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At least 523 records · Page 29

Application of Nuclear Technology to Art Identification Problems: First Annual Report

Throughout the centuries, as man has become increasingly affluent, his interest in antiquities and objects of art, and the price he has been willing to pay for them, has increased. Inevitably, one result has been to attract the unscrupulous to the production and sale of counterfeit paintings, sculptures, and other works of art. The skill of forgers varies but often is highly sophisticated. However, dealers, museum curators, and other experts have also become more skillful in the detection of forgeries. Scientific tools of increasing sensitivity and sophistication have gradually been applied to the examination of the materials of art and archaeology. Such tools frequently support and render more reliable the judgment of the experts. The quality of forgeries may improve further as their makers become acquainted with the new methods of detection and in turn learn to circumvent or confound the methods. Therefore, the development of still more advanced methods of examination has great utility in the art world. This is particularly true if the ultimate effect is to make circumvention of the methods of examination so costly that the economic incentives for producing forgeries may be substantially reduced, if not eliminated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chinese Ink: A Powerful Photothermal Material for Solar Steam Generation

Solar steam generation offers signifcant promise in alleviating fresh water crises, particularly in regions with accessible seawater and abundant insolation. Affordable, efficient, and environmentally friendly photothermal materials are needed to fabricate sunlight-driven evaporation devices. In this work, Chinese ink, a carbon-based paint used in traditional painting and calligraphy, is readily coated on diverse substrates and stabilized by atomic layer deposition (ALD) for solar steam generation. The ALD/Chinese ink coating exhibits strong and broad light absorption from the NIR to UV regions. Both ALD/Chinese-ink-coated membranes and wood display excellent photothermal properties and superior evaporation performance under simulated sunlight. This study demonstrates the potential of ALD/Chinese ink coating to achieve higher evaporation rate and efficiency by utilizing substrates with rough, structured surfaces and low thermal conductivity.

36 MATERIALS SCIENCE↗

Formulation and Assessment of a Wash-Primer Containing Lanthanum “Tannate” for Steel Temporary Protection

Tannins are polyphenols synthesized by plants and useful for the coating industry as corrosion inhibitors. In addition, lanthanum salts have a great inhibitory effect on steel corrosion. The aim of this study was to obtain lanthanum “tannate” with adequate solubility to be incorporated as the corrosion inhibitor in a wash-primer. The “tannate” was obtained from commercial “Quebracho” tannin and 0.1 M La(NO{sub 3}){sub 3}. The soluble tannin was determined by the Folin–Denis reagent, while the concentration of Lanthanum was obtained by a gravimetric procedure. The protective action of “tannate” on SAE 1010 steel was evaluated by linear polarization curves and corrosion potential measurements. Lanthanum “tannate” was incorporated in a wash-primer formulation and tested by corrosion potential and ionic resistance measurements. The corrosion rate was also determined by the polarization resistance technique. Besides, the primer was incorporated in an alkyd paint system and its anticorrosion performance assessed in the salt spray cabinet and by electrochemical impedance spectroscopy. Results showed that lanthanum “tannate” primer inhibits the development of deleterious iron oxyhydroxides on the steel substrate and incorporated into a paint system had a similar behavior to the primer formulated with zinc tetroxychromate.

36 MATERIALS SCIENCE↗

On-matrix Derivatization for Dynamic Headspace Sampling of Nonvolatile Surface Residues

The goal of this study is to extend sampling by the field and laboratory emission cell (FLEC) purge-and-trap technique to applications that target nonvolatile residues. On-matrix derivatization of residues to render analytes stable and more volatile is explored to achieve this goal. Results show that on-matrix derivatizations of nerve agent hydrolysis products (monoalkyl methylphosphonic acids and methylphosphonic acid [MPA]) with diazomethane were successful on glass and painted wallboard (at the 10-µg level). It also was successful on the more difficult concrete (at the 500-µg level) and carpet (at the 20-µg level) substrates that cannot be successfully sampled using swipe techniques. Analysis of additional chemical warfare (CW)-associated residues can be approached by on-matrix derivatization with trifluoroacetic anhydride (TFAA). For example, amines (used as stabilizers or present as decomposition products of the nerve agent VX) or thiodiglycol (hydrolysis product of sulfur mustard) could be sampled as their TFAA derivatives from glass, painted wallboard, and concrete (at the 40-µg level), as well as carpet (at the 80-µg level) surfaces. Although the amine and thiodiglycol are semi-volatile and could be sampled directly, derivatization improves the recovery and chromatographic behavior of these analytes.

