Mechanochemical preparation of adducts (co-crystals and molecular salts) of 1, 4-diazabicyclo-2.2. 2-octane with aromatic polycarboxylic acids

Solid-state adducts (co-crystals and molecular salts) of 1,4-diazabicyclo-[2.2.2]-octane (DABCO) with aromatic polycarboxylic acids (isophthalic acid, isoH2, dinicotinic acid, dinH2 and dipicolinic acid, dipH2) were prepared in the solid state by grinding and kneading techniques, and fully characterized via X-ray diffraction. The polycarboxylic acids differ for the presence/absence and position of a nitrogen atom in the aromatic ring; the extent of proton transfer, from the carboxylic groups on the acids to the nitrogen atoms on DABCO, reflects the trend of solution acidity of the three polycarboxylic acids

Supramolecular metathesis: co-former exchange in co-crystals of pyrazine with (R, R)-,(S, S)-,(R, S)-and (S, S/R, R)-tartaric acid

Co-crystals of dextro-(R,R), levo-(S,S), meso-(R,S) and racemic (R,R–S,S)-tartaric acid with pyrazine were obtained by manual kneading and slurry experiments; subsequent reactions in the solid state between these co-crystals and the various forms of tartaric acid in the solid state and via slurry show that co-former exchange takes place according to the sequence of stability [(R,S)-ta]2·py > (S,S/R,R)-ta·py > (R,R)-ta·py or (S,S)-ta·py

Direct observation of intermediates in a thermodynamically controlled solid-state dynamic covalent reaction.

We present the first polymorph interconversion study that uses solid-state dynamic covalent chemistry (DCC). This system exhibits unexpected and rich behavior, including the observation that under appropriate conditions the polymorph interconversion of a heterodimer proceeds through reversible covalent chemistry intermediates, and this route is facilitated by one of the two disulfide homodimers involved in the reaction. Furthermore, we demonstrate experimentally that in all cases a dynamic equilibrium is reached, meaning that changing the milling conditions affects the free energy difference between the two polymorphs and thus their relative stability. We suggest that this effect is due to the surface solvation energy combined with the high surface to volume ratio of the nanocrystalline powder.We are grateful to the EPSRC (AMB, JKMS and DJW) and ERC(DJW) for financial support.This is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/ja500707z

Local strain heterogeneity and elastic relaxation dynamics associated with relaxor behavior in the single-crystal perovskite Pb(I n1/2 N b1/2) O3-PbZr O3-Pb(M g1/3 N b2/3) O3-PbTi O3

© 2017 American Physical Society. Recently, Pb(In1/2Nb1/2)O3-PbZrO3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PZ-PMN-PT) relaxor single crystals were demonstrated to possess improved temperature-insensitive properties, which would be desirable for high-power device applications. The relaxor character associated with the development of local random fields (RFs) and a high rhombohedral-tetragonal (R-T) ferroelectric transition temperature (TR-T > 120°C) would be critical for the excellent properties. A significant effect of the chemical substitution of In3+ and Zr4+ in PMN-PT to give PIN-PZ-PMN-PT is the development of local strain heterogeneity, which acts to suppress the development of macroscopic shear strains without suppressing the development of local ferroelectric moments and contribute substantially to the RFs in PIN-PZ-PMN-PT. Measurements of elastic and anelastic properties by resonant ultrasound spectroscopy show that PIN-PZ-PMN-PT crystal has a quite different form of elastic anomaly due to Vogel-Fulcher freezing, rather than the a discrete cubic-T transition seen in a single crystal of PMN-28PT. It also has high acoustic loss of the relaxor phase down to TR-T. Analysis of piezoresponse force microscopy phase images at different temperatures provides a quantitative insight into the extent to which the RFs influence the microdomain structure and the short-range order correlation length (ξ)

Structural effects in UO2 thin films irradiated with fission-energy Xe ions

Uranium dioxide thin films have been successfully grown on LSAT (Al10La3O51Sr14Ta7) substrates by reactive magnetron sputtering. Irradiation by 92 MeV 129Xe23+ ions to simulate fission damage that occurs within nuclear fuels caused microstructural and crystallographic changes. Initially flat and continuous thin films were produced by magnetron sputtering with a root mean square roughness of 0.35 nm determined by AFM. After irradiation, this roughness increased to 60–70 nm, with the films developing discrete microstructural features: small grains (∼3 μm), along with larger circular (up to 40 μm) and linear formations with non-uniform composition according to the SEM, AFM and EDX results. The irradiation caused significant restructuring of the UO2 films that was manifested in significant film-substrate mixing, observed through EDX analysis. Diffusion of Al from the substrate into the film in unirradiated samples was also observed

