EP4543601A1 - Transducteur ultrasonique pour application à haute température - Google Patents
Transducteur ultrasonique pour application à haute températureInfo
- Publication number
- EP4543601A1 EP4543601A1 EP23733779.5A EP23733779A EP4543601A1 EP 4543601 A1 EP4543601 A1 EP 4543601A1 EP 23733779 A EP23733779 A EP 23733779A EP 4543601 A1 EP4543601 A1 EP 4543601A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrode
- piezoelectric
- acoustic wave
- metallic material
- acoustic
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
- B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
- B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
- B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
- B06B1/06—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
- B06B1/0644—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using a single piezoelectric element
- B06B1/0662—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using a single piezoelectric element with an electrode on the sensitive surface
- B06B1/0677—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using a single piezoelectric element with an electrode on the sensitive surface and a high impedance backing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
- B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
- B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
- B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
- B06B1/06—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
- B06B1/0644—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using a single piezoelectric element
- B06B1/0662—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using a single piezoelectric element with an electrode on the sensitive surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
- B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
- B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
- B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
- B06B1/06—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
- B06B1/0644—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using a single piezoelectric element
- B06B1/0662—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using a single piezoelectric element with an electrode on the sensitive surface
- B06B1/0681—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using a single piezoelectric element with an electrode on the sensitive surface and a damping structure
- B06B1/0685—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using a single piezoelectric element with an electrode on the sensitive surface and a damping structure on the back only of piezoelectric elements
Definitions
- the invention relates to an acoustic transducer intended for non-destructive testing, obstacle detection, telemetry, etc. operations. in environments that can be placed at high temperature, under high pressure, for example in a nuclear installation.
- Non-destructive testing by ultrasound is well suited to monitoring structures, in order to monitor resistance to aging and the appearance of possible defects, or for telemetry or obstacle detection operations.
- Some applications are performed in high temperature and/or high pressure environments. This is for example the case in the field of aircraft engines, or the oil industry, or in nuclear reactors.
- FIG. IA schematically shows an IAA ultrasonic transducer of the prior art, intended to be used in a high temperature environment.
- high temperature we generally mean a temperature above 200°C, or above 600°C.
- the active elements of the transducer are arranged in a housing 2.
- the active elements include a piezoelectric converter 10, formed of a piezoelectric material, interposed between a front electrode 11 and a rear electrode 12. Each electrode is connected to an electrical circuit 20 The front electrode is placed facing an inlet opening 15 provided in the housing 2.
- a piezoelectric converter 10 formed of a piezoelectric material
- the piezoelectric converter Under the effect of the application of an alternating voltage between the electrodes, the piezoelectric converter generates an acoustic wave EW.
- the emitted acoustic wave EW propagates towards a medium 3 external to the enclosure 2, through the opening 15.
- the transducer may include a blade 14 allowing an adaptation of acoustic impedance between the transducer and the external medium 3. The transducer thus operates in a transmission mode.
- the transducer can also operate in a reception mode, during which an acoustic wave RW propagates from the external environment 3 towards the transducer.
- the received acoustic wave RW causes vibration of the piezoelectric converter. This results in a appearance of an alternating voltage across the electrodes 11 and 12.
- the transducer thus operates in a reception mode.
- the piezoelectric material can be lithium niobate, as described in patent US9425384.
- Figure IB represents a timing diagram of the vibration amplitude of an electrical transducer of the prior art, following reception of an acoustic wave.
- the y-axis corresponds to the amplitude of the vibration wave of the piezoelectric converter, as measured by the electrical circuit, while the x-axis corresponds to time.
- the emission is triggered by an application of an alternating voltage for a few microseconds to a few tens of microseconds.
- the vibration of the piezoelectric converter extends over a much longer duration, of the order of a few hundred ps (microseconds). This results in a degradation of transducer performance.
- the damping back of a transducer can be formed of a polymer doped with particles of high density, for example particles of tungsten or lead.
- particles of high density for example particles of tungsten or lead.
- such a composition is not suitable for high temperature application.
- the inventors have developed an ultrasonic transducer, intended to be used under strong irradiation, and under high temperature, or exposed to strong temperature gradients, and this for a significant operating time, greater than a few years, or even a few tens of years. 'years.
