CN107021473A - Carbon nanotube agglomerate is in preparing purposes and its preparation method in thorn-proof composite material - Google Patents
Carbon nanotube agglomerate is in preparing purposes and its preparation method in thorn-proof composite material Download PDFInfo
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- CN107021473A CN107021473A CN201610202639.7A CN201610202639A CN107021473A CN 107021473 A CN107021473 A CN 107021473A CN 201610202639 A CN201610202639 A CN 201610202639A CN 107021473 A CN107021473 A CN 107021473A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
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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
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a kind of carbon nanotube agglomerate in preparing purposes and its preparation method in thorn-proof composite material, wherein the thorn-proof composite material includes：An at least carbon nanotube agglomerate, includes the carbon nano-tube film formed by many CNT tight clusters；And, flexible substrate, the fixed carbon nano-tube film being covered with least described in one on its at least side surface.It is preferred that, the carbon nanotube agglomerate includes the base unit of multiple orientation arrangements, the base unit includes the two-dimentional planar structure formed by the unordered intertexture of many CNTs, the plurality of base unit is densely arranged in a continuous face and is parallel to each other, make the carbon nanotube agglomerate that Microscopic order, microcosmic unordered form is presented, described continuous face is plane or curved surface.The thorn-proof composite material of the present invention has quality frivolous, flexible, suitable for wearing, anti-stab excellent performance, prepared by suitable mass the characteristics of.
Description
Technical field
Present invention relates particularly to a kind of thorn-proof composite material based on nano-carbon material and preparation method thereof.
Background technology
Anti-stab product common at present mainly has following two class, i.e.,：(1) hard stab-resistant material：Mainly by steel, alloy type material
Pass through shape and structure design, although anti-stab performance is good, but structure bulky, have a strong impact on the flexibility of individual movement；(2) it is soft
Matter stab-resistant material：By the high performance fibers such as ultra-high molecular weight polyethylene, aramid fiber by interweaving (interwoven) or without the (nothing that interweaves
Latitude cloth) form anti-stab elementary layer, then the stab-resistant material obtained by these anti-stab unit layer stackups.Than hard stab-resistant material, this
A little soft stab-resistant materials significantly reduce the weight of material.From the dynamic process analysis of the such soft stab-resistant body of cutter penetration, often
Layer stab-resistant material, which all undergoes to be sheared again after cutter bursting, cuts to fibrous fracture destruction, until the kinetic energy of cutter is complete by stab-proof body
Untill hypersorption.Therefore, for such soft stab-resistant material, the resistance to bursting and cutting performance for lifting material are crucial.To the greatest extent
Pipe industry has carried out many research to this problem, but soft stab-resistant material still generally existing some defects formed.For example,
CN101218480B discloses a kind of fabric substrate formed by the net of high-tenacity fiber, by the way that once adhesion is bonded on the matrix
Layer and rubber layer, multiple such element stacks form the thorn-proof composite material of flexibility, and material structure is complicated, poor processability,
Be not suitable for mass to prepare.And for example, US2004/0048536A1 in high-performance fiber fabric face by adhering to a certain amount of solid
Hard particles material, can be passivated cutter Penetration Depth.In US20070105471 by by coating inorganic particles in kevlar fabric
Surface is to improve the anti-stab performance of material, but its structure is hardened so that snugness of fit declines.
The content of the invention
It is a primary object of the present invention to provide a kind of carbon nanotube agglomerate in preparing purposes and its preparation in thorn-proof composite material
Method, to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The embodiments of the invention provide a kind of carbon nanotube agglomerate in preparing the purposes in thorn-proof composite material, the CNT
Aggregation includes the two-dimentional planar structure of macroscopic view formed by many CNT tight clusters.
Further, the thorn-proof composite material includes：
An at least carbon nanotube agglomerate, includes the carbon nano-tube film formed by many CNT tight clusters；And,
The fixed carbon nano-tube film being covered with least described in one on flexible substrate, its at least side surface.
More preferred, the carbon nanotube agglomerate includes the base unit of multiple orientation arrangements, and the plurality of base unit is one
It is densely arranged and be parallel to each other in individual continuous face, make the carbon nanotube agglomerate that Microscopic order, microcosmic unordered form is presented,
Described continuous face is plane or curved surface.Wherein, each base unit includes two formed by the unordered intertexture of many CNTs
Tie up planar structure.
