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Thermomechanical behavior and microstructural evolution of a Ni(Pd)-rich Ni 24.3 Ti 49.7 Pd 26 high temperature shape memory alloy

We investigated the effect of thermomechanical cycling on a slightly Ni(Pd)-rich Ni 24.3 Ti 49.7 Pd 26 (near stochiometric Ni–Ti basis with Pd replacing Ni) high temperature shape memory alloy. Furthermore, aged tensile specimens (400 °C/24 h/furnace cooled) were subjected to constant-stress thermal cycling in conjunction with microstructural assessment via in situ neutron diffraction and transmission electron microscopy (TEM), before and after testing. It was shown that in spite of the slightly Ni(Pd)-rich composition and heat treatment used to precipitation harden the alloy, the material exhibited dimensional instabilities with residual strain accumulation reaching 1.5% over 10 thermomechanical cycles. This was attributed to insufficient strengthening of the material (insufficient volume fraction of precipitate phase) to prevent plasticity from occurring concomitant with the martensitic transformation. In situ neutron diffraction revealed the presence of retained martensite while cycling under 300 MPa stress, which was also confirmed by transmission electron microscopy of post-cycled samples. Neutron diffraction analysis of the post-thermally-cycled samples under no-load revealed residual lattice strains in the martensite and austenite phases, remnant texture in the martensite phase, and peak broadening of the austenite phase. The texture we developed in the martensite phase was composed mainly of those martensitic tensile variants observed during thermomechanical cycling. Presence of a high density of dislocations, deformation twins, and retained martensite was revealed in the austenite state via in-situ TEM in the post-cycled material, providing an explanation for the observed peak broadening in the neutron diffraction spectra. Despite the dimensional instabilities, this alloy exhibited a biased transformation strain on the order of 3% and a two-way shape memory effect (TWSME) strain of ~2%, at relatively high actuation temperatures.

36 MATERIALS SCIENCE↗

Spatial variation in edaphic characteristics is a stronger control than nitrogen inputs in regulating soil microbial effects on a desert grass

Increased atmospheric nitrogen (N) deposition can have wide-ranging effects on plant community structure and ecosystem function, some of which may be indirectly mediated by soil microbial responses to an altered biogeochemical environment. In this study, soils from a field N fertilization experiment that spanned a soil texture gradient were used as inocula in the greenhouse to assess the indirect effects of soil microbial communities on growth of a desert grass. Plant performance and interaction with soil microbiota were evaluated via plant above- and belowground biomass, leaf N concentration, and root fungal colonization. Nitrogen fertilization in the field increased the benefits of soil microbial inoculation to plant leaf N concentration, but did not alter the effect of soil microbes on plant growth. Plant-microbe interaction outcomes differed most strongly among sites with different soil textures, where the soil microbial community from the sandiest site was most beneficial to host plant growth. In conclusion, the findings of this study suggest that in a desert grassland, increases in atmospheric N deposition may exert a more subtle influence on plant-microbe interactions by altering plant nutrient status, whereas edaphic factors can alter the whole-plant growth response to soil microbial associates.

54 ENVIRONMENTAL SCIENCES↗

Two-stage epitaxial growth of vertically-aligned SnO2 nano-rods on (001) ceria

Growth of high-aspect ratio oriented tin oxide, SnO2, nano-rods is complicated by a limited choice of matching substrates. We show that a (001) cerium oxide, CeO2, surface uniquely enables epitaxial growth of tin-oxide nano-rods via a two-stage process. First, (100) oriented nano-wires coat the ceria surface by lateral growth, forming a uniaxially-textured SnO2 deposit. Second, vertical SnO2 nano-rods nucleate on the deposit by homoepitaxy. We demonstrate growth of vertically oriented 1-2 mu m long nano-rods with an average diameter of approximate to 20 nm. 2014 Elsevier B.V. All rights reserved.

