CN113211828B - Phthalonitrile resin carbon fiber cloth composite material and preparation method thereof - Google Patents
Phthalonitrile resin carbon fiber cloth composite material and preparation method thereof Download PDFInfo
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- CN113211828B CN113211828B CN202110505227.1A CN202110505227A CN113211828B CN 113211828 B CN113211828 B CN 113211828B CN 202110505227 A CN202110505227 A CN 202110505227A CN 113211828 B CN113211828 B CN 113211828B
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- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
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- 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
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
- B29B13/021—Heat treatment of powders
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- 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
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/105—Coating or impregnating independently of the moulding or shaping step of reinforcement of definite length with a matrix in solid form, e.g. powder, fibre or sheet form
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- 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
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
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- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- 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
- C08K7/06—Elements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/40—Weight reduction
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Abstract
The invention provides a phthalonitrile resin carbon fiber cloth composite material and a preparation method thereof, belonging to the technical field of composite materials. The invention disperses the mixed powder of phthalonitrile resin and curing agent on the surface of carbon fiber cloth, melts and soaks the carbon fiber cloth by preheating, shapes the carbon fiber cloth by pressurizing, and solidifies phthalonitrile dipped in the carbon fiber cloth by thermocuring. The method carries out the melt mixing of the phthalonitrile resin and the curing agent at 180-190 ℃, so that the curing agent can be fully dispersed in phthalonitrile, and the subsequent curing reaction is favorably carried out; meanwhile, the curing agent and the phthalonitrile can be prevented from reacting in the melting process. The method of the invention does not use organic solvent, thereby avoiding the damage of the organic solvent to human body and the pollution to the environment, and also avoiding the problem of high porosity of the composite material caused by the residue of the organic solvent, thereby improving the mechanical property of the composite material.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a phthalonitrile resin carbon fiber cloth composite material and a preparation method thereof.
Background
Phthalonitrile resin based composite material has the characteristics of high temperature resistance, flame retardance, humidity and heat resistance, low water absorption and excellent mechanical property, and is paid more and more attention by scientific researchers. The phthalonitrile resin-based composite material is widely applied to the fields of aviation aircraft engine components, radar antenna covers, microelectronics and ships.
In the molding of phthalonitrile resin-based composite materials, at present, phthalonitrile resin is usually dissolved by using a low-boiling-point organic solvent (such as diethyl ether and acetone), and then coated on a reinforcing fiber cloth, and then a thermosetting method is performed, see patent CN 108454135 a "a phthalonitrile resin prepreg, composite material and preparation method thereof". The method has the advantages that the dosage of the low-boiling-point solvent is large, 100-185 parts by mass of the low-boiling-point solvent is required for 100 parts by mass of phthalonitrile resin, and a large amount of toxic organic solvent is volatilized in the preparation process, so that the human body damage and the environmental pollution are caused; meanwhile, the residual organic solvent causes high porosity of the composite material, resulting in reduced mechanical properties.
Disclosure of Invention
In view of the above, the present invention aims to provide a phthalonitrile resin carbon fiber cloth composite material and a preparation method thereof. The method provided by the invention can avoid the use of low-boiling-point organic solvent, and the obtained phthalonitrile resin carbon fiber cloth composite material has good mechanical properties.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a phthalonitrile resin carbon fiber cloth composite material, which does not use an organic solvent and comprises the following steps:
(1) melting and mixing phthalonitrile resin and a curing agent, and then cooling and crushing to obtain mixed powder, wherein the temperature of melting and mixing is 180-190 ℃;
(2) dispersing the mixed powder on the surface of the carbon fiber cloth, and preheating to obtain mixed powder impregnated carbon fiber cloth; the preheating temperature is 180-200 ℃;
(3) and (3) laminating the multiple layers of the mixed powder impregnated carbon fiber cloth, and sequentially performing hot pressing and thermosetting to obtain the phthalonitrile resin carbon fiber cloth composite material.
Preferably, the curing agent is one or more of 4, 4-diaminodiphenyl sulfone, ethylenediamine, hexamethylenediamine and maleic anhydride.
Preferably, the mass ratio of the phthalonitrile resin to the curing agent is 100-125: 4 to 10.
Preferably, the time for melt mixing in the step (1) is 1-3.5 h.
Preferably, in the step (2), the mass ratio of the phthalonitrile resin in the mixed powder material to the carbon fiber cloth is 100-125: 100 to 150.