In some embodiments, multiple CNT non-individual bodies continuous aggregation and densified processing on described continuous face
Described multiple base units are formed afterwards；The CNT non-individual body is formed by the unordered intertexture of many CNTs, and is being caused
Closing, semiclosed or open two dimension or three-D space structure are presented before densification process.
Further, the CNT non-individual body is prepared by floating catalyst method forms.
The embodiment of the present invention additionally provides a kind of anti-stab structure, and it includes the multiple subelements being stacked, each of which subelement
Include described thorn-proof composite material.
The embodiment of the present invention additionally provides a kind of preparation method of thorn-proof composite material, and it includes：
Multiple CNT non-individual bodies are made to form many after continuous aggregation and densified processing in a continuous plane or curved surface
The base unit of individual orientation, the plurality of base unit is densely arranged and is formed in membranaceous carbon nanotube agglomerate, wherein described
CNT non-individual body is formed by many CNTs unordered intertexture, and presented before densification close, it is semiclosed or open
Put the two dimension or three-D space structure of formula；
Fix described carbon nanotube agglomerate and be covered in flexible substrate surface, form described thorn-proof composite material.
The embodiment of the present invention additionally provides a kind of preparation method of thorn-proof composite material, and it includes：Make multiple CNT non-individual bodies
Continuously assemble on flexible substrate surface and the base unit of multiple orientations is formed after densified processing, the plurality of base unit is close
It is in membranaceous carbon nanotube agglomerate that collection, which is arranged and formed, so as to form described thorn-proof composite material；Wherein, described carbon is received
Mitron non-individual body by many CNTs it is unordered intertexture is formed, and before densification present close, it is semiclosed or open
Two dimension or three-D space structure.
The present invention by the way that by carbon nanotube agglomerate, particularly flexible carbon nano-tube film is combined with flexible substrate, especially by
Flexible carbon nano tube film is adhered into high-performance fiber fabric face and thorn-proof composite material is formed, it can effectively be passivated cutter knife
Point, reduces depth of invasion, and can effectively disperse and absorb the kinetic energy of cutter, effectively pins down the movement of high-performance fiber,
The uneven rate in fabric face is reduced, meanwhile, it is the thorn-proof composite material portable construction, flexible, do not interfered with during wearing
Human action, but also with excellent environmental resistance, such as excellent heat resistance, resistance to ultraviolet and aqueous vapor environment.
Brief description of the drawings
Fig. 1 is the schematic diagram for utilizing in an exemplary embodiments of the invention hot press to carry out compression process to carbon nanotube agglomerate；
Fig. 2 is a kind of photo of carbon nano-tube film in an exemplary embodiments of the invention.
Fig. 3 is a kind of TEM photos of carbon nano-tube film in an exemplary embodiments of the invention；
Fig. 4 is a kind of TEM photos of institute's carbon nanotubes in carbon nano-tube film in an exemplary embodiments of the invention.
Embodiment
The one side of the embodiment of the present invention provides a kind of carbon nanotube agglomerate in preparing the purposes in thorn-proof composite material.
Wherein, the thorn-proof composite material includes：
An at least carbon nanotube agglomerate, includes the carbon nano-tube film formed by many CNT tight clusters；And,
The fixed carbon nano-tube film being covered with least described in one on flexible substrate, its at least side surface.
Foregoing " tight clusters " comprising intersecting, interweave, winding, any of arranged in parallel or other suitable forms or
A variety of combinations.For example, as one of feasible scheme, the carbon nanotube agglomerate may also comprise densely arranged many and take
To CNT, described carbon nano-tube film can be for example made up of the carbon nano pipe array of super in-line arrangement.
In some embodiments, many CNTs in the carbon nanotube agglomerate interweave with forming carbon nano-tube film.Wherein,
The form of intertexture can be ordered into or unordered.
In some embodiments, the carbon nanotube agglomerate can be rendered as the carbon nano-tube film of self-supporting.
In some more preferred embodiment, the carbon nanotube agglomerate includes the base unit of multiple orientation arrangements, its
In each base unit include the two-dimentional planar structure that is formed of being interweaved by many CNTs.
