CN114989569B - Epoxy resin composite material and preparation method thereof - Google Patents

Epoxy resin composite material and preparation method thereof Download PDF

Info

Publication number
CN114989569B
CN114989569B CN202210393461.4A CN202210393461A CN114989569B CN 114989569 B CN114989569 B CN 114989569B CN 202210393461 A CN202210393461 A CN 202210393461A CN 114989569 B CN114989569 B CN 114989569B
Authority
CN
China
Prior art keywords
epoxy resin
carbon fiber
glass beads
composite material
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210393461.4A
Other languages
Chinese (zh)
Other versions
CN114989569A (en
Inventor
梅园
李振
麻一明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Jianfeng New Material Co ltd
Original Assignee
Ningbo Jianfeng New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Jianfeng New Material Co ltd filed Critical Ningbo Jianfeng New Material Co ltd
Priority to CN202210393461.4A priority Critical patent/CN114989569B/en
Publication of CN114989569A publication Critical patent/CN114989569A/en
Application granted granted Critical
Publication of CN114989569B publication Critical patent/CN114989569B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C39/10—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention belongs to the technical field of polymer composite materials, and particularly relates to an epoxy resin composite material and a preparation method thereof. The epoxy resin composite material comprises 60-80 parts of epoxy resin, 10-30 parts of gradient porous spiral carbon fiber foam and 10-20 parts of curing agent, wherein natural water-soluble high polymer chitosan is used as an adhesive of a spiral fiber catalyst, a catalyst precursor of the spiral fiber is uniformly covered on the surface of glass beads, then the spiral carbon fiber foam is grown in situ by a CVD method, the gradient porous spiral carbon fiber foam is obtained through hydrofluoric acid etching, and finally the epoxy resin composite material is prepared by mixing the gradient porous spiral carbon fiber foam with the epoxy resin by a vacuum infusion method, so that the internal microstructure of the composite material can be effectively regulated, the uneven dispersion of a traditional filler is avoided, and the preparation efficiency and the comprehensive mechanical property of the composite material are improved.

