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BaGdLaCoO (BGLC) compositions with large compositional ranges of Ba, Gd, and La have been characterised with respect to phase compositions, structure, and thermal and chemical expansion. The results show a system with large compositional flexibility, enabling tuning of functional properties and thermal and chemical expansion. We show anisotropic chemical expansion and detailed refinements of emerging phases as La is substituted for Ba and Gd. The dominating phase is the double perovskite structure Pmmm, which is A-site ordered along the c-axes and with O vacancy ordering along the b-axis in the Ln-layer. Phases emerging when substituting La for Ba are orthorhombic Ba-deficient Pbnm and cubic LaCoO-based R3̄c. When La is almost completely substituted for Gd, the material can be stabilised in Pmmm, or cubic Pm3̄m, depending on thermal and atmospheric history. We list thermal expansion coefficients for x = 0-0.3, y = 0.2., The research has been supported by the National Science Centre Poland (2016/22/Z/ST5/00691), the Spanish Ministry of Science and Innovation (PCIN-2017-125, RTI2018-102161 and IJCI-2017-34110), and the Research Council of Norway (Grant no. 272797 “GoPHy MiCO”) through the M-ERA.NET Joint Call 2016. The authors acknowledge the skilful assistance from the staff of the Swiss–Norwegian Beamline (SNBL) at the European Synchrotron Radiation Facility (ESRF), Grenoble, France. Dr. Cheng Li at POWGEN, SNS, Oak Ridge, US and Dr. Chiu C. Tang at beamline I11 at Diamond, Didcot, UK are gratefully acknowledged for PND and SR-PXD measurements, respectively.

In this paper, we report the microstructure and first hydrogenation properties of TiFe cast with 4 wt.% of Zr. Measurements were made in as-cast state and after processing by ball milling and cryomilling. It was found that ball milling and cryomilling significantly reduced the particle/crystallite sizes with most of the reduction occurring during the first 15 min of milling. While the cryomilled sample did not absorb any hydrogen, ball milling improved the initial kinetics of processed powders compared with the as-cast sample. However it also reduced the hydrogen storage capacity. The observed increased kinetics was likely caused by the reduction of crystallite sizes with longer ball milling times. However, the longer ball milling times might also be the reason of the capacity loss due to formation of new grain boundaries. Faster kinetics was not due to a change in the rate-limiting step, as all kinetics curves were fitted with the 3D growth, diffusion controlled with decreasing interface velocity model. Keywords: TiFe alloy, First hydrogenation kinetics, Rate limiting step, Ball milling, Cryomilling

Water photoelectrolysis has the potential to produce renewable hydrogen fuel, therefore addressing the intermittent nature of sunlight. Herein, a monolithic, photovoltaic ( PV)-assisted water electrolysis device of minimal engineering and of low (in the mu g range) noble-metal-free catalysts loading is presented for unassisted water splitting in alkaline media. An efficient double perovskite cobaltite catalyst, originally developed for high-temperature proton-conducting ceramic electrolyzers, possesses high activity for the oxygen evolution reaction in alkaline media at room temperatures too. Ba1-xGd1-yLax+yCo2O6-delta (BGLC) is combined with a NiMo cathode, and a solar-to-hydrogen efficiency of 6.6% in 1.0 M NaOH, under 1 sun simulated illumination for 71 h, is demonstrated. This work highlights how readily available earth-abundant materials and established PV methods can achieve high performance and stable and monolithic photoelectrolysis devices with potential for full-scale applications.

Small-angle neutron scattering combined with powder neutron diffraction was employed to study the phase formation upon absorption/desorption of hydrogen gas in Li- and Na-intercalated fullerides. The comparative system analysis, addressing changes in the sample phase compositions and the morphology of powders, revealed a higher degree of complexity in the Na-based samples. Results also showed that the disappearance of crystalline lithium/sodium hydride during desorption was accompanied by an increased surface roughness in both systems, most likely because of the formation of a local surface strain. Furthermore, an increased specific internal surface of the studied materials upon subsequent deuterium absorption/desorption cycles was demonstrated. This could indicate moderate fracturing of crystallites.