Solovyov, VF↗

Effect of amine type on acidic toxic gas adsorption at ambient conditions on modified CuBTC

We report two amine-modified copper-based Metal Organic Frameworks (MOF (CuBTC)) of different surface chemical and textural features were synthesized and used as adsorbents of acidic toxic gases (NO 2 and H 2 S) in both moist (71% relative humidity (R.H.)) and dry conditions. The initial and exhausted samples were characterized by nitrogen adsorption, powder X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis and Fourier transform infrared spectroscopy. The addition of melamine prevented full growth of CuBTC crystals and resulted in amorphous-like particles with sizes less than 200 nm. The material was non-porous with a small surface area. When urea was used as an amine source, the resulting particles maintained the overall octahedral shape of the parent CuBTC MOF and the material was more porous than the parent MOF. While the urea-modified CuBTC sample performed well as an NO 2 adsorbent in the presence of moisture, the reactivity of the melamine-modified sample and its physical properties provided a favorable environment for the removal of H 2 S. The incorporation of amines into the MOF structure also resulted in surface defects /open copper sites that favored the removal of toxic gases in dry conditions. The reactivity of the adsorbents with toxic gases was demonstrated by the changes in the adsorbent colors, in texture, and in surface chemistry (organic salts, complexes, sulfides and nitrates were formed).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Morphologic and chemical characterization of products from hydrolysis of UF 6

Characterization of the chemical speciation and morphologies of products formed from hydrolysis of uranium hexafluoride (UF 6 ) is important for predicting dispersion and contamination of released material, or health consequences from inhalation of air-borne particles. Here, we report products of hydrolysis of UF 6 in which the quantity of water was insufficient for complete formation of UO 2 F 2 . Material was deposited onto carbon tape and aluminum. Scanning electron microscopy was employed to characterize textures and particle sizes, and powder X-ray diffraction analysis and μ-Fourier transform infrared absorption spectroscopy were used to characterize chemical speciation. These results revealed that the ratio of H 2 O to UF 6 , depository substrate composition, and storage conditions must be considered when evaluating chemical speciation, morphologic texture and particles size of UF 6 hydrolysis products. LA-UR-15-23846.

36 MATERIALS SCIENCE↗

MnBi-based magnets prepared from melt-spun alloys: Effect of $α → β$ phase transformation during field annealing

The temperature of the annealing treatment applied to the MnBi alloys with the intention to stabilize the α -MnBi “low-temperature” phase – a promising material for the rare-earth-free permanent magnets – is usually kept below the range of the β -Mn 1.08 Bi “high-temperature” phase. This work is focused on the investigation of the effects of partial and complete α → β phase transformation in bulk magnetic-field-annealed magnets on their structure and magnetic properties. MnBi alloys modified with In, Mg and Sb were melt-spun, compacted to their full density and then heated in a magnetic field of 30 kOe to temperatures sufficiently high for the beginning of the α → β transformation. A heating of 15 °C/min was used which was immediately followed by cooling at the rate of 7.5 °C/min; the degree of the phase transformation was measured by in situ monitoring of changes in the sample magnetization. In all the studied alloys, the α → β transformation was found to improve the [0 0 1] fiber texture induced by the applied magnetic field, although it simultaneously decreased the coercivity. A partial transformation has resulted in a 11% increase of the maximum energy product for the Mn 50 Bi 49 Sb 0.5 In 0.5 magnet, to 8.3 MGOe, and a 3% increase for the Mn 50 Bi 46 Mg 3 Sb 0.5 In 0.5 magnet, to 12.8 MGOe. In the latter alloy, the α → β and reverse transformations were found to initially occur in well-defined pockets leading to clusters of large, highly textured α crystallites. In the Mn 50 Bi 48.5 Sb 1.5 magnet, only part of the α phase could be recovered after the transformation, which instead promoted the paramagnetic MnBi 0.9 Sb 0.1 phase.

36 MATERIALS SCIENCE↗

Spin-dependent Seebeck and Nernst effects in an ideal skyrmion gas

In this work, we theoretically and numerically study spin-dependent Seebeck and Nernst effects in 2D ferromagnetic materials with the topological spin texture (skyrmion and vortex) ideal gas. From the numerical solution of the matrix Boltzmann equation for a nonequilibrium distribution function and the Lippmann–Schwinger equation for a T-matrix we find the strong nonlinear behaviors in the thermoelectric coefficients depending on skyrmion/vortex diameters and electron concentrations. In particular, the dramatic dependences in the Seebeck and Nernst coefficients take place at larger magnetic texture sizes where the abrupt sign flip in the vortex Seebeck and Nernst coefficients occurs in the narrow region of electron concentrations. In this case the normalized Nernst coefficient changes from +5 to -7. The spin-dependent thermoelectric coefficients are proportional to T at low temperatures for all skyrmion/vortex sizes.