On-matrix derivatization, in-situ derivatization, ↗

Spatiotemporal Stability of Cu-ATSM and FLT Positron Emission Tomography Distributions During Radiation Therapy

Purpose: In dose painting, in which functional imaging is used to define biological targets for radiation therapy dose escalation, changes in spatial distributions of biological properties during treatment can compromise the quality of therapy. The goal of this study was to assess the spatiotemporal stability of 2 potential dose painting targets—hypoxia and proliferation—in canine tumors during radiation therapy. Methods and Materials: Twenty-two canine patients with sinonasal tumors (14 carcinoma and 8 sarcoma) were imaged before hypofractionated radiation therapy with copper(II)-diacetyl-bis(N4-methylthiosemicarbazone) (Cu-ATSM) positron emission tomography/computed tomography (PET/CT) for hypoxia and 3′-deoxy-3′-{sup 18}F-fluorothymidine (FLT) PET/CT for proliferation. The FLT scans were repeated after 2 fractions and the Cu-ATSM scans after 3 fractions. Midtreatment PET/CT images were deformably registered to pretreatment PET/CT images. Voxel-based Spearman correlation coefficients quantified the spatial stability of Cu-ATSM and FLT uptake distributions between pretreatment and midtreatment scans. Paired t tests determined significant differences between the patients' respective Cu-ATSM and FLT correlations coefficients. Standardized uptake value measures were also compared between pretreatment and midtreatment scans by use of paired t tests. Results: Spatial distributions of Cu-ATSM and FLT uptake were stable through midtreatment for both sarcomas and carcinomas: the population mean ± standard deviation in Spearman correlation coefficient was 0.88 ± 0.07 for Cu-ATSM and 0.79 ± 0.13 for FLT. The patients' Cu-ATSM correlation coefficients were significantly higher than their respective FLT correlation coefficients (P=.001). Changes in Cu-ATSM SUV measures from pretreatment to midtreatment were histology dependent: carcinomas experienced significant decreases in Cu-ATSM uptake (P<.05), whereas sarcomas did not (P>.20). Both histologies experienced significant decreases in FLT uptake (P<.05). Conclusions: Spatial distributions of Cu-ATSM were very stable after a few fractions of radiation therapy. FLT spatial distributions were generally stable early in therapy, although they were significantly less stable than Cu-ATSM distributions. Canine tumors had significantly lower proliferative activity at midtreatment than at pretreatment, and they experienced histology-dependent changes in Cu-ATSM uptake.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

The metal alloys from the XIX century and weathering action in the Mercado do Ver-o-Peso building, northern Brazil: Identification with the usage of laboratory analysis

The fabrication of metallic buildings started in Europe after the Industrial Revolution in the 18th century. Metallic constructions became very popular, and started being imported by several countries, due to the facility of constructing or assembling. Belém, a northern Brazilian city, holds a great number of buildings entirely made of iron, including the Ver-o-Peso, a fish market which structures were imported from England by the end of the 19th century. This building represents a unique type of architecture and it's an important part of the city's heritage. However, research so far did not focus on its construction materials. Ver-o-Peso building's metal alloys haven't been thoroughly studied concerning physical, chemical and mineralogical characterizations. This paper aims to identify the types of metal alloys used in the building, and also corrosion products' result from weathering actions. The methods used to characterize the materials were scanning electron microscopy and X-ray diffraction. Through this research it was possible to identify four types of iron alloys used in the different parts of the building, characterize the paint coats, and determine types of corrosion. The characterization of the materials in the building allows enrolling basis for restoration processes, documenting the types of metal alloy used in architectural heritage from the 19th century, as well as understanding the advances of corrosion. - Highlights: • Ver-o-peso is a heritage building from the 19th century with unidentified alloys. • Alloy and weathering product characterization was done using SEM/EDS and XRD. • Four metal alloy types were described, indicating different types of foundries. • Weathering products showed distinct mineral phases and physical characteristics. • Original paint coats were found among corrosion products.