High resolution synchrotron radiation powder X-ray diffraction (SR-PXD) and scanning transmission electron microscopy (STEM) have been employed for structural characterization of MNiSn, M0.5M′0.5NiSn and M0.5M′0.25M″0.25NiSn (M, M′, M″ = Hf, Ti, Zr) half-Heusler compounds, synthesized by arc melting and thermal annealing. Rietveld refinement results demonstrate that ternary Ti- and Hf-based compositions crystallize with only one half-Heulser phase, while two cubic phases are found in samples with nominal composition ZrNiSn. The performed analysis does not suggest obvious presence of excess Ni in any of the ternary compounds. Instead, it shows disordered distribution of the stoichiometric Ni atoms over 4c and the nominally vacant 4d sites in ZrNiSn as well as formation of Ni vacancies at the 4c site in ZrNi0.98Sn.

Results for (La,Mg)Ni3.5 and (La,Mg)(Ni,Al)3.5 systems synthesized by metallurgical and mechanochemical techniques are reported. Powder X-ray and neutron diffraction combined with Rietveld refinements and profile analysis show that depending on the applied synthesis method various structurally related phases can be obtained for the same nominal composition. The hexagonal A2B7-type structure incorporating aluminum, with the refined composition La0.77Mg0.23Ni3.41Al0.09, has been identified. Al atoms occupy 12% of the 6h site within the LaNi5 slabs. This intermetallic phase absorbs hydrogen (deuterium) when exposed to 10 bar of H2 (D2) gas at room temperature. The H(D)-containing phase expands isotropically and retains the original symmetry of the parent compound. © 2017. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/

International audience; The main objective of the present work is to study the effect of rapid solidification on the electrochemical performance of Zr-based Laves type alloy with a nominal composition Ti12Zr21.5V10Cr7.5Mn8.1Co8Ni32.2Al0.4Sn0.3. The samples were prepared from the as-cast arc melted buttons by melt spinning at different copper wheel rotation speeds of 5, 16.5, 33, and 100 Hz, which are equivalent to linear speeds of 6.3, 21, 41, and 62.8 m s−1 respectively using a cooling wheel with a diameter of 20 cm. The phase composition and morphology of the ribbons were analyzed by X-Ray diffraction (XRD) and scanning electron microscopy (SEM). The microstructural changes of the ribbons induced by the variations in the wheel rotation speed were found to be closely related to the electrochemical performances. High discharge capacities exceeding 400 mAh∙g−1 were achieved for the melt spun samples during the measurements at low current densities. Furthermore, melt spun casting performed at the highest wheel rotation speed of 100 Hz resulted in the best rate performance of the alloy. As this alloy has the smallest crystallite size, this resulted in the shortest H atoms diffusion distances, and thus increased the efficient H diffusion rate and improved the electrochemical performance.

The present work was focused on the studies of the effect of variation of stoichiometric composition of Ti–Zr based AB2±x Laves phase alloys by changing the ratio between A (Ti + Zr) and B (Mn + V + Fe + Ni) components belonging to both hypo-stoichiometric (AB1.90, AB1.95) and over-stoichiometric (AB2.08) alloys further to the stoichiometric AB2.0 composition to optimize their hydrogen storage behaviours and performances as the alloy anodes of nickel metal hydride batteries. AB2-xLa0.03 Laves type alloys (A = Ti0.15Zr0.85; B = Mn0.64–0.69V0.11–0.119Fe0.11–0.119Ni1.097–1.184; x = 0, 0.05 and 0.1) were arc melted and then homogenized by annealing. The studies involved probing of the phase-structural composition by X-Ray diffraction (XRD), together with studies of the microstructural state, hydrogen absorption–desorption and thermodynamic characteristics of gas–solid reactions and electrochemical charge-discharge performance, further to the impedance spectroscopy characterization. The alloys were probed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and XRD. These studies concluded that the alloys contained the main C15 FCC Laves type AB2 intermetallic co-existing with a secondary C14 hexagonal Laves phase and a small amount of LaNi intermetallic. The gaseous H storage capacity and electrochemical performances were found to be closely dependent on the stoichiometric compositions of the alloys. High discharge capacities approaching 500 mAh/g were achieved for the AB1.95 alloy. At 500 mA/g current density, the discharge capacity was maintained as high as 80%, with very low capacity retention after 500 cycles. The alloy which had the highest capacity retention after 500 cycles was found to be AB2.0 alloy. Furthermore, AB2.0 alloy showed an excellent cyclic stability together with a high hydrogen diffusion coefficient. Studies of hydrogen diffusion coefficients showed that annealing enhanced the H diffusion rates allowing advanced performance at high discharge current densities. This has been related to a higher content of C15 Laves compound which allows to reach a higher H mobility in contrast with higher storage capacity observed for the C14 Laves type polymorph.

