CN101525785A - Fibre and method for forming same - Google Patents
Fibre and method for forming same Download PDFInfo
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- CN101525785A CN101525785A CN200810081685A CN200810081685A CN101525785A CN 101525785 A CN101525785 A CN 101525785A CN 200810081685 A CN200810081685 A CN 200810081685A CN 200810081685 A CN200810081685 A CN 200810081685A CN 101525785 A CN101525785 A CN 101525785A
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Abstract
The invention discloses a fibre and a method for forming the same. The fibre comprises a polyester fibre and a plurality of nanometer carbon tubes dispersed in the polyester fibre, wherein the nanometer carbon tubes are mainly cis-arranged in the extending direction of the polyester fibre in sequence. The method guides the nanometer carbon tubes with flexural structures to the polyester fibre and can remarkably increase the thermal resistance of the polyester fibre. The addition of the nanometer carbon tubes can also control the strength, the wearing resistance and the elongation so as to meet the requirement on various applications.
Description
Technical field
The present invention relates to a kind of fiber, and relate in particular to the polyester fiber that contains CNT (carbon nano-tube).
Background technology
In the application of industrial fiber, polyester fiber is the important materials of using always.The application surface of polyester fiber is very wide, for example tire cord, transport tape, tarpaulin, sail cloth, camp or the like.These use used fiber need have high strength, flatness degree, and character such as abrasion performance.
In order further to promote the quality and the application surface of polyester fiber, need manage to increase the intensity and the abrasion performance characteristic of polyester fiber, and lower its degree of stretching.In addition, also need manage to promote the glass transition temperature and the crystallisation by cooling temperature of polyester fiber.The lifting of glass transition temperature helps to improve the heat endurance of polyester fiber, makes environment that its application product can be applicable to that temperature is higher and softening, increases range of application.The lifting of crystallisation by cooling temperature can impel polyester fiber just to begin crystallization in higher temperature in technology, can make crystallization rate accelerate also can obtain the more polyester fiber of crystalline phase, helps the intensity of fortifying fibre.
Except the application of above-mentioned flatness degree fiber, industry also has the demand than the heat resistance fiber of high ductility.
Therefore, industry is needed the polyester fiber and the method for making thereof of high thermal stability badly, and the intensity of polyester fiber, degree of stretching, and abrasion resistance also want can change easily to meet the demand of various different application.
Summary of the invention
Fiber that provides a kind of high thermal stability and forming method thereof is provided technical problem to be solved by this invention, and the intensity of fiber, degree of stretching, and abrasion resistance also want can change easily to meet the demand of various different application.
For achieving the above object, the invention provides a kind of fiber, comprise polyester fiber, and be scattered in a plurality of CNT (carbon nano-tube) in the polyester fiber, wherein on the whole CNT (carbon nano-tube) forward is arranged in the bearing of trend of polyester fiber.
And, for achieving the above object, the present invention provides a kind of method that forms fiber in addition, comprise the polyester grain is provided, a plurality of CNT (carbon nano-tube) are provided, CNT (carbon nano-tube) and polyester grain are carried out mixing, and carry out fusion for the CNT (carbon nano-tube) after mixing and polyester grain and reel off raw silk from cocoons and obtain polyester fiber, wherein on the whole CNT (carbon nano-tube) forward is arranged in the polyester fiber.
In sum, the present invention has CNT (carbon nano-tube) around bent structure in polyester fiber by importing, can increase the heat-resisting character of polyester fiber significantly.Also can control intensity, abrasion performance degree and the degree of stretching of polyester/nano carbon pipe fiber to meet various demands of applications by the interpolation of CNT (carbon nano-tube).
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Description of drawings
Fig. 1 is a kind of SEM photo of winding carved CNT (carbon nano-tube);
Fig. 2 a～Fig. 2 b is the SEM photo of PET/CNT fiber among the embodiment;
Fig. 3 is a kind of low around the SEM of bent CNT (carbon nano-tube) photo.
