CN109914094A - A kind of preparation method of nano-zinc oxide modified aramid fiber - Google Patents
A kind of preparation method of nano-zinc oxide modified aramid fiber Download PDFInfo
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- CN109914094A CN109914094A CN201910162679.7A CN201910162679A CN109914094A CN 109914094 A CN109914094 A CN 109914094A CN 201910162679 A CN201910162679 A CN 201910162679A CN 109914094 A CN109914094 A CN 109914094A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 314
- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 215
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 141
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000012986 modification Methods 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 119
- 239000000835 fiber Substances 0.000 claims description 118
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 96
- 239000007788 liquid Substances 0.000 claims description 64
- 239000013078 crystal Substances 0.000 claims description 53
- 235000019441 ethanol Nutrition 0.000 claims description 50
- 229960004756 ethanol Drugs 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000001291 vacuum drying Methods 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 23
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- 150000001263 acyl chlorides Chemical class 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000007306 functionalization reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- 229920002873 Polyethylenimine Polymers 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 39
- 239000003822 epoxy resin Substances 0.000 abstract description 8
- 229920000647 polyepoxide Polymers 0.000 abstract description 8
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract 1
- 229960001296 zinc oxide Drugs 0.000 description 114
- 239000000243 solution Substances 0.000 description 34
- 230000032683 aging Effects 0.000 description 19
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000002131 composite material Substances 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 229920002994 synthetic fiber Polymers 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000005289 physical deposition Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229940050549 fiber Drugs 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
本发明涉及一种表面改性的芳纶纤维。本发明中的纳米氧化锌改性的芳纶纤维制备过程包括：芳纶纤维表面功能化、在芳纶纤维表面接枝生长氧化锌纳米颗粒、在芳纶纤维表面接枝生长氧化锌纳米线。本发明具有如下优点：改性条件温和、工艺简单；纳米氧化锌与芳纶纤维的结合牢度明显提高；改性后纤维与树脂的粘结性能以及纤维的耐紫外辐照性能显著增强。与未改性的芳纶纤维相比，改性的芳纶纤维与环氧树脂的界面剪切强度可以提高37％～61％；改性的芳纶纤维经过紫外辐照测试后拉伸强度保持率从78.3％提高到96.3～97.6％。
The present invention relates to a surface-modified aramid fiber. The preparation process of the nano-zinc oxide modified aramid fiber in the present invention includes: functionalizing the surface of the aramid fiber, grafting and growing zinc oxide nanoparticles on the surface of the aramid fiber, and grafting and growing zinc oxide nanowires on the surface of the aramid fiber. The invention has the following advantages: the modification conditions are mild and the process is simple; the bonding fastness of the nano-zinc oxide and the aramid fiber is obviously improved; Compared with the unmodified aramid fiber, the interfacial shear strength of the modified aramid fiber and epoxy resin can be increased by 37% to 61%; the tensile strength of the modified aramid fiber is maintained after UV irradiation test. The rate increased from 78.3% to 96.3-97.6%.
Description
Technical field
The present invention relates to a kind of nano zinc oxide modified aramid fiber, in particular to a kind of raising aramid fiber and matrix
The method of modifying of resin-bonded property and resistance to ultraviolet irradiation.
Background technique
There is aramid fiber enhancing polymer matrix composite the characteristic of light, high specific strength and high ratio modulus to be widely used in navigating
Each field such as sky, space flight, military affairs, machinery.But a large amount of inertia phenyl ring, crystallinity are high since molecular structure contains for aramid fiber, cause
Fiber surface activity is very low, and the interface binding intensity of fiber and resin matrix is weaker；In addition, aramid fiber molecular structure is containing a large amount of
Amido bond, fracture is easy to happen under ultraviolet light leads to fiber degradation with aging.So good surface bonds in order to balance
The aramid fiber of performance and resistance to ultraviolet irradiation energy is constantly subjected to the common concern of people.
In recent years, had to study in large quantities and aramid fiber progress surface has been modified, specifically included that at (1) plasma
Reason；(2) chemical graft；(3) high-energy ray radiation treatment etc..These methods mostly all be improve aramid fiber surface-active and
The interfacial bond property of itself and resin, but the research of its resistance to ultraviolet irradiation energy is rarely reported.In addition, to aramid fiber
During progress surface is modified, in order to increase the surface roughness and surface-active of fiber, usually all to damage aramid fiber
Mechanical property as cost.
Nano zine oxide is a kind of excellent uvioresistant additive, and furthermore nano zine oxide can not only be grown in fiber surface
Regular orderly Zinc oxide nanoparticle, nano wire, nano flower-like pattern, and the preparation condition of nano zine oxide it is mild,
Simple process, it is very extensive in the modification application of aramid fiber and other fiber surfaces, also achieve significant effect.Chinese invention is special
In sharp 103590234 B of CN and 103628305 B of CN, growth of zinc oxide nano line is disclosed on pbo fiber to improve PBO
Nano zine oxide is only simply passed through physical deposition by the adhesive property and anti-atomic oxygen performance of fiber, still, researcher
Method grows into fiber surface, and binding strength is weaker between fiber and zinc oxide, and Zinc oxide coating is easy to fall off.Chinese invention
107724062 A of patent CN discloses a kind of method of growing zinc oxide nanorod on cotton fiber, although method introduces ox blood
Pure albumen is tied to increase zinc oxide nano rod in the adhesive ability of fiber surface, but between modified cotton fiber and zinc oxide
Resultant force is still weaker, is simply possible to use in the performances such as antibacterial, the uvioresistant for improving cotton fiber.On how to improve nano zine oxide and virtue
The problem of binding strength of synthetic fibre fiber, up to the present do not see correlative study also.
In conclusion researching and developing under the premise of one kind can retain fiber excellent mechanical performance, while it is viscous to promote fiber surface
The aramid fiber for tying performance and uvioresistant irradiation behaviour has important application value.
Summary of the invention
The purpose of the present invention is to provide a kind of nano zine oxides and fibre chemistry to be firmly combined, uvioresistant irradiation behaviour is high
Nano zinc oxide modified aramid fiber preparation method.