A commercially feasible, nontoxic material that would convert heat into electricity in an efficient and cheap way has not been yet identified. Half-Heusler compounds are one the most interesting candidates but to become competitive their thermoelectric properties still need to be improved. Atomic substitution and excess Ni in the crystal structure of ternary MNiSn half-Heuslers are among the most successful approaches used to boost their performance. Here, we report on the effect of both methods applied simultaneously to the series of polycrystalline Ti1−xHfxNi1.0/1.1Sn, x = 0.00, 0.10, 0.15, 0.20, samples. High-resolution synchrotron powder X-ray diffraction studies combined with transmission electron microscopy demonstrate the crystallization of single or multiple Hf-substituted half-Heusler phase(s). The analysis of their long-range atomic structures shows that most of them contain interstitial Ni atoms disorderly distributed at the nominally vacant 4d sites. However, the short-range atomic correlations suggest that, for some compositions, excess Ni creates an orderly arranged additional atomic plane at the vacant fcc sublattice, which can be seen as a defective half- and/or full-Heusler phase. The results also show that the Ni-rich samples crystallize with the micrometer-sized full-Heusler phases, while all Hf-incorporating compositions present dispersion of HfO2 nanoprecipitates in the grains of the half-Heusler matrix. This research is complemented by thermoelectric transport measurements of the studied compositions in the range of 300–750 K. The results suggest that neither Seebeck coefficient nor electrical resistivity shows an obvious correlation with the observed microstructures. These finding are discussed with respect to previously proposed transport mechanisms.

Energy density and safety are the main factors that govern the development of the rechargeable battery technology. Currently, batteries beyond typical Li-ion batteries such as those based on solid-state electrolytes (SSEs) or other active elements (e.g., Na or Mg) are being examined as alternatives. For example, SSEs that would enable stable and reliable operation of all-solid-state Li-, Na-, and Mg-based batteries, with preferably improved capacity, are considered to be one of the most desired inventions. Lightweight complex metal hydrides are a family of solid compounds that were recently discovered to have extraordinary ionic conductivities and, in some cases, electrochemical properties that enabled battery reversibility. Consequently, they have become one of the promising electrolyte materials for future development of electrochemical storage devices. In this work, we present an overview of a wide range of lightweight hydride-based materials that could be used as electrolytes and/or anodes for mono-/divalent batteries and have a pivotal role in the implementation of new technological solutions in the field of electrochemistry.

Metal hydrides are known as a potential efficient, low-risk option for high-density hydrogen storage since the late 1970s. In this paper, the present status and the future perspectives of the use of metal hydrides for hydrogen storage are discussed. Since the early 1990s, interstitial metal hydrides are known as base materials for Ni – metal hydride rechargeable batteries. For hydrogen storage, metal hydride systems have been developed in the 2010s [1] for use in emergency or backup power units, i. e. for stationary applications. With the development and completion of the first submarines of the U212 A series by HDW (now Thyssen Krupp Marine Systems) in 2003 and its export class U214 in 2004, the use of metal hydrides for hydrogen storage in mobile applications has been established, with new application fields coming into focus. In the last decades, a huge number of new intermetallic and partially covalent hydrogen absorbing compounds has been identified and partly more, partly less extensively characterized. In addition, based on the thermodynamic properties of metal hydrides, this class of materials gives the opportunity to develop a new hydrogen compression technology. They allow the direct conversion from thermal energy into the compression of hydrogen gas without the need of any moving parts. Such compressors have been developed and are nowadays commercially available for pressures up to 200 bar. Metal hydride based compressors for higher pressures are under development. Moreover, storage systems consisting of the combination of metal hydrides and high-pressure vessels have been proposed as a realistic solution for on-board hydrogen storage on fuel cell vehicles. In the frame of the “Hydrogen Storage Systems for Mobile and Stationary Applications” Group in the International Energy Agency (IEA) Hydrogen Task 32 “Hydrogen-based energy storage” different compounds have been and will be scaled-up in the near future and tested in the range of 500 g to several hundred kg for use in hydrogen storage applications, The research for the lab-scale compressor is part of the activities of SCCER HaE, which is financially supported by Innosuisse - Swiss Innovation Agency . The authors thank the Alexander von Humboldt Foundation in the frame of the post-doctoral fellowship of Dr. J. Puszkiel (No. 1187279 STP ) as well as the European Union for their funding of projects STORHY (contract Nr. SES6-CT-2004-502667 , FP6-2002-Energy-1, 6.1.3.2.2), NESSHY (contract Nr. 518271 , FP6-2004-Energy-3, 6.1.3.2.2) and the EU Horizon 2020 /RISE project HYDRIDE4MOBILITY. Financial support from the S02 and KP8 S05), the European Union's Seventh Framework Programme ( FP7/2007e2013 ) for the Fuel Cells and Hydrogen Joint Technology Initiative under grant agreement no. 256653 (SSH2S), from the European Fuel Cells and Hydrogen Joint Undertaking in the framework of BOR4STORE (Grant agreement no. 303428 ), from the Australian Research Council for grants LP120101848 , LP150100730 , and LE0989180 , The Innovation Fund Denmark (project HyFill-Fast), DST within Hydrogen South Africa/HySA programme (projects KP3 National Research Foundation/NRF of South Africa , incentive funding grant number 109092 and the Research Council of Norway (project 285147 ) is thankfully acknowledged

