Method for making copolymer-wrapped nanotube fibers
11365493 · 2022-06-21
Assignee
Inventors
Cpc classification
D01F1/09
TEXTILES; PAPER
D02G3/441
TEXTILES; PAPER
International classification
D01F1/09
TEXTILES; PAPER
Abstract
A method for making a copolymer-wrapped nanotube coaxial fiber. The method includes supplying a first dope to a spinning nozzle; supplying a second dope to the spinning nozzle; spinning the first and second dopes as a coaxial fiber into a first wet bath; and placing the coaxial fiber into a second wet bath, which is different from the first bath. The coaxial fiber has a core including parts of the first dope and a sheath including parts of the second dope. Solvent molecules of the second wet bath penetrate the sheath and remove an acid from the core.
Claims
1. A method for making a copolymer-wrapped nanotube coaxial fiber, the method comprising: supplying a first dope to a spinning nozzle; supplying a second dope to the spinning nozzle; spinning the first and second dopes as a coaxial fiber into a first wet bath; and placing the coaxial fiber into a second wet bath, which is different from the first bath, wherein the coaxial fiber has a core including parts of the first dope and a sheath including parts of the second dope, and wherein molecules of the second wet bath penetrate the sheath and remove an acid from the core.
2. The method of claim 1, wherein the core is fluid before the second wetbath and becomes solid after the second wet bath.
3. The method of claim 1, wherein the first dope includes single-walled carbon nanotubes (SWCNTs).
4. The method of claim 3, wherein the first dope further includes a dispersing agent.
5. The method of claim 4, wherein the dispersing agent is CH.sub.3SO.sub.3H.
6. The method of claim 5, wherein the second bath is an acetone bath that extracts the CH.sub.3SO.sub.3H from the core.
7. The method of claim 3, wherein the first dope includes 2% SWCNT and CH.sub.3SO.sub.3H.
8. The method of claim 3, wherein the second dope includes a thermoplastic elastomer.
9. The method of claim 8, wherein the second dope further includes CH.sub.2Cl.sub.2.
10. The method of claim 9, wherein the first bath is an ethanol coagulation bath.
11. The method of claim 10, wherein the ethanol bath extracts the CH.sub.2Cl.sub.2 from the sheath.
12. The method of claim 1, wherein the core is electrically conductive and the sheath is an insulator.
13. The method of claim 1, further comprising: flattening the coaxial fiber.
14. A method for making a copolymer-wrapped nanotube coaxial fiber, the method comprising: spinning first and second dopes as a coaxial fiber into a first wet bath; placing the coaxial fiber into a second wet bath to extract an acid from a core of the coaxial fiber; and flattening the coaxial fiber.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate one or more embodiments and, together with the description, explain these embodiments. In the drawings:
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DETAILED DESCRIPTION
(13) The following description of the embodiments refers to the accompanying drawings. The same reference numbers in different drawings identify the same or similar elements. The following detailed description does not limit the invention. Instead, the scope of the invention is defined by the appended claims. The following embodiments are discussed, for simplicity, with regard to a thermoplastic elastomer (TPE)-wrapped single-walled carbon nanotube (SWCNT) microwires. However, the invention is not limited to TPE materials or carbon nanotubes. Other co-polymers that are stretchable and electrically insulators may be used instead of the TPE and other electrically conductive materials, like carbon-black, silicon, graphene, and metal nanoparticles may be used instead of carbon for the nanotubes. Those skilled in the art would understand, after reading this description, that other materials may also be used.
(14) Reference throughout the specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with an embodiment is included in at least one embodiment of the subject matter disclosed. Thus, the appearance of the phrases “in one embodiment” or “in an embodiment” in various places throughout the specification is not necessarily referring to the same embodiment. Further, the particular features, structures or characteristics may be combined in any suitable manner in one or more embodiments.
(15) One versatile approach for the industrial fabrication of continuous fibers that have been used in the past is wet-spinning. This approach provides a robust route for engineering high-performance conductive fibers. Previously, a silver nanoparticle/thermoplastic elastomer mixture was wet-spun to construct microfiber-based strain sensors, but it was challenging to maintain a continuous conductive path in the fibers and a homogeneous distribution of the metallic fillers. Conductive polymer/thermoplastic elastomer fibers were also prepared by wet-spinning for highly stretchable sensors, but it was difficult to maintain both stretchability and sensitivity, even with a high loading of the conductive polymer fillers. In previous work (see, for example, U.S. Patent Publication 2017/0370024-A1) of the authors of this disclosure, conductive poly(3,4-ethylene-dioxythiophene)/poly(styrene sulfonate) (PEDOT/PSS) polymer microfibers were fabricated via hot-drawing-assisted wet-spinning. Electrical conductivity of 2804 S cm-1 was obtained, which was accomplished by combining the vertical hot-drawing process with solvent doping and de-doping of the microfibers. Due to the brittle nature of PEDOT/PSS, the stretchability of the conductive fiber was limited to 20% and the GF was only 1.8 at 13% strain (Zhou et al., J. Mater. Chem. C. 2015, 3, 2528-2538). The wet-spinning process has also been successfully applied to make single-walled carbon nanotube (SWCNT) microwires for strain sensors with a high GF of 105 (see, for example, International Publication WO 2018/092091 A1), though the stretchability was limited to 15% (Zhou et al., Nanoscale 2017, 9, 604-612).
