No abstract

We report the production of flexible, highly-conductive poly(vinylidene fluoride) (PVDF) and multi-walled carbon nanotube (MWCNT) composites as filament feedstock for 3D printing. This account further describes, for the first time, fused deposition modelling (FDM) derived 3D-printed objects with chemiresistive properties in response to volatile organic compounds. The typically prohibitive thermal expansion and die swell characteristics of PVDF were minimized by the presence of MWCNTs in the composites enabling straightforward processing and printing. The nanotubes form a dispersed network as characterized by helium ion microscopy, contributing to excellent conductivity (∼3 × 10 S cm). The printed composites contain little residual metal particulate relative to parts from commercial PLA-nanocomposite material visualized by micro-X-ray computed tomography (μ-CT) and corroborated with thermogravimetric analysis. Printed sensing strips, with MWCNT loadings up to 15% mass, function as reversible vapour sensors with the strongest responses arising with organic compounds capable of readily intercalating and subsequently swelling the PVDF matrix (acetone and ethyl acetate). A direct correlation between MWCNT concentration and resistance change was also observed, with larger responses (up to 161% after 3 minutes) being generated with decreased MWCNT loadings. These findings highlight the utility of FDM printing in generating low-cost sensors that respond strongly and reproducibly to target vapours. Furthermore, the sensors can be easily printed in different geometries, expanding their utility to wearable form factors. The proposed formulation strategy may be tailored to sense diverse sets of vapour classes through structural modification of the polymer backbone and/or functionalization of the nanotubes within the composite.

The magnetic susceptibilities of hexanuclear gadolinium clusters in the compounds Gd(Gd6ZI12) (Z = Co, Fe, or Mn) and CsGd(Gd6CoI12)2 are reported and subjected to theoretical analysis with the help of density functional theory (DFT) computations. The single-crystal structure of Gd(Gd6CoI12) is reported here as well. We find that the compound with a closed shell of cluster bonding electrons, Gd(Gd6CoI12), exhibits the effects of antiferromagnetic coupling over the entire range of temperatures measured (4-300 K). Clusters with unpaired, delocalized cluster bonding electrons (CBEs) exhibit enhanced susceptibilities consistent with strong ferromagnetic coupling, except at lower temperatures (less than 30 K) where intercluster antiferromagnetic coupling suppresses the susceptibilities. The presence of two unpaired CBEs, as in [Gd6MnI12]3-, yields stronger coupling than when just one unpaired CBE is present, as in [Gd6FeI12]3- or [Gd6CoI12]2-. DFT calculations on model molecular systems, [Gd6CoI12](OPH3)6 and [Gd6CoI12]2(OPH3)10, indicate that the delocalized cluster bonding electrons are highly effective at mediating intracluster ferromagnetic exchange coupling between the Gd atom 4f7 moments and that intercluster coupling is expected to be antiferromagnetic. The DFT calculations were used to calculate the relative energies of various 4f7 spin patterns and form the basis for construction of a simple spin Hamiltonian describing the coupling within the [Gd6CoI12] cluster.

The complexes formed during the extraction of neodymium(III) into hydrophobic solvents containing acidic organophosphorus extractants were probed by single-crystal X-ray diffractometry, visible spectrophotometry, and Fourier-transform infrared spectroscopy. The crystal structure of the compound Nd(DMP)3 (1, DMP = dimethyl phosphate) revealed a polymeric arrangement in which each Nd(III) center is surrounded by six DMP oxygen atoms in a pseudo-octahedral environment. Adjacent Nd(III) ions are bridged by (MeO)2POO(-) anions, forming the polymeric network. The diffuse reflectance visible spectrum of 1 is nearly identical to that of the solid that is formed when an n-dodecane solution of di(2-ethylhexyl)phosphoric acid (HA) is saturated with Nd(III), indicating a similar coordination environment around the Nd center in the NdA3 solid. The visible spectrum of the HA solution fully loaded with Nd(III) is very similar to that of the NdA3 material, both displaying hypersensitive bands characteristic of an pseudo-octahedral coordination environment around Nd. These spectral characteristics persisted across a wide range of organic Nd concentrations, suggesting that the pseudo-octahedral coordination environment is maintained from dilute to saturated conditions.

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO2(NO3)2(H2O)6] often called UNH), the trihydrate [UO2(NO3)2(H2O)3 or UNT], and in very dry environments the dihydrate form [UO2(NO3)2(H2O)2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s, the different phases were studied by infrared transmission spectroscopy but were limited both by instrumental resolution and by the ability to prepare the samples for transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparation and allows dynamic analysis while the sample is exposed to a flow of N2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO2(NO3)2(H2O)6 has a distinct uranyl asymmetric stretch band at 949.0 cm(-1) that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm(-1). The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO2(2+) sites. The dehydration of UO2(NO3)2(H2O)6 to UO2(NO3)2(H2O)3 is both a structural and morphological change that has the lustrous lime green UO2(NO3)2(H2O)6 crystals changing to the matte greenish yellow of the trihydrate solid. The phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with only one in the hexahydrate.

Executive SummaryThe UO 3 -water system is complex and has not been fully characterized, even though these species are common throughout the nuclear fuel cycle. As an example, most production processes for UO 3 result in a mixture of up to six or more different polymorphic phases, and small differences in these conditions will affect phase genesis that ultimately result in measureable changes to the end product. As a result, this polymorphic feature of the UO 3 -water system may be useful as a means for determining process history. This research effort attempts to better characterize the UO 3 -water system with a variety of optical techniques for the purpose of developing some predictive capability for estimating process history in polymorphic phases of unknown origin. Three commercially relevant production methods for the production of UO 3 were explored. Previously unreported low temperature routes to β-and γ-UO 3 were discovered. Raman and fluorescence spectroscopic libraries were established for pure and mixed polymorphic forms of UO 3 in addition to the common hydrolysis products of UO 3 . An advantage of the sensitivity of optical fluorescence microscopy over x-ray diffraction has been demonstrated. Preliminary aging studies of the α and γ forms of UO 3 have been conducted. In addition, development of a 3-D phase field model used to predict phase genesis of the system was initiated. Thermodynamic and structural constants that will feed the model have been gathered from the literature for most of the UO 3 polymorphic phases.v

No abstract

Herein, we report the synthesis and structural characterization of K[(CO)Pu](μ-η-η-O)·12HO. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M[(CO)A](μ-η-η-O)·xHO (M = alkali metal; A = Ce or Pu; x = 8, 10, 12, or 18), for which only the M = Na analogue has been previously reported when A = Pu. The previously reported crystal structure for Na[(CO)Pu](μ-η-η-O)·12HO is not isomorphous with its known Ce analogue. However, a new synthetic route to these M[(CO)A](μ-η-η-O)·12HO complexes, described below, has produced crystals of Na[(CO)Ce](μ-η-η-O)·12HO that are isomorphous with the previously reported Pu analogue. Via this synthetic method, the M = Na, K, Rb, and Cs salts of M[(CO)Ce](μ-η-η-O)·xHO have also been synthesized for a systematic structural comparison with each other and the available Pu analogues using single-crystal X-ray diffraction, Raman spectroscopy, and density functional theory calculations. The Ce salts, in particular, demonstrate subtle differences in the peroxide bond lengths, which correlate with Raman shifts for the peroxide O-O stretch (O = O atoms of the peroxide bridges) with each of the cations studied: Na [1.492(3) Å/847 cm], Rb [1.471(1) Å/854 cm], Cs [1.474(1) Å/859 cm], and K [1.468(6) Å/870 cm]. The trends observed in the O-O bond distances appear to relate to supermolecular interactions between the neighboring cations.