DEVICES AND METHODS FOR CHARACTERIZING PARTICLES DISPERSED IN A LIQUID MEDIUM
20170248510 · 2017-08-31
Assignee
Inventors
Cpc classification
G01N2015/0222
PHYSICS
G01N15/1436
PHYSICS
B82B3/009
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
A device for characterizing particles dispersed in a liquid medium includes a fibered light emission source, a fibered optical detector, and a measurement probe intended to be hermetically submerged in the liquid medium. The measurement probe includes: a confinement tube intended to pass through at least one wall of the probe in a sealed manner and suitable for receiving a sample of the liquid medium, as well as an optical measurement head including a focusing optics for the focusing of an illumination light beam in the confinement tube and a collection optics for the collection toward the optical detector of a beam of light backscattered by the dispersed particles. The characterization device also includes a processing unit suitable for the characterization of the particles based on the backscattered-light beam.
Claims
1. A device for characterizing particles dispersed in a liquid medium comprising: a fibered light emission source; a fibered optical detector; a measurement probe intended to be hermetically submerged in the liquid medium and comprising: a confinement tube intended to be arranged in an interior of said measurement probe and to hermetically pass through at least one wall of the probe in order to receive, through an end, a sample of the liquid medium; an optical measurement head intended to be arranged in the interior of said measurement probe, comprising focusing optics for focusing, in the confinement tube, an illumination light beam originating from the light emission source and a collection optics for the collection toward the optical detector of a beam of light backscattered by the particles dispersed in the confinement tube; and a processing unit suitable for the characterization of the particles based on the backscattered-light beam measured by the optical detector.
2. The device for characterizing particles according to claim 1, wherein the confinement tube passes through a lower wall of the measurement probe, and wherein the measurement probe is substantially vertical.
3. The device for characterizing particles according to claim 2, wherein the optical measurement head comprises a deflection element for deflecting the illumination beam toward the confinement tube and the backscattered-light beam toward the collection optics.
4. The device for characterizing particles according to claim 3, wherein the deflection element is moveable, enabling an adjustment of a focusing distance of the illumination beam in the confinement tube.
5. The device for characterizing particles according to claim 1, further comprising a controlled suctioning device, suitable for suctioning the liquid medium sample into the confinement tube and removing the liquid medium sample from the confinement tube.
6. The device for characterizing particles according to claim 1, wherein the confinement tube passes through a lateral wall of the measurement probe in a sealed manner through two ends of the measurement probe.
7. The device for characterizing particles according to claim 1, wherein the focusing optics and the collection optics are formed by the same optics, suitable for receiving the illumination and backscattered-light beams.
8. The device for characterizing particles according to claim 1, wherein the backscattered-light beam and the illumination beam are intended to be non-colinear.
9. The device for characterizing particles according to claim 1, wherein the focusing optics and/or the collection optics comprise a variable-focus lens enabling an adjustment of a focusing distance of the illumination beam in the confinement tube.
10. A method for characterizing particles dispersed in a liquid medium using a device for characterizing particles according to claim 1, comprising the following steps: (a1) immersion of the measurement probe in the liquid medium; (a2) introduction of a sample of the liquid medium into an interior of the confinement tube; (a3) focusing of an illumination beam emitted by the light emission source in the sample; (a4) detection of a backscattered-light beam by means of the optical detector and characterization of the particles; and (a5) release of the sample into the liquid medium.
11. The method for characterizing particles according to claim 10, wherein step (a4) of detection of the backscattered-light beam. and of characterization of the particles comprises a dynamic light scattering (DLS) analysis.
12. The method for characterizing particles according to claim 10, wherein step (a4) of deflection of the backscattered-light beam and of characterization of the particles comprises a static light backscattering analysis at a wavelength different from the wavelength of the illumination beam.
13. The method for characterizing particles according to claim 10, wherein the step (a2) of introduction of the sample of the liquid medium comprises a controlled suctioning of the liquid medium into the confinement tube by means of a suctioning device.
14. The method for characterizing particles according to claim 10, wherein: the confinement tube passes hermetically through a lateral wall of the measurement probe through two ends of the measurement probe; and the step (a2) of introduction of the liquid medium sample comprises: a rotation of the measurement probe into a first position so that the confinement tube is in a direction substantially parallel to a flow in the liquid medium, enabling the filling of the confinement tube; and once the confinement tube is filled, the rotation of the measurement probe into a second position so that the confinement tube is in a direction substantially perpendicular to the flow in the liquid medium.
15. The method for characterizing particles according to claim 10, further comprising an adaptation of a focusing distance of the illumination beam in the sample as a function of a particle concentration of the liquid medium and/or of a particle absorption.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0061] Other advantages and features of the one or more embodiments of the invention will become apparent upon reading the description, illustrated by the following figures:
[0062]
[0063]
[0064]
[0065]
[0066]
DETAILED DESCRIPTION
[0067] In the figures, identical elements are marked by identical references. For reasons pertaining to the readability of the figures, the size scales between elements represented are not observed.
[0068]
[0069] The characterization device 10 comprises a measurement probe 100 suitable for being at least partially submerged in the liquid medium 30, as well as a light emission source 200 and an optical detector 300.
[0070] The light emission source 200, hereafter referred to as the light source, can be, for example, a laser source at a given wavelength. The light source 200 is capable of emitting an illumination beam, for example, a laser beam, which is transmitted by optical fiber into the measurement probe 100 in order to illuminate a sample of the liquid medium. The light source 200 is referred to as “fibered.”
[0071] The optical detector 300, hereafter referred to simply as detector, is capable of detecting a beam of light backscattered by a sample of the liquid medium; the beam of backscattered light or “backscattered beam” is collected by the measurement probe 100 and transmitted by optical fiber from the measurement probe 100 to a detector 300 which is referred to as “fibered.” The detector 300 can be, for example, a photon counting optical detector, of the photomultiplier or avalanche photodiode type.
[0072] The optical fibers optically connecting, on the one hand, the light source 200 and the measurement probe 100, and, on the other hand, the detector 300 and said measurement probe 100 can include, for example, single-mode or multi-mode fibers, or packets of single-mode or multi-mode fibers, for example, polarization maintaining fibers.
[0073] The detector 300 is electrically connected to a processing unit 400 which performs the characterization of the particles present in a sample of the liquid medium based on the beam of backscattered light detected by the detector 300.
[0074] For example, in the case of dynamic light scattering (DLS) analysis, the processing unit analyzes the variations in the intensity of the beam of backscattered light over time in order to derive size distributions therefrom. The processing unit can comprise, for example, a correlation subunit and a calculation subunit for calculating the size of the particles. In some examples, the correlation subunit can be implemented by a specific correlator.
[0075] In the case of static light scattering analysis, for example, by inelastic light scattering, the processing unit can determine the molecular composition and the external structure of the particles from the optical spectrum of the backscattered-light beam or from the intensity of the beam of scattered light at at least one wavelength of the spectrum
[0076] The characteristics of the particles obtained by characterization of, for example, their size, can then be displayed on a display 500 connected to the processing unit 400.
[0077] A measurement probe example 100 is represented diagrammatically in
[0078] The confinement tube 150 is suitable for receiving a sample Ii of the liquid medium 30. The confinement tube 150 is for example cylindrical, having any cross section, for example round or polygonal. The cross section of the confinement tube has a transverse dimension of preferably between 0.1 and 5 mm. The confinement tube presents an optically transparent wall, advantageously chemically inert, made of glass for example.
[0079] The confinement tube 150 comprises at least one open end, referred to as opening end, intended to pass in a sealed manner through a. wall of the measurement probe, and through which the liquid of the medium 30 can be introduced into the tube. In the case of a confinement tube having only a single opening end, the liquid is also removed through said end, In certain embodiment examples, the two ends of the confinement tube can be opening, as will be described below; in this case, the liquid of the medium 30 can be introduced into the tube through one of the ends and removed through the other end. Thus, the opening end(s) of the confinement tube lead(s) into the liquid medium 30, while the central portion of the confinement tube is hermetically enclosed in the measurement probe.
[0080] The confinement tube 150 thus forms a closed measurement chamber in which a sample of the liquid medium can be isolated from said liquid medium to be characterized therein, without being subjected to the possible stirring of the liquid medium, This sample being drawn directly from the liquid medium and maintained confined in the confinement tube, it can be analyzed, or characterized, in real time, without opening the reactor or stopping the stirring and without interruption of the reaction of the liquid medium.
[0081] Moreover, since the enclosure 110 of the measurement probe is sealed, the optical measurement head remains perfectly isolated from any liquid splashes of the liquid medium 30 or of the sample to be analyzed. Thus, the probe does not need to be cleaned between two characterizations of different liquid media.
[0082] In certain embodiment examples, the confinement tube 150 can be interchangeable, that is to say that the tube in the measurement probe is replaced for each new characterization of a new liquid medium. The interchangeability of the confinement tube allows easy maintenance and repair of the device.
[0083] According to one or more embodiment examples, the characterization device comprises an optical trap 170 represented diagrammatically by a black rectangle in
[0084] According to an embodiment illustrated in
[0085]
[0089] A new liquid sample can then be introduced into the confinement tube 150 for a new characterization. Several characterizations can thus occur successively, making it possible to provide an evolution, in real time, of the characteristics of the particles of the liquid medium. Successive characterizations can be carried out until the measured characteristics of the particles correspond to predetermined characteristics. In the case of a synthesis of nanoparticles, for example, the characterizations can occur successively until the measured size of the nanoparticles corresponds to the desired size. In the case of a separation of particles, the characterizations can occur successively until the separation of the particles is achieved,
[0090]
[0091] The confinement tube can have, for example, elbow parts and an opening end that passes through a lateral wall of the measurement probe. According to one or more embodiment examples, the confinement tube is a straight tube, arranged substantially vertically in the measurement probe, in this example substantially parallel to the optical axis of the focusing optics, and it has an opening end 152 which passes through a lower wall 112 of the enclosure 110 of the measurement probe, as represented in
[0092] The measurement probe 100 illustrated in
[0093] In the example of
[0094] The optical measurement head 140 also includes a focusing optics 143 for the focusing of the illumination beam Fe in the sample E, a collection optics 144 for the collection of the beam Fr of light backscattered by the particles dispersed in the sample E, and a deflection element 148 which, in this example, makes it possible to deflect the illumination beam and the backscattered-light beam in order to illuminate the sample and collect the backscattered light, respectively, in the case in which the confinement tube is arranged so as to be substantially parallel to the optical axes of the focusing optics and/or the collection optics. The focusing optics 143 and the collection optics 144 can comprise a lens or a group of lenses. The deflection element 148 can comprise a minor, a glass slide or a deflecting prism, for example, a total reflection prism, as illustrated in the example of
[0095] As represented by the arrows in
[0096] According to one or more embodiment examples, the optical head can comprise a wavelength selective splitter for the separation of the illumination beam and the backscattered beam in the case of analysis of scattering with change of wavelength. For example, it is possible to use a dichroic filter arranged on the deflection element 148. It is also possible to provide a fluorescence rejecting filter, of the band-pass filter type, for removing fluorescence light when one seeks to characterized another scattering type, for example, a Raman scattering.
[0097] According to one or more embodiment examples, the deflection element 148 is movable in translation along a direction parallel to the optical axis of the focusing optics and/or the collection optics. This mobility of the deflection element 148 can be achieved, for example, by means of a sliding mechanical device 146, such as a pair of rails mounted on the wall 141 of the optical measurement head 140, and between which the deflection element 148 is attached. The mobility of the deflection element 148 enables an adjustment of the working distance d between the measurement zone M (where the illumination beam Fe is focused in the liquid sample E) and the internal surface 149 of the confinement tube. Thus, it is possible to adapt the positioning of the measurement zone M to the concentration and to the absorption of the sample, connected with the particle concentration of the liquid sample.
[0098] Thus, in an embodiment example, the working distance can be adjusted in a range from 0 to 5 mm by translation of the deflection element 148. In the case of a particle synthesis operation, for example, the working distance d can be selected to be greater, for example, at the beginning of the synthesis operation, when the liquid has a low particle concentration (
[0099] The adjustment of the working distance d can also be obtained by means of variable-focus illumination optics 143 and collection optics 144.
[0100]
[0101] According to an embodiment example illustrated in
[0102]
[0103] In the example illustrated in
[0104] In the example illustrated in
[0105] As explained above, several characterizations can occur successively, providing an evolution, in real time, of the characteristics of the particles of the liquid medium. Therefore, for example, an operator can follow the kinetic of the reaction in the liquid medium 30 in real time, from the time of contacting of the reactants to the end of the reaction.
