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At least 1,675 records · Page 93
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

FY22 Progress on Multicontinuum Methods in Containment

Estimation of two-phase fluid flow properties is important to understand and predict water and gas movement through the vadose zone for agricultural, hydrogeological, and engineering applications, such as containment transport and/or containment of gases in the subsurface. To estimate rock fluid flow properties and subsequently predict physically realistic processes such as patterns and timing of water, gas, and energy (e.g., heat) movement in the subsurface, laboratory spontaneous water imbibition with simultaneous temperature measurement and numerical modeling methods are presented in the FY22 progress report. A multiple-overlapping-continua conceptual model is used to explain and predict observed complex multi-phenomenological laboratory test behavior during spontaneous imbibition experiments. This report primarily addresses two complexities that arise during the experiments: 1) capturing the late-time behavior of spontaneous imbibition tests with dual porosity; and 2) understanding the thermal perturbation observed at or ahead of the imbibing wetting front, which are associated with adsorption of water in initially dry samples. We use numerical approaches to explore some of these issues, but also lay out a plan for further laboratory experimentation and modeling to best understand and leverage these unique observations.

58 GEOSCIENCES↗
DOE OSTI2016

A HARD GAMMA-RAY FLARE FROM 3C 279 IN 2013 DECEMBER

The blazar 3C 279 exhibited twin γ-ray flares of similar intensity in 2013 December and 2014 April. In this work, we present a detailed multi-wavelength analysis of the 2013 December flaring event. Multi-frequency observations reveal the uncorrelated variability patterns with X-ray and optical–UV fluxes peaking after the γ-ray maximum. The broadband spectral energy distribution (SED) at the peak of the γ-ray activity shows a rising γ-ray spectrum but a declining optical–UV flux. This observation along with the detection of uncorrelated variability behavior rules out the one-zone leptonic emission scenario. We, therefore, adopt two independent methodologies to explain the SED: a time-dependent lepto-hadronic modeling and a two-zone leptonic radiative modeling approach. In the lepto-hadronic modeling, a distribution of electrons and protons subjected to a randomly orientated magnetic field produces synchrotron radiation. Electron synchrotron is used to explain the IR to UV emission while proton synchrotron emission is used to explain the high-energy γ-ray emission. A combination of both electron synchrotron self-Compton emission and proton synchrotron emission is used to explain the X-ray spectral break seen during the later stage of the flare. In the two-zone modeling, we assume a large emission region emitting primarily in IR to X-rays and γ-rays to come primarily from a fast-moving compact emission region. We conclude by noting that within a span of four months, 3C 279 has shown the dominance of a variety of radiative processes over each other and this reflects the complexity involved in understanding the physical properties of blazar jets in general.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1992

High level cognitive information processing in neural networks

Two related research efforts were addressed: (1) high-level connectionist cognitive modeling; and (2) local neural circuit modeling. The goals of the first effort were to develop connectionist models of high-level cognitive processes such as problem solving or natural language understanding, and to understand the computational requirements of such models. The goals of the second effort were to develop biologically-realistic model of local neural circuits, and to understand the computational behavior of such models. In keeping with the nature of NASA's Innovative Research Program, all the work conducted under the grant was highly innovative. For instance, the following ideas, all summarized, are contributions to the study of connectionist/neural networks: (1) the temporal-winner-take-all, relative-position encoding, and pattern-similarity association techniques; (2) the importation of logical combinators into connection; (3) the use of analogy-based reasoning as a bridge across the gap between the traditional symbolic paradigm and the connectionist paradigm; and (4) the application of connectionism to the domain of belief representation/reasoning. The work on local neural circuit modeling also departs significantly from the work of related researchers. In particular, its concentration on low-level neural phenomena that could support high-level cognitive processing is unusual within the area of biological local circuit modeling, and also serves to expand the horizons of the artificial neural net field.

Barnden, John A.↗
NASA NTRS1994

Lower mantle thermal structure deduced from seismic tomography, mineral physics and numerical modelling

The long-wavelength thermal anomalies in the lower mantle have been mapped out using several seismic tomographic models in conjunction with thermodynamic parameters derived from high-pressure mineral physics experiments. These parameters are the depth variations of thermal expansivity and of the proportionality factor between changes in density and seismic velocity. The giant plume-like structures in the lower mantle under the Pacific Ocean and Africa have outer fringes with thermal anomalies around 300-400 K, but very high temperatures are found in the center of the plumes near the base of the core-mantle boundary. These extreme values can exceed +1500 K and may reflect large hot thermal anomalies in the lower mantle, which are supported by recent measurements of high melting temperatures of perovskite and iron. Extremely cold anomalies, around -1500 K, are found for anomalies in the deep mantle around the Pacific rim and under South America. Numerical simulations show that large negative thermal anomalies in the mid-lower mantle have modest magnitudes of around -500 K. correlation pattern exists between the present-day locations of cold masses in the lower mantle and the sites of past subduction since the Cretaceous. Results from correlation analysis show that the slab mass-flux in the lower mantle did not conform to a steady-state nature but exhibited time-dependent behavior.

Cadek, O.↗
NASA NTRS1995

Penetration experiments in aluminum 1100 targets using soda-lime glass projectiles

The cratering and penetration behavior of annealed aluminum 1100 targets, with thickness varied from several centimeters to ultra-thin foils less than 1 micrometer thick, were experimentally investigated using 3.2 mm diameter spherical soda-lime glass projectiles at velocities from 1 to 7 km/s. The objective was to establish quantitative, dimensional relationships between initial impact conditions (impact velocity, projectile diameter, and target thickness) and the diameter of the resulting crater or penetration hole. Such dimensional relationships and calibration experiments are needed to extract the diameters and fluxes of hypervelocity particles from space-exposed surfaces and to predict the performance of certain collisional shields. The cratering behavior of aluminum 1100 is fairly well predicted. However, crater depth is modestly deeper for our silicate impactors than the canonical value based on aluminum projectiles and aluminum 6061-T6 targets. The ballistic-limit thickness was also different. These differences attest to the great sensitivity of detailed crater geometry and penetration behavior on the physical properties of both the target and impactor. Each penetration experiment was equipped with a witness plate to monitor the nature of the debris plume emanating from the rear of the target. This plume consists of both projectile fragments and target debris. Both penetration hole and witness-plate spray patterns systematically evolve in response to projectile diameter/target thickness. The relative dimensions of the projectile and target totally dominate the experimental products documented in this report; impact velocity is an important contributor as well to the evolution of penetration holes, but is of subordinate significance for the witness-plate spray patterns.

Horz, Friedrich↗
NASA NTRS2011

Wallops' Low Elevation Link Analysis for the Constellation Launch/Ascent Links

Prior to the redirection of the Constellation Program, the Wallops 11.3-meter ground station was tasked to support the Orion's Dissimilar Voice (DV) link and the Ares's Development Flight Instrument (DFI) link. Detailed analysis of the launch trajectories indicates that during the launch and ascent operation, the critical events of Orion-Ares main engine cut off (MECO) and Separation occur at low elevation angle. We worked with engineers from both Wallops Flight Facility (WFF) and Johnson Space Center (JSC) to perform an intensive measurement and link analysis campaign on the DV and DFI links. The main results were as follows: (1) The DV links have more than 3 dB margin at MECO and Separation. (2) The DFI links have 0 dB margin at Separation during certain weather condition in summer season. (3) Tropospheric scintillation loss is the major impairment at low elevation angle. (4) The current scintillation models in the Recommendation ITU-R P.618 (Propagation data and prediction methods required for the design of Earth-space telecommunication systems), which are based on limited experimental and theoretical work, exhibit idiosyncratic behaviors. We developed an improved model based on the measurements of recent Shuttle mission launch and ascent links and the ITU propagation data. (5) Due to the attitude uncertainty of the Orion-Ares stack, the high dynamics of the launch and ascent trajectory, and the irregularity of the Orion and Ares antenna patterns, we employed new link analysis approach to model the spacecraft antenna gain. In this paper we discuss the details of the aforementioned results.

