CN109505117A - A kind of composite modifying method of porous fibrous structure - Google Patents
A kind of composite modifying method of porous fibrous structure Download PDFInfo
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- CN109505117A CN109505117A CN201811091859.2A CN201811091859A CN109505117A CN 109505117 A CN109505117 A CN 109505117A CN 201811091859 A CN201811091859 A CN 201811091859A CN 109505117 A CN109505117 A CN 109505117A
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- 239000013305 flexible fiber Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 13
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002657 fibrous material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 240000000203 Salix gracilistyla Species 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
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- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 241000283725 Bos Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- -1 ZrO2 compound Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 230000002459 sustained effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明涉及一种多孔纤维结构的复合改性方法，本发明利用抽滤方法进行柔性纤维改性处理，利用石墨烯最稳定的苯六元环状结构高强度在柔性纤维孔隙中起到增强效果，本发明可改善柔性纤维的增强增韧性：通过在柔性纤维中加入氧化物粒子可明显提高基体的强度，承载力，而石墨烯的片层结构可提高柔性纤维的冲击韧性，这对增强柔性纤维的抗冲击使用能力具有重要意义。本发明制备工艺简单，生产成本低，非常便于工业化生产。
The invention relates to a composite modification method of a porous fiber structure. The invention uses a suction filtration method to perform flexible fiber modification treatment, and utilizes the most stable benzene six-membered ring structure of graphene to play a reinforcing effect in the pores of the flexible fiber. , the present invention can improve the reinforcement and toughness of the flexible fibers: by adding oxide particles to the flexible fibers, the strength and bearing capacity of the matrix can be significantly improved, and the lamellar structure of graphene can improve the impact toughness of the flexible fibers, which is beneficial to the enhancement of flexibility. The impact resistance of the fiber is of great significance. The preparation process of the invention is simple, the production cost is low, and the industrial production is very convenient.
Description
Technical field
The present invention relates to technical field of nano material, and in particular to a kind of composite modifying method of porous fibrous structure.
Background technique
With the rapid development of the modern technologies such as aerospace, guided missile, high-speed carriering tool, to various armoring and human body shock resistances
More stringent requirements are proposed for the use of protective materials.The flak jackets for being currently used primarily in human body defense of resistance to impact has through sewing side
Method is soft armor material by multilayer planar fabric combination or by three-dimensional, multidimensional braiding forms, alternatively, it is also possible to by polymer and fibre
Dimension or fabric are combined, and this flexible composite is flexible, are bent, torsion, a kind of material deformed without losing performance.
Due to the bidimensional period honeycomb lattice structure that graphene is made of carbon hexatomic ring, basic structural unit is to have
Most stable of benzene six-membered cyclic structure in machine material is to be currently known most thin superpower two-dimensional layered-structure material, also than diamond
Hard, research is found before showing that graphene sample starts fragmentation, and the maximum pressure that every 100 nanometers of distances can above be born can reach
About 2.9 micro- oxen.Therefore, flexible fibrous material is modified using graphene can be the case where quality and pattern change
Under reach very high intensity.In addition, zirconium dioxide adds in modification as good chemical stability and antioxidants
Add zirconium dioxide that side effect can't occur, and the particle of zirconium dioxide can be further improved enhancing effect in the composite
Fruit, therefore test has separately designed graphene and graphene and ZrO2 compound dispersion liquid answer flexible fibrous material
Close modification.
Flexible fiber modification is carried out using suction filtration method in test, the impact of material is hit thorough performance and fallen using homemade
Hammer test carries out, and experimental implementation is simple and easy.It is used in experiment and graphene dispersing solution, graphene and ZrO2 is added dropwise on filter paper
Mixed dispersion liquid is filtered, and spread dispersing agent can sufficiently on filter paper, to reach uniform covering and osmosis.
Summary of the invention
The purpose of the present invention is obtain a kind of method and material system for improving flexible fiber intensity and tough.This
Invention carries out flexible fiber modification using suction filtration method, is existed using the most stable of benzene six-membered cyclic structure high intensity of graphene
Reinforcing effect is played in flexible fiber hole, the present invention provides one kind simply and easily to prepare graphene enhancing flexible fiber base
The method of body.Preparation process of the present invention is simple, and production cost is low, is highly convenient for industrialized production.