36 MATERIALS SCIENCE↗

Systematic analysis of diffuse rear reflectors for enhanced light trapping in silicon solar cells

Simple diffuse rear reflectors can enhance the light path length of weakly absorbed near infrared light in silicon solar cells and set a benchmark for more complex and expensive light trapping structures like dielectric gratings or plasmonic particles. We analyzed such simple diffuse rear reflectors systematically by optical and electrical measurements. We applied white paint, TiO 2 nanoparticles, white backsheets and a silver mirror to bifacial silicon solar cells and measured the enhancement of the external quantum efficiency for three different solar cell geometries: planar front and rear side, textured front and planar rear side, and textured front and rear side. We showed that an air-gap between the solar cell and the reflector decreases the absorption enhancement significantly, thus white paint and TiO 2 nanoparticles directly applied to the rear cell surface lead to the highest short circuit current density enhancements. Here, the short circuit current density gains for a 200 um thick planar solar cell reached up to 1.8 mA/cm 2 , compared to a non-reflecting black rear side and up to 0.8 mA/cm 2 compared to a high-quality silver mirror rear side. For solar cells with textured front side the short circuit current density gains are in the range between 0.5 and 1.0 mA/cm 2 compared to a non-reflecting black rear side and do not significantly depend on the angular characteristic of the rear side reflector but mainly on its absolute reflectance.

14 SOLAR ENERGY↗

Early induction of cytokines/cytokine receptors and Cox2, and activation of NF-κB in 4-nitroquinoline 1-oxide-induced murine oral cancer model

The purpose of this study was to identify the genes induced early in murine oral carcinogenesis. Murine tongue tumors induced by the carcinogen, 4-nitroquinoline 1-oxide (4-NQO), and paired non-tumor tissues were subjected to microarray analysis. Hierarchical clustering of upregulated genes in the tumor tissues revealed an association of induced genes with inflammation. Cytokines/cytokine receptors induced early were subsequently identified, clearly indicating their involvement in oral carcinogenesis. Hierarchical clustering also showed that cytokine-mediated inflammation was possibly linked with Mapk6. Cox2 exhibited the greatest extent (9–18 fold) of induction in the microarray data, and its early induction was observed in a 2 h painting experiment by RT-PCR. MetaCore analysis showed that overexpressed Cox2 may interact with p53 and transcriptionally inhibit expression of several downstream genes. A painting experiment in transgenic mice also demonstrated that NF-κB activates early independently of Cox2 induction. MetaCore analysis revealed the most striking metabolic alterations in tumor tissues, especially in lipid metabolism resulting from the reduction of Pparα and Rxrg. Reduced expression of Mapk12 was noted, and MetaCore analysis established its relationship with decreased efficiency of Pparα phosphorylation. In conclusion, in addition to cytokines/cytokine receptors, the early induction of Cox2 and NF-κB activation is involved in murine oral carcinogenesis.

60 APPLIED LIFE SCIENCES↗

Mapping Structure and Rheology of pH-Responsive Resins for Low-VOC Coatings

In recent years, the paint and coatings industry has shifted away from traditional resin formulations that require high concentrations of volatile organic compounds (VOCs) to achieve the desired rheological performance and sustainability targets. One approach to eliminate or reduce VOCs in paint and coating formulations while maintaining the final performance is to disperse stimuli-responsive polymer latex particles in water. The chemistry and architecture of these particles have been engineered such that the suspension rheology changes in response to the pH changes. The particles can also be swollen with organic solvents to illicit similar rheological changes. To understand how the particle microstructure influences the observed macroscopic properties, we use small-angle neutron scattering and dynamic light scattering to determine that these particles consist of a cross-linked core with long polymer tails that extend into the dispersing medium. Carboxylic acid groups present on the tails deprotonate with increasing pH, and the extension of the polymer chain due to charge repulsion increases the hydrodynamic drag on the particle. Here we find that adjusting the pH alone has a much more significant effect on the shear dependence of the viscosity of the studied resin than adding organic solvent alone. We also find that this resin architecture is more responsive per mole of pH-responsive group than other architectures of pH-responsive latex particles in the literature.