In order to achieve the above object, the present invention provides a kind of preparation method of nano zinc oxide modified aramid fiber,
It is characterized in that, comprising the following steps:
Step 1: the aramid fiber after hydrolysis process aramid fiber functionalization: being put into thionyl chloride and N, N- bis-
It is reacted at room temperature in the mixed liquor of methylformamide, obtains the aramid fiber that surface carries acyl chlorides；Surface is carried to the aramid fiber of acyl chlorides
Fiber, which is put into the mixed liquor of γ aminopropyltriethoxy silane and ethyl alcohol, to react, and obtains the function that surface carries silicone hydroxyl
Modification of aramid fiber can be changed；
Step 2: the growth of aramid fiber surface zinc oxide crystal seed: the surface that step 1 is obtained carries the functionalization of silicone hydroxyl
Modification of aramid fiber is immersed in zinc oxide crystal seed liquid, is stood, and is taken out, dry；Aramid fiber after drying is immersed in again
It in zinc oxide crystal seed liquid, stands, takes out, it is dry, obtain the modified aramid fiber of Zinc oxide nanoparticle；
Step 3: aramid fiber surface zinc oxide nanowire growth: what the Zinc oxide nanoparticle that step 2 is obtained was modified
Aramid fiber, which is immersed in zinc oxide growth liquid, to react, and washs after taking-up, dry, and it is fine to obtain the modified aramid fiber of zinc oxide nanowire
Dimension, i.e., nano zinc oxide modified aramid fiber.
Preferably, the aramid fiber in the step 1 is that para-aramid fiber, meta-aramid fibers and heterocycle aramid fiber are fine
One of dimension.
Preferably, the specific steps of the hydrolysis process include: that aramid fiber is immersed in concentration as 10~30wt%
Sodium hydroxide solution in, under the conditions of 30~70 DEG C of temperature, 100~200r/min of mixing speed handle 10~30min, spend
Ionized water rinses 3~5 times；By treated, fiber is immersed in 30~60s in the hydrochloric acid that concentration is 10%~35% later, spends
Ionized water rinses 3~5 times, and then 120~150 DEG C of 1~4h of vacuum drying in an oven, obtain hydrolyzing aramid fiber.
Preferably, thionyl chloride and N, N- in the thionyl chloride of the step 1 and the mixed liquor of n,N-Dimethylformamide
The volume ratio of dimethylformamide is 100:(1.0~5.0), in the mixed liquor of γ aminopropyltriethoxy silane and ethyl alcohol
The volume ratio of γ aminopropyltriethoxy silane and ethyl alcohol is 100:(1.0~5.0).
Preferably, the aramid fiber that surface carries acyl chlorides is put into gamma-amino propyl-triethoxysilicane in the step 1
The reaction temperature reacted in the mixed liquor of alkane and ethyl alcohol is 40~70 DEG C, and the reaction time is 2~10h.
Preferably, the preparation step of zinc oxide crystal seed liquid includes: by Zinc diacetate dihydrate and dehydrated alcohol in the step 2
It is mixed according to mass ratio 0.0027:1, is dissolved by heating at 300~500r/min mixing speed and 40~65 DEG C, obtain two hydrations
Zinc acetate/ethanol solution；Sodium hydroxide and dehydrated alcohol are mixed according to mass ratio 0.0008:1, stirred in 300~500r/min
It mixes and is dissolved by heating at speed and 40~65 DEG C, obtain sodium hydroxide/ethyl alcohol solution；By obtained sodium hydroxide/ethyl alcohol solution etc.
Volume is added to Zinc diacetate dihydrate/ethanol solution, and 30~120min is reacted at 50~65 DEG C, obtains zinc oxide crystal seed liquid.
Preferably, the drying in the step 2 is dry 5~20min in 80~160 DEG C of vacuum drying ovens.
Preferably, in the step 2 further include: repeat described " submerge the aramid fiber after drying again
It in zinc oxide crystal seed liquid, stands, takes out, dry " step, it carries out 2~5 times altogether.
Preferably, the preparation step of zinc oxide growth liquid includes: first by hexa and polyethylene in the step 3
Imines is dissolved in 90 DEG C of deionized water according to molar ratio 25:1~5, adds six with hexa equimolar amounts
Nitric hydrate zinc obtains zinc oxide growth liquid.
Preferably, the modified aramid fiber of the Zinc oxide nanoparticle that step 2 obtains is immersed in oxidation in the step 3
The reaction temperature reacted in zinc growth-promoting media is 85~95 DEG C, 2~10h of reaction time.
Preferably, the washing in the step 3 is to be cleaned 3~5 times with deionized water, dry in 80~150 DEG C of vacuum
Dry 1~4h in baking oven.
Compared with prior art, the beneficial effects of the present invention are:
(1) the present invention can obtain the aramid fiber surface with uniform, secured, vertical-growth zinc oxide nanowire, oxidations
The length of zinc nano wire is 0.5~2.1 μm.
(2) zinc oxide nanowire is grown into fiber surface with chemical grafting method by the present invention, zinc oxide nanowire with
The binding strength of aramid fiber improves, and can improve the adhesive property and UV resistance of aramid fiber, zinc-oxide nano simultaneously
The interface shear strength of the modified aramid fiber of line and epoxy resin improves 37%-61%, tests by 168h ultraviolet irradiation
Afterwards, the stretching strength retentivity of fiber is 96.3~97.6%.
(3) process prepared by the present invention is simple and easy without being heated at high temperature, substantially not damaged to aramid fiber.
(4) treatment conditions of the present invention are mild, preparation process is simple；The binding strength of nano zine oxide and aramid fiber is obvious
It improves；The resistance to ultraviolet irradiation of the adhesive property and fiber of modified fiber and resin can significantly increase.
Detailed description of the invention
Fig. 1 is the Zinc oxide nanoparticle modification of aramid fiber SEM figure that embodiment 3 is prepared；
Fig. 2 is the zinc oxide nanowire modification of aramid fiber SEM figure that embodiment 3 is prepared；
Fig. 3 is that embodiment 4 is schemed in the section SEM of aramid fiber surface graft growth zinc oxide nanowire；
Fig. 4 is that embodiment 6 is schemed in the section SEM of aramid fiber surface physical deposition zinc oxide nanowire；
Fig. 5 is composite material interface shear strength test schematic diagram；
Description of symbols: 1 is upper fixture, and 2 be fiber, and 3 be lower fixture, and 4 be microballoon resin.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of preparation method of nano zinc oxide modified aramid fiber is present embodiments provided, specific preparation process is as follows:
Step 1: aramid fiber functionalization:
A. it prepares hydrolysis aramid fiber: first twining aramid fiber (heterocycle aramid fiber F-368, Zhonglan Chenguang Chemical Inst)
It is wound on polytetrafluoroethylene (PTFE) box, is then submerged in the sodium hydroxide solution that concentration is 10wt%, in 30 DEG C of temperature, stirring speed
10min is handled under the conditions of degree 100r/min, is rinsed 3 times with deionized water；Fiber after naoh treatment is immersed in concentration
For 30s in 10% hydrochloric acid, 3 times are rinsed with deionized water, then 120 DEG C of vacuum drying 1h in an oven, obtain hydrolyzing aramid fiber
Fiber；
B. above-mentioned hydrolysis aramid fiber aramid fiber functionalization: is put into the thionyl chloride that volume ratio is 100:1
It is reacted at room temperature in the mixed liquor of n,N-Dimethylformamide, obtains the aramid fiber that surface carries acyl chlorides；Surface is contained into acyl chlorides
Aramid fiber put into the mixed liquor of γ aminopropyltriethoxy silane and ethyl alcohol that volume ratio is 100:1,65 DEG C are anti-
2h is answered, the functional modification aramid fiber that surface carries silicone hydroxyl is obtained；
Step 2: the growth of aramid fiber surface zinc oxide crystal seed:
A. it prepares zinc oxide crystal seed liquid: Zinc diacetate dihydrate and dehydrated alcohol is mixed according to mass ratio 0.0027:1,
It is dissolved by heating at 300r/min mixing speed and 65 DEG C, obtains Zinc diacetate dihydrate/ethanol solution；By sodium hydroxide and anhydrous second
Alcohol is mixed according to mass ratio 0.0008:1, is dissolved by heating at 300r/min mixing speed and 40 DEG C, is obtained sodium hydroxide/ethyl alcohol
Solution；Sodium hydroxide/ethyl alcohol solution is added in equal volume in Zinc diacetate dihydrate/ethanol solution, is reacted at 50 DEG C
30min obtains zinc oxide crystal seed liquid；
B. aramid fiber surface zinc oxide crystal seed is grown: the surface that step 1 is obtained carries the functional modification of silicone hydroxyl
Aramid fiber is immersed in zinc oxide crystal seed liquid, stands 10min, is taken out, and then the dry 5min in 80 DEG C of vacuum drying ovens, will do
Aramid fiber after dry is immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, and is then done in 80 DEG C of vacuum drying ovens
Dry 5min obtains the modified aramid fiber of Zinc oxide nanoparticle；
Step 3: the growth of aramid fiber surface zinc oxide nanowire:
A. zinc oxide growth liquid is prepared: by hexa, polyethyleneimine (Mn=600, Shanghai Aladdin biochemistry stock
Part Co., Ltd) it is dissolved according to molar ratio 25:1 in 90 DEG C of deionized water；Take six with hexa equimolar amounts
Nitric hydrate zinc is added in the mixed solution of above-mentioned hexa, polyethyleneimine, obtains zinc oxide growth liquid；
B. aramid fiber surface zinc oxide nanowire is grown: the modified aramid fiber of the Zinc oxide nanoparticle that step 2 is obtained
Fiber is immersed in zinc oxide growth liquid, 90 DEG C of reaction 2h, is cleaned 3 times after taking-up with deionized water, is then dried in 80 DEG C of vacuum
Dry 4h in case, obtains the modified aramid fiber of zinc oxide nanowire, i.e., nano zinc oxide modified aramid fiber.
Composite material interface method for testing shear strength: using domestic monofilament strength and elongation instrument XQ-1 (the new fine limited public affairs in Shanghai
Department) single fiber/epoxy microballoon composite material interface shearing performance is tested.Fig. 5 show micro- unsticking experiment schematic diagram.
In test process, fixed lower fixture is motionless, mobile upper fixture, test rate 10mm/min, and it is de- to record microballoon resin away from 10mm for folder
The power of viscous moment, the embedding length of fibre diameter and microballoon is measured by microscope.Interface shear strength is counted according to the following formula
It calculates.Each fiber sample need to be surveyed 20 times.
IFSS: interface shear strength, Pa
F: the load of microballoon unsticking moment, N
df: fibre diameter, m
L: fiber is embedded to the length in resin: m
Tensile strength of fiber conservation rate test method: before being tested using domestic XQ-1 type monofilament strength and elongation instrument ultraviolet ageing
Fiber afterwards carries out extension test, and test rate 10mm/min is pressed from both sides away from 10mm, and each fiber sample need to be surveyed 15 times, takes it flat
Tensile strength of the mean value as fiber；Tensile strength before the tensile strength of fiber and ultraviolet ageing are tested after ultraviolet ageing test
Ratio be fiber strength retention.
The zinc-oxide nano line length that this example obtains is 0.5 μm；Zinc oxide nanowire modification of aramid fiber and asphalt mixtures modified by epoxy resin
The interface shear strength of rouge is 42.7MPa, improves 37% compared with unmodified aramid fiber；After ultraviolet irradiation is tested
It is 96.3% that the stretching strength retentivity of fiber is increased to by 78.6%.