To achieve the above object, present invention provide the technical scheme that
A kind of composite modifying method of porous fibrous structure, comprising the following steps:
1) preparation of graphene: forming mixed solution by crystalline flake graphite, potassium nitrate and the concentrated sulfuric acid, potassium permanganate be added,
It is stirred at a temperature of 40 DEG C, adds deionized water and obtain solution A, and be heated to 65-80 ° of temperature, then persistently 20-90 points of stirring
Clock；Hydrogenperoxide steam generator is configured, solution A is poured slowly into hydrogenperoxide steam generator and stirs evenly to obtain solution B；Solution B is used
It is 5-6 that sodium hydroxide, which adjusts pH value, is centrifuged 30 minutes in the centrifuge of 8000rpm, obtains liquid and solid separates phase, will divide
Graphite oxide and hydrazine hydrate from after carry out reduction reaction, and deionized water is then added and the mixed solution is added to reaction kettle
Redox graphene is prepared in middle reaction；
2) preparation of nano zircite: a certain amount of ZrOCl is taken first2·8H2O powder is configured to deionized water
ZrOCl2Aqueous solution；Appropriate lactic acid is added into prepared solution, it is uniform with magnetic stirrer, then this is adjusted with NaOH
Mixed solution pH value is 6；Mixed solution is transferred in polytetrafluoroethyllining lining, which is placed in reaction kettle and is reacted；Instead
Should after by reaction solution centrifugal sedimentation, washed with distilled water and dehydrated alcohol, dry, obtain a nanometer ZrO2Powder；
3) graphene-nano zirconium oxide composite material preparation: by redox graphene ultrasound made from step 1) point
It dissipates in dehydrated alcohol, the bigcatkin willow acid dispersant for being 1:1 with the redox graphene mass ratio is added, obtains graphene
Disperse solution, 1:1-1:3 mass is then pressed with nano zircite obtained in step 2) than ultrasonic disperse in dehydrated alcohol, system
Obtain graphene-nano zirconium oxide composite material mixed solution；
4) it filters and is modified: flexible fibrous material is placed in cloth funnel with filter paper, dropwise addition distilled water first makes flexibility
Then fiber wetting opens pumping switch pump, starts to filter；During suction filtration, it is nano oxidized to draw a certain amount of graphene-
Zirconium composite material mixed solution, uniformly drop filters on flexible fibrous material surface, finally takes out modified sample and be placed in baking oven
Middle drying and processing.
It is the crystalline flake graphite of 2-5%, the potassium nitrate of 3-6% and the remaining concentrated sulfuric acid by mass percent in step 1)
Mixed solution is formed, is sequentially added according to the concentrated sulfuric acid, crystalline flake graphite and potassium nitrate sequence, 8- is then added in the above solution
10% potassium permanganate, and 40 DEG C at a temperature of be kept stirring 3 hours.
The volume ratio of hydrogen peroxide and deionized water is 1:21, solution A and hydrogen peroxide in step 1) hydrogenperoxide steam generator
The volume ratio of solution is 5:21.
Hydrazine hydrate reduction 2-4 hours that mass percent is 8-12% are added in graphite oxide after separation by step 1), so
Deionized water is added afterwards and the mixed solution is added in reaction kettle, in 80 DEG C of reaction 800min, prepares oxygen reduction fossil
Black alkene.
In step 2), ZrOCl2The concentration of aqueous solution is 0.3mol/L.
In step 2), mixed solution is placed in reaction kettle in polytetrafluoroethyllining lining to react 24 hours at 160 DEG C.
In step 2), drying temperature is 80 DEG C.
In step 4), filters 20 minutes, finally take out modified sample and be placed in 80 ° of drying and processings in baking oven.
Compared with prior art, the beneficial effects of the present invention are:
1) production cost of the present invention is low: graphene can be by water by Hummer legal system, rear-earth-doped nano zircite
Thermal method is made, and related manufacturing processes are more mature, at low cost, pollution-free, and process flow is relatively simple.
2) scope of application of the present invention is wider: mixed solution can be coated on various component surfaces and be prepared into film, to base
The performance of body itself, will not damaging substrate almost without influence.
3) present invention can reduce the coefficient of friction of matrix: can obviously reduce its friction system after matrix surface is prepared into film
Number improves the friction service life, to being of great significance using the time for extension workpiece.
Detailed description of the invention
Fig. 1 is the schematic device for preparing the suction filtration of graphene and its nano composite oxide enhancing flexible fiber.1- cloth
Family name's funnel；2- conical flask；3- gas bottle.
