POLYMERIZATION COMPOSITION FOR PRODUCING A SCINTILLATING HYBRID MATERIAL AND ASSOCIATED KITS
20200408937 ยท 2020-12-31
Inventors
Cpc classification
C08L101/12
CHEMISTRY; METALLURGY
International classification
C08L101/12
CHEMISTRY; METALLURGY
Abstract
Polymerization composition for manufacturing a hybrid material for plastic scintillation detection comprising: monomers, oligomers or their mixtures intended to form at least one constituent polymer of a polymeric matrix; a liquid fluorescent mixture comprising i) 95.6 molar % to 99.1 molar % of a main primary fluorophore consisting of naphthalene and ii) 0.9 molar % to 4.4 molar % of an additional primary fluorophore, the centroid of the light absorption spectrum and of the fluorescence emission spectrum, the fluorescence decay constant and the fluorescence quantum yield of which are judiciously chosen.
The decay constant of the fluorescence of the hybrid material manufactured with the polymerization composition is intermediate between that of a fast plastic scintillator material and of a slow plastic scintillator material. Further, it can be chosen over a wide range.
The invention also relates to ready-for-use kits for manufacturing a polymerization composition.
Claims
1. Polymerization composition for manufacturing a hybrid material for plastic scintillation detection comprising: monomers, oligomers or their mixtures intended to form at least one constituent polymer of a polymeric matrix; a liquid fluorescent mixture comprising, in a molar concentration with respect to the total number of moles of primary fluorophore in the liquid fluorescent mixture; i) from 95.6 molar % to 99.1 molar % of a main primary fluorophore consisting of naphthalene; and ii) from 0.9 molar % to 4.4 molar % of an additional primary fluorophore, the centroid of the light absorption spectrum and of the fluorescence emission spectrum of which respectively have a wavelength comprised between 250 nm and 340 nm and comprised between 330 nm and 380 nm, the fluorescence decay constant of which is comprised between 1 ns and 10 ns and the fluorescence quantum yield in a nonpolar solvent of which is comprised between 0.2 and 1.
2. (canceled)
3. Polymerization composition according to claim 1, wherein the liquid fluorescent mixture comprises from 96 molar % to 99.1 molar % of the main primary fluorophore.
4. Polymerization composition according to claim 1, wherein the additional primary fluorophore has a fluorescence quantum yield in a nonpolar solvent comprised between 0.5 and 1.
5. Polymerization composition according to claim 1, wherein the liquid fluorescent mixture comprises a secondary fluorophore.
6. Polymerization composition according to claim 5, wherein the secondary fluorophore has a light absorption spectrum and a fluorescence emission spectrum, the centroid of which is respectively at a wavelength comprised between 330 nm and 380 nm and comprised between 405 nm and 460 nm, and the fluorescence quantum yield in a nonpolar solvent of which is comprised between 0.5 and 1.
7. Polymerization composition according to claim 5, wherein the secondary fluorophore has a light absorption spectrum and a fluorescence emission spectrum, the centroid of which is respectively at a wavelength comprised between 330 nm and 380 nm and comprised between 460 nm and 550 nm, and the fluorescence quantum yield in a nonpolar solvent of which is comprised between 0.5 and 1.
8. Polymerization composition according to claim 5, wherein the secondary fluorophore has a light absorption spectrum and a fluorescence emission spectrum, the centroid of which is respectively at a wavelength comprised between 330 nm and 380 nm and comprised between 550 nm and 630 nm, and the fluorescence quantum yield in a nonpolar solvent of which is comprised between 0.5 and 1.
9. Polymerization composition according to claim 5, wherein the secondary fluorophore is at a concentration by weight, with respect to the weight of the polymerization composition, which is comprised between 0.002% and 0.5% by weight.
