CN105131335A - Aminated zinc oxide nano wire-carbon fiber hybrid reinforcement and preparation method thereof - Google Patents
Aminated zinc oxide nano wire-carbon fiber hybrid reinforcement and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an aminated zinc oxide nano wire-carbon fiber hybrid reinforcement. The aminated zinc oxide nano wire-carbon fiber hybrid reinforcement comprises, by mass, 94.3-96.8% of unsized or desized polyacrylonitrile-based carbon fiber, 3-5% of nano wire-type zinc oxide, 0.1-0.5% of nanometer particle-type zinc oxide and 0.1-0.2% of a silicon-containing compound. The aminated zinc oxide nano wire-carbon fiber hybrid reinforcement has a high interfacial strength conservation rate in a wet and hot environment.
Description
Technical field
The invention belongs to a kind of carbon-fibre composite interface Enhancement Method, particularly a kind of amination zinc oxide nanowire-carbon fiber hybrid reinforcement body and method for making thereof.
Technical background
Carbon-fibre composite, because of its outstanding mechanical property, is widely used in structured material field.When carbon-fibre composite is subject to External Force Acting, the interfacial layer between carbon fiber and body material plays bridge beam action, external forces is passed to primary load bearing component carbon fiber.Therefore, the bonding strength of interfacial layer directly has influence on the Stress transmit efficiency of matrix material.
In recent years, the various method in carbon fiber surface grow nanowire attracts attention.Improve the active area between carbon fiber and body material by nano wire, improve Van der Waals force therebetween and mechanical interlocking, effectively can improve the interface bond strength between carbon fiber and body material.Particularly zinc oxide nanowire, because preparation temperature is subject to the favor of vast researcher lower than 100 DEG C.The method of a kind of hydrothermal method at carbon fiber surface growth of zinc oxide nano line is disclosed in Chinese invention patent 200910119611.7, first the method prepares one deck inert metal oxides or silicon carbide, norbide, silicon nitride, aluminium nitride coating by the method for vacuum plasma spray at carbon fiber surface, then by hydrothermal method growth of zinc oxide nano line on the coating layer.The method of vacuum plasma spray coating prepares the first layer coating (Seed Layer), first by material melts, and then by lance ejection to carbon fiber surface, because carbon fiber generally occurs with the form of tow or fabric, and spray gun can only spray from one or more relative direction, be therefore difficult to accomplish that the packaging type to carbon fiber surface 360 degree evenly applies.Hydrothermal method directly can not obtain highdensity zinc oxide nano-wire array at carbon fiber surface, and therefore the quality of the first layer coating just directly has influence on the growth conditions of subsequent oxidation zinc nano-wire array.(the Increasedinterfacestrengthincarbonfibercompositesthrough aZnOnanowireinterphase such as Lin, AdvancedFunctionalMaterials, 2009,19th volume, 16th phase, 2654 pages to 2660 pages) same with hydrothermal method at carbon fiber surface growth of zinc oxide nano line, but have employed sol-gel method prepares zinc oxide seed layer at carbon fiber surface.But thickness evenness is poor on the one hand for the zinc oxide seed layer that sol-gel method obtains, and the size distribution of Zinc oxide nanoparticle is wide on the other hand, also limits the quality of zinc oxide nanowire to a certain extent.In addition, all there is the long problem of preparation time in two kinds of above-mentioned Hydrothermal Growth zinc oxide nanowires, preparation time in hour, cannot merge mutually with the processed continuously application reality of carbon fibre tow, limit the application prospect of above-mentioned two kinds of methods.
In addition, carbon-fibre composite inevitably will experience the change of temperature and humidity in the process of practical application, and the wet-hot aging performance of composite material interface is also one of important indicator needing to consider.The strengthening effect of zinc oxide nanowire to carbon-fibre composite interface is realized by simple physical action, under wet heat condition, matrix resin differs very big with the coefficient of expansion of zinc oxide nanowire, unrelieved stress will be produced at interface, the consumption of unrelieved stress dissipates by the weakest surface physics junction, the boundary strength conservation rate of therefore wet heat treatment rear oxidation zinc nano wire-between carbon fiber hybrid reinforcement body and matrix resin is low, can not meet the requirement of composite material interface to Hygrothermal Properties.
Summary of the invention
The object of this invention is to provide a kind of under hygrothermal environment, the amination zinc oxide nanowire that boundary strength conservation rate is high-carbon fiber hybrid reinforcement body and preparation method thereof.
Amination zinc oxide nanowire of the present invention-carbon fiber hybrid reinforcement body, comprises following mass percent composition:
Non-starching or the PAN-based carbon fiber except slurry are the carbon fiber of surface without groove structure as mentioned above, as the PAN-based carbon fiber adopting dry-jet wet spinning process to prepare.
The length-to-diameter ratio of the zinc oxide of nano wire form as above is 5 to 15.
Silicon-containing compound as above is NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
2cH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3or NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3in one, and be connected in the mode of chemical bonding by Si-O-Zn chemical bond between this compound with zinc oxide nanowire.
The preparation method of amination zinc oxide nanowire of the present invention-carbon fiber hybrid reinforcement body, comprises the following steps:
(1) with zinc methide or zinc ethyl for zinc source, the hydrogen peroxide being 10%-20% with deionized water or massfraction is for oxygen source, controlling zinc source temperature is-25 ~-23 DEG C, oxygen source temperature is 3-5 DEG C, at service temperature 230-240 DEG C, red-tape operati depositing time is 10-20 minute, by ald, non-starching or except slurry and surface prepare zinc-oxide nano layer without the PAN-based carbon fiber surface of groove structure;
(2) with gained carbon fiber in step (1) for anode, with the gold thread of diameter 50-60 micron for negative electrode, take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, comprising concentration in reaction soln is one in the zinc nitrate of 1.5-2.0 mole often liter or zinc acetate, and concentration is the one in the vulkacit H of 1.5-2.0 mole often liter or ammoniacal liquor, reaction soln is warming up to 85-89 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.2 ~-0.4 volt relative to reference electrode, reaction times is 15-25 minute, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried,
(3) silicon-containing compound is dissolved in moisture and purity is in the ethanol of 85%-95%, the concentration controlling silicon-containing compound is 40wt%-50wt%, and by solution warms to 50-60 DEG C, then carbon fiber coated for gained zinc oxide nanowire in step (2) is placed in this solution, reaction 30-60 minute, adopt clear water to rinse carbon fiber afterwards, until the specific conductivity of washing lotion is less than or equal to 1000 micro-Siemens per centimeter after rinsing, then under 60-80 DEG C of condition vacuum drying.
Beneficial effect of the present invention:
(1) amination zinc oxide nanowire provided by the present invention-carbon fiber hybrid reinforcement body, overcomes the simple zinc oxide nanowire that adopts and strengthens the interface cohesion shortcoming that strength retention is low under wet heat condition.
(2) amination zinc oxide nanowire provided by the present invention-carbon fiber hybrid reinforcement body, that the zinc oxide prepared with Atomic layer deposition method is for Seed Layer, Seed Layer is high at carbon fiber surface caliper uniformity, and the Zinc oxide nanoparticle size distribution homogeneity obtained is high, preparing compared with zinc oxide seed layer with adopting sol-gel method in conventional art, being more conducive to obtaining high-quality zinc oxide nano-wire array at carbon fiber surface.
Accompanying drawing explanation
Fig. 1 is the infrared spectra spectrogram of gained sample in embodiment 1, the absorption peak at 1003 wave number places in figure, for the characteristic peak of Si-O-Zn chemical bond, prove in amination zinc oxide nanowire provided by the present invention-carbon fiber hybrid reinforcement body, be connected with zinc oxide nanowire by Si-O-Zn key containing amino compound.
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
Get the non-starching T700 grade polypropylene itrile group carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's production) obtained by dry-jet wet spinning process of one section of 10 cm long, take zinc methide as zinc source, take deionized water as oxygen source, control zinc source temperature and be-25 DEG C, oxygen source temperature is 3 DEG C, at service temperature 230 DEG C, red-tape operati depositing time is 10 minutes, adopts atomic layer deposition apparatus to prepare zinc-oxide nano layer at this carbon fiber surface.With this carbon fiber for anode, with the gold thread of diameter 60 microns for negative electrode, take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, the zinc nitrate that concentration is 1.5 moles often liter is comprised in reaction soln, and concentration is the vulkacit H of 1.5 moles often liter, reaction soln is warming up to 85 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.3 volt relative to reference electrode, reaction times is 15 minutes, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried.By NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3be dissolved in moisture and purity is in the ethanol of 85%, the concentration controlling this compound is 40%, and by solution warms to 50 DEG C, then carbon fiber coated for above-mentioned gained zinc oxide nanowire is placed in this solution, react 30 minutes, adopt clear water to rinse carbon fiber afterwards, until after rinsing the specific conductivity of washing lotion not higher than 1000 micro-Siemens per centimeter, then under 60 DEG C of conditions vacuum drying.
Through amination zinc oxide nanowire-carbon fiber hybrid reinforcement body that aforesaid method obtains, comprise the non-starching T700 grade polypropylene itrile group carbon fiber obtained by dry-jet wet spinning process that massfraction is 96.8%, massfraction is the nano wire form zinc oxide of 3%, the zinc oxide length-to-diameter ratio of nano wire form is 5, massfraction is the zinc oxide of the film morphology be made up of nano particle of 0.1%, and massfraction is the NH of 0.1%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3.
Embodiment 2
Get the T700S carbon fiber of the toray company of one section of 10 cm long, remove carbon fiber surface sizing agent according to the method described in GJB1982-94 appendix A, afterwards by carbon fiber vacuum-drying 48 hours at 60 DEG C.Taking zinc ethyl as zinc source, take massfraction as the hydrogen peroxide of 20% is oxygen source, controls zinc source temperature and is-23 DEG C, oxygen source temperature is 5 DEG C, at service temperature 240 DEG C, red-tape operati depositing time is 20 minutes, adopts atomic layer deposition apparatus to prepare zinc-oxide nano layer at this carbon fiber surface.With this carbon fiber for anode, with the gold thread of diameter 50 microns for negative electrode, take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, the zinc acetate that concentration is 2 moles often liter is comprised in reaction soln, and concentration is the ammoniacal liquor of 2 moles often liter, reaction soln is warming up to 89 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.4 volt relative to reference electrode, reaction times is 25 minutes, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried.By NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
2cH
3)
3be dissolved in moisture and purity is in the ethanol of 90%, the concentration controlling this compound is 50%, and by solution warms to 60 DEG C, then carbon fiber coated for above-mentioned gained zinc oxide nanowire is placed in this solution, react 60 minutes, adopt clear water to rinse carbon fiber afterwards, until after rinsing the specific conductivity of washing lotion not higher than 1000 micro-Siemens per centimeter, then under 80 DEG C of conditions vacuum drying.
Through amination zinc oxide nanowire-carbon fiber hybrid reinforcement body that aforesaid method obtains, comprise the carbon fiber that massfraction is 94.3%, massfraction is the nano wire form zinc oxide of 4.7%, the zinc oxide length-to-diameter ratio of nano wire form is 15, massfraction is the zinc oxide of the film morphology be made up of nano particle of 0.5%, this zinc oxide film is prepared by the method for ald, and massfraction is the NH of 0.5%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
2cH
3)
3, and be connected in the mode of chemical bonding by Si-O-Zn chemical bond between this compound with zinc oxide nanowire.
Embodiment 3
Get the non-starching T700 grade polypropylene itrile group carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's production) obtained by dry-jet wet spinning process of one section of 10 cm long, take zinc methide as zinc source, take deionized water as oxygen source, control zinc source temperature and be-24 DEG C, oxygen source temperature is 4 DEG C, at service temperature 232 DEG C, red-tape operati depositing time is 12 minutes, adopts atomic layer deposition apparatus to prepare zinc-oxide nano layer at this carbon fiber surface.With this carbon fiber for anode, with the gold thread of diameter 50 microns for negative electrode, take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, the zinc nitrate that concentration is 1.6 moles often liter is comprised in reaction soln, and concentration is the vulkacit H of 1.8 moles often liter, reaction soln is warming up to 86 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.2 volt relative to reference electrode, reaction times is 17 minutes, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried.By NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3be dissolved in moisture and purity is in the ethanol of 92%, the concentration controlling this compound is 42%, and by solution warms to 52 DEG C, then carbon fiber coated for above-mentioned gained zinc oxide nanowire is placed in this solution, react 30 minutes, adopt clear water to rinse carbon fiber afterwards, until after rinsing the specific conductivity of washing lotion not higher than 1000 micro-Siemens per centimeter, then under 62 DEG C of conditions vacuum drying.
Through amination zinc oxide nanowire-carbon fiber hybrid reinforcement body that aforesaid method obtains, comprise the non-starching T700 grade polypropylene itrile group carbon fiber obtained by dry-jet wet spinning process that massfraction is 96.2%, massfraction is the nano wire form zinc oxide of 3.4%, the zinc oxide length-to-diameter ratio of nano wire form is 8, massfraction is the zinc oxide of the film morphology be made up of nano particle of 0.2%, this zinc oxide film is prepared by the method for ald, and massfraction is the NH of 0.2%
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3, and be connected in the mode of chemical bonding by Si-O-Zn chemical bond between this compound with zinc oxide nanowire.
Embodiment 4
Get the T700S carbon fiber of the toray company of one section of 20 cm long, remove carbon fiber surface sizing agent according to the method described in GJB1982-94 appendix A, afterwards by carbon fiber vacuum-drying 48 hours at 60 DEG C.Being zinc source with zinc ethyl, take deionized water as oxygen source, controls zinc source temperature and is-24 DEG C, oxygen source temperature is 4 DEG C, at service temperature 236 DEG C, red-tape operati depositing time is 16 minutes, adopts atomic layer deposition apparatus to prepare zinc-oxide nano layer at this carbon fiber surface.With this carbon fiber for anode, with the gold thread of diameter 50 microns for negative electrode, take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, the zinc nitrate that concentration is 1.8 moles often liter is comprised in reaction soln, and concentration is the ammoniacal liquor of 1.8 moles often liter, reaction soln is warming up to 87 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.3 volt relative to reference electrode, reaction times is 22 minutes, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried.By NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3be dissolved in moisture and purity is in the ethanol of 95%, the concentration controlling this compound is 48%, and by solution warms to 58 DEG C, then carbon fiber coated for above-mentioned gained zinc oxide nanowire is placed in this solution, react 50 minutes, adopt clear water to rinse carbon fiber afterwards, until after rinsing the specific conductivity of washing lotion not higher than 1000 micro-Siemens per centimeter, then under 75 DEG C of conditions vacuum drying.
Through amination zinc oxide nanowire-carbon fiber hybrid reinforcement body that aforesaid method obtains, comprise the carbon fiber that massfraction is 95.6%, massfraction is the nano wire form zinc oxide of 4.1%, the zinc oxide length-to-diameter ratio of nano wire form is 12, massfraction is the zinc oxide of the film morphology be made up of nano particle of 0.2%, this zinc oxide film is prepared by the method for ald, and massfraction is the NH of 0.1%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, and be connected in the mode of chemical bonding by Si-O-Zn chemical bond between this compound with zinc oxide nanowire.
Embodiment 5
Get the non-starching T700 grade polypropylene itrile group carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's production) obtained by dry-jet wet spinning process of one section of 10 cm long, take zinc methide as zinc source, take massfraction as the hydrogen peroxide of 20% be oxygen source, control zinc source temperature and be-25 DEG C, oxygen source temperature is 3 DEG C, at service temperature 235 DEG C, red-tape operati depositing time is 16 minutes, adopts atomic layer deposition apparatus to prepare zinc-oxide nano layer at this carbon fiber surface.With this carbon fiber for anode, with the gold thread of diameter 55 microns for negative electrode, take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, the zinc acetate that concentration is 1.7 moles often liter is comprised in reaction soln, and concentration is the vulkacit H of 1.7 moles often liter, reaction soln is warming up to 88 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.4 volt relative to reference electrode, reaction times is 19 minutes, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried.By NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3be dissolved in moisture and purity is in the ethanol of 95%, the concentration controlling this compound is 44%, and by solution warms to 54 DEG C, then carbon fiber coated for above-mentioned gained zinc oxide nanowire is placed in this solution, react 48 minutes, adopt clear water to rinse carbon fiber afterwards, until after rinsing the specific conductivity of washing lotion not higher than 1000 micro-Siemens per centimeter, then under 60 DEG C of conditions vacuum drying.
Through amination zinc oxide nanowire-carbon fiber hybrid reinforcement body that aforesaid method obtains, comprise the non-starching T700 grade polypropylene itrile group carbon fiber obtained by dry-jet wet spinning process that massfraction is 95.3%, massfraction is the nano wire form zinc oxide of 4%, the zinc oxide length-to-diameter ratio of nano wire form is 15, massfraction is the zinc oxide of the film morphology be made up of nano particle of 0.5%, this zinc oxide film is prepared by the method for ald, and massfraction is the NH of 0.2%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, and be connected in the mode of chemical bonding by Si-O-Zn chemical bond between this compound with zinc oxide nanowire.
Embodiment 6
Get the non-starching T700 grade polypropylene itrile group carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's production) obtained by dry-jet wet spinning process of one section of 10 cm long, take zinc ethyl as zinc source, take deionized water as oxygen source, control zinc source temperature and be-23 DEG C, oxygen source temperature is 4 DEG C, at service temperature 235 DEG C, red-tape operati depositing time is 17 minutes, adopts atomic layer deposition apparatus to prepare zinc-oxide nano layer at this carbon fiber surface.With this carbon fiber for anode, with the gold thread of diameter 50 microns for negative electrode, take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, the zinc nitrate that concentration is 1.9 moles often liter is comprised in reaction soln, and concentration is the vulkacit H of 1.9 moles often liter, reaction soln is warming up to 86 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.2 volt relative to reference electrode, reaction times is 16 minutes, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried.By NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3be dissolved in moisture and purity is in the ethanol of 95%, the concentration controlling this compound is 49%, and by solution warms to 51 DEG C, then carbon fiber coated for above-mentioned gained zinc oxide nanowire is placed in this solution, react 32 minutes, adopt clear water to rinse carbon fiber afterwards, until after rinsing the specific conductivity of washing lotion not higher than 1000 micro-Siemens per centimeter, then under 70 DEG C of conditions vacuum drying.
Through amination zinc oxide nanowire-carbon fiber hybrid reinforcement body that aforesaid method obtains, comprise the non-starching T700 grade polypropylene itrile group carbon fiber obtained by dry-jet wet spinning process that massfraction is 96%, massfraction is the nano wire form zinc oxide of 3.6%, the zinc oxide length-to-diameter ratio of nano wire form is 13, massfraction is the zinc oxide of the film morphology be made up of nano particle of 0.3%, this zinc oxide film is prepared by the method for ald, and massfraction is the NH of 0.1%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, and be connected in the mode of chemical bonding by Si-O-Zn chemical bond between this compound with zinc oxide nanowire.
Embodiment 7
Get the non-starching T700 grade polypropylene itrile group carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's production) obtained by dry-jet wet spinning process of one section of 10 cm long, take zinc ethyl as zinc source, take massfraction as the hydrogen peroxide of 20% be oxygen source, control zinc source temperature and be-25 DEG C, oxygen source temperature is 3 DEG C, at service temperature 230 DEG C, red-tape operati depositing time is 10 minutes, adopts atomic layer deposition apparatus to prepare zinc-oxide nano layer at this carbon fiber surface.With this carbon fiber for anode, with the gold thread of diameter 50 microns for negative electrode, take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, the zinc nitrate that concentration is 1.5 moles often liter is comprised in reaction soln, and concentration is the vulkacit H of 1.5 moles often liter, reaction soln is warming up to 85 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.2 volt relative to reference electrode, reaction times is 15 minutes, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried.By NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3be dissolved in moisture and purity is in the ethanol of 95%, the concentration controlling this compound is 40%, and by solution warms to 50 DEG C, then carbon fiber coated for above-mentioned gained zinc oxide nanowire is placed in this solution, react 30 minutes, adopt clear water to rinse carbon fiber afterwards, until after rinsing the specific conductivity of washing lotion not higher than 1000 micro-Siemens per centimeter, then under 60 DEG C of conditions vacuum drying.
Through amination zinc oxide nanowire-carbon fiber hybrid reinforcement body that aforesaid method obtains, comprise the non-starching T700 grade polypropylene itrile group carbon fiber obtained by dry-jet wet spinning process that massfraction is 96.7%, massfraction is the nano wire form zinc oxide of 3%, the zinc oxide length-to-diameter ratio of nano wire form is 7, massfraction is the zinc oxide of the film morphology be made up of nano particle of 0.2%, this zinc oxide film is prepared by the method for ald, and massfraction is the NH of 0.1%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, and be connected in the mode of chemical bonding by Si-O-Zn chemical bond between this compound with zinc oxide nanowire.
Embodiment 8
Get the non-starching T700 grade polypropylene itrile group carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's production) obtained by dry-jet wet spinning process of one section of 10 cm long, take zinc methide as zinc source, take deionized water as oxygen source, control zinc source temperature and be-23 DEG C, oxygen source temperature is 3 DEG C, at service temperature 237 DEG C, red-tape operati depositing time is 10 minutes, adopts atomic layer deposition apparatus to prepare zinc-oxide nano layer at this carbon fiber surface.With this carbon fiber for anode, with the gold thread of diameter 50 microns for negative electrode, take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, the zinc nitrate that concentration is 1.6 moles often liter is comprised in reaction soln, and concentration is the vulkacit H of 1.5 moles often liter, reaction soln is warming up to 85 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.4 volt relative to reference electrode, reaction times is 15 minutes, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried.By NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3be dissolved in moisture and purity is in the ethanol of 95%, the concentration controlling this compound is 43%, and by solution warms to 50 DEG C, then carbon fiber coated for above-mentioned gained zinc oxide nanowire is placed in this solution, react 30 minutes, adopt clear water to rinse carbon fiber afterwards, until after rinsing the specific conductivity of washing lotion not higher than 1000 micro-Siemens per centimeter, then under 68 DEG C of conditions vacuum drying.
Through amination zinc oxide nanowire-carbon fiber hybrid reinforcement body that aforesaid method obtains, comprise the non-starching T700 grade polypropylene itrile group carbon fiber obtained by dry-jet wet spinning process that massfraction is 96%, massfraction is the nano wire form zinc oxide of 3.8%, the zinc oxide length-to-diameter ratio of nano wire form is 7, massfraction is the zinc oxide of the film morphology be made up of nano particle of 0.1%, this zinc oxide film is prepared by the method for ald, and massfraction is the NH of 0.1%
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, and be connected in the mode of chemical bonding by Si-O-Zn chemical bond between this compound with zinc oxide nanowire.
Comparative example 1
Adopt (the Increasedinterfacestrengthincarbonfibercompositesthrough aZnOnanowireinterphase such as Lin, AdvancedFunctionalMaterials, 2009,19th volume, 16th phase, 2654 pages to 2660 pages) method reported, at non-starching T700 grade polypropylene itrile group carbon fiber (Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's production) the surface growth zinc oxide nanowire obtained by dry-jet wet spinning process of one section of 10 cm long.In the carbon fiber that the zinc oxide nanowire obtained is coated, the massfraction of carbon fiber is 96.8, and the massfraction of zinc oxide seed layer is 0.4, and the massfraction of zinc oxide nanowire is 2.8%.
Comparative example 2
Get the T700S carbon fiber of the toray company of one section of 20 cm long, remove carbon fiber surface sizing agent according to the method described in GJB1982-94 appendix A, afterwards by carbon fiber vacuum-drying 48 hours at 60 DEG C.Adopt (the Increasedinterfacestrengthincarbonfibercompositesthrough aZnOnanowireinterphase such as Lin, AdvancedFunctionalMaterials, 2009,19th volume, 16th phase, 2654 pages to 2660 pages) method reported, at carbon fiber surface growth of zinc oxide nano line.In the carbon fiber that the zinc oxide nanowire obtained is coated, the massfraction of carbon fiber is 97.1, and the massfraction of zinc oxide seed layer is 0.4, and the massfraction of zinc oxide nanowire is 2.5%.
Testing method
With E-51 epoxy resin for matrix, take DDS as solidifying agent, adopt droplet unsticking method, detect the interface shear strength between gained carbon fiber samples and E-51 epoxy resin in embodiment 1 to 8 and comparative example 1 and 2.Wherein, the solidification course of droplet matrix material is: heat 2 hours at 100 DEG C, heats 4 hours at 140 DEG C, heats 6 hours at 200 DEG C.Same droplet matrix material, wet heat treatment 48 hours in boiling water, then detects the interface shear strength between carbon fiber samples and E-51 epoxy resin equally.Finally, after calculating wet heat treatment, the interface shear strength conservation rate of each sample.
Test result is as shown in table 1:
Table 1
Obviously find out from test result, compared with zinc oxide nanowire carbon coated fiber traditional in comparative example, the method in embodiment significantly improves the wet-hot aging performance of carbon fiber/epoxy resin interface shear strength.This is mainly due to two reasons: the zinc-oxide nano Seed Layer 1) by adopting the method for atomic layer deposition to prepare high-quality at carbon fiber surface, thus carbon fiber surface obtain more fine and close with combine firmly zinc oxide nano-wire array; 2) amidized zinc oxide nanowire is by defining chemical bonding between amino and the epoxy group(ing) of substrate ring epoxy resins, adds the wet-hot aging performance at interface.
Claims (6)
1. amination zinc oxide nanowire-carbon fiber hybrid reinforcement body, is characterized in that comprising following mass percent composition:
Non-starching or the PAN-based carbon fiber 94.3%-96.8% except slurry,
The zinc oxide 3%-5% of nano wire form,
The zinc oxide 0.1%-0.5% of nano particle form
Silicon-containing compound 0.1%-0.2%.
2. a kind of amination zinc oxide nanowire-carbon fiber hybrid reinforcement body as claimed in claim 1, is characterized in that non-starching or the PAN-based carbon fiber except slurry are the polyacrylonitrile-based carbon carbon fiber of surface without groove structure.
3. a kind of amination zinc oxide nanowire-carbon fiber hybrid reinforcement body as claimed in claim 2, is characterized in that surface is PAN-based carbon fiber prepared by employing dry-jet wet spinning process without the polyacrylonitrile-based carbon carbon fiber of groove structure.
4. a kind of amination zinc oxide nanowire-carbon fiber hybrid reinforcement body as claimed in claim 1, is characterized in that the length-to-diameter ratio of the zinc oxide of described nano wire form is 5 to 15.
5. a kind of amination zinc oxide nanowire-carbon fiber hybrid reinforcement body as claimed in claim 1, is characterized in that described silicon-containing compound is NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, NH
2(CH
2cH
2nH)
2(CH
2)
3si (OCH
2cH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3or NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3in one.
