CN107254065A - A kind of organic amine TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body - Google Patents
A kind of organic amine TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body Download PDFInfo
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Abstract
A kind of organic amine TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body, it is related to a kind of preparation method of carbon fiber multi-scale reinforcing body.The invention aims to the interface bond strength for solving existing carbon fibre composite it is low the problem of.Method：First, clean；2nd, aoxidize；3rd, chloride；4th, carbon fiber is grafted PEI in supercritical methanol；5th, TiO2The preparation of colloidal sol；6th, prepare surface and contain TiO2The carbon fiber of film；7th, it is grafted, obtains organic amine TiO2Nano wire/carbon fiber multi-scale reinforcing body.Organic amine TiO prepared by the present invention2Nano wire/carbon fiber multi-scale reinforcing body improves 88.6%~92.1% compared with precursor.The present invention can obtain a kind of organic amine TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body.
Description
Technical field
The present invention relates to a kind of preparation method of carbon fiber multi-scale reinforcing body.
Background technology
Carbon fibre reinforced composite is the Typical Representative of composite, because it has a light weight, the spy such as Gao Biqiang, high-modulus
Property, and be developing progressively as the preferred material in Aero-Space, the sophisticated military weapon of national defence and high-grade civilian Products Industry, spy
It is not that important role is play in the new industries such as big aircraft manufacturing, wind-power electricity generation.As the carbon fiber of reinforcement, have
High specific strength, low thermal expansion, good stability of the dimension, thermal conductivity is good, the features such as excellent in weather and good heat endurance, is considered as
This century is most advanced, develops one of most ripe material.It is while a series of excellent properties are possessed, there is also some not
Avoidable problem.I.e. carbon fiber surface is in random graphits structure, and surface is smooth and inert, can not between polymeric matrix
Good wetting and combination is realized, the performance of final influence composite material interface performance and overall performance.Therefore, it is compound to improve
The interface performance and combination property of material, it is necessary to be modified to carbon fiber surface.
Monodimension nanometer material (such as nano wire, nanometer rods, nanotube) is incorporated into carbon fiber surface, formed nano material/
Carbon fiber multi-scale reinforcing body, can improve the interface bond strength between fiber and resin matrix.If adopted in Hydrothermal Synthesiss
With supercritical fluid as reaction medium, the selectivity and conversion ratio of reaction can be not only improved, but also product knot can be improved
Crystalline substance.But monodimension nanometer material lacks chemical bonding effect when introducing, often, is only sticked in weaker physical absorption form
Fiber surface, can often depart from fiber surface in composite preparation process and influence interface synergistic effect, therefore, existing modification
The interface bond strength of carbon fibre composite is low, and interface shear strength typically improves 40%~50%.
The content of the invention
The invention aims to the interface bond strength for solving existing carbon fibre composite it is low the problem of, and provide one
Plant organic amine-TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body.
A kind of organic amine-TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body, is specifically complete according to the following steps
Into：
First, clean：
1., carbon fiber is put into the apparatus,Soxhlet's equipped with acetone, used under conditions of temperature is 75 DEG C~85 DEG C
Acetone cleaning removes the impurity of carbon fiber surface, and scavenging period is 2h~8h, and the carbon fiber after cleaning is taken out, acetone is obtained clear
Carbon fiber after washing；
2. the carbon fiber after the acetone cleaning for, 1. obtaining step one is placed in overcritical device, temperature be 350 DEG C~
370 DEG C are immersion 20min~30min in 8MPa~14MPa overcritical acetone-water system with pressure, obtain removing epoxy painting
Carbon fiber after layer；
Step one 2. described in overcritical acetone-water system in acetone and water volume ratio be 5:1；
3., the carbon fiber after the removal epoxy coating for 2. obtaining step one is placed in apparatus,Soxhlet's, is 75 in temperature
DEG C~85 DEG C under conditions of using acetone clean remove epoxy coating after carbon fiber, scavenging period be 2h~4h；After cleaning
Carbon fiber take out, temperature be 70 DEG C~80 DEG C under conditions of dry 2h~4h, obtain dry cleaning after carbon fiber；
2nd, aoxidize：
1., by step one 3. obtain dry cleaning after impregnated carbon fiber into potassium peroxydisulfate/silver nitrate mixed aqueous solution,
It is heated to 60 DEG C~80 DEG C, then constant temperature 1h~2h, the carbon fiber after being aoxidized under conditions of temperature is 60 DEG C~80 DEG C；Institute
The concentration of potassium peroxydisulfate is 0.1mol/L~0.2mol/L in the potassium peroxydisulfate stated/silver nitrate mixed aqueous solution；Described over cure
The concentration of silver nitrate is 0.0001mol/L~0.005mol/L in sour potassium/silver nitrate mixed aqueous solution；
Step 2 1. described in the body for drying quality and the potassium peroxydisulfate/silver nitrate mixed aqueous solution of carbon fiber after cleaning
Product is than being 0.1g:(10mL~12mL)；
2., the carbon fiber after the oxidation for 1. obtaining step 2 under room temperature condition soaks 5min~10min in distilled water,
Carbon fiber after being soaked in distilled water is taken out, reject distilled water；The quality and distilled water of carbon fiber after described oxidation
Volume ratio be (0.001g~0.006g):1mL；
3., repeat step two 2. 3 times~5 times, obtain the carbon oxide fiber after distilled water cleaning；
4. the carbon oxide fiber after the distilled water cleaning for, 3. obtaining step 2 is under conditions of temperature is 70 DEG C~80 DEG C
2h~4h is dried, dried carbon oxide fiber is obtained；
5., the dried carbon oxide fiber that 4. step 2 obtains is placed in the apparatus,Soxhlet's equipped with absolute ethyl alcohol,
Washes of absolute alcohol carbon oxide fiber is used under conditions of temperature is 90 DEG C~100 DEG C, scavenging period is 2h~4h, obtains nothing
The carbon fiber of the oxidation of water-ethanol cleaning；
6., the carbon fiber of the oxidation for the washes of absolute alcohol for 5. obtaining step 2 is in the condition that temperature is 70 DEG C~80 DEG C
Lower dry 2h~4h, obtains dry carbon oxide fiber；
3rd, chloride：
1., load thionyl chloride/DMF mixed liquor into dry reaction bulb, 6. step 2 is obtained
The carbon oxide fiber of drying be put into reaction bulb, be heated to 70 DEG C~90 DEG C, then in temperature be under conditions of 70 DEG C~90 DEG C
Isothermal reaction 40h~50h, obtains the carbon fiber of the chloride containing impurity；
Step is mixed by the quality of the carbon oxide fiber of the drying described in 1. with thionyl chloride/N,N-dimethylformamide
The volume ratio of liquid is (0.3g~0.6g):150mL；
Step 3 1. described in thionyl chloride/N,N-dimethylformamide mixed liquor in thionyl chloride and N, N- dimethyl
The volume ratio of formamide is (80~100):(4~8)；
2. it is, residual in the carbon fiber for the chloride containing impurity that 1. method first by vacuum distillation obtains step 3
The thionyl chloride stayed is removed, and obtains the carbon fiber of chloride；It is again 70 DEG C~90 in temperature by the carbon fiber of obtained chloride
