Composition-structure Relationship Research Articles

Synthesis of Intermetallic (Mg1−x,Alx)2Ca by Combinatorial Sputtering

The synthesis–composition–structure relationship in the Mg–Ca–Al system is studied using combinatorial magnetron sputtering. With increasing deposition temperature, a drastic decrease in Mg concentration is obtained. This behavior can be understood based on density functional theory calculations yielding a desorption energy of 1.9 eV/atom for Mg from a hexagonal Mg nanocluster which is far below the desorption energy of Mg from a Mg2Ca nanocluster (3.4 eV/atom) implying desorption of excess Mg during thin film growth at elevated temperatures. Correlative structural and chemical analysis of binary Mg–Ca thin films suggests the formation of hexagonal Mg2Ca (C14 Laves phase) in a wide Mg/Ca range from 1.7 to 2.2, expanding the to date reported stoichiometry range. Pronounced thermally-induced desorption of Mg is utilized to synthesize stoichiometric (Mg1−x,Alx)2Ca thin films by additional co-sputtering of elemental Al, exhibiting a higher desorption energy (6.7 eV/atom) compared to Mg (3.4 eV/atom) from Mg2Ca, which governs its preferred incorporation during synthesis. X-ray diffraction investigations along the chemical gradient suggest the formation of intermetallic C14 (Mg1–x,Alx)2Ca with a critical aluminum concentration of up to 23 at.%. The introduced synthesis strategy, based on the thermally-induced desorption of weakly bonded species, and the preferential incorporation of strongly bonded species, may also be useful for solubility studies of other phases within this ternary system as well as for other intermetallics with weakly bonded alloying constituents.

Composition–Structure Relationship of Skeletal–Dendritic Ferrospheres Formed during Industrial Combustion of Lignite and Coal

The structure–composition relationship of skeletal–dendritic ferrospheres (FSs) isolated from fly ash from the coal and lignite combustion has been studied systematically by scanning electron micro...

Raman and Density Functional Theory Studies of Li2Mo4O13 Structures in Crystalline and Molten States.

The Li2Mo4O13 melt structure and its Raman spectral characteristics are the key for establishing the composition-structure relationship of lithium molybdate melts. In this work, Raman spectroscopy, factor group analysis, and density functional theory (DFT) were applied to investigate the structural and spectral details of the H-Li2Mo4O13 crystal and a Li2Mo4O13 melt. Factor group analysis shows that the crystal has 171 vibrational modes (84Ag + 87Au), including three acoustic modes (3Au), six librational modes (2Ag + 4Au), 21 translational modes (7Ag + 14Au), and 141 internal modes (75Ag + 66Au). All of the Ag modes are Raman-active and were assigned by the DFT method. The Li2Mo4O13 melt structure was deduced from the H-Li2Mo4O13 crystal structure and demonstrated by the DFT method. The results show that the Li2Mo4O13 melt is made up of Li+ ions and Mo4O132- groups, each of which is formed by four corner-sharing MoO3Ø/MoO2Ø2 tetrahedra (Ø = bridging oxygen). The melt has three acoustic modes (3A) and 54 optical modes (54A). All of the optical modes are Raman-active and were accurately assigned by the DFT method.

Empirical Evidence for A‐Site Order in Perovskites

Models for composition–structure relationships are useful in both the lab and industry, yet few exist for perovskites‐containing extrinsic defects or cation ordering. In this work, an empirical model is used to predict the existence of A‐site cation ordering. Specifically, four compositions in the Na(1−3x)/2La(1+x)/2TiO3 system (x = 0.0, 0.0533, 0.1733 and 0.225) were synthesized using a conventional solid‐state mixed‐oxide method. The structure of the x = 0 end‐member (Na0.5La0.5TiO3) has been reported in various space groups, but always with a random distribution of Na+ and La3+ on the A site; however, empirical modeling suggests that it is not only ordered but also that a small volume increase accompanies the ordering process. While no evidence of long‐range A‐site ordering is observed in this composition via X‐ray or neutron diffraction, electron‐diffraction data indicate short‐range ordering of Na+ and La3+ ions, with the degree of cation ordering decreasing (but the scale of ordered domains and degree of vacancy ordering generally increasing) with increasing x. First‐principles calculations via density functional theory support both conclusions that short‐range ordering in Na0.5La0.5TiO3 is stable and that it results in a volume increase with respect to the disordered analog. A similar analysis has been conducted for the Li(1−3x)/2La(1+x)/2TiO3 and Na(1−3x)/2La(1+x)/2(Mg0.5W0.5)O3 solid solutions. These systems provide additional validation of the accuracy and versatility of the empirical modeling method used.