Description

Epoxy resin composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to an epoxy resin composite material and a preparation method thereof.
Background
Epoxy resin is a generic term for a class of polymers containing more than two epoxy groups in the molecule, and due to the chemical activity of the epoxy groups, the epoxy resin can be subjected to ring opening by using various compounds containing active hydrogen, and is cured and crosslinked to generate a network structure, so that the epoxy resin is a thermosetting resin. The epoxy resin has excellent mechanical property, higher adhesive property, good chemical stability, better heat resistance and electrical insulation property, and is widely applied to the fields of coating, composite materials, casting materials, electronic packaging materials and the like. However, after the epoxy resin is cured, the epoxy resin has more crosslinking points and larger internal stress, so that the whole material is brittle, has poorer impact resistance and bending property, and directly influences the application of the epoxy resin in the aspects of being used as a structural material or a bearing part and the like.
At present, the epoxy resin toughening is mainly carried out by adding inorganic filler for blending modification, dispersing the filler in an epoxy resin matrix after surface modification, and curing to obtain the epoxy resin modified composite material. In the method, the dispersion state of the filler in the epoxy resin has close relation with the final modification effect, if the dispersion is good, the performance of the composite material can be obviously improved, and if the dispersion is uneven, the performance of the material cannot reach the expected result, and even can be obviously deteriorated. With the current dispersion technology, it is difficult to prepare epoxy resin composites with very uniform filler dispersion.
Chinese patent application publication No. CN106476365a discloses a toughened epoxy resin based glass fiber composite material and a method for preparing the same, the composite material comprises at least one composite material unit, each composite material unit comprises an epoxy resin substrate layer and a glass fiber cloth layer laid on the epoxy resin substrate layer, the epoxy resin substrate layer comprises the following components in parts by mass: 40-90 parts of epoxy resin, 20-80 parts of curing agent and 1-25 parts of toughening agent, wherein the toughening agent is one or more of liquid crystal material, nano silicon dioxide and TPU. Compared with the existing pure epoxy resin-based glass fiber composite material, the impact strength of the toughened epoxy resin-based glass fiber composite material is improved by 17% -35%, and the tensile strength of the material is not obviously improved.
Chinese patent application document (publication No. CN 112980145A) discloses a thermosetting polyesteramide modified nano CaCO 3 The toughened epoxy resin and the preparation method thereof are characterized in that the linear polyester amide is synthesized, the thermal stability of the epoxy resin can be maintained, phosphate groups containing P-OH are introduced at two ends of the polyester amide, the phosphate groups can be subjected to addition reaction with epoxy groups on the epoxy resin, the polyester amide and the epoxy resin form a crosslinked interpenetrating network structure, the phosphate groups can also play a role in promoting the carbon formation, and due to the existence of polar amide bonds, the bonding tightness of interpenetrating networks formed by the epoxy resin can be improved, so that the toughness of the epoxy resin is improved well, and the grafted and modified nano CaCO is prepared by the method 3 When the external force is applied, the effects of dispersing stress, generating silver marks and absorbing a large amount of energy by the yielding resin matrix can be effectively achieved, and the aim of toughening is achieved. By passing throughAlthough the surface modification can improve nano CaCO to a certain extent 3 The dispersibility in epoxy resins, however, the improvement effect is not obvious from the final flexural strength data, which suggests that there is a limitation in promoting nanoparticle dispersion by surface modification.
Chinese patent application document (publication No. CN112920553 a) discloses a flower-shaped layered nickel silicate/graphene oxide blend modified epoxy composite material and a preparation method thereof, wherein a layered nickel silicate with nano flower morphology is synthesized through a precipitation-deposition process, and is fully mixed with graphene oxide, and then vacuum filtration is performed to prepare a blend with a pea pod-like structure; the prepared flower-like layered nickel silicate/graphene oxide blend modified epoxy composite material has high strength, high modulus and excellent wear resistance and antifriction performance. Although this particular flower-like structure filler can improve the tensile strength and compression resistance of the epoxy to some extent, it may be detrimental to impact properties and flexural properties, thereby embrittling the epoxy material.
Disclosure of Invention
The invention aims at solving the problems that the filler of the epoxy resin composite material is difficult to disperse uniformly and has adverse effects on the strength and toughness of the material, and provides the epoxy resin composite material and the preparation method thereof, and the epoxy matrix is combined with the epoxy resin composite material in a vacuum infusion mode, so that the problem of filler dispersion can be solved, and the performance of the epoxy composite material can be obviously improved.
The epoxy resin composite material comprises the following components in parts by weight:
60-80 parts of epoxy resin;
10-30 parts of gradient porous spiral carbon fiber foam;
10-20 parts of curing agent;
the gradient porous spiral carbon fiber foam comprises a pore size structure which is gradually increased from top to bottom.
The porous spiral carbon fiber foam with the gradient pore structure has the structure similar to that of natural bamboo, and has the functions of strengthening and reinforcing the porous spiral carbon fiber, and the porous spiral carbon fiber foam with the pore diameter similar to that of bamboo has the functions of reinforcing the porous spiral carbon fiber foam with the gradient pore structure, and has the functions of providing more strain space and energy absorbing and releasing capacity for the material, improving the strength and toughness of the composite material after being combined with epoxy resin, and providing the epoxy resin with ultrahigh toughness similar to that of bamboo and excellent tensile strength. And the spiral carbon fiber is a three-dimensional carbon fiber network intertwined with each other, so that the conductivity of the epoxy composite material can be obviously improved, and the conductivity of the composite material is obviously improved.
