CN104277418A - Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof - Google Patents
Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN104277418A CN104277418A CN201310285772.XA CN201310285772A CN104277418A CN 104277418 A CN104277418 A CN 104277418A CN 201310285772 A CN201310285772 A CN 201310285772A CN 104277418 A CN104277418 A CN 104277418A
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Abstract
The invention belongs to the technical field of high polymer composite materials and relates to a carbon fiber reinforced toughened epoxy resin composite material and its preparation method. The high polymer material is prepared from the following components, by weight, 100 parts of epoxy resin, 8-120 parts of a curing agent, 0.5-1.5 parts of a promoter, 160-500 parts of carbon fiber and 5-55 parts of thermoplastic. According to the invention, engineering thermoplastic is selected as a flexibilizer, and an appropriate solvent is selected; the engineering thermoplastic is made into a solution, and the solution is uniformly mixed with epoxy resin, the curing agent and the promoter; the solvent is removed; the resin system with the solvent removed is made into a resin film; by a routine resin film melt impregnation method, the resin film and carbon fiber undergo hot melting to be combined so as to prepare a carbon fiber reinforced epoxy resin prepreg; and furthermore, the highly-toughened carbon fiber reinforced toughened epoxy resin composite material is prepared.
Description
Technical field
The invention belongs to technical field of polymer composite materials, relate to a kind of carbon-fibre reinforced epoxy resin composite material and preparation method thereof.
Background technology
Carbon-fibre reinforced epoxy resin composite material take epoxy resin as matrix, and carbon fiber is the high performance composite of reinforcement, is mainly used in the fields such as space flight and aviation, traffic, medical treatment, the energy and Leisure Sport.Along with the continuous progress of the science and technology such as space flight and aviation, carbon-fibre reinforced epoxy resin composite material is subject to people's attention day by day, but the poor weakness of impelling strength also have impact on its widespread use.Therefore, epoxy resin-base and matrix material thereof are more and more towards the future development of high-ductility.
General purpose epoxy resin is more crisp after solidifying, impact toughness, bending strength and resistance toheat are poor, and the toughness reinforcing of epoxy resin-base mainly contains the rubber toughened and toughness reinforcing two kinds of methods of thermoplastic engineering plastic.Rubber toughened the most frequently used be fluid rubber, rubber participates in the curing reaction of epoxy resin directly by its active end group, and can form tridimensional network with epoxy systems, thus plays toughness reinforcing effect.Because the glass epoxy temperature of modified rubber is lower, especially for obtain better toughness and breaking tenacity and improve rubber content time, this phenomenon is particularly remarkable, toughness reinforcing for realizing epoxy resin cure under the prerequisite not reducing mechanical property and thermal characteristics, develop again thermoplastics that is high by thermotolerance and good mechanical properties in recent years epoxy resin toughened.
The toughness reinforcing high performance epoxy resin of thermoplastic engineering plastic of high tenacity and high heat resistance is the direction of current industrialization development, but thermoplastic engineering plastic adds resin system viscosity increases severely and cause forming process difficulty, and dispersiveness is also poor; Because thermoplastic engineering plastic melt temperature is higher, not good enough with the consistency of epoxy resin again, the direct interlayer carbon-fibre reinforced epoxy resin composite material of usual employing thermoplastic engineering plastic particle, or first thermoplastics and epoxy resin hot melt are dissolved, prepare matrix material with carbon fiber again, but these technical matters are complicated, efficiency is low, poor effect, also also exists larger gap with industrialized practical application.Therefore, developing epoxy resin and the novel method of composite material toughening thereof, be adapt to China's carbon-fibre reinforced epoxy resin composite material development in the urgent need to.
In order to give full play to the toughening effect of thermoplastic engineering plastic to carbon-fibre reinforced epoxy resin composite material, this patent is first by thermoplastic engineering plastic wiring solution-forming, again epoxy-resin systems is mixed with it, stir, and then solvent is sloughed, again the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and carbon fiber thermal cladding are closed, prepare carbon-fibre reinforced epoxy resin prepreg, and then prepare carbon-fibre reinforced epoxy resin composite material.