The specific embodiment
The present invention provides a kind of polyester fiber and method for making thereof at this.Mainly be that (carbonnanotube CNT) imports in the polyester fiber and increases the heat endurance of polyester fiber with CNT (carbon nano-tube).And intensity, ABRASION RESISTANCE and the degree of stretching that can regulate fiber by different CNT (carbon nano-tube) additions increase its range of application to meet various demands of applications.
Polyester fiber provided by the present invention is of wide application, and for example can be used for tire cord, transport tape, tarpaulin, sail cloth, camp or various textile fibers etc.Particularly high strength, high abrasion, flatness degree, and the application of high heat stability degree are arranged about need.In addition, part embodiment of the present invention also can obtain to have the fiber of high heat stability degree and high ductility.Can be for example as the elastomer under the higher temperature environment.
In order to improve every character of polyester fiber, the present invention imports CNT (carbon nano-tube) in the polyester fiber, utilizes mixing mode, and CNT (carbon nano-tube) is fully mixed with the polyester grain.Then gained polyester grain/CNT (carbon nano-tube) mixed ester grain is carried out fusion and disperse to reel off raw silk from cocoons, and obtain polyester/nano carbon pipe fiber.By kind and the addition of suitably selecting CNT (carbon nano-tube) for use, and cooperate proper technical conditions, on the whole CNT (carbon nano-tube) forward arranges along the bearing of trend of polyester fiber, can overcome CNT (carbon nano-tube) when reeling off raw silk from cocoons and assemble and produce the problem that fracture of wire can't moulding.Utilize the characteristic such as small size, high strength, high tenacity, high conductivity, high fineness ratio of CNT (carbon nano-tube), can increase the intensity of polyester fiber effectively, and its ABRASION RESISTANCE and heat endurance are significantly promoted.
Below, the formation method of the fiber of the embodiment of the invention is provided.At first provide in order to form the polyester grain of polyester fiber, the material of polyester grain can comprise polyethylene terephthalate (polyethyleneterephthalate, PET), polybutylene terephthalate (PBT) (polybutylene terephthalate, PBT), polytrimethylene terephthalate (polypropylene terephthalate, PPT), Aromatic polyester (Polyarylate, PAR), polyethylene terephthalate (Glycol modifiedpolyethylene terephthalate PETG) etc. or aforesaid combination.Then, can the polyester grain evenly be mixed with the CNT (carbon nano-tube) of trace by the various suitable method of prior art.For example can adopt twin-screw mixer machine, single screw mixing machine, single screw rod extruder, twin-screw extruder, ten thousand horsepowers of machines, continuous mixer or aforesaid combinations the polyester grain fully to be mixed and forms the mixed polyester grain of polyester/nano carbon pipe with CNT (carbon nano-tube).The addition of CNT (carbon nano-tube) can be about 0.05phr to about 1phr with respect to the polyester grain.The diameter of the CNT (carbon nano-tube) that is fit to can be about 10 nanometers to about 40 nanometers, and the length that is fit to can be about 1 micron to about 25 microns.The CNT (carbon nano-tube) that is fit to also can have various degree different around bent structure.
Then, the ester grain after mixing being carried out fusion reels off raw silk from cocoons and can obtain polyester/nano carbon pipe fiber.For example, ester grain after mixing can be put into the spinning reative cell (spinning chamber) of heating and by spinning head ejection or flow out, can for example have in the spinning head about 0.005 inch of several diameters to the hole of about 0.030 inch for fiber moulding by hole ejection or outflow.Can use forced air air-flow for example that the polyester/nano carbon pipe fiber of ejection melting attitude is quickly cooled to its glass below conversion temperature and harden into silk in the process of fiberizing.Formed polyester/nano carbon pipe fiber can utilize a winding drum to collect.The winding speed of winding drum can be for example about 1000 meters/minute to about 6000 meters/minute.Fusion reel off raw silk from cocoons the temperature that adopted can be for example between about 200 ℃ to about 300 ℃.The ester grain extracts in the process of silk through melting, may form along fiber along the tensile stress (for example the pulling force of air draught and friction are at the stress that process caused of fiber hardening by cooling) that stretch direction polyester fiber and inner CNT (carbon nano-tube) thereof, this tensile stress may be impelled CNT (carbon nano-tube) on the whole to stretch direction along the edge of fiber forward to arrange.