The objective of the present work was to study an interrelation between the conditions of the rapid solidification casting and electrochemical properties of a C15 Laves-type Zr-based metal hydride battery anode alloy. A 7-component overstoichiometric with B/A>2 alloy (Ni + Mn + V + Fe/Zr + Ti + La = 2.078) was Zr- and Ni-rich. Melt spinning was performed using as cast mother ingot at different rotation speeds of 5, 16.5, and 33 Hz with a 20-cm diameter Cu cooling wheel. The phase composition and morphology of the ribbons were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) along with X-ray energy dispersive spectroscopy (EDS). Partial Mn vaporization took place during the melt spinning and became more pronounced with the increase in the quenching rate at higher wheel rotation speeds. The SEM study showed a successful refinement and a more homogeneous distribution of La in the melt-spun alloys. However, the alloys demonstrated a more difficult activation performance as compared to the as-cast sample which was associated with introduction of Zr into the composition of the secondary La-and Ni-rich phase when quenching the melt. Presence of Zr in the secondary phase results in inferior rate of its hydrogenation. The formed during the rapid solidification (La,Zr) (Ni,Mn) secondary phase also contained a significant amount of oxygen additionally worsening the activation performance. The grain size gradually decreased from 3.5 μm in the as-cast alloy to approximately 250 nm for the melt spun sample obtained at the highest cooling rate. The two-phase alloys contained a mixture of two Laves type intermetallics, C15 and C14 ones. The abundance of the secondary C14 phase decreased with increase of the cooling rate as compared to the as-cast sample. The electrochemical performance was significantly affected by the compositional and microstructural changes associated with the variation in the cooling rate. The highest electrochemical discharge capacity of 414 mAh/g was obtained for the 16.5 Hz melt spun rate because of an optimized composition of the Laves phase. Furthermore, the diffusion coefficient of hydrogen in this alloy was the highest in a full state of charge, which indicates that faster hydrogen diffusion and shorter hydrogen diffusion paths were achieved via an application of the rapid solidification process. An optimization of the rapid solidification conditions is required to improve an activation behavior of the studied Laves types metal hydride anode alloys. © 2019 The Authors. Published by Elsevier B.V. Open Access. CC BY-NC-ND 4.0

Results for binary Mg–Zr and ternary Mg–Zr–Ti mixtures ball milled at room temperature under reactive deuterium atmosphere (5.6–6.7 MPa) are reported. X-ray and neutron powder diffraction combined with Rietveld refinements show that two new cubic phases were formed during milling. Mg0.40Zr0.60D1.78 and Mg0.40Zr0.26Ti0.34D1.98 crystallize with disordered face centered cubic metal atom arrangements. Results of differential scanning calorimetry and termogravimetric measurements demonstrate that both deuterides desorb deuterium at lower temperatures than MgD2, ZrD2 or TiD2; 528 and 575 K in the Mg–Zr–D and Mg–Zr–Ti–D system, respectively. Interestingly, Mg0.40Zr0.26Ti0.34D1.98 stores deuterium reversibly at 673 K and 10 MPa of D2.

