IP Library Granted Patent US 11,479,717
Granted Patent B1
US 11,479,717 · App. 16/198,424 · Granted Oct 25, 2022

High luminescence plastic scintillators

Inventors: Nicholas Myllenbeck (Livermore, CA); Patrick L. Feng (Livermore, CA); Joseph Carlson (Castro Valley, CA)
Assignee: National Technology & Engineering Solutions of Sandia, LLC
C09K11/06C09K11/025G01T1/2033C09K2211/1011C09K2211/1014C09K2211/1018
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Quick Facts
Patent No.
US 11,479,717
App. No.
16/198,424
Granted
Oct 25, 2022
Kind
B1
Abstract

A plastic scintillator includes a polymeric matrix comprising a primary fluorophore capable of forming an amorphous glass in its pure form. The primary fluorophore is also capable of generating luminescence in the presence of ionizing radiation and includes: a central species including silicon; a luminescent organic group bonded to the central species or to an optional organic linker group, the luminescent organic group including fluorene or an analog thereof; and the optional organic linker group, if present, is bonded to the central species and the luminescent organic group.

Claims (57)

1. A plastic scintillator comprising:

a polymeric matrix;

a primary fluorophore;

wherein the primary fluorophore is capable of generating luminescence in the presence of ionizing radiation and is capable of forming an amorphous glass in its pure form, and includes:

a central species including silicon;

a luminescent organic group bonded to the central species or to an optional organic linker group, the luminescent organic group including a polycyclic aliphatic or polycyclic aromatic group or analogs thereof;

the optional organic linker group, if present, is bonded to the central species and the luminescent organic group;

wherein the luminescent organic group includes a polycyclic aromatic group that is a fluorene or an analog thereof.

2. The plastic scintillator of claim 1 , wherein the polymeric matrix is selected from one or more polymers from the following group: a vinylaromatic polymer, and a polymer containing one or more carbonate groups.

3. The plastic scintillator of claim 1 , wherein the primary fluorophore is selected from the group consisting of one or more silyl-fluorene based molecules functionalized one or more times at one or more of the 2-, 7-, or 9-positions of the fluorene group.

4. The plastic scintillator of claim 3 , wherein the silyl group is attached to the 2-position of the fluorene group and other functional groups, if present, are selected from the group consisting of: aliphatic alkanes or alkenes, aromatic hydrocarbons, methoxy, hydroxy, amine, alkylamine, phenylamine, or analogs thereof, wherein alkyl chains in any of the functional groups have 1 to 20 carbon atoms.

5. A plastic scintillator comprising:

a polymeric matrix;

a primary fluorophore;

wherein the primary fluorophore is capable of generating luminescence in the presence of ionizing radiation and is capable of forming an amorphous glass in its pure form, and includes:

a central species including silicon;

a luminescent organic group bonded to the central species or to an optional organic linker group, the luminescent organic group including a polycyclic aliphatic or polycyclic aromatic group or analogs thereof;

the optional organic linker group, if present, is bonded to the central species and the luminescent organic group;

the plastic scintillator further comprising an anti-fog agent, wherein the anti-fog agent is a chemical species that includes:

a cyclic central group, which can be aromatic, hetero-aromatic, aliphatic or hetero-aliphatic;

an oxygen-containing functional group; and

optionally, a linking group selected from the group consisting of: a C 1 to C 20 alkyl group, an ethylene glycol group, or polyethylene glycol group;

wherein if the optional linking group is not present, the cyclic central group is bonded directly to the oxygen-containing functional group; and if the optional linking group is present, the cyclic central group is bonded to the optional linking group, and the oxygen-containing functional group is also bonded to the optional linking group.

6. The plastic scintillator of claim 1 , wherein the plastic scintillator includes the primary fluorophore in a range of 0.5% to 50% by weight of the total composition.

7. The plastic scintillator of claim 1 , wherein the plastic scintillator includes the primary fluorophore in a range of 50% to 99% by weight of the total composition.

8. The plastic scintillator of claim 1 , wherein the plastic scintillator produces a light yield of 10,000 photons/MeVee to 30,000 photons/MeVee with a trans-stilbene reference.

9. The plastic scintillator of claim 1 , further comprising a wavelength shifter selected from the group consisting of: 1,4-bis(5-phenyl-2-oxazolyl)benzene (POPOP), 2,5-Bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BBOT), 1,4-bis(9,9′-dialkylfluoren-2-yl) benzene, or 4,4′-(9,9-dialkylfluoren-2-yl)biphenyl, 1,4-bis(2-methylstyrl)benzene (bis-MSB), 9,10-diphenylanthracene, 2-(1-naphthyl)-5-phenyloxazole (NPO), or pi-conjugated fluorene-based fluorophores comprising 2-bifluorene, 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl (DPVBi) and 9,10-diphenylanthracene (DPA) derivatives of these, or combinations of these.

