Boron compounds for use in scintillators and admixture to scintillators
09796921 · 2017-10-24
Assignee
Inventors
- Cory Pecinovsky (Longmont, CO, US)
- Pascale Meysing (Golden, CO, US)
- Adam Mahl (Denver, CO, US)
- John Dorgan (Golden, CO, US)
- Uwe Greife (Golden, CO, US)
- Tyler Remedes (Colorado Springsw, CO, US)
Cpc classification
G21K4/00
PHYSICS
International classification
Abstract
The present disclosure is directed to liquid boron compounds for use in scintillation. The present disclosure further relates to liquid boron compounds for admixture to plastic and liquid scintillators.
Claims
1. A compound for use in scintillation, comprising: a boron compound, wherein the boron compound is liquid borate ester and wherein the borate ester compound is soluble, wherein the boron compound is a borate ester synthesized according to B(OH).sub.3+3ROH=B(OR).sub.3+3 H.sub.2O, and R comprises at least one of ethanol, methanol, propanol, butanol, benzyl alcohol, phenol, pyrocatechol, ethylene glycol, and propylene glycol, and wherein the compound further comprises at least one of 2,5 diphenyloxazole, 1,4,4-tetraphenyl-1,3-butadiene, p-terphenyl, p-quaterphenyl, 1,4-diphenyl-1,3-butadiene, stilbene, biphenyl, 1,6-diphenyl-1,3,5-hexatriene, diphenylacetylene, diphenyldiacetylene, 2,4-bis(5-phenyloxazole-2-yl)benzene, 9,10-diphenylanthracene, 1,3-diphenyl-2-pyrazoline, diphenylethane, and 1-phenyl-1,3,3-trimethylindan.
2. The compound of claim 1, wherein the boron compound comprises a functionalized boron.
3. The compound of claim 1, wherein the boron compound is B(OR).sub.3.
4. The compound of claim 1, wherein the compound is admixed to a scintillator compound.
5. The compound of claim 4, wherein the scintillator compound is used in a plastic scintillator.
6. The compound of claim 4, wherein the scintillator compound is used in a liquid scintillator.
7. The compound of claim 1, wherein the borate ester further comprises a functional group of at least one of benzyl alcohol, propylene glycol, ethylene glycol, ethanol, methanol, propanol, butanol, phenol, and pyrocatechol.
8. The compound of claim 1, further comprising at least one of anthracene and naphthalene.
9. A method of detecting scintillation, comprising: monitoring a detection device, wherein the detection device comprises a borate ester compound, wherein the borate ester compound is soluble, and wherein the boron ester compound is a borate ester synthesized according to B(OH).sub.3+3ROH=B(OR).sub.3+3 H.sub.2O, and R comprises at least one of ethanol, methanol, propanol, butanol, benzyl alcohol, phenol, pyrocatechol, ethylene glycol, and propylene glycol, and wherein the compound further comprises at least one of 2,5 diphenyloxazole, 1,4,4-tetraphenyl-1,3-butadiene, p-terphenyl, p-quaterphenyl, 1,4-diphenyl-1,3-butadiene, stilbene, biphenyl, 1,6-diphenyl-1,3,5-hexatriene, diphenylacetylene, diphenyldiacetylene, 2,4-bis(5-phenyloxazole-2-yl)benzene, 9,10-diphenylanthracene, 1,3-diphenyl-2-pyrazoline, diphenylethane, and 1-phenyl-1,3,3-trimethylindan; and detecting scintillation.
10. The method of claim 9, wherein the detection device further comprises a fluorescent dopant.
11. The method of claim 9, wherein the borate ester compound is a non-flammable borate ester compound.
12. The method of claim 10, wherein the fluorescent dopant and the borate ester compound are combined using continuous extrusion.