Embodiment 2
A kind of preparation method of nano zinc oxide modified aramid fiber is present embodiments provided, specific preparation process is as follows:
Step 1: aramid fiber functionalization:
A. it prepares hydrolysis aramid fiber: first twining aramid fiber (heterocycle aramid fiber F-368, Zhonglan Chenguang Chemical Inst)
It is wound on polytetrafluoroethylene (PTFE) box, is then submerged in the sodium hydroxide solution that concentration is 20wt%, in 40 DEG C of temperature, stirring speed
20min is handled under the conditions of degree 150r/min, is rinsed 3 times with deionized water；Fiber after naoh treatment is immersed in concentration
For 40s in 20% hydrochloric acid, 3 times are rinsed with deionized water, then 120 DEG C of vacuum drying 1h in an oven, obtain hydrolyzing aramid fiber
Fiber；
B. above-mentioned hydrolysis aramid fiber aramid fiber functionalization: is put into the thionyl chloride that volume ratio is 100:2
It is reacted at room temperature in the mixed liquor of n,N-Dimethylformamide, obtains the aramid fiber that surface carries acyl chlorides；Surface is contained into acyl chlorides
Aramid fiber put into the mixed liquor of γ aminopropyltriethoxy silane and ethyl alcohol that volume ratio is 100:2,65 DEG C are anti-
4h is answered, the functional modification aramid fiber that surface carries silicone hydroxyl is obtained；
Step 2: the growth of aramid fiber surface zinc oxide crystal seed:
A. it prepares zinc oxide crystal seed liquid: Zinc diacetate dihydrate and dehydrated alcohol is mixed according to mass ratio 0.0027:1,
It is dissolved by heating at 300r/min mixing speed and 65 DEG C, obtains Zinc diacetate dihydrate/ethanol solution；By sodium hydroxide and anhydrous second
Alcohol is mixed according to mass ratio 0.0008:1, is dissolved by heating at 300r/min mixing speed and 40 DEG C, is obtained sodium hydroxide/ethyl alcohol
Solution；Sodium hydroxide/ethyl alcohol solution is added in equal volume in Zinc diacetate dihydrate/ethanol solution, is reacted at 55 DEG C
60min obtains zinc oxide crystal seed liquid；
B. aramid fiber surface zinc oxide crystal seed is grown: the aramid fiber that the surface that step 1 is obtained carries silicone hydroxyl soaks
Not in zinc oxide crystal seed liquid, 10min is stood, is taken out, then the dry 10min in 80 DEG C of vacuum drying ovens, by the virtue after drying
Synthetic fibre fiber is immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, then the dry 10min in 80 DEG C of vacuum drying ovens,
Repeat " aramid fiber after drying to be immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, then at 80 DEG C
Dry 10min " 1 time in vacuum drying oven, the modified aramid fiber of Zinc oxide nanoparticle is obtained；
Step 3: the growth of aramid fiber surface zinc oxide nanowire:
A. zinc oxide growth liquid is prepared: by hexa, polyethyleneimine (Mn=600, Shanghai Aladdin biochemistry stock
Part Co., Ltd) it is dissolved according to molar ratio 25:2 in 90 DEG C of deionized water；Take six with hexa equimolar amounts
Nitric hydrate zinc is added in the mixed solution of above-mentioned hexa, polyethyleneimine, obtains zinc oxide growth liquid；
B. aramid fiber surface zinc oxide nanowire is grown: the modified aramid fiber of the Zinc oxide nanoparticle that step 2 is obtained
Fiber is immersed in zinc oxide growth liquid, 90 DEG C of reaction 4h, is cleaned 3 times after taking-up with deionized water, is then dried in 80 DEG C of vacuum
Dry 1h in case, obtains the modified aramid fiber of zinc oxide nanowire, i.e., nano zinc oxide modified aramid fiber.
Composite material interface method for testing shear strength: using domestic monofilament strength and elongation instrument XQ-1 (the new fine limited public affairs in Shanghai
Department) single fiber/epoxy microballoon composite material interface shearing performance is tested.Fig. 5 show micro- unsticking experiment schematic diagram.
In test process, fixed lower fixture is motionless, mobile upper fixture, test rate 10mm/min, and it is de- to record microballoon resin away from 10mm for folder
The power of viscous moment, the embedding length of fibre diameter and microballoon is measured by microscope.Interface shear strength is counted according to the following formula
It calculates.Each fiber sample need to be surveyed 20 times.
IFSS: interface shear strength, Pa
F: the load of microballoon unsticking moment, N
df: fibre diameter, m
L: fiber is embedded to the length in resin: m
Tensile strength of fiber conservation rate test method: before being tested using domestic XQ-1 type monofilament strength and elongation instrument ultraviolet ageing
Fiber afterwards carries out extension test, and test rate 10mm/min is pressed from both sides away from 10mm, and each fiber sample need to be surveyed 15 times, takes it flat
Tensile strength of the mean value as fiber；Tensile strength before the tensile strength of fiber and ultraviolet ageing are tested after ultraviolet ageing test
Ratio be fiber strength retention.
The zinc-oxide nano line length that this example obtains is 0.9 μm；Zinc oxide nanowire modification of aramid fiber and asphalt mixtures modified by epoxy resin
The interface shear strength of rouge is 45.6MPa, improves 46% compared with unmodified aramid fiber；After ultraviolet irradiation is tested
It is 96.8% that the stretching strength retentivity of fiber is increased to by 78.6%.
