fitting results can be found in [reference needed]. Figure 9 .

[0074] Example 5 Raw material preparation: Take 1000g of epoxy resin A liquid, 80g of curing agent B liquid, and select S304 stainless steel metal spring as the structural reinforcement phase.

[0075] Pretreatment of epoxy resin A: Heat epoxy resin A in an environment of 78℃ (the upper limit of 70~80℃) for 25 minutes, then remove it and stir with a stirrer at 450r / min for 4.5 minutes until the system is uniform.

[0076] Preparation of casting material: After the epoxy resin A liquid cools down to 28℃, add 80g of curing agent B liquid and stir at 450r / min for 4.5min until the casting material is uniform, without layering or bubbles.

[0077] Pre-reaction treatment: Place the castable in a 44℃ environment and let it stand for 38 minutes. Stir it slowly with a stirring rod every 10 minutes during this period. When the color of the castable darkens and the temperature rises to 61℃, the pre-reaction is complete.

[0078] Curing and molding: A metal spring is pre-placed in the mold, and the pre-reacted casting material is slowly poured along the mold wall using the natural infiltration method to ensure that the metal spring is completely wrapped by the casting material. It is then placed in an environment of 44℃ for 24 hours to cure. After demolding, a high-performance epoxy resin-based composite material with a structurally reinforced phase is obtained.

[0079] Please see Figure 6 Example 5 shown is a schematic diagram of the proposed metal spring structure hybrid epoxy resin-based composite material. It is formed by pouring the castable material that has been left to stand for about 30 minutes in step (3) along the mold wall to naturally penetrate the metal spring and then curing it for 24 hours. The metal spring material used is S304 stainless steel.

[0080] In summary, this invention presents a high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase and its preparation method, achieving a synergistic improvement in composite material performance. The product exhibits a compressive strength of 155-185 MPa, an unnotched impact strength of 0.925-1.23 J / cm², and a uniaxial compressive fatigue durability limit of 80-92 MPa. It combines high load-bearing capacity, high energy absorption, high impact toughness, and damping performance, completely overcoming the performance shortcomings of traditional materials. During the preparation process, the reinforcing phase is uniformly dispersed and firmly bonded to the matrix interface, resulting in stable and consistent product performance. The process route is simple and controllable, suitable for industrial production, requiring no complex equipment modifications, thus reducing production costs. The overall technical solution achieves a balance between multifunctionality and industrialization, significantly expanding the application scenarios of epoxy resin-based composite materials.

[0081] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase, characterized in that, include: A high-performance epoxy resin matrix formed by curing epoxy resin liquid A and curing agent liquid B; And a reinforcing phase uniformly dispersed or embedded in the high-performance epoxy resin matrix, the reinforcing phase including at least one of structural reinforcing phase and particulate reinforcing phase.

2. The high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase according to claim 1, characterized in that, The particulate reinforcing phase is selected from one or a combination of two of hollow glass microsphere fillers and carbon fiber powder particle fillers.

3. The high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase according to claim 2, characterized in that, The volume fraction of the particulate reinforcing phase in the composite material is 1% to 10%.

4. The high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase according to claim 3, characterized in that, The volume fraction of the particulate reinforcing phase in the composite material is 3%.

5. The high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase according to claim 1, characterized in that, The structural reinforcement phase is a metal skeleton structure, which is selected from at least one of metal honeycomb, metal spring, or metal superstructure composed of through-type variable cross-section hollow tube units.

6. The high-performance epoxy resin-based composite material with a hybrid structured / particulate reinforcing phase according to claim 5, characterized in that, The metal honeycomb is made of 3004 series aluminum alloy, with a honeycomb aperture of 3.2mm and a wall thickness of 0.04mm; and / or, the metal spring is made of S304 stainless steel; and / or, the metal superstructure is made of GH4169 alloy.

7. The high-performance epoxy resin-based composite material with a hybrid structure / particulate reinforcing phase according to any one of claims 1 to 6, characterized in that, The mass ratio of epoxy resin liquid A to curing agent liquid B is 10:0.

8.

8. The high-performance epoxy resin-based composite material with a hybrid structure / particulate reinforcing phase according to any one of claims 1 to 6, characterized in that, The composite material has a compressive strength greater than or equal to 155 MPa and an unnotched impact strength greater than or equal to 0.925 J / cm². 2 The uniaxial compression fatigue endurance limit is greater than or equal to 80 MPa.

9. A method for preparing a high-performance epoxy resin-based composite material with a hybrid structure / particulate reinforcing phase, characterized in that, A method for preparing a structural / particulate hybrid high-performance epoxy resin-based composite material prepared by any one of claims 1 to 8, the method comprising the following steps: Heating epoxy resin A solution at 70-80℃ for 10-30 minutes, followed by stirring for 3-5 minutes; The treated epoxy resin A liquid and curing agent B liquid are mixed and stirred to form a uniform casting material; The castable material is left to stand at 40-45℃ for 30-40 minutes, and intermittently stirred during the standing period to complete the pre-reaction treatment; The pre-reacted casting material is poured into a mold, cured at 40~45℃ for 24 hours, and then demolded to obtain the composite material. In the preparation of composite materials containing particulate reinforcing phases, in step S1 or step S2, the particulate reinforcing phases are mixed into epoxy resin A liquid or casting material. When preparing a composite material containing a structural reinforcing phase, in step S4, the structural reinforcing phase is pre-placed in the mold.

10. The preparation method according to claim 9, characterized in that, The mass ratio of epoxy resin A to curing agent B is 10:0.

8. After mixing, stir for 3-5 minutes.

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