CONDUCTIVE ELASTOMERIC FILAMENTS AND METHOD OF MAKING SAME
20240167201 ยท 2024-05-23
Inventors
- Ladan ESKANDARIAN (Toronto, CA)
- Milad ALIZADEH-MEGHRAZI (Toronto, CA)
- Amin MAHNAM (Toronto, CA)
- Tony CHAHINE (Toronto, CA)
- Sahar Golmohammadi ROSTAMI (Toronto, CA)
- Amirali TOOSSI (Toronto, CA)
Cpc classification
D02G3/32
TEXTILES; PAPER
D10B2331/30
TEXTILES; PAPER
D02G3/02
TEXTILES; PAPER
D03D15/283
TEXTILES; PAPER
D02G3/441
TEXTILES; PAPER
D01F6/56
TEXTILES; PAPER
D01F6/42
TEXTILES; PAPER
D01F1/09
TEXTILES; PAPER
A61B2562/125
HUMAN NECESSITIES
International classification
D02G3/44
TEXTILES; PAPER
D02G3/32
TEXTILES; PAPER
D02G3/02
TEXTILES; PAPER
D01F1/09
TEXTILES; PAPER
D01F6/42
TEXTILES; PAPER
D03D15/283
TEXTILES; PAPER
Abstract
A biocompatible yarn comprising a conductive elastomeric filament, the conductive elastomeric filament comprising a elastomeric polymer and conductive filler.
Claims
1. A biocompatible yarn comprising: a conductive elastomeric filament, the conductive elastomeric filament comprising a elastomeric polymer and conductive filler.
2. The biocompatible yarn of claim 1, wherein the conductive elastomeric filament has a ?R/R.sub.0 of less than 2.3 for 100% strain, where ?R is change in resistivity (Ohm.Math.m), and R.sub.0 is resistivity at 0% strain.
3. The biocompatible yarn of claim 1, wherein the conductive elastomeric filament has a Young's modulus in the range of 1-13 MPa.
4. The biocompatible yarn of claim 1, comprising 39%-70% carbon and 30-61% elastomer, wherein the elastomer comprises silicone.
5. (canceled)
6. The biocompatible yarn of claim 1 comprising at least one of carbon polyolefin (CPO); carbon styrene butadiene copolymer (CSBC); Carbon Silicone rubber (CSR1); and carbon silicone rubber (CSR2).
7. (canceled)
8. (canceled)
9. A conductive elastomeric filament comprising a elastomeric polymer and conductive filler.
10. The conductive elastomeric filament of claim 9, wherein the conductive elastomeric filament has a ?R/R.sub.0 of less than 2.3 for 100% strain, where ?R is change in resistivity (Ohm.Math.m), and R.sub.0 is resistivity at 0% strain.
11. The conductive elastomeric filament of claim 9, wherein the conductive elastomeric filament has a Young's modulus in the range of 1-13 MPa.
12. The conductive elastomeric filament of claim 9 comprising 39%-70% carbon and 30-61% elastomer, wherein the elastomer comprises silicone.
13. (canceled)
14. The conductive elastomeric filament of claim 9 comprising at least one of carbon polyolefin (CPO); carbon styrene butadiene copolymer (CSBC); Carbon Silicone rubber (CSR1); and carbon silicone rubber (CSR2).
15. The conductive elastomeric filament of claim 9, wherein the filament has a generally uniform diameter along a length of the filament.
16. A wearable dry textile comprising the biocompatible yarn of claim 1.
17. An electrode comprising the biocompatible yarn of claim 1, the electrode configured for at least one of Electrocardiogram (ECG) measurement, electromyograms (EMG) measurement, electroencephalograms (EEG) measurement, Electrooculogram (EOG) measurement, Electrogastrogram (EGG) measurement, Functional Electrical Stimulation (FES), Transcranial Current Stimulation (TCS), High-Frequency Alternating Current Stimulation, Neuromuscular Electrical Stimulation (NMES), Transcutaneous Electrical Nerve Stimulation (TENS), Sensing pressure, Sensing strain, Heat generation, and/or creating a tactile sensation.
18. The electrode of claim 17 wherein the conductive elastomeric filament is knitted and/or woven into the yarn, and wherein the electrode is made from the yarn.
19. A method of manufacturing a conductive elastomeric filament for an electrode, the method comprising: providing elastomeric polymer pellets having desired material properties; combining the elastomeric polymer pellets and conductive filler together to form a conductive elastomer; extruding and drawing the conductive elastomer into a filament.
20. The method of claim 19, comprising forming an electrode from the filament, the electrode configured for at least one of Electrocardiogram (ECG) measurement, electromyograms (EMG) measurement, electroencephalograms (EEG) measurement, Electrooculogram (EOG) measurement, Electrogastrogram (EGG) measurement, Functional Electrical Stimulation (FES), Transcranial Current Stimulation (TCS), High-Frequency Alternating Current Stimulation, Neuromuscular Electrical Stimulation (NMES), Transcutaneous Electrical Nerve Stimulation (TENS), Sensing pressure, Sensing strain, Heat generation, and/or creating a tactile sensation, wherein the elastomeric polymer and conductive filler comprise biocompatible material for forming a biocompatible yarn and/or filament.
21. (canceled)
22. The method of claim 19, wherein the elastomeric polymer is at least one of polyolefin, styrene butadiene copolymer, and silicone rubber; and wherein the conductive filler is carbon black.
23. The method of claim 19, wherein extruding and drawing the conductive elastomer into the filament comprises melt spinning the filament.
24. (canceled)
25. (canceled)
26. The method of claim 19, comprising extruding and drawing the filament into a solvent bath, wherein the solvent bath comprises water.
27. (canceled)
28. (canceled)
29. (canceled)
30. The method of claim 19, comprising knitting and/or weaving the filament into a yarn.
Description
DESCRIPTION OF THE DRAWINGS
[0034] Reference is now made to the accompanying drawings, in which:
[0035]
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[0037]
[0038]
[0039]
[0040]
[0041]
[0042]
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DETAILED DESCRIPTION
[0050] The following description relates to elastomeric materials for creating conductive elastomeric filament (CEF) fibers which may form textile-based electrodes suitable for e.g. sensing bioiopotential signals including Electromyogram (EMG), Electroencephalogram (EEG), Electrocardiogram (ECG), Electrooculogram (EOG), and Electrogastrogram (EGG), as well as applying current/voltage to body for Functional Electrical Stimulation (FES), Transcranial Current Stimulation (TCS), Neuromuscular Electrical Stimulation (NMES), Transcutaneous Electrical Nerve Stimulation (TENS), Sensing pressure, Sensing strain, Heat generation, High-Frequency Alternating Current Stimulation, and/or creating a tactile sensation. In some embodiments, the elastomer materials may comprise conductive thermoplastic elastomer materials. Example conductive elastomer materials according this disclosure may include at least one of Carbon Polyolefin (CPO); Carbon Styrene Butadiene copolymer (CSBC); Carbon Silicone rubber (CSR1); and Carbon Silicone rubber (CSR2). The composition of these material is shown below in Tables 1 and 2. Conductive elastomer materials according to this disclosure are not limited by thermoplastic elastomers of CPO, CSBC, CSR1 and CSR2; rather, any types of conductive elastomeric polymer may form a CEF according to this disclosure. In an embodiment, a dry-textile electrodes (e.g an Electrocardiogram (ECG) electrode) comprises conductive fibers of conductive elastomeric polymer(s), e.g. at least one of CPO; CSBC; CSR1; and CSR2. The description also describes method(s) of manufacturing the conductive elastomer materials, and CEF fiber, electrode(s), and textiles comprising the conductive elastomer materials disclosed herein. Example textile-based electrodes and method of manufacturing same are described International Application No. PCT/CA2020/051809 the entire disclosure of which is hereby incorporated by reference herein.
[0051] Although terms such as maximize, minimize and optimize may be used in the present disclosure, it should be understood that such term may be used to refer to improvements, tuning and refinements which may not be strictly limited to maximal, minimal or optimal.
[0052] The term connected or coupled to may include both direct coupling (in which two elements that are coupled to each other contact each other) and indirect coupling (in which at least one additional element is located between the two elements).
[0053] The term substantially as used herein may be applied to modify any quantitative representation which could permissibly vary without resulting in a change in the basic function to which it is related.
[0054] In modern society, health policies and patients' needs are continuously changing and individuals are becoming more and more conscious to the state of their health and wellbeing. Increases in the aging populations, the need for healthcare cost containment, and the need for improved methods of monitoring the quality of healthcare services' are some of the challenges modern societies currently face..sup.[1,2] The popularity of wearable devices has generated a great deal of clinical potential for continuous health monitoring of electrophysiological biomarkers..sup.[3,4] Electrophysiological signals targeted for wearable sensing, are electrical signals resulting from the electrochemical activity of the body's neural and muscular systems..sup.[5] Examples of such signals include electrocardiograms (ECG) from the heart muscle activity, electroencephalograms (EEG) from the brain activity, and electromyograms (EMG) from various muscles' activity..sup.[6-8] These biopotential signals may contain physiological data that can be used to diagnose, monitor, treat or manage various diseases..sup.[9] At present, devices capable of long-term measurement are not widely used as they can be expensive, bulky, conspicuous, and uncomfortable for users..sub.[10]
[0055] A necessary component of devices aiming to perform long-term electrophysiological monitoring are the sensors interfacing with the body, further referred to as biopotential electrodes. The existing gold-standard biopotential electrodes have a wet interface with the skin, employing an electrolytic gel as a conduit to transfer charge from the skin to the electrode..sup.[10] An example skin-electrode interface for a wet electrode is shown in
[0056] Flexible conductive polymer dry contact electrodes have the potential to meet these requirements and overcome the disadvantages of wet gel electrodes and dry metallic electrodes (e.g. noncontact dry electrodes, micro/nano needle-based electrodes, rigid metal electrodes)..sup.[31-35] The ability to seamlessly integrate electrodes in textiles may be extremely attractive and also promising for user adoption as part of the daily clothing industry as textiles. Smart garments are considered as the second closest surrounding in contact with the body after human skin. Smart garments create a bi-directional, and continuous medium between our bodies and the world around us, and offer many possibilities for monitoring diverse range of physiological parameters..sup.[36] Additionally, smart textiles are suitable for manufacturing, as they can be produced in a single-step by combining conductive and nonconductive materials via processes such as knitting..sup.[19,37]
[0057] Conductive fibers may be one of the smallest and one of the essential building blocks of wearable and flexible textile-electrodes. The limited availability of conductive elastomeric fibers that can be produced at a sufficiently large scale (>100 m) while meeting the mechanical properties and fiber size (diameter <1 mm) requirements has restricted their integration into smart textiles for practical electrophysiological sensing applications. Conductive fibers can be manufactured through various techniques such as fiber spinning, coating on fibers, and wrapping, twisting, and coiling other conductive materials such as stainless steel yarns or metallic wires with non-conductive fibers..sup.[38-40] Even though coating is a scalable and easy, problems may occur in the manufacturing process of conductive fibers, the poor adhesion and mechanical properties, mismatch between the fiber substrate, and the coating layer often result in the degradation of the sensing response, especially after knitting or numerous abrasive cycles such as daily wash and wear of consumer products..sup.[41] Conductive stretchable yarns produced using the wrapping, twisting, and coiling, are typically fabricated at small (centimeter) scale, which will not be sufficient for integration into textiles. Spinning conducting and elastomeric fibers may prevent the delamination of conducting fillers by integrating them within elastomeric polymers, such as silicone rubber, polyolefin, and polyurethane (PU)..sup.[42-44] This approach is also scalable and has shown potential in producing conductive elastomeric filament (CEF) fibers at a length beyond a kilometer. However, imparting electrical properties while maintaining the stretchability in elastomeric polymer fibers has been a great challenge. This is because introducing conductive fillers often results in deterioration of spinnability (ability to form fibers) or can lead to fibers with low stretchability, which are not suitable for biosignal monitoring applications in a form of dry-textile electrodes since they don't have the necessary a sufficient mechanical properties to be knitted/woven into an electrode..sup.[45-47]
[0058] Conductive fibers may be used to form clothing that can sense bio potential signals or impart electrical stimulation to a person's body. Material development studies for conductive fibers have been undertaken to improve conductive fiber material compatibility with textiles and/or wearable electrodes. Durability, flexibility, breathability, being electrically conductive to allow for sensing of a body's electrophysiological activity, and the ability to impart electrical energy are among the characteristics of the conductive fibers studied according to this disclosure.
[0059] In an embodiment, this disclosure employs melt-spun conductive elastomeric filament (CEF) fibers as building blocks of dry-textile electrodes produced on industrial-scale 3D knitting machines. The properties of the conductive CEF fibers, including the electrical and mechanical properties, and the micro morphologies were investigated. The parameters of the preform, including the materials, the size and the shape of the fiber and their effect on knittability of dry-textile electrodes and electrodes' performance were systematically studied. In order to assess the performance of the dry textile electrodes in more realistic circumstances, underwear garments with embedded dry-textile electrodes were designed and knitted that can readily monitor ECG signals of a wearer in seated, standing and supine positions. To examine the durability of knitted dry electrodes, the effect of consumer wash and dry cycles on the performance of knitted dry textile electrodes was assessed by recording ECG signals using a 30 times washed garment with embedded electrodes. This work shows that a unique combination of electrical conductivity and stretchability of conductive elastomeric fibers enables them to be integrated into textiles for practical applications such as electrophysiological monitoring.
[0060] Aspects of various embodiments are described through reference to the drawings and examples.
Examples
[0061] Four different types of conductive elastomeric filament (CEF) fibers were developed using elastomeric polymer matrix and conductive carbon black filler through melt spinning technique (See Table 1). The four example types of CEF fibers used in this study were sourced from Myant Inc., Ontario, Canada. Table 1 shows a list of fiber materials and their specifications. Diameter of each fiber was measured by ImageJ software using cross-sectional SEM images.
TABLE-US-00001 TABLE 1 Fiber Materials and specifications Fiber Code.sup.a) Polymer matrix Diameter [?m] CPO Polyolefin (PO) 765 CSBC Styrene Butadiene copolymer (SBC) 596 CSR1 Silicone rubber (SR) 592 CSR2 Silicone rubber (SR) 462 .sup.a)C as the first letter of each fiber code represents the conductive carbon filler
[0062] Among various types of thermoplastic elastomeric materials, polyolefin (PO) and styrene butadiene copolymer (SBC) thermoplastic elastomers (TPEs) were chosen as polymer matrices in this example due to their high strain ability at room temperature and thermoplastic behavior at elevated temperatures..sup.[48] This feature may make these materials very unique since they can be reprocessed and recycled easily. Phase separated systems with soft and rigid segments are the main components of TPEs. While the hard phase is responsible for the strength of the polymer, the soft phase allows elastomeric behavior at room temperature. Polyolefin blends TPEs (TPos) are primarily based on ethylene-propylene random copolymer (EPM) and isotactic polypropylene (iPP)..sup.[49] TPOs are true thermoplastic elastomers, since neither of their hard and soft phases are cross-linked and both can flow. TPOs may be significant commercially due to their low cost, resilience to oil, solvents, and elevated temperatures, and high flexibility at low temperatures. SBC co-polymers are based on styrene and butadiene phases..sup.[49] While the styrene microphases are hard thermoplastic phases, the butadiene is the soft elastomeric phase.
[0063] Another group of polymers used in this disclosure is silicone rubber (SR) which is an elastomer material with a wide range of temperature resistance (?70? C. to 300? C.), good weatherability and moisture resistance, excellent oil and chemical resistance at high temperature and good mechanical properties..sup.[48,49] This material may be a very biocompatible elastomer, as it is commonly used in medical application and this feature makes it a strong candidate for textile-based biopotential electrodes.
[0064] Among different types of conductive fillers (CNTs, Graphene, Ag nanoparticles, etc), the carbon-based allotropes are usually preferred due to their low cost, low density, and superior chemical interaction with the base polymer materials. Application of safe and non-toxic materials in development of biopotential electrodes with direct skin contact is critical. Carbon Black (CB) particles are not cytotoxic and they are not soluble in either water, organic solvents, or biological fluids; therefore, CB would not be expected to be absorbed through the skin (US EPA 2005)..sup.[50-52] Therefore, in these examples, carbon black (CB) fillers were chosen as conductive fillers in CEF fibers.
[0065]
[0066] In terms of chemical compositions of four CEF fibers, XPS survey scans (See
TABLE-US-00002 TABLE 2 XPS Relative Elemental Atomic Concentrations for CEF fibers. Yarn % C % O % Si CPO 65 23 12 CSBC 70 18 12 CSR1 39 37 24 CSR2 51 24 25
[0067] Higher silicone rubber content in CSR1 and CSR2 may explain why crystallization temperature (T.sub.C) and melting temperature (T.sub.m) were not observed in a narrow Differential scanning calorimetry (DSC) temperature range (?50? C. to 300? C.) (See Table 3 and
TABLE-US-00003 TABLE 3 Thermal Analysis of CEF fibers. TGA DSC Yarn Residue wt % T(onset) [? C.] T(max) [? C.] T.sub.m[? C.] ?H.sub.m [J/g] T.sub.c[? C.] ?H.sub.c (J/g) CPO 16 268 488 154 1.934 91 2.499 CSBC 38 225 483 150 3.324 104 4.832 CSR1 54 427 557 .sup.a) CSR2 54 393 543 .sup.a)T.sub.m and T.sub.c were not detected within the available temperature range of the DSC equipment(Q2000, TA Instruments; ?50? C. to 300? C.).
[0068] Silicone rubbers (with or without carbon fillers) usually have Tc below ?50? C.; at the same time, T.sub.m largely varies and sometimes could not be observed if co-components are well distributed, and no individual domain exists..sup.[53,54] High-resolution scans on C 1s and Si 2p (See
[0069] The resistances of CEF fibers mainly depended on the weight percentage of conductive carbon fillers inside the polymer blends, where a higher filler content resulted in a lower resistance. Carbon allotrope filler particles start to degrade at temperatures over 600? C., while elastomer materials including PO, SBC, and SR degrade at temperatures below 500? C..sup.[48,58] Therefore, performing TGA on CEF fibers up to 1000? C. will eliminate almost all the base polymer and leave a residual mass corresponding to the filler content in the samples. The residual weight percentage are presented in plotted TGA curves (
[0070] Previous literature studies reported that inferior mechanical properties of conductive elastomeric composites is due to weak interfacial interactions between the conductive fillers and the polymer matrix..sup.[59,60] In order to successfully develop knitted electrode for electrophysiological applications, the mechanical properties of CEF fibers should also be paid attention. DMA results (
TABLE-US-00004 TABLE 4 Tensile Properties of CEF fibers Max Tensile Young's Yarn Strain[%] Strength[MPa] Modulus[MPa] CPO 419.42 ? 70.84 4.69 ? 0.36 3.38 ? 0.43 CSBC 523.36 ? 10.04 5.97 ? 0.39 9.63 ? 1.91 CSR1 207.08 ? 44.59 6.38 ? 0.31 11.95 ? 0.80 CSR2 494.78 ? 27.34 11.67 ? 3.28 4.96 ? 1.19 Each yarn had five segments measured
[0071] Apart from the interfacial interactions between the conductive fillers and the polymer matrix, the filler content influences both the electrical and mechanical performance of CEF fibers significantly. Therefore, the electromechanical properties of CEF fibers were characterized by elongating the CEF fiber upon 100% strain at ?100 mm/min (
[0072]
[0073] Morphological investigation of the CEF fibers and knitted dry textile electrodes using scanning electron microscopy (SEM) revealed the structure of fibers before and after knitting process. As shown in
[0074] To assess the electrical properties of various CEF fibers described in Table 4, swatch electrodes were knitted as shown in
[0075]
[0076] Electrocardiography was chosen for on-body testing of electrodes due to its wide use in electrophysiological monitoring applications. ECG electrodes were placed over the wrists and forearms as shown in
[0077]
TABLE-US-00005 TABLE 5 R-squared values for correlation calculations of Gel vs. CSBC, CPO, and CSR2 electrodes. Gel vs. Gel vs. Gel vs. Correlation CSBC CPO CSR2 Pearson r r 0.8955 0.8962 0.8532 95% 0.8746 to 0.9132 0.8754 to 0.9138 0.8245 to 0.8775 confidence interval R squared 0.8020 0.8032 0.7279 P value P (two-tailed) <0.0001 <0.0001 <0.0001 P value **** **** **** summary Significant? Yes Yes Yes (alpha = 0.05) Number of 411 411 411 XY Pairs
[0078] Collectively, the result shown in Table 5 suggest that dry textile electrodes described in this disclosure allow for high-fidelity ECG recordings comparable (i.e. CSR2 and CPO) or superior (i.e. in the case of CSBC) to that of gel electrodes. ECG recordings performed with textile electrodes also have a similar frequency distribution as that of the gel electrodes.
[0079]
[0080]
[0081] Before and after completing the 30 wash cycles, ECG recordings were performed consistent with the methods described in this disclosure with the subject seated. Results are shown in
[0082] CEF fibers and dry textile electrodes for ECG monitoring may be manufactured according to this disclosure. In an example, 3D shape textile electrodes may be knitted on a 7.2 gauge flat bed knitting machine (CMS ADF 32W E7.2). Textile electrodes may be programed and simulated using Stoll's M1PLUS? software. Surrounding fabric of the textile electrode may be polyester/spandex yarns (OMTEX/Invista). A underwear band, e.g. the underwear illustrated in
[0083] Electrical resistance and elongation measurement according to this disclosure were conducted as disclosed below. The resistance measurements were taken with a dual measurement multimeter (GW Instek GDM-8351 Dual Measurement Multimeter). The sampling rate of the multimeter was set to 0.1 seconds. A universal tensile tester was used to stretch a 7 cm segment of the CEF fiber of interest at a constant speed of 100 mm/min. The reliability of this resistance measurement protocol was evaluated by measuring the resistance of 5 samples of each CEF fiber.
[0084] Given that each CEF fiber had different diameters, resistivities were used instead of the resistances in the analysis and plotting (e.g.
[0085] Where ? stands for resistivity (Ohm.Math.m), R stands for resistance (Ohm), A stands for the cross-section area of the CEF fiber (m2), and I stands for the length of the CEF fiber (m).
[0086] Characterization of conductive elastomeric fibers and knitted electrodes according to this disclosure was conducted as discussed below. A scanning electron microscopy (JEOL, JSM 1000) was used to evaluate the morphological characteristics of the conductive elastomeric fibers and knitted electrodes. The filaments were gold sputtered for 1 min (thickness: 5-10 nm) before imaging; the textile electrodes were imaged without sputtering. Surface chemistry of conductive elastomeric fibers was analyzed by X-ray photoelectron spectroscopy (XPS) performed on a K-Alpha XPS apparatus (Thermo-Scientific) on an aluminum substrate with copper pin holders. A thermogravimetric analysis (TGA Q50, TA Instruments) was used to determine the conductive filler content of the conductive elastomeric fibers. Samples were cut to a weight of approximately 20 mg and tested to 1000? C. in a nitrogen atmosphere with a heating rate of 20? C./min.
[0087] A Dynamic Mechanical Analyzer (DMA Q800, TA Instruments) was used to perform the tensile stress-strain tests. The fibers were exposed to a ramped force (force ramp rate of 3 N/min) and the resultant deformation (strain) is monitored until the fiber's failure. All the experiments were done at room temperature. The reliability of this resistance measurement protocol was evaluated by measuring the resistance of 5 samples of each conductive elastomeric fiber. Five replicates of each CEF fiber were used in order to confirm the results presented in this work. The apparent tensile stress was determined using the cross-section of each fiber and the strain computed from the crosshead displacement. The apparent Young's modulus was computed from the first linear section of the stress-strain curve in the reloading phase.
[0088] A Fourier transform infrared spectroscopy (FTIR, Alpha, Platinum-ATR, Bruker, Inc.) was conducted in the spectral range from 4000 to 400 cm-1. The spectra were the results of 64 interferograms at a spectral resolution of 4 cm-1. Results are shown in
[0089] A Differential scanning calorimetry (DSC, Q2000, TA Instrument) was used to study the glass transition and melting behavior, During DSC testing, samples were heated from ?50? C. to 300? C. at a heating rate of 10? C./min under dry nitrogen atmosphere.
[0090] Laundry Washing described in this disclosure was conducted as discussed below. Underwear garment prototype(s) with embedded electrodes were washed 30 times according to the American Association of Textile Chemists and Colourists (AATCC) home laundry washing test method using a commercial washing machine (Whirlpool WED5600X) under a normal laundry cycle for a small load with cold water using AATCC Standard Reference Detergent Without Optical Brightener (SDL Atlas, USA). Each sample prototype was placed in a mesh laundry bag during laundering. After each laundering cycle, the sample was laid flat and left to dry at room temperature prior to the next wash cycle.
[0091] Skin-electrode electrical impedance measurements according to this disclosure were performed using the measurement protocols described by Spach et al..sup.[65] Galvanostatic electrical impedance spectroscopy measurements were done over 1 to 10 KHz frequency range and 10 uA current range, using an Ivium Vertex One potentiostat (Ivium Technologies, Eindhoven, Netherlands). Swatches were knitted containing electrodes with each of the described CEF fibers materials (n=6/material type). Knitted swatch electrodes were 2 cm?2 cm and square in shape (see
[0092] Electrocardiogram measurement according to this disclosure was tested in an example with pairs of surface electrodes. Swatch electrodes were knitted with each of the described CEF fibers (n=6/material type). In order to compare and validate the recording fidelity and performance of textile electrodes, simultaneous measurements were also done with gel adhesive electrodes.
[0093] Testing with surface electrodes embedded in a garment was done using garment-based ECG recordings simultaneously from textile electrode pairs shown in
[0094]
[0095] At block 1104, elastomer material pellets and conductive filler are combined together to form a conductive elastomeric material. In an example, the conductive elastomeric material pellets and conductive filler may be compounded to mix the conductive fillers with polymer forming conductive polymer pellets. In an embodiment, conductive filler may be carbon black particles. Carbon-based materials such as carbon nanotubes, graphene, carbon black, acetylene black, and mixture thereof may also be as conductive filler. Conductive filler is not limited to carbon material, and may be inorganic compounds such as MXenes and/or metallic nano-fillers such as silver, gold or brass. Conductive fillers may be selected based on (1) Biocompatibility of the conductive filler, (2) Size and morphology, (3) Surface area, (4) Percolation rate, (5) Conductivity, (6) Spinnability. The conductive polymer pellets may be added to a hopper of a melt spinning machine as shown in
[0096] Extrusion temperature, melt intrinsic viscosity, filler content, feed rate, and take-up velocity are influential variables for conductive elastomeric fibers in melt spinning, as they affect the molecular orientation and crystallinity of as-spun/drawn fibers. Spinning temperature may affect the melt viscosity and thereby the flow distribution through the spinneret. Reduced melt viscosity variations in a spinpack from reduced intrinsic viscosity, residence time, and temperature gradients will yield reduced denier and orientation variations from filament-to-filament. In an embodiment, the conductive elastomeric polymer pellets and conductive filler may be melted at a temperature from 130 C to 360 C. In another embodiment, the conductive elastomeric polymer pellet and conductive filler may be melted together at a temperature below 130 C. In another embodiment, the conductive elastomeric polymer pellet and conductive filler may be melted together at a temperature from 250 C to 310 C. Components of the filament yarn may include conductive polymer (such as conductive TPE), self-healing materials, far infrared (FIR) particles and microcapsules of phase-change materials for thermal regulation.
[0097] At block 1106, the conductive elastomeric material, e.g. elastomeric polymer, may be extruded and drawn into a filament. As a filament is formed, the molecules of the filament are oriented simultaneously, e.g. in a spin column. Smaller diameter fibers (overall from filament-to-filament and along each filament) may each have higher as-spun orientation (birefringence) than the larger ones. In a typical fiber process, a multifilament as-spun yarn may be drawn (extended) 3-5 times its original length to orient the molecules further and achieve its final desired tensile properties (e.g. tenacity, % elongation, modulus, etc.). Providing increased uniformity of as-spun fiber properties, particularly denier and attendant orientation along the filament, influence the improvements in properties, throughputs, and quality of drawn fibers. Uniformity of the fiber quality, in particular its tensile properties, may be influenced by the uniform structure (diameter) of the continuous fiber. Having thin and thick places along the filament would create non-uniformity which will affect the mechanical properties and ultimately the ability of the fibers to form a textile, e.g. by knitting, weaving, and/or embroidering.
[0098] Continuing the above example, as
[0099] In an example, the spinneret can be configured to provide a different cross sectional shapes and diameters of extruded filaments. In an embodiment, diameter of the spinneret can be between 50 micron to 1 mm. The extruded filament may be drawn to improve the crystallinity and create thinner filaments. Drawing a filament may increase the molecular orientation and strength of the fibers while decreasing their extensibility compared to as-spun fibers. During an example drawing process, as-spun filaments may be stretched up to 5 times of their original length. This drawing process may happen at a temperature from 10? C.-100? C. above the glass transition temperature (Tg) of the polymer, and subsequently the filaments may be heatset to impart dimensional stability. Spinning temperature and drawing steps may affect the orientation of the polymer molecules which subsequently affects the tensile properties of the final fiber. In an embodiment, the diameter of the extruded filament may be drawn to have a diameter in the range of 100 to 500 micron. In an example, the properties (e.g. spinnability, biocompatibility, and conductivity) of a monocomponent filament structure may solely depend on the type of elastomeric polymer matrix and fillers used.
[0100] Conductive elastomeric polymer may also be extruded and drawn into a filament in the presence of a gas to provide a desirable characteristics to the filament. Under certain conditions, oxygen may react with polymer materials to form crosslinked species (e.g. gels) which may have different properties from the bulk polymer. Non-uniform properties may result in broken filaments during spinning and drawing which may not be desirable. In an example, non-uniform properties may be mitigated against by sealing elastomeric material, conductive filler, and resulting filament in an inert environment (e.g. a nitrogen environment) sealed against air leaks may reduce the chance of the crosslinked species formation. In another example, inert gas (e.g. nitrogen) purging of an extruder feed throat may reduce crosslinked species formation.
[0101] Filaments from the melt spinning machine may be cooled to provide desirable characteristics. Filaments may be cooled in a quench system comprising convection heat transfer (e.g. to a gas) and/or conduction (e.g. to a liquid). Cooling gas flow may reduce along-a-filament denier and orientation variations in a filament. Applying different methods of cooling, including liquid bath (e.g. a water bath) during the melt spinning process may affect spun yarn birefringence (a measure of molecular orientation) which in turn correlates with spun yarn tenacity, % elongation, and initial modulus. Interactions between filament geometry and quench conditions may control spun fiber properties and their variability. In an example, a water bath may be used to cool extruded filaments from the melt spinning machine. In another example extruded filaments may be cooled by convection, e.g. by air convention. Filaments from the melt spinning machine may also be directed to a solvent bath, e.g. a water bath. The solvent bath may dissolve components of the filament to provide the remaining filament with a desirable shape or texture. The solvent bath may also cool the extruded filaments from the melt spinning machine. A cooling bath and/or solvent bath may be positioned a distance from a spinneret of the melt spinning machine to provide both cooling in the presence of a gas and a liquid to provide desirable characteristics of a filament.
[0102] Filaments according to the present disclosure may have different bi-component structures. Sometimes conductive pellets may not have sufficient mechanical strength to be extruded and drawn only by themselves; accordingly, another material may be used as a core material and the conductive material of the conductive pellets (which is made through compounding) may be a sheath. Filaments may have various structures such as hollow-fibers or a structures formed from polymer filaments extruded together in multi-component melt-spinning. The filaments may have various cross-section such as, for example, side-by-side, core and sheath, hollow, c-shape, trilobal, islands in the sea, and the like. In an example, an extruded filament may comprise water soluble polymer(s) (e.g. Poly(vinyl alcohol); PVA) which may be placed in a water bath after extrusion to remove the water soluble polymer(s). In another example, air may be blown during spinning to create hollow fibers where the sheath is formed from conductive polymer.
[0103] At block 1108, optionally filament yarn is formed from the filament(s). Yarn may be formed by a melt spinning machine illustrated at
[0104] At block 1110, the yarn and/or filament is knit into an electrode. In an example, flat-bed knitting machines illustrated in
[0105] An electrode according to the disclose herein may be used for different applications such that similar filament can be used in electrodes for bio-signal monitoring, functional electrical stimulation, heat generation, motion sensing, moisture sensing, respiration sensing, etc. Further, a single strand of the extruded filament may be knitted as an electrode such that material consumption may be reduced compared with other conductive filaments, e.g. carbon-contained nylon, silver plated nylon, etc. In some examples, because an extruded filament according to the disclosure herein may comprise silicone and/or rubber, an electrode made from the extruded element may have more grip when in contact with skin which may decrease motion artifact and retrieve bio-signals with higher resolution. In another example, electrodes according to the disclosure herein are biocompatible and such that they may be in contact with a human body for long-term monitoring and medical applications.
[0106] The electrode and/or conductive elastomeric filament fiber disclosed herein may also be used for strain gauge. In an embodiment, the resistance of a filament according to the disclose herein may change by stretching, causing the distance between conductive particles in filament matrix to change; in turn, causing resistance to change. By measuring the change in resistance as the electrode and/or filament may be used as a sensor for stretch/motion sensing.
[0107] The electrode and/or conductive elastomeric filament fibers disclosed herein may also be used for in heat applications. In an example, the conductive fillers, e.g. carbon-based fillers, may create high resistance so filament formed from conductive elastomeric materials, or a sheet of the conductive elastomeric materials, it can be used as a heating element by running an electric current through it. High conductivity yarns/filaments may be used as a bus and the extruded filament/sheet as heating elementdue to the high resistance of sheet/filament, it will heat up and can be used in heat applications.
[0108] The electrode and conductive elastomeric filament fibers disclosed herein may also be used as a moisture sensor. The polymer matrix may be selected such that it's sensitive to a group of solvents and it swells once it comes in contact with those types of solvents/solutions therefore the distance between its conductive particles will change so its resistance will change and it can be sensitive to moisture.
[0109] The above description is meant to be exemplary only, and one skilled in the relevant arts will recognize that changes may be made to the embodiments described without departing from the scope of the invention disclosed. The present disclosure may be embodied in other specific forms without departing from the subject matter of the claims. The present disclosure is intended to cover and embrace all suitable changes in technology. Modifications which fall within the scope of the present invention will be apparent to those skilled in the art, in light of a review of this disclosure, and such modifications are intended to fall within the appended claims. Also, the scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.
[0110] Although the embodiments have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope. Moreover, the scope of the present disclosure is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification.
[0111] As one of ordinary skill in the art will readily appreciate from the disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed, that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.
[0112] The description provides many example embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
[0113] As can be understood, the examples described above and illustrated are intended to be exemplary only.
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