[0106] Naturally, in certain embodiment examples (not represented in the figures), only one end 156 of the confinement tube 150 can be open and pass through a lateral wall 114 of the enclosure 110 of the measurement probe in order to open into the liquid medium 30. In these embodiment examples, the non-opening end 158 is connected to a suctioning device enabling the suctioning of the liquid sample E into the confinement tube 150 and its removal from said confinement tube, respectively, as explained above in relation to
[0107] According to one or more embodiment examples, the characterization device comprises, as in the preceding examples, an optical trap 170 represented diagrammatically by a black rectangle in
[0108]
[0109] In this configuration, it is no longer necessary to provide a deflection element for the optical measurement head 140. In other words, the confinement tube 150, of which only the central portion is represented here, is located below the optical measurement head 140, that is to say opposite the focusing optics 143 and the collection optics 144.
[0110] Thus, in the example of
[0111] More precisely, as represented by the arrows in
[0112] As in the preceding example, the optical head can comprise a wavelength selective splitter for the separation of the illumination and backscattered beams in the case of analysis of the scattering with change of wavelength (not represented in the figures).
[0113] In one or more embodiment examples, one can seek to adjust the working distance between the measurement zone M (where the illumination beam Fe is focused in the liquid sample E), in particular, in order to take into account the turbidity of the solution, as explained above. For this purpose, the focusing optics 143 and the collection optics 144 can comprise variable-focus lenses, for example, electrically controlled variable-focus liquid lenses marketed by the company Varioptic© or the company Optotune©. In other embodiment examples, the adjustment of the working distance d between the measurement zone M and the lower wall 149 of the confinement tube 150 can be obtained by means of electromechanical microsystems or MEMS (abbreviation of the English expression “microelectromechanical system”) by modification of the individual deflection angles.
[0114]
[0115] FIG, 5C illustrates a variant of
[0116] In particular, the optical emission head 220 and the optical reception head 330 are arranged in such a manner that the illumination beam Fe and backscattered-light beam Fr are incident in an offset manner on the common optics 142, one of the two beams being incident, for example, on the optical axis of the common optics 142 and the other being off-center. This configuration makes it possible, using a common optics 142, to detect a backscattered-light beam Fr that is not co-linear with the illumination beam.
[0117] The characterizing device which has just been described can be implemented as follows: [0118] submersion of the measurement probe 100 in the reactor 20 containing the liquid medium 30 in which several reactants react together; [0119] introduction and confinement of a sample E of the liquid medium 30 in the confinement tube 150, by rotation of the measurement probe or by suctioning; [0120] emission of an illumination beam Fe and focusing of this illumination beam toward a measurement zone M of the confinement tube 150; [0121] detection of a beam Fr of light backscattered by the particles of the liquid sample E and transmission to the processing unit 400; [0122] processing, by the processing unit 400, of the backscattered-light beam Fr and characterization of the particles, for example, by their size and/or their composition; [0123] release of the liquid sample E into the medium.
[0124] After the step of release of the sample E, a new sample E′ can be introduced in the confinement tube, then confined, and characterized by the steps mentioned above. A plurality of new samples can thus be characterized after one another until the desired characteristics are obtained.
[0125] Regardless of the embodiment examples, the characterization device according to the present description has the advantage of being compact and of having a small space requirement (typically a volume having a lateral dimension of less than 30 mm and a height dimension of less than 80 mm). In addition, it has the advantage of enabling the characterization of a sample in the interior of the reactor, without requiring any sample collection outside of the reactor and while preventing any contact of the optical measurement head with the liquid medium.
[0126] Moreover, the characterization of the particles by light scattering, as has just been described, can be coupled with other characterizations such as, for example, the temperature, the viscosity, the imaging, etc., using specific devices.
[0127] Although described by way of a certain number of detailed embodiment examples, the devices and methods for characterizing particles dispersed in a liquid medium according to the present description comprise different variants, modifications and improvements which will be obvious to the person skilled in the art, it being understood that these different variants, modifications and improvements are part of the scope of one or more embodiments of the invention as defined by the following claims.