CN105061995A - Carbon fiber/epoxy resin prepreg and preparation method thereof - Google Patents
Carbon fiber/epoxy resin prepreg and preparation method thereof Download PDFInfo
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- CN105061995A CN105061995A CN201510456879.5A CN201510456879A CN105061995A CN 105061995 A CN105061995 A CN 105061995A CN 201510456879 A CN201510456879 A CN 201510456879A CN 105061995 A CN105061995 A CN 105061995A
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Abstract
The invention discloses a carbon fiber/epoxy resin unidirectional prepreg. The prepreg is obtained by dipping modified carbon fiber filament bundles in gum and then winding the filament bundles and arraying the filaments by a filament arraying machine. The prepreg is composed of the following components in percentage by weight: 0.8 to 2.9% of zinc oxide, 0.1 to 0.2% of C6H5NHCH2Si(OCH2CH3)3 or NH2(CH2CH2NH)2(CH2)3(OCH3)3, 50 to 55% of un-sized polyacrylonitrile-based carbon fiber filament without ditches on the surface, 25 to 35% of AG-80 epoxy resin or ZEP-001 epoxy resin, 8 to 10% of 4,4'-diaminodiphenyl ether or 4,4'-diaminodiphenyl methane, and 4 to 8% of carbon fiber enhanced bismaleimide composite material powder. The carbon fiber is un-sized, the interference binding strength between the carbon fiber and resin is improved, and the inter-laminar toughness of the composite material is also improved.
Description
Technical field
The invention belongs to a kind of carbon fiber/epoxy resin prepreg and method for making thereof.
Technical background
Carbon-fibre composite, because of its outstanding mechanical property, is widely used in high-tech sector.Along with going deep into gradually of studying carbon-fibre composite, investigators find that the performance of matrix material is not only limited to each constituent materials and complete processing, are also subject to processing the impact of prepreg quality in process simultaneously.
Prepreg is intermediates important during matrix material is produced, and the quality of prepreg quality directly affects the overall performance of matrix material.It is generally directly adopt commercially available carbon fiber and resin that carbon fiber prepreg is produced, and adds certain properties-correcting agent, improve the quality of prepreg with this by optimization processing technology and later stage.But, carbon fiber needs to carry out starching process in last procedure produced, to increase the workability of carbon fiber, as convergency, wear resistance and fibrillation expanding etc., also there is material impact to the interface bond strength between carbon fiber and resin in the kind of sizing agent used simultaneously.In general, for obtaining the high interfacial bonding strength between carbon fiber and resin, need to adopt the resin identical or close with matrix resin chemical structure as sizing agent major constituent.In practical application, because resin types is various, and carbon fiber cannot predict the resin types that the later stage matches in the process of dispatching from the factory, and therefore sizing agent used can only based on the maximum epoxy resin of current usage quantity.But epoxy resin also exists different structures, therefore directly adopt commercially available carbon fiber to there is the problem that matching is limited between resin used unavoidably, limit the quality of prepreg to a certain extent.
On the other hand, because after epoxy resin solidification itself, molecular chain forms cancellated cause, there is the defect of interlaminal toughness difference in traditional carbon fiber/epoxy resin prepreg.Conventional modification mode is nano-particle toughening, and Mitsubishi Li Yang Co., Ltd. (Chinese invention patent application 201210376448.4) discloses a kind of method at least one side surface attachment of carbon fiber prepreg carborundum particle, aluminium oxide particles or kaolin particle.But, adopt the method after prepreg is prepared into matrix material, the nanoparticle of interpolation is only present in interlayer, cannot be dispersed in resin matrix, the nanoparticle that interlayer local exists is easy to produce stress concentration in loading process, reduces the mechanical property of matrix material.
The above analysis, one is needed neither to need carbon fiber starching, interface bond strength between carbon fiber and resin can be improved again, the carbon fiber/epoxy resin prepreg of matrix material interlayer toughness can also be improved, thus obtain the carbon-fibre reinforced epoxy resin composite material of high-quality.
Summary of the invention
The object of this invention is to provide one both without carbon fiber starching, interface bond strength between carbon fiber and resin can be improved again, carbon fiber/epoxy resin prepreg and the preparation method of matrix material interlayer toughness can also be improved.
Carbon fiber/epoxy resin prepreg of the present invention is unidirectional pre-immersion material, and obtain by being wound around row's silk by row's silk machine after the carbon fibre tow impregnation of modification, each component quality group becomes:
Zinc oxide 0.8%-2.9%;
C
6h
5nHCH
2si (OCH
2cH
3)
3or NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
30.1%-0.2%;
Non-starching and surface are without the PAN-based carbon fiber long filament 50%-55% of groove structure;
AG-80 epoxy resin or ZEP-001 epoxy resin 25%-35%;
4,4 '-diaminodiphenyl oxide or 4,4 '-diaminodiphenylmethane 8%-10%;
Carbon fiber reinforced bismalemide matrix material powder 4%-8%.
