METHOD FOR PRODUCING AN ELASTIC AND FLEXIBLE FIBER WITH OPTICAL, ELECTRICAL OR MICROFLUIDIC FUNCTIONALITY
20220152905 · 2022-05-19
Assignee
Inventors
- Ivan Minev (Dresden, DE)
- Dzmitry Afanasenkau (Dresden, DE)
- Anna Pak (Dresden, DE)
- Markos Athanasiadis (Dresden, DE)
Cpc classification
B33Y10/00
PERFORMING OPERATIONS; TRANSPORTING
B29C64/106
PERFORMING OPERATIONS; TRANSPORTING
B29C48/02
PERFORMING OPERATIONS; TRANSPORTING
B29C48/266
PERFORMING OPERATIONS; TRANSPORTING
B29C48/022
PERFORMING OPERATIONS; TRANSPORTING
B29L2011/0075
PERFORMING OPERATIONS; TRANSPORTING
International classification
B29C48/00
PERFORMING OPERATIONS; TRANSPORTING
B29C48/02
PERFORMING OPERATIONS; TRANSPORTING
B29C48/12
PERFORMING OPERATIONS; TRANSPORTING
B29C48/25
PERFORMING OPERATIONS; TRANSPORTING
B29C64/106
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention relates to a method for manufacturing an elastic and flexible fiber with a pre-de-termined non-circular cross-sectional geometry, the method comprising extrusion of an elasto-mer from a nozzle onto a substrate, wherein the pre-determined non-circular cross-sectional geometry of the fiber is determined by the height and velocity of the nozzle relative to the sub-strate. The invention relates to an elastic and flexible fiber produced using the method, wherein the fiber comprises an elongated indentation along a length of the fiber (groove). The invention relates to methods for producing preferably biocompatible microfluidic, electrically conducting or light-guiding fibers using the methods of the invention. The invention further re-lates to elastic and flexible fibers produced by the method.
Claims
1. Method for manufacturing an elastic and flexible fiber with a pre-determined non-circular cross-sectional geometry, the method comprising extrusion of an elastomer from a nozzle onto a substrate, wherein the pre-determined non-circular cross-sectional geometry of the fiber is determined by the height and velocity of the nozzle relative to the substrate, and wherein the fiber comprises an elongated indentation along a length of the fiber.
2. Method according to preceding claim, wherein the elastomer is extruded onto the substrate as a continuous filament by a (preferably automated) translational relative motion of the nozzle relative to the substrate, followed by a hardening of the elastomer after extrusion to produce an elastic fiber.
3. Method according to any one of the preceding claims, wherein the fiber has a maximum cross-sectional width of 10-2000 μm, preferably wherein the fiber has a maximum cross-sectional width of 50-1500 μm, more preferably about 300-1000 μm.
4. Method according to any one of the preceding claims, wherein the nozzle is essentially circular in cross-section, and preferably has a smallest internal diameter of 10-500 μm, preferably 100-300 μm, more preferably about 150-250 μm and preferably has a smallest outer diameter, greater than the internal diameter, of 20-1000 μm, preferably 100-700 μm, more preferably about 300-500 μm.
5. Method according to any one of the preceding claims, wherein the elastomer is an extrudable elastomer, allowing the elastomer to flow through the nozzle when pressure is applied and to harden into an elastic and flexible form after the elastomer is deposited on the substrate.
6. Method according to any one of the preceding claims, wherein the elastomer has a shear rate dependent viscosity and/or is a thermoplastic elastomer.
7. Method according to any one of the preceding claims, wherein the elastomer is selected from the group consisting of silicone rubber (such as polydimethylsiloxane), a (preferably biocompatible) viscoelastic polymer, polyurethane rubber, a hydrogel or microgel (such as based on polyacrylic acid), colloidal suspension (such as containing silicate particles), a polymer precursor and/or a melt (such as wax).
8. Method according to any one of the preceding claims, wherein: a. the translational speed of the nozzle relative to the substrate is slower than the extrusion speed, with which the elastomer leaves the nozzle, and/or b. the distance between the nozzle and the substrate is less than the inner diameter of the nozzle.
9. Method according to any one of the preceding claims, wherein the fiber has an elliptical cross-sectional geometry or is a flattened cylinder (ribbon), preferably wherein the ratio of width to height of the cross-sectional geometry of the fiber is 1.5 or more, preferably 2 or more.
10. Method according to any one of the preceding claims, wherein: determining the velocity of the nozzle relative to the substrate comprises setting the velocity V of the nozzle according to Equation 1:
11. Method according to any one of the preceding claims, wherein a nozzle or object of essentially the same dimensions is passed over the fiber after the elastomer is deposited on the substrate, and preferably before elastomer hardening, thereby removing elastomer (e.g. by engraving and/or suctioning) and producing an elongated indentation along a length of the fiber (groove).
12. Method according to any one of the preceding claims, wherein said elongated indentation subsequently closes at the outer edge of the cross-sectional geometry of the fiber to form an elongated (microfluidic) lumen inside the fiber.
13. Method according to any one of the preceding claims, wherein the fiber comprises an elongated indentation along a length of the fiber (groove), and an elastic, and preferably flexible, electrically conductive material is positioned in the elongated indentation, followed by sealing said elongated indentation by depositing additional elastomer onto the fiber, preferably using the method of any one of the preceding claims, thereby sealing said electrically conductive material inside the fiber.
14. Method according to any one of the preceding claims, wherein the fiber comprises an elongated indentation along a length of the fiber (groove) and an elastic, and preferably flexible, light guiding material is positioned in the elongated indentation, followed by sealing said elongated indentation by depositing additional elastomer onto the fiber, preferably using the method of any one of the preceding claims, thereby sealing said light guiding material inside the fiber.
15. Elastic fiber with a non-circular cross-sectional geometry, produced using the method of any one of the preceding claims.
16. Elastic and flexible extruded fiber with a non-circular cross-sectional geometry and a maximum cross-sectional width of 10-2000 μm, preferably produced using the method of any one of the preceding claims, wherein the fiber comprises: a. a base element comprising an elongated indentation along a length of the base element (groove), wherein the base element is obtained by extruding an elastomer from a nozzle onto a substrate thereby forming an elongated indentation, and/or optional subsequent engraving of the extruded base element to form an elongated indentation, and b. at least one sealing element bound to the base element, wherein the sealing element is obtained by extruding an elastomer from a nozzle onto the base element, wherein the sealing element is positioned to form a sealed elongated lumen along a length of the fiber between the elongated indentation of the base element and the sealing element, wherein the lumen optionally comprises an elastic and flexible electrically conductive material or an elastic and flexible light guiding material.
17. Use of the elastic fiber according to any one of the preceding claims as: an optical fiber, when a light guiding material is sealed inside the fiber, produced according to claim 14, a microfluidic channel, when an elongated (microfluidic) lumen is present inside the fiber, preferably produced according to claim 12, a pneumatic actuator, when an elongated lumen is present inside the fiber, preferably produced according to claim 12, and pressure can be applied in the lumen, or a thermal exchange device, when an elongated lumen present inside the fiber, preferably produced according to claim 12, is used to circulate a fluid with temperature different from that of the surroundings, an electrical interconnect, when an electrically conductive material is present inside the fiber, produced according to claim 13, A resistive strain sensor, when an electrically conductive material is present inside the fiber, produced according to claim 13.
Description
FIGURES
[0136] The invention is further described by the following figures. There are intended to represent a more detailed illustration of a number of preferred non-limiting embodiments or aspects of the invention without limiting the scope of the invention described herein.
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EXAMPLES
[0150] The invention is further described by the following examples. These are intended to present support for the workability of a number of preferred non-limiting embodiments or aspects of the invention without limiting the scope of the invention described herein.
Example 1: Height and Velocity Determination
[0151] In standard DIW operations, filaments have close to circular cross sections with diameter αd.sub.in. Here d.sub.in is the inner diameter of the nozzle and α is the die-swelling factor, which describes the post-extrusion expansion of the ink [16]. Stable printing is achieved by setting the translational speed of the print head v to be close to the extrusion speed C, with which ink leaves the nozzle. At the same time, the height of the nozzle above the substrate h is kept similar to αd.sub.in (
[0152] As model inks, we use two different materials: SE1700 (Dow Corning), a printable silicone elastomer in the polydimethylsiloxane family and Carbopol (Lubrizol), a microgel based on cross linked polyacrylic acid [17]. Both inks exhibit shear rate dependent viscosity (
[0153] We start by noting that when H* or V* are close to or smaller than unity, non-circular cross section filaments are produced. They can be described as elliptical cylinder, ribbon, groove and discontinuous. The same combination of H* or V* produces a similar effect in both of our model inks (
[0154] When H* or V* are less than unity, the ink is squeezed and forced to deform between the nozzle and the substrate, which results in a filament flattened in the shape of a ribbon (
[0155] The phase boundary predicted by Equation (5) is presented as a solid red line in
Example 2: Post-Extrusion Modification of the Filament Cross Section
[0156] Post-extrusion modification of the filament cross section is demonstrated below. To do this, we use the nozzle as a stylus by setting to zero (no ink leaves the nozzle). Passing the stylus over a freshly printed (not yet polymerized) ribbon/ellipse filament of SE1700 silicone can create a groove in it (
Example 3: Functional Core-Shell Fibers
[0157] Next, we combine ribbon and groove filaments to form functional core-shell fibers (
Example 3: Optical Fibers
[0158] For optical fibers, we create a core by filling groove filaments with a high refractive index silicone (OE 6520, Dow Corning, RI=1.54 compared to RI=1.44 for SE 1700). The optical core cannot be printed as a continuous filament due to the low viscosity of the optical silicone. Instead, it is dosed (using a printing nozzle) inside the groove where it spreads. A ribbon filament is printed on top, acting as the optical seal. The entire fiber is then polymerized by heating. Optical fibers produced in this way display average attenuation of 0.72±0.06 dBcm.sup.−1 (
[0159] Printed optical fibers remain functional when tied in a knot, or when stretched to at least 30% tensile strain (
Example 3: Electrical Interconnects
[0160] Similarly, electrical interconnects can be printed by filling groove filaments with a conductive material. Here we use compacted platinum microparticles as the conductive core while the groove and ribbon filaments act as electrical passivation (
[0161] Electrical interconnects remain conductive when stretched to at least 30% tensile strain (
Example 4: Optical Fiber with Steerable Tip
[0162] Fibers themselves may perform multi-modal sensing and actuating tasks. Here we present two examples where fibers of different modalities are integrated. In the first demonstration, we fabricate an optical fiber with steerable tip that may find applications in endoscope systems with adaptive illumination [22]. We print a composite fiber consisting of a microfluidic channel on top of an optical core (
Example 5: Thermal Modulation
[0163] In our second demonstration, we fabricate a system for delivering and monitoring thermal modulation on soft curvilinear surfaces (
[0164] We apply our thermal actuator to the surface of a gelatin brain model. By flowing chilled ethanol at a rate of 1-2 mLmin-1 through the thermal exchange loop, we achieved a temperature drop of 3.06° C. in the brain model as reported by the integrated temperature sensor (
SUMMARY OF THE EXAMPLES
[0165] In summary, we demonstrate a strategy for rational control of the cross sectional geometry of filaments printed with SE1700 silicone and Carbopol hydrogel. We integrate filaments in core-shell functional fibers and freeform microfluidics. As an alternative method to co-extrusion with specialized co-axial nozzles, our approach relies on simple circular nozzles. Using groove and ribbon filaments we demonstrate production of fibers with optical, electrical and microfluidic functionality. Freeform fibers may be integrated in webs of multi-modal sensors and actuators. We envisage applications in soft robots as well as in implantable systems to deliver multimodal therapeutic programs to soft organs in the body.
Experimental Section:
Ink Preparation:
[0166] Silicone elastomers, SE 1700 and OE 6520 (Dow Corning), are prepared by mixing catalyst and base at a ratio of 1:10 and 1:1 respectively, followed by degassing. Carbopol (EDT 2020, Lubrizol Corporation) is prepared by vigorous mixing in water at a concentration of 2% w/w, followed by the addition of NaOH until pH 7.0 is achieved.
Electrical Interconnects:
[0167] For electrical interconnects, conductive ink is fabricated by mixing Platinum powder (particle diameter 0.2-1.8I.Im, ChemPur, Germany) with tri(ethylene glycol) monoethyl ether (TGME, Merck KGaA) followed by sonication. The Platinum content in the suspension is around 15% by weight. The platinum suspension is deposited in groove filaments by ink-jet or by pipetting. The printed lines are then heated to 120° C. for 5 min to evaporate TGME leaving behind compacted dry Platinum powder inside groove filaments.
Printing:
[0168] Printing is done using the 3D Discovery bio-printer from RegenHU, Switzerland. Print layouts are developed in the BIOCAD software (RegenHU). Studies of filament cross-sections are conducted with the SE 1700 silicone and the Carbopol microgel. We use a plastic conical nozzle with nominal inner diameter of 200I.Im at the tip (corrected to an actual value of 210 μm following precise optical measurements). The pneumatic pressure is set at 5 and 1.2 bar for SE1700 and Carbopol respectively. Printing of the platinum ink is done with the inkjet printing head of the 3D Discovery instrument. The optical silicone OE 6520 is deposited by the nozzle extrusion method, using 100 μim inner diameter, metal nozzles (Poly Dispersing Systems). In all cases, the substrate used for printing is glass treated with 2% sodium dodecyl sulfate (Merck KGaA) to form a debonding layer.
Optical Fibers:
[0169] To create a grove in a freshly printed filament of SE 1700 the nozzle (d.sub.in=210 μm, d.sub.out=430 μm) is used as a stylus. The groove filament is then heat cured at 120° C. for 45 minutes. One end of a cleaved silica optical fiber (ø1501.im, Thor Labs) is placed inside the groove. Optical silicone (OE 6520) is then dispensed inside the groove to form the core of the optical fiber. This structure is heat cured at 120° C. for 45 minutes. A final ribbon shaped filament of SE1700 silicone forms a seal, and is heat cured at 120° C. for 45 minutes. Prior to each printing step, the structure is exposed to a brief oxygen plasma to improve interlayer adhesion. Finally, the free end of the silica optical fiber is coupled to a white light source (SCHOTT, KL 1500 electronic). Light transmission measurements are conducted by inserting the free end of the printed optical fiber into the opening of the integrating chamber of an optical powermeter (PM100D, S142C, Thor Labs). For stretching experiments, the ends of printed fibers are attached to the prongs of a caliper.
Electrical Interconnects:
[0170] Here a groove filament is filled with platinum ink by ink-jetting and heated to 120° C. for 5 minutes to remove the dispersing solvent. A ribbon shaped filament forms the electrical passivation. The two ends of the electrical interconnects are covered with, conductive epoxy (Epo-Tek H27D, Epoxy Technology) to which conventional electrical wires are attached. Printed electrical interconnects are stretched using a Dynamic Mechanical Analysis tester (SHIMADZU, EZ-SX) with a load cell of 20 N. During stretching, resistance measurements are performed using a potentiostat (AUTOLAB PGSTAT204, Metrohm).
Microfluidic Channel:
[0171] Here, a nozzle (d.sub.in=210 μm, d.sub.out=430 μm) is used as a stylus passed through a freshly printed filament of SE 1700 silicone. In doing so, the walls of the groove shaped filament collapse forming a triangular shaped channel. The microfluidic channels are heat cured at 120° C. for 45 minutes.
Steerable Optical Fibers:
[0172] A microfluidic channel is printed directly on top of an optical fiber. The end of the microfluidic channel is sealed with a small droplet of RTV silicone (734 Clear, Dow Corning). The other end is coupled to a needle mounted on a 6 ml syringe. The junction between the syringe and the microfluidic channel is secured with additional blobs of silicone. Air pressure is applied by depressing the syringe piston using a syringe pump (kdScientific).
Thermal Modulation System:
[0173] A microfluidic channel is printed in a flower shape. In the center of the flower we place a packaged digital temperature sensor (DS18B20, Maxim Integrated) interfaced with printed electrical interconnects. The microfluidic channel is coupled with silicone tubes (Fredenberg Medical, Mono Lumen Tubing). The whole system is placed upon gelatin (Sigma-Aldrich, G1890-100G) cast in the shape of a hemisphere (red food dye is added to the gelatin). A peristaltic pump (Bio-Rad, EP-1 Econo Pump) is used to pump chilled Ethanol (−25° C.) through the microchannels at different flow rates.
Imaging of Printed Structures:
[0174] A ZEISS Discovery V2.0 microscope is used for the imaging of filament and fiber cross sections. Other optical images are captured with a macro lens.
Rheology Measurements:
[0175] The rheology of SE1700 and Carbopol is investigated by oscillating plate rheometry (ARES, TA instruments, with parallel plates diameter of 8 mm). In order to quantify the shear dependent viscosity behavior of the samples, the shear rate is stepped between 1 and 100 rad/s.
Statistics:
[0176] Measurements are quoted as averages from at least three independent samples and errors represent standard deviation.
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