Further, described multiple base units are densely arranged in a continuous face and are parallel to each other, and make the carbon nanometer
The form of Microscopic order is presented in pipe aggregation, and described continuous face is plane or curved surface.
Further, the unordered intertexture of many CNTs in the base unit, is presented the carbon nanotube agglomerate microcosmic
Unordered form.Further, the unordered intertexture of many CNTs in the base unit, makes the carbon nanotube agglomerate
Microcosmic unordered form is presented.Inventor is found surprisingly that, with such a Microscopic order, microcosmic unordered special construction
Nano-sized carbon anti-ballistic materials are compared to the nano-sized carbon anti-ballistic materials with other CNT aggregated forms, in shock resistance etc.
Aspect shows more advantages, and the reason for its is possible is, in the nano-sized carbon anti-ballistic materials with the special construction, and one
Aspect allows it to absorb a large amount of impact energys because of the distinctive structure of CNT itself, on the other hand because CNT is received with carbon
There is fine and close network and abundant interface between mitron, it is fully coordinated, so as to be allowed to show excellent shock resistance.
In some preferred embodiments, multiple CNT non-individual bodies are continuous on described continuous face to be assembled and densified
Described multiple base units are formed after processing；The CNT non-individual body is formed by the unordered intertexture of many CNTs, and
Closing, semiclosed or open two dimension or three-D space structure are presented before densification.
Further, the CNT non-individual body is prepared to be formed by chemical vapour deposition technique, particularly floating catalyst method.
The CNT non-individual body is the cylinder of many many CNTs unordered interweave formation, closing or opening in certain embodiments
Shape, and with certain length, it can be formed in strip on certain base material is deposited to, and after densified processing
The base unit.
More specifically, the production technology of the CNT non-individual body may be referred to some existing documents, for example：《science》,
, 304 phases, p276 in 2004.In a more typical case, a kind of method for preparing the CNT non-individual body is included such as
Lower step：
S1, reacting furnace temperature rises to 1100 DEG C~1600 DEG C, keeping temperature is stable, and carrier gas is injected into the reacting furnace；
S2, by phase carbon source by carbon source ejection of syringe pump, phase carbon source is uniformly entered after passing sequentially through carbon source transport tube, restriction
Enter the carbon source injection tube core of carbon source ascending pipe；
S3, phase carbon source gasification；
S4, carrier gas carry the carbon source after gasification and reached in the high-temperature region of the reacting furnace, generate carbon nanotube agglomerate.
Wherein, the phase carbon source can be ethanol, ferrocene, mixed solution of thiophene etc..For example, the quality percentage of ethanol
It is 0.1~5% than the mass percent that the mass percent for 90~99.9%, ferrocene is 0.1~5%, thiophene.Wherein, it is described to carry
Gas is the mixed gas of hydrogen and nitrogen or hydrogen and inert gas, for example, the percent by volume of hydrogen can be 1~100%,
Inert gas is argon gas or helium, and gas of carrier gas flow is 1~15L/min.
It is more preferred, it is spaced apart, adjacent or mutually overlapping between longitudinal peripheral part of two neighboring base unit
Arrangement.Further, the distance between two neighboring base unit should be small as far as possible so that two neighboring base unit it
Between can preferably coordinate or mutually support so that further lifted the nano-sized carbon anti-ballistic materials reliability and shock resistance it is strong
Degree.
In some preferred embodiments, graphene is also distributed with the surface and/or inside of the carbon nanotube agglomerate.
For example, covered with graphene film at least one CNT at least one described carbon nanotube agglomerate.
Or, for example, an at least graphene film is overlapped between at least two CNTs in the carbon nanotube agglomerate.
Or, for example, the nano-sized carbon anti-ballistic materials also include the aggregation of multi-disc graphene, the multi-disc graphene it is poly-
Collective is fixedly connected with the carbon nanotube agglomerate described at least one.
Or, for example, the aggregation of the carbon nanotube agglomerate described at least one and the multi-disc graphene described at least one is in
The existing two-dimentional planar structure of macroscopic view, and this at least one described in carbon nanotube agglomerate and this at least one described in multi-disc graphite
The aggregation of alkene is stacked.
