Alite calcium sulfoaluminate cement: chemistry and thermodynamics

Calcium sulfoaluminate (C$A) cement is a binder of increasing interest to the cement industry and is undergoing rapid development. Current formulations do not contain alite; however, alite calcium sulfoaluminate (a-C$A) cements can combine the favourable characteristics of Portland cement (PC) with those of C$A cement while also having a lower carbon dioxide footprint than the current generation of PC clinkers. This paper presents two results on the formation of a-C$A clinkers. The first is a thermodynamic study demonstrating that the production of a-C$A clinker is possible without the use of mineralisers, doping with foreign elements, or using multiple stages of heating. It is established that a-C$A clinker can be readily produced in a standard process by controlling the oxygen and sulfur dioxide fugacity in the atmosphere. This allows for the stabilisation of ye’elimite to the higher temperatures required for alite stability. The second result establishes that when using fluorine to mineralise a-C$A clinker production, the iron content in the clinker is also an important variable. Although the exact mechanism of alite stabilisation is not known, it is shown that alite formation increases with the combination of calcium fluoride and iron (III) oxide in the mix

Accelerated discovery of two crystal structure types in a complex inorganic phase field

The discovery of new materials is hampered by the lack of efficient approaches to the exploration of both the large number of possible elemental compositions for such materials, and of the candidate structures at each composition1. For example, the discovery of inorganic extended solid structures has relied on knowledge of crystal chemistry coupled with time-consuming materials synthesis with systematically varied elemental ratios2,3. Computational methods have been developed to guide synthesis by predicting structures at specific compositions4,5,6 and predicting compositions for known crystal structures7,8, with notable successes9,10. However, the challenge of finding qualitatively new, experimentally realizable compounds, with crystal structures where the unit cell and the atom positions within it differ from known structures, remains for compositionally complex systems. Many valuable properties arise from substitution into known crystal structures, but materials discovery using this approach alone risks both missing best-in-class performance and attempting design with incomplete knowledge8,11. Here we report the experimental discovery of two structure types by computational identification of the region of a complex inorganic phase field that contains them. This is achieved by computing probe structures that capture the chemical and structural diversity of the system and whose energies can be ranked against combinations of currently known materials. Subsequent experimental exploration of the lowest-energy regions of the computed phase diagram affords two materials with previously unreported crystal structures featuring unusual structural motifs. This approach will accelerate the systematic discovery of new materials in complex compositional spaces by efficiently guiding synthesis and enhancing the predictive power of the computational tools through expansion of the knowledge base underpinning them

Does optimal foraging theory explain why suburban Florida scrub-jays (Aphelocoma coerulescens) feed their young human-provided food?

Optimal foraging theory assumes that a forager can adequately assess the quality of its prey and predicts that parents feed their young low-quality foods only when suffering unpredicted reductions in their ability to provision. Wildland Florida scrub-jays feed their young exclusively arthropods, but suburban parents include human-provided foods in the nestling diet, with possible costs in terms of reduced growth and survival. We tested experimentally whether parents feed human-provided foods, given the apparent costs, because: 1) they do not discriminate between food types, 2) they switch to low-quality, abundant foods when natural food availability in the environment is low, or 3) they switch when the time needed to obtain natural food is high. Parents discriminated between natural and human-provided foods by showing a preference for natural foods when rearing young. When the handling time of natural foods was increased experimentally, parents in the suburban and wildland habitats switched to human-provided foods. Supplementation with natural foods increased preference for this food in both habitats. Suburban parents chose more natural foods than wildland parents, suggesting that they have a greater preference for natural foods. Regardless of preferences demonstrated at feeders, parents in both the suburbs and wildlands delivered mostly natural foods to nestlings, independent of natural food availability. Nonetheless, natural foods are likely to be scarcer in the environment than in our experimental tests. Because natural food availability is lower in the suburbs than in the wildland habitat, parents in the suburbs may be forced to switch to human-provided foods when feeding nestlings

Halilsarpite, a new arsenate analogue of walentaite, from the Oumlil mine, Bou Azzer district, Morocco

Halilsarpite, [Mg(H2O)6][CaAs23+(Fe2.673+Mo0.336+)(AsO4)2O7], is a new secondary mixed arsenate/arsenite mineral from the Oumlil mine, Bou Azzer district, Morocco. It forms lemon-yellow spherules, about 0.1&thinsp;mm in diameter, composed of platelets, some tens of micrometres in diameter but only 1–2&thinsp;µm thick. The platelets are flattened on {100} and exhibit perfect cleavage on {100}. The calculated density is 2.89&thinsp;g&thinsp;cm−3. Optically, halilsarpite is biaxial (−), with α=1.646(calc), β=1.765(5), γ=1.815(5) (white light), and 2V (meas.)&thinsp;=&thinsp;62(1)∘. The partial orientation is X=a. Dispersion is weak with r&lt;v, and pleochroism is in shades of yellow, X&lt;Y≈Z. Electron microprobe analyses coupled with crystal-structure refinement results give the empirical formula [(Mg0.42Ca0.19Fe0.113+ □0.28)Σ1.00 (H2O)6][((Ca0.5Mg0.2Na0.11□0.14)Σ0.95 (As3+)2.05)∑3.00(Fe2.443+ Mo0.566+)Σ3.00 ((As0.9855+P0.0155+)Σ1.00O4)2O6.9(OH)0.1]. Halilsarpite is orthorhombic, Imma, with a=26.4890(10), b=7.4205(3), c=10.4378(4) Å, V=2051.67(14) Å3, and Z=4. The structure was solved and refined using single-crystal X-ray data to wRobs=0.046 for 1402 unique reflections to a resolution of 0.75&thinsp;Å. Halilsarpite is isostructural with walentaite and natrowalentaite, which have structures based on heteropolyhedral layers of configuration [M1(M2)2(TO4)2(O,OH)6] with surface-attached As3+O3 groups and Ca and Na cations, and with interlayer hydrated cations and H2O molecules. The octahedrally coordinated sites M1 and M2 are occupied by Fe3+ in walentaite, while M2 =&thinsp;Fe0.673+W0.336+ in natrowalentaite. Walentaite and natrowalentaite are phosphates, with T=P5+. Halilsarpite differs from these minerals in having T=As5+ and in having partial replacement of Fe3+ by Mo6+ in the M2-centred octahedra.</p