The heat resisting temperature (being glass transition temperature) of the polyester/nano carbon pipe fiber of the embodiment of the invention can be greater than about 86 ℃, and it is about 12% that intensity can promote, and degree of stretching is less than about 27.9%, and abrasion performance intensity can promote about 41%.In addition, the polyester/nano carbon pipe fiber of the embodiment of the invention can reel off raw silk from cocoons continuously and make its length can be greater than about more than 100 meters.For example, can per minute 800 meters speed reeled off raw silk from cocoons continuously 5 minutes and obtain the about 4000 meters polyester/nano carbon pipe fiber of length.Can optionally obtain the polyester/nano carbon pipe fiber of Len req with the different speed of reeling off raw silk from cocoons.
The size of the CNT (carbon nano-tube) that imports, kenel, and addition very big to the property effect of polyester/nano carbon pipe fiber.The present invention has CNT (carbon nano-tube) around bent structure in polyester fiber by importing, can increase the heat-resisting character of polyester fiber significantly.The less CNT (carbon nano-tube) of caliber can use the fiber of the CNT (carbon nano-tube) that caliber is bigger around Qu Chengdu is lower that higher heat stability be arranged around Qu Chengdu is big in the polyester/nano carbon pipe fiber employing of one embodiment of the invention.Addition by the control CNT (carbon nano-tube) can make CNT (carbon nano-tube) on the whole forward be arranged in the bearing of trend of polyester fiber, and the moulding of can reeling off raw silk from cocoons smoothly.Suitable CNT (carbon nano-tube) addition can make the polyester fiber strength enhancing and degree of stretching decline.The less polyester fiber of addition can have higher degree of stretching and good heat resistance.In addition, CNT (carbon nano-tube) also can optionally adjust around degree or its size (comprising caliber and length) of song.The CNT (carbon nano-tube) that is imported also not necessarily only limits to a kind of structure or form, for example can import two or morely to have different-diameter, different length, different CNT (carbon nano-tube) around curvature or different additions in fiber.Below, will enumerate embodiments of the invention and explain.
Embodiment 1
Get about 100 grams of PET ester grain and mix with the CNT (carbon nano-tube) of 0.15g, 0.3g, 0.5g, 1g, by twin-screw mixer with the full and uniform mixed polyester grain that mixes and form PET/CNT of CNT (carbon nano-tube) (CNT) and PET ester grain.Among this embodiment, the screw diameter of used twin-screw mixer machine is about 45 millimeters (mm), and its draw ratio (L/D) is about 30, and screw speed is about 200rpm.Adopt ten sections temperature to carry out twin-screw mixer altogether, be respectively 180 ℃, 210 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃, 260 ℃, 260 ℃, 260 ℃, reach 250 ℃.In this embodiment, the CNT (carbon nano-tube) that is adopted belongs to winding carved, and its SEM photo is shown among Fig. 1, and its diameter is about 20nm, and its length is about 1 micron to about 25 microns, and its structure is that essence is around song.The addition of CNT (carbon nano-tube) is respectively about 0phr to about 1phr with respect to PET ester grain.Then, to the PET/CNT ester grain after the twin-screw mixer carry out fusion reel off raw silk from cocoons (fusion reel off raw silk from cocoons temperature be about 270 ℃ to about 280 ℃) obtain the PET/CNT fiber.
Fig. 2 a shows the SEM photo of PET/CNT fiber, and Fig. 2 b shows the SEM photo of the PET/CNT fiber that enlargement ratio is higher.Shown in Fig. 2 a and Fig. 2 b, on the whole CNT (carbon nano-tube) forward is arranged in the bearing of trend of PET fiber, and still part is possessed it around bent structure.Via the addition and the control of process parameters of the size of suitably selecting CNT (carbon nano-tube) for use, control CNT (carbon nano-tube), on the whole gained PET/CNT fiber forward is arranged in the bearing of trend of fiber and is not easy fracture of wire, and the shaping of can reeling off raw silk from cocoons smoothly.For example reeled off raw silk from cocoons 5 minutes, and obtain length greater than about 4000 meters fiber with 800 meters/minute speed.Table one is listed every material character of the PET/CNT fiber that has different winding carved CNT (carbon nano-tube) additions among this embodiment, and the every character that lists file names with the PET fiber that does not contain CNT (carbon nano-tube) is for relatively.