The impact of ultra-short milling at liquid nitrogen temperatures on structural and magnetic properties of cobalt ferrite (CoFe 2 O 4 ) powders has been explored for the first time. Cryomilling for only up to 9 min increases the coercivity of the isotropic powder from 139 to 306 kA/m (1.74–3.85 kOe) and results in its modifications comparable with milling for hours at room temperature. A thermal treatment of processed CoFe 2 O 4 enables further optimization of powder magnetic properties and leads to a high value of energy product (13.5 kJ/m 3 ) for the sample treated at 600 °C. Systematic studies, comprising analysis of structural and microstructural properties, based on synchrotron powder X-ray diffraction, scanning and transmission electron microscopy demonstrate the high efficiency of cryomilling in reduction of crystallite sizes and formation of lattice strain in the processed cobalt ferrite samples.

Thermoelectric application of half-Heusler compounds suffers from their fairly high thermal conductivities. Insight into how effective various scattering mechanisms are in reducing the thermal conductivity of fabricated XNiSn compounds (X = Hf, Zr, Ti, and mixtures thereof) is therefore crucial. Here, we show that such insight can be obtained through a concerted theory-experiment comparison of how the lattice thermal conductivity κLat(T) depends on temperature and crystallite size. Comparing theory and experiment for a range of Hf0.5Zr0.5NiSn and ZrNiSn samples reported in the literature and in the present paper revealed that grain boundary scattering plays the most important role in bringing down κLat, in particular so for unmixed compounds. Our concerted analysis approach was corroborated by a good qualitative agreement between the measured and calculated κLat of polycrystalline samples, where the experimental average crystallite size was used as an input parameter for the calculations. The calculations were based on the Boltzmann transport equation and ab initio density functional theory. Our analysis explains the significant variation of reported κLat of nominally identical XNiSn samples, and is expected to provide valuable insights into the dominant scattering mechanisms even for other materials.

La2−xMgxNi7 and its hydrides/deuterides were investigated by high resolution synchrotron powder X-ray and neutron diffraction. Upon deuteration the single phase sample of the intermetallic compound with the refined composition La1.63Mg0.37Ni7 (space group: P63/mmc) expands isotropically, in contrast to the Mg free phase. The hydrogen uptake, ∼9 D/f.u., is higher than in La2Ni7D6.5. The refined composition accounts for La1.63Mg0.37Ni7D8.8 (beta-phase). Rietveld refinements using the neutron and synchrotron diffraction data suggest that deuterium atoms occupy 5 different interstitial sites within both AB2 and AB5 slabs, either in an ordered or a disordered way. All determined D sites have an occupancy >50% and the shortest D–D contact is 1.96(3) A. It is supposed that a competition between the tendency to form directional bonds and repulsive D–D (H–H) interactions is the most important factor that influences the distribution of deuterium atoms in this structure. A hitherto unknown second, alpha-phase with composition La1.63Mg0.37Ni7D0.56, crystallizing with the same hexagonal symmetry as La1.63Mg0.37Ni7D8.8, has been discovered. The unit cell parameters for this D-poor phase differ slightly from those of the intermetallic. Alpha-phase displays only one D site (4f, space group: P63/mmc) occupied >50%, which is not populated in the D-rich beta-phase. This hydrogen/deuterium induced site depopulation can be explained by repulsive D–D (H–H) interactions that are likely to influence non-occupancy of certain interstices in metal lattice when absorbing hydrogen.

Zirconium and mixed zirconium/titanium carbodeuteride samples of nominal compositions ZrC 0.44 D 0.89 , Ti 0.66 Zr 0.33 C 0.57 D 0.92 and Ti 0.66 Zr 0.33 C 0.53 D 0.29 have been investigated by powder X-ray and neutron diffraction and joint Rietveld structure refinements. They contain two types of phases, one crystallizing with a face-centred cubic (fcc) metal atom arrangement and the other with a hexagonal close-packed (hcp) metal atom arrangement having trigonal symmetry. While the pure Zr sample contains both a cubic and a trigonal phase, the mixed Zr/Ti samples contain either a cubic phase only (C/D-poor sample), or two trigonal phases having different Ti/Zr ratios (C/D-rich sample). The carbon atoms occupy octahedral interstices in nearly ordered (hcp) or disordered (fcc) arrangements, and the deuterium atoms occupy either tetrahedral (hcp) or octahedral (fcc) interstices. In the hcp phase metal octahedra around carbon atoms contract while metal tetrahedra around deuterium atoms expand. The structure results are consistent with the assumption of repulsive interactions between non-metal atoms resulting in their longest possible separation (D–D > 2.1 A, C–D > 2.6 A).