In foregoing embodiments, by the way that CNT is combined with graphene, also using the architectural feature of the big lamella of graphene
Dispersive stress ripple, the impact energy reduction for making anti-ballistic materials be subject in unit area, so as to further lift protection effect.
In foregoing each embodiment, the caliber of the CNT can be 2~100nm, it is possible to selected from single wall, double-walled,
Any one in multi-walled carbon nanotube or a variety of combinations.
More preferred, the content of CNT is in more than 99wt% in the carbon Micelle-like Nano-structure of Two.
In some embodiments, when the carbon nanotube agglomerate is the two-dimentional planar structure of macroscopic view, the carbon of for example, self-supporting is received
During mitron film, its stress >=10MPa, elongation >=2%, the absolute value of the difference of the tensile stress on length and width direction is small
In or equal to tensile stress in length or width 20%, and the difference of the elongation at break on length and width direction
The 10% of the elongation at break that the absolute value of value is less than or equal in length or width.
It is more preferred, the thickness of thickness≤flexible substrate of the carbon nano-tube film.
Further, described carbon nanotube agglomerate has loose structure, and the aperture of hole is contained by the loose structure
10nm~200nm, porosity is 10%~60%.The presence of this loose structure, will not both make the carbon nanotube agglomerate
Mechanical property is influenceed by big, also the carbon nanotube agglomerate can be made to show preferable gas permeability.
Further, the thickness of described carbon nanotube agglomerate is 1~100 μm, preferably 5~15 μm.
Further, the surface density of described carbon nanotube agglomerate is 2~20g/m2, preferably 5~10g/m2。
Further, the tensile strength of described carbon nanotube agglomerate is in more than 10MPa, and modulus is in more than 10GPa.
Further, the tensile strength of described carbon nanotube agglomerate is in more than 90Mpa, preferably in more than 200MPa, modulus
In more than 30Gpa, preferably in more than 60GPa.
Further, the tolerable temperature scope of described carbon nanotube agglomerate is -600 DEG C~500 DEG C.
It is more preferred, constitute intensity >=2.0GPa of the high-performance fiber of the flexible substrate, modulus >=80GPa, elongation is 3~
5%.
More preferred, the flexible substrate is selected from laminated cloth, and the surface density of the laminated cloth is 35~180g/m2。
In some embodiments, the base fabric includes ultra-high molecular weight polyethylene unidirectional cloth or aramid fiber unidirectional cloth.
In some embodiments, the flexible substrate and the carbon nanotube agglomerate are through hot binding.
In some embodiments, the flexible substrate and the carbon nanotube agglomerate are also through adhesive bonds.It is wherein described viscous
Knot agent may be selected from PVA (polyvinyl alcohol), silicon class, polyethylene kind or polyurethanes binding agent etc., and not limited to this.
In some embodiments, carbon nanotube agglomerate and/or the flexible substrate surface has resin film.Wherein, it is described
The material of resin film includes epoxy, polyethylene kind or polyesters compound etc., such as PP (polypropylene), PE (polyethylene),
PPS (polyphenylene sulfide) or PVB (polyvinyl butyral resin), and not limited to this.
The embodiment of the present invention another aspect provides a kind of anti-stab structure, it includes the multiple subelements being stacked, wherein
Each subelement includes described thorn-proof composite material.
More preferred, the anti-stab structure includes N number of subelement, and N is 4 integral multiple.
In some embodiments, in two neighboring subelement, the base unit of the carbon nanotube agglomerate in a subelement
The base unit of carbon nanotube agglomerate in orientation arrangement in the first direction, another subelement is orientated arrangement in a second direction,
Form 0 °~180 ° of angle between the first direction and second direction, for example preferred at 45 °~135 ° of angle.
Another aspect of the embodiment of the present invention provides a kind of preparation method of thorn-proof composite material, and it includes：
Multiple CNT non-individual bodies are made to form many after continuous aggregation and densified processing in a continuous plane or curved surface
The base unit of individual orientation, the plurality of base unit is densely arranged and is formed in membranaceous carbon nanotube agglomerate, wherein described
CNT non-individual body is formed by many CNTs unordered intertexture, and presented before densification close, it is semiclosed or open
Put the two dimension or three-D space structure of formula；
Fix described carbon nanotube agglomerate and be covered in flexible substrate surface, form described thorn-proof composite material.
