EP3187252A1 - Procédé et dispositif de génération d'émulsions micrométriques simples et composées - Google Patents

Procédé et dispositif de génération d'émulsions micrométriques simples et composées Download PDF

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Publication number
EP3187252A1
EP3187252A1 EP15836842.3A EP15836842A EP3187252A1 EP 3187252 A1 EP3187252 A1 EP 3187252A1 EP 15836842 A EP15836842 A EP 15836842A EP 3187252 A1 EP3187252 A1 EP 3187252A1
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Prior art keywords
ranges
liquid
cst
emulsions
viscosity
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EP15836842.3A
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German (de)
English (en)
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EP3187252A4 (fr
EP3187252B1 (fr
Inventor
José Manuel GORDILLO ARIAS DE SAAVEBRA
Francisco DEL CAMPO CORTÉS
Álvaro EVANGELIO SÁNCHEZ
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DEL CAMPO CORTES, FRANCISCO
EVANGELIO SANCHEZ, ALVARO
GORDILLO ARIAS DE SAAVEDRA, JOSE MANUEL
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Universidad de Sevilla
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30—Micromixers
    • B01F33/301—Micromixers using specific means for arranging the streams to be mixed, e.g. channel geometries or dispositions
    • B01F33/3011—Micromixers using specific means for arranging the streams to be mixed, e.g. channel geometries or dispositions using a sheathing stream of a fluid surrounding a central stream of a different fluid, e.g. for reducing the cross-section of the central stream or to produce droplets from the central stream
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2215/00—Auxiliary or complementary information in relation with mixing
    • B01F2215/04—Technical information in relation with mixing
    • B01F2215/0413—Numerical information
    • B01F2215/0418—Geometrical information
    • B01F2215/0431—Numerical size values, e.g. diameter of a hole or conduit, area, volume, length, width, or ratios thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2215/00—Auxiliary or complementary information in relation with mixing
    • B01F2215/04—Technical information in relation with mixing
    • B01F2215/0413—Numerical information
    • B01F2215/0436—Operational information
    • B01F2215/045—Numerical flow-rate values
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2215/00—Auxiliary or complementary information in relation with mixing
    • B01F2215/04—Technical information in relation with mixing
    • B01F2215/0413—Numerical information
    • B01F2215/0486—Material property information
    • B01F2215/0495—Numerical values of viscosity of substances