We report on a comparative study of high performance isotropic cobalt ferrite (CoFe2O4) powder processed by dry and surfactant assisted (wet) ball milling. Milling times as short as 1.5 min (dry) and 6 min (wet) have resulted in a 4-fold increase in coercivity, with a maximum achieved value above 318 kA/m (4 kOe). The use of surfactant is shown to be advantageous in the formation of a more homogeneous structure constituted by non-agglomerated and strained nanoparticles. A record (BH) max value of 18.6 kJ m −3 (2.34 MGOe) has been obtained for isotropic powder after post-processing annealing. This magnetic performance combined with the required short processing times and the unnecessary requirement of oxygen avoidance in the milling process, makes this CoFe2O4 powder a good candidate for permanent magnet applications.

The bimetallic complexes [{M(NO)(TpMe2)X}2(OCH2CH2O)] [TpMe2 = HB(3,5-Me2C3HN2)3; M = Mo, X = Cl, Br or I; M = W, X = Cl] have been synthesised and characterised spectroscopically and electrochemically. These species can occur as mixture of two diastereoisomers and one of them could be separated following a thermal treatment of the mixture. A direct synthesis of single diastereoisomers (M = Mo, X = I; M = W, X = Cl) is also described. The bimetallic species exhibit two one-electron reduction processes separated by a modest potential difference, ΔE1/2, ca. 300 mV (M = Mo, X = Cl, Br) indicating an intermediate metal–metal interaction. In the crystal structure of anti-[{Mo(NO)(TpMe2)(OCH2CH2O)}2] · 4CHCl3 two nonequivalent dinuclear molecules (point group C2h) are found, with crystallographically identical, doubly bridged {Mo(NO)(TpMe2)} distorted octahedral units.

The effect of transition metal fluorides on the decomposition of NaBH4 has been investigated for NaBH4 ball milled with TiF3, MnF3 or FeF3. The compounds were examined by thermal programmed desorption with residual gas analysis, thermo gravimetric analysis and volumetric measurements using a Sieverts-type apparatus. The phase formation process during thermal decomposition was studied by in situ synchrotron radiation powder X-ray diffraction on the as-milled powders. NaBF4 was among the products in all mechano-chemical reactions. (11)B-NMR spectra analysis gave NaBF4 : NaBH4 ratios of 1 : 150 for Na-Ti, 1 : 40 for Na-Mn, and 1 : 10 for Na-Fe. Pure NaBH4 possessed a hydrogen release onset temperature of 430 °C. The hydrogen release in the NaBH4-MnF3 system began as low as 130 °C. FeF3 decreased the onset temperature to 161 °C and TiF3 to 200 °C. TiF3 reacted completely with NaBH4 below 320 °C. All the examined systems have negligible emissions of diborane species. H-sorption studies performed at selected temperatures above 300 °C exhibited relatively fast desorption kinetics. Partial hydrogen re-absorption was observed for the Na-Mn and Na-Fe samples.

The thermal phase behaviour of cryomilled α′-AlD3 and α-AlD3 was investigated by in situsynchrotron powder X-ray diffraction (SR-PXD), differential scanning calorimetry and first principles atomic modelling. In situ measurements showed that α′-AlD3 decomposes directly into Al and D2 at around 80 °C during heating at 1 °C min−1. At higher temperatures the transformation of α′-AlD3 to α-AlD3 was observed by DSC measurements at 5 °C min−1, and tentatively by in situSR-PXD at 1 °C min−1. Atomic modelling was carried out to investigate possible structural relationships and transformation pathways between the α- and α′-phase. Group–subgroup relation analyses and direct method lattice dynamics were used to rule out a possible displacive transformation pathway between the α′- and α-phases. The likelihood of a reconstructive transformation was demonstrated by partial transformation of an interface between α′ and α domains during elevated temperature molecular dynamics. Such an α′- to α-phase transformation may be possible when kinetic barriers can be overcome at elevated temperatures or during long time periods. These insights are also relevant to the transformation mechanisms of the β-AlD3 and γ-AlD3 isomorphs to the α-phase.