(16) Most of the aforementioned sensors show a large nonlinearity. Moreover, the conductive surface of the fibers is exposed in most of these sensors, so they have the risk of short-circuiting when used as strain sensors. The consequence is poor stability and durability.
(17) According to an embodiment, the coaxial wet-spinning approach is combined with a post-treatment process to prepare TPE-wrapped SWCNT fibers for use in high-performance strain sensors. The as-spun fibers containing SWCNT/acid dope in their core are post-treated in an acetone bath to remove acid residue, and the SWCNT core is then densified by pressing on the surface of the fibers, leading to a belt-like coaxial fiber. The fibers fragment with a high density of cracks when stretched above their crack-onset strain. The entangled networks of SWCNTs bridging the cracked fragments play a positive role during the strain sensing. As discussed next, these novel coaxial fibers are found to be suitable for high-performance strain sensors because of their capabilities as deformable and wearable electronics.
(18) According to an embodiment illustrated in
(19) The first dope 113 is supplied, for example, from a first storage container 118 that is in fluid communication with the inner channel 112 and the second dope 115 is supplied, for example, from a second storage container 120 that is in fluid communication with the outer channel 114.
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(21) The first SWCNT/CH.sub.3SO.sub.3H dope 113 from the inner channel 112 and the second TPE/CH.sub.2Cl.sub.2 solution 115 from the outer channel 114 are simultaneously introduced, after being spun, into an ethanol coagulation bath 130, which is hosted in a container 142. The ethanol bath 130 extracts the CH2Cl2 from the second TPE/CH2Cl2 dope, while the CH.sub.3SO.sub.3H still remains in the SWCNT core 124.
(22) As a result of this process, a single TPE-wrapped SWCNT coaxial fiber 123 (see both
(23) Then, a post-treatment process was applied as illustrated in
(24) After taking the fiber 123 out of the acetone bath 140, which is hold in a container 142, the acetone residue has evaporated, which resulted in an uneven surface. Therefore, the fiber 123 was pressed into a belt-like shape, as illustrated in
(25) To investigate the morphology of the SWCNTs 113 in the core 124, the TPE layer 122 was dissolved in CH.sub.2Cl.sub.2. The porous structure of the SWCNT core 124 with randomly distributed SWCNT networks has been observed in SEM images. Some SWCNTs joined together and formed larger bundles, which played a positive role in reducing the overall resistance of the fiber 143. Experiments with this fiber show that the coaxial fiber 143 acted as an insulator when measured on its surface, due to the protection of the insulating TPE sheath 122. After connecting a 2 cm long SWCNT core 124 with silver paste and copper wire, the fiber was measured to have a low resistance of 142.6Ω. The experiments confirmed that the conductive coaxial fiber made of a TPE-wrapped SWCNT core was achieved through the wet-spinning and post-treatment process. The successful production of these coaxial fibers should make them desirable for adoption in wearable electronics.
(26) A method for producing the above noted coaxial fiber is now discussed with regard to
(27) In a specific embodiment, the following materials are used to generate the fiber. The materials used for the first dope were: SWCNTs functionalized with 2.7% carboxyl groups were purchased from CheapTubes, Inc., with over 90 wt % purity and containing more than 5 wt % of MWCNT. The true density of these SWCNTs was 2.1 g cm.sup.−3. The materials used for the second dope were: polystyrene-block-polyisoprene-block-polystyrene (TPE) (styrene, 22 wt %), methanesulfonic acid (CH.sub.3SO.sub.3H), ethanol, and dichloromethane (CH.sub.2Cl.sub.2), which were purchased from Sigma Aldrich.
(28) Preparation of the SWCNT dope and TPE solution includes: a 2 wt % SWCNT dope was prepared by adding 0.2 g of SWCNTs into 9.8 g of CH.sub.3SO.sub.3H and stirring for 2 min, followed by sonication using a Brason 8510 bath sonicator (250 W) (Thomas Scientific) for 60 min. The mixture was further stirred for 24 h, then passed through a 30 μm syringe filter (Pall Corporation) to remove aggregates. A 30 wt % TPE solution was prepared by mixing 9 g of TPE with 21 g of CH.sub.2Cl.sub.2 solvent at 200 rpm for 10 h.