Zinc oxide as above is nano wire form, and diameter is 80 to 120 nanometers.
Non-starching as above and surface are without the PAN-based carbon fiber long filament of groove structure, and PAN-based carbon fiber prepared by employing dry-jet wet spinning process, carbon fiber length is not less than 20 centimetres.
Carbon fiber reinforced bismalemide matrix material powder as above is ground by the waste and old carbon fiber reinforced bismalemide matrix material reclaimed to obtain, the value of the D50 of this powder particle size distribution is 1 to 5 micron, in powder, the massfraction of bimaleimide resin is 35%-45%, and this powder is dispersed in AG-80 epoxy resin or ZEP-001 epoxy resin.
The preparation method of carbon fiber/epoxy resin prepreg of the present invention, be a kind of can directly compatibility and quantity-produced method with carbon fiber production process, carbon fibre tow is after charing process and anodic oxidation treatment, directly enter in preparation technology provided by the invention, without starching and the process receiving silk, after preparation technology provided by the invention, collect with the form of unidirectional prepreg cloth, enter the technique of prepreg cloth heating precrosslink afterwards, thus obtain carbon fiber/epoxy resin prepreg of the present invention, prepare particular by following methods:
(1) be wire deflector roll with graphite in zinc oxide nanowire growth groove, with unsized carbon fiber filament for anode, take saturated calomel electrode as reference electrode, take diameter as the gold thread of 50-60 micron be negative electrode, three is placed in zinc oxide nanowire and grows below the reaction soln liquid level of groove, be energized to three by D.C. regulated power supply, the voltage controlling to put on carbon fibre tow is-1.1 ~-1.3 volts relative to reference electrode, reaction soln temperature controls between 80-85 DEG C, reaction times is 35-45 minute, tow enters the washed with de-ionized water groove being placed with ultrasonic generator afterwards, the power controlling ultrasonic generator is 10-30 watt, enter loft drier after cleaning to dry, control bake out temperature is 100-150 DEG C, drying time is 3-5 minute,
(2) tow after drying enters aminofunctional groove, fills the C that concentration is 0.5-0.8 mole often liter in groove
6h
5nHCH
2si (OCH
2cH
3)
3or NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3one in the aqueous solution, and regulate its pH value to be between 4-5 by acetic acid or hydrochloric acid, controlling the reaction times of tow in aminofunctional groove is 30-40 minute, and then tow enters loft drier and dries at 60-80 DEG C;
(3) by 4, 4 '-diaminodiphenyl oxide or 4, 4 '-diaminodiphenylmethane is dissolved in acetone, be configured to the solution that massfraction is 20%-40%, and by stating the proportioning of each component of carbon fiber/epoxy resin prepreg, AG-80 epoxy resin or ZEP-001 epoxy resin is added in this solution, and carbon fiber reinforced bismalemide matrix material powder, pour into after stirring in steeping vat, and ultrasonic generator is placed with in steeping vat, control operating power is 100-150 watt, then the tow after step (2) oven dry enters in steeping vat, controlling the impregnation time is 10-20 second, tow tension is 160-200 gram, tow after impregnation removes unnecessary resin adhesive liquid by a spreading roller,
(4) tow after step (3) impregnation adopts the mode be wound around to arrange silk by row's silk machine, is repeatedly wound around layer 2-4 altogether, forms unidirectional prepreg cloth;
(5) taken off by prepreg cloth, vacuum drying 6-12 hour under 40-60 DEG C of condition, then dries 4-6 hour under 100-120 DEG C of condition, obtains carbon fiber/epoxy resin prepreg.
Comprise zinc nitrate or zinc carbonate that concentration is 1.5-2.0 mole often liter in reaction soln as above, concentration is vulkacit H or the sodium hydroxide of 1.5-2.0 mole often liter.
Beneficial effect of the present invention:
(1) carbon fiber/epoxy resin prepreg preparation method provided by the invention, adopt the method connected with carbon fiber production process, eliminate the sizing process of carbon fiber, avoid the defect that the interfacial combined function that causes due to sizing agent major constituent and matrix resin poor compatibility declines.
(2) by continuous print process at the coated amino modified zinc oxide nanowire of carbon fiber surface, by the chemical bonding between amino and matrix resin, improve carbon fiber/epoxy resin interface to the tolerance level of wet heat condition, further enhance interface cohesion.
(3) add the powder of the carbon fiber reinforced bismalemide matrix material of recovery in the present invention in resin matrix, provide the approach of thermoset carbon-fibre composite recycling, the toughness of matrix material can be improved simultaneously.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.
It should be noted that embodiment herein only for illustration of the present invention instead of limit the scope of the invention.
It shall yet further be noted that, after reading content of the present invention, the various change that those skilled in the art make the present invention or amendment, these equivalent form of values belong in the limited range of appended claims equally.