Definitions

  • the invention described in this specification pertains to the Scientific and Technical Area of Microfluidics.
  • the study of microfluids is a multi-disciplinary field that includes elements from Physics, Chemistry, Engineering and Biotechnology. It conducts research on the behaviour of micro-scale fluids, wherein the motion regime is laminar, the gravity and the inertia are negligible, and the viscosity and the surface tension are dominant.
  • This scientific and technical area comprises designing systems - devices and processes - for the controlled production of simple and compound steady jets that break up due to capillary forces, to produce simple and compound droplets which, in turn, are used for the production of micrometre- and submicrometre-sized fibres, tubes and capsules.
  • both methods present a genuine axial symmetry (axially symmetric) in the area of the interface wherein the jet is produced, although there exist embodiments of flow-focusing devices with geometries that are practically two-dimensional ( Anna et al., Appl. Phys. Lett. (2003), 82, 364-366 , Gordillo et al., Phys. Fluids (2004), 16, 2828-2834 ).
  • the main disadvantages originate from (i) the inherent, inevitable dependency of the phenomenon on the electrical properties of the liquid, which greatly limits the physical-chemical parametric freedom of the method (even though some highly relevant applications have appeared in biochemistry - mass spectrometry for biological molecules -), (ii) the low productivity of the method (very low mass flow rate) and the difficulty in "scaling” or “multiplexing” it, and (iii) the mediocre robustness of the method due to its great dependency on the surface conditions and the sizes of the liquid feeding tubes.
  • the capsules are generated by means of chemical substance deposition on the surface of a droplet containing an active compound or principle.
  • the purpose of the external cover which is usually elastic or rigid, is to protect the active principle contained inside.
  • processes initially patented at the University of Seville, which follow a different method for encapsulating liquids or generating emulsions. Both are based on causing two immiscible fluid streams to flow in a coaxial manner. It is well-known that cylindrical jets break up into droplets due to the growth of capillary instability, also known as Rayleigh instability. When this break-up takes place simultaneously in the inner and outer jets, droplets are generated which contain other smaller-sized droplets inside.
  • the external cover is made solid by means of any process (for example, by using a photopolymer that increases its viscosity or becomes rigid with ultraviolet light as the outer fluid), solid capsules may be generated. Emulsions may be generated in these devices by simply injecting a liquid, using any of the aforementioned processes, into a bath containing a liquid that is immiscible with the injected fluid.
  • the first process belongs to the family of devices known as flow focusing, which is protected by patents US 6174469 , US 6187214 and US 6450189 . In this case, similarly to what occurs with atomisers of the flow focusing type, the two concentric fluid streams are accelerated due to the favourable pressure gradient that exists between a gas-pressurised chamber and the exterior.
  • the diameters of the inner and outer jets decrease and, finally, thanks to a primarily capillary mechanism, the compound droplets are generated. These compound droplets may have diameters of the order of 100 microns.
  • the concentric inner and outer jets are accelerated using an electric field.
  • the capsules generated may have nanometric sizes (the capsules produced using this process are the smallest ever generated) and are protected by patents P200100231 , PCT ES02/00047 and PCT US 02/02787 .
  • this process has a disadvantage as compared to flow focusing devices; namely, that electric fields are necessary and the liquid flow rates are of the order of 1000 to 100 times lower than those that may be used in flow focusing technology.
  • the present descriptive specification includes, as an integral part thereof, two diagrams which show, for illustrative, non-limiting purposes, two prototype models for generating simple and compound emulsions ( Fig. 1 and Fig. 2 , respectively), as well as two sets of images that show the actual production of emulsions, both simple and compound (Fig. 3 and Fig. 4), with prototypes of both classes.
  • Figure 1 The figure consists of a diagram of a prototype device for generating simple emulsions.
  • the device is composed of the injection tube (1), designed to inject the liquid to be emulsified, which has an inner diameter d i and is coaxially aligned with, and separated by a distance h from, the extraction tube (3), which has a length I and a square cross-section with an inner side l o , and an outlet to the exterior, contained inside a discharge chamber (4) equipped with an orifice (5) designed for the inlet of the emulsifying liquid.
  • the figure shows the velocity profile (6) of the liquid to be emulsified flowing inside the injection tube, and the streamlines (10) and the velocity profile (8) of the emulsifying liquid flowing in the surroundings of the inlet section of the extraction tube and downstream in the interior thereof, respectively.
  • Figure 2 The figure is a diagram of a prototype device for generating compound emulsions.
  • the different parts that make it up are a composite injection tube formed by an inner capillary tube (1), which has a diameter d i , is designed to inject the inner liquid and is coaxially centered inside a second outer capillary tube (2), with a diameter d o , through which the intermediate liquid is injected, and which is coaxially aligned with, and separated by a distance h from, the extraction tube (3), which has a length I and a square cross-section with an inner side l o , and an outlet to the exterior, contained inside a discharge chamber (4) equipped with an orifice (5) designed for the inlet of the emulsifying liquid.
  • the figure shows the velocity profile of the inner liquid (6) flowing inside the inner injection tube, the velocity profile of the intermediate liquid (7) flowing inside the outer injection tube, and the streamlines (10) and the velocity profile (8) of the emulsifying liquid flowing in the surroundings of the inlet section of the extraction tube and downstream in the interior thereof, respectively.
  • Figure 3 The set of images in the figure shows the actual production of simple emulsions by means of the process of the invention in a prototype device of the invention with different geometrical configurations of the components thereof.
  • the outer liquid is silicone oil with a viscosity of 100 cSt and the inner liquid is distilled water (viscosity of 1 cSt).
  • the flow rate of the outer liquid is 900 ml/h and the flow rate of the inner liquid is 0.5 ml/h, in all four cases.
  • the inner dimensions of the discharge chamber in the four prototypes are 3 cm x 3 cm x 3 cm.
  • the inner dimensions of the discharge chamber are 3 cm x 3 cm x 3 cm.
  • the outer liquid is silicone oil with a viscosity of 1000 cSt
  • the intermediate liquid is a mixture of glycerol and distilled water, with a viscosity of 400 cSt at 25°C
  • the inner liquid is silicone oil with a viscosity of 10 cSt.
  • the flow rate of the outer liquid is 200 ml/h and the flow rate of the intermediate liquid is 2.00 ml/h.
  • the object of the present invention is a process for generating simple and compound emulsions, from the formation of a simple or compound, as applicable, capillary micro-jet when a liquid or two immiscible or barely miscible liquids that flow coaxially are suctioned by means of a viscous outer liquid, which is immiscible or barely miscible with the simple or compound liquid to be emulsified, and which flows at the suitable velocity, as well as the device wherein and with which to perform said process.
  • the specifications whereof are the essence of the process of the invention, in the case of the generation of simple emulsions, the suctioned liquid forms a steady capillary jet with a micrometre-sized, controllable diameter, due to the action of the co-flowing outer liquid and the favourable pressure gradient that it produces.