10-11. (canceled)
12. Ready-for-use kit with mixed fluorophores for the manufacture of a polymerization composition as defined according to claim 1 comprising, separately for the purpose of the assembling thereof, the following components of the kit: i) monomers, oligomers or their mixtures intended to form at least one constituent polymer of a polymeric matrix, as defined in claim 1 and; ii) a fluorescent mixture for a polymerization kit comprising, as a molar concentration with respect to the total number of moles of primary fluorophore in the fluorescent mixture for a polymerization kit: i) from 95.6 molar % to 99.1 molar % of a main primary fluorophore consisting of naphthalene; and ii) from 0.9 molar % to 4.4 molar % of an additional primary fluorophore, the centroid of the light absorption spectrum and of the fluorescence emission spectrum of which respectively have a wavelength comprised between 250 nm and 340 nm and comprised between 330 nm and 380 nm, the fluorescence decay constant of which is comprised between 1 ns and 10 ns and the fluorescence quantum yield in a nonpolar solvent of which is comprised between 0.2 and 1.
13. Ready-for-use kit with mixed fluorophores according to claim 12, comprising first compartment I) containing the monomers, the oligomers or their mixtures; a second compartment II) containing the fluorescent mixture for a polymerization kit.
14-15. (canceled)
16. Ready-for-use kit with mixed fluorophores according to claim 12, wherein a secondary fluorophore, a polymerization solvent or their mixture is mixed with the i) monomers, oligomers or their mixtures and/or ii) the fluorescent mixture for a polymerization kit.
17. Ready-for-use kit with separate fluorophores for the manufacture of a polymerization composition for manufacturing an hybrid material for plastic scintillation detection, comprising: monomers, oligomers or their mixtures intended to form at least one constituent polymer of a polymeric matrix; a liquid fluorescent mixture comprising, in a molar concentration with respect to the total number of moles of primary fluorophore in the liquid fluorescent mixture: i) from 80 molar % to 99.6 molar % of a main primary fluorophore consisting of naphthalene; and ii) from 0.4 molar % to 20 molar % of an additional primary fluorophore, the centroid of the light absorption spectrum and of the fluorescence emission spectrum of which respectively have a wavelength comprised between 250 nm and 340 nm and comprised between 330 nm and 380 nm, the fluorescence decay constant of which is comprised between 1 ns and 10 ns and the fluorescence quantum yield in a nonpolar solvent of which is comprised between 0.2 and 1; the ready-for-use kit with separate fluorophores comprising, separately for the purpose of the assembling thereof, the following components of the kit: i) a first polymerization mixture comprising monomers, oligomers or their mixtures intended to form at least one constituent polymer of the polymeric matrix; and, in a molar concentration with respect to the total number of moles of primary fluorophore in the kit, from 80 molar % to 99.6 molar % of a main primary fluorophore consisting of naphthalene; ii) a second polymerization mixture comprising monomers, oligomers or their mixtures intended to form at least one constituent polymer of the polymeric matrix; and, at a molar concentration with respect to the total number of moles of primary fluorophore in the kit, from 0.4 molar % to 20 molar % of an additional primary fluorophore, the centroid of the light absorption spectrum and of the fluorescence emission spectrum of which respectively have a wavelength comprised between 250 nm and 340 nm and comprised between 330 nm and 380 nm, the fluorescence decay constant of which is comprised between 1 ns and 10 ns and the fluorescence quantum yield in a nonpolar solvent of which is comprised between 0.2 and 1.
18. Ready-for-use kit with separate fluorophores according to claim 17, comprising: a first compartment I) containing the first polymerization mixture; a second compartment II) containing the second polymerization mixture.
19. (canceled)
20. Ready-for-use kit with separate fluorophores according to claim 17, wherein the first polymerization mixture and/or the second polymerization mixture comprise a secondary fluorophore, a polymerization solvent or their mixture.
21-23. (canceled)
24. Ready-for-use kit according to claim 12, further comprising at least one ancillary compartment each containing III) a crosslinking agent or a polymerization initiator.
25. Ready-for-use kit with polymers for the manufacture of an extrusion mixture comprising, separately for the purpose of the assembling thereof, the following components of the kit: i) polymerized ingredients intended to form a polymeric matrix which comprises at least one constituent polymer formed from monomers, oligomers or their mixtures; ii) a fluorescent mixture for an extrusion kit comprising, at a molar concentration with respect to the total number of moles of primary fluorophore in the fluorescent mixture for an extrusion kit: i) from 80 molar % to 99.6 molar % of a main primary fluorophore consisting of naphthalene; and ii) from 0.4 molar % to 20 molar % of an additional primary fluorophore, the centroid of the light absorption spectrum and of the fluorescence emission spectrum of which respectively have a wavelength comprised between 250 nm and 340 nm and comprised between 330 nm and 380 nm, the fluorescence decay constant of which is comprised between 1 ns and 10 ns, and the fluorescence quantum yield in a nonpolar solvent of which is comprised between 0.2 and 1.
26. Ready-for-use kit with polymers according to claim 25, comprising: a first compartment I) containing the polymerized ingredients; a second compartment II) containing the liquid fluorescent mixture for an extrusion kit.
27. (canceled)
28. Ready-for-use kit with polymers according to claim 25, wherein a secondary fluorophore, a polymerization solvent or their mixture is mixed with i) the polymerized ingredients and/or ii) the fluorescent mixture for an extrusion kit.
29. Ready-for-use kit with polymers according to claim 25, further comprising: a secondary compartment containing a secondary fluorophore and/or a polymerization solvent.
30-32. (canceled)
33. Ready-for-use kit according to claim 17, further comprising at least one ancillary compartment each containing III) a crosslinking agent or a polymerization initiator.
Description
BRIEF DESCRIPTION OF THE FIGURES
[0341]
[0342]
[0343] By way of comparison,
[0344]
[0345]
[0346]
[0347]
[0348]
DESCRIPTION OF SPECIFIC EMBODIMENTS
[0349] Unless otherwise indicated, the examples are carried out at atmospheric pressure and ambient temperature.
1. Manufacture of a Hybrid Material for Plastic Scintillation Measurement According to the Invention.
[0350] 1.1. Example 1 of Manufacture of a Plastic Scintillator with a Secondary Fluorophore.
[0351] A liquid mixture comprising fluorescent molecules (5% by weight (3.624 g) of naphthalene as main primary fluorophore+0.2% by weight (183 mg) of 2,5-diphenyloxazole (PPO) as additional primary fluorophore and 0.02% by weight (15.2 mg) of 9,10-diphenylanthracene (DPA) as secondary fluorophore), to which styrene (80 ml, i.e. 94.78% by weight) is subsequently added, is introduced into a single-necked round-bottomed flask dried beforehand under an inert argon atmosphere.
[0352] After five degassings under cold conditions under vacuum (known as freeze-pump-thaw method in English), the polymerization medium obtained, returned to ambient temperature, is poured into a mold capable of giving the final shape to the plastic scintillator.
[0353] After heating the sealed mold under an inert argon atmosphere at 140 C. for five days, the plastic scintillator is removed from the mold, precision ground and then polished.
[0354] 1.2. Example 2 of Manufacture of a Plastic Scintillator with a Secondary Fluorophore.
[0355] A liquid mixture comprising fluorescent molecules (5% by weight of naphthalene (3.624 g)+0.2% by weight of 2,5-diphenyloxazole (PPO, 183 mg) as primary fluorophores and 0.02% by weight of 1,4-bis(4-methyl-5-phenyl-2-oxazolyl)benzene (dimethylPOPOP, 15.2 mg) as secondary fluorophore), to which styrene (80 ml, 94.78% by weight) is subsequently added, is introduced into a single-necked round-bottomed flask dried beforehand under an inert argon atmosphere.
