CN102086593A - Method for preparing carbon nano tube composite fibers with excellent performance - Google Patents
Method for preparing carbon nano tube composite fibers with excellent performance Download PDFInfo
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- CN102086593A CN102086593A CN2009102000096A CN200910200009A CN102086593A CN 102086593 A CN102086593 A CN 102086593A CN 2009102000096 A CN2009102000096 A CN 2009102000096A CN 200910200009 A CN200910200009 A CN 200910200009A CN 102086593 A CN102086593 A CN 102086593A
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Abstract
The invention belongs to the field of functional materials, and relates to a method for preparing carbon nano tube composite fibers with excellent mechanical performance, electrical performance and discoloration performance. In the method, carbon nano tubes are infiltrated by a diyne monomer, and are subjected to topological chemical polymerization; and by measuring tensile strength and conductivity and comparing with other polymer/carbon nano tube composite fibers and pure carbon nano tube fibers, a result shows that a poly-diyne network structure is formed among the carbon nano tubes which are arranged sequentially, so that the composite fibers have better mechanical and electrical performance. The tensile strength of the composite fibers is up to 1.1 GPa, and the conductivity is up to 350 S/cm at room temperature. The preparation method is simple, and the prepared composite fibers have the discoloration behavior, so the composite fibers have the huge potential in aspects of sensing, particularly nondestructive flaw detection.
Description
Technical field
The invention belongs to field of functional materials, relate to carbon nano tube composite fibre, be specifically related to a kind of preparation and have the method for excellent properties carbon nano tube composite fibre, relate in particular to the method that a kind of preparation has very good mechanical properties, electric property and discoloration carbon nano tube composite fibre.
Background technology
In recent years, CNT (CNTs) because of its particular structure and excellent machinery and electric property by extensive studies
1-3, maximum in the carbon nano tube compound material research is the composite of CNT and polymer-matrix
1Often be used to improve the mechanical strength and the electrical conductivity of nano composite material at the field of functional materials CNT, the typical preparation method of these nano composite materials adopts solwution method, is about to CNT and is coated with film forming or makes powder according to different requirements with mixed with polymers solution
4-6But practice shows, be that the CNT of making is as stated above assembled after solvent evaporates easily, and random dispersion causes the polymer/carbon nano-tube composite can not give full play to CNT favorable mechanical and electric property in polymeric matrix
3,7,8, this problem has limited its application in a lot of fields.For example the TENSILE STRENGTH of nylon/carbon nano tube compound material is lower than 93MPa
9, the electrical conductivity of polymethyl methacrylate/carbon nano tube compound material at room temperature has only 10
-6S/cm
10In order to address the above problem, having research to disclose CNT can be spun into macroscopical visible carbon nano-tube fibre by the upright row of high-sequential carbon nanotubes arranged
11-16, this carbon nano-tube fibre provides synthetic method highly significant for the composite that preparation improves mechanical strength and electrical conductivity.
Poly-diine (PDA) is owing to the sensing capabilities of its simple synthetic method and uniqueness is studied widely.The method of the poly-diine of typical preparation is by self assembly and photo polymerization subsequently, and the poly-diine that polymerization obtains is blue, can change redness into by environmental stimuli, and these stimuluss comprise temperature
17-20, the pH value
21-25, ion
26, solvent
27Perhaps part effect
28-30The reason of poly-diine variable color under environmental stimuli is that the conjugation chain length of poly-diine shortens
17
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Summary of the invention
The purpose of this invention is to provide the method that a kind of preparation has the excellent properties carbon nano tube composite fibre, relate in particular to the method that a kind of preparation has very good mechanical properties, electric property and discoloration carbon nano tube composite fibre (poly-diine/carbon nano tube composite fibre).
Poly-diine (PDA)/CNT (CNT) composite fibre that the present invention has synthesized, the diine monomer is soaked into CNT, carry out topochemical polymerization then, by measure TENSILE STRENGTH and electrical conductivity and with other polymer/carbon nano-tube composite fibre and pure carbon nano-tube fibre relatively, further relatively composite fibre is heated to TENSILE STRENGTH and electrical conductivity that different temperatures or oxolane are handled.The result shows, the poly-diine (PDA) that the present invention makes/CNT (CNT) composite fibre has excellent mechanical strength and electrical conductivity and discoloration, can be applicable on the sensor.