36 MATERIALS SCIENCE↗

Tandem Catalytic Antioxidant Nanoparticles Comprising Cerium Carbonate and Photoactive Metal Oxides

While photoactive metal oxides such as TiO 2 find widespread use in paints and coatings as well as cosmetics and suncare products, they also generate reactive oxygen species (ROS), which degrade materials and are associated with human-health pathologies. Here, we demonstrate a robust and potent catalytic antioxidant consisting of earth-abundant cerium carbonate nanoparticles and micron-size Ce 2 (CO 3 ) 3 . 8H 2 O, which are characterized by powder X-ray diffraction and scanning nanobeam electron diffraction. When dispersed with photoactive metal oxides, these cerium carbonate catalysts decrease the photodecomposition rate of organic dyes and commercial pigment colorants in aqueous media by up to 820-fold, as well as in acrylic coatings. X-ray photoelectron spectroscopy and kinetic experiments support the same tandem catalysis mechanism of photoprotection when using both micron-size Ce 2 (CO 3 ) 3 . 8H 2 O and cerium carbonate nanoparticles. This mechanism involves ROS disproportionation (catalyzed by cerium carbonate) and H 2 O 2 decomposition (partially catalyzed by TiO 2 ) pathways, both of which cerium carbonate also catalyzes on its own, crudely mimicking the function of the cascade system of superoxide dismutase and catalase enzymes. When cerium carbonate nanoparticles were dispersed at 2 wt % in polymethylmethacrylate, the transparency of the polymer film was preserved and the photo-oxidative degradation of the polymer was prevented following UV irradiation at 254 nm, which otherwise resulted in the loss of optical properties and hydroxylation as characterized by ATR-FTIR spectroscopy, in the control polymer lacking cerium carbonate. Similar observations were made regarding color preservation in paint films comprising dye and insoluble commercial colorant pigments. The material chemistry associated with this photoprotection catalysis is subtle and emphasizes the importance of both Ce(III) and carbonate together, as both CePO 4 and Na 2 CO 3 are inactive. In conclusion, this emphasis is also apparent in comparisons of photoprotection catalysis with previously reported cerium oxide nanoparticles, which are significantly less active compared with Ce 2 (CO 3 ) 3 . 8H 2 O under the same conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Application of Synchrotron Microprobe Methods to Solid-Phase Speciation of Metals and Metalloids in House Dust

Determination of the source and form of metals in house dust is important to those working to understand human and particularly childhood exposure to metals in residential environments. We report the development of a synchrotron microprobe technique for characterization of multiple metal hosts in house dust. We have applied X-ray fluorescence for chemical characterization and X-ray diffraction for crystal structure identification using microfocused synchrotron X-rays at a less than 10 {micro}m spot size. The technique has been evaluated by application to archived house dust samples containing elevated concentrations of Pb, Zn, and Ba in bedroom dust, and Pb and As in living room dust. The technique was also applied to a sample of soil from the corresponding garden to identify linkages between indoor and outdoor sources of metals. Paint pigments including white lead (hydrocerussite) and lithopone (wurtzite and barite) are the primary source of Pb, Zn, and Ba in bedroom dust, probably related to renovation activity in the home at the time of sampling. The much lower Pb content in the living room dust shows a relationship to the exterior soil and no specific evidence of Pb and Zn from the bedroom paint pigments. The technique was also successful at confirming the presence of chromated copper arsenate treated wood as a source of As in the living room dust. The results of the study have confirmed the utility of this approach in identifying specific metal forms within the dust.