(29) Wet spinning of the coaxial fibers was performed as follows: the SWCNT dope was loaded into a 10 ml syringe and spun into an ethanol bath though an inner stainless steel needle (21 G). The flow rate of the ink was fixed at 150 μl/min by using a Fusion 200 syringe pump (Chemyx Inc.). The TPE solution in a 10 ml syringe was spun into the ethanol bath though an outer stainless steel needle (15 G). The flow rate of the ink was 200 μl/min. The fibers were continuously collected on a 50 mm winding spool, at a line speed of 2 to 4 m min.sup.−1. Then, the fibers were soaked in an acetone bath for 6 h to remove the acid residue. The resulting fibers were removed from the acetone and densified by pressing with glass slides as shown in
(30) The obtained fibers were characterized as follows: Scanning electron microscopy (SEM) was performed on the fibers using a Quanta 3D machine (FEI Company). The stretching and relaxing of the coaxial fibers were captured by a BX61 materials microscope (Olympus Corporation). The loading and unloading of the sample were controlled by a 5944 mechanical testing machine (Instron Corporation). Then, both ends of the 2 cm long fibers were dipped into colloidal silver ink, connected with copper wires and painted with conductive silver epoxy. The resistance change of the fibers was monitored by a 34461A digital multimeter. The incremental, cyclic stretching and relaxing program were applied to initiate the fragmentation of the SWCNT core inside the coaxial fiber. The program was set to an incremental strain of 50%, starting at 0% and continuing until 250%, at a speed of 5 mm min.sup.−1. Then, a cyclic stretching and relaxing program with maximum strains of 100% was applied at the same speed to the fibers for five cycles. The sensitivities of the strain sensors were defined as GF=(ΔR/R.sub.0)/ε, where R.sub.0 is the initial resistance, ΔR/R.sub.0 is the relative change in resistance, and c is the applied strain.
(31) For the electrical impedance spectroscopy (EIS), the moduli of impedance, Z, was measured with an Agilent E4980A Precision LCR meter in a two-probe configuration with Kelvin clips. The frequency range was from 20 Hz to 2 MHz with a 1000 Hz step and a sweeping current of 50 mA. To understand the sensing mechanism of the fiber-based sensors, it was investigated the change in impedance across a wide range of frequencies at different applied strains (0%, 5%, 15%, 20%, 40%, 60%, and 100%).
(32) The good linearity of the fiber 123 obtained with the method discussed above is believed to be a result of the following process.
(33) To determine the full properties of the fiber 123, various stresses were applied as now discussed with regard to
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(35) To use fiber 123 in a strain sensor, it needs to show high stretchability, high GF, and high sensitivity. The change in resistance of a coaxial fiber 123 with strains from 0% to 250% has been studied. The resistance increased with strain. After unloading from the 250% strain, the fragmented structure of the coaxial fiber with a high crack density of 17 mm.sup.−1 could be used as the sensing component in strain sensors. Repetitive cyclic testing has been performed on the fibers at lower strains (0% to 100% strain), which may be more representative of strains encountered in real applications (e.g., wearable electronics). After the first cyclic test (0% to 100% strain), the subsequent cycles overlapped with minimal signs of hysteresis.
(36) To determine the sensitivity of the fiber, the relative change in resistance (ΔR/R.sub.0) with the applied strain has been determined. The change in resistance of this coaxial fiber was ΔR/R.sub.0=340 at the 100% strain. The sensing performance of the fiber-based sensor featured two linear regions with two slopes (the applied strain from 0% to 5% with a linearity of 0.99, and the applied strain from 20% to 100% with a linearity of 0.98). These values reflect the GF at different strain ranges: the GF was 48 at 0% to 5% strain and 425 at 20% to 100% strain.
(37) However, conventional metal gauges have a GF of only around 2.0 at strains less than 5%. The GF was higher than conventional fiber-based strain sensors, as illustrated in
(38) To illustrate the sensing mechanism of the strain sensor made with coaxial fibers 123, a characterization of the electrical impedance response of the fibers was performed with a wide range of frequencies.
(39) Indeed, the capacitive response at high frequencies was ascribed to this electron tunneling mechanism. These results suggest that the sensing mechanism was similar to that of SWCNT paper embedded in PDMS, where the SWCNT paper between PDMS layers and the CNT interface on PDMS play different roles at different strain levels.
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(41) To demonstrate the performance of the coaxial fibers 123 as deformable sensors 802, eleven 4 cm long fibers 123 were attached to the back and front sides of a 70 cm long deformable, hollow cable 800 (see
(42) By manipulating the cable 800 into “S” (see
(43) The potential for the coaxial fibers 123 in wearable electronics for sensor/human interface interactions has been demonstrated as illustrated in
(44) The coaxial fibers discussed above can find a wide range of applications in deformable and wearable electronic devices. The examples discussed above can be extended to other electrically conductive materials, e.g., carbon nanomaterials, metal nanoparticles, and conductive polymers, offering another approach to the next generation of deformable and wearable devices.
(45) The disclosed embodiments provide methods and mechanisms for generating a fiber suitable for a strain sensor. It should be understood that this description is not intended to limit the invention. On the contrary, the embodiments are intended to cover alternatives, modifications and equivalents, which are included in the spirit and scope of the invention as defined by the appended claims. Further, in the detailed description of the embodiments, numerous specific details are set forth in order to provide a comprehensive understanding of the claimed invention. However, one skilled in the art would understand that various embodiments may be practiced without such specific details.
(46) Although the features and elements of the present embodiments are described in the embodiments in particular combinations, each feature or element can be used alone without the other features and elements of the embodiments or in various combinations with or without other features and elements disclosed herein.
(47) This written description uses examples of the subject matter disclosed to enable any person skilled in the art to practice the same, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the subject matter is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims.
REFERENCES
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