Further, the diameter of the carbon fiber in the gradient porous spiral carbon fiber foam is 10-100nm, preferably 10-20nm, and the pore size of the gradient pores is 1-250 μm, preferably 10-200 μm.
Further, the epoxy resin is one of bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol type glycidyl ether epoxy resin and aliphatic glycidyl ether epoxy resin.
Further, the curing agent is one or more of aromatic diamine, polyamine, aromatic polyamine, organic acid and anhydride.
The preparation method of the gradient porous spiral carbon fiber foam comprises the following steps:
a1: adding the hollow glass beads into a chitosan aqueous solution, stirring, taking out, drying, adding the hollow glass beads and magnesium oxide into a copper chloride solution, then dropwise adding a potassium sodium tartrate solution for reaction, taking out the hollow glass beads, and then cleaning and drying;
a2: and (3) paving the hollow glass beads obtained in the step (A1) in a porcelain boat, sequentially placing in a tubular furnace with argon atmosphere and acetylene atmosphere for high-temperature reaction to obtain spiral carbon fiber foam wrapped with the glass beads, placing in hydrofluoric acid for full reaction, fishing out, cleaning and drying to obtain the gradient porous spiral carbon fiber foam.
The natural water-soluble polymer chitosan is used as an adhesive of the spiral fiber catalyst, the catalyst precursor of the spiral fiber is uniformly covered on the surfaces of the glass beads, and the spiral fiber can uniformly grow around the hollow glass beads in the CVD growth process, so that the uniformity of the spiral fiber foam structure is ensured. And (3) performing carbonization reaction at high temperature to generate spiral carbon fibers, and performing hydrofluoric acid etching to obtain the gradient porous spiral carbon fiber foam.
Further, the hollow glass beads in the step A1 have a particle size of 1 to 250. Mu.m, preferably 10 to 200. Mu.m.
Further, the size of the hollow glass beads in the step A1 is reduced from the particle size of the bottom layer 200um to 10um layer by layer, and the hollow glass beads with different particle sizes are paved and arranged from bottom to top from large to small.
Further, the hollow glass beads in the step A1 are a mixture of hollow glass beads with various particle sizes ranging from 190 to 200 mu m, 140 to 150 mu m, 95 to 100 mu m, 75 to 80 mu m, 45 to 50 mu m, 20 to 25 mu m and 10 to 15 mu m.
Further, the concentration of the chitosan aqueous solution is 10-20%, the concentration of the copper chloride solution is 0.01-10 mol/L, preferably 0.05-1 mol/L, and the concentration of the potassium sodium tartrate solution is 0.01-10 mol/L, preferably 0.05-1 mol/L.
Further, the mass ratio of the copper chloride to the magnesium oxide is 1-10:1, preferably 1-5:1.
Further, the mass ratio of the hollow glass beads to the copper chloride is 1-20:1, preferably 2-10:1.
Further, in the step A1, the stirring speed is 300-500 rpm, the stirring time is 30-40 min, the drying temperature is 80-120 ℃, and the time is 12-24 h.
Further, the high-temperature reaction temperature in the step A2 is 270-280 ℃ and the time is 30-90 min.
Further, in the step A2, the concentration of hydrofluoric acid is 0.1-0.2 mol/L, and the etching time is 12-24 hours.
The preparation method of the epoxy resin composite material comprises the steps of mixing epoxy resin and a curing agent, adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, keeping a vacuum state for a certain time, and raising the temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
The epoxy resin composite material is prepared by mixing the epoxy resin and the vacuum infusion method, so that the internal microstructure of the composite material can be effectively regulated and controlled, uneven dispersion of the traditional filler is avoided, and the preparation efficiency and comprehensive mechanical property of the composite material are improved.
Further, the time for maintaining the epoxy resin in a vacuum state is 30-120 min, the temperature gradient of curing the epoxy resin is 110-120 ℃, 150-160 ℃, 190-200 ℃, and each temperature is maintained for 2-3 h.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) According to the method, hollow glass beads are used as templates, nano spiral fibers are grown in situ, gradient porous spiral carbon fiber foam is obtained through high-temperature carbonization and hydrofluoric acid etching, and the gradient porous spiral carbon fiber foam is mixed with epoxy resin and solidified to obtain an epoxy resin composite material, so that the strength of the epoxy resin is improved, and meanwhile, the material is endowed with super-strong toughness;
(2) The porous spiral carbon fiber foam with the gradient pore structure has the structure similar to that of natural bamboo, and can simultaneously improve the strength and toughness of the composite material after being combined with epoxy resin, so that the epoxy resin has ultrahigh toughness similar to that of bamboo and higher tensile strength;
(3) The three-dimensional carbon fiber network intertwined with each other in the gradient porous spiral carbon fiber foam can obviously reduce the self resistance of the composite material and endow the epoxy resin with better conductivity;
(4) The method adopts the vacuum infusion method to prepare the epoxy composite material, solves the problem of dispersion of the filler in the epoxy resin, and is beneficial to enhancing the mechanical strength of the material.
Drawings
FIG. 1 is a flow chart of example 1 for preparing an epoxy resin composite.
Detailed Description
The technical solution of the present invention will be further described by means of specific examples and drawings, it being understood that the specific examples described herein are only for aiding in understanding the present invention and are not intended to be limiting. And the drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure. Unless otherwise indicated, all materials used in the examples of the present invention are those commonly used in the art, and all methods used in the examples are those commonly used in the art.
The epoxy resin selected in the following examples and comparative examples was E44 type epoxy resin, and the curing agent was 4,4' -diaminodiphenyl sulfone (DDS).
Example 1