- a first object of the invention is an acoustic transduction device, comprising
- a piezoelectric converter formed of a piezoelectric material, interposed between a front electrode and a rear electrode;
- - a housing, containing the piezoelectric converter, the front electrode and the rear electrode;
- the device being configured to emit an acoustic wave towards the front opening or to detect an acoustic wave propagating from the front opening; the device comprising a rear component, applied against the rear electrode or forming the rear electrode, the rear component forming a shock-absorbing back of the device, the device being characterized in that the rear component is a porous metallic material whose melting temperature is greater than 200°C.
- the device may include one of the following characteristics, taken individually or in technically feasible combinations.
- the rear component forms the rear electrode.
- the melting temperature of the metallic material is greater than 600 °C.
- the piezoelectric material has a Curie temperature and the melting temperature of the metallic material is greater than the Curie temperature of the piezoelectric material;
- the Curie temperature of the piezoelectric material is greater than 1000°C.
- the volume fraction of the pores of the porous metallic material is between 20% and 60% or between 25% and 50% or between 25% and 40%.
- the average size of the pores is less than 100 ⁇ m, the average size corresponding to an average diameter of each pore.
- the piezoelectric material is chosen from lithium niobate or barium titanate.
- the metallic material comprises at least one element chosen from: Ni, Fe, Pd, Ag, Au, Cu, Pd, Al.
- the metal material is a stainless steel type alloy.
- Another object of the invention is a use of a device according to the first object of the invention for emitting or receiving an acoustic wave, the emitted or received acoustic wave propagating through the opening, the device being arranged in an environment whose temperature is greater than 200°C.
- Figure IA schematizes a transducer according to the prior art.
- Figure IB a vibration of a transducer.
- Figure 2A represents a first embodiment of a transducer according to the invention.
- Figure 2B represents a second embodiment of a transducer according to the invention.
- Figure 3A schematically shows a poor impedance matching between a piezoelectric converter and a component forming a shock absorber back, assembled to the converter.
- Figure 3B shows a good impedance matching between a piezoelectric converter and a component forming a damping back, assembled to the converter.
- Figure 4 schematically shows a test bench, aimed at determining the propagation speed of an acoustic wave through different materials.
- Figures 5A and 5B show detection echograms obtained with the test bench shown schematically in Figure 4, respectively in the presence and in the absence of the sample studied.
- Figure 6A represents the propagation speed (or celerity) of an acoustic wave (y axis - unit ms 1 ) as a function of the volume fraction of the pores (x axis - %).
- Figure 6B represents the acoustic impedance of a porous stainless steel material (y-axis - Rayls unit x 10 7 ) as a function of the volume fraction of the pores (x-axis - %).
- Figure 6C represents a linear attenuation coefficient (y-axis - unit dB/mm) as a function of the pore volume fraction (x-axis - %).
- FIG. 2A illustrates a first embodiment of a transducer 1 according to the invention.
- the transducer comprises a converter 10 formed by a piezoelectric material, interposed between a front electrode 11 and a rear electrode 12.
- the assembly, formed by the piezoelectric converter 10, the front electrode and the rear electrode, a housing 2 is arranged comprising an opening 15.
- the front electrode 11 extends between the opening 15 and the piezoelectric converter 10.
- the device preferably comprises an acoustic impedance matching blade 14, interposed between the front electrode 11 and the opening 15.
- the impedance matching blade is for example made of aluminum.
- the transducer is connected to an electrical circuit 20, making it possible to apply or measure an alternating voltage between the front electrode and the rear electrode.
- an acoustic wave EW is emitted through the opening 15, and propagates through an ambient medium 3.
- the medium ambient can in particular be liquid or solid. It can be water, a liquid material or a solid material.
- an alternating electrical signal is detected by the electrical circuit 20, the amplitude of which corresponds to the amplitude of vibration of the piezoelectric converter under the effect of reception of the acoustic wave RW.
- the piezoelectric converter 10 can take the form of a disk with a thickness of 1 mm and a diameter of between 5 mm and 50 mm.
- the material used is compatible with use at high temperatures, for example between 200°C and 700°C, or even more, for example above 1000°C.
- the piezoelectric material can be Lithium Niobate (LiNbOs).
- the resonant frequency of the piezoelectric converter can be from a few hundred kHz up to several MHz, for example 4 MHz or 5 MHz.
- the thickness of each electrode can be of the order of 1 mm.
- Each electrode can take the shape of a disk, the diameter of which corresponds to that of the piezoelectric converter 10.
- the electrical circuit 20 is connected to a central unit 30, configured to control the electrical circuit when the transducer operates in transmission mode and/or analyze the voltage measured between the electrodes when the transducer operates in reception mode.
- the transducer 1 comprises a rear component 13, applied against the rear electrode 12.
- the rear component is intended to form a “damping back” with respect to the piezoelectric converter 10. As mentioned in the prior art, it is acts to attenuate the echoes of the acoustic wave transmitted towards the rear of the piezoelectric converter.
- Back thickness shock absorber is preferably greater than 5 mm, or even 10 mm. It can be between 10 mm and 100 mm, for example 40 mm.
- the shock-absorbing back 13 is formed by a porous metallic material (pure metal or metal alloy), the melting temperature of which is greater than 200°C, and preferably greater than 600°C or 700 °C, and preferably at 1000 °C. It may for example be a steel, for example stainless steel, or aluminum, or a metal chosen from: Ni, Fe, Pd, Ag, Au, Cu, Pd, Al. may be a metal alloy such as bronze or brass.
- the shock absorber back can be formed from the same material as the rear electrode, making their assembly easier.
- An advantage of the metallic material, in particular stainless steel, is the good resistance to corrosion and ionizing radiation, in particular neutrons or gamma, which makes it compatible with use in a nuclear installation.
- the shock absorber back is formed of the same material as the rear electrode, in this case a conductive metal, a phase of assembling the back on the electrode is avoided.
- the shock absorber back is made of ceramic, the assembly involves the use of glue or brazing.
- glue or brazing Such an assembly may not be resistant over time, particularly when the transducer is subjected to strong thermal gradients.
- the respective thermal expansion coefficients of a ceramic and a metal electrode are generally different from each other. This can lead to degradation of the assembly over time, particularly during repeated exposure to strong thermal gradients.
- the material forming the piezoelectric converter 10 has a Curie temperature, beyond which it is considered that the piezoelectric behavior disappears. It is preferable that the melting temperature of the metallic material forming the shock-absorbing back is greater than the Curie temperature of the piezoelectric converter. Lithium niobate has a Curie temperature above 1100°C.
- FIG 2B schematically shows an embodiment in which the shock absorber back and the rear electrode form the same part.
- the rear electrode is formed from the porous, electrically conductive metallic material.
- the damping back 13 is configured to maximize transmission of a vibration wave produced by the piezoelectric transducer, and minimize reflection of said wave.
- FIGs 3A and 3B there is shown a configuration as shown in Figure 2B, in which the piezoelectric converter 10 is directly arranged in contact with the shock-absorbing back 13, the latter acting as a rear electrode.
- the transmission coefficient T corresponds to a ratio between the amplitude of a wave, called incident wave, propagating from the piezoelectric converter 10 and incident on the damping back 13, this amplitude being denoted Ai in Figures 3A and 3B; the amplitude of a transmitted wave A t , which corresponds to the part of the incident wave propagating through the damping back.
- the reflection coefficient R corresponds to a ratio between: the amplitude of the incident wave Ai; the amplitude of a reflected wave A r , which corresponds to the part of the incident wave reflected by the damping back 13 and propagating towards the piezoelectric converter 10.
- Figure 3A schematizes a configuration according to which the reflection coefficient is, in absolute value, high and the transmission coefficient is low.
- a degradation of the spatial resolution of the measurement results.
- Figure 3B schematizes a configuration according to which the reflection coefficient is close to 0, and the transmission coefficient is close to 1, which corresponds to an ideal case.
- the formation of echoes at the interface between the piezoelectric converter 10 and the damping back 13 is low. This results in a shorter emitted (or detected) acoustic wave, which favors the temporal resolution of the measurement.
- the invention aims to get closer to this configuration.
- Expression (3) shows that such a configuration is obtained if the acoustic impedances of the two contiguous media are close to each other, in other words Z x ⁇ Z 2 .
- the acoustic impedance of the piezoelectric converter 10 is generally a few tens of MRayls, typically between 25 and 40 MRayls (Mega Rayls), to be compared with the acoustic impedance of air, which is 430 Rayls or that of the water, which is 1.5 MRayls.
- the configuration shown in Figure 3A corresponds to a piezoelectric/air converter interface.
- the configuration shown in Figure 3B corresponds to a piezoelectric converter/porous metal shock absorber interface that we wish to obtain.
- the impedance and acoustic attenuation of the damping back 13 are controlled by the size and volume fraction of the air-filled pores.
- Various experimental tests were carried out, in order to define ranges of pore sizes and volume fractions making it possible to obtain a transmission coefficient close to 1 and sufficient attenuation. It should be noted that the effect, on the impedance, of the size of the pores, and their volume fraction, depends on the material used. The values obtained on one material cannot be transposed to another material.
- a key parameter is the acoustic propagation speed c, from which the acoustic impedance Z can be calculated according to the expression:
- Figure 4 schematically shows an echometry test bench 100.
- Metal samples 103 of different porosities are placed between an acoustic transmitter 101 and an acoustic receiver 102.
- the assembly is immersed in water 104.
- Figure 5A represents a pulse received by the acoustic receiver 102 in the absence of a sample interposed between the transmitter and the receiver, t corresponds to an instant of detection of the acoustic wave.
- the y-axis corresponds to amplitude and the x-axis corresponds to time.
- the propagation of the acoustic wave through the water 104 is shown by a dotted arrow.
- Figure 5B shows the pulses received by the acoustic receiver 102 after a sample 103, of thickness e, has been interposed between the transmitter and the receiver.
- the y-axis corresponds to amplitude and the x-axis corresponds to time.
- the propagation of the acoustic wave through the water 104 is shown by a solid line arrow.
- two pulses are detected: a first pulse, at time t 1 ( corresponds to the wave having propagated through the sample, without reflection.
- the instant t x is before the instant t, due to the speed of propagation of the acoustic wave being greater in the sample 103 than in the water 104.
- c w denotes the speed of acoustic propagation in water.
- Samples of type 316L stainless steel of varying thicknesses (5 mm or 10 mm), presenting different porosity volume fractions (between 25% and 53%) and different average pore sizes (average diameter between 2 p.m. and 60 p.m.).
- the table below presents the characteristics of the samples tested.
- Each sample 103 was in the form of a plate measuring 50 mm by 50 mm.
- the porosity volume fraction of each sample was determined by measuring the density.
- the average pore sizes were determined by optical microscopy. Table 1 shows the main characteristics of the tested samples.
- Figure 6A shows the propagation speeds of the acoustic wave determined from expression (6), as a function of the porosity volume fraction.
- the ordinate axis corresponds to the speed (unit ms -1 ) and the abscissa axis corresponds to the porosity (%).
- Figure 6B shows the acoustic impedance, calculated according to (4), from the knowledge of the density p of the materials tested and the celerities obtained by implementing expression (6).
- the ordinate axis corresponds to the speed (unit m/s) and the abscissa axis corresponds to the volume fraction of the pores (%).
- a linear attenuation coefficient was determined, per millimeter, denoted a, taking into account: the thickness of the sample e when considering Att a ; twice the thickness e of the sample when we consider Att b .
- Figure 6C represents the attenuation coefficients a obtained from expression (7).
- the y-axis corresponds to the attenuation (unit dB/mm) and the x-axis corresponds to the pore volume fraction (%).
- each point corresponds to a measured value.
- the interpolation is linear.
- the function resulting from the interpolation is polynomial.
- Figure 6B makes it possible to define a range of porosity volume fraction, expressed in%, for which the impedance is sufficiently close to the impedance of the piezoelectric material, that is to say in the range 10 - 40 MRayls. According to Figure 6B, this corresponds to a volume fraction of porosity less than 50%.
- Figure 6C makes it possible to define a range of porosity volume fraction, expressed in%, for which the attenuation is sufficient.
- sufficient attenuation we mean an attenuation coefficient a greater than or equal to 1 dB/mm. According to Figure 6C, this corresponds to a porosity volume fraction greater than 25%.
- the optimal porosity range is that for which: the impedance of the porous metallic material forming the damping back is sufficiently high (close to the impedance of the piezoelectric material), knowing that the impedance decreases with the volume fraction of porosity: cf. Figure 6B; the attenuation is sufficiently high, knowing that the linear attenuation coefficient a increases with the volume fraction of porosity: cf. Figure 6C.
- the optimal range of porosity volume fraction is between 25% and 50%.
- the optimal porosity volume fraction range may be different for another material.
- the characteristics of the porous metallic material forming the damping back 13 of the transducer are: an average pore diameter of less than 500 pm, and less than 200 pm or 100 pm; and/or a porosity volume fraction of between 20% and 60%, and preferably between 25% and 50%, and even more preferably between 25% and 40%.
- the piezoelectric material forming the converter is made of lithium niobate.
- Other piezoelectric materials suitable for high temperature environments can be used, for example barium titanate
- BaTiO 3 bismuth titanate
- AIN aluminum nitride
- langatates lanthanum oxide, gallium and tantalum
- the transducer according to the invention can be used in any application under high temperature, for non-destructive testing or diagnostic or telemetry or obstacle detection or flow measurement purposes.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Investigating Or Analyzing Materials By The Use Of Ultrasonic Waves (AREA)
- Transducers For Ultrasonic Waves (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2206279A FR3137252B1 (fr) | 2022-06-23 | 2022-06-23 | Transducteur ultrasonique pour application à haute température |
| PCT/EP2023/066838 WO2023247639A1 (fr) | 2022-06-23 | 2023-06-21 | Transducteur ultrasonique pour application à haute température |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4543601A1 true EP4543601A1 (fr) | 2025-04-30 |
Family
ID=85036995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23733779.5A Pending EP4543601A1 (fr) | 2022-06-23 | 2023-06-21 | Transducteur ultrasonique pour application à haute température |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20250256302A1 (fr) |
| EP (1) | EP4543601A1 (fr) |
| JP (1) | JP2025520741A (fr) |
| KR (1) | KR20250027262A (fr) |
| CN (1) | CN119403633A (fr) |
| FR (1) | FR3137252B1 (fr) |
| WO (1) | WO2023247639A1 (fr) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4420707A (en) * | 1982-08-09 | 1983-12-13 | Automation Industries, Inc. | Backing for ultrasonic transducer crystal |
| US10602289B2 (en) * | 2010-03-09 | 2020-03-24 | Baker Hughes, A Ge Company, Llc | Acoustic transducer with a liquid-filled porous medium backing and methods of making and using same |
| FR2977377B1 (fr) * | 2011-06-30 | 2015-04-24 | Commissariat Energie Atomique | Traducteur ultrasonore haute temperature utilisant un cristal de niobate de lithium brase avec de l'or et de l'indium |
| GB201501923D0 (en) * | 2015-02-05 | 2015-03-25 | Ionix Advanced Technologies Ltd | Piezoelectric transducers |
-
2022
- 2022-06-23 FR FR2206279A patent/FR3137252B1/fr active Active
-
2023
- 2023-06-21 US US18/878,183 patent/US20250256302A1/en active Pending
- 2023-06-21 WO PCT/EP2023/066838 patent/WO2023247639A1/fr not_active Ceased
- 2023-06-21 JP JP2024575699A patent/JP2025520741A/ja active Pending
- 2023-06-21 KR KR1020257001958A patent/KR20250027262A/ko active Pending
- 2023-06-21 EP EP23733779.5A patent/EP4543601A1/fr active Pending
- 2023-06-21 CN CN202380048871.8A patent/CN119403633A/zh active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN119403633A (zh) | 2025-02-07 |
| KR20250027262A (ko) | 2025-02-25 |
| US20250256302A1 (en) | 2025-08-14 |
| FR3137252B1 (fr) | 2025-01-17 |
| FR3137252A1 (fr) | 2023-12-29 |
| JP2025520741A (ja) | 2025-07-03 |
| WO2023247639A1 (fr) | 2023-12-28 |
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