Composite material based on thermosetting resin and porous metal matrix and preparation method thereof

Abstract

The invention relates to the field of porous metal materials, in particular to a composite material based on thermosetting resin and a porous metal matrix and a preparation method thereof.The composite material is composed of, by mass, 20-25 parts of porous aluminum particles, 50-55 parts of modified epoxy resin, 6-10 parts of phenolic resin, 4-6 parts of liquid crystal epoxy monomers, 4-6 parts of modified boron nitride and 10-14 parts of aramid fibers. Compared with the prior art, the preparation method has the advantages that through multi-stage interface strengthening and functional filler space sequential design, and by combining a gradient impregnation process and thermal stability regulation, breakthrough improvement of interface bonding strength and multifunctional synergism is realized; wide application prospects are realized in the fields of electronic device heat dissipation, military protection, new energy automobile battery pack brackets and the like.

Description

Technical Field

[0001] This invention relates to the field of porous metal materials, and more particularly to a composite material based on thermosetting resin and porous metal matrix and its preparation method. Background Technology

[0002] Thermosetting resin is a polymer matrix that forms an irreversible three-dimensional network through heating or the action of a curing agent. It is then used as a structural framework of porous aluminum metal and impregnated with thermosetting resin to form a lightweight composite system. This composite matrix can provide high rigidity, heat resistance and dimensional stability, and also has the thermal and electrical conductivity of metals.

[0003] In existing technologies, the lack of chemical bonding in traditional physical roughening of aluminum matrix leads to fragile interfacial bonding and easy delamination during high and low temperature cycling. At the same time, a single filler cannot meet the multifunctional requirements of thermal conductivity, reinforcement, etc., and its functional synergy is poor. In addition, the mismatch between resin viscosity and pore size under high porosity leads to pore filling defects, which in turn limits its application range.

[0004] Therefore, based on the relevant technologies mentioned above, there is an urgent need to develop a composite material based on thermosetting resin and porous metal matrix and its preparation method. Summary of the Invention

[0005] In view of this, the purpose of this invention is to propose a composite material based on thermosetting resin and porous metal matrix and its preparation method, so as to solve the problems of weak interfacial bonding, poor functional synergy and pore filling defects in the prior art.

[0006] To achieve the above objectives, the present invention provides a composite material based on thermosetting resin and porous metal matrix and a method for preparing the same.

[0007] A composite material based on thermosetting resin and porous metal matrix, comprising the following components in parts by weight: 20-25 parts porous aluminum matrix, 50-55 parts modified epoxy resin, 6-10 parts phenolic resin, 4-6 parts liquid crystal epoxy monomer, 4-6 parts modified boron nitride, and 10-14 parts aramid fiber.

[0008] Preferably, the porous aluminum particles are prepared using the following steps:

[0009] Step A1: Place the aluminum alloy plate in acetone solvent and ultrasonically clean it for 10-20 minutes. Then place it in a drying oven, heat it to 70-90℃, and dry it for 1-3 hours. Next, place it under a fiber pulse laser with a power of 250-350w to create holes with a diameter of 150-250μm. After the holes are created, add aluminum powder, pressurize it to 45-55MPa, and hold the pressure for 4-6 minutes to obtain the aluminum substrate.

[0010] Step A2: Add 0.8wt% titanium dihydrogen pore-forming agent to the aluminum matrix, ball mill and mix for 20-40 min, place in a tube furnace, introduce nitrogen gas, heat to 460-500℃, sinter for 20-40 min, reduce pressure to -0.1MPa, heat to 660-700℃, sinter for 40-50 min, after sintering is complete, cool to 20-30℃ to obtain porous aluminum;

[0011] Step A3: Add porous aluminum to a solution of 10wt% sulfuric acid and 2wt% nitric acid, heat to 30-50℃, soak for 8-12 minutes, rinse with deionized water, blow dry with nitrogen, remove, put into 0.1mol / L cesium nitrate and 1.5wt% phytic acid, soak for 10-20 minutes, heat to 20-30℃, rinse with deionized water, dry, and obtain etched porous aluminum;

[0012] Step A4: Under a nitrogen and argon atmosphere, the etched porous aluminum is placed in a plasma chamber at a power of 350-450W for 4-6 minutes. Then it is placed in an ethanol solution of 3wt% modified silane coupling agent, heated to 90-110℃, and refluxed for 1-3 hours. After cleaning with ethanol and drying, a porous aluminum substrate is obtained.

[0013] Step A5: Under a nitrogen atmosphere, add the porous aluminum matrix into a ball mill, add zirconia grinding balls and zinc stearate lubricant, grind at 250-350 rpm for 15-30 minutes, sieve, the particle size is 2-3 mm, dry to obtain porous aluminum particles.

[0014] By constructing a micron-scale honeycomb structure on the surface of an aluminum substrate through chemical etching, a mechanical anchoring effect is generated when the resin penetrates. At the same time, the silane coupling agent forms Si-O-Al covalent bonds at the interface. Combined with the energy dissipation capability of dynamic sulfur bonds, the interfacial shear strength is improved compared with traditional materials. Moreover, this mechanism works synergistically from micro-roughening to molecular bonding, completely solving the problem of delamination failure.

[0015] Preferably, the mass ratio of aluminum alloy plate to aluminum powder in step A1 is 1:0.24-0.26;

[0016] The mass ratio of aluminum matrix to pore-forming agent in step A2 is 1:0.006-0.01;

[0017] The volume ratio of the 10wt% sulfuric acid to the 2wt% nitric acid solution in step A3 is 5:1;

[0018] The volume ratio of 0.1 mol / L cesium nitrate to 1.5 wt% phytic acid in step A3 is 1:1;

[0019] The mass ratio of the etched porous aluminum to the ethanol solution of 3wt% modified silane coupling agent in step A4 is 1:7.8-8.2;

[0020] The mass ratio of the porous aluminum matrix, zirconium oxide and lubricant in step A5 is 1:2-3:0.005-0.01.