[0356] After five degassings under cold conditions under vacuum, the polymerization medium obtained, returned to ambient temperature, is poured into a mold.
[0357] After heating the sealed mold under an inert argon atmosphere at 140 C. for five days, the plastic scintillator is removed from the mold, precision ground and then polished.
[0358] 1.3. Example 3 of Manufacture of a Plastic Scintillator with a Crosslinked Polymeric Matrix and a Secondary Fluorophore.
[0359] A liquid mixture comprising fluorescent molecules (5% by weight of naphthalene (3.624 g)+0.2% by weight of 2,5-diphenyloxazole (PPO, 183 mg) as primary fluorophores and 0.02% by weight of 9,10-diphenylanthracene (DPA, 15.2 mg) as secondary fluorophore), to which 80% by weight of styrene (64 ml) and then 14.78% by weight of 1,4-butanediyl dimethacrylate (10.3 ml) as crosslinking agent are subsequently added, is introduced into a single-necked round-bottomed flask dried beforehand under an inert argon atmosphere.
[0360] After five degassings under cold conditions under vacuum, the polymerization medium obtained, returned to ambient temperature, is poured into a mold.
[0361] After heating the sealed mold under an inert argon atmosphere at 65 C. for ten days, the plastic scintillator is removed from the mold, precision ground and then polished.
2. Manufacture of a Range of Plastic Scintillators with a Variable Proportion Between the Primary Fluorophores.
[0362] Plastic scintillators are manufactured according to the characteristics specified in the table of
[0363] They differ in the chemical composition of the polymeric matrix (St=polystyrene; St/1,4=mixture of styrene and of 1,4-butanediyl dimethacrylate which are polymerized in a proportion by weight between the two monomers respectively of 5 to 1) and in the molar ratio of the main primary fluorophore (naphthalene) to the additional primary fluorophore (2,5-diphenyloxazole=PPO). The concentration by weight of each primary fluorophore is shown as percentage with respect to the total weight of the plastic scintillator, the remainder thus being constituted by the percentage by weight of the polymeric matrix, of the other primary fluorophore, and also by a constant concentration of 0.02% by weight of 9,10-diphenylanthracene (9,10-DPA) added as secondary fluorophore, not shown in the table of
[0364] The decay constant tau of the fluorescence is measured by time-correlated single photon counting as described above. It is in this instance generally obtained by adjustment of biexponential type of the values obtained, weighting factors for each exponential component being shown as percentage in brackets. In order to facilitate the comparison between the different plastic scintillators, the biexponential tau is converted into median monoexponential tau in accordance with the equation below, for which the quality of the adjustment of the measurement with respect to the light pulse is evaluated by the chi squared, which should ideally be as close as possible to 1. Alternatively, commercial items of time-correlated single photon counting equipment automatically calculate the median monoexponential tau, indeed even the biexponential tau, from the data recorded.
[0365] The median decay constant monoexponential tau of the fluorescence can be calculated from the following formula:
.sub.median=.sub.fast%.sub.fast+.sub.slow%.sub.slow
[0366] The percentages % fast and % slow represent the respective weights of the fast and slow decay. They are adjusted in order to give the best possible description of the median decay. Their sum is equal to 100%.
[0367] Thus,
[0368] By way of comparison, the main primary fluorophore according to
##STR00005##
[0369] The change in the fluorescence decay constant median monoexponential tau (median monoexponential tau) is studied as a function of the pyrene/PPO molar ratio in a similar way to the study of
[0370] Another advantage of the use of a hybrid material for the plastic scintillation measurement is demonstrated by
[0374] The recording profile used (500 ns with a noise of 10 counts/second) is superimposed on the pulses of these three plastic scintillators.
[0375]
[0376] The acquisition is carried out by the opening of a time window for recording these pulses. As indicated above, the duration of this recording is generally chosen in order to be from 6 to 10 times greater than the highest fluorescence decay constant, this decay constant corresponding, for each pulse, to the width on the abscissa of the pulse, expressed in nanoseconds. In the case of high count rates, such as, for example, when a radioactive source of high activity is brought into the presence of the phoswich device, the use of a slow compartment thus involves using a much longer recording window: several pulses can then coexist in the same time window (pile-up phenomenon), which is then reflected by acquisition errors in the absence of discrimination of these pulses.
[0377] These properties of a hybrid compartment are thus particularly advantageous for the discrimination of the beta particle in an environment of gamma rays with a phoswich device comprising a hybrid compartment (in particular when it is the thinnest compartment) and a fast compartment, each of these two compartments respectively detecting the beta particle and the gamma radiation.
3. Example of Qualitative or Quantitative Measurement of a Radioactive Substance in Plastic Scintillation According to the Measurement Method of the Invention.
[0378] 3.1. Measurement Protocol.
[0379] A plastic scintillator comprising the hybrid material of the invention in which a secondary fluorophore is incorporated is connected by means of optical grease to a photomultiplier tube which performs the function of photodetector of an electronic acquisition module.
[0380] Subsequent to its exposure to the radioactive substance, the plastic scintillator emits scintillation photons which are converted into an electrical signal by the photomultiplier tube supplied with high voltage.
[0381] The electrical signal is subsequently acquired and then analyzed with an oscilloscope, spectrometry software or an electronic acquisition board. The data thus collected is subsequently processed by computer.
[0382] This analysis results in an energy spectrum histogram representing, on the abscissa, the channels (derived from an output energy) and, on the ordinate, the number of counts/second. After calibration with a gamma-emitting source of known energy, the energy of the radioactive substance to be measured is determined.
[0383] 3.2. Quantitative Measurement with the Scintillator.
[0384] On the basis of this measurement protocol, a quantitative measurement is carried out with a chlorine-36 beta radioactive source of 4n activity equal to 6 kBq. This source is placed on the upper part of the plastic scintillator.
[0385] A cylindrical plastic scintillator of circular section, with a diameter of 49 mm and height of 35 mm (reference F30B of the table of
[0386] In a first step, an energy calibration of the system (scintillator+photomultiplier) is carried out by means of 2 radioactive sources: one emitting gamma rays in the [0-200 keV] range and the other in the [500-1.3 MeV] range. This energy calibration is carried out by locating the channel corresponding to 80% of the amplitude of the Compton edge. For example, if the ordinate of the Compton edge corresponds to 100 counts per second, the abscissa on the falling slope of the Compton edge at 80 counts per second associates the energy of the Compton edge (in keV) with the channel.
[0387] In a second step, this calibration having been carried out, the chlorine-36 beta source is joined to the upper face of the plastic scintillator. The analysis of the energy spectrum gives a read activity of 2.1 kBq (and thus an intrinsic efficiency according to which 70% of the incident radiation is measured) and a photoelectric peak centered at approximately 250 keV.
[0388] The energy spectrum of the hybrid plastic scintillator obtained is represented in
4. Geometries of a Device for Plastic Scintillation Detection According to the Invention.
[0389] Such a device is described with reference to
[0390] 4.1. Device with a Bonding Layer.
[0391] According to a first embodiment illustrated by
[0392] The upstream hybrid scintillator 1 and the downstream fast scintillator 2 are optionally contained in a shell 8 which can constitute the housing or the frame of the device. They are attached to one another with an optical interface layer forming a bonding layer 5.
[0393] The bonding layer 5 is generally a layer distinct from the upstream hybrid scintillator 1 and from the downstream fast scintillator 2, for example an attaching layer. However, it can be a layer composed of an intermediate material resulting from the melting of the upstream hybrid scintillator material 1 and of the downstream fast scintillator 2, as for plastic scintillation detectors comprising two scintillators bonded to one another by thermomechanical pressing.