Embodiment 1
Domestic T700 level 12K carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences), via dry-jet wet spinning process spinning, again after peroxidation, charing and anodic oxidation treatment, without starching and closing wire technology, directly enter zinc oxide nanowire growth groove.Be wire deflector roll with graphite in this trough, with unsized carbon fiber for anode, take saturated calomel electrode as reference electrode, take diameter as the gold thread of 60 microns be negative electrode, three is placed in zinc oxide nanowire and grows below the reaction soln liquid level of groove, be energized to three by D.C. regulated power supply, the voltage controlling to put on carbon fibre tow is-1.2 volts relative to reference electrode, the zinc nitrate that concentration is 1.5 moles often liter is comprised in reaction soln used, and concentration is the vulkacit H of 1.5 moles often liter, it is 80 degrees Celsius that reaction soln temperature controls, and controlling the reaction times of tow in reaction soln is 35 minutes, tow enters the washed with de-ionized water groove being placed with ultrasonic generator afterwards, the power controlling ultrasonic generator is 10 watts, tow after cleaning enters drying baker and dries, controlling bake out temperature is 100 degrees Celsius, drying time is 5 minutes.Tow after oven dry enters aminofunctional groove, fills the C that concentration is 0.8 mole often liter in trough
6h
5nHCH
2si (OCH
2cH
3)
3the aqueous solution, and regulate its pH value to be 4 by hydrochloric acid, controlling the reaction times of tow in aminofunctional groove is 40 minutes, and then tow enters drying baker, dries at 80 degrees celsius.Tow after oven dry then enters steeping vat, glue in steeping vat is prepared by the following method: by 4, 4 '-diaminodiphenyl oxide is dissolved in acetone, be configured to 4, 4 '-diaminodiphenyl oxide massfraction is the solution of 20%, and according to AG-80 epoxy resin: 4, 4 '-diaminodiphenyl oxide: the fibre reinforced span of recovery draws the mass ratio of imide resin powder to be 35:10:4 and total mass is 5 kilograms, AG-80 epoxy resin is added in this solution, and recycling and the value of the D50 of size distribution is the carbon fiber reinforced bismalemide matrix material powder of 1 micron, in powder, the massfraction of bimaleimide resin is 35%, pour into after stirring in steeping vat, and ultrasonic generator is placed in steeping vat, controlling operating power is 100 watts.Tow is by steeping vat, and controlling the impregnation time is 10 seconds, and tow tension is 160 grams, and the tow after impregnation removes unnecessary resin adhesive liquid by a spreading roller.Then the tow after impregnation utilizes row's silk machine row silk by the mode be wound around, and amounts to the row's of winding silk 2 layers repeatedly, forms unidirectional prepreg cloth.Afterwards, prepreg cloth is taken off, vacuum drying 6 hours under 40 degrees celsius, then dry 6 hours under 100 degrees celsius, just obtain carbon fiber/epoxy resin prepreg of the present invention.
In this carbon fiber/epoxy resin prepreg, comprising massfraction is the zinc oxide nanowire of 2.9%, the C of 0.1%
6h
5nHCH
2si (OCH
2cH
3)
3, 48% carbon fiber filament, the AG-80 epoxy resin of 35%, 10% 4,4 '-diaminodiphenyl oxide and 4% the fibre reinforced span of recovery draw imide resin powder.
Embodiment 2
Domestic T700 level 12K carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences), via dry-jet wet spinning process spinning, again after peroxidation, charing and anodic oxidation treatment, without starching and closing wire technology, directly enter zinc oxide nanowire growth groove.Be wire deflector roll with graphite in this trough, with unsized carbon fiber for anode, take saturated calomel electrode as reference electrode, take diameter as the gold thread of 50 microns be negative electrode, three is placed in zinc oxide nanowire and grows below the reaction soln liquid level of groove, be energized to three by D.C. regulated power supply, the voltage controlling to put on carbon fibre tow is-1.3 volts relative to reference electrode, the zinc carbonate that concentration is 2.0 moles often liter is comprised in reaction soln used, and concentration is the vulkacit H of 2.0 moles often liter, it is 85 degrees Celsius that reaction soln temperature controls, and controlling the reaction times of tow in reaction soln is 45 minutes, tow enters the washed with de-ionized water groove being placed with ultrasonic generator afterwards, the power controlling ultrasonic generator is 30 watts, tow after cleaning enters drying baker and dries, controlling bake out temperature is 150 degrees Celsius, drying time is 3 minutes.Tow after oven dry enters aminofunctional groove, fills the C that concentration is 0.5 mole often liter in trough
6h
5nHCH
2si (OCH
2cH
3)
3the aqueous solution, and regulate its pH value to be 5 by acetic acid, controlling the reaction times of tow in aminofunctional groove is 30 minutes, and then tow enters drying baker, dries at 60 c.Tow after oven dry then enters steeping vat, glue in steeping vat is prepared by the following method: by 4, 4 '-diaminodiphenylmethane is dissolved in acetone, be configured to 4, 4 '-diaminodiphenylmethane massfraction is the solution of 40%, and according to AG-80 epoxy resin: 4, 4 '-diaminodiphenyl oxide: the fibre reinforced span of recovery draws the mass ratio of imide resin powder to be 35:8:4 and total mass is 5 kilograms, add in this solution AG-80 epoxy resin and recycling and the value of the D50 of size distribution is the carbon fiber reinforced bismalemide matrix material powder of 5 microns, in powder, the massfraction of bimaleimide resin is 45%, pour into after stirring in steeping vat, and ultrasonic generator is placed in steeping vat, controlling operating power is 150 watts.Tow is by steeping vat, and controlling the impregnation time is 20 seconds, and tow tension is 200 grams, and the tow after impregnation removes unnecessary resin adhesive liquid by a spreading roller.Then the tow after impregnation utilizes row's silk machine row silk by the mode be wound around, and amounts to the row's of winding silk 4 layers repeatedly, forms unidirectional prepreg cloth.Afterwards, prepreg cloth is taken off, vacuum drying 12 hours under 60 degrees celsius, then dry 4 hours under 120 degrees celsius, just obtain carbon fiber/epoxy resin prepreg of the present invention.