[0021] Preferably, the modified epoxy resin is prepared using the following steps:

[0022] Step B1: Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to toluene solvent, heat to 60-80℃, add bisphenol A type epoxy resin, heat to 110-120℃ to obtain a mixed solution.

[0023] Step B2: Under a nitrogen atmosphere, add the mixed solution to a beaker, add the catalyst triphenylphosphine, heat to 125-135℃, stir for 2-3 hours, cool to 70-90℃, and distill under reduced pressure to obtain the modified epoxy resin.

[0024] Preferably, the mass ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to bisphenol A epoxy resin in step B1 is 1:5.5-6.5;

[0025] The mass ratio of the mixed solution to the catalyst in step B2 is 1:0.0035-0.0045.

[0026] Preferably, the modified boron nitride preparation steps are as follows:

[0027] Step C1: Add carboxylated multi-walled carbon nanotubes to Tris-HCl buffer, sonicate for 20-40 min at 700-900 W, add dopamine hydrochloride, purge with nitrogen, heat to 20-30 °C, react for 10-14 h, centrifuge, wash, and dry to obtain modified multi-walled carbon nanotubes.

[0028] Step C2: Add boron nitride to a mixed solution of ethanol and deionized water, stir and disperse, add ammonia, sonicate for 1-3 hours, add trimethyl borate, heat to 70-90℃, react for 2-4 hours, centrifuge and purify to obtain hydroxylated boron nitride suspension;

[0029] Step C3: Add the modified multi-walled carbon nanotubes to deionized water, then add the hydroxylated boron nitride suspension, sonicate for 20-40 min, place in a high-pressure reactor, heat to 170-190℃, react for 5-7 h, cool, filter, and vacuum dry to obtain modified boron nitride.

[0030] Magnetic field induction causes the core-shell filler to align in a specific direction, while the boron nitride shell reduces phonon scattering and creates an efficient heat conduction path. Flow field shearing causes the aramid fibers to align axially, forming a reinforcing network. This spatial ordering decouples and optimizes thermal conductivity and reinforcement at the molecular scale, overcoming the bottleneck of functional incompatibilities in traditional composite materials.

[0031] Preferably, the mass ratio of carboxylated multi-walled carbon nanotubes to dopamine hydrochloride in step C1 is 1:1.8-2.2.

[0032] In step C2, the mass ratio of boron nitride, trimethyl borate, and ammonia is 1:0.05-0.07:0.2-0.3.

[0033] The volume ratio of ethanol to deionized water in step C2 is 1:1;

[0034] The mass ratio of the modified multi-walled carbon nanotubes to the hydroxylated boron nitride suspension in step C3 is 1:0.45-0.55.

[0035] Preferably, the preparation steps of the modified silane coupling agent are as follows:

[0036] Step D1: Under a nitrogen atmosphere, γ-chloropropyltriethoxysilane and thiourea are added to anhydrous ethanol solvent, stirred and dissolved, then tetrabutylammonium bromide catalyst is added, the temperature is raised to 70-80℃, and the reaction is stirred for 3-5 hours to obtain the reaction mixture.

[0037] Step D2: Add the reaction mixture to a beaker, heat to 30-50℃, add 30% sodium hydroxide solution, heat to 60-70℃, reflux and stir for 1-3 hours. Once the reaction is complete, wash with neutralized water, and distill under reduced pressure to obtain the modified silane coupling agent.

[0038] The mass ratio of γ-chloropropyltriethoxysilane, thiourea, and catalyst is 1:0.42-0.45:0.004-0.006;

[0039] The mass ratio of the reaction mixture to the sodium hydroxide solution is 1:0.14-0.16.

[0040] A method for preparing a composite material based on thermosetting resin and porous metal matrix, wherein the preparation steps are as follows:

[0041] Step S1: Add modified epoxy resin, phenolic resin and liquid crystal ring monomer to a reaction vessel, heat to 50-70℃, stir for 50-70 min, add modified boron nitride and aramid fiber, place in a 1.1-1.3T vertical magnetic field, stir for 20-40 min to obtain a mixture;

[0042] Step S2: Add porous aluminum particles to the mixture, heat to 50-70℃, reduce pressure to -0.095MPa, react for 20-40min, introduce nitrogen, pressurize to 5.8-6.2MPa, heat to 75-85℃, react for 40-50min to obtain the preform;

[0043] Step S3: Place the blank into a tube furnace, heat to 75-85℃, sinter for 50-70 min, heat to 110-130℃, sinter for 50-70 min, heat to 140-160℃, sinter for 100-140 min, heat to 170-190℃, sinter for 100-140 min, sintering complete, cool to 50-70℃, demold and cure to obtain the composite material;

[0044] The first-stage low-pressure impregnation preferentially fills millimeter-sized macropores, while the second-stage high-pressure infiltration overcomes the capillary resistance of micropores. Furthermore, through dynamic matching of resin viscosity and pore size, the pore filling rate is improved, performance fluctuations are reduced, and the performance of large-size components is homogenized. In addition, the phosphorus-based structure in 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide can decompose at high temperatures to generate PO· radicals, interrupting the combustion chain reaction in the gas phase. Simultaneously, the self-assembled nanodomains of the liquid crystal epoxy pin crack propagation, and the phosphorus-oxygen crosslinking network increases the glass transition temperature. Through the synergy of these three factors, the strength retention rate of the material in high-temperature environments is improved, resulting in a higher heat resistance limit compared to traditional materials.