36 MATERIALS SCIENCE↗

Origins of high ductility exhibited by an extruded magnesium alloy Mg-1.8Zn-0.2Ca: Experiments and crystal plasticity modeling

Low ductility and strength are major bottlenecks against Mg alloys' wide applications. In this work, we systematically design the composition and fabrication process for a low-alloyed Mg-Zn-Ca alloy, showing that it can be extruded at low temperatures (~ 250 degrees C) and high speeds (~2 mm/s). After the extrusion, this alloy exhibits a substantially weakened basal texture, relatively small grain size, very high tensile elongation (~ 30%), and good strength. The origin of the considerably improved ductility was studied using a combination of three-dimensional atom probe tomography (3D-APT), transmission electron microscopy (TEM), electron backscattered diffraction (EBSD) in conjunction with surface slip trace analysis, in-situ synchrotron X-ray diffraction, and elasto-plastic self-consistent (EPSC) modeling. Co-segregation of Zn and Ca atoms at a grain boundary is observed and associated with texture weakening and grain boundary mediated plasticity, both improving the ductility. While basal slip and prismatic slip are identified as the dominant deformation systems in the alloy, the ratio between their slip resistances is substantially reduced relative to pure Mg and most other Mg alloys, significantly contributing to the improved ductility of the alloy. This Mg-Zn-Ca alloy exhibiting excellent mechanical properties and low fabrication cost is a promising candidate for industrial productions.

36 MATERIALS SCIENCE↗

Investigating microstructural evolution in SolidStir™ extruded oxide dispersion strengthened 14YWT alloy fuel cladding tube

Structural components for extreme environments require advanced materials and manufacturing processes. One such advanced material is oxide dispersion strengthened (ODS) Fe–14 wt.%Cr–3W–0.4Ti–0.3Y 2 O 3 (14YWT), which is developed for components to be used in Gen IV and fusion nuclear reactors. However, the conventional manufacturing processes to produce components, such as fuel cladding tubes, either do not retain the desired microstructural attributes or are costly and less efficient. As a result, a more attractive option is a novel manufacturing process developed on the principle of friction stir welding or processing (FSW/P) and commercially referred to as SolidStir™ Extrusion (SSE). Here this study used the SSE technique to study the manufacturing and microstructural evolution of a fuel cladding tube made of ODS 14YWT alloy. The cladding extrusion by the SSE technique involved the use of ball-milled 14YWT powders with Y, Ti, and O in the solid solution and the use of a specially designed W-25Re-Hf tool for consolidation and extrusion of the powders. A scanning electron microscope (SEM), electron backscattered diffraction (EBSD), and transmission electron microscope (TEM) were utilized for microstructural characterization. A Keyence microscope captured macrostructural photographs of the extruded tube. EBSD examination of the extruded tube on both transverse and longitudinal cross-sections showed the presence of dynamically recrystallized grains and revealed that the average grain size of the transverse cross-section was smaller than that of the longitudinal cross-section. The texture was weak and consisted of some amount of shear texture. The presence of nano-oxide clusters or precipitates of Y, Ti, and O (pyrochlores) in the extruded tube was determined by TEM. Aging heat treatment caused the average precipitate size to decrease and the density to increase compared to the as-processed condition. The results indicated that SSE is a viable tool for manufacturing fuel cladding tubes with the desired microstructural attributes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Deformation Strengthening of Uranium and Dilute Uranium Alloys

The strength and ductility of uranium and dilute uranium alloys can be substantially improved by deformation strengthening. The yield strength of unalloyed uranium can be nearly doubled by rolling in the vicinity of 250°C. The embrittling effect of hydrogen is also overcome, eliminating the need for vacuum outgassing to obtain good ductility. Significant differences in longitudinal versus transverse tensile properties result, in part, from texture introduced by unidirectional rolling. Warm rolling of U-2.3%Nb results in both traditional strain hardening and a significant Bauschinger effect, resulting in differences between tensile and compressive yield strength. A similar combination of strain hardening and Bauschinger effect also occurs in deformation strengthened U-0.75%Ti. Warm rolling of U-0.75%Ti results in significantly better combinations of tensile yield strength and ductility than can be obtained by conventional age hardening. Warm rolling prior to aging also reduces the loss of ductility which typically accompanies conventional age hardening. Here, an approach is developed in which the effects of prior deformation on tensile and compressive yield strengths are analyzed in terms of texture, long-range dislocation, and Bauschinger effects. The Bauschinger effect is shown to vary in sign with the type of deformation, thus providing opportunities to tailor tensile and compressive properties.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High energy X-ray characterization of the microstructure of PuGa alloy samples at macroscopic depths and non-ambient conditions

High energy (95 keV) X-rays were utilized to characterize the microstructure of eight PuGa alloy samples at room temperature and during cooling to ∼10 K. The samples had different Ga content (nominally 0-3.4 at.%), age, and history. A ninth sample, similarly characterized with neutron diffraction, was included to extend the Ga range to 7 at.%. The samples span the range from single phase α (monoclinic) to δ (face-centered cubic) PuGa, as well as a two-phase α′/δ sample. The crystallographic textures, phase fractions, lattice parameters and dislocation densities of each sample were evaluated through distinct analysis techniques. The textures of the samples were modest. In each case, the dislocation densities were relatively high, comparable to cold worked metals and metals exposed to similar radiation dose. At room temperature, the lattice parameters determined in the predominantly single-phase samples were larger than expected based on the nominal Ga concentration. The observed lattice thermal expansions of the single-phase δ samples to 10 K are self-consistent across the samples and consistent with previous measurements reported in the literature. Significantly larger thermal lattice strain is observed in the δ phase of the two-phase material due to mechanical constraint from the α′ phase, which has a three times larger thermal expansion and is much harder than the δ phase. In conclusion, the results demonstrate the unique value of high-energy X-rays for relatively routine microstructural characterization of Pu alloy samples.

36 MATERIALS SCIENCE↗

Slate – A new record for crystal preferred orientation

This report describes microstructures and preferred orientation of a Devonian slate from the Belgian Ardennes (La Fortelle quarry). The sample, composed largely of muscovite, chlorite, and quartz, displays extraordinary texture strength of muscovite, exceeding 100 multiples of random distribution (m.r.d.) for (001) pole figures and thus setting a new record for preferred orientation in rocks. Quantitative texture analysis was performed with the Rietveld method on synchrotron X-ray diffraction images. Interestingly, quartz also displays strong shape preferred orientation (SPO) as revealed by X-ray microtomography and SEM imaging but largely random crystallographic preferred orientation (CPO). In conclusion, microstructural evidence suggests that this fine-grained rock formed by recrystallization of shale under stress, with growth of phyllosilicates and dissolution and growth of quartz.

58 GEOSCIENCES↗

Utilization of Pebax 1657 as structure directing agent in fabrication of ultra-porous ZIF-8

Ultra porous ZIF-8 particles synthesized using PEO/PA6 based poly(ether-block-amide) (Pebax 1657) as structure directing agent. Structural properties of ZIF-8 samples prepared under different synthesis parameters were investigated by laser particle size analysis, XRD, N{sub 2} adsorption analysis, BJH and BET tests. The overall results showed that: (1) The mean pore size of all ZIF-8 samples increased remarkably (from 0.34 nm to 1.1–2.5 nm) compared to conventionally synthesized ZIF-8 samples. (2) Exceptional BET surface area of 1869 m{sup 2}/g was obtained for a ZIF-8 sample with mean pore size of 2.5 nm. (3) Applying high concentrations of Pebax 1657 to the synthesis solution lead to higher surface area, larger pore size and smaller particle size for ZIF-8 samples. (4) Both, Increase in temperature and decrease in molar ratio of MeIM/Zn{sup 2+} had increasing effect on ZIF-8 particle size, pore size, pore volume, crystallinity and BET surface area of all investigated samples. - Highlights: • The pore size of ZIF-8 samples synthesized with Pebax 1657 increased remarkably. • The BET surface area of 1869 m{sup 2}/gr obtained for a ZIF-8 synthesized sample with Pebax. • Increase in temperature had increasing effect on textural properties of ZIF-8 samples. • Decrease in MeIM/Zn{sup 2+} had increasing effect on textural properties of ZIF-8 samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the correlation between the porous structure and the electrochemical response of powdered and monolithic carbon aerogels as electrodes for capacitive deionization