The present invention's preparation has the method for excellent properties carbon nano tube composite fibre, it is characterized in that, use the synthetic upright row of CNT of chemical gaseous phase depositing process with spinnability, spinning obtains carbon nano-tube fibre, then carbon nano-tube fibre is immersed in a period of time taking-up in the certain density diine monomer solution, solvent flashing under the room temperature, carbon nano-tube fibre soaks in the diine monomer solution, allow solvent evaporates under the room temperature, polymerization under ultra violet lamp aggregates into blue or orange composite fibre.The method comprising the steps of:
At first, preparation carbon nano-tube fibre;
(spinning synthetic and carbon nano-tube fibre of the upright row of CNT was before reported from the upright row of CNT
16) pull out the CNT band, connect to live the CNT band with the spindle that has the tip probe, the rotation that does not stop spins fiber;
Described spindle is connected with RAMPRO500SETB spinning instrument, Ram Products Inc;
CNT in the upright row of described CNT is a multi-walled carbon nano-tubes, and its diameter is 6-15nm, length 200-800 μ m.
Among the present invention, the process of spinning can clearly be observed at microscopically;
Secondly, the poly-diine/carbon nano tube composite fibre of preparation: pure carbon nano-tube fibre is immersed in diine monomer solution the inside, and topochemical polymerization makes under UV-irradiation then,
With diine monomer CH
3(CH
2)
11C ≡ C-C ≡ C (CH
2)
8COOH, HOOC (CH
2)
8C ≡ C-C ≡ C (CH
2)
8COOH and HOCH
2C ≡ C-C ≡ CCH
2OH is dissolved in oxolane respectively or other can dissolve in the solvent of diine monomer, be made into the solution that concentration is 1mg/ml～10mg/ml, pure carbon nano-tube fibre is dipped in respectively in the different monomer solutions, solvent flashing under the room temperature, and the diine monomer carried out the ultraviolet light that wavelength is 254nm (uviol lamp, power 4W, irradiation distance 17cm) irradiation polymerization, make three kinds of carbon nano tube composite fibres after the polymerization, comprise two kinds of bluenesss, a kind of orange carbon nano tube composite fibre;
Among the present invention, described carbon nano-tube fibre, diameter 4-22 μ m.
Among the present invention, the time that described carbon nano-tube fibre is immersed in the diine monomer solution is 5～30 minutes.
Among the present invention, irradiation time does not wait from 15 minutes by 4 hours according to the diameter difference of fiber,
Among the present invention, described ultraviolet light comprises ultraviolet ray, X ray and radiation gamma, and ultraviolet light source is apart from composite fibre 10～17cm.
Among the present invention, describedly aggregate into blue or orange composite fibre is monomer CH
3(CH
2)
11C ≡ C-C ≡ C (CH
2)
8COOH and HOOC (CH
2)
8C ≡ C-C ≡ C (CH
2)
8Present blueness after the COOH polymerization, HOCH
2C ≡ C-C ≡ CCH
2Be rendered as after the OH polymerization orange, be heated to uniform temperature after, contain monomer CH
3(CH
2)
11C ≡ C-C ≡ C (CH
2)
8COOH and HOOC (CH
2)
8C ≡ C-C ≡ C (CH
2)
8The composite fibre temperature of COOH blueness becomes redness when being 81 ℃, temperature range is 55-110 ℃, becomes yellow when surpassing 132 ℃, contains HOCH
2C ≡ C-C ≡ CCH
2The orange composite fibre of OH becomes brown.
In being dipped in oxolane, oxolane volatilization naturally in air under the room temperature, the composite fibre of above-mentioned blueness becomes redness, and orange composite fibre becomes brown.
The carbon nano-tube fibre that the present invention makes is spun into by the upright row of CNT.Shown in Fig. 1 scanning electronic microscope (SEM) figure, the fiber of described carbon nano-tube fibre is axially even along it, the width control of the CNT band when its diameter is mainly begun by spinning.
The present invention is further with CH
3(CH
2)
11C ≡ C-C ≡ C (CH
2)
8COOH monomer preparation have similar machinery and the electric property composite fibre is that example is set forth.