Cheung, Kar-Ming↗
NASA NTRS2006

Mechanisms for Diurnal Variability of Global Tropical Rainfall Observed from TRMM

The behavior and various controls of diurnal variability in tropical-subtropical rainfall are investigated using Tropical Rainfall Measuring Mission (TRMM) precipitation measurements retrieved from the three level-2 TRMM standard profile algorithms for the 1998 annual cycle. Results show that diurnal variability characteristics of precipitation are consistent for all three algorithms, providing assurance that TRMM retrievals are producing consistent estimates of rainfall variability. As anticipated, most ocean areas exhibit more rainfall at night, while over most land areas, rainfall peaks during daytime; however, important exceptions are noted. The dominant feature of the oceanic diurnal cycle is a rainfall maximum in late-evening-early-morning (LE-EM) hours, while over land the dominant maximum occurs in the mid- to late afternoon (MLA). In conjunction with these maxima are pronounced seasonal variations of the diurnal amplitudes. Amplitude analysis shows that the diurnal pattern and its seasonal evolution are closely related to the rainfall accumulation pattern and its seasonal evolution. In addition, the horizontal distribution of diurnal variability indicates that for oceanic rainfall, there is a secondary MLA maximum coexisting with the LE-EM maximum at latitudes dominated by large-scale convergence and deep convection. Analogously, there is a preponderancy for an LE EM maximum over land coexisting with the stronger MLA maximum, although it is not evident that this secondary continental feature is closely associated with the large-scale circulation. Neither of the secondary maxima exhibit phase behavior that can be considered semidiurnal in nature. Diurnal rainfall variability over the ocean associated with large-scale convection is clearly an integral component of the general circulation. Phase analysis reveals differences in regional and seasonal features of the diurnal cycle, indicating that underlying forcing mechanisms differ from place to place. This is underscored by the appearance of secondary ocean maxima in the presence of large-scale convection, along with other important features. Among these, there are clear-cut differences between the diurnal variability of seasonal rainfall over the mid-Pacific and Indian Ocean Basins. The mid-Pacific exhibits double maxima in spring and winter but only LE-EM maxima in summer and autumn, while the Indian Ocean exhibits double maxima in spring and summer and only an LE-EM maximum in autumn and winter. There are also evident daytime maxima within the major large-scale marine stratocumulus regions off the west coasts of continents. The study concludes with a discussion concerning how the observational evidence either supports or repudiates possible forcing mechanisms that have been suggested to explain diurnal rainfall variability.

Yang, Song↗
DOE OSTI2018

Machine learning for graph-based representations of three-dimensional discrete fracture networks

Structural and topological information play a key role in modeling flow and transport through fractured rock in the subsurface. Discrete fracture network (DFN) computational suites such as dfnWorks (Hyman et al. Comput. Geosci. 84, 10–19 2015) are designed to simulate flow and transport in such porous media. Flow and transport calculations reveal that a small backbone of fractures exists, where most flow and transport occurs. Restricting the flowing fracture network to this backbone provides a significant reduction in the network’s effective size. However, the particle-tracking simulations needed to determine this reduction are computationally intensive. Such methods may be impractical for large systems or for robust uncertainty quantification of fracture networks, where thousands of forward simulations are needed to bound system behavior. In this paper, we develop an alternative network reduction approach to characterizing transport in DFNs, by combining graph theoretical and machine learning methods. We consider a graph representation where nodes signify fractures and edges denote their intersections. Using random forest and support vector machines, we rapidly identify a subnetwork that captures the flow patterns of the full DFN, based primarily on node centrality features in the graph. Our supervised learning techniques train on particle-tracking backbone paths found by dfnWorks, but run in negligible time compared to those simulations. In conclusion, we find that our predictions can reduce the network to approximately 20% of its original size, while still generating breakthrough curves consistent with those of the original network.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Spatially-resolved lithiation dynamics from operando X-ray diffraction and electrochemical modeling of lithium-ion cells

In this study, energy dispersive X-ray diffraction is used to profile the time evolution of ordered Li x C 6 phases in solid electrodes of lithium-ion cells charged at rates between 0.2 and 4.7C (where 1C corresponds to full discharge in 1 h). The methods for quantifying lithium concentration in these phases from the acquired diffraction patterns are described. Compact expressions for time-dependent concentration gradients in the solid electrodes using orthogonal polynomial expansions are presented. Experimentally, these gradients persisted in lithiated graphite electrodes even after the cells rested at open-circuit for over 9 h. A multiphase electrochemical model of graphite intercalation captured many of the observed behaviors, including the progression of phase transitions and the persistent gradients at zero current. However, the magnitude of concentration gradients in both the oxide cathode and graphite anode is underestimated by the model, even at moderate currents.