13. A scintillation device, comprising: a borate ester compound, wherein the borate ester compound is soluble, and wherein the boron ester compound is a borate ester synthesized according to B(OH).sub.3+3ROH=B(OR).sub.3+3 H.sub.2O, and R comprises at least one of ethanol, methanol, propanol, butanol, benzyl alcohol, phenol, pyrocatechol, ethylene glycol, and propylene glycol, and wherein the compound further comprises at least one of 2,5 diphenyloxazole, 1,4,4-tetraphenyl-1,3-butadiene, p-terphenyl, p-quaterphenyl, 1,4-diphenyl-1,3-butadiene, stilbene, biphenyl, 1,6-diphenyl-1,3,5-hexatriene, diphenylacetylene, diphenyldiacetylene, 2,4-bis(5-phenyloxazole-2-yl)benzene, 9,10-diphenylanthracene, 1,3-diphenyl-2-pyrazoline, diphenylethane, and 1-phenyl-1,3,3-trimethylindan.
14. The device of claim 13, wherein the borate ester compound is a standalone scintillator and a product of commercially available 10-B boric acid.
15. The device of claim 14, wherein the borate ester compound is a non-flammable borate ester compound that is soluble as an additive in a liquid scintillator solution.
16. The device of claim 13, wherein the detection device further comprises an electronic light sensor.
17. The device of claim 13, wherein the device uses a pulse shape discriminator in the scintillation.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(21) The present disclosure relates to methods of producing boron compounds for use in scintillators and as admixtures to scintillators. More specifically, the present disclosure relates to methods of producing boron compounds for use as transparent admixtures to commercially available or widely used liquid and plastic scintillator formulations. Such scintillators can be used to detect neutron radiation through the formation of a light signal upon interaction with neutrons, for example. Thus, in embodiments, the boron esters disclosed herein by themselves can act as scintillators when fluorescent dopants are admixed.
(22) In embodiments, scintillators of the present disclosure include liquid scintillators having a boron compound, as well as scintillators having a plastic matrix, one or more fluorescent dopants, and a boron compound that is soluble in the plastic. In further embodiments, methods to functionalize boron compounds to enhance solubility in specific plastics are disclosed. In addition, methods of producing a boron compound that shows improved solubility in polystyrene and other plastics, and/or improved transparency, and/or that acts as a fluorescent dopant, are disclosed. Further, methods that use inexpensive plastic matrices, boron-containing compounds, and fluorescent dopants combined with continuous extrusion processing are disclosed.
(23) As discussed above, efficient neutron detection usually requires large detectors which need to employ a mechanism to distinguish the neutron and gamma radiation. Exemplary methods to accomplish this introduce into the detector material atoms or compounds containing an isotope with which neutrons undergo a nuclear reaction with a high probability. It is thereby possible to produce a unique signature detecting the neutron radiation field. This technique may be used in liquid or plastic scintillators into which .sup.6Li, .sup.10B, or gadolinium containing compounds are dissolved.
(24) Various embodiments of the present disclosure relate to transparent boron compounds, including compounds that are neither flammable nor combustible and can be easily produced from commercially available enriched .sup.10boricacid. The compounds include compounds that have been admixed to standard recipes for extruded and cast polystyrene based plastic scintillators, as well as to commercially available liquid scintillator mixtures. In addition, in various embodiments of the compounds disclosed herein, neutron sensitivity via neutron capture on .sup.10B is exhibited, and neutron-gamma PSD is retained in scintillators that exhibited it prior to the admixture.
(25) In neutron detection, incoming fast neutrons lose energy through elastic collisions with (predominantly) the hydrogen nuclei (protons) in the scintillator. This interaction produces a first signal in a scintillator. In some types of scintillators, a pulse shape of the photon pulse can provide information on the incident radiation type (e.g., neutron-gamma discrimination). After the neutrons have been slowed down (e.g., following several collisions) they can undergo nuclear reactions with a neutron sensitive dopant, represented by the following equations:
.sup.10B+.sup.1n.sub.th.sup.7Li (1.0 MeV)+α (1.8 MeV) Q=2.792 MeV 7% (1)
.sup.10B+.sup.1n.sub.th.sup.7Li* (0.83 MeV)+α (1.47 MeV) Q=2.310 MeV 93%.fwdarw..sup.7Li*
.sup.7Li+γ (0.48 MeV) (2)
(26) However, due to the fact that natural boron or .sup.10B loaded scintillators are commercially available but very expensive, it is advantageous to have alternatives for such scintillators. Such alternatives would make use of new and/or easier to produce compounds, which could be admixed (e.g., loaded in) to commonly used scintillator materials. Thus, in embodiments disclosed herein, liquid compounds containing boron display scintillation properties and may be used as transparent admixtures to commercially available or widely used liquid and plastic scintillator formulations. Various embodiments disclosed herein use several liquid, boron containing, compounds that by themselves exhibit scintillating properties.
