WO2018161071A1 - Encapsulation facile de colorants par électropulvérisation à commande pneumatique - Google Patents

Encapsulation facile de colorants par électropulvérisation à commande pneumatique Download PDF

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Publication number
WO2018161071A1
WO2018161071A1 PCT/US2018/020885 US2018020885W WO2018161071A1 WO 2018161071 A1 WO2018161071 A1 WO 2018161071A1 US 2018020885 W US2018020885 W US 2018020885W WO 2018161071 A1 WO2018161071 A1 WO 2018161071A1
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WO
WIPO (PCT)
Prior art keywords
capillary
air
fluid samples
electrospray
polymer
Prior art date
Application number
PCT/US2018/020885
Other languages
English (en)
Inventor
Timothy Batty
Yong Lak Joo
Mani KORAH
Yevgen ZHMAYEV
Original Assignee
Idealchain, Llc
Cornell University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idealchain, Llc, Cornell University filed Critical Idealchain, Llc
Publication of WO2018161071A1 publication Critical patent/WO2018161071A1/fr

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/0255Discharge apparatus, e.g. electrostatic spray guns spraying and depositing by electrostatic forces only
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5089Processes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51Nanocapsules; Nanoparticles
    • A61K9/5192Processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/04Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/043Drying and spraying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/03Discharge apparatus, e.g. electrostatic spray guns characterised by the use of gas, e.g. electrostatically assisted pneumatic spraying
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/008Preparations of disperse dyes or solvent dyes
    • C09B67/0082Preparations of disperse dyes or solvent dyes in liquid form
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes

Definitions

  • the invention relates generally to a system and method for nanoencapsulation and more particularly, nanoencapsulation of dyes via an air-controlled electrospray system.
  • mechanical coating techniques of substrates include various conventional techniques, such as roll coating, knife coating, etc.
  • such mechanical coating techniques can often result in a surface coating having a non-uniform thickness differential that is greater than about 5 micrometers ( ⁇ ) over the substrates.
  • the materials, such as solvents utilized during such processes can further contribute to the issues related to the uniformity due, at least in part, to issues, such as solubility, compatibility, stability and the like.
  • electrospray technique is a method of electrostatic atomization of a liquid or a solution to obtain charged micron-sized droplets, resulting in charged clusters and ions.
  • the nozzle of the atomizer utilized in the electrospray process is typically made in the form of a metal capillary, which is biased by a high voltage.
  • a solution of the material that is to be deposited onto the substrate is introduced into the metal capillary and the application of high voltage results in instability of the solution.
  • the solution is then dispersed into small charged droplets that are about 0.3 to 20 microns in diameter. These droplets typically cover an upper surface of the substrate and coalesce to form a continuous coating over the substrate.
  • the present invention is directed to, inter alia, a method for providing a coating layer over a substrate, such as a nanofiber.
  • one or more fluid sample(s) may be introduced into an electrospray apparatus which, for instance, may include a capillary that is charged to a high electric potential by a high power supply.
  • the fluid sample(s) may be, or may include, chemical components, such as a dye material, a polymer material, a solvent and the like. Each of these chemical components facilitates forming discrete droplets of a dye material that is encapsulated within a polymer material.
  • each of these polymer-encapsulated dye droplets may be dispersed as capsules via the electrospray apparatus disclosed herein to provide a uniform coating layer over the nanofiber substrate.
  • the electrospray apparatus includes an air-flow system that is, at least in part, coaxially aligned with the capillary so as to provide high-speed, circumferentially uniform air flow which can provide enhanced deformation of the droplets.
  • such enhanced deformation of the droplets provides several benefits such as: (i) enhanced production rate (i.e., that is ten to hundred fold order of magnitude than that of conventional electrospray apparatus); (ii) better control of dispersion of nanoinclusions in each droplet; and (iii) better control of directing each droplet toward the collector so as to provide uniform sub-micron scale coating layers over the substrate.
  • an electrospray apparatus includes: a capillary having a spray area for ejecting a plurality of fluid samples; an air-flow system that is, at least in part, coaxially aligned with the spray area of the capillary; a collector located, at least in part, spaced perpendicular to the capillary, the capillary including a substrate; and a voltage supply means that creates a potential difference between the spray area of the capillary and the collector, the potential difference being sufficient to eject the fluid as a uniform stream of droplets, wherein circumferentially uniform air-flow from the air-flow system defines a size of each of the droplets.
  • a method for providing a coating layer over a substrate includes: providing a plurality of fluid samples disposed, at least in part, within an electrospray apparatus, the electrospray apparatus comprising: a capillary having a spray area for ejecting a plurality of fluid samples; an airflow system that is, at least in part, coaxially aligned with the spray area of the capillary; a collector located, at least in part, spaced perpendicular to the capillary, the capillary including a substrate; and electrostatically atomizing the plurality of fluid samples to form a uniform stream of droplets, the plurality of fluid samples being electrostatically atomized in presence of circumferentially uniform air-flow from the air-flow system that defines a size of each of the droplets.
  • an electrospray apparatus includes: a capillary having a spray area for ejecting a plurality of fluid samples; a collector located, at least in part, spaced perpendicular to the capillary, the capillary including a substrate; and a voltage supply means that creates a potential difference between the spray area of the capillary and the collector, the potential difference being sufficient to eject the fluid as a uniform stream of droplets.
  • a method for providing a coating layer over a substrate includes: providing a plurality of fluid samples disposed, at least in part, within an electrospray apparatus, the electrospray apparatus comprising: a capillary having a spray area for ejecting a plurality of fluid samples; a collector located, at least in part, spaced perpendicular to the capillary, the capillary including a substrate; and electrostatically atomizing the plurality of fluid samples to form a uniform stream of droplets.
  • FIG. 1 is a schematic representation of a conventional electrospray system
  • FIG. 2A is a schematic representation of an illustrative embodiment of an air-controlled electrospray system
  • FIG. 2B is an alternative schematic representation of an illustrative embodiment of an air-controlled electrospray system
  • FIG. 3 is a schematic representation of an illustrative embodiment of the air-controlled electrospray system for providing a coating layer over a nanofiber;
  • FIG. 4 depicts representative examples of scanning electron microscope (SEM) micrographs of each of one or more droplets having a polymer-encapsulated dye material that is dispersed via air-controlled electrospray system;
  • FIG. 5 depicts additional representative examples of scanning electron microscope (SEM) micrographs of a nanofiber coated with the dye encapsulated with polymer(s) via the air-controlled electrospray system, in accordance with one or more aspects of the present invention.
  • SEM scanning electron microscope
  • FIG. 6 depicts a representative example of mechanochromic response of the nanofiber coated with the dye encapsulated with polymer(s) to compressive deformation
  • FIG. 7 depicts additional representative example of mechanochromic response of the nanofiber coated with the dye encapsulated with polymer(s) to extensional deformation.
  • FIG. 1 there is shown a conventional electrospray system.
  • the depicted conventional electrospray system includes a capillary, which applies high voltage to a solution when the solution is injected into the capillary.
  • the solution is atomized into fine charged droplets, as shown.
  • the charged droplets produced by the conventional electrospray system are relatively large and are dispersed one at a time.
  • conventional electrospray systems have a low throughput.
  • the dimensions, size, and geometries of the droplets dispersed are not controllable with the conventional electrospray system shown in FIG. 1.
  • the enhanced size of each droplet produced by the conventional electrospray system inadvertently damages the substrate material on which it is electrosprayed.
  • the damage is due, at least in part, to issues related to stress, such as compressive stress and/or tensile stress.
  • FIGs. 2A-2B there are shown a schematic representation of an illustrative embodiment of an air-controlled electrospray system 100.
  • the air-controlled electrospray system 100 includes an electrospray apparatus 102 having a capillary 104 that is charged to a high electric (HV) potential, by high voltage (HV) power supply.
  • a collector 106 that includes a substrate 108 is located, at least in part, spaced perpendicular to the capillary 104 during use of the air- controlled electrospray system 100.
  • the collector 106 that includes the substrate 108 may be located at an angle of about 10° to approximately 100° relative to the capillary 104.
  • one or more fluid samples are injected into the capillary 104 of the electrospray apparatus 102.
  • the fluid sample(s) may be injected or otherwise inserted into the capillary 104 via a feeder (not shown), such as a syringe pump or a reservoir, either of which is attached, at least in part, to the electrospray apparatus 102.
  • the electrospray apparatus 102 may include an air-flow system that is, at least in part, coaxially aligned with the capillary 104, thereby defining an air-controlled electrospray apparatus 102.
  • the air-flow system that is coaxially aligned with the capillary 104 advantageously provides high-speed, circumferentially uniform air flow which can provide enhanced deformation of the droplets 110 as disclosed further below.
  • the polymer-encapsulated dye material is subjected to electrostatic atomization by exposing the chemical components to an intense electric field 112 (i.e., between the charged atomizer (e.g., capillary 104) and the collector 106) in the presence of high-speed, circumferentially uniform air-flow (that, for instance, is obtained from the air-flow system) to form the discrete polymer-encapsulate dye capsules.
  • an intense electric field 112 i.e., between the charged atomizer (e.g., capillary 104) and the collector 106) in the presence of high-speed, circumferentially uniform air-flow (that, for instance, is obtained from the air-flow system) to form the discrete polymer-encapsulate dye capsules.
  • electrostatic atomization refers to conversion of the fluid material into very fine particles or droplets 110 by electrostatic forces
  • the fluid sample(s) injected into the capillary 104 of the electrospray apparatus 102 includes chemical components, such as a dye material (e.g., oil red), a polymer material (e.g., polystyrene and polyvinylidene fluoride), and a solvent.
  • a dye material e.g., oil red
  • a polymer material e.g., polystyrene and polyvinylidene fluoride
  • solvent e.g., a solvent
  • each of these chemical components is combined, at least in part, within the electrospray apparatus 102 to form the dye material that is encapsulated within the polymer material (referred to herein as "polymer-encapsulated dye material").
  • the polymer-encapsulated dye material is electrostatically atomized to form discrete polymer-encapsulate dye droplets 110, which are then dispersed as capsules to provide a uniform coating layer over the substrate 108.
  • the substrate 108 is a nanofiber, although, in alternative embodiments, the substrate 108 is a different webbing product or micro-fiber.
  • the fluid sample comprising the chemical components, such as the dye material (e.g., oil red), polymer material (e.g., polystyrene and polyvinylidene fluoride), and solvent is injected into the electrospray apparatus 102.
  • the dye material is dissolved in the solvent, such as an organic solvent, for example.
  • the chemical components are then electrosprayed with the air-controlled electrospray system 100. Atomization in the electrospraying process causes the solvent to evaporate.
  • the solvent is evaporated while the dye material is encapsulated within the polymer, which results in stretching (i.e., deforming) of each droplet 110 as it proceeds towards the collector 106.
  • Such enhanced deformation of each droplet 110 advantageously, facilitates solidifying each droplet 110 into minute capsules that are deposited over the substrate 108 material.
  • the polymer material migrates to the surface of the dye material, forming the polymer- encapsulated dye droplet 110, because the solvent is a poor solvent to the polymer.
  • the capsules produced by the air-controlled electrospray system 100 are 70% smaller in diameter as compared to capsules produced by conventional electrospray systems. Accordingly, the capsules produced by the air-controlled electrospray system 100 can be sub-micron size.
  • the size of each of the droplets 110 may vary between microns to sub-micron sizes, the size depends upon various parameters, such as the flow rate of the chemical components being dispersed, applied voltage and fluid electric conductivity, and air-flow pressure. For example, the size of each of these droplets/capsules 110 is reduced by an order of magnitude of about micron to sub-micron size, owing to surface tension.
  • each droplet 110 is defined by the size of encapsulation of the dye material by the polymer material.
  • the high-speed, circumferentially uniform air-flow from the coaxially-aligned air-flow system advantageously facilitates enhanced deformation of each droplet 110 by stretching and breaking the droplet 110 into minute capsules, thereby providing enhanced atomization of the polymer-encapsulated dye material.
  • production of the capsules increases at least 10-fold with the air-controlled electrospray system 100.
  • solvent evaporation occurs at a faster rate (as compared to that for conventional electrospray systems)
  • the size and shape of the capsules is more uniform when the air-controlled electrospray system 100 is used.
  • FIG. 4 there are shown representative examples of scanning electron microscope (SEM) micrographs of each of one or more droplets 110 having a polymer-encapsulated dye material that are dispersed via air-controlled electrospray system 100.
  • SEM scanning electron microscope
  • the SEM micrographs depicted in FIG. 4 reveal the size of each of these capsules that include polymer-encapsulated dye material.
  • the dye material is encapsulated within polymers, such as, polystyrene and polyvinylidene fluoride.
  • the exemplary polymers of FIG. 4 are presented by way of example only. Those skilled in the art will understand that other polymers, dye materials, and various other materials that are typically used with a conventional electrospray apparatus (in FIG. 1) could be employed for providing a coating layer over the substrate 108, such as nylon nanofibers or any conventional webbing products and/or micro-fibers.
  • droplets 110 of the dye material encapsulated within a polyvinylidene fluoride polymer having an average diameter of about 3 ⁇ are dispersed at a flow rate of about 0.009 mL/min, as depicted from the SEM micrographs depicted in FIG. 4.
  • each of these droplets 110 exit from the capillary 104 (for instance, having a 16/12 gauge capillary tube with a diameter of about 18 cm) in the presence of an air-flow (i.e., from the co-axially aligned air-flow system) at a pressure of about 8 psi, at an applied voltage of about 12 kV.
  • droplets 100 of the dye material encapsulated within a polystyrene polymer having an average diameter of about 0.96 nm are dispersed at a flow rate of about 0.03 mL/min, as depicted from the SEM micrographs depicted in FIG. 4.
  • each of these droplets 100 exit from the capillary 104 (for instance, having a 20/10 gauge capillary tube with a diameter of about 20 cm) in the presence of an air-flow (i.e., from the co-axially aligned air-flow system) at a pressure of about 8 psi, at an applied voltage of about 18 kV.
  • an air-flow i.e., from the co-axially aligned air-flow system
  • the size distributions for each of the polystyrene-encapsulated dye capsule and polyvinylidene fluoride-encapsulated dye capsule are about 3 ⁇ ⁇ 1.3 ⁇ and 0.96 nm ⁇ 0.28 nm, respectively.
  • the small droplet 110 size and their uniform size distribution resulted from the effective atomization of air-controlled electrospray where both controlled high-speed air stream and high electric field gradient enable synergistically breaking the jet into small uniform droplets 110.
  • each of the polymer-encapsulated dye material can be directly electrosprayed using the air-controlled electrospray apparatus 100 to provide a uniform coating layer over the substrates, such as, such as, nylon nanofibers or any conventional webbing products and/or micro-fibers, as depicted in FIG. 5.
  • the resulting polymer-encapsulated dye material that is incorporated in substrates 108 such as, nylon nanofibers (referred to herein as "nanofiber composite material") has been found to undergo compression. As depicted in FIG. 6, the rupture of polymer-encapsulated dye capsule increased with increase in the compressive force, revealing more of the dye material disposed therein.
  • This effective mechanochromic response to compressive deformation may be used as an indicator of stress (for instance, such as, compressive stress) that each of the capsule that is exposed to in various safety equipment, such as, helmets, fall protection devices, fall restriction devices, fall arrest devices, fall restraint systems, work positioning devices, shock indicating devices, personal protection devices, harnesses, lifelines, anchorage systems, personal access systems, connecting devices, wear protection devices, rescue devices, webbing, rope and wire, descent devices, load arresting devices and the like.
  • various safety equipment such as, helmets, fall protection devices, fall restriction devices, fall arrest devices, fall restraint systems, work positioning devices, shock indicating devices, personal protection devices, harnesses, lifelines, anchorage systems, personal access systems, connecting devices, wear protection devices, rescue devices, webbing, rope and wire, descent devices, load arresting devices and the like.
  • “mechanochromism” refers to the change of color that occurs when chemicals, such as, polymer-encapsulated dye capsule/droplet are subjected to stress in their solid state by deformation, such as, mechanical grinding, crushing or milling, and the like.
  • FIG. 7 there are shown additional representative example of mechanochromic response of the nanofiber coated with the dye encapsulated with polymer(s) to extensional deformation, in accordance with one or more aspects of the present invention.
  • elongation of spirally wound polymer-encapsulated dye capsule incorporated, at least in part, within the substrate, such as, nanofiber leads to compression and rupture of each of these capsules.
  • the rupture of each of these capsules is dependent upon the binding and/or the strength, for instance, of the nanofiber, as evident from FIG. 7.
  • the capsules that include dye material encapsulated within the polystyrene polymer exhibited more sensitive rupture upon extension, possibly due to their large capsule sizes, while the sub-micro sized capsules that include the dye material encapsulated within the polyvinylidene fluoride polymer may withstand extensional deformation.
  • a method or device that "comprises”, “has”, “includes” or “contains” one or more steps or elements possesses those one or more features, but is not limited to possessing only those one or more features.
  • a device or structure that is configured in a certain way is configured in at least that way, but may also be configured in ways that are not listed.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Veterinary Medicine (AREA)
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  • Nanotechnology (AREA)
  • Biomedical Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un appareil d'électropulvérisation (100) et une méthode pour fournir une couche de revêtement sur un substrat (108), qui comprennent : un capillaire (104) ayant une zone de pulvérisation pour éjecter une pluralité d'échantillons de fluide; un système d'écoulement d'air qui est, au moins en partie, aligné de manière coaxiale avec la zone de pulvérisation du capillaire; un collecteur (106) situé, au moins en partie, à distance perpendiculaire du capillaire (104), le collecteur (106) comprenant un substrat (108); et un moyen d'alimentation en tension qui crée une différence de potentiel entre la zone de pulvérisation du capillaire (104) et le collecteur (106), la différence de potentiel étant suffisante pour éjecter la pluralité d'échantillons de fluide sous la forme d'un flux uniforme de gouttelettes (110), le flux d'air uniforme de manière circonférentielle provenant du système d'écoulement d'air définissant une taille de chacune des gouttelettes (110).
PCT/US2018/020885 2017-03-03 2018-03-05 Encapsulation facile de colorants par électropulvérisation à commande pneumatique WO2018161071A1 (fr)

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US201762466739P 2017-03-03 2017-03-03
US62/466,739 2017-03-03

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4779805A (en) * 1982-10-13 1988-10-25 Imperial Chemical Industries Plc Electrostatic sprayhead assembly
US4795330A (en) * 1986-02-21 1989-01-03 Imperial Chemical Industries Plc Apparatus for particles
US20010003148A1 (en) * 1997-07-22 2001-06-07 Coffee Ronald Alan Dispensing device and method for forming material
US20150352592A1 (en) * 2006-01-31 2015-12-10 Nanocopoeia, Inc. Electrospray coating of objects
WO2016140570A1 (fr) * 2015-03-05 2016-09-09 Technische Universiteit Delft Micro-particules sur mesure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4779805A (en) * 1982-10-13 1988-10-25 Imperial Chemical Industries Plc Electrostatic sprayhead assembly
US4795330A (en) * 1986-02-21 1989-01-03 Imperial Chemical Industries Plc Apparatus for particles
US20010003148A1 (en) * 1997-07-22 2001-06-07 Coffee Ronald Alan Dispensing device and method for forming material
US20150352592A1 (en) * 2006-01-31 2015-12-10 Nanocopoeia, Inc. Electrospray coating of objects
WO2016140570A1 (fr) * 2015-03-05 2016-09-09 Technische Universiteit Delft Micro-particules sur mesure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JAWOREK ET AL: "Electrospraying route to nanotechnology: An overview", JOURNAL OF ELECTROSTATICS, ELSEVIER SCIENCE PUBLISHERS B.V. AMSTERDAM, NL, vol. 66, no. 3-4, 28 January 2008 (2008-01-28), pages 197 - 219, XP022510125, ISSN: 0304-3886, DOI: 10.1016/J.ELSTAT.2007.10.001 *

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