Another aspect of the embodiment of the present invention provides a kind of preparation method of thorn-proof composite material, and it includes：Multiple carbon are made to receive
Mitron non-individual body is continuously assembled on flexible substrate surface and the base unit of multiple orientations is formed after densified processing, the plurality of
Base unit is densely arranged and is formed in membranaceous carbon nanotube agglomerate, so as to form described thorn-proof composite material；Wherein,
Described CNT non-individual body is formed by the unordered intertexture of many CNTs, and closing is presented before densification, partly seals
Close or open two dimension or three-D space structure.
In some embodiments, the CNT non-individual body is prepared by floating catalyst method forms, and it is specific such as institute above
State.
In some embodiments, described preparation method also includes：The CNT combined to flexible substrate and with flexible substrate
Aggregation carries out hot-pressing processing.
In some embodiments, the condition of the hot-pressing processing includes：Temperature is room temperature~140 DEG C, and pressure is 1~30MPa,
Time is more than 1min.
For example, described hot-pressing processing includes：
First stage：Temperature is 110~120 DEG C, and pressure is 1~4MPa, and the time is 10~30min；
Second stage：Described hot-pressing processing includes：Temperature is 120~140 DEG C, and pressure is 15~30MPa, and the time is 1~3min.
In some embodiments, described hot-pressing processing includes：Temperature is room temperature, and pressure is 1~30MPa, the time is 1~
30min。
The thorn-proof composite material of the present invention has frivolous quality, anti-stab excellent performance, is adapted to prepared by mass the characteristics of.
Technical scheme is further described below in conjunction with some embodiments.
Embodiment 1：
1) preparation of carbon nano-tube film：Carbon-source gas are in the presence of metallic catalyst, the continuous carbon nanometer of hot conditions growth
(the reference of pipe non-individual body《science》, 304 phases, p276 in 2004), by non-individual body in two dimensional surface constantly aggregation and
Formation carbon nano-tube film arranged in parallel, CNT therein include single wall, double-walled, many walls one or two kinds of therein and
More than, caliber is combined between 2-100nm between carbon pipe by Van der Waals force, thin using press compression process CNT afterwards
Film (refers to Fig. 1), and further to improve the density of film, the pressure used is 15MPa, about 90 DEG C of temperature, time about 2h,
The final averaged areal density about 5g/m of obtained carbon nano-tube film (pattern refers to Fig. 2-Fig. 4)2, average tensile strength about 300MPa,
Average modulus about 60Gpa, average extension at break about 10%
2) ultra-high molecular weight polyethylene unidirectional cloth：By the superhigh molecular weight polyethylene fibers of surface impregnation, (tensile strength is about
22CN/dtex) planar formation unidirectional cloth arranged in parallel, the surface density about 40g/m of unidirectional cloth2。
3) by 1 layer of step 1) obtain carbon nano-tube film and 1 layer of ultra-high molecular weight polyethylene unidirectional cloth hot pressing is compound obtains as one
Subelement, hot-pressing processing method includes：
First stage：Temperature is 110 DEG C, pressure 2MPa, time：10min；
Second stage：Temperature is 130 DEG C, pressure 25MPa, time：1min, afterwards natural cooling.
4) by step 3) obtained 4 subelements according to 0/90/45/-45 (unidirectional cloth warp, which is orientated, in first subelement is set to 0 °,
Unidirectional cloth warp orientation is set to unidirectional cloth warp orientation in 90 °, the 3rd subelement and is set to 45 °, the 4th in second subelement
Unidirectional cloth warp orientation is set to -45 ° in subelement, is abbreviated as 0/90/45/-45) it is stacked as a structure sheaf；
5) 30 structure sheafs are stacked to form anti-stab structure, enters Mobile state and puncture experiment.
Embodiment 2：
1) preparation of carbon nano-tube film：Carbon-source gas are in the presence of metallic catalyst, the continuous carbon nanometer of hot conditions growth
Pipe non-individual body (refers to foregoing typical embodiments), constantly aggregation and the formation arranged in parallel in two dimensional surface by non-individual body
Carbon nano-tube film, CNT therein include single wall, double-walled, many walls one or two kinds of therein and more than, caliber exists
Between 2-100nm, combined between carbon pipe by Van der Waals force, afterwards using press compression process carbon nano-tube film, with further
Improve the density of film, the pressure about 2MPa of use, about 90 DEG C of temperature, about 4 hours time, finally obtained carbon nano-tube film
Averaged areal density about 5.5g/m2, average tensile strength about 200MPa, average modulus about 45Gpa, average extension at break about 18%.
2) aramid fiber unidirectional cloth：By the aramid fiber (tensile strength about 22CN/dtex) of surface impregnation planar parallel
Row form unidirectional cloth, the surface density about 110g/m of unidirectional cloth2。
3) by 1 layer of step 1) obtain carbon nano-tube film and 1 layer of aramid fiber unidirectional cloth hot pressing is compound obtains as a subelement,
Hot-pressing processing method includes：
First stage：Temperature is 110 DEG C, pressure 2MPa, time：10min；
Second stage：Temperature is 130 DEG C, pressure 25MPa, time：1min, afterwards natural cooling.
4) by step 3) obtained 4 subelements according to 0/90/45/-45 (unidirectional cloth warp, which is orientated, in first subelement is set to 0 °,
Unidirectional cloth warp orientation is set to unidirectional cloth warp orientation in 90 °, the 3rd subelement and is set to 45 °, the 4th in second subelement
Unidirectional cloth warp orientation is set to -45 ° in subelement, is abbreviated as 0/90/45/-45) it is stacked as a structure sheaf；
5) 30 structure sheafs are stacked to form anti-stab structure, enters Mobile state and puncture experiment.
Embodiment 3：
1) preparation of carbon nano-tube film：Carbon-source gas are in the presence of metallic catalyst, and the continuous carbon of hot conditions growth is received
Mitron non-individual body (with reference to embodiment 2), non-individual body is constantly assembled in two dimensional surface and formation CNT arranged in parallel is thin
Film, CNT therein include single wall, double-walled, many walls one or two kinds of therein and more than, caliber between 2-100nm,
Combined between carbon pipe by Van der Waals force, afterwards using press compression process, further improve the density of film, suppress at room temperature,
Pressure about 120MPa, about 1 hour time, the finally averaged areal density of obtained film about 5g/m2, average tensile strength about 200MPa,
Average modulus about 45Gpa, average extension at break about 18%.
2) ultra-high molecular weight polyethylene unidirectional cloth：By the superhigh molecular weight polyethylene fibers of surface impregnation planar shape arranged in parallel
Into unidirectional cloth, the surface density of unidirectional cloth is 40g/m2。
3) by 1 layer of step 1) obtain that carbon nano-tube film and 1 strata ethene unidirectional cloth hot pressing are compound to be obtained as a subelement, heat
Pressure processing method includes：
First stage：Temperature is 110 DEG C, pressure 2MPa, time：10min；
Second stage：Temperature is 130 DEG C, pressure 25MPa, time：1min, afterwards natural cooling.
4) by step 3) obtained 4 subelements are stacked as a structure sheaf according to 0/45/90/-45；
5) 10 structure sheafs are stacked to form anti-stab structure, enters Mobile state and puncture experiment.
Comparative example 1：Using the ultra-high molecular weight polyethylene in embodiment 1, totally 10 element stacks do dynamic test.
Comparative example 2：Using the aramid fiber in embodiment 2, totally 8 element stacks make dynamic test.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Fiber type | UHMWPE | Aramid fiber | UHMWPE | UHMWPE | Aramid fiber |
| Film surface density g/m2 | 5 | 5 | 5 | -- | -- |
| Composite surface density g/m2 | 6 | 6 | 6 | 6 | 6 |
| Stack angle | 0/90/45/-45 | 0/90/45/-45 | 0/45/90/-45 | 0/90/45/-45 | 0/90/45/-45 |
| Maximum paracentesis depth (cm) | 12 | 13 | 9 | 43 | 50 |
| Maximum load (N) | 935 | 900 | 961 | 604 | 581 |
Embodiment 4：
Commercially available carbon nanotube dust is taken, prepares to form Buckie paper-like carbon nano-tube film using filtration method, its thickness about 40um, face
Density about 12g/m2, tensile strength about 10MPa, modulus about 2GPa, elongation at break about 3%.