Design of Metastable Alloys for Energy Conversion

The design and discovery of new semiconductors with targeted multi-property functionalities for applications in solar energy conversion is a current challenge in developing new (photo-)electrode materials. Traditionally, theoretical predictions of ground state structures and their thermodynamic stability have facilitated the discovery of new materials and the optimization of known compounds. However, the field of materials design is experiencing a paradigm shift from near-equilibrium materials towards a much larger design space that includes materials far from equilibrium. In this work, we use theoretical and computational screening methods to identify and design metastable metal nitride and metal oxide alloys with desirable semiconducting properties for solar energy conversion applications. The materials design principles utilize both structure-property and composition-structure relationships to enable tunable multi-property functionalities. We leverage the possibility to overcome thermodynamic solubility limits by nonequilibrium thin-film growth to realize these novel semiconducting alloy electrode materials. Our theory guided synthesis employs a high-throughput combinatorial approach with reactive magnetron sputtering to rapidly screen composition and growth parameters to synthesize metastable spinel (Sn1-xTix)3N4 and polymorphic Mn1-xZnxO alloys. A proof of principle is provided by initial photo-electrocatalytic device measurements that corroborate the materials by design features of tunable band properties and transport mechanisms to improve solar hydrogen generation using the novel alloy electrodes. Our results demonstrate a broadly applicable approach for synthesis of metastable materials and establish the predictive design and discovery of far from equilibrium materials for energy conversion. Figure 1

Design of Semiconducting TetrahedralMn1−xZnxOAlloys and Their Application to Solar Water Splitting

Both structure-property and composition-structure relationships are exploited to design and realize novel wurtzite-structure Mn1-xZnxO alloys. A proof of principle is provided that corroborates, in particular, the predicted favorable hole-transport properties of these alloys.

Structural effect of aliovalent doping in lead perovskites

Composition–structure relationships are needed for various applications, including lattice-matching for heteroepitaxy; however, a general model to predict lattice constants in defective perovskites is not yet available because the exact nature of A-site vacancies in perovskites remains largely unknown. In this study, it has been shown experimentally via Le Bail refinements of x-ray diffraction data that such vacancies in (Pb1−3xLa2x□x)TiO3 and (Pb1−3xLa2x□x)(Zr0.6Ti0.4)O3 have an effective size due to both Coulombic repulsion of coordinating oxygen ions and bond relaxation. For the first time, cell volume can be predicted in this system from stoichiometry and published ionic radii data alone to within 0.2% accuracy within 0≤x≤13 compositional range and <0.3% accuracy all the way to x=13. The model may be applied to other perovskite systems and eventually provide tailored properties (magnetic, dielectric, and other) based on improved structure predictions.

Local Structure of Ba1–xSrxTiO3 and BaTi1–yZryO3 Nanocrystals Probed by X-ray Absorption and X-ray Total Scattering

The effect of isovalent chemical substitution on the magnitude and coherence length of local ferroelectric distortions present in sub-20 nm Ba(1-x)Sr(x)TiO3 (x = 0.0, 0.30, 0.50, 1.0) and BaTi(1-y)Zr(y)O3 (y = 0.0, 0.15, 0.50, 1.0) nanocrystals synthesized at room temperature is investigated using X-ray absorption near edge structure (XANES) and pair distribution function analysis of X-ray total scattering data (PDF). Although the average crystal structure of the nanocrystals is adequately described by a centrosymmetric, cubic Pm3m space group, local ferroelectric distortions due to the displacement of the titanium atom from the center of the perovskite lattice are observed for all compositions, except BaZrO3. The symmetry of the ferroelectric distortions is adequately described by a tetragonal P4mm space group. The magnitude of the local displacements of the titanium atom in BaTiO3 nanocrystals is comparable to that observed in single crystals and bulk ceramics, but the coherence length of their ferroelectric coupling is much shorter (≤20 Å). Substitution of Sr(2+) for Ba(2+) and of Zr(4+) for Ti(4+) induces a tetragonal-to-cubic transition of the room temperature local crystal structure, analogous to that observed for single crystals and bulk ceramics at similar compositions. This transition is driven by a reduction of the magnitude of the local displacements of the titanium atom and/or of the coherence length of their ferroelectric coupling. Replacing 50% of Ba(2+) with Sr(2+) slightly reduces the magnitude of the titanium displacement, but the coherence length is not affected. In contrast, replacing 15% of the ferroelectrically active Ti(4+) with Zr(4+) leads to a significant reduction of the coherence length. Deviations from the ideal solid solution behavior are observed in BaTi(1-y)Zr(y)O3 nanocrystals and are attributed to an inhomogeneous distribution of the barium atoms in the nanocrystal. Composition-structure relationships derived for Ba(1-x)Sr(x)TiO3 and BaTi(1-y)Zr(y)O3 nanocrystals demonstrate that the evolution of the room temperature local crystal structure with chemical composition parallels that of single crystals and bulk ceramics, and that chemical control over ferroelectric distortions is possible in the sub-20 nm size range. In addition, the potential of PDF analysis of total scattering data to probe compositional fluctuations in nanocrystals is demonstrated.