10. The plastic scintillator of claim 1 , further comprising a 10 B-containing or an 6 Li containing compound including a group selected from the group consisting of: carborane, boronic acid, boronic ester, boronic pinacol ester, borane, a lithium salt of an aliphatic or aromatic acid, lithium benzoate, or Li-oxazolecarboxylate, lithium benzoate, lithium biphenylcarboxylate, lithium salicylate, lithium phenylsalicylate, lithium alkoxybenzoic acid, or analogs thereof.

11. The plastic scintillator of claim 1 , further comprising an organometallic compound selected from the group of: metalloalkyl compounds, alkylmetallomethacrylates, alkylmetalloacrylates, metallomethacrylates, alkylmetallostyrenes, metalloacrylates, and metallostyrenes.

12. The plastic scintillator of claim 1 , wherein the plastic scintillator has a thickness of 1 micrometer to 5 meters.

13. The plastic scintillator of claim 1 , wherein the primary scintillation lifetime is between 500 picoseconds and 5 nanoseconds.

14. The plastic scintillator of claim 1 , wherein the plastic scintillator is capable of neutron and gamma pulse-shape discrimination at 1 keVee to 30 MeVee.

15. The plastic scintillator of claim 1 , wherein the plastic scintillator is capable of gamma-ray spectroscopy at 5 keVee to 1.3 MeVee.

16. A method of making a plastic scintillator comprising the steps of either (a) or (b):

(a) dissolving a primary fluorophore in a monomer;

then in-situ polymerizing the monomer via a radical addition mechanism or a condensation reaction; or

(b) blending a polymer and a primary fluorophore with one or more of mechanical mixing, heating, or co-dissolution in a solvent to form a blended material; and

thermally processing the plastic scintillator into a desired shape;

wherein the primary fluorophore is capable of generating luminescence in the presence of ionizing radiation and is capable of forming an amorphous glass in its pure form, and includes:

a central species including silicon;

a luminescent organic group bonded to the central species or to an optional organic linker group, the luminescent organic group including a polycyclic aliphatic or polycyclic aromatic group or analog thereof;

the optional organic linker group, if present, is bonded to the central species and the luminescent organic group;

wherein the luminescent organic group includes fluorene or an analog thereof.

17. The method of claim 16 , wherein the plastic scintillator further comprises an anti-fog agent, wherein the anti-fog agent is a chemical species that includes:

a cyclic central group, which can be aromatic, hetero-aromatic, aliphatic or hetero-aliphatic;

an oxygen-containing functional group; and

optionally, a linking group selected from the group consisting of: a C 1 to C 20 alkyl group, an ethylene glycol group, or polyethylene glycol group;

wherein if the optional linking group is not present, the cyclic central group is bonded directly to the oxygen-containing functional group; and if the optional linking group is present, the cyclic central group is bonded to the optional linking group, and the oxygen-containing functional group is also bonded to the optional linking group.

18. The method of claim 16 , wherein the following steps are conducted: (a) dissolving the primary fluorophore in the monomer;

then in-situ polymerizing the monomer via the radical addition mechanism or the condensation reaction.

19. The method of claim 16 , wherein the following steps are conducted:

(b) blending the polymer and the primary fluorophore with one or more of mechanical mixing, heating, or co-dissolution in a solvent to form a blended material; and thermally processing the plastic scintillator into a desired shape.

20. The plastic scintillator of claim 1 , further comprising an anti-fog agent, wherein the anti-fog agent is a chemical species that includes:

a cyclic central group, which can be aromatic, hetero-aromatic, aliphatic or hetero-aliphatic;

an oxygen-containing functional group; and

optionally, a linking group selected from the group consisting of: a C 1 to C 20 alkyl group, an ethylene glycol group, or polyethylene glycol group;

wherein if the optional linking group is not present, the cyclic central group is bonded directly to the oxygen-containing functional group; and if the optional linking group is present, the cyclic central group is bonded to the optional linking group, and the oxygen-containing functional group is also bonded to the optional linking group.

Assignments (2)
CONFIRMATORY LICENSE Recorded Feb 11, 2020
From: NATIONAL TECHNOLOGY & ENGINEERING SOLUTIONS OF SANDIA, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 051781/0113 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 5, 2020
From: MYLLENBECK, NICHOLAS; FENG, PATRICK L.; CARLSON, JOSEPH
To: NATIONAL TECHNOLOGY & ENGINEERING SOLUTIONS OF SANDIA, LLC
Reel/Frame 051725/0381 →