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying at 100 ℃ for 24 hours, and sequentially treating the rest hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 3:2:2:1:1:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for terminating the reaction, closing heating, cooling to room temperature along with the furnace to obtain spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol after fishing out, and then putting the spiral carbon fiber into the oven for 12h at 120 ℃ to obtain gradient porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and maintaining the temperature for 2h at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Example 2
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.2mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying at 100 ℃ for 24 hours, and sequentially treating the rest hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 4:2:2:1:1:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for terminating the reaction, closing heating, cooling to room temperature along with the furnace, preparing the spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber foam into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol for 3 times after fishing out, and then putting into the oven for baking at 120 ℃ for 12h to obtain the gradient porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 minutes, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 115 ℃, 155 ℃ and 195 ℃ and maintaining the temperature for 2 hours at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Example 3
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 15%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying at 100 ℃ for 24 hours, and sequentially treating the rest hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 4:3:2:1:1:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 275 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 275 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for terminating the reaction, closing heating, cooling to room temperature along with the furnace, preparing the spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber foam into 0.2mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol for 3 times after fishing out, and then putting into the oven for baking at 120 ℃ for 12h to obtain the gradient porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and maintaining the temperature for 2h at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Example 4
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying at 100 ℃ for 24 hours, and sequentially treating the rest hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 4:2:2:2:1:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 275 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 275 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for terminating the reaction, closing heating, cooling to room temperature along with the furnace to obtain spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber foam into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol for 3 times after fishing out, and then putting into the oven for baking at 120 ℃ for 12h to obtain gradient porous spiral carbon fibers;
a3: and uniformly mixing 60 parts of E51 epoxy resin monomer and 10 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fibers, vacuumizing and maintaining the vacuum state for 60 minutes, closing the vacuum after the epoxy resin monomer is completely immersed into the gradient porous spiral carbon fiber foam, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and maintaining the temperature at each temperature for 2 hours to completely cure the epoxy resin, thereby obtaining the epoxy resin composite material.
Example 5
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.5mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying at 100 ℃ for 24 hours, and sequentially treating the rest hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 4:2:3:3:1:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 280 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 280 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for terminating the reaction, closing the heating, cooling to room temperature along with the furnace to prepare spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber foam into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol for 3 times after fishing out, and then putting the spiral carbon fiber foam into the oven for baking at 120 ℃ for 12h to obtain gradient porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 minutes, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 115 ℃, 155 ℃ and 195 ℃ and maintaining the temperature for 2 hours at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Example 6
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 20%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying at 100 ℃ for 24 hours, and sequentially treating the rest hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 4:3:3:2:2:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 280 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 280 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for terminating the reaction, closing the heating, cooling to room temperature along with the furnace to prepare spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber foam into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol for 3 times after fishing out, and then putting the spiral carbon fiber foam into the oven for baking at 120 ℃ for 12h to obtain gradient porous spiral carbon fiber foam;
a3: uniformly mixing 70 parts of E51 epoxy resin monomer and 15 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and maintaining the temperature for 2h at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Example 7
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.8mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying at 100 ℃ for 24 hours, and sequentially treating the rest hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 4:3:3:3:2:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for terminating the reaction, closing heating, cooling to room temperature along with the furnace, preparing the spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber foam into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol for 3 times after fishing out, and then putting into the oven for baking at 120 ℃ for 12h to obtain the gradient porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and maintaining the temperature for 3h at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Example 8
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.5mol/L, adding 10 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying at 100 ℃ for 24 hours, and sequentially treating the rest hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 3:2:2:1:1:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 40min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for terminating the reaction, closing heating, cooling to room temperature along with the furnace, preparing the spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber foam into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol after fishing out, and then putting into the oven for drying at 120 ℃ for 12h to obtain the gradient porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and maintaining the temperature for 2h at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Example 9
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.05mol/L, adding 1 part of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying at 100 ℃ for 24 hours, and sequentially treating the rest hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 3:2:2:1:1:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 80min, closing the acetylene to introduce argon for terminating the reaction, closing heating, cooling to room temperature along with the furnace, preparing the spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber foam into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol after fishing out, and then putting into the oven for 12h at 120 ℃ to obtain the gradient porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 80 minutes, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and maintaining the temperature for 2 hours at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Example 10
The preparation method of the epoxy resin composite material comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.025mol/L, adding 0.5 part of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after dripping, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, putting into the oven for drying for 24 hours at the temperature of 100 ℃, and sequentially treating the hollow glass beads with the particle sizes of 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m according to the method;
a2: paving the hollow glass beads in a rectangular porcelain boat from top to bottom according to the mass ratio of 3:2:2:1:1:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas to acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for terminating the reaction, closing heating, cooling to room temperature along with the furnace, preparing the spiral carbon fiber foam containing the hollow glass beads, then putting the spiral carbon fiber foam into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning with clear water and ethanol after fishing out, and then putting into the oven for 12h at 120 ℃ to obtain the gradient porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and maintaining the temperature for 2h at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Example 11
The preparation method of the epoxy resin composite material comprises the following steps:
a1: laying hollow glass beads with the particle diameters of 200 mu m, 150 mu m, 100 mu m, 80 mu m, 50 mu m, 20 mu m and 10 mu m in a rectangular porcelain boat from top to bottom according to the mass ratio of 3:2:2:1:1:1:1, putting the porcelain boat into a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then closing the gas to 5 mL/min, closing the heating, cooling the furnace to room temperature, switching the gas to acetylene (30 mL/min), slowly heating to 270 ℃ (< 1 ℃/min), reacting for 90min, closing the acetylene to introduce argon to terminate the reaction, closing the heating, cooling the furnace to room temperature, preparing spiral carbon fiber foam containing hollow glass beads, then putting the spiral carbon fiber foam into 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning the foam with clear water and ethanol for 3 times, and then putting the foam into the furnace for 12h at 120 ℃ to obtain gradient porous spiral carbon fiber foam;
a2: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with gradient porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the gradient porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and maintaining the temperature for 2h at each temperature to completely cure the epoxy resin to obtain the epoxy resin composite material.
Comparative example 1
The preparation method of the epoxy resin composite material of the comparative example comprises the following steps:
a1: taking 80 parts of copper chloride solution with the concentration of 0.1mol/L and 2 parts of magnesium oxide, stirring at 500rpm for 30min, slowly dripping 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, filtering after dripping, obtaining precipitate, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, and then placing in a baking oven for baking at 100 ℃ for 24h;
a2: placing the precipitate into a porcelain boat, placing the porcelain boat into a tube furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing the heating, cooling the furnace to room temperature, switching the gas into acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for stopping the reaction, closing the heating, and cooling the furnace to room temperature to obtain the spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with the spiral carbon fiber foam, vacuumizing and keeping the vacuum state for 60 minutes, closing the vacuum after the epoxy resin monomer is completely immersed into the porous spiral carbon fiber foam, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃ and keeping the temperature at each temperature for 2 hours to completely cure the epoxy resin, thereby obtaining the epoxy resin composite material.
Comparative example 2
The preparation method of the epoxy resin composite material of the comparative example comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 200 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dropwise adding 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after the dropwise adding, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, and putting into the oven for drying at 100 ℃ for 24 hours;
a2: placing the hollow glass beads obtained by the treatment in a rectangular porcelain boat, placing the porcelain boat in a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas into acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for stopping the reaction, closing heating, cooling to room temperature along with the furnace, preparing spiral carbon fiber foam containing the hollow glass beads, then placing the spiral carbon fiber foam in 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning for 3 times after fishing out, and then placing the spiral carbon fiber foam in an oven for baking at 120 ℃ for 12h to obtain porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃, and maintaining the temperature at each temperature for 2h to completely cure the epoxy resin to obtain the epoxy resin composite material.