6. the preparation technique of writing of a kind of amination zinc oxide nanowire-carbon fiber hybrid reinforcement body as described in any one of claim 1-5, is characterized in that comprising the following steps:
(1) with zinc methide or zinc ethyl for zinc source, the hydrogen peroxide being 10%-20% with deionized water or massfraction is for oxygen source, controlling zinc source temperature is-25 ~-23 DEG C, oxygen source temperature is 3-5 DEG C, at service temperature 230-240 DEG C, red-tape operati depositing time is 10-20 minute, by ald, non-starching or except slurry and surface prepare zinc-oxide nano layer without the PAN-based carbon fiber surface of groove structure;
(2) with gained carbon fiber in step (1) for anode, with the gold thread of diameter 50-60 micron for negative electrode,
Take silver-silver chloride electrode as reference electrode, three is placed in reaction soln, comprising concentration in reaction soln is one in the zinc nitrate of 1.5-2.0 mole often liter or zinc acetate, and concentration is the one in the vulkacit H of 1.5-2.0 mole often liter or ammoniacal liquor, reaction soln is warming up to 85-89 DEG C, again by D.C. regulated power supply to carbon fiber, gold thread and silver-silver chloride electrode energising, the voltage controlling to put on carbon fiber is-0.2 ~-0.4 volt relative to reference electrode, reaction times is 15-25 minute, reaction terminates rear employing washed with de-ionized water carbon fiber, and carbon fiber is dried,
(3) silicon-containing compound is dissolved in moisture and purity is in the ethanol of 85%-95%, the concentration controlling silicon-containing compound is 40wt%-50wt%, and by solution warms to 50-60 DEG C, then carbon fiber coated for gained zinc oxide nanowire in step (2) is placed in this solution, reaction 30-60 minute, adopt clear water to rinse carbon fiber afterwards, until the specific conductivity of washing lotion is less than or equal to 1000 micro-Siemens per centimeter after rinsing, then under 60-80 DEG C of condition vacuum drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976607A (en) * | 2018-08-11 | 2018-12-11 | 安徽华祺汽车装饰有限公司 | A kind of antistatic automobile interior material preparation method |
| CN112391698A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Nano material and preparation method thereof and quantum dot light-emitting diode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531038A (en) * | 2009-03-24 | 2009-09-16 | 中国航空工业第一集团公司北京航空材料研究院 | Method for growing zinc oxide crystal whisker on surface of carbon fiber and fabric thereof |
| CN101823759A (en) * | 2010-04-01 | 2010-09-08 | 江苏工业学院 | Continuous large-area zinc oxide nano-sheet and preparation method thereof |
| CN102628214A (en) * | 2012-04-09 | 2012-08-08 | 天津大学 | Carbon fiber composite material with ZnO layer electrolytically deposited on surface as well as preparation method and application thereof |
| CN103243544A (en) * | 2013-05-07 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Method for modifying carbon fiber surface |
-
2015
- 2015-10-12 CN CN201510456917.7A patent/CN105131335B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531038A (en) * | 2009-03-24 | 2009-09-16 | 中国航空工业第一集团公司北京航空材料研究院 | Method for growing zinc oxide crystal whisker on surface of carbon fiber and fabric thereof |
| CN101823759A (en) * | 2010-04-01 | 2010-09-08 | 江苏工业学院 | Continuous large-area zinc oxide nano-sheet and preparation method thereof |
| CN102628214A (en) * | 2012-04-09 | 2012-08-08 | 天津大学 | Carbon fiber composite material with ZnO layer electrolytically deposited on surface as well as preparation method and application thereof |
| CN103243544A (en) * | 2013-05-07 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Method for modifying carbon fiber surface |
Non-Patent Citations (1)
| Title |
|---|
| 魏荣慧，等: "碳纤维/ZnO复合材料的制备和性能研究", 《河南大学学报（自然科学版）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976607A (en) * | 2018-08-11 | 2018-12-11 | 安徽华祺汽车装饰有限公司 | A kind of antistatic automobile interior material preparation method |
| CN112391698A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Nano material and preparation method thereof and quantum dot light-emitting diode |
| CN112391698B (en) * | 2019-08-19 | 2022-10-11 | Tcl科技集团股份有限公司 | Nano material and preparation method thereof and quantum dot light-emitting diode |
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