  • This simple jet breaks up due to capillary instability, to produce droplets of a micro- and submicrometric size, with a limited size distribution.
  • the suction causes a compound capillary jet, due to the action of the co-flowing outer liquid and the favourable pressure gradient produced on the intermediate liquid and, similarly, of the latter on the inner liquid.
  • the interior of this compound jet breaks up into droplets due to capillary instability, which induces break-up of the intermediate liquid, to produce the coating of the inner liquid droplets and, consequently, the formation of compound micrometre-sized droplets.
  • the parametric determination in the generation of compound emulsions allows for control of both the size of the inner liquid droplets and the thickness of the coating with the intermediate liquid.
  • the process of the invention may be applied to all those technological demands that require the generation of simple monodisperse, micrometre-sized emulsions of the phase to be dispersed, as well as to those technological demands that require the generation of compound homogeneous emulsions, the dispersed phase whereof requires micrometre-sized, controllable droplet diameters and coating thicknesses.
  • the object of the present invention is a process and a device for generating simple and compound micrometre-sized emulsions.
  • the device that generates the emulsions is formed by the following elements: a discharge chamber with dimensions of the order of one centimetre, the interior whereof contains two coaxially aligned tubes, an extraction tube, with a diameter or inner side l o of the order of one millimetre and a length l, and a simple capillary injection tube, with an inner diameter d i of the order of one millimetre, or a compound capillary injection tube, formed by two concentric capillary tubes, the exterior whereof have an inner size d o of the order of one millimetre.
  • the outlet section of the simple or compound capillary tube is separated from the inlet section of the extraction tube by a distance h of the order of one millimetre.
  • the geometrical dimensions d i , d o , l o and h of the elements of the device constitute its geometrical configuration.
  • the suction produces a capillary jet composed of the intermediate liquid, which forms the outermost layer of the jet, and the inner liquid, which is at the centre of the compound jet.
  • the compound jet is formed due to the action of the co-flowing outer fluid and the favourable pressure gradient that the outer fluid exerts on the intermediate fluid.
  • the viscosities of the inner, intermediate and outer liquids, and the surface tensions between the inner and outer liquids, in the case of the generation of simple emulsions, and between the outer and intermediate liquids, and the intermediate and inner liquids, in the case of the generation of compound emulsions, are essential physical properties for the production of the emulsions described in this invention and constitute what we will call the dimensional configuration thereof.
  • the flow rates of the inner, intermediate and outer liquids, q i , q m and q e , respectively, or, alternatively, the flow rates of the inner and intermediate liquids, q ⁇ and q m , respectively, and the manometric discharge pressure of the outer fluid ⁇ p e , which is related to the outer flow rate q e according to the formula ⁇ p e Kq e , K being a constant that depends solely on the geometry of the device, are the operating control variables or parameters in the generation of emulsions produced by means of this technology and constitute what we will call the operational configuration thereof.
  • the process of the present invention involves the adequate selection of the aforementioned geometrical, dimensional and operating parameters or variables, i.e. the specification of the geometrical, dimensional and operational configurations.
  • the specification of the geometrical, dimensional and operational configurations define a parametric determination or a mode of production.
  • the scaling law that predicts the diameter of the droplets that form the emulsion is the following: 0.25[4Q i /( ⁇ U o )] 1/2 ⁇ d ⁇ 4[4Q i /( ⁇ U o )] 1/2 .
  • the invention described in this specification has applications in those industrial sectors wherein the production of simple and compound monodisperse, homogeneous emulsions with controllable, micrometre-sized diameters and coatings is an essential part of the process.
  • Image 3.2 of Figure 3 of the present descriptive specification shows the actual production of simple emulsions by means of this invention. Moreover, Figure 1 presents a diagram of the device used.
  • the discharge chamber contains two pairs of windows, in order to allow for real-time control of the production of simple emulsions.
  • the outer and inner liquids used in this embodiment of the invention for generating simple emulsions are 100-cSt silicone oil and distilled water (with a viscosity of 1 cSt), respectively, with a surface tension between them of 40 mN/m.
  • the flow rates of the outer and inner liquids, q e and q i were varied between 450 ml/h and 1400 ml/h, and 0.1 ml/h and 10 ml/h, respectively, to produce emulsions with droplets sizes ranging between 10 ⁇ m and 100 ⁇ m, and a production frequency ranging between 1000 Hz and 10000 Hz.
  • the rest of the images in the series i.e. images 3.1, 3.3 and 3.4 of Figure 3, show the actual simple emulsions according to different geometrical configurations, without varying the rest of the specifications of the mode of production described above.
  • Image 4.2 of Figure 4 of the present descriptive specification shows the actual production of compound emulsions by means of this invention. Moreover, Figure 2 shows a diagram of the device used.
  • the discharge chamber contains two pairs of windows, in order to allow for real-time control of the production of simple emulsions.
  • the outer, intermediate and inner liquids used in this embodiment of the invention for generating compound emulsions are 1000-cSt silicone oil, a mixture of glycerin and distilled water, with a viscosity of 400 cSt at 25°C, and silicone oil with a viscosity of 10 cSt, respectively, with a surface tension between both pairs of liquids (outer and intermediate liquids, and intermediate and inner liquids) of 50 mN/m.
  • the flow rates of the outer, intermediate and inner liquids, q e , q m and q i were varied between 100 ml/h and 200 ml/h, 0.1 ml/h and 10.0 ml/h, and 0.1 ml/h and 10 ml/h, respectively, to produce compound emulsions with droplets having inner diameters ranging between 10 ⁇ m and 100 ⁇ m, and coatings ranging between 10 ⁇ m and 40 ⁇ m, with a production frequency ranging between 100 Hz and 2000 Hz.
  • the rest of the images in the series, i.e. images 4.1, 4.3 and 4.4 of Figure 4 show the actual production of compound emulsions with different inner liquid flow rates, ranging between 0.1 ml/h and 0.7 ml/h, without varying the rest of the specifications of the mode of production described above.
  • any continuous feeding methods for the outer, intermediate and inner liquids may be used (pressure reservoirs, syringe pumps, etc.).
  • the aforementioned embodiments of the invention describe the process and the device, or individual cell, for generating simple or compound emulsions with the production limitations involved. If an increase in production is required, the device may be multiplexed. In this case, the flow rate of the inner liquid, or the intermediate and inner liquids, as applicable, should be as homogeneous as possible across the different cells, which may require discharge through multiple capillary needles, porous media, or any other medium capable of distributing a homogeneous flow rate across different feeding points.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Colloid Chemistry (AREA)
  • Cosmetics (AREA)
EP15836842.3A 2014-08-25 2015-08-25 Procédé et dispositif de génération d'émulsions micrométriques simples et composées Active EP3187252B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES201400698A ES2564893B2 (es) 2014-08-25 2014-08-25 Procedimiento y dispositivo de generación de emulsiones micrométricas simples y compuestas
PCT/ES2015/000113 WO2016030551A1 (fr) 2014-08-25 2015-08-25 Procédé et dispositif de génération d'émulsions micrométriques simples et composées

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EP3187252A1 true EP3187252A1 (fr) 2017-07-05
EP3187252A4 EP3187252A4 (fr) 2018-02-14
EP3187252B1 EP3187252B1 (fr) 2020-12-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108159976A (zh) * 2018-01-03 2018-06-15 西南交通大学 一种油包水包水（w/w/o）单分散双重乳液制备方法及其微流控装置
CN114058495A (zh) * 2021-10-29 2022-02-18 浙江大学 一种工业级非对称液滴发生装置及数字核酸扩增检测系统

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020525269A (ja) 2017-07-04 2020-08-27 ユニヴェルシテ・リブレ・ドゥ・ブリュッセル 液滴および／または気泡生成器
CN114210378B (zh) * 2021-11-22 2023-04-28 广东省科学院健康医学研究所 一种基于微孔毛细管的液滴生成装置及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2283158B1 (es) * 2003-11-10 2008-09-16 Universidad De Sevilla Procedimiento y dispositivo para la generacion de espumas y emulsiones mediante pares de tubos enfrentados.
US9039273B2 (en) * 2005-03-04 2015-05-26 President And Fellows Of Harvard College Method and apparatus for forming multiple emulsions
EP2729238A2 (fr) * 2011-07-06 2014-05-14 President and Fellows of Harvard College Émulsions multiples et techniques de formation d'émulsions multiples

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108159976A (zh) * 2018-01-03 2018-06-15 西南交通大学 一种油包水包水（w/w/o）单分散双重乳液制备方法及其微流控装置
CN114058495A (zh) * 2021-10-29 2022-02-18 浙江大学 一种工业级非对称液滴发生装置及数字核酸扩增检测系统

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Publication number Publication date
ES2564893B2 (es) 2016-07-08
ES2564893A1 (es) 2016-03-29
ES2872473T3 (es) 2021-11-02
EP3187252A4 (fr) 2018-02-14
WO2016030551A1 (fr) 2016-03-03
EP3187252B1 (fr) 2020-12-30

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