The combined effect of resorcinol/catalyst (100≤R/C≤800) and resorcinol/water (0.04≤R/W≤0.13) molar ratio on the textural and capacitive properties of carbon aerogels with potential application for capacitive deionization has been evaluated. Activated and pyrolyzed aerogels were synthesized by the sol-gel polymerization of resorcinol-formaldehyde mixtures and dried in supercritical conditions. Data show that high R/C and R/W molar ratios lead to materials with large pores in the mesopore range, whereas the surface area and micropore volumes remain somewhat the same. The activation of the aerogels increased the differences in the specific surface and micropore volumes due to the development of microporosity. This effect was more remarkable for the samples with low R/C whatever the R/W ratio, indicating that the carbon aerogel obtained using high amounts of catalyst are more prone to be activated. Regarding the electrochemical features of the aerogels, low capacitance values were measured in aerogels combining low R/W and high R/C and reciprocally low R/C and high R/W molar ratios, due to their higher resistance. Polarization resistances were found to be slightly higher for the pyrolyzed than for activated aerogels, and followed a decreasing trend with the mesoporosity, indicating the outstanding contribution of the mesoporous network to provide a good kinetic response. The desalting capacity of monolithic aerogels showed a simultaneous dependence with the surface area and the resistivity of the electrodes, pointing out the importance of performing electrochemical measurements in adequate cell configurations (i.e., desalting units) upon the intended application. - Graphical abstract: The textural properties of carbon aerogels are strongly influenced by the synthesis parameters precursor to catalyst (R/C) and water (R/C) ratios. The volumetric capacitance measured in a symmetric cell with monolithic electrodes of carbon aerogel strongly correlates with both surface area and electrical resistivity. - Highlights: • Influence of the synthesis conditions on the properties of carbon aerogels is reported. • Specific surface decreases in the activated samples when either R/C or R/W increase. • An enhanced decrease of the capacitance was observed when R/C and R/W increase. • Ohmic resistance of the electrodes that strongly depends on the R/W and R/C. • Electrosorption capacity is successfully correlated to surface area and resistivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rod-shaped silica particles derivatized with elongated silver nanoparticles immobilized within mesopores

Silver-derivatized silica particles possessing a non-spherical morphology and surface plasmon resonance properties have been achieved. Nanometer-sized silica rods with uniformly sized mesopore channels were prepared first making use of alkyltrimethyl ammonium surfactants as porogens and the 1:0.10 tetraethyl orthosilicate (TEOS) : 3-aminopropyltriethoxysilane (APTES) mixture as a silicon source. Silica rods were subsequently functionalized by introducing elongated silver nanoparticles within the intra-particle mesopores thanks to the AgNO{sub 3} reduction procedure based on the action of hemiaminal groups previously located on the mesopore walls. The textural and structural features of the samples were inferred from the combined characterization studies including SEM and TEM microscopy, nitrogen adsorption-desorption at 77 K, powder XRD in the small- and wide-angle region, as well as UV–visible spectroscopy. {sup 129}Xe NMR spectroscopy appeared particularly useful to obtain a correct information about the porous structure of rod-shaped silica particles and the silver incorporation within their intra-particle mesopores. - Highlights: • Mesoporous monodisperse submicron-sized silica rods were achieved. • Silver nanoparticles were located lengthwise within the intra-particle mesopores. • Textural and plasmonic properties of particles studied by {sup 129}Xe NMR and UV–Vis.