25 ENERGY STORAGE↗
DOE OSTI2025

Neutron Total Scattering Analysis of Materials for the Nuclear Fuel Cycle

Here, this paper reviews recent experimental efforts at the University of Tennessee and Oak Ridge National Laboratory to comprehensively characterize the structural details of materials relevant for the nuclear fuel cycle by employing advanced neutron scattering techniques. For the study of nuclear ceramics, neutron scattering offers distinct advantages over traditional laboratory or synchrotron X-ray diffraction, including enhanced sensitivity to elements with a low atomic mass, such as oxygen, nitrogen, and carbon. The key to these efforts is the recent advancement in the neutron scattering infrastructure at the high-flux diffractometers at the Spallation Neutron Source. The high neutron flux at these instruments enables neutron total scattering, a nondestructive bulk technique that simultaneously captures both short-range structural effects through pair distribution function analysis and long-range order through diffraction pattern analysis. This approach is particularly important for a comprehensive description of defective, disordered, or amorphous nuclear materials. The case studies presented here include analyses of the local defect structure in hyperstoichiometric uranium oxides and short-range order of ion-irradiated ceramics. This advanced analytical methodology will improve our understanding of the behavior of materials in extreme environments and contribute to the development of more resilient nuclear materials.

Neutron scattering↗
DOE OSTI2023

Finite element modeling of biomass hopper flow

Hoppers are widely used biomass handling devices that channel bulk biomass from storage to subsequent handling equipment. Jenike’s longstanding approach, based on the Mohr-Coulomb model, has been successfully used to design hoppers handling cohesionless granular materials such as grains and other agricultural produces. However, designing a hopper to ensure reliable biomass flow is found to be challenging due to cohesion, irregular particle shape, and bulk material elastoplasticity. This study aims to address the biomass handling engineering challenge with alternative constitutive material models concerning the flow behavior of bulk solids. Finite element modeling is an approach that allows for implementation of different material models, whose underlying constitutive theories assist in investigating the origin and manifestation of bulk mechanical behavior of granular materials. This study focuses on the incipient gravity hopper flow of two types of biomass feedstocks, i.e., ground corn stover and Douglas fir wood. Three widely used constitutive material models, i.e., Mohr-Coulomb model, modified Cam-Clay model, and Drucker-Prager/Cap model, are implemented. Using the flow pattern represented by the volume of biomass exhibiting more than 7% of axial strain (Kamath and Puri, 1999), the finite element model predicts that the bulk corn stover particulate material forms an arch, which represents a hampered transition from the static state to the dynamic flow-state out of the hopper, whereas bulk Douglas fir wood particulate material develops a reliable mass flow pattern. A laboratory scale hopper was used to experimentally determine the biomass flow conditions, which were subsequently compared with the predicted onset of flow by a finite element model (FEM). The developed FEM was found to correctly predict the initiation of mass flow for the milled Douglas fir wood, whereas corn stover was predicted to establish a strong core flow suggesting an unreliable handling characteristic. This observation aligns with the reported poor handling of milled corn stover.

09 BIOMASS FUELS↗
DOE OSTI2022

Between Harmonic Crystal and Glass: Solids with Dimpled Potential-Energy Surfaces Having Multiple Local Energy Minima

Solids with dimpled potential-energy surfaces are ubiquitous in nature and, typically, exhibit structural (elastic or phonon) instabilities. Dimpled potentials are not harmonic; thus, the conventional quasiharmonic approximation at finite temperatures fails to describe anharmonic vibrations in such solids. At sufficiently high temperatures, their crystal structure is stabilized by entropy; in this phase, a diffraction pattern of a periodic crystal is combined with vibrational properties of a phonon glass. As temperature is lowered, the solid undergoes a symmetry-breaking transition and transforms into a lower-symmetry phase with lower lattice entropy. Here, we identify specific features in the potential-energy surface that lead to such polymorphic behavior; we establish reliable estimates for the relative energies and temperatures associated with the anharmonic vibrations and the solid–solid symmetry-breaking phase transitions. We show that computational phonon methods can be applied to address anharmonic vibrations in a polymorphic solid at fixed temperature. To illustrate the ubiquity of this class of materials, we present a range of examples (elemental metals, a shape-memory alloy, and a layered charge-density-wave system); we show that our theoretical predictions compare well with known experimental data.

36 MATERIALS SCIENCE↗
NASA NTRS1995

Emission line signatures of anisotropic turbulence in accretion disks

We investigate observable effects of anisotropic turbulence on the velocity profiles and eclipse behavior of emission lines from accretion disks. Turbulence expands the local line broadening profile, enhancing the surface brightness of saturated emission lines. Anisotropic turbulence produces anisotropic emission in such lines. The effects become observable when the turbulence exceeds the thermal velocity. Each term in the velocity-velocity correlation matrix produces a distinctive azimuthal pattern of enhanced emission-line surface brightness on the face of the accretion disk. These patterns express themselves as changes in the observable shapes of the disk's emission lines. The best place to look for turbulence effects is in saturated emission lines of heavy elements such as Ca, Mg, and Fe, which have a smaller thermal velocity at a given sound speed and at moderate inclination (60-70 degrees), since the Keplerian shear broadening dominates at higher inclinations.

Horne, Keith↗
DOE OSTI2024

Comparison of Gas Phase Fragmentation Behaviors of Nuclear Fuel Cycle Ligands in Lanthanide and Americium Metal Ligand Nitrate Clusters

Introduction (120 words): Transport of metal ions across the aqueous-organic phase boundary is an essential step in a hydrometallurgical nuclear fuel reprocessing strategy. The study of transport agents for nuclear fuel elements is imperative to guide the design of ligands that boost the separation efficiency of the recovery process from fission products. However, limited studies have been made on the chemistry of these transport agents when complexing with transuranic elements in gas-phase where all surrounding factors are essentially excluded. This work investigates the reagent ligand complexations to transuranic and other metals and their dissociations in the gas phase. Comparisons are made between 4f and 5f elements and between ligands. Methods (120 words): (N,N-diisobutylcarbamoylmethyl)phenyloctylphosphine oxide (CMPO) and N,N,N',N'-tetraoctyldiglycolamide (TODGA) have been selected to complex with metal nitrates. The actinide americium and lanthanides neodymium, samarium, and europium were investigated as part of this work. The lanthanides were selected to act as size and electron configuration analogues of the minor actinides. Metal complexes with two ligands and two nitrates ([M(NO3)2(CMPO)2]+, for example) are studied in Bruker micrOTOF-Q II mass spectrometer equipped with collision-induced dissociation capability. The comparisons of the mass spectra are made in groups of homogenous ligands and mixed TODGA-CMPO ligands clusters. Comparisons are also made based on the complexed metals (Am and lanthanides). Preliminary data (300 words): Collision-induced dissociation mass spectrometry data are collected on two ligands complexed with metal nitrates where the two ligands are homogenous, with (CMPO)2 or (TODGA)2, or heterogeneous, with (TODGA)(CMPO). Several fragmentation patterns are observed among complexes with the CMPO ligand whereas the TODGA ligand commonly dissociates intact from the complex. Most of the metal complexes exhibit similar fragmentation patterns, but there are a few notable deviations in fragmentation patterns between the Am and Ln-bearing complexes. For the [M(CMPO)2(NO3)2]+ complexes, the initial loss of nitrate in the form of nitric acid is observed in all four complexes. However, [Am(CMPO)2(NO3)2]+ exhibits an additional fragmentation not found in the lanthanide complexes. Also, a significantly different ratio of the second nitric acid loss is found in the Am complex. These deviations may indicate the different interaction behaviors between actinides and lanthanides. The [M(TODGA)2(NO3)2]+ complexes exhibit the fragmentation as the loss of one TODGA ligand as an intact form and the loss of nitrate as nitric acid. The Am complex exhibits an additional fragmentation after losing the TOGDA ligand, which is not observed among the Ln complexes. The heterogeneous [M(TODGA)(CMPO)(NO3)2]+ complexes exhibit both similarities and differences between the Am and Ln complexes. For example, the heterogenous Am complex does not exhibit the loss of an intact TODGA ligand while all three Ln complexes do. This indicates that TODGA may bind more strongly to Am than Ln. Additionally, the intensity of the loss of CMPO ligand (as partially or whole) is found to be significantly larger than that of the loss of TODGA (as partially of whole) indicating that TODGA is bound to the metal significantly stronger than CMPO. Planned computational analysis will help understand the deviation in fragmentation behaviors between americium and lanthanide metal centers, or between TODGA and CMPO ligands. Novel aspect (20 words): Gas-phase actinide and lanthanide complex formation and fragmentation provide insight into the coordination environment differences of f-element metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Single crystal structure and photocatalytic behavior of grafted uranyl on the Zr-node of a pyrene-based metal–organic framework

Accurately characterizing actinide oxides bound to metal–organic frameworks (MOFs) is important for designing MOFs as radioactive waste sorbents and catalytic supports. Here, the zirconium MOF NU-1000 was post-synthetically modified through solvothermal deposition to include the uranyl (UO 2 2+ ) ion and characterized via single-crystal X-ray diffraction. Additonally, bond lengths derived from the diffraction pattern and Raman spectroscopy indicate that UO 2 2+ maintains its chemical properties upon deposition, while alcohol oxidation photocatalysis reveals photo-interactions between the pyrene linkers and the UO 2 2+ ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

Unsteady behavior of a reattaching shear layer

A detailed investigation of the unsteadiness in a reattaching, turbulent shear layer is reported. Laser-Doppler velocimeter measurements were conditionally sampled on the basis of instantaneous flow direction near reattachment. Conditions of abnormally short reattachment and abnormally long reattachment were considered. Ensemble-averaging of measurements made during these conditions was used to obtain mean velocities and Rreynolds stresses. In the mean flow, conditional streamlines show a global change in flow pattern which correlates with wall-flow direction. This motion can loosely be described as a 'flapping' of the shear layer. Tuft probes show that the flow direction reversals occur quite randomly and are shortlived. Streses shown also vary with the change in flow pattern. Yet, the global'flapping' motion does not appear to contribute significantly to the stress in the flow. A second type of unsteady motion was identified. Spectral analysis of both wall static pressure and streamwise velocity shows that most of the energy in the flow resides in frequencies that are significantly lower than that of the turbulence. The dominant frequency is at a Strouhal number equal to 0.2, which is the characteristic frequency of roll-up and pairing of vortical structure seen in free shear layers. It is conjectured that the 'flapping' is a disorder of the roll-up and pairing process occurring in the shear layer.

Driver, D. M.↗
DOE OSTI2017

Spatio-temporal distribution of Oklahoma earthquakes: Exploring relationships using a nearest-neighbor approach: Nearest-neighbor analysis of Oklahoma

Determining the spatiotemporal characteristics of natural and induced seismic events holds the opportunity to gain new insights into why these events occur. Linking the seismicity characteristics with other geologic, geographic, natural, or anthropogenic factors could help to identify the causes and suggest mitigation strategies that reduce the risk associated with such events. The nearest-neighbor approach utilized in this work represents a practical first step toward identifying statistically correlated clusters of recorded earthquake events. Detailed study of the Oklahoma earthquake catalog’s inherent errors, empirical model parameters, and model assumptions is presented. We found that the cluster analysis results are stable with respect to empirical parameters (e.g., fractal dimension) but were sensitive to epicenter location errors and seismicity rates. Most critically, we show that the patterns in the distribution of earthquake clusters in Oklahoma are primarily defined by spatial relationships between events. This observation is a stark contrast to California (also known for induced seismicity) where a comparable cluster distribution is defined by both spatial and temporal interactions between events. These results highlight the difficulty in understanding the mechanisms and behavior of induced seismicity but provide insights for future work.

58 GEOSCIENCES↗
DOE OSTI2019

New hints on Maya Blue formation process by PCA-assisted in situ XRPD/PDF and optical spectroscopy

The exact recipe to prepare the ancient Maya Blue (MB), an incredibly resistant and brilliant pigment prepared from indigo (dye) and Paligorskite (clay), is lost to the ages. To unravel the key features of the MB formation process, several inorganic-dye couples were heated to 200°C and cooled to RT, to investigate their reactivity and the diffusion and degree of sequestration of the dye into the inorganic host. In situ XRPD/PDF and fiber optic reflectance spectroscopy (FORS) data, sided by TGA, provided a comprehensive overview on MB formation mechanism. XRPD/PDF gave information on long/short range behaviors of water desorption/adsorption and indigo sequestration, while TGA and in situ FORS gave information on mass and optical changes within temperature. Ex situ dye removal was used to understand the sample stability after the thermal treatments. A statistical approach based on Principal Component Analysis was exploited to efficiently and jointly analyze the ~3000 collected patterns. MB formation starts below 110°C with disordered distribution of indigo within the channels, reaching maximum reaction speed and higher ordering at 150°C. Above 175°C, color changes and a stronger sequestration of indigo into framework channels are observed, while the affinity for water is dramatically reduced. The origin of different colors, hues and stability in historical MB samples can then explained in term of different thermal history of the starting mechanical indigo-palygorskite mixture.

36 MATERIALS SCIENCE↗