Fig. 2 is the Raman map of graphene and its compound zirconia.
Fig. 3 is the untreated flexible fiber of the thorough crackle result (a) of the anti-impact of different samples under the same conditions, (b) through stone
The modified flexible fiber of black alkene and (c) ZrO is added in graphene2Result after composite modified.
Fig. 4 is rear flexible fibrous material energy absorption situation under different height percussion before modified.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
(1) preparation of graphene and its composite nano oxide
The preparation of graphene: the crystalline flake graphite for being 3% by mass percent, 5% potassium nitrate and remaining concentrated sulfuric acid group
At mixed solution, is sequentially added according to the concentrated sulfuric acid, crystalline flake graphite and potassium nitrate sequence, 8% is then added in the above solution
Potassium permanganate, and 40 DEG C at a temperature of be kept stirring 3 hours.Ionized water is added in solution to 100ml again, and is heated to temperature
65-80 ° of degree, then persistently stir 60 minutes.20ml hydrogen peroxide is added in 400ml deionized water and is stirred evenly, it will be above-mentioned
The solution of preparation is poured slowly into hydrogenperoxide steam generator and stirs evenly.It is 5-6 with sodium hydroxide adjustment pH value, in 8000rpm
Centrifuge in be centrifuged 30 minutes, obtain liquid and solid and separate phase, mass percent, which is added, in the graphite oxide after separation is
Then 10% hydrazine hydrate reduction 2 hours is added deionized water and the mixed solution is added in reaction kettle, reacts at 80 DEG C
800min prepares redox graphene.
The preparation of nano zircite: a certain amount of ZrOCl is taken first2·8H2O powder and deionized water are configured to 0.3mol/
The ZrOCl of L2Aqueous solution；The lactic acid of 5ml is added into prepared solution, it is uniform with magnetic stirrer；Again with NaOH tune
Saving this mixed solution pH value is 6；Mixed solution is transferred in polytetrafluoroethyllining lining by pH after regulating, which is placed in
It is reacted 24 hours at 160 DEG C in reaction kettle；It by reaction solution centrifugal sedimentation, is washed with distilled water and dehydrated alcohol, is dried through 80 DEG C
Dry-cure obtains a nanometer ZrO2Powder.
The preparation of graphene-nano zirconium oxide composite material: by redox graphene ultrasonic disperse obtained above in
In dehydrated alcohol, the bigcatkin willow acid dispersant for being 1:1 with the redox graphene mass ratio is added, obtains the dispersion of graphene
Solution then presses 1:1-1:3 mass than ultrasonic disperse in dehydrated alcohol with nano zircite obtained, and obtained graphene-is received
Rice zirconium oxide composite material mixed solution.
(2) it the suction filtration technique of graphene and its nano composite oxide enhancing flexible fiber: is carried out according to Fig. 1 device flexible
Fiber surface filters the assembling of reforming apparatus, and then filter paper is placed in flexible fibrous material in cloth funnel (1 in Fig. 1 to
Place), dropwise addition distilled water first soaks flexible fiber, to guarantee to be completely embedded with funnel, then opens pumping switch pump, opens
Begin to filter.During suction filtration, the above-mentioned mixed solution of 3ml is drawn, uniformly drop filters 20 points on flexible fibrous material surface
Clock finally takes out modified sample and is placed in 80 ° of drying and processings in baking oven.
By Fig. 2 graphene and its compound zirconia Raman map show flexible fiber in added graphene and its
The result feature of composite Nano zirconium oxide.
As seen from Figure 3, as the addition of graphene and its compound ZrO2 nano particle is so that when breakdown flexible fiber
Crack length is reduced, and illustrates that the addition of the two helps to improve the toughness of flexible fiber.
By the Fig. 4 it will be evident that height is higher, the loss of energy is bigger, in sustained height, is highly less than
When 100cm, with the modified flexible fiber of graphene and with the compound ZrO of graphene2The shock resistance phase of modified flexible fiber
It is poor little but better than the flexible fibrous material effect of unmodified processing, illustrate that both of these case makes to a certain extent really
The toughness of flexible fiber is improved.It is greater than 100cm, the compound ZrO of graphene in height2The modified effect ratio of nanoparticle is only used
The modified effect of graphene is well very much, and reason may is that zirconia particles are distributed between the gap of graphene, play
Therefore reinforcing effect can get obvious using graphene prepared by suction filtration method and its composite modification flexible fiber body
Activeness and quietness effect, be as a result better than unmodified material.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to the above reality
Any simple modifications, equivalent substitutions and improvements etc. made by example are applied, it is fallen within the scope of protection of the technical scheme of the present invention
It is interior.
Claims (8)
1. a kind of composite modifying method of porous fibrous structure, it is characterised in that: the following steps are included:
1) preparation of graphene: mixed solution is formed by crystalline flake graphite, potassium nitrate and the concentrated sulfuric acid, potassium permanganate is added, at 40 DEG C
At a temperature of stir, add deionized water and obtain solution A, and be heated to 65-80 ° of temperature, then persistently stir 20-90 minutes；Match
Hydrogenperoxide steam generator is set, solution A is poured slowly into hydrogenperoxide steam generator and stirs evenly to obtain solution B；By solution B hydroxide
It is 5-6 that sodium, which adjusts pH value, is centrifuged 30 minutes in the centrifuge of 8000rpm, obtains liquid and solid separates phase, after separation
Graphite oxide and hydrazine hydrate carry out reduction reaction, and deionized water is then added and the mixed solution is added in reaction kettle and reacts
Prepare redox graphene；
2) preparation of nano zircite: a certain amount of ZrOCl is taken first2·8H2O powder and deionized water are configured to ZrOCl2Water
Solution；Appropriate lactic acid is added into prepared solution, it is uniform with magnetic stirrer, then this mixed solution is adjusted with NaOH
PH value is 6；Mixed solution is transferred in polytetrafluoroethyllining lining, which is placed in reaction kettle and is reacted；It will be anti-after reaction
Liquid centrifugal sedimentation is answered, is washed with distilled water and dehydrated alcohol, dries, obtains a nanometer ZrO2Powder；
3) graphene-nano zirconium oxide composite material preparation: by redox graphene ultrasonic disperse made from step 1) in
In dehydrated alcohol, the bigcatkin willow acid dispersant for being 1:1 with the redox graphene mass ratio is added, obtains the dispersion of graphene
Solution then presses 1:1-1:3 mass than ultrasonic disperse in dehydrated alcohol, obtained stone with nano zircite obtained in step 2)
Black alkene-nano zirconium oxide composite material mixed solution；
4) it filters and is modified: flexible fibrous material is placed in cloth funnel, dropwise addition distilled water first soaks flexible fiber, so
Pumping switch pump is opened afterwards, starts to filter；During suction filtration, a certain amount of graphene-nano zirconium oxide composite material is drawn
Mixed solution, uniformly drop filters on flexible fibrous material surface, finally takes out modified sample and be placed in baking oven at drying
Reason.
2. the composite modifying method of porous fibrous structure according to claim 1, it is characterised in that: in step 1), by matter
The crystalline flake graphite that percentage is 2-5% is measured, the potassium nitrate of 3-6% and the remaining concentrated sulfuric acid form mixed solution, according to dense sulphur
Acid, crystalline flake graphite and potassium nitrate sequence sequentially add, and the potassium permanganate of 8-10% are then added in the above solution, and at 40 DEG C
At a temperature of be kept stirring 3 hours.
3. the composite modifying method of porous fibrous structure according to claim 1, it is characterised in that: step 1) hydrogen peroxide
The volume ratio of hydrogen peroxide and deionized water is 1:21 in solution, and the volume ratio of solution A and hydrogenperoxide steam generator is 5:21.
4. the composite modifying method of porous fibrous structure according to claim 1, it is characterised in that: after step 1) will separate
Graphite oxide mass percent is added is hydrazine hydrate reduction 2-4 hour of 8-12%, then addition deionized water and this is mixed
It closes solution to be added in reaction kettle, in 80 DEG C of reaction 800min, prepares redox graphene.
5. the composite modifying method of porous fibrous structure according to claim 1, it is characterised in that: in step 2), ZrOCl2
The concentration of aqueous solution is 0.3mol/L.
6. the composite modifying method of porous fibrous structure according to claim 1, it is characterised in that: in step 2), mixing
Solution is placed in reaction kettle in polytetrafluoroethyllining lining to react 24 hours at 160 DEG C.
7. the composite modifying method of porous fibrous structure according to claim 1, it is characterised in that: in step 2), drying
Temperature is 80 DEG C.
8. the composite modifying method of porous fibrous structure according to claim 1, it is characterised in that: in step 4), filter
It 20 minutes, finally takes out modified sample and is placed in 80 ° of drying and processings in baking oven.
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