DEG C vacuum drying chamber in dry 2h~4h, obtain the carbon fiber of dry chloride, it is finally that the carbon of dry chloride is fine
Dimension is placed on sealing preserve in drier；
4th, carbon fiber is grafted PEI in supercritical methanol：
1., absolute methanol is placed in teat glass at room temperature, polyethyleneimine is then added, then by dry chloride
Carbon fiber be added in teat glass, reuse glass stopper with holes and press the carbon fiber of dry chloride in people's methanol,
Obtain in the teat glass equipped with reactant；
Step 4 1. described in polyethyleneimine and absolute methanol volume ratio be (3~6):(50~60)；
Step 4 1. described in drying chloride carbon fiber quality and absolute methanol volume ratio for (0.3g~
0.6g):(50mL~60mL)；
2. it is put into the teat glass that, will be equipped with reactant in stainless steel cauldron, then stainless steel cauldron is closed, then
Stainless steel cauldron is heated to 230 DEG C~250 DEG C using salt bath furnace, then is 5MPa~7MPa in pressure and temperature is 230 DEG C
Grafting processing 5min~20min, obtains surface grafting PEI carbon fiber under conditions of~250 DEG C；
3. stainless steel cauldron, is cooled down into 10min~15min at room temperature, cold water spray is reused by stainless steel reaction
Kettle is cooled to room temperature, then opens stainless steel cauldron, and surface grafting PEI carbon fiber is taken out；
4., surface grafting PEI carbon fiber is cleaned using deionized water, the pH value to cleaning fluid is 7, then surface is connect
Branch PEI carbon fiber, which is put into absolute ethyl alcohol, to be cleaned 3 times~5 times, then surface grafting PEI carbon fiber is placed in into apparatus,Soxhlet's
In, surface grafting PEI carbon fiber 20min~30min is cleaned using acetone under conditions of temperature is 75 DEG C~85 DEG C；Again will
The carbon fiber of surface grafting PEI in apparatus,Soxhlet's is overturn, then uses third under conditions of temperature is 75 DEG C~85 DEG C
Ketone cleaning surface grafting PEI carbon fiber 20min~30min, is dried in temperature is 80 DEG C~120 DEG C of baking oven again after taking-up
4h~8h, obtains dry surface grafting PEI carbon fiber
5th, TiO2The preparation of colloidal sol：
Absolute ethyl alcohol and butyl titanate are mixed, solution of tetrabutyl titanate is obtained；It is added dropwise into solution of tetrabutyl titanate
Diethanol amine, then low whipping speed are stirring 20min~30min under conditions of 5r/min~8r/min, then in the condition of stirring
Under Aqueous Solutions of Polyethylene Glycol is added dropwise with 3 drops/min~5 drops/min rate of addition, then low whipping speed is 5r/min~8r/min
Lower stirring reaction 3h~5h, obtains TiO2Colloidal sol；
The volume ratio of butyl titanate and absolute ethyl alcohol described in step 5 is (3~8):(20~25)；
The volume ratio of diethanol amine and absolute ethyl alcohol described in step 5 is (0.5~2):(20~25)；
The quality of Aqueous Solutions of Polyethylene Glycol described in step 5 and the volume ratio of absolute ethyl alcohol are (0.5g~1g):
(20mL~25mL)；
The mass fraction of polyethylene glycol is 2%~5% in Aqueous Solutions of Polyethylene Glycol described in step 5；
6th, prepare surface and contain TiO2The carbon fiber of film：
1., by dry surface grafting PEI impregnated carbon fiber to TiO2In colloidal sol, then ultrasonic power be 600W~
Ultrasonic disperse 5min~12min under 1200W, then stand after 5min~7min, by dry surface grafting PEI carbon fiber at the uniform velocity
Upwards, vertical lifting, in one layer of uniform TiO of carbon fiber surface formation2Wet film；Surface is formed into one layer of uniform TiO again2It is wet
The carbon fiber of film dries 15min~25min in the case where temperature is 100 DEG C, and room temperature is naturally cooled to after taking-up；
2., repeat step six 1. 3 times~4 times, obtain surface and contain TiO2The carbon fiber of film；
7th, it is grafted：
1., butyl titanate is added in the hydrochloric acid that mass fraction is 35%~37%, then added under conditions of stirring
Enter deionized water, then low whipping speed is stirring reaction 2h~4h under 5r/min~8r/min, obtains precursor solution；
Step 7 1. described in butyl titanate and mass fraction be 35%~37% the volume ratio of hydrochloric acid be 3:
(0.8~1.5)；
Step 7 1. described in mass fraction for 35%~37% hydrochloric acid and deionized water volume ratio 1:1；
2., precursor solution is added in the autoclave of polytetrafluoroethyllining lining, then TiO is contained on surface2It is thin
The carbon fiber of film is immersed in precursor solution, then the autoclave of polytetrafluoroethyllining lining is sealed, after then sealing
Autoclave be 370 DEG C~390 DEG C in temperature and pressure is to keep 10min~30min under 20MPa~22.5MPa, obtain
Carbon fiber after processing；
3. autoclave, is naturally cooled into room temperature, then the carbon fiber after processing is taken out from precursor solution, it is first
First the carbon fiber after processing is cleaned by ultrasonic 3 times~5 times using deionized water, absolute ethyl alcohol is reused to the carbon fiber after processing
It is cleaned by ultrasonic 3 times~5 times, then dries naturally at room temperature, obtains organic amine-TiO2Nano wire/carbon fiber multi-scale reinforcing body.
Advantages of the present invention：
First, the present invention is polymerize using supercritical water as reaction dissolvent using carbon fiber surface dendrimer is grafted on
A large amount of terminal amine groups functional groups and similar compatibility principle that thing polyethyleneimine (PEI) molecule highly -branched is brought, realize with super
Strongly hydrophilic TiO2NWs in the grafting pattern of carbon fiber surface more high density and more high uniformity, prepared organic amine-
TiO2NWs/ carbon fiber multi-scale reinforcing bodies are there is provided a kind of method for effectively improving composite material interface binding ability, while can
Carbon fiber and applications to nanostructures scope are further expanded, the new material being more potential is provided for some popular research fields；
2nd, organic amine-TiO prepared by the present invention2Ti the and O constituent contents of nano wire/carbon fiber multi-scale reinforcing body are bright
Aobvious increase, Ti elements bring up to 13%~15.62%, O constituent contents by 4.49% by untreated 0% and bring up to 53.39%
~57.82%.Illustrate more TiO2Nanowire growth is in aminated carbon fiber surface.Organic amine-TiO2Nano wire/carbon fiber
Multi-scale reinforcing body contact angle reduction become apparent, in water and diiodomethane in contact angle drop to respectively 28.74 °~
30 ° and 27.32 °~29 °, surface can bring up to 70mN/m~72.95mN/m；
3rd, organic amine-TiO prepared by the present invention2The interface shear strength of nano wire/carbon fiber multi-scale reinforcing body is by original
The 64.9MPa of silk brings up to 122.4MPa~124.7MPa, improves 88.6%~92.1%.
The present invention can obtain a kind of organic amine-TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body.
Brief description of the drawings
Fig. 1 is 1 XPS for drying carbon fiber after the cleaning songs 3. obtained for the step one of embodiment one in the full spectrograms of XPS, Fig. 1
Line, 2 be the organic amine-TiO that 3. step 7 of embodiment one obtains2The XPS curves of nano wire/carbon fiber multi-scale reinforcing body；
Fig. 2 is the SEM for drying carbon fiber after the cleaning figures that 3. step one of embodiment one obtains；
Fig. 3 is the organic amine-TiO that 3. step 7 of embodiment one obtains2The SEM of nano wire/carbon fiber multi-scale reinforcing body
Figure；
Fig. 4 is 1 boundary for drying carbon fiber after cleaning 3. obtained for the step one of embodiment one in interface shear strength, Fig. 4
Face shear strength, 2 be the organic amine-TiO that 3. step 7 of embodiment one obtains2The boundary of nano wire/carbon fiber multi-scale reinforcing body
Face shear strength.
