WO2020092688A1 - Efficient production of nanofiber structures - Google Patents
Efficient production of nanofiber structures Download PDFInfo
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- WO2020092688A1 WO2020092688A1 PCT/US2019/059027 US2019059027W WO2020092688A1 WO 2020092688 A1 WO2020092688 A1 WO 2020092688A1 US 2019059027 W US2019059027 W US 2019059027W WO 2020092688 A1 WO2020092688 A1 WO 2020092688A1
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- distance
- substrate
- electrospinning apparatus
- nanofiber mat
- spinning electrode
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
Definitions
- Electrospinning is a fiber production method in which an electric force is applied to a polymer solution present at a spinning electrode. The application of the electric field pulls a charged thread of the solution from the spinning electrode towards a collecting electrode. This thread of polymer solution dries in flight, forming a fiber that is deposited on a substrate typically positioned at the collecting electrode. Depending upon the specific parameters applied to the electrospinning process, the produced fibers can have diameters ranging from a few nanometers up to several micrometers.
- Electrospinning apparatuses are designed to adjust the position of the substrate and collector simultaneously. Most electrospinning studies utilize a grounded collector which serves both as the counter electrode and as the collecting substrate. This design makes it impossible to decouple the impacts of substrate distance vs. electric field strength, limiting the ability to independently test the effect of changes in these distances on electrospinning efficiency. Since the interelectrode gap needs to be maintained at a safe distance to prevent electrical discharge, especially at higher voltages, lower substrate distances have not been investigated as an independent variable.
- electrospinning apparatuses and methods of producing nanofiber structures with increased productivity e.g ., nanofiber mats.
- electrospinning apparatuses that comprise: (a) a spinning electrode; (b) a substrate that is a first distance from the spinning electrode (the substrate distance); and (c) a collecting electrode that is a second distance from the spinning electrode (the interelectrode distance), wherein the substrate is positioned between the spinning electrode and the collecting electrode.
- the ratio of the substrate distance to the interelectrode distance is less than 1 (e.g., no greater than 0.77).
- electrospinning apparatuses comprising: (a) a spinning electrode; (b) a substrate that is a first distance from the spinning electrode (the substrate distance); and (c) a collecting electrode that is a second distance from the spinning electrode (the interelectrode distance), wherein the apparatus is configured such that the substrate distance and the interelectrode distance are separately adjustable and capable of being configured such that the ratio of the substrate distance to the interelectrode distance is less than 1.0 ( e.g ., no greater than 0.77).
- a nanofiber structure e.g., a nanofiber mat
- the method comprises electrospinning a polymer solution from the spinning electrode of the apparatus provided herein onto its substrate.
- a nanofiber structure e.g, a nanofiber mat
- methods for producing a nanofiber structure comprising electrospinning a polymer solution from a spinning electrode onto a substrate that is positioned between the spinning electrode and a collecting electrode, wherein the ratio of the substrate distance to the interelectrode distance is less than 1 (e.g, no greater than 0.77).
- Figure 1 shows a schematic depiction of certain conditions applied during the electrospinning experiments described in Example 1.
- Figure 2 is a graph depicting the relationship between substrate distance, electric field, basis weight and fiber diameter during exemplary electrospinning processes.
- Figure 3 shows a schematic depiction of certain conditions applied during in certain of the electrospinning experiments described in Example 2.
- Figure 4 shows a schematic depiction of conditions applied during electrospinning experiments described in Example 3 (Production unit). Runs 8 and 9 and well as 10 and 11 have identical experimental conditions. Each of these pairs have a differentiating line speed.
- Figure 6 shows the ability of certain embodiments disclosed herein to increase productivity while maintaining a product unifority.
- Panel a depicts the increase in productivity per electrode (in g/m-min) achieved by decreasing the substrate distance while maintaining a constant electrode distance.
- Panel b shows that decreasing the substrate distance while maintaining a constant electrode distance does not adversely impact the count fiber mean diameter of the nanofiber mat produced.
- the hatched bar graph in panel b represents low-distance ratio.
- Higher productivity is augmented by combination of increasing the electric field and decreasing the distance ratio (d-s/d-ie).
- FIG. 7 shows representative Scanning Electron Microscope (SEM) images of electrospun nanofiber generated at (a) standard and (b) high productivity settings using production equipment. The micrograph shows that comparable fiber structures were obtained at both settings.
- Electrospinning is a technique that can produce non-woven fibrous material with fiber diameters ranging from tens of nanometers to microns, a size range that is otherwise difficult to control by conventional non-woven fiber fabrication techniques.
- the quality and quantity of the fibers produced depend on several parameters. These parameters include molecular weight, molecular weight distribution and structure of the polymer; solution properties (i.e., viscosity, conductivity, and surface tension); electrical potential, flow rate, and concentration; distance between the spinning electrode and the substrate; environmental parameters (i.e., temperature, humidity, and air velocity in the chamber); motion and size of the collector; and needle gauge.
- the electrospinning apparatuses that can produce uniform nanofibers while improving process productivity without compromising the microstructure of the nanofiber mat by reducing the distance between spinning electrode and the substrate relative to the distance between the spinning electrode and the collecting electrode.
- the electrospinning apparatuses provided herein comprise (a) a spinning electrode; (b) a grounded substrate that is a first distance from the spinning electrode (the substrate distance); and (c) a collecting electrode that is a second distance from the spinning electrode (the interelectrode distance) wherein, the ratio of the substrate distance to the interelectrode distance is no greater than 1 ( e.g ., less than 0.86).
- the apparatus is configured such that the substrate distance can be
- an electrospun structure such as an electrospun mat, using an apparatus provided herein.
- the productivity improvements provided by the methods and compositions disclosed herein have implications at the industrial production level. Certain embodiments of the methods and compositions provided herein can be used to increase amount of material being produced in an existing manufacturing line and, in doing so, decrease the production cost of a particular filter structure produced on that line. In some embodiments the methods and compositions provided herein can be used to make higher basis weight filter structures on an existing manufacturing line without increasing the production cost and without reducing the amount of material being produced.
- variable and“coefficient of variation” are used interchangeably herein and refer to a standardized measure of dispersion of a probability distribution or frequency distribution. It is often expressed as a percentage and is defined as the ratio of the standard deviation to the mean.
- productivity is a measure of the quantity of fiber produced per unit time per unit length of the spinning electrode (g/m-min). In certain embodiments, productivity is calculated as the product of the basis weight (g / m 2 ) and line speed (m/min) and is directly related to the process economy.
- high productivity settings refers to electrospinning apparatus settings in which the ratio of the substrate distance to the interelectrode distance is less than 0.88 ( e.g ., no greater than 0.75, 0.70, 0.65, 0.60. 0.55, 0.50, etc.). In some embodiments high productivity settings are applied in combination with the use of a high electric field (e.g., an electric field of at least 0.7 kV/mm).
- polymer refers to a relatively high molecular weight organic compound, natural or synthetic, whose structure can be represented by a repeated small unit, the monomer ( e.g ., polyethylene, rubber, cellulose). Synthetic polymers are typically formed by addition or condensation polymerization of monomers. Polymers that are suitable for use in the nanofiber substrate layer of the invention include, but are not limited to,
- polyethersulfones polysulfones, polyimides, polyvinylidene fluorides, polyethylene terephthalates, polybutylene terephthalates, polypropylene terephthalates, polypropylenes, polyethylenes, polyacrylonitriles, polyamides, and polyaramids.
- nanofiber refers to fibers having a number average diameter or cross-section less than about 1000 nm, even less than about 800 nm, even between about 50 nm and 500 nm, and even between about 100 and 400 nm.
- diameter as used herein includes the greatest cross-section of non-round shapes.
- nonwoven means a web including a multitude of randomly distributed fibers.
- the fibers generally can be bonded to each other or can be unbonded.
- the fibers can be staple fibers or continuous fibers.
- the fibers can comprise a single material or a multitude of materials, either as a combination of different fibers or as a combination of similar fibers each comprised of different materials.
- an electrospinning apparatus consists of a spinning electrode that is connected to a high-voltage direct current power supply, a grounded collecting electrode, and optionally a needle for dispensing a polymer solution.
- apparatuses having a ratio of distance between the spinning electrode and the substrate (the substrate distance) to distance between the spinning electrode and the collecting electrode (the interelectrode distance) of less than 1.
- electrospinning apparatuses that comprise: (a) a spinning electrode; (b) a substrate that is a first distance from the spinning electrode (the substrate distance); and (c) a collecting electrode that is a second distance from the spinning electrode (the interelectrode distance), wherein the substrate is positioned between the spinning electrode and the collecting electrode.
- the ratio of the substrate distance to the interelectrode distance is less than 1 ( e.g ., less than 0.86).
- the ratio of substrate distance to interelectrode distance is no more than 0.95, 0.90, 0.85, 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, or 0.35. In certain embodiments, the ratio of substrate distance to interelectrode distance is no greater than 0.86. In some embodiments, the ratio of substrate distance to interelectrode distance is at least 0.20, 0.25, or 0.30. In some embodiments, the ratio of the substrate distance to the interelectrode is from about 0.86 to about 0.3.
- the ratio of the substrate distance to the interelectrode distance is between 0.80 and 0.70, 0.75 and 0.65, 0.70 and 0.60, 0.65 and 0.55, 0.60 and 0.50, 0.55 and 0.45, 0.50 and 0.40, 0.45 and 0.35, or 0.40 and 0.30. In some embodiments, the ratio of the substrate distance to the interelectrode distance is about 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, 0.35 or 0.30.
- the substrate distance is no more than about 200 mm, 190 mm, 180 mm, 170 mm, 160 mm, 150 mm, 140 mm, 130 mm, 120 mm, 110 mm, 100 mm, 90 mm, 80 mm, 70 mm, or 60 mm. In some embodiments, the substrate distance is at least about 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, or 70 mm. In some embodiments, the substrate distance is from about 140 mm to about 55 mm.
- the substrate distance is about 200 mm, 195 mm, 190 mm, 185 mm, 180 mm, 175 mm, 170 mm, 165 mm, 160 mm, 155 mm, 150 mm, 145 mm, 140 mm, 135 mm, 130 mm, 125 mm, 120 mm, 115 mm, 110 mm, 105 mm, 100 mm, 95 mm, 90 mm, 85 mm, 80 mm, 75 mm, 70 mm, 65 mm, 60 mm, or 55 mm.
- the interelectrode distance is such that the electrospinning apparatus maintains an electric field at least 0.2 kV/mm. In some embodiments, the interelectrode distance is such that the apparatus maintains an electric field of at least 0.2 kV/mm, 0.3 kV/mm, 0.4 kV/mm, 0.5 kV/mm, 0.6 kV/mm, or 0.7 kV/mm. In some embodiments, the interelectrode distance is such that the apparatus maintains an electric field of no more than 0.8 kV/mm, 0.70 kV/mm, or 0.6 kV/mm. In some embodiments, the interelectrode distance is such that the apparatus maintains an electric field of 0.2 kV/mm to 0.8 kV/mm. In some embodiments, the interelectrode distance is such that the
- electrospinning apparatus maintains an electric field of about 0.2 kV/mm, 0.25 kV/mm, 0.3 kV/mm, 0.35 kV/mm, 0.4 kV/mm, 0.45 kV/mm, 0.5 kV/mm, 0.55 kV/mm, 0.6 kV/mm,
- the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 30 pm at a rate of at least 0.30 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 30 pm at a rate of at least 0.35 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 35 pm at a rate of at least 0.30 m/min.
- the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 35 pm at a rate of at least 0.35 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of 37 pm at a rate of 0.35 m/min.
- the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 15 pm at a line speed of at least 0.80 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 15 pm at a line speed of at least 0.85 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 15 pm at a rate of at least 0.90 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 15 pm at a rate of at least 0.95 m/min.
- the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 15 pm at a rate of at least 1.0 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 19 pm at a rate of at least 0.80 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 19 pm at a rate of at least 0.85 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 19 pm at a rate of at least 0.90 m/min.
- the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of at least 19 pm at a rate of at least 0.95 m/min. In some embodiments, the electrospinning apparatus is capable of generating a nanofiber mat having a thickness of 19 pm at a rate of 0.98 m/min.
- the electrospinning apparatus is capable of generating a nanofiber mat (e.g., a nanofiber mat having a fiber diameter of no more than 200 nm) with a productivity of above at least 0.20 g/(m-min), above at least 0.21 g/(m-min), above at least 0.22 g/(m-min), above at least 0.23 g/(m-min), above at least 0.24 g/(m-min), above at least 0.25 g/(m-min), above at least 0.26 g/(m-min), above at least 0.27 g/(m-min), above at least 0.28 g/(m-min), above at least 0.29 g/(m-min), above at least 0.30 g/(m-min), above at least 0.31 g/(m-min), above at least 0.32 g/(m-min), or above at least 0.33 g/(m-min).
- a nanofiber mat e.g., a nanofiber mat having a fiber diameter of no
- the electrospinning apparatus is capable of generating a nanofiber mat having a fiber diameter variation of no more than 36%, no more than 29%, no more than 28%, no more than 27%, no more than 26%, no more than 25%, no more than 24%, no more than 23%, no more than 22%, no more than 21%, no more than 20%, no more than 19%, no more than 18%, no more than 17%,.
- electrospinning apparatuses comprising: (a) a spinning electrode; (b) a substrate that is a first distance from the spinning electrode (the substrate distance); and (c) a collecting electrode that is a second distance from the spinning electrode (the interelectrode distance), wherein the apparatus is configured such that the substrate distance and the interelectrode distance are separately adjustable and capable of being configured such that the ratio of the substrate distance to the interelectrode distance is no greater than 1.0.
- the substrate distance can be adjusted without adjusting the interelectrode distance (e.g ., using a knob, lever, motor or button).
- the position of the substrate can be changed (e.g., using a knob, lever, motor or button) without changing the position of the spinning electrode or the collecting electrode.
- the position of the collecting electrode can be changed (e.g, using a knob, lever, motor or button) without changing the position of the spinning electrode or the substrate.
- the position of the spinning electrode, substrate and/or collecting electrode can be independently adjusted remotely (e.g, using a motor controlled by an electronic input, such as computer or other electronic device).
- the position of the spinning electrode, substrate and/or collecting electrode can be adjusted manually without disassembling the apparatus (e.g, using a knob, lever, or button).
- the substrate distance and the interelectrode distance are separately adjustable and capable of being configured such that the ratio of the substrate distance to the interelectrode distance is no more than 0.95, 0.90, 0.85, 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, or 0.35. In certain embodiments, the substrate distance and the interelectrode distance are separately adjustable and capable of being configured such that the ratio of the substrate distance to the interelectrode distance is no greater than 0.77. In some embodiments, the substrate distance and the interelectrode distance are separately adjustable and capable of being configured such that the ratio of the substrate distance to the interelectrode distance is at least 0.20, 0.25, or 0.30.
- the substrate distance and the interelectrode distance are separately adjustable and capable of being configured such that the ratio of the substrate distance to the interelectrode distance is from about 0.77 to about 0.3. In some embodiments, the substrate distance and the interelectrode distance are separately adjustable and capable of being configured such that the ratio of the substrate distance to the interelectrode distance is between 0.80 and 0.70, 0.75 and 0.65, 0.70 and 0.60, 0.65 and 0.55, 0.60 and 0.50, 0.55 and 0.45, 0.50 and 0.40, 0.45 and 0.35, or 0.40 and 0.30.
- the substrate distance and the interelectrode distance are separately adjustable and capable of being configured such that the ratio of the substrate distance to the interelectrode distance is about 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, 0.35 or 0.30.
- the substrate distance can be adjusted to be less than about 200 mm, 190 mm, 180 mm, 170 mm, 160 mm, 150 mm, 140 mm, 130 mm, 120 mm, 110 mm, 100 mm, 90 mm, 80 mm, 70 mm, or 60 mm. In some embodiments, the substrate distance can be adjusted to be at least about 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, or 70 mm. In some embodiments, the substrate distance can be adjusted to be from about 140 mm to about 55 mm.
- the substrate distance can be adjusted to be about 200 mm, 195 mm, 190 mm, 185 mm, 180 mm, 175 mm, 170 mm, 165 mm, 160 mm, 155 mm, 150 mm, 145 mm, 140 mm, 135 mm, 130 mm, 125 mm, 120 mm, 115 mm, 110 mm, 105 mm, 100 mm, 95 mm, 90 mm, 85 mm, 80 mm,
- the interelectrode distance can be adjusted to be such that the electrospinning apparatus maintains an electric field at least 0.2 kV/mm. In some embodiments, the interelectrode distance can be adjusted to be such that the apparatus maintains an electric field of at least 0.2 kV/mm, 0.3 kV/mm, 0.4 kV/mm, 0.5 kV/mm, 0.6 kV/mm, or 0.7 kV/mm. In some embodiments, the interelectrode distance can be adjusted to be such that the apparatus maintains an electric field of no more than 0.8 kV/mm, 0.70 kV/mm, or 0.6 kV/mm.
- the interelectrode distance can be adjusted to be such that the apparatus maintains an electric field of 0.2 kV/mm to 0.8 kV/mm. In some embodiments, the interelectrode distance can be adjusted to be such that the electrospinning apparatus maintains an electric field of about 0.2 kV/mm, 0.25 kV/mm, 0.3 kV/mm, 0.35 kV/mm, 0.4 kV/mm, 0.45 kV/mm, 0.5 kV/mm, 0.55 kV/mm, 0.6 kV/mm,
- the substrate of the apparatuses provided herein can be formed from any material.
- the substrate is a nonwoven fiber substrate.
- the substrate is a non-porous film substrate or paper.
- the substrate is a porous substrate.
- the spinning electrode of the apparatuses provided herein further comprise a nozzle. In some embodiments the spinning electrode is nozzleless. In some embodiments, the spinning electrode comprises a rotating roller or rotating drum or wire.
- the collecting electrode of the apparatuses provided herein comprise a conductive surface.
- the collecting electrode is a flat plate, moving plate or belt, tube, wire, or rotating drum.
- Electrospinning is process of producing nanofibers from a mixture of polymers, for example, polymer solution or polymer melt. The process involves applying an electric potential to such a polymer solution or polymer melt. Certain details of the electrospinning process for making an electrospun nanofiber mat or membrane, including suitable apparatuses for performing the electrostatic spinning process, are described in International Patent Application Publications W02005/024101, W02006/131081, and W02008/106903, each of which is incorporated herein by reference in its entirety.
- fibers are generated from a spinning electrode by applying a high voltage to the electrodes and a polymer solution where fibers are charged or spun toward a collecting electrode and collected as a highly porous non-woven mat on a substrate between the electrodes.
- Needle electrospinning is typically set up where the spinning electrode is a metal syringe, which also dispenses the polymer solution via a syringe pump. Needle electrospinning set- ups are typically performed in custom lab scale or smaller commercially produced machines.
- Needle-less electrospinning provides greater productivity of fiber mass per unit time and length of the spinning electrode and the ability to operate on a wider area and on moving basis to collect continuous roll stock of non-woven fiber mat membranes.
- ELMARCO electrospinning machines function with two types of dispensing of the polymer solution onto the spinning electrode.
- ELMARCO electrospinning machine NS 3S1000ET is a pilot scale unit equipped with 1 to 3 wire spinning electrodes and can deposit nanofiber on a 1.0 m wide moving or stationary substrate.
- ELMARCO electrospinning machine NS 8S1600ET is a production unit, equipped with 1 to 8 wire spinning electrodes and can deposit nanofiber on 1.6 m wide moving or stationary substrate.
- provided herein are methods of producing a non-woven fiber mat using the electrospinning apparatuses disclosed herein comprising an electrospinning a polymer solution from the spinning electrode of the electrospinning apparatus onto the substrate of the electrospinning apparatus, are also provided.
- a nanofiber structure e.g ., a nanofiber mat
- the method comprises electrospinning a polymer solution from the spinning electrode of the apparatus provided herein onto its substrate.
- a nanofiber structure e.g., a nanofiber mat
- methods for producing a nanofiber structure comprising electrospinning a polymer solution from a spinning electrode onto a substrate that is positioned between the spinning electrode and a collecting electrode, wherein the ratio the substrate distance to the interelectrode distance is less than 1.
- the ratio of substrate distance to interelectrode distance is no more than 0.95, 0.90, 0.85, 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, or 0.35. In certain embodiments, the ratio of substrate distance to interelectrode distance is no greater than 0.77. In some embodiments, the ratio of substrate distance to interelectrode distance is at least 0.20, 0.25, or 0.30. In some embodiments, the ratio of the substrate distance to the interelectrode is from about 0.77 to about 0.3.
- the ratio of the substrate distance to the interelectrode distance is between 0.80 and 0.70, 0.75 and 0.65, 0.70 and 0.60, 0.65 and 0.55, 0.60 and 0.50, 0.55 and 0.45, 0.50 and 0.40, 0.45 and 0.35, or 0.40 and 0.30. In some embodiments, the ratio of the substrate distance to the interelectrode distance is about 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, 0.35 or 0.30.
- the substrate distance is no more than about 200 mm, 190 mm, 180 mm, 170 mm, 160 mm, 150 mm, 140 mm, 130 mm, 120 mm, 110 mm, 100 mm, 90 mm, 80 mm, 70 mm, or 60 mm. In some embodiments, the substrate distance is at least about 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, or 70 mm. In some embodiments, the substrate distance is from about 140 mm to about 55 mm.
- the substrate distance is about 200 mm, 195 mm, 190 mm, 185 mm, 180 mm, 175 mm, 170 mm, 165 mm, 160 mm, 155 mm, 150 mm, 145 mm, 140 mm, 135 mm, 130 mm, 125 mm, 120 mm, 115 mm, 1 10 mm, 105 mm, 100 mm, 95 mm, 90 mm, 85 mm, 80 mm, 75 mm, 70 mm, 65 mm, 60 mm, or 55 mm.
- the nanofibers are N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-oxide-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the nanofibers are electrospun at a voltage of 10 kV to 20 kV, 15 kV to 25 kV, 20 kV to 30 kV, 25 kV to 35 kV, 30 kV to 40 kV, 35 kV to 45 kV, 40 kV to 50 kV, 45 kV to 55 kV, 50 kV to 60 kV, 55 kV to 65 kV, 60 kV to 70 kV, 65 kV to 75 kV, 70 kV to 80 kV, 75 kV to 85 kV, 80 kV to 90 kV, 85 kV to 95 kV, 90 kV to 100 kV, 95
- the interelectrode distance is such that the electrospinning apparatus maintains an electric field at least 0.2 kV/mm. In some embodiments, the interelectrode distance is such that the apparatus maintains an electric field of at least 0.2 kV/mm, 0.3 kV/mm, 0.4 kV/mm, 0.5 kV/mm, 0.6 kV/mm, or 0.7 kV/mm. In some embodiments, the interelectrode distance is such that the apparatus maintains an electric field of no more than 0.8 kV/mm, 0.70 kV/mm, or 0.6 kV/mm. In some embodiments, the interelectrode distance is such that the apparatus maintains an electric field of 0.2 kV/mm to 0.8 kV/mm. In some embodiments, the interelectrode distance is such that the
- electrospinning apparatus maintains an electric field of about 0.2 kV/mm, 0.25 kV/mm, 0.3 kV/mm, 0.35 kV/mm, 0.4 kV/mm, 0.45 kV/mm, 0.5 kV/mm, 0.55 kV/mm, 0.6 kV/mm,
- the polymer solution comprises a polymer or a polymer blend.
- the polymer or polymer blend is selected from nylon-6, nylon-46, nylon-66, polyaramids, polyurethane (PU), polybenzimidazole, polycarbonate, polyacrylonitrile, polyvinyl alcohol, polylactic acid (PLA), polyethylene-co- vinyl acetate (PEVA), PEVA/PLA, polymethylmethacrylate (PMMA),
- PMMA/tetrahydroperfluorooctylacrylate TAN
- polyethylene oxide PEO
- collagen-PEO collagen-PEO
- polystyrene PS
- polyaniline PANI
- PANI polyaniline
- polyvinylcarbazole polyethylene terephthalate
- PET polyacrylic acid-polypyrene methanol
- PAA-PM polyacrylic acid-polypyrene methanol
- PA polyamide
- PA silk/PEO
- PVP polyvinylphenol
- PVC polyvinylchloride
- CA cellulose acetate
- PAA- RM/REG polyvinyl alcohol (PVA)/silica
- PAAm polyacrylamide
- PAAm poly(lactic-co-glycolic acid)
- PCL polycarprolactone
- HEMA poly(2-hydroxyethyl methacrylate)
- PVDF poly(vinylidene difluoride)
- PVDF PVDF/PMMA
- PCL polyvinyl porrolidone
- polymetha-phenylene isophthalamide polyethylene (PE), polypropylene (PP), nylon- 12, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), polyvinyl butyral (PVB), PET/PEN, or a blend thereof.
- the substrate of the apparatuses provided herein can be formed from any material.
- the substrate is a nonwoven fiber substrate.
- the substrate is a non-porous film substrate.
- the substrate is a porous substrate.
- the substrate is a paper.
- the substrate is grounded.
- the spinning electrode of the apparatuses provided herein further comprise a nozzle. In some embodiments the spinning electrode is nozzleless. In some embodiments, the spinning electrode comprises a rotating roller or rotating drum or wire.
- the collecting electrode of the apparatuses provided herein comprise a conductive surface.
- the collecting electrode is a flat plate, moving plate, tube, wire, or rotating drum.
- the nanofiber mat is generated at a line speed of 0.03 m/min to 1 m/min.
- the line speed is at least about 0.03 m/min, 0.04 m/min, 0.05 m/min, 0.06 m/min, 0.07 m/min, 0.08 m/min, 0.09 m/min, 0.10 m/min, 0.11 m/min, 0.12 m/min, 0.13 m/min, 0.14 m/min, 0.15 m/min, 0.16 m/min, 0.17 m/min, 0.18 m/min, 0.19 m/min, 0.20 m/min, 0.21 m/min, 0.22 m/min,.
- the line speed is about 0.03 m/min, 0.04 m/min, 0.05 m/min, 0.06 m/min, 0.07 m/min, 0.08 m/min, 0.09 m/min, 0.10 m/min, 0.11 m/min, 0.12 m/min, 0.13 m/min, 0.14 m/min, 0.15 m/min, 0.16 m/min, 0.17 m/min, 0.18 m/min, 0.19 m/min, 0.20 m/min, 0.21 m/min, 0.22 m/min,.
- the product of the method is a nanofiber mat.
- the produced nanofiber mat has a thickness from about 1 pm to about 500 pm.
- the nanofiber mat has a thickness of at least 5 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 35 pm, 40 pm, 45 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm,
- the nanofiber mat has a thickness of about 5 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 35 pm, 40 pm, 45 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm, 175 pm, 180 pm, 185 pm, 190 pm, 195 pm, 200 pm, 205 pm, 210 pm, 215 pm, 220 pm, 225 pm, 230 pm, 235 pm, 240 pm, 245 pm, 250 pm, 255 pm, 260 pm, 265 pm, 270 pm, 275 pm, 280 pm, 285 pm, 290 pm, 295 pm, 300 pm, 305 pm, 310 pm, 315 pm, 320 pm, 325 pm, 330 pm, 335 pm, 340
- the produced nanofiber structure (e.g ., nanofiber mat) has an average fiber diameter from about 10 nm to about 1000 nm.
- the fiber diameter has a wide distribution ranging 16-36 % CoV.
- the average nanofiber diameter is no more than 1000 nm, 950 nm, 900 nm, 850 nm, 800 nm.
- the average nanofiber diameter is 10 nm to 20 nm, 15 nm to 25 nm, 20 nm to 30 nm, 25 nm to 35 nm, 30 nm to 40 nm, 35 nm to 45 nm, 40 nm to 50 nm, 45 nm to 55 nm, 50 nm to 60 nm, 55 nm to 65 nm, 60 nm to 70 nm, 65 nm to 75 nm, 70 nm to 80 nm, 75 nm to 85 nm,
- the produced nanofiber structure e.g ., nanofiber mat
- has a maximum pore size as determined by bubble point test i.e., as set forth in ASTM
- Designation F316-03 “Standard Test Methods for Pore Size Characteristic of Membrane Filters by Bubble Point and Mean Flow Pore Test”, as reapproved in 2011) of no more than 500 nm, 450 nm, 400 nm, 350 nm, 300 nm, 250 nm 200 nm, 150 nm, 100 nm, or 50 nm.
- the produced nanofiber structure (e.g ., nanofiber mat) has a maximum pore size as determined by bubble point test of 10 nm to 20 nm, 15 nm to 25 nm, 20 nm to 30 nm, 25 nm to 35 nm, 30 nm to 40 nm, 35 nm to 45 nm, 40 nm to 50 nm, 45 nm to 55 nm, 50 nm to 60 nm, 55 nm to 65 nm, 60 nm to 70 nm, 65 nm to 75 nm, 70 nm to 80 nm,
- the produced electrospun structure (e.g., electrospun mat) has a porosity of at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%. In some embodiments, the porosity is 70% to 95%, 75% to 95%, 80% to 95%, 85% to 95%. or 90% to 95%.
- the produced electrospun structure (e.g., electrospun mat) has a basis weight of at least about 1 gsm. In some, the electrospun structure has a basis weight of at least about 4 gsm. In some, the electrospun structure has a basis weight of at least about 5 gsm. In some, the electrospun structure has a basis weight of at least about 6 gsm. In some, the electrospun structure has a basis weight of at least about 7 gsm. In some, the electrospun structure has a basis weight of at least about 8 gsm.
- the method provided herein generates a nanofiber mat having a thickness of at least 35 pm and is generated at a line speed rate of at least 0.3 m/min. In some embodiments, the method provided herein generates a nanofiber mat having a thickness of at least 35 pm and is generated at a line speed rate of at least 0.35 m/min. In some embodiments, the method provided herein generates a nanofiber mat having a thickness of at least 15 pm and is generated at a line speed rate of at least 0.8 m/min. In some embodiments, the method provided herein generates a nanofiber mat having a thickness of at least 15 pm and is generated at a line speed rate of at least 0.9 m/min. In some embodiments, the method provided herein generates a nanofiber mat having a thickness of at least 15 pm and is generated at a line speed rate of at least 0.95 m/min.
- the method provided herein generates a nanofiber mat having a basis weight of at least 4.5 gsm and is generated at a line speed of at least 0.35 m/min. In some embodiments, the method provided herein generates a nanofiber mat having a basis weight of at least 2.4 gsm and is generated at a line speed of at least 0.60 m/min. In some embodiments, the method provided herein generates a nanofiber mat having a basis weight of at least 4.0 gsm and is generated at a line speed of at least 0.5 m/min. In some embodiments, the method provided herein generates a nanofiber mat having a basis weight of at least 2.3 gsm and is generated at a line speed of at least 0.9 m/min.
- the methods provided herein have a line speed of about 0.1 m/min, a ratio of the substrate distance to the interelectrode distance of about 0.25 to about 0.35, an electric field of about 0.57 kV/mm, and the produced electrospun mat has an average fiber diameter of about 100 nm to about 200 nm, and a basis weight of at least about 1.5 gsm, at least about 1.75 gsm, or at least about 2.0 gsm.
- the methods provided herein have a line speed of about 0.1 m/min, a ratio of the substrate distance to the interelectrode distance of about 0.45 to about 0.55, an electric field of about 0.7 kV/mm, and the produced electrospun mat has an average fiber diameter of about 100 nm to about 200 nm and a basis weight of at least about 3.1 gsm, at least about 3.2 gsm, or at least about 3.3 gsm.
- the nanofiber mat (e.g ., a nanofiber mat having a fiber diameter of no more than 200 nm) is generated with a productivity of above at least 0.20 g/(m-min), above at least 0.21 g/(m-min), above at least 0.22 g/(m-min), above at least 0.23 g/(m-min), above at least 0.24 g/(m-min), above at least 0.25 g/(m-min), above at least 0.26 g/(m-min), above at least 0.27 g/(m-min), above at least 0.28 g/(m-min), above at least 0.29 g/(m-min), above at least 0.30 g/(m-min), above at least 0.31 g/(m-min), above at least 0.32 g/(m-min), or above at least 0.33 g/(m-min).
- the nanofiber mat is produced with a productivity that is at least 5%, 10%, 15%, 20%, 25%, 30%, 30%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% higher than it would have been under identical conditions except that the ratio of the distance between the spinning electrode and the substrate (the substrate distance) to the distance between the spinning electrode and the collecting electrode (the interelectrode distance) been 1.
- the nanofiber mat is produced with a productivity that is at least 5%, 10%, 15%, 20%, 25%, 30%, 30%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% higher than it would have been under identical conditions except that the ratio of the distance between the spinning electrode and the substrate (the substrate distance) to the distance between the spinning electrode and the collecting electrode (the interelectrode distance) been 0.88.
- the generated nanofiber mat has a fiber diameter variation of no more than 30%, no more than 29%, no more than 28%, no more than 27%, no more than 26%, no more than 25%, no more than 24%, no more than 23%, no more than 22%, no more than 21%, no more than 20%, no more than 19%, no more than 18%, no more than 17%.
- the nanofiber mat has a fiber diameter variation that is within 5%, 10%, 15%, or 20%, of what it would have been under identical conditions except that the ratio of the distance between the spinning electrode and the substrate (the substrate distance) to the distance between the spinning electrode and the collecting electrode (the interelectrode distance) been 1. In some embodiments, the nanofiber mat has a fiber diameter variation that is within 5%, 10%, 15%, or 20%, of what it would have been under identical conditions except that the ratio of the distance between the spinning electrode and the substrate (the substrate distance) to the distance between the spinning electrode and the collecting electrode (the interelectrode distance) been 0.88. Test Methods
- basis weight is determined according to ASTM procedure D- 3776 /D3776M -09a (2017),“Standard Test Methods for Mass Per Unit Area (Weight) of Fabric,” and reported in g/m 2 .
- fiber diameter is determined as follows: A scanning electron microscope (SEM) image was taken at ( e.g ., at 20,000, 40,000 or 60,000 times
- Irregularities were not included (i.e., lumps of nanofibers, polymer drops, intersections of nanofibers, etc.).
- the average fiber diameter for both sides of each sample is calculated and averaged to result in a single average fiber diameter value for each sample.
- nanofiber mat thickness is determined according to ASTM procedure 01777-96,“Standard Test Method for Thickness of Textile Materials,” and is reported in nanometers (nm) or micrometers (pm).
- Productivity is calculated as the product of the basis weight (g/m 2 ) and line speed (m/min) and is directly related to the process economy.
- productivity is normalized on a per-electrode basis (i.e., total productivity divided by the number of electrodes).
- maximum pore size is determined by bubble point test as set forth in ASTM Designation F316-03,“Standard Test Methods for Pore Size Characteristic of Membrane Filters by Bubble Point and Mean Flow Pore Test”, as reapproved in 2011, and is reported in nanometers (nm).
- substrate distance is the shortest distance between the substrate and the spinning electrode.
- inter electrode distance is the shortest distance between the spinning electrode and the collecting electrode. Such distances can be measured using any method known in the art (e.g., using measuring tape).
- the electrospinning solution was prepared by dissolving Nylon 6,6 obtained from Sigma Aldrich in a mixture of three parts formic acid and one-part acetic acid at 80°C for five hours.
- Samples were produced on a modified NS 3S1000U electrospinning apparatus (Elmarco s.r.o. Liberec. CZ) retrofitted with a 50 cm long, l-wire spinning electrode. On this instrument, samples were produced continuously in a roll to roll fashion in which the substrate moved over spinning electrodes at a constant speed. Samples were spun at 21 °C temperature, 4°C dew point and 0.1 m/min line speed. BPM 85 Paper from Branopac, GmbH was used as a substrate on which the Nylon 6,6 nanofibers were collected.
- the solution was spun with nominal voltage of 80 kV and 100 kV, and electric field of 0.57 kV/mm and 0.70 kV/mm at substrate distances of 140 mm and 55 mm for 30 minutes.
- the electrospun nanofiber mats were then characterized to determine their basis weight (BW), thickness and fiber diameter.
- FIG. 5 shows a schematic of the electrospinning apparatus based on the parameters of ( Figure 5, rows 5-7).
- An electrospinning solution was prepared by dissolving 14% Nylon 6 obtained from BASF (Grade B17E) in a mixture of one-part formic acid and two-parts acetic acid at 80°C for five hours. Samples were produced on a modified NS8S1600U electrospinning apparatus, (Elmarco s.r.o. Liberec. CZ). On this equipment, samples were produced continuously in a roll to roll fashion where the substrate moves over spinning electrodes at a constant speed. All samples were spun at 22 °C temperature, 4°C dew point. Reemay 6125 nonwoven, commercially available from Berry Global (Waynesboro, VA) was used as a substrate on which Nylon 6 nanofibers were collected. Figure 5 (rows 8-11) summarizes the results of these conditions.
- Figure 4 provides a schematic of two sets of process settings used on above mentioned equipment to electrospun fibers.
- the first set of process settings consisted of nominal voltage of 100 kV, electric field of 0.49 kV/mm and substrate distance of 180 mm. The samples were collected at line speeds of 0.35 and 0.54 m/min.
- the second set of process settings consisted of nominal voltage of 104 kV, electric field of 0.5lkV/mm and substrate distance of 155 mm. The samples were collected at line speeds ranging 0.35-0.98 m/min.
- the electrospun nanofiber mats were then characterized to determine their basis weight (BW), thickness and fiber diameter.
- Figure 5 (rows 8-11) summarizes the process settings used and the properties of the membranes produced.
- Comparison of the results obtained in experiment 8 and with those obtained in experiment 10 demonstrated ability to achieve the same membrane properties (basis weight, thickness, and fiber diameter) at a 1.4-fold faster line speed, just by lowering the substrate distance to interelectrode distance ratio.
- comparing the results of experiment 9 and experiment 11 demonstrated ability to achieve the same membrane properties (basis weight, thickness, and fiber diameter) at 1.5-fold faster line speed by lowering the substrate distance to interelectrode distance ratio.
- Faster line speed represents higher productivity. Specifically, the increase in productivity was possible, even by keeping electric field approximately the same, by reducing the substrate distance, or ratio of substrate distance to interelectrode distance from 0.9 to 0.8.
- the comparison is primarily based on the distance ratio.
- Figure 7 shows Scanning Electron Microscope (SEM) images of the electrospun nanofiber generated at (a) standard conditions in experiment 9 and (b) high productivity settings in experiment 10. The micrograph shows comparable fiber structures were obtained at both settings.
- Figure 6 (Exp # 1, 2 and 4,3 ) shows that 1.6 fold and 1.1 fold increase in productivity was acheived at electric field of 0.57 and 0.7 kV/mm, respectively.
- Figure 6, panel-b (Exp# 6 and 7) shows another example of productivity improvement, particularly at a lower substrate speed (0.04 m/min), where 1.6 fold increase was observed even at high electric field of 0.7 kV/mm.
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Abstract
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Priority Applications (7)
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EP19806360.4A EP3877574A1 (en) | 2018-11-01 | 2019-10-31 | Efficient production of nanofiber structures |
CA3116905A CA3116905A1 (en) | 2018-11-01 | 2019-10-31 | Efficient production of nanofiber structures |
CN201980081896.1A CN113195802A (en) | 2018-11-01 | 2019-10-31 | Efficient production of nanofiber structures |
KR1020217013160A KR20210058979A (en) | 2018-11-01 | 2019-10-31 | Efficient production of nanofiber structures |
JP2021523066A JP2022505970A (en) | 2018-11-01 | 2019-10-31 | Efficient manufacturing of nanofiber structures |
US17/290,024 US20210355606A1 (en) | 2018-11-01 | 2019-10-31 | Efficient production of nanofiber structures |
SG11202103725VA SG11202103725VA (en) | 2018-11-01 | 2019-10-31 | Efficient production of nanofiber structures |
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