In this carbon fiber/epoxy resin prepreg, comprising massfraction is the zinc oxide nanowire of 0.8%, the C of 0.2%
6h
5nHCH
2si (OCH
2cH
3)
3, 52% carbon fiber filament, the AG-80 epoxy resin of 35%, 8% 4,4 '-diaminodiphenyl oxide and 4% the fibre reinforced span of recovery draw imide resin powder.
Embodiment 3
Domestic T700 level 12K carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences), via dry-jet wet spinning process spinning, again after peroxidation, charing and anodic oxidation treatment, without starching and closing wire technology, directly enter zinc oxide nanowire growth groove.Be wire deflector roll with graphite in this trough, with unsized carbon fiber for anode, take saturated calomel electrode as reference electrode, take diameter as the gold thread of 50 microns be negative electrode, three is placed in zinc oxide nanowire and grows below the reaction soln liquid level of groove, be energized to three by D.C. regulated power supply, the voltage controlling to put on carbon fibre tow is-1.1 volts relative to reference electrode, the zinc nitrate that concentration is 1.8 moles often liter is comprised in reaction soln used, and concentration is the vulkacit H of 1.8 moles often liter, it is 82 degrees Celsius that reaction soln temperature controls, and controlling the reaction times of tow in reaction soln is 40 minutes, tow enters the washed with de-ionized water groove being placed with ultrasonic generator afterwards, the power controlling ultrasonic generator is 10 watts, tow after cleaning enters drying baker and dries, controlling bake out temperature is 120 degrees Celsius, drying time is 4 minutes.Tow after oven dry enters aminofunctional groove, fills the C that concentration is 0.7 mole often liter in trough
6h
5nHCH
2si (OCH
2cH
3)
3the aqueous solution, and regulate its pH value to be 4.6 by hydrochloric acid, controlling the reaction times of tow in aminofunctional groove is 35 minutes, and then tow enters drying baker, dries under 70 degrees Celsius.Tow after oven dry then enters steeping vat, glue in steeping vat is prepared by the following method: by 4, 4 '-diaminodiphenylmethane is dissolved in acetone, be configured to 4, 4 '-diaminodiphenylmethane massfraction is the solution of 30%, and according to AG-80 epoxy resin: 4, 4 '-diaminodiphenylmethane: the fibre reinforced span of recovery draws the mass ratio of imide resin powder to be 25:10:4 and total mass is 6 kilograms, AG-80 epoxy resin is added in this solution, and recycling and the value of the D50 of size distribution is the carbon fiber reinforced bismalemide matrix material powder of 3 microns, in powder, the massfraction of bimaleimide resin is 40%, pour into after stirring in steeping vat, and ultrasonic generator is placed in steeping vat, controlling operating power is 130 watts.Tow is by steeping vat, and controlling the impregnation time is 15 seconds, and tow tension is 180 grams, and the tow after impregnation removes unnecessary resin adhesive liquid by a spreading roller.Then the tow after impregnation utilizes row's silk machine row silk by the mode be wound around, and amounts to the row's of winding silk 3 layers repeatedly, forms unidirectional prepreg cloth.Afterwards, prepreg cloth is taken off, vacuum drying 9 hours under 50 degrees celsius, then dry 5 hours under 110 degrees celsius, just obtain carbon fiber/epoxy resin prepreg of the present invention.
In this carbon fiber/epoxy resin prepreg, comprising massfraction is the zinc oxide nanowire of 2.9%, the C of 0.2%
6h
5nHCH
2si (OCH
2cH
3)
3, 57.9% carbon fiber filament, the AG-80 epoxy resin of 25%, 10% 4,4 '-diaminodiphenylmethane and 4% the fibre reinforced span of recovery draw imide resin powder.