, will with the carbon nano-tube film in the Buckie paper-like carbon nano-tube film alternative embodiment 1, and with reference to the scheme of embodiment 1
The Buckie paper-like carbon nano-tube film combines to form thorn-proof composite material with ultra-high molecular weight polyethylene unidirectional cloth, its averaged areal density
About 170g/m2, maximum paracentesis depth about 50cm.
Embodiment 5：
Take can spinning carbon nano pipe array draw to form super in-line arrangement carbon nano-tube film, about 7 μm of its thickness, surface density about 6g/m2、
Tensile strength about 400MPa, modulus about 45GPa, elongation at break about 3%.
, will with the carbon nano-tube film in the super in-line arrangement carbon nano-tube film alternative embodiment 2, and with reference to the scheme of embodiment 2
The super in-line arrangement carbon nano-tube film combines to form thorn-proof composite material with aramid fiber unidirectional cloth, its averaged areal density about 115
g/m2, maximum paracentesis depth about 18cm.Maximum load about 850N.
It should be appreciated that the foregoing is only the preferred embodiments of the present invention, it is not intended to limit the invention, for this
For the technical staff in field, the present invention can have various modifications and variations.Within the spirit and principles of the invention, made
Any modification, equivalent substitution and improvements etc., should be included in the scope of the protection.
Claims (25)
1. carbon nanotube agglomerate includes in preparing the purposes in thorn-proof composite material, the thorn-proof composite material：
An at least carbon nanotube agglomerate, includes the carbon nano-tube film formed by many CNT tight clusters；And,
The fixed carbon nano-tube film being covered with least described in one on flexible substrate, its at least side surface.
2. purposes according to claim 1, it is characterised in that：Many CNTs in the carbon nanotube agglomerate are handed over
Knit to form carbon nano-tube film.
3. the purposes according to any one of claim 1-2, it is characterised in that：The carbon nanotube agglomerate includes multiple take
To the base unit of arrangement, the two-dimentional planar structure that each of which base unit is formed including being interweaved by many CNTs.
4. the purposes according to any one of claim 1-3, it is characterised in that：Described multiple base units are continuous at one
Face in it is densely arranged and be parallel to each other, make the carbon nanotube agglomerate that the form of Microscopic order, described continuous face is presented
For plane or curved surface.
5. the purposes according to any one of claim 1-4, it is characterised in that：Many CNTs in the base unit
It is unordered to interweave, make the carbon nanotube agglomerate that microcosmic unordered form is presented.
6. the purposes according to any one of claim 1-5, it is characterised in that：Multiple CNT non-individual bodies are in described company
On continuous face described multiple base units are formed after continuous aggregation and densified processing；The CNT non-individual body is by more
The unordered formation that interweaves of root CNT, and presentation closing, semiclosed or open two dimension or three-dimensional space before densification
Between structure.
7. the purposes according to any one of claim 1-6, it is characterised in that：The CNT non-individual body is by floating catalytic
Cracking process prepares to be formed.
8. the purposes according to any one of claim 1-7, it is characterised in that：Longitudinal peripheral part of two neighboring base unit
Between arrangement to be spaced, adjacent or mutually overlapping.
9. the purposes according to any one of claim 1-8, it is characterised in that：The surface of the carbon nanotube agglomerate and/
Or graphene is also distributed with inside.
10. the purposes according to any one of claim 1-9, it is characterised in that：At least one described carbon nanotube agglomerate
In at least one CNT on covered with graphene film.
11. the purposes according to any one of claim 1-10, it is characterised in that：At least a graphene film is overlapped on the carbon
Between at least two CNTs in Nanotube Aggregates.