Embodiment
Embodiment one：Present embodiment is a kind of organic amine-TiO2Nano wire/carbon fiber multi-scale reinforcing body
Preparation method, what preparation method was specifically realized by the following steps：
First, clean：
1., carbon fiber is put into the apparatus,Soxhlet's equipped with acetone, used under conditions of temperature is 75 DEG C~85 DEG C
Acetone cleaning removes the impurity of carbon fiber surface, and scavenging period is 2h~8h, and the carbon fiber after cleaning is taken out, acetone is obtained clear
Carbon fiber after washing；
2. the carbon fiber after the acetone cleaning for, 1. obtaining step one is placed in overcritical device, temperature be 350 DEG C~
370 DEG C are immersion 20min~30min in 8MPa~14MPa overcritical acetone-water system with pressure, obtain removing epoxy painting
Carbon fiber after layer；
Step one 2. described in overcritical acetone-water system in acetone and water volume ratio be 5:1；
3., the carbon fiber after the removal epoxy coating for 2. obtaining step one is placed in apparatus,Soxhlet's, is 75 in temperature
DEG C~85 DEG C under conditions of using acetone clean remove epoxy coating after carbon fiber, scavenging period be 2h~4h；After cleaning
Carbon fiber take out, temperature be 70 DEG C~80 DEG C under conditions of dry 2h~4h, obtain dry cleaning after carbon fiber；
2nd, aoxidize：
1., by step one 3. obtain dry cleaning after impregnated carbon fiber into potassium peroxydisulfate/silver nitrate mixed aqueous solution,
It is heated to 60 DEG C~80 DEG C, then constant temperature 1h~2h, the carbon fiber after being aoxidized under conditions of temperature is 60 DEG C~80 DEG C；Institute
The concentration of potassium peroxydisulfate is 0.1mol/L~0.2mol/L in the potassium peroxydisulfate stated/silver nitrate mixed aqueous solution；Described over cure
The concentration of silver nitrate is 0.0001mol/L~0.005mol/L in sour potassium/silver nitrate mixed aqueous solution；
Step 2 1. described in the body for drying quality and the potassium peroxydisulfate/silver nitrate mixed aqueous solution of carbon fiber after cleaning
Product is than being 0.1g:(10mL~12mL)；
2., the carbon fiber after the oxidation for 1. obtaining step 2 under room temperature condition soaks 5min~10min in distilled water,
Carbon fiber after being soaked in distilled water is taken out, reject distilled water；The quality and distilled water of carbon fiber after described oxidation
Volume ratio be (0.001g~0.006g):1mL；
3., repeat step two 2. 3 times~5 times, obtain the carbon oxide fiber after distilled water cleaning；
4. the carbon oxide fiber after the distilled water cleaning for, 3. obtaining step 2 is under conditions of temperature is 70 DEG C~80 DEG C
2h~4h is dried, dried carbon oxide fiber is obtained；
5., the dried carbon oxide fiber that 4. step 2 obtains is placed in the apparatus,Soxhlet's equipped with absolute ethyl alcohol,
Washes of absolute alcohol carbon oxide fiber is used under conditions of temperature is 90 DEG C~100 DEG C, scavenging period is 2h~4h, obtains nothing
The carbon fiber of the oxidation of water-ethanol cleaning；
6., the carbon fiber of the oxidation for the washes of absolute alcohol for 5. obtaining step 2 is in the condition that temperature is 70 DEG C~80 DEG C
Lower dry 2h~4h, obtains dry carbon oxide fiber；
3rd, chloride：
1., load thionyl chloride/DMF mixed liquor into dry reaction bulb, 6. step 2 is obtained
The carbon oxide fiber of drying be put into reaction bulb, be heated to 70 DEG C~90 DEG C, then in temperature be under conditions of 70 DEG C~90 DEG C
Isothermal reaction 40h~50h, obtains the carbon fiber of the chloride containing impurity；
Step is mixed by the quality of the carbon oxide fiber of the drying described in 1. with thionyl chloride/N,N-dimethylformamide
The volume ratio of liquid is (0.3g~0.6g):150mL；
Step 3 1. described in thionyl chloride/N,N-dimethylformamide mixed liquor in thionyl chloride and N, N- dimethyl
The volume ratio of formamide is (80~100):(4~8)；
2. it is, residual in the carbon fiber for the chloride containing impurity that 1. method first by vacuum distillation obtains step 3
The thionyl chloride stayed is removed, and obtains the carbon fiber of chloride；It is again 70 DEG C~90 in temperature by the carbon fiber of obtained chloride
DEG C vacuum drying chamber in dry 2h~4h, obtain the carbon fiber of dry chloride, it is finally that the carbon of dry chloride is fine
Dimension is placed on sealing preserve in drier；
4th, carbon fiber is grafted PEI in supercritical methanol：
1., absolute methanol is placed in teat glass at room temperature, polyethyleneimine is then added, then by dry chloride
Carbon fiber be added in teat glass, reuse glass stopper with holes and press the carbon fiber of dry chloride in people's methanol,
Obtain in the teat glass equipped with reactant；
Step 4 1. described in polyethyleneimine and absolute methanol volume ratio be (3~6):(50~60)；
Step 4 1. described in drying chloride carbon fiber quality and absolute methanol volume ratio for (0.3g~
0.6g):(50mL~60mL)；
2. it is put into the teat glass that, will be equipped with reactant in stainless steel cauldron, then stainless steel cauldron is closed, then
Stainless steel cauldron is heated to 230 DEG C~250 DEG C using salt bath furnace, then is 5MPa~7MPa in pressure and temperature is 230 DEG C
Grafting processing 5min~20min, obtains surface grafting PEI carbon fiber under conditions of~250 DEG C；
3. stainless steel cauldron, is cooled down into 10min~15min at room temperature, cold water spray is reused by stainless steel reaction
Kettle is cooled to room temperature, then opens stainless steel cauldron, and surface grafting PEI carbon fiber is taken out；
4., surface grafting PEI carbon fiber is cleaned using deionized water, the pH value to cleaning fluid is 7, then surface is connect
Branch PEI carbon fiber, which is put into absolute ethyl alcohol, to be cleaned 3 times~5 times, then surface grafting PEI carbon fiber is placed in into apparatus,Soxhlet's
In, surface grafting PEI carbon fiber 20min~30min is cleaned using acetone under conditions of temperature is 75 DEG C~85 DEG C；Again will
The carbon fiber of surface grafting PEI in apparatus,Soxhlet's is overturn, then uses third under conditions of temperature is 75 DEG C~85 DEG C
Ketone cleaning surface grafting PEI carbon fiber 20min~30min, is dried in temperature is 80 DEG C~120 DEG C of baking oven again after taking-up
4h~8h, obtains dry surface grafting PEI carbon fiber
5th, TiO2The preparation of colloidal sol：
Absolute ethyl alcohol and butyl titanate are mixed, solution of tetrabutyl titanate is obtained；It is added dropwise into solution of tetrabutyl titanate
Diethanol amine, then low whipping speed are stirring 20min~30min under conditions of 5r/min~8r/min, then in the condition of stirring
Under Aqueous Solutions of Polyethylene Glycol is added dropwise with 3 drops/min~5 drops/min rate of addition, then low whipping speed is 5r/min~8r/min
Lower stirring reaction 3h~5h, obtains TiO2Colloidal sol；
The volume ratio of butyl titanate and absolute ethyl alcohol described in step 5 is (3~8):(20~25)；
The volume ratio of diethanol amine and absolute ethyl alcohol described in step 5 is (0.5~2):(20~25)；
The quality of Aqueous Solutions of Polyethylene Glycol described in step 5 and the volume ratio of absolute ethyl alcohol are (0.5g~1g):
(20mL~25mL)；
The mass fraction of polyethylene glycol is 2%~5% in Aqueous Solutions of Polyethylene Glycol described in step 5；
6th, prepare surface and contain TiO2The carbon fiber of film：
1., by dry surface grafting PEI impregnated carbon fiber to TiO2In colloidal sol, then ultrasonic power be 600W~
Ultrasonic disperse 5min~12min under 1200W, then stand after 5min~7min, by dry surface grafting PEI carbon fiber at the uniform velocity
Upwards, vertical lifting, in one layer of uniform TiO of carbon fiber surface formation2Wet film；Surface is formed into one layer of uniform TiO again2It is wet
The carbon fiber of film dries 15min~25min in the case where temperature is 100 DEG C, and room temperature is naturally cooled to after taking-up；
2., repeat step six 1. 3 times~4 times, obtain surface and contain TiO2The carbon fiber of film；
7th, it is grafted：
1., butyl titanate is added in the hydrochloric acid that mass fraction is 35%~37%, then added under conditions of stirring
Enter deionized water, then low whipping speed is stirring reaction 2h~4h under 5r/min~8r/min, obtains precursor solution；
Step 7 1. described in butyl titanate and mass fraction be 35%~37% the volume ratio of hydrochloric acid be 3:
(0.8~1.5)；
Step 7 1. described in mass fraction for 35%~37% hydrochloric acid and deionized water volume ratio 1:1；
2., precursor solution is added in the autoclave of polytetrafluoroethyllining lining, then TiO is contained on surface2It is thin
The carbon fiber of film is immersed in precursor solution, then the autoclave of polytetrafluoroethyllining lining is sealed, after then sealing
Autoclave be 370 DEG C~390 DEG C in temperature and pressure is to keep 10min~30min under 20MPa~22.5MPa, obtain
Carbon fiber after processing；
3. autoclave, is naturally cooled into room temperature, then the carbon fiber after processing is taken out from precursor solution, it is first
First the carbon fiber after processing is cleaned by ultrasonic 3 times~5 times using deionized water, absolute ethyl alcohol is reused to the carbon fiber after processing
It is cleaned by ultrasonic 3 times~5 times, then dries naturally at room temperature, obtains organic amine-TiO2Nano wire/carbon fiber multi-scale reinforcing body.