Ferroelectric precursor behavior in PbSc0.5Ta0.5O3 detected by field-induced resonant piezoelectric spectroscopy

A novel experimental technique, resonant piezoelectric spectroscopy (RPS), has been applied to investigate polar precursor effects in highly (65%) B-site ordered PbSc0.5Ta0.5O3 (PST), which undergoes a ferroelectric phase transition near 300 K. The cubic-rhombohedral transition is weakly first order, with a coexistence interval of ∼4 K, and is accompanied by a significant elastic anomaly over a wide temperature interval. Precursor polarity in the cubic phase was detected as elastic vibrations generated by local piezoelectric excitations in the frequency range 250–710 kHz. The RPS resonance frequencies follow exactly the frequencies of elastic resonances generated by conventional resonant ultrasound spectroscopy (RUS) but RPS signals disappear on heating beyond an onset temperature, Tonset, of 425 K. Differences between the RPS and RUS responses can be understood if the PST structure in the precursor regime between Tonset and the transition point, Ttrans=300 K, has locally polar symmetry even while it remains macroscopically cubic. It is proposed that this precursor behavior could involve the development of a tweed microstructure arising by coupling between strain and multiple order parameters, which can be understood from the perspective of Landau theory. As a function of temperature the transition is driven by the polar displacement P and the order parameter for cation ordering on the crystallographic B site Qod. Results in the literature show that, as a function of pressure, there is a separate instability driven by octahedral tilting for which the assigned order parameter is Q. The two mainly displacive order parameters, P and Q, are unfavorably coupled via a biquadratic term Q2P2, and complex tweedlike fluctuations in the precursor regime would be expected to combine aspects of all the order parameters. This would be different from the development of polar nanoregions, which are more usually evoked to explain relaxor ferroelectric behavior, such as occurs in PST with a lower degree of B-site order

Structural effects in UO2 thin films irradiated with U ions

This work presents the results of a detailed structural characterisation of irradiated and unirradiated single crystal thin films of UO2. Thin films of UO2 were produced by reactive magnetron sputtering onto (0 0 1), (1 1 0) and (1 1 1) single crystal yttria-stabilised zirconia (YSZ) substrates. Half of the samples were irradiated with 110 MeV 238U31+ ions to fluences of 5 × 1010, 5 × 1011 and 5 × 1012 ions/cm2 to induce radiation damage, with the remainder kept for reference measurements. It was observed that as-produced UO2 films adopted the crystallographic orientation of their YSZ substrates. The irradiation fluences used in this study however, were not sufficient to cause any permanent change in the crystalline nature of UO2. It has been demonstrated that the effect of epitaxial re-crystallisation of the induced radiation damage can be quantified in terms of kernel average misorientation (KAM) and different crystallographic orientations of UO2 respond differently to ion irradiation

Ferroelectric precursor behavior in PbSc0.5Ta0.5O3 detected by field-induced resonant piezoelectric spectroscopy

A novel experimental technique, resonant piezoelectric spectroscopy (RPS), has been applied to investigate polar precursor effects in highly (65%) B-site ordered PbSc0.5Ta0.5O3 (PST), which undergoes a ferroelectric phase transition near 300 K. The cubic-rhombohedral transition is weakly first order, with a coexistence interval of ∼4 K, and is accompanied by a significant elastic anomaly over a wide temperature interval. Precursor polarity in the cubic phase was detected as elastic vibrations generated by local piezoelectric excitations in the frequency range 250–710 kHz. The RPS resonance frequencies follow exactly the frequencies of elastic resonances generated by conventional resonant ultrasound spectroscopy (RUS) but RPS signals disappear on heating beyond an onset temperature, Tonset, of 425 K. Differences between the RPS and RUS responses can be understood if the PST structure in the precursor regime between Tonset and the transition point, Ttrans=300 K, has locally polar symmetry even while it remains macroscopically cubic. It is proposed that this precursor behavior could involve the development of a tweed microstructure arising by coupling between strain and multiple order parameters, which can be understood from the perspective of Landau theory. As a function of temperature the transition is driven by the polar displacement P and the order parameter for cation ordering on the crystallographic B site Qod. Results in the literature show that, as a function of pressure, there is a separate instability driven by octahedral tilting for which the assigned order parameter is Q. The two mainly displacive order parameters, P and Q, are unfavorably coupled via a biquadratic term Q2P2, and complex tweedlike fluctuations in the precursor regime would be expected to combine aspects of all the order parameters. This would be different from the development of polar nanoregions, which are more usually evoked to explain relaxor ferroelectric behavior, such as occurs in PST with a lower degree of B-site order