Summary of the invention
Object of the present invention is exactly provide a kind of fibre reinforced tough epoxy resin composite materials and preparation method thereof to overcome defect that the existing toughening technology of above-mentioned carbon-fibre reinforced epoxy resin composite material exists.
For achieving the above object, the present invention is by the following technical solutions:
Thermoplastic engineering plastic is have selected as toughner in the present invention, select suitable solvent, thermoplastic engineering plastic is mixed with solution, mix with epoxy resin, solidifying agent and promotor again, then desolvation, then the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and carbon fiber thermal cladding are closed, prepares carbon-fibre reinforced epoxy resin prepreg, and then prepare carbon-fibre reinforced epoxy resin composite material.
A kind of fibre reinforced tough epoxy resin composite materials, is characterized in that: be made up of the component comprising following weight part:
Epoxy resin 100 parts,
8 ~ 120 parts, solidifying agent,
Promotor 0 ~ 1.5 part,
Thermoplastics 5 ~ 55 parts,
160 ~ 500 parts, carbon fiber.
Described epoxy resin is diglycidyl ether type, glycidyl ester type or glycidyl amine type epoxy resin, one or more in preferred AG-80, AFG-90, E-20, E-31, E-44, E-51, F-44, F-46, F-51 or TDE-85.
Described solidifying agent is amine curing agent or acid anhydride type curing agent, preferred Dyhard RU 100, Boron Trifluoride Ethylamine, mphenylenediamine, diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone(DDS)s, methylnadic anhydride, dodecyl succinic anhydride or methylhexahydrophthalic anhydride.
Described promotor is imidazoles or quaternary ammonium salt promotor, preferred glyoxal ethyline, 2-ethyl-4-methylimidazole or benzyltriethylammoinium chloride, its parts by weight preferably 0.5 ~ 1.5 part.
Described thermoplastics is thermoplastic engineering plastic, preferred, polyethers imide (PEI), polysulfones (PSF), polyethersulfone (PES), polyether-ether-ketone (PEEK) or polyetherketone (PEK).
Described carbon fiber is Unidirectional fiber or carbon fibre fabric.
A preparation method for above-mentioned fibre reinforced tough epoxy resin composite materials, comprises the following steps:
(1) 5 ~ 55 parts of thermoplasticss are dissolved in a solvent, be made into thermoplastics solution, then 100 parts of epoxy resin, 8 ~ 120 parts of solidifying agent and 0.5 ~ 1.5 part of promotor added above-mentioned solution, and mix;
(2) solution in (1) is removed desolventizing at a certain temperature, again the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 160 ~ 500 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, in certain temperature, cure under pressure reaction;
(4) matrix material plate temperature above-mentioned steps (3) be cured drops to room temperature, the demoulding colding pressing, then composite panel cutting that will be obtained, surveys its mechanical property.
In described step (1), solvent is selected from N,N-dimethylacetamide, DMF or METHYLPYRROLIDONE.
In described step (1), the concentration of thermoplastics is 0.5 ~ 10wt%.
Desolventizing condition in described step (2): first desolventize 15 ~ 30min under 120 ~ 140 DEG C of normal pressures, then desolventize 10 ~ 20min under 120 ~ 140 DEG C of vacuum.
Hot-press solidifying condition in described step (3) is: solidification value is 120 ~ 180 DEG C, and set time is 4h ~ 10h, and pressure is 0.5 ~ 5MPa.
In described step (4), the condition of colding pressing is: cold pressing pressure 3 ~ 6MPa, and cold pressing time 10 ~ 30min.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the glass epoxy temperature due to modified rubber is lower, especially for obtain better toughness and breaking tenacity and improve rubber content time, this phenomenon is particularly remarkable, select the thermoplastic engineering plastic of high tenacity and high heat resistance epoxy resin toughened in this patent, can not reduce or less reduction mechanical property and thermal characteristics prerequisite under to realize epoxy resin cure toughness reinforcing.