(27) Also, similar to other scintillators, the scintillation performance of these compounds may be enhanced by the admixture of fluorescent dopants at the few percent level. Fluorescent dopants not only provide more efficient fluorescence light production but also shift the light emission to wavelengths where common photo-detectors are most sensitive.
(28) Boron containing compounds, including synthesized boron containing compounds, of the present disclosure are borate esters. The material may use natural boron 10B-enriched material produced starting with commercially easily available boric acid or .sup.10B-acid. The borate ester may include natural boron, boron-10 enriched boron, or some combination of boron and/or isotopically enriched borons. The borate ester can contain a single boron atom per molecule or have a repetitive cyclic or polymeric structure. The borate ester can be functionalized to increase solubility in the plastic matrix. The borate ester can contain phenyl rings or other chemical groups to enhance scintillation performance by acting as a primary, secondary, or tertiary fluor.
(29) For example, natural boron may be used. Also, commercially available boric acid or .sup.10B-acid may be used to produce .sup.10B-enriched material. A synthesis of borate esters can be performed with a Dean-Stark apparatus, as described herein. In various embodiments, a boron compound (e.g., boric acid, boron oxide, boronic acids, borinic acids, and phenylboronic acids, among others) may be combined with a functional group (e.g., benzyl alcohol, propylene glycol, ethylene glycol, ethanol, and methanol, propanol, butanol, phenol, pyrocatechol, among others) to provide a neutron sensitive scintillator base which is advantageously nonflammable. In contrast, some neutron sensitive scintillator bases are problematic. For example, methanol has been used as an additive to other scintillators in the form trimethyl borate, but is problematic because it has a low boiling point and is flammable. Embodiments of the present disclosure are advantageous over trimethylborate due to lower flammability. Thus, in various embodiments, trimethylborate is excluded as a scintillator in the present disclosure.
(30) The synthesis of borate esters can be performed with a Dean-Stark apparatus by reacting one equivalent of boric acid with 3 equivalents alcohol, according to the reaction shown in the following equation:
B(OH).sub.3+3ROH═B(OR).sub.3+3H.sub.2O (3)
(31) In Equation 3, the R-group represents a chemical functional group and may be chosen to enhance scintillation efficiency or other parameters, such as solubility of the borate ester in the polymer host, which might be relevant for a specific application. Examples include, but are not limited to, ethanol, methanol, propanol, butanol, benzyl alcohol, phenol, pyrocatechol, ethylene glycol, and propylene glycol. The R-group can also serve as a fluorescent moiety that improves the scintillation performance.
(32) Synthesized borate ester can include trimethyl borate, which may be used in scintillator applications; however, trimethyl borate is problematic due to its low flash point of −6° Celsius. Thus, in various embodiments, trimethylborate is excluded in the synthesized compounds of the present disclosure. Additionally, synthesized borate esters may include any combination of a boron compound (e.g., boric acid, boron oxide, boronic acids, borinic acids, and phenylboronic acids) with a functional group (e.g., benzyl alcohol, propylene glycol, ethylene glycol, ethanol, methanol, propanol, butanol, phenol, and pyrocatechol) to provide a neutron sensitive scintillator compound which is non-flammable. The functional group(s) may be chosen based on various properties. In addition, to enhance scintillation efficiency, standard fluorescent dopants may be added (e.g., 2,5-diphenyloxazole (PPO), 9,10-diphenylanthracene (DPA), 1,4-bis(5-phenyloxazol-2-yl)benzene (POPOP), and fluorene).