Diine monomer porous in prepared poly-diine/carbon nano tube composite fibre is to the inside of fiber, and laser confocal scanning microscope photo has as shown in Figure 2 shown that poly-diine disperses equably at fibrous inside;
When temperature is heated to greater than 55 ℃ and during less than 110 ℃, described poly-diine/carbon nano tube composite fibre promptly became redness (shown in Figure 3) by blueness in 1 minute, reach when being higher than 132 ℃, poly-diine/carbon nano tube composite fibre becomes yellow, and this is to be caused by the disordering of gathering the diine side chain
31In being exposed to chemical reagent, as oxolane, described composite fibre becomes redness by blueness.，
Compared with the prior art, the present invention has outstanding advantage:
1, described diine monomer can penetrate into less space or defective, obviously improves poly-diine/carbon nano tube composite fibre mechanical performance.The mechanical performance of pure nano-carbon tube fiber is owing to the existence of space and defective is significantly reduced, usually between 0.15-0.18GPa
14,32For space and this negative effect of defective with inside drop to minimum, prior art is with other component, for example polymer
9,33Join in the carbon nano-tube fibre, use mean molecule quantity to be about 350, the polymethyl methacrylate of 000g/mol can be brought up to 0.27GPa with TENSILE STRENGTH
34,, but because big polymer molecule is mainly filled out in big space or defective (polymer molecule enters the size that mainly depends on molecular weight in the hole) that little space or defective still exist
35So,, the amount that is improved still fails to satisfy actual requirement,
2, poly-diine/carbon nano tube composite fibre of making of the present invention soaks in the space and defective of carbon nano-tube fibre except poly-diine molecule, the poly-network structure of diine in CNT causes its mechanical strength obviously to improve (shown in Figure 4), the synthetic poly-diine/carbon nano tube composite fibre mechanical strength that makes of the present invention is 0.89GPa, and the intensity of pure nano-carbon tube fiber has only 0.17Gpa; The TENSILE STRENGTH of pure nano-carbon tube fiber is 0.15-0.35GPa, and the TENSILE STRENGTH of pure poly-diine crystal fibre is about 0.32GPa
34, well-known, single-root carbon nano-tube slightly up to 150GPa
36The fracture of carbon nano-tube fibre is most likely owing to the slip of adjacent carbons nanotube under strong stress effect, and among the present invention, poly-diine is crosslinked with CNT in polymerization process, stop it to slide, make the mechanical performance of poly-diine/carbon nano tube composite fibre improve.
In addition, when being heated to 81 ℃, the TENSILE STRENGTH of composite fibre reaches 0.99GPa; When being heated to 132 ℃, TENSILE STRENGTH only reaches 0.91GPa, and this is because after temperature is higher than 110 ℃, the disordering of poly-diine
37Among the present invention, realize the raising of TENSILE STRENGTH by solvent processing.Among the present invention, the TENSILE STRENGTH of poly-diine/carbon nano tube composite fibre of being handled by oxolane is brought up to 0.92Gpa by the 0.89GPa before handling, and can reach 1.1GPa.
Table 1 is the TENSILE STRENGTH of pure nano-carbon tube fiber and poly-diine/carbon nano tube composite fibre, wherein demonstrates other two groups of composite fibres and also has similar characteristic.
A wherein, b represents three groups of different samples with c.
3, compare with single-root carbon nano-tube, the electrical conductivity of carbon nano-tube fibre has reduced significantly, because the existence of a large amount of contact resistances between the adjacent carbons nanotube, the formation of polymer/carbon nano-tube composite fibre also further reduces.For example, polyvinyl alcohol is compounded on the carbon nano-tube fibre, the electrical conductivity of the composite fibre that obtains at room temperature has only 2S/cm, and the electrical conductivity of pure carbon nano-tube fibre is 300S/cm.Big polymer molecule is easy to assemble, especially in the space and defective of fibrous inside.Among the present invention, make poly-diine disperse (Fig. 2) equably in littler space and the defective because the diine monomer soaks into, what the polymerization of diine made combination between the CNT has more closely reduced contact resistance.Therefore, the polymer/carbon nano-tube composite fibre has higher electrical conductivity than the composite fibre that directly obtains with polymer.In fact, polymer/carbon nano-tube composite fibre high conductivity at room temperature can reach 350S/cm.It should be noted that pure poly-diine crystal is 10 in the electrical conductivity of room temperature
-6S/cm.The present invention improves the composite fibre electrical conductivity.
4, the resistance of poly-diine/carbon nano tube composite fibre of making of the present invention significantly increases (as shown in Figure 5, wherein poly-diine/carbon nano tube composite fibre and pure nano-carbon tube fibre diameter and length are respectively 6.6nm and 2.3mm).The resistance of pure nano-carbon tube fiber is calculated by Fig. 5 a, is 8.26K Ω.Among the present invention, form after the blue polymer/carbon nano-tube composite fibre, resistance reaches 9.62K Ω; When temperature reached 81 ℃, the resistance of composite fibre was increased to 10.16K Ω, and during 132 ℃ of higher temperature, resistance further is increased to 10.26K Ω; After oxolane was handled, resistance reached 9.94K Ω.Wherein reason is that the increase hot and resistance that solvent processing causes is owing to gather the disordering of diine in the composite fibre
37
Table 2 is electricity observed results of pure nano-carbon tube fiber and poly-diine/carbon nano tube composite fibre under the room temperature.
A wherein, b represents three groups of different samples with c.
The present invention carries out the synthetic of novel poly-diine/carbon nano tube composite fibre on the basis of prior art solution methods, especially provide one to have a method of good physical polymer/carbon nano-tube composite fibre by monomer is synthetic.The present invention makes the composite fibre that makes have better machinery and electric property forming poly-diine network structure in order between the carbon nanotubes arranged.Under the room temperature, the TENSILE STRENGTH of composite fibre is up to 1.1GPa, and electrical conductivity is up to 350S/cm.Preparation method of the present invention is simple, and the composite fibre that makes has the variable color behavior, makes this composite fibre have very big potentiality on especially nondestructive inspection context of detection of many sensings is used.
Description of drawings
Fig. 1 is ESEM (SEM) figure of carbon nano-tube fibre, and wherein, the CNT high-sequential of carbon nano-tube fibre inside is arranged.
Fig. 2 is the laser confocal scanning microscope figure of poly-diine/carbon nano tube composite fibre, wherein, under the irradiation of 488nm excitation wavelength, send red fluorescence after the polymerization, illustrate that the diine monomer infiltration has arrived the inside of fiber, the poly-diine that obtains disperses equably at fibrous inside, and does not just rest on the surface.
Fig. 3 is heated to 81 ℃ of poly-diines/carbon nano tube composite fibre change color figure, wherein, heat 81 ℃ after, blue poly-diine/carbon nano tube composite fibre becomes redness.
Fig. 4 is the mechanical performance figure of pure nano-carbon tube fiber and poly-diine/carbon nano tube composite fibre, wherein, and (a, f, k) pure nano-carbon tube fiber; (i) (c, h m) are heated to 81 ℃ to Lan Se poly-diine/carbon nano tube composite fibre, red poly-diine/carbon nano tube composite fibre for b, g; (d, i n) are heated to 132 ℃, yellow poly-diine/carbon nano tube composite fibre; (e, j, o) the poly-diine/carbon nano tube composite fibre of the redness handled of oxolane; Poly-diine/carbon nano tube composite fibre has improved mechanical performance to a great extent.
Fig. 5 is the current-voltage curve of pure nano-carbon tube fiber and poly-diine/carbon nano tube composite fibre, and wherein, three groups of different samples are denoted as (a), (b) and (c); (1) pure nano-carbon tube fiber, poly-diine/carbon nano tube composite fibre that (2) are blue, (3) are heated to 81 ℃, red poly-diine/carbon nano tube composite fibre, (4) are heated to 132 ℃, yellow poly-diine/carbon nano tube composite fibre.
Fig. 6 is the current-voltage curve of pure nano-carbon tube fiber and poly-diine/carbon nano tube composite fibre, and wherein, three groups of different samples are denoted as (a), (b) and (c); (1) pure nano-carbon tube fiber, poly-diine/carbon nano tube composite fibre that (2) are blue, the poly-diine/carbon nano tube composite fibre of the redness that (3) oxolane was handled.
The specific embodiment
Use the chemical gaseous phase depositing process synthesizing carbon nanotubes, and it is spun into fiber, the mechanical performance and the electrical conductivity of test fiber.With monomer CH3 (CH2) 11C ≡ C-C ≡ C (CH2) 8COOH is example.Monomer CH3 (CH2) 11C ≡ C-C ≡ C (CH2) 8COOH is dissolved in the oxolane, is made into the diine monomer solution of 10mg/ml.Be that the carbon nano-tube fibre of 9 μ m was immersed in the diine monomer solution 10 minutes then with diameter, solvent flashing at room temperature after the taking-up.Be placed on fume hood interior 24 hours, the uviol lamp that with wavelength is 254nm makes the diine monomer polymerization on the fiber apart from fiber 17cm irradiation 2 hours, obtains blue carbon nano-tube/poly diine composite fibre.The mechanical performance of test compound fiber and electrical conductivity.Composite fibre is heated to 81 ℃, and composite fibre becomes redness, test compound fibre machinery performance and electrical conductivity.Continuation becomes yellow when fiber is heated to 132 ℃, the mechanical performance and the electrical conductivity of test fiber.Composite fibre is immersed in the oxolane oxolane volatilization naturally in air under the room temperature.Blue composite fibre becomes red composite fibre, test mechanical performance and electrical conductivity.Concrete TENSILE STRENGTH and electric property are as shown in Table 1 and Table 2.