Comparative example 3
The preparation method of the epoxy resin composite material of the comparative example comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 100 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dropwise adding 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after the dropwise adding, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, and putting into the oven for drying at 100 ℃ for 24 hours;
a2: placing the hollow glass beads obtained by the treatment in a rectangular porcelain boat, placing the porcelain boat in a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas into acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for stopping the reaction, closing heating, cooling to room temperature along with the furnace, preparing spiral carbon fiber foam containing the hollow glass beads, then placing the spiral carbon fiber foam in 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning for 3 times after fishing out, and then placing the spiral carbon fiber foam in an oven for baking at 120 ℃ for 12h to obtain porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃, and maintaining the temperature at each temperature for 2h to completely cure the epoxy resin to obtain the epoxy resin composite material.
Comparative example 4
The preparation method of the epoxy resin composite material of the comparative example comprises the following steps:
a1: preparing 50 parts of chitosan aqueous solution with the mass concentration of 10%, then adding 10 parts of hollow glass beads with the particle size of 10 mu m respectively, fully stirring, taking out, putting into a 100 ℃ oven for drying for 12 hours, taking 80 parts of copper chloride solution with the concentration of 0.1mol/L, adding 2 parts of magnesium oxide and 20 parts of treated hollow glass beads, stirring at 500rpm for 30 minutes, slowly dropwise adding 80 parts of potassium sodium tartrate aqueous solution with the concentration of 0.1mol/L, taking out the hollow glass beads from the solution after the dropwise adding, repeatedly cleaning for 3 times by using clear water and absolute ethyl alcohol, and putting into the oven for drying at 100 ℃ for 24 hours;
a2: placing the hollow glass beads obtained by the treatment in a rectangular porcelain boat, placing the porcelain boat in a tubular furnace, introducing argon (50 mL/min) to raise the temperature to 270 ℃ for reaction for 30min, then turning off the gas to 5 mL/min, closing heating, cooling to room temperature along with the furnace, switching the gas into acetylene (30 mL/min), slowly heating to 270 ℃ (1 ℃/min) for reaction for 90min, closing the acetylene to introduce argon for stopping the reaction, closing heating, cooling to room temperature along with the furnace, preparing spiral carbon fiber foam containing the hollow glass beads, then placing the spiral carbon fiber foam in 0.1mol/L hydrofluoric acid for etching for 24h, repeatedly cleaning for 3 times after fishing out, and then placing the spiral carbon fiber foam in an oven for baking at 120 ℃ for 12h to obtain porous spiral carbon fiber foam;
a3: uniformly mixing 80 parts of E51 epoxy resin monomer and 20 parts of DDS curing agent, slowly adding the mixture into a closed container filled with porous spiral carbon fiber foam, vacuumizing and maintaining the vacuum state for 60 min, closing the vacuum after the porous spiral carbon fiber foam is completely immersed by the epoxy resin monomer, and respectively raising the temperature to 120 ℃, 160 ℃ and 200 ℃, and maintaining the temperature at each temperature for 2h to completely cure the epoxy resin to obtain the epoxy resin composite material.
The epoxy composites obtained in the above examples and comparative examples were tested for tensile strength according to ASTM D638, flexural strength according to ASTM D790, notched impact strength according to ASTM D256, and surface resistivity according to GB/T1410-1989.
Table 1 mechanical properties and conductivity properties of examples and comparative examples
Figure SMS_1
FIG. 1 is a flow chart of a preparation process of an epoxy resin composite material of example 1, wherein the tensile strength of the epoxy resin composite material obtained in examples 1-10 is greater than 120MPa, the elongation at break is greater than 40%, the bending strength is greater than 168MPa, the bending strain is greater than 17%, untreated hollow glass beads are adopted in example 11, structural dispersion in the spiral carbon fiber foam is irregular, the spiral carbon fibers in the obtained epoxy resin composite material are unevenly distributed, the mechanical properties of the material are poor, the hollow glass beads are not used as templates in comparative example 1, the spiral carbon fiber foam with compact structure is obtained, the epoxy resin composite material shows higher mechanical strength and poor strain capacity, the hollow glass beads with the particle size of 200 mu m are adopted in comparative example 2, single large pore diameter is shown in the spiral carbon fiber structure, the strain capacity of the obtained epoxy resin composite material is better, the mechanical strength is poor, the hollow glass beads with the particle size of 100 mu m are adopted in comparative example 3, the hollow glass beads with the particle size of 10 mu m are adopted in the spiral carbon fiber structure, the obtained epoxy resin composite material has poor strain capacity and mechanical strength, and the obtained epoxy resin composite material has poor elongation at break. Therefore, after the porous spiral carbon fiber foam with the gradient pore structure is combined with epoxy resin, the strength and toughness of the composite material can be improved, the epoxy resin is endowed with ultrahigh toughness similar to bamboo and higher tensile strength, the three-dimensional carbon fiber network intertwined with each other can obviously reduce the self resistance of the composite material, and the epoxy resin is endowed with better conductive performance.
Finally, it should be noted that the specific embodiments described herein are merely illustrative of the spirit of the invention and are not limiting of the invention's embodiments. Those skilled in the art to which the invention pertains may make various modifications or additions to the described embodiments or may be substituted in a similar manner, without and without all of the embodiments herein being fully understood. While these obvious variations and modifications, which come within the spirit of the invention, are within the scope of the invention, they are to be construed as being without departing from the spirit of the invention.

Claims (5)

1. The epoxy resin composite material is characterized by comprising the following components in parts by weight:
60-80 parts of epoxy resin;
10-30 parts of gradient porous spiral carbon fiber foam;
10-20 parts of curing agent;
the porous spiral carbon fiber comprises a pore diameter structure which gradually increases from top to bottom;
in the porous spiral carbon fiber foam, the diameter of the carbon fiber is 10-100nm, and the aperture of the gradient pore is 1-250 mu m;
the preparation method of the gradient porous spiral carbon fiber foam comprises the following steps:
a1: adding the hollow glass beads into a chitosan aqueous solution, stirring, taking out, drying, adding the hollow glass beads and magnesium oxide into a copper chloride solution, then dropwise adding a potassium sodium tartrate solution for reaction, taking out the hollow glass beads, and then cleaning and drying;
a2: paving the hollow glass beads obtained in the step A1 in a porcelain boat, sequentially placing in a tubular furnace with argon atmosphere and acetylene atmosphere for high-temperature reaction to obtain spiral carbon fiber foam, placing in hydrofluoric acid for full reaction, fishing out, cleaning and drying to obtain gradient porous spiral carbon fiber foam;
the particle size of the hollow glass beads in the step A1 is 1-250 mu m;
step A1, the size of hollow glass beads is reduced from the particle size of a bottom layer of 200um to 10um layer by layer, and the hollow glass beads with different particle sizes are paved and arranged from bottom to top from large to small;
the hollow glass beads in the step A1 are a mixture of hollow glass beads with various particle sizes in the range of 190-200 mu m, 140-150 mu m, 95-100 mu m, 75-80 mu m, 45-50 mu m, 20-25 mu m and 10-15 mu m.
2. The epoxy resin composite material according to claim 1, wherein the high-temperature reaction in the step A2 is carried out at 270-280 ℃ for 30-90 min.
3. The epoxy resin composite material according to claim 1, wherein the concentration of hydrofluoric acid in the step A2 is 0.1-0.2 mol/L, and the etching time is 12-24 hours.
4. The method for preparing an epoxy resin composite material according to claim 1, wherein the epoxy resin and the curing agent are mixed and then added into a closed container filled with gradient porous spiral carbon fiber foam, and after the vacuum state is maintained for a certain time, the temperature is raised to completely cure the epoxy resin, so as to obtain the epoxy resin composite material.
5. The method for preparing an epoxy resin composite material according to claim 4, wherein the epoxy resin is cured at a temperature gradient of 110-120 ℃, 150-160 ℃, 190-200 ℃ and each temperature for 2-3 hours.
CN202210393461.4A 2022-04-15 2022-04-15 Epoxy resin composite material and preparation method thereof Active CN114989569B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210393461.4A CN114989569B (en) 2022-04-15 2022-04-15 Epoxy resin composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210393461.4A CN114989569B (en) 2022-04-15 2022-04-15 Epoxy resin composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114989569A CN114989569A (en) 2022-09-02
CN114989569B true CN114989569B (en) 2023-04-25

Family

ID=83024071

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210393461.4A Active CN114989569B (en) 2022-04-15 2022-04-15 Epoxy resin composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114989569B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000027072A (en) * 1998-07-10 2000-01-25 Seiji Motojima Coil-like carbon fiber, its production and electromagnetic wave shielding material
JP2001146644A (en) * 1999-11-19 2001-05-29 Seiji Motojima Coiled carbon fiber having ferromagnetism, method for producing the same, coiled carbon fiber composite having ferromagnetism and electric wave absorber
JP2004091985A (en) * 2002-08-30 2004-03-25 Seiji Motojima Coil-like fiber substance, method for producing the same and application
JP2006083494A (en) * 2004-09-16 2006-03-30 Gifu Univ Singly coiled coil-shaped carbon fiber, method for producing the same and touch sensor element using the same
CN107698937A (en) * 2017-09-08 2018-02-16 常熟市瑞思知识产权服务有限公司 A kind of helical spring composite and preparation method thereof
CN113480833B (en) * 2021-07-30 2023-08-22 宁波石墨烯创新中心有限公司 Preparation method of graphene/spiral carbon fiber/epoxy resin composite material

Also Published As

Publication number Publication date
CN114989569A (en) 2022-09-02

Similar Documents

Publication Publication Date Title
CN103146147B (en) A kind of epoxy resin toughened/glass fibre prepreg and preparation method
CN108454135B (en) Phthalonitrile resin prepreg, composite material and preparation method thereof
US11167991B2 (en) Method for preparing carbon nanotube/polymer composite
CN103031058B (en) Room temperature vulcanized silicone rubber electromagnetic shielding paint and preparation method thereof
CN108035143B (en) Method for simultaneously improving interface strength and toughness of carbon fiber epoxy composite material
CN108794942A (en) A kind of preparation method of polymer and the compound Meta Materials of three-dimensional porous graphene
CN107459774A (en) A kind of graphene/nanometer silica/epoxy resin composite material and preparation method thereof
CN109942848B (en) Preparation method of hydrophobic polyimide aerogel film with surface structure
CN109608668A (en) A kind of preparation of carbon fiber/graphene oxide/epoxy prepreg and carbon fibre composite
CN112694715B (en) Glass fiber composite material and preparation method thereof
CN111423700A (en) Carbon fiber resin matrix composite material with multi-scale rapid self-assembly interface and preparation method thereof
CN112791606A (en) Modified halloysite nanotube/polyether copolyamide mixed matrix film and preparation method thereof
CN110424064B (en) Graphene quantum dot modified PBO fiber and preparation method thereof
CN114989569B (en) Epoxy resin composite material and preparation method thereof
CN105418923A (en) Modified bismaleimide resin and preparation method thereof
CN109056336A (en) Aqueous sizing agent of a kind of carbon fiber Wesy heat resistant type and its preparation method and application
CN110130101B (en) Method for modifying surface function of meta-aramid fabric
CN104151827A (en) Preparation method of carbon fiber/carbon nanotube/organic silicone resin multidimensional hybrid composite material
CN109232891A (en) A kind of low dielectric bismaleimide resin system performed polymer
CN108276736B (en) Oxatyl-containing lateral group hyperbranched polyarylether copolymer cured modified epoxy resin composition, preparation method and application
CN102329431B (en) Preparation method of epoxy resin composite material strengthened by in situ growth of CNT (carbon nano tube) on surface of quartz fibre
CN111363989A (en) Preparation method of fiber reinforced composite material
CN109679295B (en) Method for enhancing composite performance of carbon fiber and resin matrix
CN111500064A (en) High-strength flame-retardant SiO2-GO modified bismaleimide composite material and preparation method thereof
CN114855444A (en) Surface coating modification method for ultra-high molecular weight polyethylene fiber

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant