Statics and dynamics of domain patterns in hexagonal-orthorhombic ferroelastics

We study the statics and the dynamics of domain patterns in proper hexagonal-orthorhombic ferroelastics; these patterns are of particular interest because they provide a rare physical realization of disclinations in crystals. Both our static and dynamical theories are based entirely on classical, nonlinear elasticity theory; we use the minimal theory consistent with stability, symmetry and ability to explain qualitatively the observed patterns. After scaling, the only parameters of the static theory are a temperature variable and a stiffness variable. For moderate to large stiffness, our static results show nested stars, unnested stars, fans and other nodes, triangular and trapezoidal regions of trapped hexagonal phase, etc observed in electron microscopy of Ta4N and Mg-Cd alloys, and also in lead orthovanadate (which is trigonal-monoclinic); we even find imperfections in some nodes, like those observed. For small stiffness, we find patterns like those observed in the mineral Mg-cordierite. Our dynamical studies of growth and relaxation show the formation of these static patterns, and also transitory structures such as 12-armed bursts, streamers and striations which are also seen experimentally. The major aspects of the growth-relaxation process are quite unlike those in systems with conventional order parameters, for it is inherently nonlocal; for example, the changes from one snapshot to the next are not predictable by inspection.Comment: 9 pages, 3 figures (1 b&w, 2 colour); animations may be viewed at http://huron.physics.utoronto.ca/~curnoe/sim.htm

Order/disorder phase transition in cordierite and its possible relationship to the development of symplectite reaction textures in granulites

Based on a consistent set of empirical interatomic potentials, static structure energy calculations of various Al/Si configurations in the supercell of Mg-cordierite and Monte Carlo simulations the phase transition between the orthorhombic and hexagonal modifications of cordierite (Crd) is predicted at 1623 K. The temperature dependences of the enthalpy, entropy, and free energy of the Al/Si disorder were calculated using the method of thermodynamic integration. The simulations suggest that the commonly observed crystallization of cordierite in the disordered hexagonal form could be related to a tendency of Al to occupy T1 site, which is driven by local charge balance. The increase in the Al fraction in the T1 site over the ratio of 2/3(T1): 1/3(T2), that characterizes the ordered state, precludes formation of the domains of the orthorhombic phase. This intrinsic tendency to the crystallization of the metastable hexagonal phase could have significantly postponed the formation of the association of orthorhombic cordierite and orthopyroxene over the association of quartz and garnet in metapelites subjected to granulite facies metamorphism. The textures of local metasomatic replacement (the formation of Crd + Opx or Spr + Crd symplectites between the grains of garnet and quartz) indicate the thermodynamic instability of the association of Qtz + Grt at the moment of the metasomatic reaction. This instability could have been caused by the difficulty of equilibrium nucleation of orthorhombic cordierite

Qualitative and quantitative characterization of a coal power plant waste by TG/DSC/MS, XRF and XRD

SO2 removal from coal-fired power plant flue gases can be done by dry, semi-dry or wet desulphurization processes, using limestone or lime-containing products as sorbents. In a Brazilian coal power plant, there is a dry desulphurization unit to capture SO2 with hydrated lime from the combustion gases. A part of the flying ashes produced is mixed with the bottom coal ashes and the spent sulphated product generated after SO2 capture. This residual solid blend is then buried in a non-productive area, from which coal was already extracted and is studied in this work. According to the authors’ experience in the development and characterization of adsorbents for low temperature dry desulphurization processes and in thermogravimetric analysis, this paper shows and discusses a method which was developed to characterize qualitatively and quantitatively the chemical and mineral composition of this waste by using thermogravimetry coupled with mass spectrometry, X-ray fluorescence and X-ray diffraction, to preview new potential industrial applications for this waste.We are thankful to the University of Cantabria for the financial support under the Project: 51.VP61.64005, to the Brazilian Research Council, under the project CNPq no. 407005/2013-7, and to the Brazilian Education Council CAPES

Rehabilitation versus surgical reconstruction for non-acute anterior cruciate ligament injury (ACL SNNAP): a pragmatic randomised controlled trial

Background: Anterior cruciate ligament (ACL) rupture is a common debilitating injury that can cause instability of the knee. We aimed to investigate the best management strategy between reconstructive surgery and non-surgical treatment for patients with a non-acute ACL injury and persistent symptoms of instability. Methods: We did a pragmatic, multicentre, superiority, randomised controlled trial in 29 secondary care National Health Service orthopaedic units in the UK. Patients with symptomatic knee problems (instability) consistent with an ACL injury were eligible. We excluded patients with meniscal pathology with characteristics that indicate immediate surgery. Patients were randomly assigned (1:1) by computer to either surgery (reconstruction) or rehabilitation (physiotherapy but with subsequent reconstruction permitted if instability persisted after treatment), stratified by site and baseline Knee Injury and Osteoarthritis Outcome Score—4 domain version (KOOS4). This management design represented normal practice. The primary outcome was KOOS4 at 18 months after randomisation. The principal analyses were intention-to-treat based, with KOOS4 results analysed using linear regression. This trial is registered with ISRCTN, ISRCTN10110685, and ClinicalTrials.gov, NCT02980367. Findings: Between Feb 1, 2017, and April 12, 2020, we recruited 316 patients. 156 (49%) participants were randomly assigned to the surgical reconstruction group and 160 (51%) to the rehabilitation group. Mean KOOS4 at 18 months was 73·0 (SD 18·3) in the surgical group and 64·6 (21·6) in the rehabilitation group. The adjusted mean difference was 7·9 (95% CI 2·5–13·2; p=0·0053) in favour of surgical management. 65 (41%) of 160 patients allocated to rehabilitation underwent subsequent surgery according to protocol within 18 months. 43 (28%) of 156 patients allocated to surgery did not receive their allocated treatment. We found no differences between groups in the proportion of intervention-related complications. Interpretation: Surgical reconstruction as a management strategy for patients with non-acute ACL injury with persistent symptoms of instability was clinically superior and more cost-effective in comparison with rehabilitation management. Funding: The UK National Institute for Health Research Health Technology Assessment Programme

Pseudomorphic replacement of single calcium carbonate crystals by polycrystalline apatite

During chemical weathering and natural hydrothermal reactions, apatite can form by replacing calcium carbonates. In hydrothermal experiments in which aragonite and calcite single crystals have been reacted with phosphate solutions, the carbonates are replaced by polycrystalline hydroxylapatite (HAP). In both cases the crystals have retained their overall morphology while their compositions have changed significantly. The HAP appears to have a crystallographic relationship to the parent carbonate crystals. The textural relationships are consistent with an interface-coupled dissolution-precipitation mechanism. Structural relationships and relative molar volumes and solubilities appear to be factors that greatly affect replacement reactions. © 2008 The Mineralogical Society

The experimental replacement of ilmenite by rutile in HCl solutions

To determine the mechanism of acid-leaching of ilmenite to ultimately forming rutile, we have carried out an experimental study of ilmenite alteration in autoclaves at 150°C in HCl solutions. The resulting products were studied by X-ray diffraction, scanning electron microscopy, electron microprobe and Raman spectroscopy. In some experiments the solution was initially enriched in 18O and the distribution of the isotope in the alteration products mapped from the frequency shift of cation-oxygen stretching bands in the Raman spectra. The alteration begins at the original ilmenite crystal surface and has also taken place along an intricate branching network of fractures in the ilmenite, generated by the reaction. Element-distribution maps and chemical analyses of the reaction product within the fractures show marked depletion in Fe and Mn and a relative enrichment of Ti. Chemical analyses however, do not correspond to any stoichiometric composition, and may represent mixtures of TiO2 and Fe2O3. The fracturing is possibly driven by volume changes associated with dissolution of ilmenite and simultaneous reprecipitation of the product phases (including rutile) from an interfacial solution along an inward moving dissolution-reprecipitation front. Raman spectroscopy shows that the 18O is incorporated in the rutile structure during the recrystallization. Throughout the alteration process, the original morphology of the ilmenite is preserved although the product is highly porous. The rutile inherits crystallographic information from the parent ilmenite, resulting in a triply-twinned rutile microstructure. The results indicate that the ilmenite is replaced directly by rutile without the formation of any intermediate reaction products. The reaction is described in terms of an interface-coupled dissolution-precipitation mechanism. © 2010 Mineralogical Society

Macro- to nanoscale study of the effect of aqueous sulphate on calcite growth

Calcite growth rates were measured in the presence of sulphate using mixed-flow reactors and in situ Atomic Force Microscopy. Preliminary observations reveal that the kinetics and mechanism of the calcite growth was altered by the presence of sulphate. Calcite growth rates in the presence of sulphate (= 5 mM) were decreased and two-dimensional nuclei tend to grow on top of existing nuclei, rather than spreading. The height of new nuclei was ~4 Å, 1 Å greater than that of pure calcite growth. This difference reflects the incorporation of tetrahedral SO42- anions into the calcite lattice. © 2008 The Mineralogical Society

Mechanistic Principles of Barite Formation: From Nanoparticles to Micron-Sized Crystals

This study reports on the early stages of barite (BaSO4) precipitation from aqueous solution. TEM observations indicate that BaSO4 is formed by two levels of oriented aggregation of nanosized solid particles (nonclassical crystallization pathways). Oriented alignment of nanoparticles within micron-sized aggregates is observed, resulting in the formation of perfect monocrystalline particles of barite formed after a recrystallization process that reduces the number of grain boundaries within the aggregates. When an organic copolymer is present in solution, a dense liquid precursor phase seems to be stabilized, forming a PILP (polymer induced liquid precursor). Additionally, secondary nanoparticles are temporarily stabilized retarding recrystallization leading to the formation of BaSO4 mesocrystals