Table one
| Winding carved CNT content | Tm (℃) | Tg (℃) | Tcc (℃) | Fineness (den) | Abrasion (%) | Intensity (g/d) | Degree of stretching (%) |
| PET(blank) | 250 | 70 | 186 | 612 | 0.161 | 1.74±0.4 | 67.2±31.9 |
| 0.15phr | 259 | 86 | 209 | 577 | - | 1.32±0.3 | 102.8±46.1 |
| 0.3phr | 258 | 85 | 207 | 583 | - | 1.53±0.08 | 100.2±3.6 |
| 0.5phr | 260 | 84 | 206 | 560 | 0.103 | 1.95±0.12 | 33.8±4.9 |
| 1phr | 258 | 83 | 211 | - | 0.096 | - | - |
Wherein, phr (part per hundred resin): the gram number that adds other additives in per 100 gram polyester; Den (red Buddhist nun's number): the weight kilogram number of per 9000 meters fibers.
As shown in Table 1, can find out that the importing of winding carved CNT (carbon nano-tube) can promote the heat endurance of PET fiber significantly.The glass transition temperature of PET/CNT fiber (Tg) can promote at least about more than 10 ℃ compared to PET (blank) fiber, can improve the heat resisting temperature (greater than about 70 ℃) of fiber, and enable application is in the environment of higher temperatures.Except glass transition temperature, the crystallisation by cooling temperature (Tcc) of PET/CNT fiber has also promoted about more than 20 ℃ compared to PET (blank) fiber.The lifting of crystallisation by cooling temperature can impel the fusion fiber that reels off raw silk from cocoons just to begin crystallization in higher chilling temperature, crystallization rate is accelerated and is obtained the more fiber of crystalline phase, helps to promote the intensity of fiber.The reason of PET/CNT fiber crystallisation by cooling temperature increase it be not immediately clear, do not get rid of is because the interpolation of winding carved CNT (carbon nano-tube) has formed many CNT/PET interfaces, PET is easy near interface and produces heterogeneous nucleation, crystallization is early taken place, thereby improved the crystallisation by cooling temperature.When the addition of winding carved CNT (carbon nano-tube) increases to 0.5phr, the intensity of PET/CNT fiber begins to reach about 1.95 ± 0.12g/d greater than 1.74 ± 0.4g/d of PET (blank) fiber, and its degree of stretching significantly is reduced to 33.8 ± 4.9% compared to 67.2 ± 31.9% of PET (blank) fiber.Wherein, the about 0.15phr of CNT content has preferable heat endurance to the fiber of about 0.3phr, but its intensity is lower and degree of stretching is higher, and its reason it be not immediately clear.The fiber that these are more heat-resisting and degree of stretching is higher still can have many other to use, and for example can be used as the elastomer under the higher temperature environment.Table one is also listed the abrasion performance assay of part PET/CNT fiber, it shows that each fiber is under identical abrasion condition, the percentage by weight that is worn away (before the abrasion of ratio), can find from table one, lifting along with the CNT (carbon nano-tube) addition, can effectively reduce the abrasion loss (reducing about more than 35%) of PET/CNT fiber, promote its abrasion performance degree.Wherein, CNT content be 0.5phr with the PET/CNT fiber of 0.1phr under identical abrasion condition, the PET (blank) of its abrasion loss ratio has reduced 35.627% and 40.277% respectively, more helps the application of PET/CNT fiber under higher abrasion environment.
Embodiment 2
Prepare PET/CNT fiber among the embodiment 2 in the mode that is same as embodiment 1, only the winding carved CNT (carbon nano-tube) among the embodiment is replaced with lower and that diameter is bigger is low around bent CNT (carbon nano-tube) around Qu Chengdu.Used hanging down is shown among Fig. 3 around the SEM of bent CNT (carbon nano-tube) photo among this embodiment, and its diameter is extremely about 90nm of about 30nm, and its length is about 1 micron to about 2 microns.Every character of the PET/CNT fiber of gained is listed in the table two.