[0045] Preferably, the mass ratio of modified epoxy resin, phenolic resin, liquid crystal ring monomer, modified boron nitride, and aramid fiber in step S1 is 1:0.3-0.34:0.18-0.22:0.18-0.22:0.45-0.50.

[0046] The mass ratio of porous aluminum particles to the mixed liquid in step S2 is 1:0.8-0.82.

[0047] The beneficial effects of this invention are:

[0048] This invention provides a composite material based on thermosetting resin and porous metal matrix and its preparation method. By using multi-level interface strengthening and spatial ordered design of functional fillers, combined with gradient impregnation process and thermal stability control, this invention achieves a breakthrough improvement in interface bonding strength and multifunctional synergy compared with the prior art. It has broad application prospects in fields such as heat dissipation of electronic devices, military protection and battery pack brackets for new energy vehicles. Attached Figure Description

[0049] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only for this invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0050] Figure 1 This is a SEM micrograph of the cross-section of the composite material in Example 13 of this invention. Detailed Implementation

[0051] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0052] Example 1: The preparation steps of the modified silane coupling agent are as follows:

[0053] S1: Under a nitrogen atmosphere, 100g of γ-chloropropyltriethoxysilane and 42g of thiourea were added to 200mL of anhydrous ethanol solvent, stirred and dissolved, and 0.4g of tetrabutylammonium bromide catalyst was added. The mixture was heated to 70℃ and stirred for 5h to obtain the reaction mixture.

[0054] S2: Add 100g of the reaction mixture to a beaker, heat to 30℃, add 14g of 30% sodium hydroxide solution, heat to 70℃, reflux and stir for 1h. After the reaction is complete, wash with neutralization water, and distill under reduced pressure to obtain the modified silane coupling agent.

[0055] Example 2: The preparation steps of the modified silane coupling agent are as follows:

[0056] S1: Under a nitrogen atmosphere, 100g of γ-chloropropyltriethoxysilane and 43g of thiourea were added to 200mL of anhydrous ethanol solvent, stirred and dissolved, 0.5g of tetrabutylammonium bromide catalyst was added, the temperature was raised to 75℃, and the reaction was stirred for 4h to obtain the reaction mixture.

[0057] S2: Add 100g of the reaction mixture to a beaker, heat to 40℃, add 15g of 30% sodium hydroxide solution, heat to 65℃, reflux and stir for 2h. After the reaction is complete, wash with neutralization water, and distill under reduced pressure to obtain the modified silane coupling agent.

[0058] Example 3: The preparation steps of the modified silane coupling agent are as follows:

[0059] S1: Under a nitrogen atmosphere, 100g of γ-chloropropyltriethoxysilane and 45g of thiourea were added to 200mL of anhydrous ethanol solvent, stirred and dissolved, 0.6g of tetrabutylammonium bromide catalyst was added, the temperature was raised to 80℃, and the reaction was stirred for 3h to obtain the reaction mixture.

[0060] S2: Add 100g of the reaction mixture to a beaker, heat to 50℃, add 16g of 30% sodium hydroxide solution, heat to 60℃, reflux and stir for 3h. After the reaction is complete, wash with neutralization water, and distill under reduced pressure to obtain the modified silane coupling agent.

[0061] Example 4: Preparation steps of porous aluminum particles:

[0062] S1: Place 100g of aluminum alloy plate in 200mL of acetone solvent, ultrasonically clean for 10min, place in a drying oven, heat to 90℃, dry for 1h, then place under a fiber pulse laser with a power of 350w to create holes with a diameter of 150-250μm. After the hole creation is completed, add aluminum powder, pressurize to 55MPa, and hold for 4min to obtain the aluminum matrix.

[0063] S2: Add 0.6g of pore-forming agent (0.8wt% titanium dihydrogen) to 100g of aluminum matrix, ball mill and mix for 20min, place in a tube furnace, introduce nitrogen gas, heat to 500℃, sinter for 20min, reduce pressure to -0.1MPa, heat to 700℃, sinter for 40min, after sintering is complete, cool to 30℃ to obtain porous aluminum;

[0064] S3: Add 100g of porous aluminum to 200mL of 10wt% sulfuric acid and 40mL of 2wt% nitric acid solution, heat to 30℃, soak for 12min, rinse with deionized water, blow dry with nitrogen, take out, put into 80mL of 0.1mol / L cesium nitrate and 80mL of 1.5wt% phytic acid, soak for 10min, heat to 30℃, rinse with deionized water, dry, and obtain etched porous aluminum;

[0065] S4: Under a nitrogen and argon atmosphere, 100g of etched porous aluminum was placed in a plasma chamber at a power of 350W for 6 minutes, then placed in 780g of an ethanol solution of 3wt% modified silane coupling agent, heated to 110℃, refluxed for 1 hour, cleaned with ethanol, and dried to obtain a porous aluminum substrate.

[0066] S5: Under a nitrogen atmosphere, add 100g of porous aluminum matrix to a ball mill, add 200g of zirconia grinding balls and 0.5g of zinc stearate lubricant, grind at 250rpm for 30min, sieve, the particle size is 2-3mm, dry, and porous aluminum particles are obtained.