The walentaite group and the description of a new member, alcantarillaite, from the Alcantarilla mine, Belalcázar, Córdoba, Andalusia, Spain

The general structural formula for the walentaite group is [((A), A], based on heteropolyhedral layers of configuration [M], with surface-coordinated species at the B, As2 and As3 sites, and with interlayer hydrated cation groups centred at the A sites. The group is divided into walentaite and halilsarpite subgroups based on T = P5+ and As5+, respectively. Alcantarillaite, (IMA2019-072), [Fe3+], is a new member of the walentaite group from the Alcantarilla wolframite mine, Belalcázar, Córdoba, Andalusia, Spain. It occurs most commonly as lemon-yellow fillings together with massive scorodite in fissures and cracks in quartz adjacent to löllingite. It is also found as tiny yellow rosettes lining vugs and as spheroids of ultrathin blades. It is associated with scorodite, pharmacosiderite, ferberite and schneiderhöhnite. Optically it is biaxial (–), with α = 1.703(calc), β = 1.800(5), γ = 1.850(5) and 2V = 68(1)° (white light). Dispersion is r &gt; v, moderate. The optical orientation is X = a, Y = c and Z = b. The calculated density is 3.06 g cm–3. Electron microprobe analyses together with crystal structure refinement results gives the empirical formula [Fe3+]. Alcantarillaite is orthorhombic, with an average structure described in Imma, and with a = 24.038(8) Å, b = 7.444(3) Å, c = 10.387(3) Å, V = 1858.6(11) Å3 and Z = 4. The structure (wR = 0.078 for 651 reflections to a resolution of 0.91 Å) differs most significantly from other walentaite-group members in having an interlayer A2 site occupied. Square-pyramidal polyhedra centred at the A2 sites form edge-shared dimers, (Fe3+. The dimers share vertices with T anions in the layers on either side to form 8-sided channels along [010] occupied by H2O molecules

Impaction grafting in the femur in cementless modular revision total hip arthroplasty: a descriptive outcome analysis of 243 cases with the MRP-TITAN revision implant

<p>Abstract</p> <p>Background</p> <p>We present a descriptive and retrospective analysis of revision total hip arthroplasties (THA) using the MRP-TITAN stem (Peter Brehm, Weisendorf, GER) with distal diaphyseal fixation and metaphyseal defect augmentation. Our hypothesis was that the metaphyseal defect augmentation (Impaction Bone Grafting) improves the stem survival.</p> <p>Methods</p> <p>We retrospectively analyzed the aggregated and anonymized data of 243 femoral stem revisions. 68 patients with 70 implants (28.8%) received an allograft augmentation for metaphyseal defects; 165 patients with 173 implants (71.2%) did not, and served as controls. The mean follow-up was 4.4 ± 1.8 years (range, 2.1–9.6 years). There were no significant differences (p > 0.05) between the study and control group regarding age, body mass index (BMI), femoral defects (types I-III as described by Paprosky), and preoperative Harris Hip Score (HHS). Postoperative clinical function was evaluated using the HHS. Postoperative radiologic examination evaluated implant stability, axial implant migration, signs of implant loosening, periprosthetic radiolucencies, as well as bone regeneration and resorption.</p> <p>Results</p> <p>There were comparable rates of intraoperative and postoperative complications in the study and control groups (p > 0.05). Clinical function, expressed as the increase in the postoperative HHS over the preoperative score, showed significantly greater improvement in the group with Impaction Bone Grafting (35.6 ± 14.3 vs. 30.8 ± 15.8; p ≤ 0.05). The study group showed better outcome especially for larger defects (types II C and III as described by Paprosky) and stem diameters ≥ 17 mm. The two groups did not show significant differences in the rate of aseptic loosening (1.4% vs. 2.9%) and the rate of revisions (8.6% vs. 11%). The Kaplan-Meier survival for the MRP-TITAN stem in both groups together was 93.8% after 8.8 years. [Study group 95.7% after 8.54 years ; control group 93.1% after 8.7 years]. Radiologic evaluation showed no significant change in axial implant migration (4.3% vs. 9.3%; p = 0.19) but a significant reduction in proximal stress shielding (5.7% vs. 17.9%; p < 0.05) in the study group. Periprosthetic radiolucencies were detected in 5.7% of the study group and in 9.8% of the control group (p = 0.30). Radiolucencies in the proximal zones 1 and 7 according to Gruen occurred significantly more often in the control group without allograft augmentation (p ≤ 0.05).</p> <p>Conclusion</p> <p>We present the largest analysis of the impaction grafting technique in combination with cementless distal diaphyseal stem fixation published so far. Our data provides initial evidence of improved bone regeneration after graft augmentation of metaphyseal bone defects. The data suggests that proximal metaphyseal graft augmentation is beneficial for large metaphyseal bone defects (Paprosky types IIC and III) and stem diameters of 17 mm and above. Due to the limitations of a retrospective and descriptive study the level of evidence remains low and prospective trials should be conducted.</p