Table two
| Low around bent CNT content | Tm(℃) | Tg(℃) | Tcc(℃) |
| PET(blank) | 250 | 70 | 186 |
| 0.3phr | 222 | 72 | 175 |
| 1phr | 246 | 78 | 195 |
Wherein, Den (red Buddhist nun's number): the weight kilogram number of per 9000 meters fibers.
As shown in Table 2, importing low heat endurance around the PET/CNT of bent CNT (carbon nano-tube) fiber also can obtain to promote.Along with hanging down when the addition of bent CNT (carbon nano-tube) increases to 1phr, its glass transition temperature (Tg) can increase to about 78 ℃, and its crystallisation by cooling temperature (Tcc) can increase to about 195 ℃.Comparison sheet one can find out that with table two adding the low amplitude that is promoted around the glass transition temperature or the crystallisation by cooling temperature of the PET/CNT of bent CNT (carbon nano-tube) fiber is significantly less than the PET/CNT fiber that adds winding carved CNT (carbon nano-tube).Its reason it be not immediately clear, do not get rid of be because among the embodiment 2 among the embodiment 1 of used CNT (carbon nano-tube) ratio used CNT (carbon nano-tube) have bigger diameter with more not around the structure of song, than major diameter with more not less with the area of the contact interface of PET fiber on every side around the CNT (carbon nano-tube) of song, therefore the nucleating point of heterogeneous nucleation is less between PET and CNT (carbon nano-tube), causes amplitude that the crystallisation by cooling temperature increases less and around the PET/CNT of song fiber less than the diameter that adopts CNT (carbon nano-tube).
By embodiment 1 and embodiment 2 as can be known the pattern of CNT (carbon nano-tube) (as around Qu Chengdu), size, and addition influence the character of polyester fiber very huge, can selecting for use and add every character of adjusting polyester fiber by CNT (carbon nano-tube).
In sum, the present invention has CNT (carbon nano-tube) around bent structure in polyester fiber by importing, can increase the heat-resisting character of polyester fiber significantly.Also can control intensity, abrasion performance degree and the degree of stretching of polyester/nano carbon pipe fiber to meet various demands of applications by the interpolation of CNT (carbon nano-tube).Wherein, add 0.5phr has 84 ℃ glass transition temperature (exceeding 14 ℃ than PET blank), 1.95 ± 0.12g/d around the PET/CNT of bent CNT (carbon nano-tube) fiber intensity (exceeding about 12%), and about degree of stretching of 33% (be about PET blank degree of stretching half) than PET blank.In addition, the abrasion performance degree of PET/CNT fiber also can improve along with the increase of CNT (carbon nano-tube) addition, helps the application of PET/CNT fiber under higher abrasion environment.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (22)
1. a fiber is characterized in that, comprising:
One polyester fiber; And
A plurality of CNT (carbon nano-tube) are scattered in this polyester fiber, and on the whole those CNT (carbon nano-tube) forward are arranged in the bearing of trend of this polyester fiber.
2. fiber according to claim 1, it is characterized in that the material of this polyester fiber comprises polyethylene terephthalate, polybutylene terephthalate (PBT), polytrimethylene terephthalate, Aromatic polyester, polyethylene terephthalate or aforesaid combination.
3. fiber according to claim 1 is characterized in that, about 10 nanometer to 40 nanometers of the diameter of those CNT (carbon nano-tube).
4. fiber according to claim 1 is characterized in that, the length of those CNT (carbon nano-tube) is 1 micron to 25 microns.
5. fiber according to claim 1 is characterized in that, those CNT (carbon nano-tube) that forward are arranged in this polyester fiber have one around bent structure.
6. fiber according to claim 1 is characterized in that, the content that per 100 grams of this polyester fiber have those CNT (carbon nano-tube) is that 0.05 gram is to 1 gram.
7. fiber according to claim 1 is characterized in that its heat resisting temperature is greater than 70 ℃.
8. fiber according to claim 1 is characterized in that its degree of stretching is less than 27.9%.
9. fiber according to claim 1 is characterized in that, it reduces more than 35% than the polyester fiber abrasion loss that does not comprise CNT (carbon nano-tube) under identical abrasion condition.