[0067] Example 5: Preparation steps of porous aluminum particles:

[0068] S1: Place 100g of aluminum alloy plate in 200mL of acetone solvent, ultrasonically clean for 15min, place in a drying oven, heat to 80℃, dry for 2h, then place under a fiber pulse laser with a power of 300w to create holes with a diameter of 150-250μm. After the hole creation is completed, add aluminum powder, pressurize to 50MPa, and hold for 5min to obtain an aluminum matrix.

[0069] S2: Add 0.8g of pore-forming agent (0.8wt% titanium dihydrogen) to 100g of aluminum matrix, ball mill and mix for 30min, place in a tube furnace, introduce nitrogen gas, heat to 480℃, sinter for 30min, reduce pressure to -0.1MPa, heat to 680℃, sinter for 45min, after sintering is complete, cool to 25℃ to obtain porous aluminum;

[0070] S3: Add 100g of porous aluminum to 200mL of 10wt% sulfuric acid and 40mL of 2wt% nitric acid solution, heat to 40℃, soak for 10min, rinse with deionized water, blow dry with nitrogen, take out, put into 80mL of 0.1mol / L cesium nitrate and 80mL of 1.5wt% phytic acid, soak for 15min, heat to 25℃, rinse with deionized water, dry, and obtain etched porous aluminum;

[0071] S4: Under a nitrogen and argon atmosphere, 100g of etched porous aluminum is placed in a plasma chamber at a power of 400W for 5 minutes, then placed in an ethanol solution of 3wt% modified silane coupling agent, heated to 100℃, refluxed for 2 hours, cleaned with ethanol, and dried to obtain a porous aluminum matrix.

[0072] S5: Under a nitrogen atmosphere, add 100g of porous aluminum matrix into a ball mill, add 250g of zirconia grinding balls and 0.8g of zinc stearate lubricant, grind at 300rpm for 20min, sieve, the particle size is 2-3mm, dry, and porous aluminum particles are obtained.

[0073] Example 6: Preparation steps of porous aluminum matrix:

[0074] S1: Place 100g of aluminum alloy plate in 200mL of acetone solvent, ultrasonically clean for 20min, place in a drying oven, heat to 70℃, dry for 3h, then place under a fiber pulse laser with a power of 250w to create holes with a diameter of 150-250μm. After the hole creation is completed, add aluminum powder, pressurize to 55MPa, and hold for 4min to obtain the aluminum matrix.

[0075] S2: Add 1g of pore-forming agent (0.8wt% titanium dihydrogen) to 100g of aluminum matrix, ball mill and mix for 40min, place in a tube furnace, introduce nitrogen gas, heat to 460℃, sinter for 40min, reduce pressure to -0.1MPa, heat to 660℃, sinter for 50min, after sintering is complete, cool to 20℃ to obtain porous aluminum;

[0076] S3: Add 100g of porous aluminum to 200mL of 10wt% sulfuric acid and 40mL of 2wt% nitric acid solution, heat to 50℃, soak for 8min, rinse with deionized water, blow dry with nitrogen, take out, put into 80mL of 0.1mol / L cesium nitrate and 80mL of 1.5wt% phytic acid, soak for 20min, heat to 20℃, rinse with deionized water, dry, and obtain etched porous aluminum;

[0077] S4: Under a nitrogen and argon atmosphere, 100g of etched porous aluminum was placed in a plasma chamber at a power of 450W for 4 minutes, and then placed in an ethanol solution of 820g of 3wt% modified silane coupling agent. The temperature was raised to 90℃ and refluxed for 3 hours. The mixture was then cleaned with ethanol and dried to obtain a porous aluminum substrate.

[0078] S5: Under a nitrogen atmosphere, add 100g of porous aluminum matrix into a ball mill, add 300g of zirconia grinding balls and 1g of zinc stearate lubricant, grind at 350rpm for 15min, sieve, the particle size is 2-3mm, dry, and porous aluminum particles are obtained.

[0079] Example 7: The preparation steps of the modified epoxy resin are as follows:

[0080] S1: Add 100g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 1000mL of toluene solvent, heat to 60℃, add 550g of bisphenol A type epoxy resin, heat to 120℃, and obtain a mixed solution.

[0081] S2: Under a nitrogen atmosphere, 100g of the mixed solution was added to a beaker, along with 0.35g of the catalyst triphenylphosphine. The mixture was heated to 125°C and stirred for 3 hours. The temperature was then lowered to 70°C, and the mixture was distilled under reduced pressure to obtain the modified epoxy resin.

[0082] Example 8: The preparation steps of the modified epoxy resin are as follows:

[0083] S1: Add 100g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 1000mL of toluene solvent, heat to 70℃, add 600g of bisphenol A type epoxy resin, heat to 115℃, and obtain a mixed solution.

[0084] S2: Under a nitrogen atmosphere, 100g of the mixed solution was added to a beaker, along with 0.4g of the catalyst triphenylphosphine. The mixture was heated to 130℃ and stirred for 2.5h. The mixture was then cooled to 80℃ and distilled under reduced pressure to obtain the modified epoxy resin.

[0085] Example 9: The preparation steps of the modified epoxy resin are as follows:

[0086] S1: Add 100g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 1000mL of toluene solvent, heat to 80℃, add 650g of bisphenol A type epoxy resin, heat to 110℃, and obtain a mixed solution.

[0087] S2: Under a nitrogen atmosphere, 100g of the mixed solution was added to a beaker, along with 0.45g of the catalyst triphenylphosphine. The mixture was heated to 135℃ and stirred for 3 hours. The temperature was then lowered to 70℃ and distilled under reduced pressure to obtain the modified epoxy resin.