Embodiment 3
A kind of preparation method of nano zinc oxide modified aramid fiber is present embodiments provided, specific preparation process is as follows:
Step 1: aramid fiber functionalization:
A. it prepares hydrolysis aramid fiber: first twining aramid fiber (heterocycle aramid fiber F-368, Zhonglan Chenguang Chemical Inst)
It is wound on polytetrafluoroethylene (PTFE) box, is then submerged in the sodium hydroxide solution that concentration is 30wt%, in temperature 50 C, stirring speed
30min is handled under the conditions of degree 200r/min, is rinsed 4 times with deionized water；Fiber after naoh treatment is immersed in concentration
For 30s in 30% hydrochloric acid, 4 times are rinsed with deionized water, then 120 DEG C of vacuum drying 1h in an oven, obtain hydrolyzing aramid fiber
Fiber；
B. above-mentioned hydrolysis aramid fiber aramid fiber functionalization: is put into the thionyl chloride that volume ratio is 100:3
It is reacted at room temperature in the mixed liquor of n,N-Dimethylformamide, obtains the aramid fiber that surface carries acyl chlorides；Surface is contained into acyl chlorides
Aramid fiber put into the mixed liquor of γ aminopropyltriethoxy silane and ethyl alcohol that volume ratio is 100:3,65 DEG C are anti-
6h is answered, the functional modification aramid fiber that surface carries silicone hydroxyl is obtained；
Step 2: the growth of aramid fiber surface zinc oxide crystal seed:
A. it prepares zinc oxide crystal seed liquid: Zinc diacetate dihydrate and dehydrated alcohol is mixed according to mass ratio 0.0027:1,
It is dissolved by heating at 400r/min mixing speed and 50 DEG C, obtains Zinc diacetate dihydrate/ethanol solution；By sodium hydroxide and anhydrous second
Alcohol is mixed according to mass ratio 0.0008:1, is dissolved by heating at 400r/min mixing speed and 50 DEG C, is obtained sodium hydroxide/ethyl alcohol
Solution；Sodium hydroxide/ethyl alcohol solution is added in equal volume in Zinc diacetate dihydrate/ethanol solution, is reacted at 60 DEG C
120min obtains zinc oxide crystal seed liquid；
B. aramid fiber surface zinc oxide crystal seed is grown: the aramid fiber that the surface that step 1 is obtained carries silicone hydroxyl soaks
Not in zinc oxide crystal seed liquid, 10min is stood, is taken out, then the dry 15min in 120 DEG C of vacuum drying ovens, by the virtue after drying
Synthetic fibre fiber is immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, then the dry 15min in 80 DEG C of vacuum drying ovens,
Repeat " aramid fiber after drying to be immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, then 120
It dry 15min " 2 times in DEG C vacuum drying oven, carries out 3 times altogether, the modified aramid fiber of Zinc oxide nanoparticle is obtained, such as Fig. 1 institute
Show；
Step 3: the growth of aramid fiber surface zinc oxide nanowire:
A. zinc oxide growth liquid is prepared: by hexa, polyethyleneimine (Mn=600, Shanghai Aladdin biochemistry stock
Part Co., Ltd) it is dissolved according to molar ratio 25:3 in 90 DEG C of deionized water；Take six with hexa equimolar amounts
Nitric hydrate zinc is added in the mixed solution of above-mentioned hexa, polyethyleneimine, obtains zinc oxide growth liquid；
B. aramid fiber surface zinc oxide nanowire is grown: the modified aramid fiber of the Zinc oxide nanoparticle that step 2 is obtained
Fiber is immersed in zinc oxide growth liquid, 90 DEG C of reaction 6h, is cleaned 4 times after taking-up with deionized water, is then dried in 100 DEG C of vacuum
Dry 2h in case, obtains the modified aramid fiber of zinc oxide nanowire, i.e., nano zinc oxide modified aramid fiber, as shown in Figure 2.
Composite material interface method for testing shear strength: using domestic monofilament strength and elongation instrument XQ-1 (the new fine limited public affairs in Shanghai
Department) single fiber/epoxy microballoon composite material interface shearing performance is tested.Fig. 5 show micro- unsticking experiment schematic diagram.
In test process, fixed lower fixture is motionless, mobile upper fixture, test rate 10mm/min, and it is de- to record microballoon resin away from 10mm for folder
The power of viscous moment, the embedding length of fibre diameter and microballoon is measured by microscope.Interface shear strength is counted according to the following formula
It calculates.Each fiber sample need to be surveyed 20 times.
IFSS: interface shear strength, Pa
F: the load of microballoon unsticking moment, N
df: fibre diameter, m
L: fiber is embedded to the length in resin: m
Tensile strength of fiber conservation rate test method: before being tested using domestic XQ-1 type monofilament strength and elongation instrument ultraviolet ageing
Fiber afterwards carries out extension test, and test rate 10mm/min is pressed from both sides away from 10mm, and each fiber sample need to be surveyed 15 times, takes it flat
Tensile strength of the mean value as fiber；Tensile strength before the tensile strength of fiber and ultraviolet ageing are tested after ultraviolet ageing test
Ratio be fiber strength retention.
The zinc-oxide nano line length that this example obtains is 1.5 μm；Zinc oxide nanowire modification of aramid fiber and asphalt mixtures modified by epoxy resin
The interface shear strength of rouge is 47.3.MPa, improves 52% compared with unmodified aramid fiber；It is tested by ultraviolet irradiation
It is 97.2% that the stretching strength retentivity of fiber is increased to by 78.6% afterwards.
Embodiment 4
A kind of preparation method of nano zinc oxide modified aramid fiber is present embodiments provided, specific preparation process is as follows:
Step 1: aramid fiber functionalization:
A. it prepares hydrolysis aramid fiber: first twining aramid fiber (heterocycle aramid fiber F-368, Zhonglan Chenguang Chemical Inst)
It is wound on polytetrafluoroethylene (PTFE) box, is then submerged in the sodium hydroxide solution that concentration is 30wt%, in temperature 60 C, stirring speed
30min is handled under the conditions of degree 200r/min, is rinsed 4 times with deionized water；Fiber after naoh treatment is immersed in concentration
For 60s in 30% hydrochloric acid, 4 times are rinsed with deionized water, then 150 DEG C of vacuum drying 1h in an oven, obtain hydrolyzing aramid fiber
Fiber；
B. above-mentioned hydrolysis aramid fiber aramid fiber functionalization: is put into the thionyl chloride that volume ratio is 100:4
It is reacted at room temperature in the mixed liquor of n,N-Dimethylformamide, obtains the aramid fiber that surface carries acyl chlorides；Surface is contained into acyl chlorides
Aramid fiber put into the mixed liquor of γ aminopropyltriethoxy silane and ethyl alcohol that volume ratio is 100:4,65 DEG C are anti-
8h is answered, the functional modification aramid fiber that surface carries silicone hydroxyl is obtained；
Step 2: the growth of aramid fiber surface zinc oxide crystal seed:
A. it prepares zinc oxide crystal seed liquid: Zinc diacetate dihydrate and dehydrated alcohol is mixed according to mass ratio 0.0027:1,
It is dissolved by heating at 500r/min mixing speed and 65 DEG C, obtains Zinc diacetate dihydrate/ethanol solution；By sodium hydroxide and anhydrous second
Alcohol is mixed according to mass ratio 0.0008:1, is dissolved by heating at 500r/min mixing speed and 65 DEG C, is obtained sodium hydroxide/ethyl alcohol
Solution；Sodium hydroxide/ethyl alcohol solution is added in equal volume in Zinc diacetate dihydrate/ethanol solution, is reacted at 65 DEG C
120min obtains zinc oxide crystal seed liquid；
B. aramid fiber surface zinc oxide crystal seed is grown: the aramid fiber that the surface that step 1 is obtained carries silicone hydroxyl soaks
Not in zinc oxide crystal seed liquid, 10min is stood, is taken out, then the dry 20min in 160 DEG C of vacuum drying ovens, by the virtue after drying
Synthetic fibre fiber is immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, then the dry 20min in 120 DEG C of vacuum drying ovens,
Repeat " aramid fiber after drying to be immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, then 160
It dry 20min " 3 times in DEG C vacuum drying oven, carries out 4 times altogether, obtains the modified aramid fiber of Zinc oxide nanoparticle；
Step 3: the growth of aramid fiber surface zinc oxide nanowire:
A. zinc oxide growth liquid is prepared: by hexa, polyethyleneimine (Mn=600, Shanghai Aladdin biochemistry stock
Part Co., Ltd) it is dissolved according to molar ratio 25:4 in 90 DEG C of deionized water；Take six with hexa equimolar amounts
Nitric hydrate zinc is added in the mixed solution of above-mentioned hexa, polyethyleneimine, obtains zinc oxide growth liquid；
B. aramid fiber surface zinc oxide nanowire is grown: the modified aramid fiber of the Zinc oxide nanoparticle that step 2 is obtained
Fiber is immersed in zinc oxide growth liquid, 90 DEG C of reaction 8h, is cleaned 5 times after taking-up with deionized water, is then dried in 150 DEG C of vacuum
Dry 4h in case, obtains the modified aramid fiber of zinc oxide nanowire, i.e., nano zinc oxide modified aramid fiber, as shown in Figure 3.