12. the purposes according to any one of claim 1-11, it is characterised in that：The caliber of the CNT be 2~
100nm；And/or, the content of CNT is in more than 99wt% in the carbon Micelle-like Nano-structure of Two；And/or, the carbon nano-tube film
Stress >=10MPa, elongation >=2%, the absolute value of the difference of the tensile stress on length and width direction is less than or equal to
20% of tensile stress in length or width, and the absolute value of the difference of elongation at break on length and width direction
Less than or equal to 10% of the elongation at break in length or width；And/or, the thickness of the carbon nano-tube film≤described
The thickness of flexible substrate；And/or, intensity >=2.0GPa of the high-performance fiber of the flexible substrate is constituted, modulus >=80GPa is stretched
Long rate is 3~5%.
13. the purposes according to any one of claim 1-12, it is characterised in that：The flexible substrate is selected from laminated cloth, institute
The surface density for stating laminated cloth is 35~180g/m2。
14. the purposes according to any one of claim 1-13, it is characterised in that：The flexible substrate and carbon nanometer
Pipe aggregation is through hot binding；And/or, the flexible substrate and the carbon nanotube agglomerate are described viscous also through adhesive bonds
Tying agent includes PVA, silicon class, polyethylene kind or polyurethanes binding agent；And/or, the carbon nanotube agglomerate and/or flexible base
Cloth surface has resin film, and the material of the resin film includes epoxy, polyethylene kind or polyesters compound.
15. a kind of anti-stab structure, it is characterised in that comprising the multiple subelements being stacked, each of which subelement includes right
It is required that the thorn-proof composite material any one of 1-14.
16. anti-stab structure according to claim 15, it is characterised in that：The anti-stab structure includes N number of subelement, and N is
4 integral multiple.
17. the anti-stab structure according to any one of claim 15-16, it is characterised in that：In two neighboring subelement, one
The base unit of carbon nanotube agglomerate in individual subelement is orientated arrangement in the first direction, the CNT in another subelement
The base unit of aggregation is orientated arrangement in a second direction, and 0 °~180 ° of angle is formed between the first direction and second direction,
It is preferred that at 45 °~135 ° of angle.
18. a kind of preparation method of thorn-proof composite material, it is characterised in that including：
Multiple CNT non-individual bodies are made to form many after continuous aggregation and densified processing in a continuous plane or curved surface
The base unit of individual orientation, the plurality of base unit is densely arranged and is formed in membranaceous carbon nanotube agglomerate, wherein described
CNT non-individual body is formed by many CNTs unordered intertexture, and presented before densification close, it is semiclosed or open
Put the two dimension or three-D space structure of formula；
Fix described carbon nanotube agglomerate and be covered in flexible substrate surface, form described thorn-proof composite material.
19. preparation method according to claim 18, it is characterised in that：The CNT non-individual body is split by floating catalytic
Solution prepares to be formed.
20. the preparation method according to any one of claim 18-19, it is characterised in that also include：To flexible substrate and with
The carbon nanotube agglomerate that flexible substrate is combined carries out hot-pressing processing.
21. the preparation method according to any one of claim 18-20, it is characterised in that the condition bag of the hot-pressing processing
Include：Temperature is room temperature~140 DEG C, and pressure is 1~30MPa, and the time is more than 1min.
22. the preparation method according to any one of claim 18-21, it is characterised in that the hot-pressing processing includes：
First stage：Temperature is 110~120 DEG C, and pressure is 1~4MPa, and the time is 10~30min；
Second stage：Temperature is 120~140 DEG C, and pressure is 15~30MPa, and the time is 1~3min；
Or, temperature is room temperature, and pressure is 1~30MPa, and the time is 1~30min.
23. a kind of preparation method of thorn-proof composite material, it is characterised in that including：Make multiple CNT non-individual bodies in flexible base
Cloth surface continuously forms the base units of multiple orientations after aggregation and densified processing, the plurality of base unit it is densely arranged and
It is in membranaceous carbon nanotube agglomerate to be formed, so as to form described thorn-proof composite material；Wherein, described CNT is continuous
Body is formed by many CNTs unordered intertexture, and closing is presented before densification, it is semiclosed or open two-dimentional or
Three-D space structure.
24. preparation method according to claim 23, it is characterised in that：The CNT non-individual body is split by floating catalytic
Solution prepares to be formed.
25. the preparation method according to any one of claim 23-24, it is characterised in that also include：To flexible substrate and with
The carbon nanotube agglomerate that flexible substrate is combined carries out hot-pressing processing.
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