[0088] Example 10: The preparation steps of modified boron nitride are as follows:

[0089] S1: Add 100g of carboxylated multi-walled carbon nanotubes to 200mL of Tris-HCl buffer, sonicate for 20min at 900W, add 180g of dopamine hydrochloride, purge with nitrogen, heat to 20℃, react for 14h, centrifuge, wash, and dry to obtain modified multi-walled carbon nanotubes.

[0090] S2: Add 100g of boron nitride to a mixed solution of 100mL of ethanol and 100mL of deionized water, stir to disperse, add 20g of ammonia, sonicate for 1h, add 5g of trimethyl borate, heat to 70℃, react for 4h, centrifuge to purify, and obtain hydroxylated boron nitride suspension.

[0091] S3: Add 100g of modified multi-walled carbon nanotubes to 200mL of deionized water, then add 45g of hydroxylated boron nitride suspension, sonicate for 20min, place in a high-pressure reactor, heat to 190℃, react for 5h, cool, filter, and vacuum dry to obtain modified boron nitride.

[0092] Example 11: The preparation steps of modified boron nitride are as follows:

[0093] S1: Add 100g of carboxylated multi-walled carbon nanotubes to 200mL of Tris-HCl buffer, sonicate for 30min at 800W, add 200g of dopamine hydrochloride, purge with nitrogen, heat to 25℃, react for 12h, centrifuge, wash, and dry to obtain modified multi-walled carbon nanotubes.

[0094] S2: Add 100g of boron nitride to a mixed solution of 100mL of ethanol and 100mL of deionized water, stir to disperse, add 25g of ammonia, sonicate for 2h, add 6g of trimethyl borate, heat to 80℃, react for 3h, centrifuge to purify, and obtain hydroxylated boron nitride suspension.

[0095] S3: Add 100g of modified multi-walled carbon nanotubes to 200mL of deionized water, then add 50g of hydroxylated boron nitride suspension, sonicate for 30min, place in a high-pressure reactor, heat to 180℃, react for 6h, cool, filter, and vacuum dry to obtain modified boron nitride.

[0096] Example 12: The preparation steps of modified boron nitride are as follows:

[0097] S1: Add 100g of carboxylated multi-walled carbon nanotubes to 200mL of Tris-HCl buffer, sonicate for 40min at 700W, add 220g of dopamine hydrochloride, purge with nitrogen, heat to 30℃, react for 10h, centrifuge, wash, and dry to obtain modified multi-walled carbon nanotubes.

[0098] S2: Add 100g of boron nitride to a mixed solution of 100mL of ethanol and 100mL of deionized water, stir to disperse, add 30g of ammonia, sonicate for 3h, add 7g of trimethyl borate, heat to 70℃, react for 2h, centrifuge to purify, and obtain hydroxylated boron nitride suspension.

[0099] S3: Add 100g of modified multi-walled carbon nanotubes to 200mL of deionized water, then add 55g of hydroxylated boron nitride suspension, sonicate for 40min, place in a high-pressure reactor, heat to 170℃, react for 7h, cool, filter, and vacuum dry to obtain modified boron nitride.

[0100] Example 13: A method for preparing a composite material based on thermosetting resin and porous metal matrix.

[0101] S1: Add 100g of modified epoxy resin, 30g of phenolic resin and 18g of liquid crystal ring monomer to a reaction vessel, heat to 50℃, stir for 70min, add 18g of modified boron nitride and 45g of aramid fiber, place in a 1.1T vertical magnetic field, stir for 40min to obtain a mixture.

[0102] S2: Add 100g of porous aluminum particles to 80g of mixed solution, heat to 50℃, reduce pressure to -0.095MPa, react for 40min, introduce nitrogen gas, pressurize to 5.8MPa, heat to 85℃, react for 40min to obtain the preform;

[0103] S3: Place 100g of preform into a tube furnace, heat to 75℃, sinter for 70min, heat to 110℃, sinter for 70min, heat to 140℃, sinter for 140min, heat to 170℃, sinter for 140min, sintering is complete, cool to 50℃, demold and cure to obtain composite material.

[0104] Example 14: A method for preparing a composite material based on thermosetting resin and porous metal matrix.

[0105] S1: Add 100g of modified epoxy resin, 32g of phenolic resin and liquid crystal ring monomer to a reaction vessel, heat to 60℃, stir for 60min, add 20g of modified boron nitride and 20g of aramid fiber, place in a 1.2T vertical magnetic field, stir for 30min to obtain a mixture.

[0106] S2: Add 100g of porous aluminum particles to 81g of mixed solution, heat to 60℃, reduce pressure to -0.095MPa, react for 30min, introduce nitrogen gas, pressurize to 6MPa, heat to 80℃, react for 45min to obtain the preform;

[0107] S3: Place 100g of preform into a tube furnace, heat to 80℃, sinter for 60min, heat to 120℃, sinter for 60min, heat to 150℃, sinter for 120min, heat to 180℃, sinter for 120min, sintering is complete, cool to 60℃, demold and cure to obtain composite material.

[0108] Example 15: A method for preparing a composite material based on thermosetting resin and porous metal matrix.

[0109] S1: Add 100g of modified epoxy resin, 34g of phenolic resin and 22g of liquid crystal ring monomer to a reaction vessel, heat to 70℃, stir for 50min, add 22g of modified boron nitride and 50g of aramid fiber, place in a 1.3T vertical magnetic field, stir for 20min to obtain a mixture.

[0110] S2: Add 100g of porous aluminum particles to 82g of mixed solution, heat to 70℃, reduce pressure to -0.095MPa, react for 20min, introduce nitrogen gas, pressurize to 6.2MPa, heat to 75℃, react for 50min to obtain the preform;

[0111] S3: Place 100g of the preform into a tube furnace, heat to 85℃, sinter for 50min, heat to 130℃, sinter for 50min, heat to 160℃, sinter for 100min, heat to 190℃, sinter for 100min, sintering is complete, cool to 70℃, demold and cure to obtain the composite material.

