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Scintillating Cocktail Mixtures and the Role of Water on the Optophysical Properties.

Two types of water - containing liquid scintillation mixtures were prepared in the present work. In the first, m ixtures of 2 - phenylethanol, water, diphenyl phosphate, sodium phenyl phosphate dibasic dihydrate, and the dye 2,5 - diphenyloxazole (PPO) have been investigated as liquid scintillators. In the second system, nonionic and mixed surfactant systems were investigated in conjunction with water and small amounts of toluene. In both cases, increasing amounts of water led to reductions in the scintillation light yield. Understanding what factors contr ibute to this phenomenon is the focus of this report. Changes in the solution microphase structure, diminishing aromatic content of the cocktail mixtures, and inefficient energy transfer to the dye a ppear to be responsible for the decreased light yield as more water is added . In the 2 - phenylethanol system, the observed experimental results are consistent with the formation of a bicontinuous microemulsion at higher water concentrations, which incorporates PPO and shields it from the quenching effects of the increasing polar matrix. Evidence for this proposed phase change comes from light scattering data, photo - and x - ray luminescence measurements, and optical transparency measurements . In the surfactant - based system, the quenching effect of water was found to be less than both commercially - available dioxane - naphthalene mixtures used for scintillation counting as well as the 2 - phenylethanol mixtures described above. The effect of different surfactant mixtures and concentrations were studied, revealing a benefic ial effect upon the scintillation light yield for mixed surfactant mixtures. These results are interpreted in the context of reactive radical species formation following water ionization , which leads to light - yield quenching in aqueous systems . The presence of surfactant(s) in these mixtures enables the formation of organic - rich regions that are spatially separated from the reactive radicals. This hypothesis is consistent with subsequent experiments that showed reduced light - yield quenching in the presence of radical - trapping additives. A notable result from these surfactant studies was the preparation of an aqueous scintillator that was transparent and showed neutron/gamma pulse - shape discrimination. Section II below provides background information on the significance of this finding. The combined work described herein has implications on other efforts to make water - based solution scintillators -- without aromatic content an efficient mechanism for ionizing radiation to sensitize emission from a dye is limited.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Mixed Material Scintillator Systems for Neutron Detection

Scintillators are a fundamental technology that enables radiation detection. Their use has historically enabled the detection of incoming gamma radiation, with recent advances in plastic scintillator development enabling detection and discrimination of neutron and gamma radiation through pulse shape discrimination. However, scintillators have so far consisted of a single material, typically one primary dye and one secondary dye embedded in a plastic matrix. Based on the simulation studies described previously, mixed material scintillator systems with multiple secondary dyes arranged in alternating, periodic micro-sized regions opens the door for scintillators with a wide variety of different capability, such as directional sensing, positional reconstruction, particle identification, and pulse shape discrimination. However, fabrication of a mixed material scintillator system by conventional manufacturing methods is difficult to manufacture and scale, creating a barrier to their wide spread implementation. On the other hand, additive manufacturing additive manufacturing presents itself as the optimal method for fabricating mixed material scintillator systems based on its flexibility, ability to fabricate fine features, and potential for multimaterial fabrication.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DRiFT - Release 1.0.0 Organic Scintillators

DRiFT (a Detector Response Function Toolkit) is LANL-developed software that postprocesses output from the extensively validated radiation transport code, MCNP [1], and generates realistic nuclear instrumentation response. DRiFT is designed to be flexible, enabling users to specify detector type and many experimental settings, as well as accommodating the addition of their own desired features. Although DRiFT development has included scintillator [2], gas [3], and semiconductor features [4], the focus of this release is on organic scintillator and associated capabilities. Organic scintillators are widely used in the areas of nuclear safeguards and nuclear non-proliferation efforts [5, 6]. DRiFT has several diagnostic and detector physics features relevant to detailed scintillator simulations including: tracking source particle information, scintillation light production, the effects of PMT quantum efficiency and gain, and digitizer settings. Users can select responses from many scintillator and PMT types supported natively by DRiFT, or add their own by following the instructions in this document. We acknowledge that DRiFT is under active development, bug reports and general questions and comments should be directed to Madison Andrews, madison@lanl.gov. This manual is divided into four parts: I) An overview of DRiFT, including how to obtain and install the executable, II) A description of the detector physics related to scintillators available, III) a description of more general DRiFT features the user may find useful, and IV) a description of the test suite and examples made available with the code release.

61 RADIATION PROTECTION AND DOSIMETRY↗

DRiFT - Release 1.1.1: Organic Scintillators

DRiFT (a Detector Response Function Toolkit) is LANL-developed software that postprocesses output from the extensively validated radiation transport code, MCNP, and generates realistic nuclear instrumentation response. DRiFT is designed to be flexible, enabling users to specify detector type and many experimental settings, as well as accommodating the addition of their own desired features. Although DRiFT development has included scintillator, gas, and semiconductor features, the focus of this release is on organic scintillator and associated capabilities. Organic scintillators are widely used in the areas of nuclear safeguards and nuclear non-proliferation efforts. DRiFT has several diagnostic and detector physics features relevant to detailed scintillator simulations including: tracking source particle information, scintillation light production, the effects of PMT quantum efficiency and gain, and digitizer settings. Users can select responses from many scintillator and PMT types supported natively by DRiFT, or add their own by following the instructions in this document. We acknowledge that DRiFT is under active development, bug reports and general questions and comments should be directed to Madison Andrews, madison@lanl.gov. This manual is divided into four parts: I) An overview of DRiFT, including how to obtain and install the executable, II) A description of the detector physics related to scintillators available, III) a description of more general DRiFT features the user may find useful, and IV) a description of the test suite and examples made available with the code release.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Solar cycle variation of interplanetary disturbances observed as Doppler scintillation transients

Interplanetary disturbances characterized by plasma that is more turbulence and/or moves faster than the background solar wind are readily defected as transients in Doppler scintillation measurements of the near-Sun solar wind. Systematic analysis of over 23,000 hours of Pioneer Venus Orbiter Doppler measurements obtained inside 0.5 AU during 1979-1987 have made it possible for the first time to investigate the frequency of occurrence of Doppler scintillation transients under solar minimum conditions and to determine its dependence on solar cycle. On the basis of a total of 142 transients, Doppler scintillation transient rates vary from a high of 0.22 in 1979 (one every 4.6 days) to a low of 0.077 transients/d in 1986 (one every 13 days), a decrease by almost a factor of 3 from solar maximum to solar minimum. This solar cycle variation, the strongest yet of any solar wind Doppler scintillation property, is highly correlated with both solar activity characterized by sunspot number and the coronal mass ejection rates deduced from Solswind and Solar Maximum Mission (SMM) coronagraph observations. These results indicate that coronal mass ejections and Doppler scintillation transients are closely related not just during solar maximum, as occasional individual comparisons have shown in the past, but throughout the entire solar cycle, and strengthen the notation that the Doppler scintillation and optical transients are different manifestations of the same physical phenomenon. The magnitudes of the transients, as described by the ratio of peak to pretransient scintillation levels (EF for enhancement factor), and their distribution iwth heliocentric distance also vary with solar cycle. While EF tends to diminish with increasing heliocentric distance during high solar activity, it is more evenly distributed during low solar activity. EF is also lower during solar minimum, as 13% of the transients during solar maximum have values exceeding 23, the highest EF observed during solar minimum. These results are consistent with the fact that occasional major fast-moving interplanetary shocks that are observed during solar maximum are very rate during solar minimum.

Woo, Richard↗

Scintillation Breakdowns in Chip Tantalum Capacitors

Scintillations in solid tantalum capacitors are momentarily local breakdowns terminated by a self-healing or conversion to a high-resistive state of the manganese oxide cathode. This conversion effectively caps the defective area of the tantalum pentoxide dielectric and prevents short-circuit failures. Typically, this type of breakdown has no immediate catastrophic consequences and is often considered as nuisance rather than a failure. Scintillation breakdowns likely do not affect failures of parts under surge current conditions, and so-called "proofing" of tantalum chip capacitors, which is a controllable exposure of the part after soldering to voltages slightly higher than the operating voltage to verify that possible scintillations are self-healed, has been shown to improve the quality of the parts. However, no in-depth studies of the effect of scintillations on reliability of tantalum capacitors have been performed so far. KEMET is using scintillation breakdown testing as a tool for assessing process improvements and to compare quality of different manufacturing lots. Nevertheless, the relationship between failures and scintillation breakdowns is not clear, and this test is not considered as suitable for lot acceptance testing. In this work, scintillation breakdowns in different military-graded and commercial tantalum capacitors were characterized and related to the rated voltages and to life test failures. A model for assessment of times to failure, based on distributions of breakdown voltages, and accelerating factors of life testing are discussed.

Teverovsky, Alexander↗

Scintillation Detector for the Measurement of Ultra-Heavy Cosmic Rays on the Super-TIGER Experiment

We discuss the design and construction of the scintillation detectors for the Super-TIGER experiment. Super-TIGER is a large-area (5.4sq m) balloon-borne experiment designed to measure the abundances of cosmic-ray nuclei between Z= 10 and Z=56. It is based on the successful TIGER experiment that flew in Antarctica in 2001 and 2003. Super-TIGER has three layers of scintillation detectors, two Cherenkov detectors and a scintillating fiber hodoscope. The scintillation detector employs four wavelength shifter bars surrounding the edges of the scintillator to collect the light from particles traversing the detector. PMTs are optically coupled at both ends of the bars for light collection. We report on laboratory performance of the scintillation counters using muons. In addition we discuss the design challenges and detector response over this broad charge range including the effect of scintilator saturation.

Link, Jason↗

Optical properties of halide and oxide scintillators

Knowledge of optical properties of scintillators is important both for the optimization of scintillator systems and the development of new materials particularly ceramic scintillators. Recent theoretical developments, especially new density functionals that enable accurate prediction of band gaps, have made it possible to perform quantitative calculations of the optical properties of scintillator materials. We used these techniques to obtain optical properties of a large number of high light output halide scintillators. These calculations showed that many halide scintillators have remarkably little optical anisotropy and may be good candidates for development as ceramic scintillators. These include materials such as CaI{sub 2}:Eu{sup 2+} that have very high light output and other favorable properties but are difficult to develop due to crystal growth issues. We review some of our recent results and present new results for CeCl{sub 3}.

36 MATERIALS SCIENCE↗

Plastic Scintillators Light Yield Energy Calibration.

Currently we are investigating the inclusion of organotin compounds in polystyrene material to improve plastic scintillators full gamma-ray energy sensitivity with the ultimate goal of achieving spectroscopy. Accurate evaluation of light yield from the newly developed scintillators is crucial to assess merits of compounds and chemical process used in the scintillators development. Full gamma-ray energy peak in measured gammaray spectrum, resulting from total absorption of gamma-ray energy, would be ideal in evaluating the light yield from the new scintillators. However, full energy sensitivity achieved thus far is not statistically viable for fast and accurate light yield energy calibration from the new scintillators. The Compton edge in measured gamma-ray spectrum has been found as an alternate gamma-ray spectrum feature that can be exploited for characterizing the light yield energy from the newly developed plastic scintillators. In this study we present technique implemented for accurate light yield energy calibration using the Compton edge. Results obtained were very encouraging and promise the possibility of using the Compton edge for energy calibration in detectors with poor energy resolution such as plastic and liquid scintillators.

36 MATERIALS SCIENCE↗

Gallium oxide semiconductor-based large volume ultrafast radiation hard spectroscopic scintillators

We report on the development of the first-ever inorganic radiation-hard moisture-insensitive large volume spectroscopic semiconductor-based scintillator with less than 2 ns decay time and light yields as high as 8000 ph/MeV. Despite extensive research into scintillator materials, the quest for an ideal scintillator combining ultrafast decay times (akin to BaF 2 and Yb-doped scintillators such as Lu 2 O 3 :Yb), high light yields (exceeding 2000 photons per MeV), spectroscopic capabilities, and exceptional radiation hardness remain unfulfilled. In this study, we demonstrate and report for the first time the viability of large-volume (up to 20 mm thickness) gallium oxide (β-Ga 2 O 3 ) semiconductor-based scintillators for applications requiring these properties. These β-Ga 2 O 3 scintillators were grown using the fast turnaround (~2 days) crucible-free optical float zone (FZ) technique. The high light yield and ultrafast decay time of these high-purity n-type semiconductors with free carrier concentration of 6 × 10 17 cm –3 are attributed to native defects, specifically oxygen vacancies (V O ) and gallium–oxygen vacancy pairs (V Ga –V O ), generated during optimized FZ growth. The ultrafast decay, along with high light yield, enables excellent timing resolution and high count rate detection for applications like time-of-flight positron emission tomography, physics experiments, and nuclear safety. The radiation hardness of these devices has been documented in a separate publication.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Distance dependent quenching and gamma-ray spectroscopy in tin-loaded polystyrene scintillators

In this study, we report the synthesis and inclusion of rationally designed organotin compounds in polystyrene matrices as a route towards plastic scintillators capable of gamma-ray spectroscopy. Tin loading ratios of up to 15% w/w have been incorporated, resulting in photopeak energy resolution values as low as 10.9% for 662 keV gamma-rays. Scintillator constituents were selected based upon a previously reported distance-dependent quenching mechanism. Data obtained using UV-Vis and photoluminescence measurements are consistent with this phenomenon and are correlated with the steric and electronic properties of the respective organotin complexes. We also report fast scintillation decay behavior that is comparable to the quenched scintillators 0.5% trans-stilbene doped bibenzyl and the commercial plastic scintillator BC-422Q-1%. These observations are discussed in the context of practical considerations such as optical transparency, ease-of-preparation/scale-up, and total scintillator cost.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Low Level Calibration of Liquid Scintillation Counting

Liquid Scintillation Counting (LSC) is an analytical laboratory method that quantifies the concentrations of alpha and beta emitting isotopes. The LSC method can be utilized for the detection of tritium, both environmentally and at nuclear facilities. Most LSC samples are aqueous-based and prepared as a radioactive sample dissolved or suspended in a high efficiency scintillation cocktail that converts radioactive energy into light pulses. When placed in counting vials, the liquid scintillation cocktail allows for optical coupling in which energy is released from the samples radioactive decay, and transferred to the scintillator. That energy is then absorbed to produce excited electrons that fall back to their ground-state and emit a pulse of light that is detected by the liquid scintillation analyzers photomultiplier tubes. Quench is a signal attenuation due to physical, chemical, or color interferences. To compensate for quench, quench standards of a known concentration are implemented at increasing increments of quench per vial to create a quench curve. Quench standards can be purchased pre-made or customized from the manufacturer, however, there are several issues that arise from purchasing the pre-made quench standards. The main issues with ordering pre-made quench standards is that they use higher count values, between 30,000 and 250,000 disintegrations per minute (dpm) of tritium per vial and only come in glass vials. Using higher counting standards in glass vials makes it hard to see lower concentrations in plastic vials. Additionally, when using higher energy standards the accuracy of the calibration readings tend to be lower. On the other hand, making a set of quench standards in-house allows for the customization of the dpm concentration to roughly 1,500-3,000 and preparation in plastic vials. This allows for lower activity readings that results in closer precision of the samples' true concentration. Technical Objectives: Create a quench curve and calibrate the LSA for tritium. Verify the calibration of the quench curve prior to cross sample runs. Check calibration against Quality Control (QC) reference value. Conclusion: a tritium quench curve calibration was performed using a scintillation cocktail with ultima gold (AB and AB/F), acetone (only with AB), and water (only with AB/F). By performing the tritium quench curve calibration, the counting efficiency was correlated to various levels of quench. Calibration checks with quality control standards were also performed to verify that the calibration was correct. The observed results provided acceptable values that matched the quality control standard reference values with an acceptable uncertainty. The next step will be fine tuning and cross comparison checks with legacy instrumentation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Neutron response characterization for an EJ299-33 plastic scintillation detector

Organic scintillation detectors have shown promise as neutron detectors for characterizing special nuclear materials in various arms-control and homeland security applications. Recent advances have yielded a new plastic scintillator - EJ299-33 - with pulse-shape-discrimination (PSD) capability. Plastic scintillators would have a much expanded range of deployment relative to liquids and crystals. Here in this paper, we present a full characterization of pulse height response to fission-energy neutrons for an EJ299-33 detector with 7.62-by-7.62-cm cylindrical active volume, and compare with an EJ309 liquid scintillator in the same assembly. Scintillation light output relations, energy resolutions, and response matrices are presented for both detectors. A Continuous spectrum neutron source, obtained via the bombardment of 27 Al with 7.44-MeV deuterons at the Edwards Accelerator Facility at Ohio University, was used for the measurement. A new procedure for evaluating and comparing PSD performance is presented which accounts for the effect of the light output relation on the ability to detect low energy neutrons. The EJ299-33 is shown to have considerable deficit in matrix condition, and in PSD figure of merit when compared to EJ309, especially when neutron energy is taken into account. Furthermore the EJ299 is likely to bring a modest PSD capability into a array of held applications that are not accessible to liquids or crystals.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Evaluation of polyvinyl toluene scintillators for fast neutron imaging

We evaluated here polyvinyl toluene (PVT) scintillators fabricated with different emitting dopants and scintillator optical configurations for fast neutron imaging. A neutron imaging apparatus was constructed to study scintillators under MeV neutron exposure. PVT with 2% Xylyl Flrpic emitter was identified as the brightest. The addition of a black backing to the scintillator, compared with a specular reflector film backing, improved the resolution of the neutron image obtained with the PVT scintillator by about 2 ×. It is concluded that a PVT imaging screen with 2% Xylyl Flrpic, configured with a black backing, provides the best quality fast neutron image of the scintillators tested.

36 MATERIALS SCIENCE↗

Influence of fluorescent dopants on the vat photopolymerization of acrylate-based plastic scintillators for application in neutron/gamma pulse shape discrimination

Plastic scintillators, a class of solid-state materials used for radiation detection, were additively manufactured with vat photopolymerization. The photopolymer resins consisted of a primary dopant and a secondary dopant dissolved in a bisphenol A ethoxylate diacrylate-based matrix. The absorptive dopants significantly influence important print parameters, for example, secondary dopants decrease the light penetration depth by a factor > 12×. The primary dopant 2,5-diphenyloxazole had minimal impact on the printing process even when loaded at 25 % by mass of the resin. Working curve measurements, which relate energy dose to cure depth, were performed as a function of feature size to further assess the influence of dopants. Photopatterns smaller than 150 µm width had apparent increases in critical energy dose compared to larger photopatterns, while all resins maintained printed features in line gratings with 50 µm of separation. Printed scintillator monoliths were compared to scintillators cast by traditional molding, demonstrating that the layer-by-layer printing process does not decrease scintillation response. In conclusion, a maximum light output of 31 % of a benchmark plastic scintillator (EJ-200) and successful pulse shape discrimination were achieved with 20 % by mass 2,5-diphenyloxazole as the primary dopant and 0.1 % by mass 9,9-dimethyl-2,7-distyrylfluorene as the secondary dopant in printed scintillator samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Further Investigations of the Effect of Replacing Lithium by Sodium on Lithium Silicate Scintillating Glass Efficiency

Ce3+ doped lithium (6Li) silicate glasses are thermal neutron detectors. Prior work showed that when sodium (Na) is substituted for Li the scintillation efficiency, under beta particle stimulation, increased and then decreased as the sodium (Na) content was increased [1]. When all the 6Li was replaced by Na no scintillation was observed. Raman spectra, acquired using a visible excitation source provided no evidence of anomalous behavior. SEM microscopy did show some phase separation, but there was no obvious correlation with the scintillation efficiency. We have reexamined these glass samples using deep UV Raman excitation which reduces fluorescence interference. The newly acquired spectra show evidence of phase separation in the glasses. Specifically we see a peak at 800 cm-1 Raman shift which can be assigned to a vitreous silica moiety that results from phase separation. There is a strong correlation between this peak's area, the scintillation efficiency, and the Na content. The observed trend suggests that phase separation enhances scintillation and addition of Na reduces the amount of phase separation. We also see evidence of at least two defect structures that can be tentatively assigned to a three-membered ring structure and an oxygen vacancy. The latter is fairly strongly correlated with enhanced scintillation efficiency.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Photoluminescence, photoacoustic, and scintillation properties of Te4+-doped Cs2HfCl6 crystals

Highlights: • Cs{sub 2}HfCl{sub 6}:Te{sup 4+} crystals were grown using the vertical Bridgman–Stockbarger method. • The PL, PA, and scintillation properties of the crystals were characterized. • An inverse correlation between scintillation LY and PA intensity was confirmed. - Abstract: Photoluminescence, photoacoustic, and scintillation properties are reported for 1.0, 3.0, 5.0, and 10 mol% Te{sup 4+}-doped Cs{sub 2}HfCl{sub 6} crystals grown using the vertical Bridgman–Stockbarger method. The UV − VIS light excited emission spectra showed an emission band peaking at 575 nm which can be ascribed to transitions from the {sup 3}T{sub 1u} and {sup 3}A{sub 1u} states to the {sup 1}A{sub 1g} state of Te{sup 4+} ions. Excitation spectra monitored at emission wavelength of 575 nm showed bands at 230–250 (charge transfer on a HfCl{sub 6}{sup 2−}), 275–300 ({sup 1}A{sub 1g} → {sup 3}T{sub 1u}), 300–340 ({sup 1}A{sub 1g} → {sup 3}T{sub 2u}, {sup 3}E{sub u}), and 360–460 nm ({sup 1}A{sub 1g} → {sup 1}T{sub 1u}). The X-ray induced scintillation spectra exhibited a yellow emission band at 575 nm, which is similar to the emission band for excitation by UV–VIS light. Scintillation light yields of the crystals were estimated to be approximately 11,700 (1.0 mol%), 13,100 (3.0 mol%), 9600 (5.0 mol%), and 9000 (10 mol%) photons/MeV, respectively. Scintillation light yield was inversely correlated with the PA intensity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Improved lithium iodide neutron scintillator with Eu 2+ activation: The elimination of Suzuki-Phase precipitates

Monovalent alkali halides such as NaI, CsI, and LiI are widely used as inorganic scintillators for radiation detection due to their light yield, the capability for the growth of large single crystals, relatively low cost, and other favorable characteristics. These materials are frequently activated through the addition of small amounts (e.g., a few hundred ppm) of elements such as thallium - or sodium in the case of CsI. The monovalent alkali halide scintillators can also be activated with low concentrations of Eu 2+ , however Eu activation has previously not been widely employed due to the non-uniform segregation of the divalent Eu dopant that leads to the formation of unwanted phases during Bridgman or other solidification crystal-growth methods. Specifically, for Eu concentrations near and above ~0.5%, Suzuki Phase precipitates form in the course of the melt-growth process, and these Suzuki Phase particles scatter the scintillation light. This adversely affects the scintillator performance via reduction in the optical transmission of the material, and depending on the crystal thickness and precipitated-particle concentration, this reduction can occur up to the point of opacity. Here we describe a post-growth process for the removal of Suzuki Phase precipitates from single crystals of the neutron scintillator LiI activated with Eu 2+ at concentrations up to and in excess of 3 wt.%, and we correlate the resulting neutron-detection performance with the thermal processing methods used to remove the Suzuki Phase particles. Furthermore, the resulting improved scintillator properties using increased Eu activator levels are applicable to neutron imaging and active interrogation systems, and pulse-height gamma-ray spectroscopy rather than pulse-shape discrimination can be used to discriminate between gamma ray and neutron interaction events.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