Preferably, the dispersion amount of the mixed powder in the mixed powder impregnated carbon fiber cloth obtained in the step (2) is 0.5-1.5 g/cm 3 。
Preferably, the preheating time in the step (2) is 20-30 min.
Preferably, the number of the laminated layers of the mixed powder impregnated carbon fiber cloth in the step (3) is 10-15.
Preferably, the hot pressing in step (3) includes: sequentially carrying out first gradient hot pressing and second gradient hot pressing;
the first gradient hot pressing comprises the following steps: sequentially preserving heat for 10-15 min at the temperature of 180-200 ℃, boosting the pressure to 0.5-2 MPa, preserving heat and maintaining pressure for 5-15 min, boosting the pressure to 3-4.5 MPa, preserving heat and maintaining pressure for 5-15 min, and boosting the pressure to 5-6.5 MPa, preserving heat and maintaining pressure for 5-15 min;
the second gradient hot pressing comprises the following steps: boosting the pressure to 7-8.5 MPa, and keeping the pressure and heat at 180-185 ℃ for 5-7 h, raising the temperature to 190-195 ℃ for 5-7 h, and raising the temperature to 200-205 ℃ for 5-7 h under the condition of 7-8.5 MPa.
Preferably, the temperature of the thermal curing in the step (3) is 200-230 ℃, and the time is 4-6 h.
The invention provides a preparation method of a phthalonitrile resin carbon fiber cloth composite material, which does not use an organic solvent and comprises the following steps: (1) melting and mixing phthalonitrile resin and a curing agent, and then cooling and crushing to obtain mixed powder, wherein the temperature of melting and mixing is 180-190 ℃; (2) dispersing the mixed powder on the surface of the carbon fiber cloth, and preheating to obtain mixed powder impregnated carbon fiber cloth; the preheating temperature is 180-200 ℃; (3) and (3) laminating the multiple layers of mixed powder impregnated carbon fiber cloth, and sequentially carrying out hot pressing and thermosetting to obtain the phthalonitrile resin carbon fiber cloth composite material.
The method can avoid the use of organic solvent, the invention disperses the mixed powder of phthalonitrile resin and curing agent on the surface of the carbon fiber cloth, melts and soaks the carbon fiber cloth by preheating, shapes the carbon fiber cloth by pressurizing, and solidifies the phthalonitrile resin soaked in the carbon fiber cloth by thermocuring. The method carries out the melt mixing of the phthalonitrile resin and the curing agent at 180-190 ℃, so that the curing agent can be fully dispersed in the phthalonitrile resin, and the subsequent curing reaction is favorably carried out; meanwhile, the curing agent and the phthalonitrile resin can be prevented from reacting in the melting process. According to the method, an organic solvent is not used, so that the damage of the organic solvent to a human body and the pollution to the environment are avoided, and the problem of high porosity (30-55%) of the composite material caused by the residue of the organic solvent is also avoided, so that the mechanical property of the composite material is improved. The embodiment results show that the phthalonitrile resin carbon fiber cloth composite material obtained by the invention has good mechanical properties at room temperature, the tensile strength at room temperature is 650.6MPa, the tensile modulus is 68.1GPa, the bending strength is 850.1MPa, the bending modulus is 70.4GPa, the interlaminar shear strength is 20.5MPa, the compressive strength is 580.4MPa, and the compressive modulus is 96.4 GPa; the tensile strength at 400 ℃ was 580.4MPa, the tensile modulus was 62.8GPa, the flexural strength was 350.2MPa, the flexural modulus was 50.2GPa, the interlaminar shear strength was 15.9MPa, the compressive strength was 204.1MPa, and the compressive modulus was 58.7 GPa.
Meanwhile, the preparation method provided by the invention has high production efficiency and is suitable for industrial mass production.
Detailed Description
The invention provides a preparation method of a phthalonitrile resin carbon fiber cloth composite material, which does not use an organic solvent and comprises the following steps:
(1) melting and mixing phthalonitrile resin and a curing agent, and then cooling and crushing to obtain mixed powder, wherein the temperature of melting and mixing is 180-190 ℃;
(2) dispersing the mixed powder on the surface of the carbon fiber cloth, and preheating to obtain mixed powder impregnated carbon fiber cloth; the preheating temperature is 180-200 ℃;
(3) and (3) laminating the multiple layers of the mixed powder impregnated carbon fiber cloth, and sequentially performing hot pressing and thermosetting to obtain the phthalonitrile resin carbon fiber cloth composite material.