[0394] The bonding layer 5 can be an optical layer which is transparent to luminescent radiation. It can be composed of a bonding substance chosen from greases, adhesives, gels, optical cements, elastomeric compounds or silicone compounds ordinarily employed in the optical field. Such a substance allows the light radiation leaving the downstream scintillator to pass.
[0395] A photodetector 3 (such as, for example, a photomultiplier) is attached to the downstream fast scintillator with an optical interface layer 6. It is capable of collecting the radioluminescent radiation resulting from the contact of an ionizing particle or of ionizing radiation with the scintillators 1 and 2.
[0396] The face of the upstream hybrid scintillator 1 which first receives the incident radiation according to the direction of propagation R to be detected is covered with a metal layer 4 which is in this instance thin. This metal layer 4 constitutes an inlet window with which the incident radiation (or the incident particle) comes into contact, while preventing the ambient light from also coming into contact with the upstream scintillator by isolating it from the light. The side faces of the upstream and downstream scintillators are covered with a light reflector or diffuser 7 composed of a reflecting substance comprising, for example, aluminum (aluminized Mylar, aluminum paper, and the like) or composed of a scattering substance comprising, for example, Teflon, a paint based on titanium oxide TiO.sub.2, a paint based on magnesium oxide MgO or Millipore filter paper.
[0397] 4.2. Device without a Bonding Layer.
[0398] According to a second embodiment illustrated by
[0399]
[0400] The plastic scintillation detection device D of the invention without the bonding layer illustrated by
[0401] The upstream hybrid scintillator 1 and the downstream fast scintillator 2 are in direct contact and are attached to one another by an autogenous coupling process. In this coupling process, a first crosslinked plastic scintillator is prepared and then polymerized. After this first solid formulation, the monomer solution containing the fluorescence mixture in order to manufacture the second scintillator is poured onto the first scintillator, and the assembly is subsequently heated.
[0402] The scintillators 1 and 2 are optionally contained in a shell 8 which can constitute the housing or the frame of the device.
[0403] A photodetector 3 (such as, for example, a photomultiplier) is attached to the downstream fast scintillator with an optical interface layer 6. It is capable of collecting the radioluminescent radiation resulting from the contact of an ionizing particle or of ionizing radiation with the scintillators 1 and 2.
[0404] The face of the upstream hybrid scintillator 1 which first receives the incident radiation (or the incident particle), according to the direction of propagation R, to be detected is covered with a light-opaque layer 9. This opaque layer 9 constitutes an inlet window with which the incident radiation comes into contact, while limiting the contact of the ambient light with the upstream scintillator.
[0405] The side faces of the upstream and downstream scintillators are covered with a light reflector or diffuser 7. The light-opaque layer 9 is permeable to the passage of beta radiation and gamma radiation. It is composed of an opaque substance, such as, for example, Mylar.
[0406] As indicated above, the upstream hybrid scintillator 1 can have a lower thickness than the downstream fast scintillator 2. Such a configuration is represented in
[0407] 4.3. Scintillating Optical Fiber.
[0408]
[0409] The present invention is not limited to the embodiments described and represented, and a person skilled in the art will know how to combine them and to contribute thereto with his general knowledge of numerous alternative forms and modifications.
[0410] The invention is applicable to the fields where scintillators are used, in particular: [0411] in the industrial field, for example for the measurement of physical parameters of parts during manufacture, for the nondestructive inspection of materials, for the monitoring of radioactivity at the entrance and exit points of sites and for the monitoring of radioactive waste, [0412] in the geophysical field, for example for the evaluation of the natural radioactivity of soils, [0413] in the field of fundamental physics and in particular nuclear physics, [0414] in the field of the safety of goods and people, for example for the safety of critical infrastructures, the monitoring of moving goods (luggage, containers, vehicles, and the like), and also for the protection from radiation of workers in the industrial, nuclear and medical sectors, [0415] in the field of medical imaging.
REFERENCES CITED
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