(2) thermoplastic engineering plastic adds the sharp increase of resin system viscosity and causes forming process difficulty, and dispersiveness is also poor, this patent selects suitable solvent, thermoplastic engineering plastic is mixed with solution, again with epoxy resin, solidifying agent and promotor mix, then desolvation, again the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and carbon fiber thermal cladding are closed, prepare carbon-fibre reinforced epoxy resin prepreg, and then prepare carbon-fibre reinforced epoxy resin composite material, not only reduce thermoplastic engineering plastic and epoxy-resin systems hot melt dissolution process, reduce energy consumption, and high toughness reinforcing carbon-fibre reinforced epoxy resin composite material can be obtained.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, and wherein the test of carbon-fibre reinforced epoxy resin composite material bending property is with reference to GB3356-1999, adopts short strutbeam 3 loading, sample thickness is 2mm, width is 12.5mm, is 32:1 across thickness rate, and loading velocity is 5mm/min; Interlaminar shear strengths testing method is with reference to JC/T773-96, and sample thickness is 2mm, and width is 6mm, and loading velocity is 2mm/min; Interlaminar fracture toughness test is with reference to HB7402-96 standard, and loading velocity is 2mm/min.
Embodiment 1
(1) 5 parts of thermoplastic engineering plastics polyetherketone (PEK) are dissolved in N, in dinethylformamide solvent, be made into 0.5wt% solution, then 55 parts of epoxy resin E-44s, 20 parts of epoxy resin F-44,25 parts of epoxy resin E-20,8 parts of curing agent dicyandiamides and 0.5 part of promotor glyoxal ethyline are added above-mentioned solution, and mix;
(2) solution in (1) is desolventized 15min under 120 DEG C of normal pressures, 10min is desolventized again under 120 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 160 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 120 DEG C/2h/0.5MPa+160 DEG C/2h/2.75MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 3MPa/10min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 2
(1) 8 parts of thermoplastic engineering plastics polyetherimide (PEI) are dissolved in N, in N-dimethylacetamide solvent, be made into 1.0wt% solution, then 60 parts of epoxy resin E-31,15 parts of epoxy resin E-51,25 parts of epoxy resin F-51 and 22.2 part of solidifying agent Boron Trifluoride Ethylamines are added above-mentioned solution, and mix;
(2) solution in (1) is desolventized 20min under certain 130 DEG C of normal pressures, 15min is desolventized again under 130 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 227 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 130 DEG C/2h/0.5MPa+170 DEG C/2h/3.0MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 4MPa/15min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 3
(1) 12 parts of thermoplastic engineering plastics polysulfones (PSF) are dissolved in METHYLPYRROLIDONE solvent, be made into 2.0wt% solution, then 50 parts of epoxy resin E-51,50 parts of epoxy resin E-20 and 22.2 part solidifying agent 4,4'-diaminodiphenylsulfone(DDS)s are added above-mentioned solution, and mix;
(2) solution in (1) is desolventized 30min under 140 DEG C of normal pressures, 20min is desolventized again under 140 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 226 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 140 DEG C/2h/0.5MPa+160 DEG C/2h/4MPa+180 DEG C/2h/4MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 4.5MPa/20min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 4
(1) 22 parts of thermoplastic engineering plastics polyethersulfone (PES) are dissolved in METHYLPYRROLIDONE solvent, be made into 3.0wt% solution, then 70 parts of epoxy resin E-20,30 parts of epoxy resin TDE-85,64 parts of solidifying agent methylnadic anhydride and 0.75 part of promotor benzyltriethylammoinium chloride are added above-mentioned solution, and mix;
(2) solution in (1) is desolventized 22.5min under 120 DEG C of normal pressures, 15min is desolventized again under 120 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 330 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 120 DEG C/2h/0.5MPa+160 DEG C/2h/3MPa+180 DEG C/1h/5MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 5MPa/25min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 5
(1) 30 parts of thermoplastic engineering plastics polyether-ether-ketone (PEEK) are dissolved in N, in dinethylformamide solvent, be made into 4.0wt% solution, then 90 parts of epoxy resin TDE-85,10 parts of epoxy resin AG-80,22.8 parts of solidifying agent phenylenediamines added above-mentioned solution, and mix;
(2) solution in (1) is desolventized 22.5min under 120 DEG C of normal pressures, 15min is desolventized again under 120 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 228 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 120 DEG C/2h/0.5MPa+140 DEG C/2h/1.5MPa+160 DEG C/2h/3MPa+180 DEG C/4h/5MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 5MPa/30min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 6
(1) 32 parts of thermoplastic engineering plastics polyetherimide (PEI) are dissolved in N, in N-dimethylacetamide solvent, be made into 5.25wt% solution, then 35 parts of epoxy resin E-51,65 parts of epoxy resin E-20,52 parts of solidifying agent methylhexahydrophthalic anhydrides and 1.5 parts of promotor 2-ethyl-4-methylimidazoles are added above-mentioned solution, and mix;
(2) solution in (1) is desolventized 20min under 130 DEG C of normal pressures, 20min is desolventized again under 130 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 285 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 130 DEG C/3h/0.5MPa+170 DEG C/4h/3.0MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 3.0MPa/15min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 7
(1) 34 parts of thermoplastic engineering plastics polysulfones (PSF) are dissolved in N, in dinethylformamide solvent, be made into 6.5wt% solution, then 80 parts of epoxy resin TDE-85,20 parts of epoxy resin E-51,38.8 parts of solidifying agent diaminodiphenylmethane added above-mentioned solution, and mix;
(2) solution in (1) is desolventized 15min under 140 DEG C of normal pressures, 15min is desolventized again under 140 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 258 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 140 DEG C/3h/0.5MPa+180 DEG C/6h/4.0MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 4.0MPa/20min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 8
(1) 55 parts of thermoplastic engineering plastics polyethersulfone (PES) are dissolved in N, in dinethylformamide solvent, be made into 8.0wt% solution, then 100 parts of epoxy resin F-46,120 parts of solidifying agent dodecyl succinic anhydrides and 1.0 parts of promotor 2-ethyl-4-methylimidazoles are added above-mentioned solution, and mix;
(2) solution in (1) is desolventized 30min under 130 DEG C of normal pressures, 10min is desolventized again under 130 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 500 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 130 DEG C/2h/0.5MPa+150 DEG C/2h/2.0MPa+180 DEG C/2h/4.0MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 4.0MPa/20min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 9
(1) 35 parts of thermoplastic engineering plastics polyetherimide (PEI) are dissolved in N, in N-dimethylacetamide solvent, be made into 10.0wt% solution, then 70 parts of epoxy resin TDE-85,30 parts of epoxy resin AGF-90,42.8 parts of solidifying agent diaminodiphenylmethane are added above-mentioned solution, and mix;
(2) solution in (1) is desolventized 20min under 140 DEG C of normal pressures, 15min is desolventized again under 140 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 333 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 140 DEG C/2h/0.5MPa+160 DEG C/2h/2.0MPa+180 DEG C/2h/4.0MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 4.0MPa/20min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 10
(1) 6 parts of thermoplastic engineering plastics polyetherimide (PEI) are dissolved in METHYLPYRROLIDONE solvent, be made into 5.0wt% solution, then by 50 parts of epoxy resin E-51,50 parts of epoxy resin E-20 and 22.2 part solidifying agent 4,4'-diaminodiphenylsulfone(DDS) adds above-mentioned solution, and mixes;
(2) solution in (1) is desolventized 30min under 140 DEG C of normal pressures, 20min is desolventized again under 140 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 226 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 140 DEG C/2h/0.5MPa+160 DEG C/2h/4MPa+180 DEG C/2h/4MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 4.5MPa/20min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 11
(1) 18 parts of thermoplastic engineering plastics polyetherimide (PEI) are dissolved in METHYLPYRROLIDONE solvent, be made into 5.0wt% solution, then by 50 parts of epoxy resin E-51,50 parts of epoxy resin E-20 and 22.2 part solidifying agent 4,4'-diaminodiphenylsulfone(DDS) adds above-mentioned solution, and mixes;
(2) solution in (1) is desolventized 30min under 140 DEG C of normal pressures, 20min is desolventized again under 140 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 226 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 140 DEG C/2h/0.5MPa+160 DEG C/2h/4MPa+180 DEG C/2h/4MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 4.5MPa/20min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Embodiment 12
(1) 30 parts of thermoplastic engineering plastics polyetherimide (PEI) are dissolved in METHYLPYRROLIDONE solvent, be made into 5.0wt% solution, then by 50 parts of epoxy resin E-51,50 parts of epoxy resin E-20 and 22.2 part solidifying agent 4,4'-diaminodiphenylsulfone(DDS) adds above-mentioned solution, and mixes;
(2) solution in (1) is desolventized 30min under 140 DEG C of normal pressures, 20min is desolventized again under 140 DEG C of vacuum, the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 226 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, curing reaction under 140 DEG C/2h/0.5MPa+160 DEG C/2h/4MPa+180 DEG C/2h/4MPa;
(4) the matrix material plate temperature that above-mentioned steps (3) is cured is dropped to room temperature at 4.5MPa/20min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Comparative example
(1) by 50 parts of epoxy resin E-51,50 parts of epoxy resin E-20 and 22.2 part solidifying agent 4,4'-diaminodiphenylsulfone(DDS) is 140 DEG C of stirrings, mix, deaeration 20min under 140 DEG C of vacuum again, resin system after deaeration is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 226 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(2) according to material desired size, by the prepreg cutting in (1), lamination laying, puts into mould, curing reaction under 140 DEG C/2h/0.5MPa+160 DEG C/2h/4MPa+180 DEG C/2h/4MPa;
(3) the matrix material plate temperature that above-mentioned steps (2) is cured is dropped to room temperature at 4.5MPa/20min, the demoulding, then by obtained composite panel cutting, survey its mechanical property, as shown in table 1.
Table 1
| Performance | Flexural strength (MPa) | Modulus in flexure (MPa) | Interlaminar shear strength (MPa) | Interlaminar fracture toughness (kJ/m 2） |
| Embodiment 1 | 1205 | 109.1 | 73.0 | 0.49 |
| Embodiment 2 | 1078 | 106.7 | 70.4 | 0.53 |
| Embodiment 3 | 1355 | 111.8 | 78.7 | 0.78 |
| Embodiment 4 | 1250 | 109.4 | 74.1 | 0.86 |
| Embodiment 5 | 1586 | 115.1 | 83.5 | 1.22 |
| Embodiment 6 | 1123 | 108.6 | 71.2 | 0.64 |
| Embodiment 7 | 1489 | 114.5 | 81.5 | 1.13 |
| Embodiment 8 | 1200 | 108.8 | 72.2 | 0.66 |
| Embodiment 9 | 1620 | 116.2 | 85.2 | 1.35 |
| Embodiment 10 | 1402 | 112.5 | 80.3 | 0.62 |
| Embodiment 11 | 1311 | 109 | 77.0 | 1.07 |
| Embodiment 12 | 1215 | 106.5 | 74.6 | 1.18 |
| Comparative example | 1448 | 113.1 | 81.8 | 0.45 |
Embodiment 1 ~ 9 as can be seen from table 1, select thermoplastic engineering plastic as the toughner of epoxy resin, the carbon-fibre reinforced epoxy resin composite material of preparation has higher interlaminar shear strength and interlaminar fracture toughness.Can draw from embodiment 10 ~ 12 and comparative example, adding of thermoplastic engineering plastic, serve toughening effect, greatly enhance interlaminar shear strength and the interlaminar fracture toughness of carbon-fibre reinforced epoxy resin composite material, illustrate that thermoplastics type's engineering plastics have good toughening effect to carbon-fibre reinforced epoxy resin composite material, serve high toughness reinforcing effect.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. a fibre reinforced tough epoxy resin composite materials, is characterized in that: be made up of the component comprising following weight part:
Epoxy resin 100 parts,
8 ~ 120 parts, solidifying agent,
Promotor 0 ~ 1.5 part,
Thermoplastics 5 ~ 55 parts,
160 ~ 500 parts, carbon fiber.