10. fiber according to claim 1 is characterized in that its intensity is greater than 2.07g/d.
11. fiber according to claim 1 is characterized in that, its length is greater than 100 meters.
12. a method that forms fiber is characterized in that, comprising:
One polyester grain is provided;
A plurality of CNT (carbon nano-tube) are provided;
This CNT (carbon nano-tube) and this polyester grain are carried out one mixing; And
This CNT (carbon nano-tube) for this after mixing and this polyester grain carry out a fusion and reel off raw silk from cocoons and obtain a polyester/nano carbon pipe fiber;
On the whole those CNT (carbon nano-tube) forward are arranged in this polyester/nano carbon pipe fiber.
13. the method for formation fiber according to claim 12, it is characterized in that the material of this polyester grain comprises polyethylene terephthalate, polybutylene terephthalate (PBT), polytrimethylene terephthalate, Aromatic polyester, polyethylene terephthalate or aforesaid combination.
14. the method for formation fiber according to claim 12 is characterized in that, the diameter of those CNT (carbon nano-tube) is 10 nanometer to 40 nanometers.
15. the method for formation fiber according to claim 12 is characterized in that, the length of those CNT (carbon nano-tube) is 1 micron to 25 microns.
16. the method for formation fiber according to claim 12 is characterized in that, those CNT (carbon nano-tube) that forward are arranged in this polyester/nano carbon pipe fiber have one around bent structure.
17. the method for formation fiber according to claim 12 is characterized in that, being provided as of this polyester grain and those CNT (carbon nano-tube) whenever provides 100 these polyester grains that restrain, and 0.05 gram those CNT (carbon nano-tube) to 1 gram just are provided.
18. the method for formation fiber according to claim 12 is characterized in that, the heat resisting temperature of this polyester/nano carbon pipe fiber is greater than 70 ℃.
19. the method for formation fiber according to claim 12 is characterized in that, the degree of stretching of this polyester/nano carbon pipe fiber is less than 27.9%.
20. the method for formation fiber according to claim 12 is characterized in that, this polyester/nano carbon pipe fiber reduces more than 35% than the polyester fiber abrasion loss that does not comprise CNT (carbon nano-tube) under identical abrasion condition.
21. the method for formation fiber according to claim 12 is characterized in that, the intensity of this polyester/nano carbon pipe fiber is greater than 2.07g/d.
22. the method for formation fiber according to claim 12 is characterized in that, the length of this polyester/nano carbon pipe fiber is greater than 100 meters.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100816851A CN101525785B (en) | 2008-03-05 | 2008-03-05 | Fibre and method for forming same |
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| CN2008100816851A CN101525785B (en) | 2008-03-05 | 2008-03-05 | Fibre and method for forming same |
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| CN101525785A true CN101525785A (en) | 2009-09-09 |
| CN101525785B CN101525785B (en) | 2012-05-23 |
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| CN2008100816851A Active CN101525785B (en) | 2008-03-05 | 2008-03-05 | Fibre and method for forming same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104264270A (en) * | 2014-10-13 | 2015-01-07 | 张家港市安顺科技发展有限公司 | Carbon nano tube regenerated polyester staple fiber production method |
| CN108950864A (en) * | 2018-07-27 | 2018-12-07 | 望江汇通纺织有限公司 | A kind of medical sheath core fiber non-woven fabrics of hydrophilic and oleophilic |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1869291B (en) * | 2005-05-23 | 2010-09-08 | 中国科学院化学研究所 | Fibre structure of polyester/carbone nanotube nano composite and its preparation method |
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2008
- 2008-03-05 CN CN2008100816851A patent/CN101525785B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104264270A (en) * | 2014-10-13 | 2015-01-07 | 张家港市安顺科技发展有限公司 | Carbon nano tube regenerated polyester staple fiber production method |
| CN108950864A (en) * | 2018-07-27 | 2018-12-07 | 望江汇通纺织有限公司 | A kind of medical sheath core fiber non-woven fabrics of hydrophilic and oleophilic |
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| CN101525785B (en) | 2012-05-23 |
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