[0112] Comparative Example 1:

[0113] Compared with Example 13, this comparative example did not perform magnetic field and flow field orientation processes in the preparation of a composite material based on thermosetting resin and porous metal matrix. All other steps and parameters were the same, and will not be repeated in this comparative example. The final composite material was obtained.

[0114] Comparative Example 2:

[0115] Compared with Example 13, this comparative example only replaces "modified silane coupling agent" with "KH-550 silane coupling agent". All other steps and parameters are the same, and will not be repeated in this comparative example. The final composite material is obtained.

[0116] Comparative Example 3:

[0117] This comparative example differs from Example 13 only in that "modified epoxy resin" is replaced with "epoxy resin". All other steps and parameters are the same, and will not be repeated here. The final composite material is obtained.

[0118] Comparative Example 4:

[0119] Compared with Example 13, this comparative example only uses -0.095MPa vacuum impregnation in the preparation process of a composite material based on thermosetting resin and porous metal matrix. All other steps and parameters are the same, and will not be repeated in this comparative example. The final composite material is obtained.

[0120] Performance testing:

[0121] Interfacial shear strength:

[0122] A universal testing machine was used in accordance with the ASTM-D3165 testing standard.

[0123] 1. Take the porous aluminum substrates of Examples 13-15 and Comparative Examples 1-4 respectively, cut them into 25mm×10mm×2mm pieces, coat the surface with the mixture of Examples 13-15 and Comparative Examples 1-4, the coating area is 10mm×10mm, and the rest is covered with high temperature resistant tape to prevent spillage.

[0124] 2. Two aluminum test pieces with resin-filled areas are stacked together, heated to 80℃ and cured for 1 hour, then heated to 150℃ and cured for 2 hours to obtain the sample;

[0125] 3. Room temperature test: Temperature 23±2℃, humidity 50%RH, constant temperature for 24 hours;

[0126] Extreme test: The sample was placed in a high and low temperature chamber and cooled to -40℃ for 2 hours. The sample was then placed in an oven and heated to 150℃ for 1 hour. Load-displacement data were recorded.

[0127] 4. Strength calculation: τ: Shear strength / MPa; P max : Maximum load / N; A: Overlap area / mm 2 ;

[0128] Table 1

[0129] project τ (at room temperature) (MPa) τ(extreme)(MPa) Example 13 39.2 37.8 Example 14 38.5 37.0 Example 15 40.1 38.5 Comparative Example 1 22.3 18.7 Comparative Example 2 24.8 20.1 Comparative Example 3 26.5 21.9 Comparative Example 4 19.7 16.3

[0130] Flame retardancy test:

[0131] Referring to the UL94-2018 test standard, an FTT cone calorimeter was used to take the composite materials of Examples 13-15 and Comparative Examples 1-4, cut them into 125mm×13mm×3mm pieces, burn them vertically for 10s, and record the self-extinguishing time and molten droplets.

[0132] Conductivity test:

[0133] According to the ASTM D257 test standard, a 6517B high resistance meter was used to cut the composite materials of Examples 13-15 and Comparative Examples 1-4 into Φ100mm×2mm circular pieces. The samples were placed in an environment with a temperature of 23±1℃ and a humidity of RH<40% for 48h. The test voltage was 500V, and the stable current value I was recorded.

[0134] Volume resistivity: ρ v : Volume resistivity (Ω·cm); V: Test voltage (V); I: Leakage current (A); A: Main electrode area (cm2); t: Sample thickness (cm).

[0135] Thermal conductivity test:

[0136] Referring to the ISO 22007-2 testing standard, a laser thermal conductivity meter was used. The composite materials of Examples 13-15 and Comparative Examples 1-4 were cut into Φ12.7mm×2mm circular pieces, polished on both sides, ultrasonically cleaned, vacuum dried, and uniformly sprayed with graphite layers on both sides. The samples were placed on an alumina support, and thermocouples were placed close to the edge to monitor the actual temperature. The laser energy was 300V, the sampling frequency was 200kHz, and the pulse width was 0.8ms.

[0137] Thermal conductivity calculation formula: λ=α×ρ×C p λ: thermal conductivity (W / (m·K)), α: thermal diffusivity (mm²) 2 / s), ρ: density (g / cm³) 3 Cp: ​​Specific heat capacity (J / (g·K)).

[0138] Table 2

[0139]

[0140]

[0141] Interlaminar shear strength:

[0142] According to the ISO 14130:1988 testing standard, a universal testing machine was used to cut the composite materials of Examples 13-15 and Comparative Examples 1-4 into 20mm×10mm×2mm pieces. The specimens were placed on the two supporting blades and the indenter was applied vertically to the center of the specimen.

[0143] Formula for calculating interlaminar shear strength: Pmax: Maximum load, b: Specimen width, h: Thickness.

[0144] Impact resistance test:

[0145] Following the ASTM D7136 testing standard, an impact testing machine was used. Composite materials from Examples 13-15 and Comparative Examples 1-4 were cut into 100mm × 100mm × 4mm flat plates. The samples were horizontally fixed on a ring clamp, and the punch was dropped freely from a set height to impact the center, with an impact energy of 30J.

[0146] Impact resistance per unit volume: t: thickness, A: damaged area.

[0147] Compressive strength test:

[0148] Referring to the ASTM D695 testing standard, a universal testing machine was used to cut the composite materials of Examples 13-15 and Comparative Examples 1-4 into cylinders with a diameter of Φ10.0±0.1mm and 15.0±0.2mm, respectively. The loading rate was 1.0mm / min, and the samples were continuously compressed until they broke. The compressive strength was recorded.

[0149] Table 3

[0150]

[0151]

[0152] Salt spray aging test:

[0153] Following the ASTM B117 testing standard, a CCT1100 circulating salt spray chamber was used. Composite materials from Examples 13-15 and Comparative Examples 1-4 were cut into 100mm × 100mm × 4mm pieces, heated to 35℃, and sprayed with a 5±1wt% NaCl solution for 500 hours. After rinsing with deionized water and drying, the materials were placed in the testing chamber to test the interlaminar strength and strength retention rate.

[0154]

[0155] High temperature aging test

[0156] Referring to the IEC 60068-2-2 test standard, using a UF260 high-temperature oven, the composite materials of Examples 13-15 and Comparative Examples 1-4 were cut into 25mm×10mm×2mm pieces, heated to 80℃, dried for 24 hours, and then placed in a high-temperature oven, heated to 200±1.0℃, and maintained for 1000 hours.

[0157] Strength retention rate:

[0158] Table 4

[0159]

[0160]

[0161] Data Analysis:

[0162] As can be seen from Tables 1-4, the composite material based on thermosetting resin and porous metal matrix prepared by the present invention has ultra-high interfacial bonding strength, better thermal conductivity, better electrical conductivity, better flame retardancy and extreme environmental stability.

[0163] In contrast, Comparative Example 1, due to the lack of magnetic field and flow field orientation processes, experienced a 44% decrease in interfacial shear strength, a 51% decrease in thermal conductivity, and a 45% reduction in impact resistance. This was caused by the disordered distribution of fillers interrupting the heat conduction path, the lack of axial arrangement of aramid fibers leading to the failure of the reinforcing network, and stress concentration caused by pore filling defects.

[0164] Comparative Example 2, due to the lack of modified silane coupling agent, resulted in a strength retention rate of only 64.1% after salt spray and a flame retardant rating of V-1. This was because KH-550 silane has low Si-O-Al bond hydrolysis energy, making it prone to breakage in humid and hot environments; it also lacks a sulfur bond toughening mechanism and cannot form a PON flame retardant composite.

[0165] Comparative Example 3, due to the lack of modified epoxy resin, resulted in a strength retention rate of only 77.4% after high temperature and a flame retardancy rating of V-2. This was because ordinary epoxy resin lacked phosphorus-based free radicals to interrupt the combustion chain, and the insufficient crosslinking density led to deterioration of thermal stability and inability to catalyze char formation.

[0166] Comparative Example 4 suffered a 50% drop in compressive strength due to the lack of stepped pressure impregnation, and the thermal conductivity was only 9.1 W / (m·K) due to pore filling defects. This was because single-stage vacuum impregnation prevented the resin from overcoming the capillary resistance of micropores, and the macropores were not fully filled, resulting in excessive porosity. The interruption of graded densification weakened the structural continuity.

[0167] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.

[0168] This invention is intended to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A composite material based on thermosetting resin and porous metal matrix, characterized in that, It is composed of the following components in parts by weight: 20-25 parts porous aluminum particles, 50-55 parts modified epoxy resin, 6-10 parts phenolic resin, 4-6 parts liquid crystal epoxy monomer, 4-6 parts modified boron nitride, and 10-14 parts aramid fiber.

2. The composite material based on thermosetting resin and porous metal matrix according to claim 1, characterized in that, The porous aluminum particles are prepared in the following steps: Step A1: Place the aluminum alloy plate in acetone solvent and ultrasonically clean it for 10-20 minutes. Then place it in a drying oven, heat it to 70-90℃, and dry it for 1-3 hours. Next, place it under a fiber pulse laser with a power of 250-350w to create holes with a diameter of 150-250μm. After the holes are created, add aluminum powder, pressurize it to 45-55MPa, and hold the pressure for 4-6 minutes to obtain the aluminum substrate. Step A2: Add 0.8wt% titanium dihydrogen pore-forming agent to the aluminum matrix, ball mill and mix for 20-40 min, place in a tube furnace, introduce nitrogen gas, heat to 460-500℃, sinter for 20-40 min, reduce pressure to -0.1MPa, heat to 660-700℃, sinter for 40-50 min, after sintering is complete, cool to 20-30℃ to obtain porous aluminum; Step A3: Add porous aluminum to a solution of 10wt% sulfuric acid and 2wt% nitric acid, heat to 30-50℃, soak for 8-12 minutes, rinse with deionized water, blow dry with nitrogen, remove, put into 0.1mol / L cesium nitrate and 1.5wt% phytic acid, soak for 10-20 minutes, heat to 20-30℃, rinse with deionized water, dry, and obtain etched porous aluminum; Step A4: Under a nitrogen and argon atmosphere, the etched porous aluminum is placed in a plasma chamber at a power of 350-450W for 4-6 minutes. Then it is placed in an ethanol solution of 3wt% modified silane coupling agent, heated to 90-110℃, and refluxed for 1-3 hours. After cleaning with ethanol and drying, a porous aluminum substrate is obtained. Step A5: Under a nitrogen atmosphere, add the porous aluminum matrix into a ball mill, add zirconia grinding balls and zinc stearate lubricant, grind at 250-350 rpm for 15-30 minutes, sieve, the particle size is 2-3 mm, dry to obtain porous aluminum particles.

3. The composite material based on thermosetting resin and porous metal matrix according to claim 2, characterized in that, The mass ratio of aluminum alloy plate to aluminum powder in step A1 is 1:0.24-0.26; The mass ratio of aluminum matrix to pore-forming agent in step A2 is 1:0.006-0.01; The volume ratio of the 10wt% sulfuric acid to the 2wt% nitric acid solution in step A3 is 5:1; The volume ratio of 0.1 mol / L cesium nitrate to 1.5 wt% phytic acid in step A3 is 1:1; The mass ratio of the etched porous aluminum to the ethanol solution of 3wt% modified silane coupling agent in step A4 is 1:7.8-8.2; The mass ratio of the porous aluminum matrix, zirconium oxide and lubricant in step A5 is 1:2-3:0.005-0.

01.

4. The composite material based on thermosetting resin and porous metal matrix according to claim 1, characterized in that, The modified epoxy resin is prepared in the following steps: Step B1: Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to toluene solvent, heat to 60-80℃, add bisphenol A type epoxy resin, heat to 110-120℃ to obtain a mixed solution. Step B2: Under a nitrogen atmosphere, add the mixed solution to a beaker, add the catalyst triphenylphosphine, heat to 125-135℃, stir for 2-3 hours, cool to 70-90℃, and distill under reduced pressure to obtain the modified epoxy resin.

5. A composite material based on thermosetting resin and porous metal matrix according to claim 4, characterized in that, The mass ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to bisphenol A epoxy resin in step B1 is 1:5.5-6.5; The mass ratio of the mixed solution to the catalyst in step B2 is 1:0.0035-0.0045.

6. The composite material based on thermosetting resin and porous metal matrix according to claim 1, characterized in that, The modified boron nitride is prepared in the following steps: Step C1: Add carboxylated multi-walled carbon nanotubes to Tris-HCl buffer, sonicate for 20-40 min at 700-900 W, add dopamine hydrochloride, purge with nitrogen, heat to 20-30 °C, react for 10-14 h, centrifuge, wash, and dry to obtain modified multi-walled carbon nanotubes. Step C2: Add boron nitride to a mixed solution of ethanol and deionized water, stir and disperse, add ammonia, sonicate for 1-3 hours, add trimethyl borate, heat to 70-90℃, react for 2-4 hours, centrifuge and purify to obtain hydroxylated boron nitride suspension; Step C3: Add the modified multi-walled carbon nanotubes to deionized water, then add the hydroxylated boron nitride suspension, sonicate for 20-40 min, place in a high-pressure reactor, heat to 170-190℃, react for 5-7 h, cool, filter, and vacuum dry to obtain modified boron nitride.

7. A composite material based on thermosetting resin and porous metal matrix according to claim 6, characterized in that, The mass ratio of carboxylated multi-walled carbon nanotubes to dopamine hydrochloride in step C1 is 1:1.8-2.

2. In step C2, the mass ratio of boron nitride, trimethyl borate, and ammonia is 1:0.05-0.07:0.2-0.

3. The volume ratio of ethanol to deionized water in step C2 is 1:1; The mass ratio of the modified multi-walled carbon nanotubes to the hydroxylated boron nitride suspension in step C3 is 1:0.45-0.

55.

8. A composite material based on thermosetting resin and porous metal matrix according to claim 2, characterized in that, The preparation steps of the modified silane coupling agent are as follows: Step D1: Under a nitrogen atmosphere, γ-chloropropyltriethoxysilane and thiourea are added to anhydrous ethanol solvent, stirred and dissolved, then tetrabutylammonium bromide catalyst is added, the temperature is raised to 70-80℃, and the reaction is stirred for 3-5 hours to obtain the reaction mixture. Step D2: Add the reaction mixture to a beaker, heat to 30-50℃, add 30% sodium hydroxide solution, heat to 60-70℃, reflux and stir for 1-3 hours. Once the reaction is complete, wash with neutralized water, and distill under reduced pressure to obtain the modified silane coupling agent. The mass ratio of γ-chloropropyltriethoxysilane, thiourea, and catalyst is 1:0.42-0.45:0.004-0.006; The mass ratio of the reaction mixture to the sodium hydroxide solution is 1:0.14-0.

16.

9. A method for preparing a composite material based on a thermosetting resin and a porous metal matrix according to any one of claims 1-8, characterized in that, The preparation steps are as follows: Step S1: Add modified epoxy resin, phenolic resin and liquid crystal ring monomer to a reaction vessel, heat to 50-70℃, stir for 50-70 min, add modified boron nitride and aramid fiber, place in a 1.1-1.3T vertical magnetic field, stir for 20-40 min to obtain a mixture; Step S2: Add porous aluminum particles to the mixture, heat to 50-70℃, reduce pressure to -0.095MPa, react for 20-40min, introduce nitrogen, pressurize to 5.8-6.2MPa, heat to 75-85℃, react for 40-50min to obtain the preform; Step S3: Place the blank into a tube furnace, heat to 75-85℃, sinter for 50-70 minutes, heat to 110-130℃, sinter for 50-70 minutes, heat to 140-160℃, sinter for 100-140 minutes, heat to 170-190℃, sinter for 100-140 minutes. After sintering is complete, cool to 50-70℃, demold and cure to obtain the composite material.

10. The method for preparing a composite material based on thermosetting resin and porous metal matrix according to claim 9, characterized in that, The mass ratio of modified epoxy resin, phenolic resin, liquid crystal ring monomer, modified boron nitride, and aramid fiber in step S1 is 1:0.3-0.34:0.18-0.22:0.18-0.22:0.45-0.

50. The mass ratio of porous aluminum particles to the mixed liquid in step S2 is 1:0.8-0.82.

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