36 MATERIALS SCIENCE↗

Morphological and electrochemical characterization of electrodeposited Zn–Ag nanoparticle composite coatings

Silver nanoparticles with an average size of 23 nm were chemically synthesized and used to fabricate Zn–Ag composite coatings. The Zn–Ag composite coatings were generated by electrodeposition method using a simple sulfate plating bath dispersed with 0.5, 1 and 1.5 g/l of Ag nanoparticles. Scanning electron microscopy, X-ray diffraction and texture co-efficient calculations revealed that Ag nanoparticles appreciably influenced the morphology, micro-structure and texture of the deposit. It was also noticed that agglomerates of Ag nanoparticles, in the case of high bath load conditions, produced defects and dislocations on the deposit surface. Ag nanoparticles altered the corrosion resistance property of Zn–Ag composite coatings as observed from Tafel polarization, electrochemical impedance analysis and an immersion test. Reduction in corrosion rate with increased charge transfer resistance was observed for Zn–Ag composite coatings when compared to a pure Zn coating. However, the particle concentration in the plating bath and their agglomeration state directly influenced the surface morphology and the subsequent corrosion behavior of the deposits. - Highlights: • Synthesis of Ag nanoparticles with an average size of 23 nm • Fabrication of Zn/nano Ag composite coating on mild steel • Composite coatings showed better corrosion resistance. • Optimization of particle concentration is necessary.

36 MATERIALS SCIENCE↗

Effect of heat input on the microstructure, residual stresses and corrosion resistance of 304L austenitic stainless steel weldments

Austenitic stainless steels are widely used in high performance pressure vessels, nuclear, chemical, process and medical industry due to their very good corrosion resistance and superior mechanical properties. However, austenitic stainless steels are prone to sensitization when subjected to higher temperatures (673 K to 1173 K) during the manufacturing process (e.g. welding) and/or certain applications (e.g. pressure vessels). During sensitization, chromium in the matrix precipitates out as carbides and intermetallic compounds (sigma, chi and Laves phases) decreasing the corrosion resistance and mechanical properties. In the present investigation, 304L austenitic stainless steel was subjected to different heat inputs by shielded metal arc welding process using a standard 308L electrode. The microstructural developments were characterized by using optical microscopy and electron backscattered diffraction, while the residual stresses were measured by X-ray diffraction using the sin{sup 2}ψ method. It was observed that even at the highest heat input, shielded metal arc welding process does not result in significant precipitation of carbides or intermetallic phases. The ferrite content and grain size increased with increase in heat input. The grain size variation in the fusion zone/heat affected zone was not effectively captured by optical microscopy. This study shows that electron backscattered diffraction is necessary to bring out changes in the grain size quantitatively in the fusion zone/heat affected zone as it can consider twin boundaries as a part of grain in the calculation of grain size. The residual stresses were compressive in nature for the lowest heat input, while they were tensile at the highest heat input near the weld bead. The significant feature of the welded region and the base metal was the presence of a very strong texture. The texture in the heat affected zone was almost random. - Highlights: • Effect of heat input on microstructure, residual stresses and corrosion is studied. • HAZ and width of dendrite in the welded region increase with heat input. • Residual stresses are tensile near the welded region after the highest heat input. • Welded region has the highest pit density after highest heat input. • Dendrites and δ-ferrite were highly oriented in the welded region.

36 MATERIALS SCIENCE↗

Characterization of raw and burnt oil shale from Dotternhausen: Petrographical and mineralogical evolution with temperature

The Toarcian Posidonia shale from Dotternhausen, Germany, is quarried and burnt in a fluidized bed reactor to produce electricity. The combustion residue, namely burnt oil shale (BOS), is used in the adjacent cement work as an additive in blended cements. The starting material is a typical laminated oil shale with an organic matter content ranging from 6 to 18%. Mineral matter consists principally of quartz, feldspar, pyrite and clays. After calcination in the range, the resulting product, burnt oil shale, keeps the macroscopic layered texture however with different mineralogy (anhydrite, lime, iron oxides) and the formation of an amorphous phase. This one, studied under STEM, reveals a typical texture of incipient partial melting due to a long retention time (ca. 30 min) and quenching. An in-situ high temperature X-ray diffraction (HTXRD) allowed studying precisely the mineralogical changes associated with the temperature increase. - Highlights: • We present oil shale/burnt oil shale characterization. • The Posidonia Shale is burnt in a fluidized bed. • Mineralogical evolution with temperature is complex. • The burnt oil shale is used in composite cements.

36 MATERIALS SCIENCE↗

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