(33) Suitable fluorescent dopants may include 2,5 diphenyloxazole, 1,4,4-tetraphenyl-1,3-butadiene, p-terphenyl, p-quaterphenyl, anthracene, 1,4-diphenyl-1,3-butadiene, naphthalene, stilbene, biphenyl, 1,6-diphenyl-1,3,5-hexatriene, diphenylacetylene, diphenyldiacetylene, 2,4-bis(5-phenyloxazole-2-yl)benzene, 9,10-diphenylanthracene, 1,3-diphenyl-2-pyrazoline, diphenylethane, and 1-phenyl-1,3,3-trimethylindan, for example.
(34) Various methods may be used to combine the plastics, borate esters, and dopants. Exemplary methods may include, but are not limited to, extrusion, injection molding, bulk polymerization, polymerization in a solvent, compression molding, blow molding, and fiber spinning. Plastic matrices may include, but are not limited to, polystyrene, polycarbonate, polyvinyltoluene, polymethylmethacrylate, and silicone rubbers, among others. The plastic raw material can be monomeric or a preformed polymer. The preformed polymer may be powder, pellets, other solid forms, in the rubbery state, or in liquid form. In embodiments, plastics containing only low atomic number elements may be used.
(35) Thermodynamic calculations based on solubility parameters can be used to choose any suitable alcohols, phenols, glycols, or pyrocathecols to improve solubility of the borate ester. Solubility parameters can be computed by group contribution methods, which are techniques to estimate and predict thermodynamic and other properties from molecular structures. Exemplary group contribution methods include Fedor's or Hansen's methods. Other boron compounds containing one or several B—O bonds can also be used, including but not limited to, boron oxide, boronic acids, and borinic acids.
EXAMPLES
(36) The following natural boron containing compounds as displayed in
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(38) Such exemplary methods disclosed herein are transferable to other liquid scintillators as well as to other plastic solid matrices. Standard primary and secondary fluorescent dopants like fluorene, PPO, POPOP, and p-bis-(o-methylstyryl)-benzene (MSB) may be used for scintillation enhancement and wavelength shifting. Other fluorescent dopants may also be used.
(39) Illustrative examples discussed herein show, e.g., transparent boron containing admixtures that may be used in cast plastic scintillators, extruded plastic scintillators, and liquid scintillators. In the following examples, neutron sensitivity was shown by detecting the thermal neutron capture on .sup.10B.
Example 1
(40) In Example 1, a cast polystyrene containing 20% of the boric ester of propylene glycol, 1% PPO, and 0.3% POPOP was formed.
(41) A 137-Cs source (e.g., 667 keV) was used to test for the response to gamma excitation.
(42) Neutron sensitivity was tested using a 244Cm/13C fast neutron source in two configurations. Initially, lead shielding was used to reduce gamma radiation at the scintillator location and let the fast neutron spectrum pass nearly uninhibited.
(43) To test where to expect the thermal neutron capture signal on .sup.10B, which may lead to fast alpha particles in the exit channel, the response to energetic alpha particles was tested by placing a 241Am source onto the surface of the scintillator on the side of the scintillator opposite the photomultiplier.
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(45) To enhance the thermal neutron flux, a plastic, hydrogen rich shielding was placed around the scintillator sample. A significant increase in the thermal neutron capture signal on .sup.10B at the expected location in the low energy spectrum was observed, as shown in
Example 2
(46) Example 2 uses the same test conditions as Example 1. Example 2 is an extruded polystyrene containing 20% of boric ester of propylene glycol, 1% PPO, and 0.3% POPOP.
Example 3
(47) Example 3 uses the same test conditions as Examples 1 and 2. Example 3 is a liquid scintillator mixture containing 50% of tribenzyl borate and 50% of commercially available EJ-301 liquid scintillator.
(48) Thus, as disclosed herein, various exemplary boron compounds of the present disclosure provide transparent mixtures with standard formulations of liquid and cast or extruded plastic scintillators. As shown herein, for example, the mixtures are sensitive to thermal neutron capture on the .sup.10B introduced by the compounds. Scintillator mixtures may also show pulse shape discrimination for their fast neutron signals.
(49) In addition, advantageously, the boron compounds disclosed herein may be produced using tabletop methods (e.g., using easily available materials worth approximately $55 per liter (for example, tribenzyl borate), and $600 per liter (for example, .sup.10B enriched tribenzyl borate). Also, with a flashpoint above 100° C., the boron containing compounds are neither flammable nor combustible.