2. fibre reinforced tough epoxy resin composite materials according to claim 1, it is characterized in that: described epoxy resin is diglycidyl ether type, glycidyl ester type or glycidyl amine type epoxy resin, one or more in preferred AG-80, AFG-90, E-20, E-31, E-44, E-51, F-44, F-46, F-51 and TDE-85.
3. fibre reinforced tough epoxy resin composite materials according to claim 1, it is characterized in that: described solidifying agent is amine curing agent or acid anhydride type curing agent, preferred Dyhard RU 100, Boron Trifluoride Ethylamine, mphenylenediamine, diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone(DDS)s, methylnadic anhydride, dodecyl succinic anhydride or methylhexahydrophthalic anhydride.
4. fibre reinforced tough epoxy resin composite materials according to claim 1, is characterized in that: described promotor is imidazoles or quaternary ammonium salt promotor, preferred glyoxal ethyline, 2-ethyl-4-methylimidazole or benzyltriethylammoinium chloride;
Or the weight part of promotor is 0.5 ~ 1.5 part.
5. fibre reinforced tough epoxy resin composite materials according to claim 1, is characterized in that: described thermoplastics is thermoplastic engineering plastic, preferred, polyethers imide, polysulfones, polyethersulfone, polyether-ether-ketone or polyetherketone.
6. fibre reinforced tough epoxy resin composite materials according to claim 1, is characterized in that: described carbon fiber is Unidirectional fiber or carbon fibre fabric.
7. a preparation method for fibre reinforced tough epoxy resin composite materials described in any one of claim 1 ~ 6, is characterized in that: comprise the following steps:
(1) 5 ~ 55 parts of thermoplasticss are dissolved in a solvent, be made into thermoplastics solution, then 100 parts of epoxy resin, 8 ~ 120 parts of solidifying agent and 0.5 ~ 1.5 part of promotor added above-mentioned solution, and mix;
(2) solution in (1) is removed desolventizing at a certain temperature, again the resin system eliminating solvent is prepared into resin molding, adopt routine techniques resin molding melt impregnation, resin molding and 160 ~ 500 parts of carbon fiber thermal claddings are closed, prepares carbon-fibre reinforced epoxy resin prepreg;
(3) according to material desired size, by the prepreg cutting in (2), lamination laying, puts into mould, in certain temperature, cure under pressure reaction;
(4) matrix material plate temperature above-mentioned steps (3) be cured drops to room temperature, the demoulding colding pressing, then composite panel cutting that will be obtained, surveys its mechanical property.
8. the preparation method of fibre reinforced tough epoxy resin composite materials according to claim 7, is characterized in that: in described step (1), solvent is selected from N,N-dimethylacetamide, DMF or METHYLPYRROLIDONE;
Or the concentration of thermoplastics is 0.5 ~ 10wt% in described step (1).
9. the preparation method of carbon-fibre reinforced epoxy resin composite material according to claim 7, it is characterized in that: desolventizing condition in described step (2): first under 120 ~ 140 DEG C of normal pressures, desolventize 15 ~ 30min, then desolventize 10 ~ 20min under 120 ~ 140 DEG C of vacuum.
10. the preparation method of fibre reinforced tough epoxy resin composite materials according to claim 7, it is characterized in that: the hot-press solidifying condition in described step (3) is: solidification value is 120 ~ 180 DEG C, set time is 4h ~ 10h, and pressure is 0.5 ~ 5MPa;
Or the condition of colding pressing is in described step (4): cold pressing pressure 3 ~ 6MPa, cold pressing time 10 ~ 30min.
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| CN104610529A (en) * | 2015-02-04 | 2015-05-13 | 广东博汇新材料科技有限公司 | Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade |
| CN105131255A (en) * | 2015-09-30 | 2015-12-09 | 西安超码复合材料有限公司 | High-temperature-resistant resin |
| CN105694372A (en) * | 2016-04-15 | 2016-06-22 | 湖州新奥克化工有限公司 | Carbon fiber reinforced epoxy resin composite and preparation method thereof |
| CN105733193A (en) * | 2016-03-23 | 2016-07-06 | 航天材料及工艺研究所 | Preparation method of epoxy resin based composite material with controllable toughness |
| CN105778428A (en) * | 2016-03-24 | 2016-07-20 | 湖州新奥克化工有限公司 | Epoxy resin-carbon fiber composite material and manufacturing method thereof |
| CN105820513A (en) * | 2016-05-27 | 2016-08-03 | 江苏兆鋆新材料股份有限公司 | High-temperature-resistant cured epoxy resin carbon fiber prepreg and preparing method and application thereof |
| CN105885357A (en) * | 2016-06-28 | 2016-08-24 | 周易 | Heterogeneous toughened resin, carbon fiber prepreg and carbon fiber composite material |
| CN105885358A (en) * | 2016-06-29 | 2016-08-24 | 西安超码复合材料有限公司 | Halogen-free high temperature resistant resin |
| CN105968731A (en) * | 2016-05-27 | 2016-09-28 | 江苏兆鋆新材料股份有限公司 | Low-temperature curing epoxy resin carbon fiber prepreg and preparing method thereof |
| CN106009531A (en) * | 2016-05-20 | 2016-10-12 | 江苏兆鋆新材料股份有限公司 | Method for preparing high-rigidity high-modulus carbon fiber prepreg |
| CN106046780A (en) * | 2016-06-03 | 2016-10-26 | 中蓝晨光化工研究设计院有限公司 | Bulletproofing material with thermoset epoxy resin and preparation method thereof |
| CN106317767A (en) * | 2016-08-22 | 2017-01-11 | 苏州聚冠复合材料有限公司 | Preparation method of ultrahigh-conductivity 3D printing carbon fiber composite wire |
| CN106496941A (en) * | 2016-11-04 | 2017-03-15 | 江苏澳盛复合材料科技有限公司 | One kind can repairing type carbon cloth reinforced epoxy sheet material and its preparation, restorative procedure |
| CN106832752A (en) * | 2017-01-05 | 2017-06-13 | 厦门复晟复合材料有限公司 | A kind of carbon fiber epoxy prepreg |
| CN106883556A (en) * | 2017-03-21 | 2017-06-23 | 常州翔诺新材料科技有限公司 | A kind of recycled plastic regenerated fiber cooperates with reinforced epoxy composite and preparation method thereof with glass fibre |
| CN109575334A (en) * | 2018-11-27 | 2019-04-05 | 哈尔滨工业大学 | A kind of shape memory epoxy resin prepreg and preparation method thereof |
| CN109836775A (en) * | 2017-11-29 | 2019-06-04 | 中国航空工业集团公司济南特种结构研究所 | Preparation method suitable for Laser Direct Deposition technology epoxy resin-matrix prepreg |
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| CN113861619A (en) * | 2021-08-27 | 2021-12-31 | 航天材料及工艺研究所 | Liquid oxygen leakage prevention composite material and preparation method thereof |
| CN114702831A (en) * | 2022-03-23 | 2022-07-05 | 株洲中铁电气物资有限公司 | Modified resin composite material, preparation method thereof and cable support |
| CN115260704A (en) * | 2022-08-10 | 2022-11-01 | 重庆科技学院 | Carbon fiber reinforced epoxy resin composite material and preparation method thereof |
| CN115418079A (en) * | 2021-11-09 | 2022-12-02 | 中国科学院山西煤炭化学研究所 | Tough epoxy resin system and preparation method and application thereof |
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| CN104610529A (en) * | 2015-02-04 | 2015-05-13 | 广东博汇新材料科技有限公司 | Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade |
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| CN105885358A (en) * | 2016-06-29 | 2016-08-24 | 西安超码复合材料有限公司 | Halogen-free high temperature resistant resin |
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| CN109575334A (en) * | 2018-11-27 | 2019-04-05 | 哈尔滨工业大学 | A kind of shape memory epoxy resin prepreg and preparation method thereof |
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