Embodiment 4
Domestic T700 level 12K carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences), via dry-jet wet spinning process spinning, again after peroxidation, charing and anodic oxidation treatment, without starching and closing wire technology, directly enter zinc oxide nanowire growth groove.Be wire deflector roll with graphite in this trough, with unsized carbon fiber for anode, take saturated calomel electrode as reference electrode, take diameter as the gold thread of 50 microns be negative electrode, three is placed in zinc oxide nanowire and grows below the reaction soln liquid level of groove, be energized to three by D.C. regulated power supply, the voltage controlling to put on carbon fibre tow is-1.2 volts relative to reference electrode, the zinc nitrate that concentration is 1.6 moles often liter is comprised in reaction soln used, and concentration is the sodium hydroxide of 1.9 moles often liter, it is 80 degrees Celsius that reaction soln temperature controls, and controlling the reaction times of tow in reaction soln is 35 minutes, tow enters the washed with de-ionized water groove being placed with ultrasonic generator afterwards, the power controlling ultrasonic generator is 10 watts, tow after cleaning enters drying baker and dries, controlling bake out temperature is 100 degrees Celsius, drying time is 5 minutes.Tow after oven dry enters aminofunctional groove, fills the NH that concentration is 0.8 mole often liter in trough
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3the aqueous solution, and regulate its pH value to be 4 by hydrochloric acid, controlling the reaction times of tow in aminofunctional groove is 40 minutes, and then tow enters drying baker, dries at 80 degrees celsius.Tow after oven dry then enters steeping vat, glue in steeping vat is prepared by the following method: by 4, 4 '-diaminodiphenyl oxide is dissolved in acetone, be configured to 4, 4 '-diaminodiphenyl oxide massfraction is the solution of 20%, and according to ZEP-001 epoxy resin: 4, 4 '-diaminodiphenyl oxide: the fibre reinforced span of recovery draws the mass ratio of imide resin powder to be 25:8:4 and total mass is 5 kilograms, ZEP-001 epoxy resin is added in this solution, and recycling and the value of the D50 of size distribution is the carbon fiber reinforced bismalemide matrix material powder of 4 microns, in powder, the massfraction of bimaleimide resin is 37%, pour into after stirring in steeping vat, and ultrasonic generator is placed in steeping vat, controlling operating power is 100 watts.Tow is by steeping vat, and controlling the impregnation time is 10 seconds, and tow tension is 160 grams, and the tow after impregnation removes unnecessary resin adhesive liquid by a spreading roller.Then the tow after impregnation utilizes row's silk machine row silk by the mode be wound around, and amounts to the row's of winding silk 2 layers repeatedly, forms unidirectional prepreg cloth.Afterwards, prepreg cloth is taken off, vacuum drying 10 hours under 40 degrees celsius, then dry 5 hours under 110 degrees celsius, just obtain carbon fiber/epoxy resin prepreg of the present invention.
In this carbon fiber/epoxy resin prepreg, comprising massfraction is the zinc oxide nanowire of 0.8%, the NH of 0.1%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, 62.1% carbon fiber filament, the ZEP-001 epoxy resin of 25%, 8% 4,4 '-diaminodiphenyl oxide and 4% the fibre reinforced span of recovery draw imide resin powder.
Embodiment 5
Domestic T700 level 12K carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences), via dry-jet wet spinning process spinning, again after peroxidation, charing and anodic oxidation treatment, without starching and closing wire technology, directly enter zinc oxide nanowire growth groove.Be wire deflector roll with graphite in this trough, with unsized carbon fiber for anode, take saturated calomel electrode as reference electrode, take diameter as the gold thread of 50 microns be negative electrode, three is placed in zinc oxide nanowire and grows below the reaction soln liquid level of groove, be energized to three by D.C. regulated power supply, the voltage controlling to put on carbon fibre tow is-1.3 volts relative to reference electrode, the zinc carbonate that concentration is 2.0 moles often liter is comprised in reaction soln used, and concentration is the vulkacit H of 2.0 moles often liter, it is 85 degrees Celsius that reaction soln temperature controls, and controlling the reaction times of tow in reaction soln is 45 minutes, tow enters the washed with de-ionized water groove being placed with ultrasonic generator afterwards, the power controlling ultrasonic generator is 30 watts, tow after cleaning enters drying baker and dries, controlling bake out temperature is 150 degrees Celsius, drying time is 3 minutes.Tow after oven dry enters aminofunctional groove, fills the NH that concentration is 0.5 mole often liter in trough
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3the aqueous solution, and regulate its pH value to be 5 by acetic acid, controlling the reaction times of tow in aminofunctional groove is 30 minutes, and then tow enters drying baker, dries at 60 c.Tow after oven dry then enters steeping vat, glue in steeping vat is prepared by the following method: by 4, 4 '-diaminodiphenylmethane is dissolved in acetone, be configured to 4, 4 '-diaminodiphenylmethane massfraction is the solution of 40%, and according to AG-80 epoxy resin: 4, 4 '-diaminodiphenylmethane: the fibre reinforced span of recovery draws the mass ratio of imide resin powder to be 35:10:8 and total mass is 5 kilograms, add in this solution AG-80 epoxy resin and recycling and the value of the D50 of size distribution is the carbon fiber reinforced bismalemide matrix material powder of 5 microns, in powder, the massfraction of bimaleimide resin is 43%, pour into after stirring in steeping vat, and ultrasonic generator is placed in steeping vat, controlling operating power is 150 watts.Tow is by steeping vat, and controlling the impregnation time is 20 seconds, and tow tension is 200 grams, and the tow after impregnation removes unnecessary resin adhesive liquid by a spreading roller.Then the tow after impregnation utilizes row's silk machine row silk by the mode be wound around, and amounts to the row's of winding silk 4 layers repeatedly, forms unidirectional prepreg cloth.Afterwards, prepreg cloth is taken off, vacuum drying 12 hours under 60 degrees celsius, then dry 4 hours under 120 degrees celsius, just obtain carbon fiber/epoxy resin prepreg of the present invention.
In this carbon fiber/epoxy resin prepreg, comprising massfraction is the zinc oxide nanowire of 1.4%, the NH of 0.1%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, 45.5% carbon fiber filament, the AG-80 epoxy resin of 35%, 10% 4,4 '-diaminodiphenylmethane and 8% the fibre reinforced span of recovery draw imide resin powder.
Embodiment 6
The present embodiment is from the different of embodiment 5, the glue that in the present embodiment, carbon fibre tow impregnation uses, prepare by the following method: by 4, 4 '-diaminodiphenylmethane is dissolved in acetone, be configured to 4, 4 '-diaminodiphenylmethane massfraction is the solution of 40%, and according to ZEP-001 epoxy resin: 4, 4 '-diaminodiphenylmethane: the fibre reinforced span of recovery draws the mass ratio of imide resin powder to be 35:8:8 and total mass is 5 kilograms, add in this solution ZEP-001 epoxy resin and recycling and the value of the D50 of size distribution is the carbon fiber reinforced bismalemide matrix material powder of 5 microns.
In this carbon fiber/epoxy resin prepreg, comprising massfraction is the zinc oxide nanowire of 1.9%, the NH of 0.1%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, 47% carbon fiber filament, the ZEP-001 epoxy resin of 35%, 8% 4,4 '-diaminodiphenylmethane and 8% the fibre reinforced span of recovery draw imide resin powder.
Embodiment 7
The present embodiment is from the different of embodiment 5, the glue that in the present embodiment, carbon fibre tow impregnation uses, prepare by the following method: by 4, 4 '-diaminodiphenylmethane is dissolved in acetone, be configured to 4, 4 '-diaminodiphenylmethane massfraction is the solution of 40%, and according to ZEP-001 epoxy resin: 4, 4 '-diaminodiphenylmethane: the fibre reinforced span of recovery draws the mass ratio of imide resin powder to be 25:10:8 and total mass is 5 kilograms, add in this solution ZEP-001 epoxy resin and recycling and the value of the D50 of size distribution is the carbon fiber reinforced bismalemide matrix material powder of 2 microns.
In this carbon fiber/epoxy resin prepreg, comprising massfraction is the zinc oxide nanowire of 1.8%, the NH of 0.2%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, 55% carbon fiber filament, the ZEP-001 epoxy resin of 25%, 10% 4,4 '-diaminodiphenylmethane and 8% the fibre reinforced span of recovery draw imide resin powder.
Embodiment 8
The present embodiment is from the different of embodiment 5, the glue that in the present embodiment, carbon fibre tow impregnation uses, prepare by the following method: by 4, 4 '-diaminodiphenylmethane is dissolved in acetone, be configured to 4, 4 '-diaminodiphenylmethane massfraction is the solution of 40%, and according to ZEP-001 epoxy resin: 4, 4 '-diaminodiphenylmethane: the fibre reinforced span of recovery draws the mass ratio of imide resin powder to be 25:8:8 and total mass is 5 kilograms, add in this solution ZEP-001 epoxy resin and recycling and the value of the D50 of size distribution is the carbon fiber reinforced bismalemide matrix material powder of 3 microns.
In this carbon fiber/epoxy resin prepreg, comprising massfraction is the zinc oxide nanowire of 2.1%, the NH of 0.1%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, 56.8% carbon fiber filament, the ZEP-001 epoxy resin of 25%, 8% 4,4 '-diaminodiphenylmethane and 8% the fibre reinforced span of recovery draw imide resin powder.
Comparative example 1
Domestic T700 level 12K carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences), via dry-jet wet spinning process spinning, again through peroxidation, charing and anodic oxidation treatment after, without starching and closing wire technology, directly enter steeping vat, glue in steeping vat is prepared by the following method: by 4, 4 '-diaminodiphenylmethane is dissolved in acetone, be configured to 4, 4 '-diaminodiphenylmethane massfraction is the solution of 40%, and according to AG-80 epoxy resin: 4, the mass ratio of 4 '-diaminodiphenylmethane is 35:10 and total mass is 5 kilograms, AG-80 epoxy resin is added in this solution, pour into after stirring in steeping vat, and ultrasonic generator is placed in steeping vat, controlling operating power is 150 watts.Tow is by steeping vat, and controlling the impregnation time is 20 seconds, and tow tension is 200 grams, and the tow after impregnation removes unnecessary resin adhesive liquid by a spreading roller.Then the tow after impregnation utilizes row's silk machine row silk by the mode be wound around, and amounts to the row's of winding silk 4 layers repeatedly, forms unidirectional prepreg cloth.Afterwards, prepreg cloth is taken off, vacuum drying 12 hours under 60 degrees celsius, then dry 4 hours under 120 degrees celsius, just obtain the carbon fiber/epoxy resin prepreg of this comparative example.
Comparative example 2
Domestic T700 level 12K carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences), via dry-jet wet spinning process spinning, again through peroxidation, charing and anodic oxidation treatment after, without starching and closing wire technology, directly enter steeping vat, glue in steeping vat is prepared by the following method: by 4, 4 '-diaminodiphenyl oxide is dissolved in acetone, be configured to 4, 4 '-diaminodiphenyl oxide massfraction is the solution of 20%, and according to ZEP-001 epoxy resin: 4, the mass ratio of 4 '-diaminodiphenyl oxide is 25:8 and total mass is 5 kilograms, ZEP-001 epoxy resin is added in this solution, pour into after stirring in steeping vat, and ultrasonic generator is placed in steeping vat, controlling operating power is 100 watts.Tow is by steeping vat, and controlling the impregnation time is 10 seconds, and tow tension is 160 grams, and the tow after impregnation removes unnecessary resin adhesive liquid by a spreading roller.Then the tow after impregnation utilizes row's silk machine row silk by the mode be wound around, and amounts to the row's of winding silk 2 layers repeatedly, forms unidirectional prepreg cloth.Afterwards, prepreg cloth is taken off, vacuum drying 10 hours under 40 degrees celsius, then dry 5 hours under 110 degrees celsius, just obtain the carbon fiber/epoxy resin prepreg of the present embodiment.
Test
By the prepreg in whole embodiment and comparative example by thermocompressor prepared layer pressing plate, pressure used is 5MPa, and time temperature history is: 140 DEG C of heating 2h, 180 DEG C of heating 4h, heating terminates rear pressurize and is cooled to room temperature.Resultant layer pressing plate employing diamond cutter is cut to the size required for testing standard.According to document (H.Yuan, etal.Surfacemodificationofcarbonfibersbyapolyethersulfon eemulsionsizingforincreasedinterfacialadhesionwithpolyet hersulfone, AppliedSurfaceScience, 317 (2014) 737-744.) interlaminar shear strength of method detection layers pressing plate reported, in order to characterize the interface bond strength between carbon fiber and resin, again according to document (T.Lyashenko, etal.ImprovedModeIIdelaminationfracturetoughnessofcompos itematerialsbyselectiveplacementofprotein-surfacetreated CNT, CompositesScienceandTechnology, 85 (2013) 29-35.) method reported, the interlaminar fracture toughness of detection layers pressing plate, test result is as shown in table 1.
Table 1
| Sample | Interlaminar shear strength (MPa) | Interlaminar fracture toughness (MPa) |
| Embodiment 1 | 117 | 94 |
| Embodiment 2 | 119 | 92 |
| Embodiment 3 | 125 | 91 |
| Embodiment 4 | 109 | 88 |
| Embodiment 5 | 114 | 89 |
| Embodiment 6 | 118 | 97 |
| Embodiment 7 | 116 | 96 |
| Embodiment 8 | 114 | 87 |
| Comparative example 1 | 81 | 68 |
| Comparative example 2 | 74 | 75 |
Obviously can see from table, compared with comparative example, adopt the veneer sheet that prepared by the open method of the present invention, prepreg obtains, possess higher interlaminar shear strength and interlaminar fracture toughness.Prepreg in comparative example is directly by carbon fiber impregnation, and glue used does not comprise the Bismaleimide composites powder of modification.Therefore, can reach a conclusion be carbon fiber surface growth of zinc oxide nano line technique and adopt the method for Bismaleimide composites powder modification, obtain the high-performance of veneer sheet prepared by prepreg in the present invention.
Claims (7)
1. a carbon fiber/epoxy resin prepreg, is characterized in that carbon fiber/epoxy resin prepreg is unidirectional pre-immersion material, and obtain by being wound around row's silk by row's silk machine after the carbon fibre tow impregnation of modification, wherein each component quality group becomes:
Zinc oxide 0.8%-2.9%;
C
6h
5nHCH
2si (OCH
2cH
3)
3or NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
30.1%-0.2%;
Non-starching and surface are without the PAN-based carbon fiber long filament 50%-55% of groove structure;
AG-80 epoxy resin or ZEP-001 epoxy resin 25%-35%;
4,4 '-diaminodiphenyl oxide or 4,4 '-diaminodiphenylmethane 8%-10%;
Carbon fiber reinforced bismalemide matrix material powder 4%-8%.
2. a kind of carbon fiber/epoxy resin prepreg as claimed in claim 1, it is characterized in that described zinc oxide is nano wire form, diameter is 80 to 120 nanometers.
3. a kind of carbon fiber/epoxy resin prepreg as claimed in claim 1, is characterized in that described non-starching and the surperficial PAN-based carbon fiber long filament without groove structure is the PAN-based carbon fiber adopting dry-jet wet spinning process to prepare.
4. a kind of carbon fiber/epoxy resin prepreg as claimed in claim 1, is characterized in that described non-starching and the surperficial PAN-based carbon fiber long filament without groove structure is that carbon fiber length is not less than 20 centimetres.
5. a kind of carbon fiber/epoxy resin prepreg as claimed in claim 1, it is characterized in that described non-starching and surface is described carbon fiber reinforced bismalemide matrix material powder without the PAN-based carbon fiber long filament of groove structure is obtained by the waste and old carbon fiber reinforced bismalemide matrix material grinding of reclaiming, the value of the D50 of this powder particle size distribution is 1 to 5 micron, in powder, the massfraction of bimaleimide resin is 35%-45%, and this powder is dispersed in AG-80 epoxy resin or ZEP-001 epoxy resin.
6. the preparation method of a kind of carbon fiber/epoxy resin prepreg as described in any one of claim 1-5, is characterized in that comprising the following steps:
(1) be wire deflector roll with graphite in zinc oxide nanowire growth groove, with unsized carbon fiber filament for anode, take saturated calomel electrode as reference electrode, take diameter as the gold thread of 50-60 micron be negative electrode, three is placed in zinc oxide nanowire and grows below the reaction soln liquid level of groove, be energized to three by D.C. regulated power supply, the voltage controlling to put on carbon fibre tow is-1.1 ~-1.3 volts relative to reference electrode, reaction soln temperature controls between 80-85 DEG C, reaction times is 35-45 minute, tow enters the washed with de-ionized water groove being placed with ultrasonic generator afterwards, the power controlling ultrasonic generator is 10-30 watt, enter loft drier after cleaning to dry, control bake out temperature is 100-150 DEG C, drying time is 3-5 minute,
(2) tow after drying enters aminofunctional groove, fills the C that concentration is 0.5-0.8 mole often liter in groove
6h
5nHCH
2si (OCH
2cH
3)
3or NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3one in the aqueous solution, and regulate its pH value to be between 4-5 by acetic acid or hydrochloric acid, controlling the reaction times of tow in aminofunctional groove is 30-40 minute, and then tow enters loft drier and dries at 60-80 DEG C;
(3) by 4, 4 '-diaminodiphenyl oxide or 4, 4 '-diaminodiphenylmethane is dissolved in acetone, be configured to the solution that massfraction is 20%-40%, and by stating the proportioning of each component of carbon fiber/epoxy resin prepreg, AG-80 epoxy resin or ZEP-001 epoxy resin is added in this solution, and carbon fiber reinforced bismalemide matrix material powder, pour into after stirring in steeping vat, and ultrasonic generator is placed with in steeping vat, control operating power is 100-150 watt, then the tow after step (2) oven dry enters in steeping vat, controlling the impregnation time is 10-20 second, tow tension is 160-200 gram, tow after impregnation removes unnecessary resin adhesive liquid by a spreading roller,
(4) tow after step (3) impregnation adopts the mode be wound around to arrange silk by row's silk machine, is repeatedly wound around layer 2-4 altogether, forms unidirectional prepreg cloth;
(5) taken off by prepreg cloth, vacuum drying 6-12 hour under 40-60 DEG C of condition, then dries 4-6 hour under 100-120 DEG C of condition, obtains carbon fiber/epoxy resin prepreg.
7. the preparation method of a kind of carbon fiber/epoxy resin prepreg as claimed in claim 6, it is characterized in that comprising zinc nitrate or the zinc carbonate that concentration is 1.5-2.0 mole often liter in described reaction soln, concentration is vulkacit H or the sodium hydroxide of 1.5-2.0 mole often liter.
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| CN116892117A (en) * | 2023-09-08 | 2023-10-17 | 江苏国望高科纤维有限公司 | Modified copper calcium titanate nanofiber and preparation method and application thereof |
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