09 BIOMASS FUELS↗

Photonic thermal management of coloured objects

The colours of outdoor structures, such as automobiles, buildings and clothing, are typically chosen for functional or aesthetic reasons. With a chosen colour, however, one must control the radiative thermal load for heating or cooling purposes. Here we provide a comprehensive calculation of the tunable range of radiative thermal load for all colours. The range exceeds 680 Wm –2 for all colours, and can be as high as 866 Wm –2 , resulting from effects of metamerism, infrared solar absorption and radiative cooling. We experimentally demonstrate that two photonic structures with the same pink colour can have their temperatures differ by 47.6 °C under sunlight. These structures are over 20 °C either cooler or hotter than a commercial paint with a comparable colour. Furthermore, the hotter pink structure is 10 °C hotter than a commercial black paint. Here, these results elucidate the fundamental potentials of photonic thermal management for coloured objects.

42 ENGINEERING↗

Patchy nanoparticles by atomic stencilling

Stencilling, in which patterns are created by painting over masks, has ubiquitous applications in art, architecture and manufacturing. Modern, top-down microfabrication methods have succeeded in reducing mask sizes to under 10 nm, enabling ever smaller microdevices as today’s fastest computer chips. Meanwhile, bottom-up masking using chemical bonds or physical interactions has remained largely unexplored, despite its advantages of low cost, solution-processability, scalability and high compatibility with complex, curved and three-dimensional (3D) surfaces. Here we report atomic stencilling to make patchy nanoparticles (NPs), using surface-adsorbed iodide submonolayers to create the mask and ligand-mediated grafted polymers onto unmasked regions as ‘paint’. We use this approach to synthesize more than 20 different types of NP coated with polymer patches in high yield. Polymer scaling theory and molecular dynamics (MD) simulation show that stencilling, along with the interplay of enthalpic and entropic effects of polymers, generates patchy particle morphologies not reported previously. These polymer-patched NPs self-assemble into extended crystals owing to highly uniform patches, including different non-closely packed superlattices. We propose that atomic stencilling opens new avenues in patterning NPs and other substrates at the nanometre length scale, leading to precise control of their chemistry, reactivity and interactions for a wide range of applications, such as targeted delivery, catalysis, microelectronics, integrated metamaterials and tissue engineering.

36 MATERIALS SCIENCE↗

Evidence for an unorthodox firing sequence employed by the Berlin Painter. Deciphering ancient ceramic firing conditions through high-resolution material characterization and replication

XANES spectroscopy was used to complement the results previously obtained with Raman spectroscopy by the same group to determine the firing conditions used in the production of a single vessel painted by the Berlin Painter in the 5th century B.C. The vessel, part of the collection of the J. Paul Getty Museum, presents a complicated layered architecture of black and red gloss, with different stratigraphies present on the interior and exterior surfaces. The study of two samples, one each from the interior and exterior surface of the vessel, was performed with the complementary analytical techniques of X-ray nano- and micro-spectroscopy (X-ray fluorescence spectroscopy (XRF) and full-field transmission X-ray micro-spectroscopy (FF-XANES) across the Fe K edge), and supported by a replication study. The replicates, made in a laboratory furnace providing complete control over the firing temperature and oxygen partial pressure, provided a paradigm for the comparison of the mineralogical phases observed in the ancient samples, which led to a deeper understanding of the firing conditions necessary for the production of the Berlin Painter's vessel. Our results confirm the necessity of multiple firings and painting applications to obtain the Berlin Painter's architecture and provide a further example of the multiplicity of techniques and practices employed by the potters of the Kerameikos in ancient Athens.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DNP-enhanced ultrawideline 207 Pb solid-state NMR spectroscopy: an application to cultural heritage science

Dynamic nuclear polarization (DNP) is used to enhance the (ultra)wideline 207 Pb solid-state NMR spectra of lead compounds of relevance in the preservation of cultural heritage objects. The DNP SSNMR experiments enabled, for the first time, the detection of the basic lead carbonate phase of the lead white pigment by 207 Pb SSNMR spectroscopy. Variable-temperature experiments revealed that the short T'2 relaxation time of the basic lead carbonate phase hinders the acquisition of the NMR signal at room temperature. We additionally observe that the DNP enhancement is twice as large for lead palmitate (a lead soap, which is a degradation product implicated in the visible deterioration of lead-based oil paintings), than it is for the basic lead carbonate. As a result, this enhancement has allowed us to detect the formation of a lead soap in an aged paint film by 207 Pb SSNMR spectroscopy; which may aid in the detection of deterioration products in smaller samples removed from works of art.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of Low Dose Silicon Carbide Temperature Monitors

Thermocouples are generally used to provide real-time temperature indications in instrumented tests performed at materials and test reactors. Melt wires or paint spots are often included in such tests as an independent technique of detecting peak temperatures incurred during irradiation. In addition, less expensive static capsule tests, which have no leads attached for real-time data transmission, often rely on melt wires and paint spots as a post-irradiation technique for peak temperature indication. Unfortunately, these techniques are limited in that they can only detect whether a single temperature is or is not exceeded. Silicon carbide (SiC) monitors are advantageous because a single monitor can be used to determine the peak temperature reached within a relatively broad range (200 – 800°C). Although the use of SiC monitors was proposed more than five decades ago, the ultimate performance limits of this technique are not fully understood. The Nuclear Science User Facilities (NSUF) is the United States Department of Energy Office of Nuclear Energy's only designated nuclear energy user facility. Its mission is to provide nuclear energy researchers access to world-class capabilities and to facilitate the advancement of nuclear science and technology. This mission is supported by providing access to state-of-the-art experimental irradiation testing, post irradiation examination facilities, and high performance computing capabilities as well as technical and scientific assistance for the design and execution of projects. As part of an NSUF project, low dose silicon carbide monitors were irradiated in the Belgian Reactor 2 and were then evaluated both at the SCK•CEN and at Idaho National Laboratory's High Temperature Test Laboratory to determine their peak temperature achieved during irradiation. The technical significance of this work was that the monitors were irradiated to a dose that was significantly less than recommended in published literature. This paper will discuss the evaluation process, the irradiation test, and the performance of the low dose silicon carbide temperature monitors.

36 MATERIALS SCIENCE↗

Insights from high-fidelity modeling of industrial rotary bell atomization

The global automotive industry sprayed over 2.6 billion liters of paint in 2018, much of which through electrostatic rotary bell atomization, a highly complex process involving the fluid mechanics of rapidly rotating thin films tearing apart into micrometer-thin filaments and droplets. Coating operations account for 65% of the energy usage in a typical automotive assembly plant, representing 10,000s of gigawatt-hours each year in the United States alone. Optimization of these processes would allow for improved robustness, reduced material waste, increased throughput, and significantly reduced energy usage. Here, we introduce a high-fidelity mathematical and algorithmic framework to analyze rotary bell atomization dynamics at industrially relevant conditions. Our approach couples laboratory experiment with the development of robust non-Newtonian fluid models; devises high-order accurate numerical methods to compute the coupled bell, paint, and gas dynamics; and efficiently exploits high-performance supercomputing architectures. These advances have yielded insight into key dynamics, including i) parametric trends in film, sheeting, and filament characteristics as a function of fluid rheology, delivery rates, and bell speed; ii) the impact of nonuniform film thicknesses on atomization performance; and iii) an understanding of spray composition via primary and secondary atomization. These findings result in coating design principles that are poised to improve energy- and cost-efficiency in a wide array of industrial and manufacturing settings.

97 MATHEMATICS AND COMPUTING↗

Glimpsing Colour in a World of Black and White

The past 40 years have taught us that nucleons are built of constituents that carry colour charges with interactions governed by Quantum Chromodynamics (QCD). How experiments (past, present and future) at Jefferson Lab probe colourless nuclei to map out these internal colour degrees of freedom is presented. When combined with theoretical calculations, these will paint a picture of how the confinement of quarks and gluons, and the structure of the QCD vacuum, determine the properties of all (light) strongly interacting states.

Pennington, M. R.↗