Composite material interface method for testing shear strength: using domestic monofilament strength and elongation instrument XQ-1 (the new fine limited public affairs in Shanghai
Department) single fiber/epoxy microballoon composite material interface shearing performance is tested.Fig. 5 show micro- unsticking experiment schematic diagram.
In test process, fixed lower fixture is motionless, mobile upper fixture, test rate 10mm/min, and it is de- to record microballoon resin away from 10mm for folder
The power of viscous moment, the embedding length of fibre diameter and microballoon is measured by microscope.Interface shear strength is counted according to the following formula
It calculates.Each fiber sample need to be surveyed 20 times.
IFSS: interface shear strength, Pa
F: the load of microballoon unsticking moment, N
df: fibre diameter, m
L: fiber is embedded to the length in resin: m
Tensile strength of fiber conservation rate test method: before being tested using domestic XQ-1 type monofilament strength and elongation instrument ultraviolet ageing
Fiber afterwards carries out extension test, and test rate 10mm/min is pressed from both sides away from 10mm, and each fiber sample need to be surveyed 15 times, takes it flat
Tensile strength of the mean value as fiber；Tensile strength before the tensile strength of fiber and ultraviolet ageing are tested after ultraviolet ageing test
Ratio be fiber strength retention.
The zinc-oxide nano line length that this example obtains is 2.0 μm；Zinc oxide nanowire modification of aramid fiber and asphalt mixtures modified by epoxy resin
The interface shear strength 50.2MPa of rouge, improves 59% compared with unmodified aramid fiber；It is fine after ultraviolet irradiation is tested
It is 97.6% that the stretching strength retentivity of dimension is increased to by 78.6%.
Embodiment 5
A kind of preparation method of nano zinc oxide modified aramid fiber is present embodiments provided, specific preparation process is as follows:
Step 1: aramid fiber functionalization:
A. it prepares hydrolysis aramid fiber: first twining aramid fiber (heterocycle aramid fiber F-368, Zhonglan Chenguang Chemical Inst)
It is wound on polytetrafluoroethylene (PTFE) box, is then submerged in the sodium hydroxide solution that concentration is 30wt%, in temperature 70 C, stirring speed
30min is handled under the conditions of degree 200r/min, is rinsed 5 times with deionized water；Fiber after naoh treatment is immersed in concentration
For 60s in 30% hydrochloric acid, 5 times are rinsed with deionized water, then 150 DEG C of vacuum drying 1h in an oven, obtain hydrolyzing aramid fiber
Fiber；
B. above-mentioned hydrolysis aramid fiber aramid fiber functionalization: is put into the thionyl chloride that volume ratio is 100:5
It is reacted at room temperature in the mixed liquor of n,N-Dimethylformamide, obtains the aramid fiber that surface carries acyl chlorides；Surface is contained into acyl chlorides
Aramid fiber put into the mixed liquor of γ aminopropyltriethoxy silane and ethyl alcohol that volume ratio is 100:5,65 DEG C are anti-
10h is answered, the functional modification aramid fiber that surface carries silicone hydroxyl is obtained；
Step 2: the growth of aramid fiber surface zinc oxide crystal seed:
A. it prepares zinc oxide crystal seed liquid: Zinc diacetate dihydrate and dehydrated alcohol is mixed according to mass ratio 0.0027:1,
It is dissolved by heating at 500r/min mixing speed and 65 DEG C, obtains Zinc diacetate dihydrate/ethanol solution；By sodium hydroxide and anhydrous second
Alcohol is mixed according to mass ratio 0.0008:1, is dissolved by heating at 500r/min mixing speed and 65 DEG C, is obtained sodium hydroxide/ethyl alcohol
Solution；Sodium hydroxide/ethyl alcohol solution is added in equal volume in Zinc diacetate dihydrate/ethanol solution, is reacted at 65 DEG C
60min obtains zinc oxide crystal seed liquid；
B. aramid fiber surface zinc oxide crystal seed is grown: the aramid fiber that the surface that step 1 is obtained carries silicone hydroxyl soaks
Not in zinc oxide crystal seed liquid, 10min is stood, is taken out, then the dry 20min in 160 DEG C of vacuum drying ovens, by the virtue after drying
Synthetic fibre fiber is immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, then the dry 20min in 160 DEG C of vacuum drying ovens,
Repeat " aramid fiber after drying to be immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, then 160
It dry 20min " 4 times in DEG C vacuum drying oven, carries out 5 times altogether, obtains the modified aramid fiber of Zinc oxide nanoparticle；
Step 3: the growth of aramid fiber surface zinc oxide nanowire:
A. zinc oxide growth liquid is prepared: by hexa, polyethyleneimine (Mn=600, Shanghai Aladdin biochemistry stock
Part Co., Ltd) (please supplement the parameters such as producer and model or molecular weight, the degree of polymerization) be dissolved in 90 DEG C according to molar ratio 25:5
In deionized water；It takes and is added to above-mentioned hexa, poly- second with the zinc nitrate hexahydrate of hexa equimolar amounts
In the mixed solution of alkene imines, zinc oxide growth liquid is obtained；
B. aramid fiber surface zinc oxide nanowire is grown: the modified aramid fiber of the Zinc oxide nanoparticle that step 2 is obtained
Fiber is immersed in zinc oxide growth liquid, and 90 DEG C of reaction 10h are cleaned 5 times after taking-up with deionized water, then in 150 DEG C of vacuum
Dry 4h in baking oven, obtains the modified aramid fiber of zinc oxide nanowire, i.e., nano zinc oxide modified aramid fiber.
Composite material interface method for testing shear strength: using domestic monofilament strength and elongation instrument XQ-1 (the new fine limited public affairs in Shanghai
Department) single fiber/epoxy microballoon composite material interface shearing performance is tested.Fig. 5 show micro- unsticking experiment schematic diagram.
In test process, fixed lower fixture is motionless, mobile upper fixture, test rate 10mm/min, and it is de- to record microballoon resin away from 10mm for folder
The power of viscous moment, the embedding length of fibre diameter and microballoon is measured by microscope.Interface shear strength is counted according to the following formula
It calculates.Each fiber sample need to be surveyed 20 times.
IFSS: interface shear strength, Pa
F: the load of microballoon unsticking moment, N
df: fibre diameter, m
L: fiber is embedded to the length in resin: m
Tensile strength of fiber conservation rate test method: before being tested using domestic XQ-1 type monofilament strength and elongation instrument ultraviolet ageing
Fiber afterwards carries out extension test, and test rate 10mm/min is pressed from both sides away from 10mm, and each fiber sample need to be surveyed 15 times, takes it flat
Tensile strength of the mean value as fiber；Tensile strength before the tensile strength of fiber and ultraviolet ageing are tested after ultraviolet ageing test
Ratio be fiber strength retention.
The zinc-oxide nano line length that this example obtains is 2.31 μm；Zinc oxide nanowire modification of aramid fiber and asphalt mixtures modified by epoxy resin
The interface shear strength of rouge is 46.5MPa, improves 49% compared with unmodified aramid fiber；After ultraviolet irradiation is tested
It is 97.4% that the stretching strength retentivity of fiber is increased to by 78.6%.
Embodiment 6
A kind of preparation method of nano zinc oxide modified aramid fiber is present embodiments provided, specific preparation process is as follows:
Step 1: the growth of aramid fiber surface zinc oxide crystal seed:
A. it prepares zinc oxide crystal seed liquid: Zinc diacetate dihydrate and dehydrated alcohol is mixed according to mass ratio 0.0027:1,
It is dissolved by heating at 300r/min mixing speed and 40 DEG C, obtains Zinc diacetate dihydrate/ethanol solution；By sodium hydroxide and anhydrous second
Alcohol is mixed according to mass ratio 0.0008:1, is dissolved by heating at 300r/min mixing speed and 40 DEG C, is obtained sodium hydroxide/ethyl alcohol
Solution；Sodium hydroxide/ethyl alcohol solution is added in equal volume in Zinc diacetate dihydrate/ethanol solution, is reacted at 65 DEG C
120min obtains zinc oxide crystal seed liquid；
B. aramid fiber surface zinc oxide crystal seed is grown: the aramid fiber without any processing is immersed in zinc oxide crystal seed
In liquid, 10min is stood, then the dry 20min in 80 DEG C of vacuum drying ovens, is immersed in oxidation for the aramid fiber after drying again
In zinc crystal seed liquid, 10min is stood, is taken out, then the dry 20min in 80 DEG C of vacuum drying ovens, repeats " by the virtue after drying
Synthetic fibre fiber is immersed in again in zinc oxide crystal seed liquid, stands 10min, is taken out, then the dry 20min " 3 in 80 DEG C of vacuum drying ovens
It is secondary, it carries out 4 times altogether, obtains the modified aramid fiber of Zinc oxide nanoparticle；
Step 2: the growth of aramid fiber surface zinc oxide nanowire:
A. zinc oxide growth liquid is prepared: by hexa, polyethyleneimine (Mn=600, Shanghai Aladdin biochemistry stock
Part Co., Ltd) it is dissolved according to molar ratio 25:4 in 90 DEG C of deionized water；Take six with hexa equimolar amounts
Nitric hydrate zinc is added in the mixed solution of above-mentioned hexa, polyethyleneimine, obtains zinc oxide growth liquid；
B. aramid fiber surface zinc oxide nanowire is grown: the modified aramid fiber of the Zinc oxide nanoparticle that step 1 is obtained
Fiber is immersed in zinc oxide growth liquid, and 90 DEG C of reaction 8h are cleaned 3~5 times after taking-up with deionized water, then 80~150
Dry 4h in DEG C vacuum drying oven, obtains the modified aramid fiber of zinc oxide nanowire, i.e., nano zinc oxide modified aramid fiber, such as
Shown in Fig. 4.
Composite material interface method for testing shear strength: using domestic monofilament strength and elongation instrument XQ-1 (the new fine limited public affairs in Shanghai
Department) single fiber/epoxy microballoon composite material interface shearing performance is tested.Fig. 5 show micro- unsticking experiment schematic diagram.
In test process, fixed lower fixture is motionless, mobile upper fixture, test rate 10mm/min, and it is de- to record microballoon resin away from 10mm for folder
The power of viscous moment, the embedding length of fibre diameter and microballoon is measured by microscope.Interface shear strength is counted according to the following formula
It calculates.Each fiber sample need to be surveyed 20 times.
IFSS: interface shear strength, Pa
F: the load of microballoon unsticking moment, N
df: fibre diameter, m
L: fiber is embedded to the length in resin: m
Tensile strength of fiber conservation rate test method: before being tested using domestic XQ-1 type monofilament strength and elongation instrument ultraviolet ageing
Fiber afterwards carries out extension test, and test rate 10mm/min is pressed from both sides away from 10mm, and each fiber sample need to be surveyed 15 times, takes it flat
Tensile strength of the mean value as fiber；Tensile strength before the tensile strength of fiber and ultraviolet ageing are tested after ultraviolet ageing test
Ratio be fiber strength retention.
This example is blank assay, and aramid fiber does not carry out functionalization, and obtained zinc-oxide nano line length is 2.1
μm；The interface shear strength of zinc oxide nanowire modification of aramid fiber and epoxy resin is 37.2MPa, fine with unmodified aramid fiber
Dimension is compared and improves 19%；After ultraviolet irradiation is tested the stretching strength retentivity of fiber by 78.6% be increased to for
94.3%.
Claims (10)
1. a kind of preparation method of nano zinc oxide modified aramid fiber, which comprises the following steps:
Step 1: the aramid fiber after hydrolysis process aramid fiber functionalization: being put into thionyl chloride and N, N- dimethyl
It is reacted at room temperature in the mixed liquor of formamide, obtains the aramid fiber that surface carries acyl chlorides；Surface is carried to the aramid fiber of acyl chlorides
It puts into the mixed liquor of γ aminopropyltriethoxy silane and ethyl alcohol and reacts, obtain the functionalization that surface carries silicone hydroxyl
Modification of aramid fiber；
Step 2: the growth of aramid fiber surface zinc oxide crystal seed: the surface that step 1 is obtained carries the functional modification of silicone hydroxyl
Aramid fiber is immersed in zinc oxide crystal seed liquid, is stood, and is taken out, dry；Aramid fiber after drying is immersed in oxidation again
It in zinc crystal seed liquid, stands, takes out, it is dry, obtain the modified aramid fiber of Zinc oxide nanoparticle；
Step 3: aramid fiber surface zinc oxide nanowire growth: the modified aramid fiber of the Zinc oxide nanoparticle that step 2 is obtained
Fiber, which is immersed in zinc oxide growth liquid, to react, and washs after taking-up, dry, obtains the modified aramid fiber of zinc oxide nanowire,
I.e. nano zinc oxide modified aramid fiber.
2. the preparation method of nano zinc oxide modified aramid fiber as described in claim 1, which is characterized in that in the step 1
Aramid fiber be one of para-aramid fiber, meta-aramid fibers and Heterocyclic Aramid Fibre.
3. the preparation method of nano zinc oxide modified aramid fiber as described in claim 1, which is characterized in that at the hydrolysis
The specific steps of reason include: by aramid fiber be immersed in concentration be 10~30wt% sodium hydroxide solution in, temperature 30~
70 DEG C, 10~30min is handled under the conditions of 100~200r/min of mixing speed, rinsed 3~5 times with deionized water；It later will processing
Fiber afterwards is immersed in 30~60s in the hydrochloric acid that concentration is 10%~35%, is rinsed 3~5 times with deionized water, then in baking oven
In 120~150 DEG C of 1~4h of vacuum drying, obtain hydrolysis aramid fiber.
4. the preparation method of nano zinc oxide modified aramid fiber as described in claim 1, which is characterized in that the step 1
The volume ratio of thionyl chloride and N,N-dimethylformamide is 100 in the mixed liquor of thionyl chloride and N,N-dimethylformamide:
γ aminopropyltriethoxy silane and second in the mixed liquor of (1.0~5.0), γ aminopropyltriethoxy silane and ethyl alcohol
The volume ratio of alcohol is 100:(1.0~5.0).
5. the preparation method of nano zinc oxide modified aramid fiber as described in claim 1, which is characterized in that in the step 1
Aramid fiber of the surface containing acyl chlorides puts into the reaction temperature reacted in γ aminopropyltriethoxy silane/ethanol solution
40~70 DEG C, the reaction time is 2~10h.
6. the preparation method of nano zinc oxide modified aramid fiber as described in claim 1, which is characterized in that in the step 2
The preparation step of zinc oxide crystal seed liquid includes: to mix Zinc diacetate dihydrate and dehydrated alcohol according to mass ratio 0.0027:1,
It is dissolved by heating at 300~500r/min mixing speed and 40~65 DEG C, obtains Zinc diacetate dihydrate/ethanol solution；By hydroxide
Sodium and dehydrated alcohol are mixed according to mass ratio 0.0008:1, are heated at 300~500r/min mixing speed and 40~65 DEG C molten
Solution, obtains sodium hydroxide/ethyl alcohol solution；Obtained sodium hydroxide/ethyl alcohol solution is added to Zinc diacetate dihydrate/second in equal volume
Alcoholic solution reacts 30~120min at 50~65 DEG C, obtains zinc oxide crystal seed liquid.
7. the preparation method of nano zinc oxide modified aramid fiber as described in claim 1, which is characterized in that the step 2
In further include: described in repeating " aramid fiber after drying is immersed in again in zinc oxide crystal seed liquid, is stood, is taken out,
It is dry " step, it carries out 2~5 times altogether.
8. the preparation method of nano zinc oxide modified aramid fiber as described in claim 1, which is characterized in that in the step 2
Drying be dry 5~20min in 80~160 DEG C of vacuum drying ovens.
9. the preparation method of nano zinc oxide modified aramid fiber as described in claim 1, which is characterized in that in the step 3
The preparation step of zinc oxide growth liquid includes: first to dissolve hexa and polyethyleneimine according to molar ratio 25:1~5
In 90 DEG C of deionized water, the zinc nitrate hexahydrate with hexa equimolar amounts is added, zinc oxide growth is obtained
Liquid.
10. the preparation method of nano zinc oxide modified aramid fiber as described in claim 1, which is characterized in that in the step 3
The modified aramid fiber of the Zinc oxide nanoparticle that step 2 obtains, which is immersed in the reaction temperature reacted in zinc oxide growth liquid, is
85~95 DEG C, 2~10h of reaction time；Washing in the step 3 is clean 3~5 times with deionized water, it is dry be 80~
Dry 1~4h in 150 DEG C of vacuum drying ovens.
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| CN116377708A (en) * | 2023-04-21 | 2023-07-04 | 东华大学 | Nondestructive modification method for simultaneously improving ultraviolet radiation resistance and adhesive property of aramid fiber |
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