In the present embodiment, carbon nano-tube fibre is by scanning electronic microscope (SEM, JEOL 6300FXV operating voltage is that 5kV and Hitachi FE-SEM S-4800 operating voltage are 1kV) and transmission electron microscope (TEM, JEOL JEM-2100F andPhilips CM30 operating voltage is 200kV) sign.Carbon nano-tube fibre spray one layer thickness before by scanning electron microscope test is gold/platinum of 5nm, is directly to drop in CNT/ethanolic solution on the copper mesh in air when testing by transmission electron microscope; Experiments of Machanics are carried out above the universl tester on the table of Tianjin, island, and CNT is bonded on the paper with the 5mm full-length, and fibre diameter is by determining that by SEM the laser confocal scanning microscope model is Olympus FV300, and excitation wavelength is 488nm.
Claims (10)
1. one kind prepares the method with excellent properties carbon nano tube composite fibre, it is characterized in that, adopt the upright row of CNT of the synthetic spinnability of chemical gaseous phase depositing process, spinning obtains carbon nano-tube fibre, then carbon nano-tube fibre is immersed in a period of time taking-up in the certain density diine monomer solution, solvent flashing under the room temperature, polymerization under ultra violet lamp aggregates into the blue or orange excellent properties carbon nano tube composite fibre that has.
2. preparation according to claim 1 has the method for excellent properties carbon nano tube composite fibre, it is characterized in that, described excellent properties carbon nano tube composite fibre is the carbon nano tube composite fibre of very good mechanical properties, electric property and discoloration.
3. method according to claim 1 is characterized in that, described carbon nano-tube fibre is by following step: pull out the CNT band from the upright row of CNT earlier, connect to live the CNT band with the spindle that has the tip probe, the rotation that does not stop spins fiber.
4. method according to claim 1 is characterized in that, the CNT in the upright row of described CNT is a multi-walled carbon nano-tubes, and its diameter is 6-15nm, length 200-800 μ m.
5. method according to claim 1 is characterized in that, its diameter of described carbon nano-tube fibre is 4-22 μ m.
6. method according to claim 1 is characterized in that, described diine monomer solution is with diine monomer CH
3(CH
2)
11C ≡ C-C ≡ C (CH
2)
8COOH, HOOC (CH
2)
8C ≡ C-C ≡ C (CH
2)
8COOH and HOCH
2C ≡ C-C ≡ CCH
2OH is dissolved in oxolane respectively or other can dissolve in the solvent of diine monomer, the solution that is made into, and its concentration is 1mg/ml～10mg/ml.
7. method according to claim 1 is characterized in that, the time that described carbon nano-tube fibre is immersed in the diine monomer solution is 5～30 minutes.
8. method according to claim 1 is characterized in that, polymerization is polymerization under ultraviolet ray, X ray or radiation gamma under the described ultra violet lamp, and ultraviolet light source is apart from composite fibre 10～17cm, and the irradiation polymerization time is 15 minutes～4 hours.
9. method according to claim 1 is characterized in that describedly aggregating into blue or orange composite fibre is monomer CH
3(CH
2)
11C ≡ C-C ≡ C (CH
2)
8COOH and HOOC (CH
2)
8C ≡ C-C ≡ C (CH
2)
8Present blueness after the COOH polymerization, HOCH
2C ≡ C-C ≡ CCH
2Be rendered as after the OH polymerization orange, be heated to uniform temperature after, contain monomer CH
3(CH
2)
11C ≡ C-C ≡ C (CH
2)
8COOH and HOOC (CH
2)
8C ≡ C-C ≡ C (CH
2)
8The composite fibre temperature of COOH blueness becomes redness when being 81 ℃, become yellow when surpassing 132 ℃, contains HOCH
2C ≡ C-C ≡ CCH
2The orange composite fibre of OH becomes brown.
10. method according to claim 1, it is characterized in that describedly aggregating into blue or orange composite fibre is immersed in the oxolane, oxolane volatilization naturally in air under the room temperature, blue composite fibre becomes redness, and orange composite fibre becomes brown.
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