Example 4
(50) The three compounds of
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(52) In addition, apart from the tests with the fluorescence spectrometer, a 137-Cs source (667 keV) was used to test for the response to gamma excitation. The results are shown in
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(54) Further, neutron sensitivity was tested using a 244Cm/13C fast neutron source in two configurations. Initially lead shielding was used to reduce gamma radiation at the scintillator location but let the fast neutron spectrum pass nearly uninhibited.
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(56) In order to establish that the scintillator would be sensitive to the thermal neutron capture on .sup.10B, which leads to fast alpha particles in the exit channel, the response to energetic alpha particles was also tested by immersing a 241Am source into the scintillator liquids. The results are shown in
(57) As can be seen in
(58) Thus, there are indications from the data collected with the fast neutron source that thermal neutron capture in the low energy spectrum may be slightly above the electronic noise at around Pulse area 11 and the delayed area 0.23, as shown in
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(60) In particular,
(61) Thus, the combination of boron compounds with functional groups to produce scintillation may advantageously lead to a liquid scintillator that is neutron sensitive via neutron-proton scattering, and neutron capture on .sup.10B. The scintillator also advantageously may exhibit gamma-neutron pulse shape discrimination, which is important for the identification of fast neutrons. Also, the scintillator can advantageously be produced with tabletop methods using easily available materials (e.g., worth approximately $55/liter (for tribenzyl borate) and $600/liter (for .sup.10B enriched tribenzyl borate)). In addition, with flashpoints above 150° C., the scintillators are advantageously neither flammable nor combustible.
(62) In various embodiments, an illustrative extrusion process may include drying polycarbonate overnight under vacuum at a temperature of 140° C. and mixing 2 grams of PPO and 0.04 g of POPOP dissolved in 40 g of warm CPA51 (CPA51 is 2-alpha-methylbenzyloxy-1,3,2-dioxaborinan). CPA51 is a borate ester obtained using methods disclosed herein, and using one unit of alpha-methylbenzyl alcohol and one unit of propanediol for every unit of boric acid. CPA51 is advantageously more soluble in polycarbonate than the other exemplary borate esters.
(63) In further embodiments, additional illustrative samples were tested. The samples contained 20 weight (wt.) % of CPA51, 1 wt. % of PPO and 0.02 wt. % of POPOP in a polycarbonate matrix. The mixture was extruded at temperatures between 220° C. and 240° C. in a single-screw extruder.
(64) In still further embodiments, additional illustrative boron-loaded polycarbonate samples scintillated and reached about 40% of the efficiency of a commercial sample of Eljen plastic scintillator EJ-204. The boron-loaded polycarbonate samples had a Glass Transition Temperature (Tg) around about 80° C., which is improved over polystyrene samples with the same amount of boron, which had a Tg around 40° C.
(65) Although the present disclosure describes components and functions implemented in the embodiments with reference to particular standards and protocols, the disclosure is not limited to such standards and protocols. Other similar standards and protocols not mentioned herein are in existence and are considered to be included in the present disclosure. Moreover, the standards and protocols mentioned herein and other similar standards and protocols not mentioned herein are periodically superseded by faster or more effective equivalents having essentially the same functions. Such replacement standards and protocols having the same functions are considered equivalents included in the present disclosure.
(66) The present disclosure, in various embodiments, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various embodiments, subcombinations, and subsets thereof. Those of skill in the art will understand how to make and use the present disclosure after understanding the present disclosure. The present disclosure, in various embodiments, includes providing devices and processes in the absence of items not depicted and/or described herein or in various embodiments hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and\or reducing cost of implementation.
(67) The foregoing discussion of the disclosure has been presented for purposes of illustration and description. The foregoing is not intended to limit the disclosure to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the disclosure are grouped together in one or more embodiments for the purpose of streamlining the disclosure. The features of the embodiments of the disclosure may be combined in alternate embodiments other than those discussed above.
(68) Moreover, though the description of the disclosure has included description of one or more embodiments and certain variations and modifications, other variations, combinations, and modifications are within the scope of the disclosure, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter.