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At least 145 records · Page 8

Preliminary Chlorine Worth Study Benchmark Evaluation

The Chlorine Worth Studies (CWS) experiments with polyvinyl chloride (PVC with chemical formula (C 2 H 3 Cl) n ), chlorinated polyvinyl chloride (CPVC with chemical formula (C 9 H 11 Cl 7 ) n ), and high density polyethylene (HDPE with chemical formula (CH 2 ) n ) were a series of measurements performed at the National Criticality Experiments Research Center (NCERC). The purpose of the CWS experiments was to perform integral experiments that were highly sensitive to the thermal 35 Cl(n,γ) reaction and matched the sensitivities of aqueous chloride operations at the plutonium facility at Los Alamos National Laboratory (LANL). The CWS experiments were performed on the Planet critical assembly machine at NCERC and utilized weapons grade plutonium (WGPu) plates as fuel. The design process and design of the CWS experiment were discussed previously. This paper discusses the benchmark evaluation of the experiment, intended for the International Criticality Safety Benchmark Evaluation Project (ICSBEP). Criticality calculations were performed with MCNP version 6.3. Results presented here are preliminary, as the benchmark has not yet been submitted to the ICSBEP.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Polymer Compositions in Critical Experiments: Possibly Not What You Think

The Chlorine Worth Study (CWS) Experiment was performed at the National Criticality Experiments Research Center (NCERC) in December 2021. Its goal was to provide a validation benchmark experiment with chlorine and plutonium in the thermal neutron spectrum. This purpose is necessary to reduce the margin of subcriticality in aqueous chloride operations at the Los Alamos National Laboratory Plutonium Facility (PF-4). Reducing the margin of subcriticality will enable higher throughput, required to meet NNSA mission needs. The experiment used layers of plutonium plates, polyethylene (HDPE), aluminum, and polyvinyl chloride (PVC) or chlorinated polyvinyl chloride (CPVC). They were optimized to match plutonium-chloride solutions of 30 g/L, 300 g/L, and 600 g/L. Upon completion of the experiment, a International Criticality Safety Benchmark Evaluation Program (ICSBEP) report was immediately started. The compositions of all materials were assumed pure unless additional information was known (such as for the plutonium plates). During the benchmark analysis, the assumed CPVC composition was questioned. The follow-on work led to lessons learned on compositions in benchmarks. Materials, and specifically polymers, are often much more complex than a basic chemical formula. The CWS experiment is used as an example in this paper to document the lessons learned.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Redox‐Functionalized Semiconductor Interfaces for Photoelectrochemical Separations

Redox-mediated electrosorption is a promising platform for selective electrochemical (EC) separations, due to its molecular selectivity, high uptake, and tunability for target ions. However, the electrical energy required is mainly generated by non-renewable energy sources, which limits its sustainability and overall impact to decarbonization. Here, a redox-mediated photoelectrochemical (PEC) separation process using polyvinyl ferrocene functionalized TiO 2 nanorod electrodes is proposed, which integrates direct solar energy as a driver for the selective electrosorption. The photoelectrochemically-driven oxidation and reduction with both homogeneous and heterogeneous ferrocene-systems is investigated to establish the underlying mechanism. The PEC system can separate heavy metal oxyanions at lower voltages or even without electrical energy. At 0.3 V versus SCE, a 124 mg g −1 uptake for Mo is achieved, which is comparable to the performance of EC cells at 0.75 V versus SCE. Thus, PEC systems not only can generate energy for spontaneous redox-separations, but also can reduce electrical energy consumption by 51.4% compared to EC cells for separation processes when coupled with an external electrical energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strong ultralight foams based on nanocrystalline cellulose for high-performance insulation

Environmentally friendly, sustainable, and high-performance thermal insulators are in high demand. Petroleum based insulator foams usually have high thermal conductivity and pose health hazards. In this paper, we report ultralight composite foams that are highly strong, elastic, and super-insulating. The foams are composed of nanocrystalline cellulose (NCC) (74 wt%), polyvinyl alcohol (7.5 wt%), and a crosslinking agent (18.5 wt%). The fabrication process is simple and uses only water. The composite foams exhibit an elastic strain of ⁻13% at a modulus of 250 K Pa and a stress of 73 K Pa at 50% strain (100+ and 18 times, respectively, higher than those of pure NCC foam); both exceed the values of reported nanocellulose-based foams with no reinforcement. The foams exhibit a thermal conductivity of 0.027 Wm -1 K -1 , which is superior to those of traditional insulating materials. The structural integrity is also preserved after burning. Our results show that NCC-based materials can be engineered towards high-performance insulation applications.

36 MATERIALS SCIENCE↗

Controllable synthesis and growth mechanism of {alpha}-Co(OH){sub 2} nanorods and nanoplates by a facile solution-phase route

A facile chemical precipitation route has been developed to control synthesis of {alpha}-cobalt hydroxide nanostructures with rod-like and plate-like morphologies. The {alpha}-Co(OH){sub 2} nanorods were achieved in large quantity when the experiments were carried out in the presence of a suitable shape-controlling reagent polyvinyl pyrrolidone (PVP), while the {alpha}-Co(OH){sub 2} nanoplates were obtained when the experiments were conducted in the absence of PVP, whilst keeping other experimental conditions constant. The chemical composition and morphologies of the as-prepared {alpha}-Co(OH){sub 2} nanoparticles were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effect of polymer PVP on the morphologies of {alpha}-Co(OH){sub 2} nanoparticles were discussed in detail. The results indicated that PVP played a key role for the formation of {alpha}-Co(OH){sub 2} nanorods. The growth mechanism of the as-synthesized nanorods and nanoplates were discussed in detail based on the experimental results. A possible growth mechanism has been proposed to illustrate the growth of {alpha}-Co(OH){sub 2} nanorods. - Graphical abstract: A facile solution-phase route has been developed to synthesize {alpha}-Co(OH){sub 2} nanorods and nanoplates. The possible growth mechanism of nanorods and nanoplates was proposed. Highlights: Black-Right-Pointing-Pointer A facile controllable route was described for {alpha}-Co(OH){sub 2} nanowires and nanoplates. Black-Right-Pointing-Pointer The {alpha}-Co(OH){sub 2} nanowires were achieved in the presence of shape controller PVP. Black-Right-Pointing-Pointer The {alpha}-Co(OH){sub 2} nanoplates were obtained in the absence of shape controller PVP. Black-Right-Pointing-Pointer The shape controller PVP played a key role in the formation of {alpha}-Co(OH){sub 2} nanowires.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Root cause analysis and solutions for plastic gamma detector degradation in challenging environments—An overview

Polyvinyl toluene (PVT) plastic is often used to make gamma ray sensitive scintillators and is used in many important applications. For example, PVT is used to scan recycled steel going into a plant to be processed. It is also used in personnel portals to scan employees, and is used at the borders of many countries to scan cargo and cars passing through. In recent years, it was discovered that PVT can become degraded when it absorbs water and then is subjected to daily temperature swings, as is evidence by a reduction in scintillation light. Water absorption by PVT was notionally associated with temporary fogging (i.e., a rapid decrease in opacity which was reversible over time) and permanent fogging (i.e., permanent crack-like defects) and was for some time suspected to be the leading cause of the fogging due to circumstantial evidence. However, definitive proof was not established and in particular the specific mechanisms by which water entered the plastic and ultimately created temporary and permanent point-like defects was not fully understood. This paper is an overview of an effort initiated to reveal the fundamental root cause and also the dynamics of the fogging and degradation processes. This understanding is important not only to solve degradation problems for PVT in fielded systems, but also (1) to provide direction for future procurements for new equipment, and (2) to provide direction for future R&D efforts into advanced plastics with enhanced spectroscopic capabilities or dual particle gamma/neutron capabilities. Unexpected outcomes of this investigation included (1) the capability to predict the onset of fogging based on models using weather data alone, and (2) new modified formulations of PVT and PS which are fog-resistant. This paper provides an overview of the water uptake and associated mechanisms for various compositions, characterization of resulting temporary and permanent defects, predictive modeling of fogging, and possible solutions including encapsulation, heaters and new formulations. While this paper is an overview of the root cause analysis and solution, five accompanying papers (Lance et al., 2018, Myllenbeck and Feng, 2018, Payne et al., 2018, Zaitseva et al. 2018, Kouzes et al., 2018) from the same conference (SORMA 2018) delve further into the details and also expand upon the scope of what will be reported herein.

36 MATERIALS SCIENCE↗

Investigations of degradation and encapsulation of plastic scintillator

Studies have revealed that plastic scintillators such as polyvinyl toluene and polystyrene can undergo environmentally related material damage (“fogging”) that adversely affects detection performance under certain conditions and histories. A significant decrease in sensitivity has been seen in some gamma-ray detectors as they age as a result of this damage. Performance degradation due to such damage is characterized by a signal change from the detector, which shifts to lower energy, and ultimately a reduction in the ability to detect gamma radiation. This degradation is due to the permeation of water into the plastic, which can then cause temporary fogging and permanent damage to the material. As an example, a 1-mm thick barrier of high-density polyethylene with an area of 1 m 2 would allow 5 g per year of water transmission at 100% relative humidity. Thus, significant amounts of water can penetrate plastics over time and provide the potential for damage to the plastic. Such damage to plastic scintillator can cause problems for radiation detection applications in uncontrolled environments. Mitigation approaches that have been proposed to prevent damage to plastic scintillator include encapsulation of the plastic scintillator to prevent water intrusion that leads to damage during cold cycles. It is concluded that an encapsulation material with a moisture vapor transmission rate on the order of 10 -4 g∙m -2 ∙d -1 or better is needed for protecting large pieces of plastic scintillator from fogging over years of use. This article presents information on testing of bare and encapsulated plastic scintillator samples and on diagnostic approaches to measure the nature and progression of the fogging condition. It is shown that several encapsulation approaches fail to prevent water intrusion, while a couple methods can successfully encapsulate plastic and prevent water from penetrating the plastic and producing fogging.

36 MATERIALS SCIENCE↗

Nature of Moisture-Induced fogging defects in scintillator plastic

Polyvinyl toluene (PVT) scintillator plastic may degrade in the field due to inward water diffusion at elevated temperatures, which exceeds the saturation limit at lower temperatures, and after long periods of time (e.g., many years), leads to the formation of disk-like defects that attenuate scintillation light, leading to detector degradation. In this work, using fractography and high-magnification optical and electron microscopy to characterize the water-induced defects, a model of the fogging process is hypothesized as follows: excess water present at low temperatures diffuses to spheroids to minimize contact with the hydrophobic polymer. Through the hydrophobic effect, the entropy of water increases by forming nanoclusters which minimizes the contact between the water and the PVT. As the water nanoclusters grow, they break and fold the polymer into densely-packed crystalline regions creating more space for water within the spheroids. The polymer outside the spheroid resists the shrinkage which builds up tension within the spheroid. Once the tensile stress exceeds the yield strength of the plastic, the spheroid is torn in half resulting in a defect. Excess water then drains into the cavities along the disk thereby further increasing its entropy. Slower cooling (over 1 day) leads to larger spheroids and hence, larger “permanent” defects. Freezing causes some defects to further grow due to the expansion of water to ice. These findings imply that the remaining lifetime of scintillator plastic in the field could be predicted using temperature and humidity data thereby mitigating security risks of degraded radiation portal monitors.

36 MATERIALS SCIENCE↗

Characteristics and radiolysis behavior of polyvinylchloride under accelerated proton and γ-irradiation

Here the effect of high energy protons and γ-irradiation on the structural properties, surface-energies, and toxicological properties of polyvinyl chloride (PVC) were studied due to the role PVC products play in many technologies including the nuclear industry. Accelerated 1–4 MeV protons impacting on PVC in vacuum lead to the formation of polyenyl radicals as shown by EPR and to an increase in free surface energy due to functionalization of the surface of the irradiated polymer. γ-irradiation leads to the formation of unsaturated bonds, carbonyl and hydroxyl groups as shown by IR and to the release of HCl. Correlated molecular orbital theory calculations of reaction thermodynamics were used to aid in the development of a mechanism in the absence of oxygen. The formation and accumulation of chromophores and auxochromic groups during γ-radiolysis of PVC leads to a gradual change of the initial white color of the polymer to yellow and then to brown and black with high sensitivity. A mixture of powdered PVC and silicate glue was used to determine the profile of a 60 Co γ-radiation beam on targets with a complex relief. γ-irradiated polymer does not have a local irritating effect due to a single application to the skin of mice in an adhesive mixture at a concentration of up to 5000 mg/kg. γ-radiolysis of PVC powder in air with a dose of up to 1400 kGy does not affect its acute toxicity when administered intragastrically to BDF1 mice. PVC and its γ-irradiated analogs are non-toxic at doses ≤5000 mg/kg.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Pyrolysis of plastic packaging waste: A comparison of plastic residuals from material recovery facilities with simulated plastic waste

Highlights: Black-Right-Pointing-Pointer Pyrolysis of plastic waste. Black-Right-Pointing-Pointer Comparison of different samples: real waste, simulated and real waste + catalyst. Black-Right-Pointing-Pointer Study of the effects of inorganic components in the pyrolysis products. - Abstract: Pyrolysis may be an alternative for the reclamation of rejected streams of waste from sorting plants where packing and packaging plastic waste is separated and classified. These rejected streams consist of many different materials (e.g., polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), aluminum, tetra-brik, and film) for which an attempt at complete separation is not technically possible or economically viable, and they are typically sent to landfills or incinerators. For this study, a simulated plastic mixture and a real waste sample from a sorting plant were pyrolyzed using a non-stirred semi-batch reactor. Red mud, a byproduct of the aluminum industry, was used as a catalyst. Despite the fact that the samples had a similar volume of material, there were noteworthy differences in the pyrolysis yields. The real waste sample resulted, after pyrolysis, in higher gas and solid yields and consequently produced less liquid. There were also significant differences noted in the compositions of the compared pyrolysis products.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thermodynamic Properties of Aggregate Coated by Different Types of Waste Plastic: Adhesion and Moisture Resistance of Asphalt-Aggregate Systems

The utilization of acidic aggregates in hot-mix asphalt (HMA) is often inevitable due to the limited supply of locally available aggregates, posing a potential threat of moisture damage to asphalt pavements. In this regard, the use of urban waste plastic to coat the low-quality aggregates is a promising way to improve the moisture resistance. This study fundamentally evaluated the compatibility between asphalt and plastic-coated aggregate by measuring surface energy, and for the first time compared the effects of different types of waste plastic including high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), and polypropylene (PP). The plastic-coating significantly altered the chemistry of aggregate surface by increasing the nonpolar components and reducing the polar components. Such changes remarkably increased the dry adhesion energy between asphalt and aggregate and enhanced the wettability of aggregate. For the acidic aggregates, the polymeric treatment could decrease the value of wet adhesive, which indicated the debonding tendency in the presence of water was reduced. Finally, the energy ratios of the asphalt-aggregate combinations significantly increased by the surface pretreatment, which proved the effect of waste plastic coating on improving the moisture damage resistance of asphalt mixtures. By comparison, the HDPE coating was the most effective way to enhance the compatibility with asphalt, followed by PP and LDPE coatings. The PVC and PET coatings were investigated as the least effective way. In conclusion, this study cannot only contribute to the potential large-scale utilization of waste plastic but also remove the obstacles of using large quantities of acidic natural aggregate in asphalt pavements.

36 MATERIALS SCIENCE↗

Electrical and Surface Morphology of Polyvinylchloride Composites Filled with Aluminum Powder

In this work, the electrical and surface morphology of polyvinyl chloride (PVC) composites filled with different concentration of aluminum powder varying from 0 to 40 wt.% have been prepared by solution costing method. The electrical conductivity of these composites were investigated in the frequency range 100 Hz-10 MHz at room temperature. The conductivity of the composites system exhibited a strong frequency dependence particularly in the vicinity of percolation threshold (20 wt.%). It was observed that the electrical conductivity gradually increased with filler concentration and frequency and explained in terms of hopping conduction mechanism. The electrical conductivity of the composites obeys universal power law (i.e. {sigma} = Af{sup n}), where, n is power exponent. The scanning electron microscope (SEM) micrographs indicate the agglomeration of aluminum particles dispersed within the PVC at the higher aluminum concentration, yielding a conductive path through the composites. It is also corroborated with electrical conductivity result.

36 MATERIALS SCIENCE↗

Polarization of positronium in amorphous polar polymers: A case study

The features of positronium in an amorphous copolymer (polyvinyl acetate-crotonic acid) in a range of temperatures including the glass transition were investigated by means of positron annihilation lifetime spectroscopy. In particular, para-positronium lifetime was found to be longer than in a vacuum and to decrease with the temperature. This was attributed to the electron density at the positron (contact density), which is lower than in vacuo due to the presence of polar groups in the copolymer. A three quantum yield experiment confirmed the lifetime results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly sensitive pseudo-differential ac-nanocalorimeter for the study of the glass transition

We present a nanocalorimeter designed for the measurement of the dynamic heat capacity of thin films. The microfabricated sensor, the thermal conditioning of the sensor, as well as the highly stable and low noise electronic chain allow measurements of the real and imaginary parts of the complex specific heat with a resolution Δ C/C of about 10{sup −5}. The performances of this quasi-differential nanocalorimeter were tested on a model of polymeric glass-former, the polyvinyl acetate (PVAc). The high stability and low noise of the device are essential for accurate studies on non-equilibrium slow relaxing systems such as glasses.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Use of Melt Flow Rate Test in Reliability Study of Thermoplastic Encapsulation Materials in Photovoltaic Modules

Use of thermoplastic materials as encapsulants in photovoltaic (PV) modules presents a potential concern in terms of high temperature creep, which should be evaluated before thermoplastics are qualified for use in the field. Historically, the issue of creep has been avoided by using thermosetting polymers as encapsulants, such as crosslinked ethylene-co-vinyl acetate (EVA). Because they lackcrosslinked networks, however, thermoplastics may be subject to phase transitions and visco-elastic flow at the temperatures and mechanical stresses encountered by modules in the field, creating the potential for a number of reliability and safety issues. Thermoplastic materials investigated in this study include PV-grade uncured-EVA (without curing agents and therefore not crosslinked);polyvinyl butyral (PVB); thermoplastic polyurethane (TPU); and three polyolefins (PO), which have been proposed for use as PV encapsulation. Two approaches were used to evaluate the performance of these materials as encapsulants: module-level testing and a material-level testing.

14 SOLAR ENERGY↗

PVT-NG Sensor Final Report

This document is a final report for the polyvinyl toluene (PVT) neutron-gamma (PVT-NG) project, which was sponsored by the Domestic Nuclear Detection Office (DNDO). The PVT-NG sensor uses PVT detectors for both gamma and neutron detection. The sensor exhibits excellent spectral resolution and gain stabilization, which are features that are beneficial for detection of both gamma-ray and neutron sources. In fact, the ability to perform isotope identification based on spectra that were measured by the PVT-NG sensor was demonstrated. As described in a previous report, the neutron sensitivity of the first version of the prototype was about 25% less than the DNDO requirement of 2.5 cps/ng for bare 252 Cf. This document describes design modifications that were expected to improve the neutron sensitivity by about 50% relative to the PVT-NG prototype. However, the project was terminated before execution of the design modifications after portal vendors demonstrated other technologies that enable neutron detection without the use of 3 He. Nevertheless, the PVT-NG sensor development demonstrated several performance goals that may be useful in future portal designs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Characterization of CNC Nanoparticles Prepared via Ultrasonic-Assisted Spray Drying and Their Application in Composite Films

The ultrasonic-assisted spray dryer, also known as a nano spray dryer and predominantly used on a lab scale in the pharmaceutical and food industries, enables the production of nanometer-sized particles. In this study, the nano spray dryer was applied to cellulosic materials, such as cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs). CNC suspensions were successfully dried, while the CNF suspensions could not be dried, attributable to their longer fibril lengths. The nano spray drying process was performed under different drying conditions, including nebulizer hole sizes, solid concentrations, and gas flow rates. It was confirmed that the individual particle size of nano spray-dried CNCs (nano SDCNCs) decreased as the nebulizer hole sizes and solid contents of the suspensions decreased. The production rate of the nano spray dryer increased with higher solid contents and lower gas flow rates. The resulting nano SDCNCs were added to a polyvinyl alcohol (PVA) matrix as a reinforcing material to evaluate their reinforcement behavior in a plastic matrix using solvent casting. After incorporating the 20 wt.% nano SDCNCs into the PVA matrix, the tensile strength and tensile modulus elasticity of the neat PVA nanocomposite film increased by 22% and 32%, respectively, while preserving the transparency of the films.

36 MATERIALS SCIENCE↗