The invention mixes phthalonitrile resin and firming agent, then cools and crushes them, obtains mixed powder. The invention has no special requirements on the type and source of the phthalonitrile resin, and can use the conventional phthalonitrile resin sold on the market in the field. In the invention, the curing agent is preferably one or more of 4, 4-diaminodiphenyl sulfone, ethylenediamine, hexamethylenediamine and maleic anhydride. In the invention, the mass ratio of the phthalonitrile resin to the curing agent is preferably 100-125: 4 to 10, preferably 105 to 120:5 to 8.
In the invention, the temperature of the melt mixing is 180-190 ℃, preferably 182-186 ℃, and the time is preferably 1-3.5 h, and more preferably 2-3 h. In the invention, the melt mixing is preferably carried out under the condition of stirring, and the stirring speed is preferably 200-300 rpm. The present invention does not require any particular cooling means, such as natural cooling, which is well known to those skilled in the art. The invention has no special requirements on the crushing mode, and the crushing mode known by the technicians in the field can be used; in the present invention, the particle diameter of the mixed powder obtained after the pulverization is preferably 1 to 2.5 μm, and more preferably 1.5 to 2 μm.
After the mixed powder is obtained, the mixed powder is dispersed on the surface of the carbon fiber cloth and preheated to obtain the mixed powder impregnated carbon fiber cloth. The invention has no special requirements on the type and specification of the carbon fiber cloth, and the carbon fiber cloth which is well known by the technicians in the field can be used; as a specific embodiment of the present invention, the specification of the carbon fiber cloth is 12K carbon fiber cloth.
In the invention, the mass ratio of the phthalonitrile resin to the carbon fiber cloth in the mixed powder is preferably (100-125): (100-150), more preferably (105-120): (120-140). In the invention, the dispersion amount of the mixed powder on the surface of the carbon fiber cloth is preferably 0.5-1.5 g/cm 3 More preferably 0.8 to 1.2g/cm 3 。
The present invention preferably performs the preheating in an oven. In the invention, the preheating temperature is preferably 180-200 ℃, and more preferably 185-195 ℃; the time is preferably 20-30 min, and more preferably 25 min. In the preheating process, the mixed powder is melted and impregnated into the carbon fiber cloth.
After the carbon fiber cloth is impregnated with the mixed powder, multiple layers of the carbon fiber cloth impregnated with the mixed powder are stacked, and hot pressing and thermosetting are sequentially carried out to obtain the phthalonitrile resin carbon fiber cloth composite material. In the present invention, the number of stacked layers of the mixed powder impregnated carbon fiber cloth is preferably 10 to 15, and more preferably 12 to 14.
The present invention preferably uses a press for the hot pressing. In the present invention, the hot pressing preferably includes a first gradient hot pressing and a second gradient hot pressing which are sequentially performed;
the first gradient hot pressing comprises the following steps: sequentially preserving heat for 10-15 min at the temperature of 180-200 ℃, boosting the pressure to 0.5-2 MPa, preserving heat and maintaining pressure for 5-15 min, boosting the pressure to 3-4.5 MPa, preserving heat and maintaining pressure for 5-15 min, and boosting the pressure to 5-6.5 MPa, preserving heat and maintaining pressure for 5-15 min; (pressure increasing rate of 0.1 to 0.25MPa/min, temperature increasing rate of 4 to 7 ℃/min)
The second gradient hot pressing comprises the following steps: boosting the pressure to 7-8.5 MPa, and keeping the pressure and heat at 180-185 ℃ for 5-7 h, raising the temperature to 190-195 ℃ for 5-7 h, and raising the temperature to 200-205 ℃ for 5-7 h under the condition of 7-8.5 MPa.
In the invention, in the first gradient hot pressing and the second gradient hot pressing, the boosting speed is preferably 0.1-0.25 MPa/min independently, and more preferably 0.15-0.2 MPa/min independently; the independent heating rate is preferably 4-7 ℃/min, and more preferably 5-6 ℃/min.
According to the invention, the carbon fiber cloth can be molded more uniformly through the hot pressing.
In the first hot pressing process, the mixed powder is soaked in the phthalonitrile resin in the carbon fiber cloth to be melted by keeping the temperature of 180-200 ℃ for 10-15 min. According to the invention, through gradient pressure boosting, air between the carbon fiber cloth can be fully discharged, and the porosity of the load material is reduced.
In the second hot pressing process, the composite material can be molded more uniformly by gradient temperature rise.
After the hot pressing is finished, the hot-pressed mixed powder impregnated carbon fiber cloth is preferably cooled. The cooling method is not particularly required by the invention, and the cooling method known to those skilled in the art can be used, such as natural cooling to room temperature.
The present invention preferably uses an oven for the thermal curing. In the invention, the temperature of the heat curing is preferably 200-230 ℃, and more preferably 210-220 ℃; the time is preferably 4-6 h, and more preferably 5 h. In the process of thermal curing, under the action of a curing agent, phthalonitrile resin dispersed on the surface and inside the carbon fiber cloth is cured, so that the phthalonitrile resin and the carbon fiber cloth are compounded.
In the invention, the phthalonitrile resin carbon fiber cloth composite material has low porosity, and the porosity is 5.2-7.6%.
The phthalonitrile resin carbon fiber cloth composite material and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Raw material dosage: 100 parts of phthalonitrile resin, 4 parts of 4, 4-diamino diphenyl sulfone curing agent and 100 parts of 12K carbon fiber cloth.
The preparation method of the phthalonitrile resin carbon fiber cloth composite material comprises the following steps:
(1) stirring phthalonitrile resin and a curing agent at 180 ℃ for 1h at the speed of 200rpm, carrying out melt mixing, then cooling, and crushing the cooled solid into mixed powder with the particle size of 1-2.5 mu m;
(2) dispersing the mixed powder on the surface of carbon fiber cloth, wherein the dispersion amount is 0.5g/cm 3 Preheating for 20min at 180 ℃ to obtain mixed powder impregnated carbon fiber cloth;
(3) laminating 12 layers of mixed powder impregnated carbon fiber cloth, placing into a press, standing at 180 ℃ for 15min, pressurizing at 2MPa, continuously preserving heat and maintaining pressure for 5min, exhausting air between the fiber cloth, pressurizing at 3MPa, continuously preserving heat and maintaining pressure for 5min, pressurizing at 4MPa, and continuously preserving heat and maintaining pressure for 5 min; then pressurizing to 6Mpa at 180 deg.C for 5h, 190 deg.C for 5h, 200 deg.C for 5h, and naturally cooling to room temperature;
(4) and (3) putting the hot-pressed product into an oven, and performing hot curing at 200 ℃ for 4h to obtain the phthalonitrile resin carbon fiber cloth composite material.
Example 2
Raw material dosage: 110 parts of phthalonitrile resin, 4.4 parts of ethylenediamine curing agent and 100 parts of 12K carbon fiber cloth.
The preparation method of the phthalonitrile resin carbon fiber cloth composite material comprises the following steps:
(1) stirring phthalonitrile resin and a curing agent at 190 ℃ at a speed of 250rpm for 2h, carrying out melt mixing, then cooling, and crushing the cooled solid into mixed powder with the particle size of 1-2.5 mu m;
(2) dispersing the mixed powder on the surface of the carbon fiber cloth, wherein the dispersion amount is 1.5g/cm 3 Preheating for 20min at 190 ℃ to obtain mixed powder impregnated carbon fiber cloth;
(3) laminating 10 layers of mixed powder impregnated carbon fiber cloth, placing into a press, standing at 190 deg.C for 10min, pressurizing at 2Mpa for 5min, discharging air between the fiber cloth, pressurizing at 3Mpa for 5min, and pressurizing at 4Mpa for 5 min; then pressurizing under 6Mpa at 180 deg.C for 5 hr, 190 deg.C for 5 hr, 200 deg.C for 5 hr, and naturally cooling to room temperature;
(4) and (3) putting the hot-pressed product into an oven, and performing hot curing at 220 ℃ for 4h to obtain the phthalonitrile resin carbon fiber cloth composite material.
Example 3
Raw material dosage: 125 parts of phthalonitrile resin, 5 parts of 4, 4-diamino diphenyl sulfone curing agent and 100 parts of 12K carbon fiber cloth.
The preparation method of the phthalonitrile resin carbon fiber cloth composite material comprises the following steps:
(1) stirring phthalonitrile resin and a curing agent at 190 ℃ at a speed of 300rpm for 2.5h, carrying out melt mixing, then cooling, and crushing the cooled solid into mixed powder with the particle size of 1-2.5 mu m;
(2) dispersing the mixed powder on the surface of the carbon fiber cloth, wherein the dispersion amount is 1.0g/cm 3 Preheating for 30min at 200 ℃ to obtain mixed powder impregnated carbon fiber cloth;
(3) laminating 8 layers of mixed powder impregnated carbon fiber cloth, placing into a press, standing at 200 deg.C for 15min, pressurizing at 2MPa for 5min, discharging air between the fiber cloth, pressurizing at 3MPa for 5min, and pressurizing at 4MPa for 5 min; then pressurizing to 6Mpa at 180 deg.C for 5h, 190 deg.C for 5h, 200 deg.C for 5h, and naturally cooling to room temperature;
(4) and (3) putting the hot-pressed product into an oven, and performing hot curing at 220 ℃ for 4h to obtain the phthalonitrile resin carbon fiber cloth composite material.
Performance testing
The phthalonitrile resin carbon fiber cloth composite materials obtained in examples 1 to 3 were tested for tensile strength, tensile modulus, flexural strength, flexural modulus, interlaminar shear strength, compressive strength, and compressive modulus at room temperature and 400 ℃, and the results are shown in table 1.
In the invention, the tensile strength and the tensile modulus are tested by a universal testing machine; the bending strength and the bending modulus are tested by adopting a three-point bending test; the interlaminar shear strength, the compressive strength and the compressive modulus are tested by a compression test method.
TABLE 1 mechanical Properties of the composites obtained in examples 1 to 3
As can be seen from Table 1, the phthalonitrile resin carbon fiber cloth composite material obtained by the invention has good mechanical properties at room temperature and high temperature.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A preparation method of a phthalonitrile resin carbon fiber cloth composite material does not use an organic solvent and comprises the following steps:
(1) melting and mixing phthalonitrile resin and a curing agent, and then cooling and crushing to obtain mixed powder, wherein the temperature of melting and mixing is 180-190 ℃;
the curing agent is one or more of 4, 4-diaminodiphenyl sulfone, ethylenediamine, hexamethylenediamine and maleic anhydride;
(2) dispersing the mixed powder on the surface of the carbon fiber cloth, and preheating to obtain mixed powder impregnated carbon fiber cloth; the preheating temperature is 180-200 ℃;
(3) laminating a plurality of layers of mixed powder impregnated carbon fiber cloth, and sequentially performing hot pressing and thermosetting to obtain a phthalonitrile resin carbon fiber cloth composite material;
the hot pressing comprises: sequentially carrying out first gradient hot pressing and second gradient hot pressing;
the first gradient hot pressing comprises the following steps: sequentially preserving heat for 10-15 min, boosting pressure to 0.5-2 MPa, preserving heat and maintaining pressure for 5-15 min, boosting pressure to 3-4.5 MPa, preserving heat and maintaining pressure for 5-15 min, and boosting pressure to 5-6.5 MPa, preserving heat and maintaining pressure for 5-15 min at the temperature of 180-200 ℃;
the second gradient hot pressing comprises the following steps: boosting the pressure to 7-8.5 MPa, and keeping the pressure and heat at 180-185 ℃ for 5-7 h, raising the temperature to 190-195 ℃ for 5-7 h, and raising the temperature to 200-205 ℃ for 5-7 h under the condition of 7-8.5 MPa.
2. The preparation method according to claim 1, wherein the mass ratio of the phthalonitrile resin to the curing agent is 100 to 125: 4 to 10.
3. The preparation method according to claim 1, wherein the time for melt mixing in the step (1) is 1 to 3.5 hours.
4. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the phthalonitrile resin in the mixed powder to the carbon fiber cloth is 100-125: 100 to 150.
5. The method according to claim 1 or 4, wherein the amount of the mixed powder dispersed in the mixed powder-impregnated carbon fiber cloth obtained in the step (2) is 0.5 to 1.5g/cm 3 。
6. The method according to claim 1, wherein the preheating time in the step (2) is 20 to 30 min.
7. The method according to claim 1, wherein the number of the layers of the mixed powder impregnated carbon fiber cloth in the step (3) is 10 to 15.
8. The preparation method according to claim 1, wherein the temperature of the thermosetting in the step (3) is 200-230 ℃ and the time is 4-6 h.
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| CN113211828A (en) | 2021-08-06 |
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