The advantage of present embodiment：
First, present embodiment using supercritical water as reaction dissolvent, using being grafted on carbon fiber surface dendrimer
A large amount of terminal amine groups functional groups and similar compatibility principle that polymer polyethylenimine (PEI) molecule highly -branched is brought, realize tool
There is ultrahydrophilic TiO2NWs in the grafting pattern of carbon fiber surface more high density and more high uniformity, prepared organic amine-
TiO2NWs/ carbon fiber multi-scale reinforcing bodies are there is provided a kind of method for effectively improving composite material interface binding ability, while can
Carbon fiber and applications to nanostructures scope are further expanded, the new material being more potential is provided for some popular research fields；
2nd, organic amine-TiO prepared by present embodiment2Ti the and O elements of nano wire/carbon fiber multi-scale reinforcing body contain
Amount substantially increase, Ti elements bring up to 13%~15.62%, O constituent contents by untreated 0% and brought up to by 4.49%
53.39%~57.82%.Illustrate more TiO2Nanowire growth is in aminated carbon fiber surface.Organic amine-TiO2Nano wire/
Becoming apparent for the contact angle reduction of carbon fiber multi-scale reinforcing body, is dropped to respectively in water with the contact angle in diiodomethane
28.74 °~30 ° and 27.32 °~29 °, surface can bring up to 70mN/m~72.95mN/m；
3rd, organic amine-TiO prepared by present embodiment2The interface shear strength of nano wire/carbon fiber multi-scale reinforcing body
122.4MPa~124.7MPa is brought up to by the 64.9MPa of precursor, 88.6%~92.1% is improved.
Present embodiment can obtain a kind of organic amine-TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body.
Embodiment two：Present embodiment is with the difference of embodiment one：Step 3 is 1. to dry anti-
Loading thionyl chloride/DMF mixed liquor in bottle is answered, the carbon oxide fiber for the drying that 6. step 2 is obtained is put
Enter in reaction bulb, be heated to 70 DEG C~76 DEG C, then isothermal reaction 45h~48h under conditions of temperature is 70 DEG C~76 DEG C, obtain
The carbon fiber of chloride containing impurity.Other steps are identical with embodiment one.
Embodiment three：One of present embodiment and embodiment one or two difference is：Step 4 2. in
It is put into the teat glass that will be equipped with reactant in stainless steel cauldron, then stainless steel cauldron is closed, reuses salt bath furnace
Stainless steel cauldron is heated to 230 DEG C~240 DEG C, then in the bar that pressure is 5MPa~6MPa and temperature is 230 DEG C~240 DEG C
Grafting processing 5min~10min, obtains surface grafting PEI carbon fiber under part.Other steps and embodiment one or two
It is identical.
Embodiment four：One of present embodiment and embodiment one to three difference is：Step 4 2. in
It is put into the teat glass that will be equipped with reactant in stainless steel cauldron, then stainless steel cauldron is closed, reuses salt bath furnace
Stainless steel cauldron is heated to 240 DEG C~245 DEG C, then is 6MPa~6.5MPa in pressure and temperature is 240 DEG C~245 DEG C
Under the conditions of grafting processing 10min~20min, obtain surface grafting PEI carbon fiber.Other steps and embodiment one to
Three is identical.
Embodiment five：One of present embodiment and embodiment one to four difference is：Institute in step 5
The butyl titanate and the volume ratio of absolute ethyl alcohol stated are (5~8):5.Other steps are identical with embodiment one to four.
Embodiment six：One of present embodiment and embodiment one to five difference is：Institute in step 5
The diethanol amine and the volume ratio of absolute ethyl alcohol stated are (1~2):25.Other steps are identical with embodiment one to five.
Embodiment seven：One of present embodiment and embodiment one to six difference is：Step 6 1. in
By dry surface grafting PEI impregnated carbon fiber to TiO2In colloidal sol, then the ultrasonic disperse 5min in the case where ultrasonic power is 600W
~10min, then stand after 5min~6min, dry surface grafting PEI carbon fiber is at the uniform velocity upward, vertical lifting, in carbon
One layer of uniform TiO of fiber surface formation2Wet film；Surface is formed into one layer of uniform TiO again2The carbon fiber of wet film is in temperature
15min~20min is dried at 100 DEG C, room temperature is naturally cooled to after taking-up.Other steps and the phase of embodiment one to six
Together.
Embodiment eight：One of present embodiment and embodiment one to seven difference is：Step 7 2. in
Precursor solution is added in the autoclave of polytetrafluoroethyllining lining, then TiO is contained on surface2The carbon fiber leaching of film
Enter into precursor solution, then the autoclave of polytetrafluoroethyllining lining is sealed, then by the autoclave after sealing
It is 370 DEG C~375 DEG C in temperature and pressure is to keep 10min~20min under 20MPa~22.5MPa, the carbon fibre after handle
Dimension.Other steps are identical with embodiment one to seven.
Embodiment nine：One of present embodiment and embodiment one to eight difference is：Step 7 3. in
Every time using deionized water to after processing carbon fiber be cleaned by ultrasonic power be 600W~1200W, the time be 5min~
10min.Other steps are identical with embodiment one to eight.
Embodiment ten：One of present embodiment and embodiment one to nine difference is：Step 7 3. in
Every time using absolute ethyl alcohol to after processing carbon fiber be cleaned by ultrasonic power be 600W~1200W, the time be 5min~
10min.Other steps are identical with embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of organic amine-TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body be specifically press with
What lower step was completed：
First, clean：
1., 0.4g carbon fibers are put into the apparatus,Soxhlet's equipped with acetone, third is used under conditions of temperature is 80 DEG C
Ketone cleaning removes the impurity of carbon fiber surface, and scavenging period is 4h, and the carbon fiber after cleaning is taken out, and obtains after acetone cleaning
Carbon fiber；
2. the carbon fiber after the acetone cleaning for, 1. obtaining step one is placed in overcritical device, temperature be 360 DEG C and
Pressure obtains removing the carbon fiber after epoxy coating to soak 20min in the 10MPa overcritical acetone-water systems of 30mL；
Step one 2. described in overcritical acetone-water system in acetone and water volume ratio be 5:1；
3., the carbon fiber after the removal epoxy coating for 2. obtaining step one is placed in apparatus,Soxhlet's, is 80 in temperature
The carbon fiber removed after epoxy coating is cleaned under conditions of DEG C using acetone, scavenging period is 2h；Carbon fiber after cleaning is taken
Go out, 2h is dried under conditions of temperature is 70 DEG C, obtain drying carbon fiber after cleaning；
2nd, aoxidize：
1. the impregnated carbon fiber after cleaning of drying that 3. step one obtains, is mixed water-soluble to 40mL potassium peroxydisulfates/silver nitrate
In liquid, 70 DEG C, then constant temperature 1h, the carbon fiber after being aoxidized under conditions of temperature is 70 DEG C are heated to；Described persulfuric acid
The concentration of potassium peroxydisulfate is 0.1mol/L in potassium/silver nitrate mixed aqueous solution；Described potassium peroxydisulfate/silver nitrate mixed aqueous solution
The concentration of middle silver nitrate is 0.001mol/L；
2., the carbon fiber after the oxidation for 1. obtaining step 2 under room temperature condition soaks 5min in distilled water, will be through steaming
Carbon fiber after being soaked in distilled water takes out, reject distilled water；The quality of carbon fiber after described oxidation and the volume of distilled water
Than for 0.006g:1mL；
3., repeat step two 2. 3 times, obtain the carbon oxide fiber after distilled water cleaning；
4. the carbon oxide fiber after the distilled water cleaning for, 3. obtaining step 2 is dried under conditions of temperature is 70 DEG C
2h, obtains dried carbon oxide fiber；
5., the dried carbon oxide fiber that 4. step 2 obtains is placed in the apparatus,Soxhlet's equipped with absolute ethyl alcohol,
Washes of absolute alcohol carbon oxide fiber is used under conditions of temperature is 90 DEG C, scavenging period is 2h, obtains washes of absolute alcohol
Oxidation carbon fiber；
6., the carbon fiber of the oxidation for the washes of absolute alcohol for 5. obtaining step 2 is dried under conditions of temperature is 70 DEG C
2h, obtains dry carbon oxide fiber；
3rd, chloride：
1., load thionyl chloride/DMF mixed liquor into dry reaction bulb, 6. step 2 is obtained
The carbon oxide fiber of drying be put into reaction bulb, be heated to 70 DEG C, then in temperature be isothermal reaction 40h under conditions of 70 DEG C,
Obtain the carbon fiber of the chloride containing impurity；
Step is mixed by the quality of the carbon oxide fiber of the drying described in 1. with thionyl chloride/N,N-dimethylformamide
The volume ratio of liquid is 0.3g:150mL；
Step 3 1. described in thionyl chloride/N,N-dimethylformamide mixed liquor in thionyl chloride and N, N- dimethyl
The volume ratio of formamide is 80:4；
2. it is, residual in the carbon fiber for the chloride containing impurity that 1. method first by vacuum distillation obtains step 3
The thionyl chloride stayed is removed, and obtains the carbon fiber of chloride；It is again that the carbon fiber of obtained chloride is true for 70 DEG C in temperature
3h is dried in empty drying box, the carbon fiber of dry chloride is obtained, finally the carbon fiber by dry chloride is placed on drying
Sealing preserve in device；
4th, carbon fiber is grafted PEI in supercritical methanol：
1., 50mL absolute methanols are placed in teat glass at room temperature, 5mL polyethyleneimines are then added, then by 0.3g
The carbon fiber of dry chloride is added in teat glass, reuses glass stopper with holes by the carbon fiber of dry chloride
Press in people's methanol, obtain in the teat glass equipped with reactant；
2. it is put into the teat glass that, will be equipped with reactant in stainless steel cauldron, then stainless steel cauldron is closed, then
Stainless steel cauldron is heated to 240 DEG C using salt bath furnace, then is 6MPa in pressure and temperature is under conditions of 240 DEG C at grafting
10min is managed, surface grafting PEI carbon fiber is obtained；
3. stainless steel cauldron, is cooled down into 10min at room temperature, cold water spray is reused and is cooled to stainless steel cauldron
Room temperature, then stainless steel cauldron is opened, surface grafting PEI carbon fiber is taken out；
4., surface grafting PEI carbon fiber is cleaned using deionized water, the pH value to cleaning fluid is 7, then surface is connect
Branch PEI carbon fiber, which is put into absolute ethyl alcohol, to be cleaned 5 times, then surface grafting PEI carbon fiber is placed in apparatus,Soxhlet's,
Temperature is the carbon fiber 30min under conditions of 80 DEG C using acetone cleaning surface grafting PEI；Again by the surface in apparatus,Soxhlet's
Grafting PEI carbon fiber is overturn, then the carbon fiber under conditions of temperature is 80 DEG C using acetone cleaning surface grafting PEI
30min, dries 4h in temperature is 80 DEG C of baking oven again after taking-up, obtains dry surface grafting PEI carbon fiber
5th, TiO2The preparation of colloidal sol：
20mL absolute ethyl alcohols and 5mL butyl titanates are mixed, solution of tetrabutyl titanate is obtained；To solution of tetrabutyl titanate
Middle dropwise addition 1mL diethanol amine, then low whipping speed are to stir 30min under conditions of 5r/min, then with 3 under conditions of stirring
0.5g Aqueous Solutions of Polyethylene Glycol is added dropwise in drop/min rate of addition, then low whipping speed is stirring reaction 4h under 6r/min, is obtained
TiO2Colloidal sol；
The mass fraction of polyethylene glycol is 2% in Aqueous Solutions of Polyethylene Glycol described in step 5；
6th, prepare surface and contain TiO2The carbon fiber of film：
1., by dry surface grafting PEI impregnated carbon fiber to TiO2In colloidal sol, then ultrasonic power be 600W under surpass
Sound disperses 10min, then stands after 5min, and dry surface grafting PEI carbon fiber is at the uniform velocity upward, vertical lifting, fine in carbon
Dimension table face forms one layer of uniform TiO2Wet film；Surface is formed into one layer of uniform TiO again2The carbon fiber of wet film is 100 in temperature
20min is dried at DEG C, room temperature is naturally cooled to after taking-up；
2., repeat step six 1. 3 times, obtain surface and contain TiO2The carbon fiber of film；
7th, it is grafted：
1., 30mL butyl titanates are added in the hydrochloric acid that 10mL mass fractions are 37%, then under conditions of stirring
Deionized water is added, then low whipping speed is stirring reaction 3h under 5r/min, obtains precursor solution；
Step 7 1. described in mass fraction for 37% hydrochloric acid and deionized water volume ratio 1:1；
2., precursor solution is added in the autoclave of polytetrafluoroethyllining lining, then TiO is contained on surface2It is thin
The carbon fiber of film is immersed in precursor solution, then the autoclave of polytetrafluoroethyllining lining is sealed, after then sealing
Autoclave be 375 DEG C in temperature and pressure is to keep 10min under 22.5MPa, the carbon fiber after being handled；
3. autoclave, is naturally cooled into room temperature, then the carbon fiber after processing is taken out from precursor solution, it is first
First the carbon fiber after processing is cleaned by ultrasonic 4 times using deionized water, absolute ethyl alcohol is reused to the carbon fiber ultrasound after processing
Cleaning 4 times, then dry naturally at room temperature, obtain organic amine-TiO2Nano wire/carbon fiber multi-scale reinforcing body；
Step 7 3. in the power that is cleaned by ultrasonic every time using deionized water to the carbon fiber after processing be 600W, the time is
5min；
Step 7 3. in the power that is cleaned by ultrasonic every time using absolute ethyl alcohol to the carbon fiber after processing be 600W, the time is
5min。
Fig. 1 is 1 XPS for drying carbon fiber after the cleaning songs 3. obtained for the step one of embodiment one in the full spectrograms of XPS, Fig. 1
Line, 2 be the organic amine-TiO that 3. step 7 of embodiment one obtains2The XPS curves of nano wire/carbon fiber multi-scale reinforcing body；
Table 1 is Fig. 1 constituent content.
Table 1
It was found from Fig. 1 and table 1, carbon fiber is after aminated and nanowire growth, and Ti constituent contents substantially increase, by not
The 0% of processing brings up to 13.81%.Polyethyleneimine (PEI) is grafted to carbon fiber surface, can introduce primary in carbon fiber surface
Amine, secondary amine, polarity more big easier and TiO2Polar hydroxyl groups in NWs are combined, so surface grafting PEI carbon fiber surface meeting
Grow more TiO2NWs。
Fig. 2 is the SEM for drying carbon fiber after the cleaning figures that 3. step one of embodiment one obtains；
Fig. 3 is the organic amine-TiO that 3. step 7 of embodiment one obtains2The SEM of nano wire/carbon fiber multi-scale reinforcing body
Figure；
It was found from Fig. 2 and Fig. 3, the organic amine-TiO that 3. step 7 of embodiment one obtains2Nano wire/carbon fiber multi-dimension increases
The TiO of strong body superficial growth2Nano wire is more finer and close, it may be possible to the polar group brought due to grafting branched polymer PEI
Group is more, makes the amido and TiO of carbon fiber surface2Nano wire combines stronger, when its polymer matrix composites is by destroying, will
More energy can be absorbed, the interface bond strength between carbon fiber and resin matrix is largely improved.
Table 2
As known from Table 2, the organic amine-TiO that 3. step 7 of embodiment one obtains2Nano wire/carbon fiber multi-scale reinforcing body
Superficial growth TiO2Contact angle after nano wire in water and diiodomethane is significantly more reduced, polar component and dispersion point
Amount is correspondingly improved, and surface can also be increased substantially, and 71.36mN/m is increased to by 30.13mN/m.This explanation PEI and TiO2Receive
Rice noodles are grafted to the organic amine-TiO of carbon fiber surface preparation2Nano wire/carbon fiber multi-scale reinforcing body wettability of the surface has
Obvious improvement.This will be helpful to the raising of the interface performance of final composite.
Interface shear strength tests (one)：
(1) this experiment is using FA620 type composite material interfaces evaluating apparatus (Japanese Dong Rong Co., Ltd.).First by carbon
Fibre single thread is pasted onto on metallic support securely with double faced adhesive tape, then it is 100 to weigh mass ratio:32 epoxy resin E-51 and solid
Agent H-256 is simultaneously well mixed, and dips a dropping point on carbon mono-filaments surface with draw point, and epoxy resin can be made because of surface tension
With resin droplet is formed, then constant temperature keeps 2h, 2h and 3h to be solidified respectively at 90 DEG C, 120 DEG C and 150 DEG C, so as to make
Obtain carbon fiber/epoxy resin droplet composite.In test process, the resin droplet for choosing 80 μm or so of diameter is used as test
Object, resin bulb diameter is too big, and easily by break of CFRP, resin balls do not depart from fiber, if resin balls are too small, the equipment edge of a knife
It can't clip, the effect edge of a knife that test process does not test power is just slipped over from resin balls, load loading velocity is 0.5 μm of s-1,
Every group of sample measures 50 valid data and calculates its average value, and described carbon fiber is doing that 3. step one of embodiment one obtains
Carbon fiber after dry cleaning.Interface shear strength (IFSS) can be obtained according to formula (1)：
F in formulamax--- the load peaks (N) during fiber pull-out；
D --- fiber filament diameter (m)；
L --- epoxy resin droplet embedding length (m).
The interface shear strength for drying carbon fiber after cleaning 3. obtained to the step one of embodiment one according to the method described above enters
Row test；
Interface shear strength tests (two)：The difference that this test tests (one) with interface shear strength is：Described carbon
Fiber is the organic amine-TiO that 3. step 7 of embodiment one obtains2Nano wire/carbon fiber multi-scale reinforcing body.Other steps and survey
Method for testing is identical with interface shear strength test (one).
Interface shear strength tests (one) and interface shear strength test (two) test result is as shown in Figure 4；Fig. 4 is implementation
The interface shear strength for drying carbon fiber after cleaning that 3. step one of example one obtains, 2 be having that 3. step 7 of embodiment one obtains
Machine amine-TiO2The interface shear strength of nano wire/carbon fiber multi-scale reinforcing body.
As can be seen from Figure 4, the organic amine-TiO that 3. step 7 of embodiment one obtains2Nano wire/carbon fiber multi-scale reinforcing body
Interface shear strength 122.4MPa is brought up to by the 64.9MPa of precursor, improve 88.6%；This is due to：(1)TiO2Nano wire
It is close with a large amount of amido polarity of carbon fiber surface, associativity enhancing, while it has good wellability between resin matrix,
Fine and close TiO2Nano wire can preferably transmit load and absorb energy of rupture, so its interface bonding energy equivalent to boundary layer
Power strengthens；
Embodiment two：A kind of organic amine-TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body, is specifically pressed
What following steps were completed：
First, clean：
1., 0.6g carbon fibers are put into the apparatus,Soxhlet's equipped with acetone, third is used under conditions of temperature is 82 DEG C
Ketone cleaning removes the impurity of carbon fiber surface, and scavenging period is 4h, and the carbon fiber after cleaning is taken out, and obtains after acetone cleaning
Carbon fiber；
2. the carbon fiber after the acetone cleaning for, 1. obtaining step one is placed in overcritical device, temperature be 365 DEG C and
Pressure obtains removing the carbon fiber after epoxy coating to soak 30min in the 12MPa overcritical acetone-water systems of 30mL；
Step one 2. described in overcritical acetone-water system in acetone and water volume ratio be 5:1；
3., the carbon fiber after the removal epoxy coating for 2. obtaining step one is placed in apparatus,Soxhlet's, is 82 in temperature
The carbon fiber removed after epoxy coating is cleaned under conditions of DEG C using acetone, scavenging period is 2h；Carbon fiber after cleaning is taken
Go out, 2h is dried under conditions of temperature is 70 DEG C, obtain drying carbon fiber after cleaning；
2nd, aoxidize：
1. the impregnated carbon fiber after cleaning of drying that 3. step one obtains, is mixed water-soluble to 70mL potassium peroxydisulfates/silver nitrate
In liquid, 75 DEG C, then constant temperature 1.5h, the carbon fiber after being aoxidized under conditions of temperature is 75 DEG C are heated to；Described over cure
The concentration of potassium peroxydisulfate is 0.1mol/L in sour potassium/silver nitrate mixed aqueous solution；Described potassium peroxydisulfate/silver nitrate mixing is water-soluble
The concentration of silver nitrate is 0.001mol/L in liquid；
2., the carbon fiber after the oxidation for 1. obtaining step 2 under room temperature condition soaks 10min in distilled water, will be through steaming
Carbon fiber after being soaked in distilled water takes out, reject distilled water；The quality of carbon fiber after described oxidation and the volume of distilled water
Than for 0.006g:1mL；
3., repeat step two 2. 5 times, obtain the carbon oxide fiber after distilled water cleaning；
4. the carbon oxide fiber after the distilled water cleaning for, 3. obtaining step 2 is dried under conditions of temperature is 70 DEG C
2h, obtains dried carbon oxide fiber；
5., the dried carbon oxide fiber that 4. step 2 obtains is placed in the apparatus,Soxhlet's equipped with absolute ethyl alcohol,
Washes of absolute alcohol carbon oxide fiber is used under conditions of temperature is 92 DEG C, scavenging period is 4h, obtains washes of absolute alcohol
Oxidation carbon fiber；
6., the carbon fiber of the oxidation for the washes of absolute alcohol for 5. obtaining step 2 is dried under conditions of temperature is 70 DEG C
2h, obtains dry carbon oxide fiber；
3rd, chloride：
1., load thionyl chloride/DMF mixed liquor into dry reaction bulb, 6. step 2 is obtained
The carbon oxide fiber of drying be put into reaction bulb, be heated to 76 DEG C, then in temperature be isothermal reaction 48h under conditions of 76 DEG C,
Obtain the carbon fiber of the chloride containing impurity；
Step is mixed by the quality of the carbon oxide fiber of the drying described in 1. with thionyl chloride/N,N-dimethylformamide
The volume ratio of liquid is 0.6g:150mL；
Step 3 1. described in thionyl chloride/N,N-dimethylformamide mixed liquor in thionyl chloride and N, N- dimethyl
The volume ratio of formamide is 100:5；
2. it is, residual in the carbon fiber for the chloride containing impurity that 1. method first by vacuum distillation obtains step 3
The thionyl chloride stayed is removed, and obtains the carbon fiber of chloride；It is again that the carbon fiber of obtained chloride is true for 80 DEG C in temperature
2h is dried in empty drying box, the carbon fiber of dry chloride is obtained, finally the carbon fiber by dry chloride is placed on drying
Sealing preserve in device；
4th, carbon fiber is grafted PEI in supercritical methanol：
1., 60mL absolute methanols are placed in teat glass at room temperature, 6mL polyethyleneimines are then added, then by drying
The carbon fiber of chloride be added in teat glass, reuse glass stopper with holes and the carbon fiber of dry chloride pressed into people
In methanol, obtain in the teat glass equipped with reactant；
Step 4 1. described in drying chloride carbon fiber quality and absolute methanol volume ratio be 0.6g:
60mL；
2. it is put into the teat glass that, will be equipped with reactant in stainless steel cauldron, then stainless steel cauldron is closed, then
Stainless steel cauldron is heated to 245 DEG C using salt bath furnace, then is 6.5MPa in pressure and temperature is grafting under conditions of 245 DEG C
20min is handled, surface grafting PEI carbon fiber is obtained；
3. stainless steel cauldron, is cooled down into 15min at room temperature, cold water spray is reused and is cooled to stainless steel cauldron
Room temperature, then stainless steel cauldron is opened, surface grafting PEI carbon fiber is taken out；
4., surface grafting PEI carbon fiber is cleaned using deionized water, the pH value to cleaning fluid is 7, then surface is connect
Branch PEI carbon fiber, which is put into absolute ethyl alcohol, to be cleaned 4 times, then surface grafting PEI carbon fiber is placed in apparatus,Soxhlet's,
Temperature is the carbon fiber 20min under conditions of 80 DEG C using acetone cleaning surface grafting PEI；Again by the surface in apparatus,Soxhlet's
Grafting PEI carbon fiber is overturn, then the carbon fiber under conditions of temperature is 80 DEG C using acetone cleaning surface grafting PEI
30min, dries 4h in temperature is 80 DEG C of baking oven again after taking-up, obtains dry surface grafting PEI carbon fiber
5th, TiO2The preparation of colloidal sol：
25mL absolute ethyl alcohols and 8mL butyl titanates are mixed, solution of tetrabutyl titanate is obtained；To solution of tetrabutyl titanate
Middle dropwise addition 2mL diethanol amine, then low whipping speed are to stir 20min under conditions of 5r/min, then with 3 under conditions of stirring
1g Aqueous Solutions of Polyethylene Glycol is added dropwise in drop/min rate of addition, then low whipping speed is stirring reaction 4h under 8r/min, is obtained
TiO2Colloidal sol；
The mass fraction of polyethylene glycol is 5% in Aqueous Solutions of Polyethylene Glycol described in step 5；
6th, prepare surface and contain TiO2The carbon fiber of film：
1., by dry surface grafting PEI impregnated carbon fiber to TiO2In colloidal sol, then it is super for 1200 times in ultrasonic power
Sound disperses 10min, then stands after 5min, and dry surface grafting PEI carbon fiber is at the uniform velocity upward, vertical lifting, fine in carbon
Dimension table face forms one layer of uniform TiO2Wet film；Surface is formed into one layer of uniform TiO again2The carbon fiber of wet film is 100 in temperature
20min is dried at DEG C, room temperature is naturally cooled to after taking-up；
2., repeat step six 1. 3 times, obtain surface and contain TiO2The carbon fiber of film；
7th, it is grafted：
1., 40mL butyl titanates are added in the hydrochloric acid that 15mL mass fractions are 37%, then under conditions of stirring
Deionized water is added, then low whipping speed is stirring reaction 2h under 8r/min, obtains precursor solution；
Step 7 1. described in mass fraction for 37% hydrochloric acid and deionized water volume ratio 1:1；
2., precursor solution is added in the autoclave of polytetrafluoroethyllining lining, then TiO is contained on surface2It is thin
The carbon fiber of film is immersed in precursor solution, then the autoclave of polytetrafluoroethyllining lining is sealed, after then sealing
Autoclave be 375 DEG C in temperature and pressure is to keep 10min under 22.5MPa, the carbon fiber after being handled；
3. autoclave, is naturally cooled into room temperature, then the carbon fiber after processing is taken out from precursor solution, it is first
First the carbon fiber after processing is cleaned by ultrasonic 4 times using deionized water, absolute ethyl alcohol is reused to the carbon fiber ultrasound after processing
Cleaning 4 times, then dry naturally at room temperature, obtain organic amine-TiO2Nano wire/carbon fiber multi-scale reinforcing body；
Step 7 3. in every time using deionized water to after processing carbon fiber be cleaned by ultrasonic power be 1200W, the time
For 10min；
Step 7 3. in every time using absolute ethyl alcohol to after processing carbon fiber be cleaned by ultrasonic power be 1200W, the time
For 10min.
Organic amine-TiO prepared by embodiment two2Ti the and O constituent contents of nano wire/carbon fiber multi-scale reinforcing body are obvious
Increase, Ti elements bring up to 15.62%, O constituent contents by 4.49% by untreated 0% and bring up to 57.82%.Illustrate more
TiO2Nanowire growth is in aminated carbon fiber surface.Organic amine-TiO2The contact of nano wire/carbon fiber multi-scale reinforcing body
Becoming apparent for angle reduction, drops to 28.74 ° and 27.32 °, surface can be improved respectively in water with the contact angle in diiodomethane
To 72.95mN/m.Carbon fiber-organic amine-TiO2The interface shear strength of nano wire is brought up to by the 64.9MPa of precursor
124.7MPa, improve 92.1%.
Claims (10)
1. a kind of organic amine-TiO2The preparation method of nano wire/carbon fiber multi-scale reinforcing body, it is characterised in that a kind of organic amine-
TiO2What the preparation method of nano wire/carbon fiber multi-scale reinforcing body was specifically realized by the following steps：
First, clean：
1., carbon fiber is put into the apparatus,Soxhlet's equipped with acetone, acetone is used under conditions of temperature is 75 DEG C~85 DEG C
Cleaning removes the impurity of carbon fiber surface, and scavenging period is 2h~8h, and the carbon fiber after cleaning is taken out, and is obtained after acetone cleaning
Carbon fiber；
2. the carbon fiber after the acetone cleaning for, 1. obtaining step one is placed in overcritical device, is 350 DEG C~370 in temperature
DEG C and pressure for 8MPa~14MPa overcritical acetone-water system in soak 20min~30min, obtain remove epoxy coating after
Carbon fiber；
Step one 2. described in overcritical acetone-water system in acetone and water volume ratio be 5:1；
3., the carbon fiber after the removal epoxy coating for 2. obtaining step one is placed in apparatus,Soxhlet's, temperature be 75 DEG C~
The carbon fiber removed after epoxy coating is cleaned under conditions of 85 DEG C using acetone, scavenging period is 2h~4h；By the carbon after cleaning
Fiber is taken out, and 2h~4h is dried under conditions of temperature is 70 DEG C~80 DEG C, obtains drying carbon fiber after cleaning；
2nd, aoxidize：
1., the impregnated carbon fiber after cleaning of drying that 3. step one obtains, into potassium peroxydisulfate/silver nitrate mixed aqueous solution, is heated
To 60 DEG C~80 DEG C, then constant temperature 1h~2h, the carbon fiber after being aoxidized under conditions of temperature is 60 DEG C~80 DEG C；Described
The concentration of potassium peroxydisulfate is 0.1mol/L~0.2mol/L in potassium peroxydisulfate/silver nitrate mixed aqueous solution；Described potassium peroxydisulfate/
The concentration of silver nitrate is 0.0001mol/L~0.005mol/L in silver nitrate mixed aqueous solution；
Step 2 1. described in the volume ratio for drying quality and the potassium peroxydisulfate/silver nitrate mixed aqueous solution of carbon fiber after cleaning
For 0.1g:(10mL~12mL)；
2., the carbon fiber after the oxidation for 1. obtaining step 2 under room temperature condition soaks 5min~10min in distilled water, will be through
Carbon fiber after being soaked in distilled water takes out, reject distilled water；The quality of carbon fiber after described oxidation and the body of distilled water
Product is than being (0.001g~0.006g):1mL；
3., repeat step two 2. 3 times~5 times, obtain the carbon oxide fiber after distilled water cleaning；
4. the carbon oxide fiber after the distilled water cleaning for, 3. obtaining step 2 is dried under conditions of temperature is 70 DEG C~80 DEG C
2h~4h, obtains dried carbon oxide fiber；
5., the dried carbon oxide fiber that 4. step 2 obtains is placed in the apparatus,Soxhlet's equipped with absolute ethyl alcohol, in temperature
Spend to use washes of absolute alcohol carbon oxide fiber under conditions of 90 DEG C~100 DEG C, scavenging period is 2h~4h, obtains anhydrous second
The carbon fiber of the oxidation of alcohol cleaning；
6., the carbon fiber of the oxidation for the washes of absolute alcohol for 5. obtaining step 2 is done under conditions of temperature is 70 DEG C~80 DEG C
Dry 2h~4h, obtains dry carbon oxide fiber；
3rd, chloride：
1. thionyl chloride/DMF mixed liquor, is loaded into dry reaction bulb, by doing that 6. step 2 obtains
Dry carbon oxide fiber is put into reaction bulb, is heated to 70 DEG C~90 DEG C, then the constant temperature under conditions of temperature is 70 DEG C~90 DEG C
40h~50h is reacted, the carbon fiber of the chloride containing impurity is obtained；
Step by the carbon oxide fiber of the drying described in 1. quality and thionyl chloride/N,N-dimethylformamide mixed liquor
Volume ratio is (0.3g~0.6g):150mL；
Step 3 1. described in thionyl chloride/N,N-dimethylformamide mixed liquor in thionyl chloride and N, N- dimethyl formyl
The volume ratio of amine is (80~100):(4~8)；
2., remained in the carbon fiber for the chloride containing impurity that 1. method first by vacuum distillation obtains step 3
Thionyl chloride is removed, and obtains the carbon fiber of chloride；It it is again 70 DEG C~90 DEG C in temperature by the carbon fiber of obtained chloride
2h~4h is dried in vacuum drying chamber, the carbon fiber of dry chloride is obtained, finally the carbon fiber by dry chloride is put
The sealing preserve in drier；
4th, carbon fiber is grafted PEI in supercritical methanol：
1., absolute methanol is placed in teat glass at room temperature, polyethyleneimine is then added, then by the carbon of dry chloride
Fiber is added in teat glass, is reused glass stopper with holes and is pressed the carbon fiber of dry chloride in people's methanol, obtains
In teat glass equipped with reactant；
Step 4 1. described in polyethyleneimine and absolute methanol volume ratio be (3~6):(50~60)；
Step 4 1. described in drying chloride carbon fiber quality and absolute methanol volume ratio for (0.3g~
0.6g):(50mL~60mL)；
2. it is put into the teat glass that, will be equipped with reactant in stainless steel cauldron, then stainless steel cauldron is closed, is reused
Stainless steel cauldron is heated to 230 DEG C~250 DEG C by salt bath furnace, then is 5MPa~7MPa in pressure and temperature is 230 DEG C~250
Grafting processing 5min~20min, obtains surface grafting PEI carbon fiber under conditions of DEG C；
3. stainless steel cauldron, is cooled down into 10min~15min at room temperature, cold water spray is reused and drops stainless steel cauldron
Warm to room temperature, then open stainless steel cauldron, surface grafting PEI carbon fiber is taken out；
4., surface grafting PEI carbon fiber is cleaned using deionized water, the pH value to cleaning fluid is 7, then by surface grafting
PEI carbon fiber is put into absolute ethyl alcohol and cleaned 3 times~5 times, then surface grafting PEI carbon fiber is placed in into apparatus,Soxhlet's
In, surface grafting PEI carbon fiber 20min~30min is cleaned using acetone under conditions of temperature is 75 DEG C~85 DEG C；Again will
The carbon fiber of surface grafting PEI in apparatus,Soxhlet's is overturn, then uses third under conditions of temperature is 75 DEG C~85 DEG C
Ketone cleaning surface grafting PEI carbon fiber 20min~30min, is dried in temperature is 80 DEG C~120 DEG C of baking oven again after taking-up
4h~8h, obtains dry surface grafting PEI carbon fiber
5th, TiO2The preparation of colloidal sol：
Absolute ethyl alcohol and butyl titanate are mixed, solution of tetrabutyl titanate is obtained；Diethyl is added dropwise into solution of tetrabutyl titanate
Hydramine, then low whipping speed are stirring 20min~30min under conditions of 5r/min~8r/min, then with 3 under conditions of stirring
Drop/min~5 drops/min rate of addition is added dropwise Aqueous Solutions of Polyethylene Glycol, then low whipping speed to stir under 5r/min~8r/min
Reaction 3h~5h is mixed, TiO is obtained2Colloidal sol；
The volume ratio of butyl titanate and absolute ethyl alcohol described in step 5 is (3~8):(20~25)；
The volume ratio of diethanol amine and absolute ethyl alcohol described in step 5 is (0.5~2):(20~25)；
The quality of Aqueous Solutions of Polyethylene Glycol described in step 5 and the volume ratio of absolute ethyl alcohol are (0.5g~1g):(20mL~
25mL)；
The mass fraction of polyethylene glycol is 2%~5% in Aqueous Solutions of Polyethylene Glycol described in step 5；
6th, prepare surface and contain TiO2The carbon fiber of film：
1., by dry surface grafting PEI impregnated carbon fiber to TiO2In colloidal sol, then in the case where ultrasonic power is 600W~1200W
Ultrasonic disperse 5min~12min, then stand after 5min~7min, dry surface grafting PEI carbon fiber is at the uniform velocity upward, hang down
Straight lifting, in one layer of uniform TiO of carbon fiber surface formation2Wet film；Surface is formed into one layer of uniform TiO again2The carbon of wet film is fine
Dimension dries 15min~25min in the case where temperature is 100 DEG C, and room temperature is naturally cooled to after taking-up；
2., repeat step six 1. 3 times~4 times, obtain surface and contain TiO2The carbon fiber of film；
7th, it is grafted：
1., butyl titanate is added in the hydrochloric acid that mass fraction is 35%~37%, then adds and goes under conditions of stirring
Ionized water, then low whipping speed is stirring reaction 2h~4h under 5r/min~8r/min, obtains precursor solution；
Step 7 1. described in butyl titanate and mass fraction be 35%~37% the volume ratio of hydrochloric acid be 3:(0.8~
1.5)；
Step 7 1. described in mass fraction for 35%~37% hydrochloric acid and deionized water volume ratio 1:1；
2., precursor solution is added in the autoclave of polytetrafluoroethyllining lining, then TiO is contained on surface2The carbon of film
Fiber is immersed in precursor solution, then the autoclave of polytetrafluoroethyllining lining is sealed, then by the high pressure after sealing
Reactor is 370 DEG C~390 DEG C in temperature and pressure is to keep 10min~30min under 20MPa~22.5MPa, obtains after processing
Carbon fiber；
3. autoclave, is naturally cooled into room temperature, then the carbon fiber after processing is taken out from precursor solution, is made first
The carbon fiber after processing is cleaned by ultrasonic 3 times~5 times with deionized water, absolute ethyl alcohol is reused to the carbon fiber ultrasound after processing
Cleaning 3 times~5 times, then dry naturally at room temperature, obtain organic amine-TiO2Nano wire/carbon fiber multi-scale reinforcing body.
2. a kind of organic amine-TiO according to claim 12The preparation method of nano wire/carbon fiber multi-scale reinforcing body, its
It is characterised by that 1. step 3 loads thionyl chloride/DMF mixed liquor into dry reaction bulb, by step 2
6. the carbon oxide fiber of the drying obtained is put into reaction bulb, is heated to 70 DEG C~76 DEG C, then in temperature is 70 DEG C~76 DEG C
Under the conditions of isothermal reaction 45h~48h, obtain the carbon fiber of the chloride containing impurity.
3. a kind of organic amine-TiO according to claim 12The preparation method of nano wire/carbon fiber multi-scale reinforcing body, its
It is put into the teat glass that reactant is will be equipped with being characterised by step 4 2. in stainless steel cauldron, then by stainless steel cauldron
Closing, reuses salt bath furnace and stainless steel cauldron is heated into 230 DEG C~240 DEG C, then in pressure is 5MPa~6MPa and temperature
For grafting processing 5min~10min under conditions of 230 DEG C~240 DEG C, surface grafting PEI carbon fiber is obtained.
4. a kind of organic amine-TiO according to claim 12The preparation method of nano wire/carbon fiber multi-scale reinforcing body, its
It is put into the teat glass that reactant is will be equipped with being characterised by step 4 2. in stainless steel cauldron, then by stainless steel cauldron
Closing, reuses salt bath furnace and stainless steel cauldron is heated into 240 DEG C~245 DEG C, then in pressure is 6MPa~6.5MPa and temperature
Spend and handle 10min~20min for grafting under conditions of 240 DEG C~245 DEG C, obtain surface grafting PEI carbon fiber.
5. a kind of organic amine-TiO according to claim 12The preparation method of nano wire/carbon fiber multi-scale reinforcing body, its
The butyl titanate and the volume ratio of absolute ethyl alcohol being characterised by described in step 5 are (5~8):5.
6. a kind of organic amine-TiO according to claim 12The preparation method of nano wire/carbon fiber multi-scale reinforcing body, its
The diethanol amine and the volume ratio of absolute ethyl alcohol being characterised by described in step 5 are (1~2):25.
7. a kind of organic amine-TiO according to claim 12The preparation method of nano wire/carbon fiber multi-scale reinforcing body, its
By dry surface grafting PEI impregnated carbon fiber to TiO in being characterised by step 6 1.2In colloidal sol, then in ultrasonic power it is
Ultrasonic disperse 5min~10min under 600W, then stand after 5min~6min, by dry surface grafting PEI carbon fiber at the uniform velocity
Upwards, vertical lifting, in one layer of uniform TiO of carbon fiber surface formation2Wet film；Surface is formed into one layer of uniform TiO again2It is wet
The carbon fiber of film dries 15min~20min in the case where temperature is 100 DEG C, and room temperature is naturally cooled to after taking-up.
8. a kind of organic amine-TiO according to claim 12The preparation method of nano wire/carbon fiber multi-scale reinforcing body, its
Precursor solution is added in the autoclave of polytetrafluoroethyllining lining in being characterised by step 7 2., then surface is contained
TiO2The carbon fiber of film is immersed in precursor solution, then the autoclave of polytetrafluoroethyllining lining is sealed, and then will
Autoclave after sealing temperature be 370 DEG C~375 DEG C and pressure be keep under 20MPa~22.5MPa 10min~
20min, the carbon fiber after being handled.
9. a kind of organic amine-TiO according to claim 12The preparation method of nano wire/carbon fiber multi-scale reinforcing body, its
In being characterised by step 7 3. every time using deionized water to after processing carbon fiber be cleaned by ultrasonic power for 600W~
1200W, the time is 5min~10min.
10. a kind of organic amine-TiO according to claim 12The preparation method of nano wire/carbon fiber multi-scale reinforcing body,
It is characterized in that step 7 3. in every time using absolute ethyl alcohol to after processing carbon fiber be cleaned by ultrasonic power for 600W~
1200W, the time is 5min~10min.
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| CN112795137A (en) * | 2021-01-18 | 2021-05-14 | 陕西科技大学 | ZIF-8 nanocrystal modified carbon fiber reinforced poly-hexahydrotriazine composite material and preparation method thereof |
| CN113430832A (en) * | 2021-07-18 | 2021-09-24 | 陕西科技大学 | Modified carbon fiber based on macromolecular amine concave-convex structure and preparation method thereof |
| CN113463395A (en) * | 2021-07-18 | 2021-10-01 | 陕西科技大学 | Preparation method of one-dimensional nano material/macromolecular amine head-to-tail alternately arranged modified carbon fiber |
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| CN113430832A (en) * | 2021-07-18 | 2021-09-24 | 陕西科技大学 | Modified carbon fiber based on macromolecular amine concave-convex structure and preparation method thereof |
| CN113463395A (en) * | 2021-07-18 | 2021-10-01 | 陕西科技大学 | Preparation method of one-dimensional nano material/macromolecular amine head-to-tail alternately arranged modified carbon fiber |
| CN114277578A (en) * | 2021-12-13 | 2022-04-05 | 中国科学院宁波材料技术与工程研究所 | Multilayer composite carbon fiber capable of being pyrolyzed and recycled and preparation method thereof |
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