Mesoporous bioactive glasses: structure characteristics, drug/growth factor delivery and bone regeneration application

The impact of bone diseases and trauma in the whole world has increased significantly in the past decades. Bioactive glasses are regarded as an important bone regeneration material owing to their generally excellent osteoconductivity and osteostimulativity. A new class of bioactive glass, referred to as mesoporous bioglass (MBG), was developed 7 years ago, which possess a highly ordered mesoporous channel structure and a highly specific surface area. The study of MBG for drug/growth factor delivery and bone tissue engineering has grown significantly in the past several years. In this article, we review the recent advances of MBG materials, including the preparation of different forms of MBG, composition-structure relationship, efficient drug/growth factor delivery and bone tissue engineering application. By summarizing our recent research, the interaction of MBG scaffolds with bone-forming cells, the effect of drug/growth factor delivery on proliferation and differentiation of tissue cells and the in vivo osteogenesis of MBG scaffolds are highlighted. The advantages and limitations of MBG for drug delivery and bone tissue engineering have been compared with microsize bioactive glasses and nanosize bioactive glasses. The future perspective of MBG is discussed for bone regeneration application by combining drug delivery with bone tissue engineering and investigating the in vivo osteogenesis mechanism in large animal models.

High-temperature X-ray analysis of phase evolution in Sr-doped zinc-silicate glasses

Bone grafts are required in many clinical situations. Autografts are the traditional gold standard for treating conditions requiring bone grafts. However autografts have inherent drawbacks such as donor site morbidity, pain and increased operative time. An alternative for autografts are synthetic grafts. A series of strontium doped zinc silicate glasses were developed which were investigated using high temperature X-ray diffraction (HT-XRD) in order to establish phase transformations, which occur up to the first crystallization temperature, (T p1), thus identifying the composition–structure relationships which arise during this thermal processing. In analysing BT110 it was observed that all glass material crystallised into 4 phases including strontium zinc silicate, sodium calcium silicate, calcium silicate and strontium silicate, leaving no residual glass phase. BT111 and BT112 were shown to contain a residual glassy phase alongside for BT111, sodium zinc silicate, larnite and silicon oxide and for BT112 strontium silicate, calcium silicate, sodium silicate and silicon oxide. In the case of BT111 the residual glass phase appears to be rich in strontium. The residual glass phase being Sr enriched with respect to the glass-ceramic may offer increased release of Sr 2+ from the material; important for the regulation of osteoblastic and osteoclastic activity. BT113 crystallized to form strontium silicate, sodium silicate, and strontium zinc silicate. BT114 crystallized to form strontium silicate and sodium silicate. The biocompatibility of phases formed in BT113 and BT114 is as yet unknown. Further knowledge will be generated by later work examining the biocompatibility of these phases identified in this research. However, on the basis of these results, the materials (BT110–BT112) exhibit potential as a bone graft substitutes, whilst BT113–BT114 give rise to phases with unknown biocompatibility and so warrant further investigation.

Composition-Structure Relationships in Simplified Nuclear Waste Glasses: 1. Mixed Alkali Borosilicate Glasses

Mixed alkali borosilicate glasses show a complex relationship between composition and structure. These relationships are often difficult to fully investigate using standard laboratory methods. Therefore, we present here a systematic molecular dynamics (MD) study of composition–structure relationships in sodium lithium borosilicate glasses. Results are compared with the published laboratory glass data. These glasses are of importance to the U.K. nuclear waste vitrification program where an understanding of glass structure can improve greatly the understanding of long-term glass properties and waste element solubility. The MD-simulated glasses produced in this work show close agreement with laboratory glasses for bond lengths, atom coordinations and bond angles of all species. Particularly, the change in coordination of boron is accurately reproduced over a wide compositional range without the use of a three-body potential for the O–B–O angle. The change in the polymerization and mixing of the silicate and borate networks with composition in the MD-simulated glasses was shown to agree well with that seen in laboratory glasses.

Crystal structure and transformation behavior of Ni–Mn–Ga martensites

Abstract The crystal structure of the martensitic phase Ni–Mn–Ga ferromagnetic shape memory alloys has been found to be extremely sensitive to composition. A systematic exploration of the composition–structure relationship has been performed using X-ray diffraction on several single crystals having large composition gradients. Also, temperature-dependent magnetic measurements show the martensitic transition to orthorhombic martensite is broader than to tetragonal martensite. This distinct character can be understood by considering the relative importance of strain energy effects in the two martensite phases.

Composition—Structure Relationships in Polar Intermetallics: Experimental and Theoretical Studies of LaNi1+xAl6‐x (x = 0.44).

AbstractFor Abstract see ChemInform Abstract in Full Text.

Lipid composition-structure relationship in lens and retinal rod membranes: Borchman, D., Lamba, O. Deptartment of Ophthalmology & Visual Sciences, Univiversity of Louisville, Louisville KY 40292 U.S.A.

Lipid composition-structure relationship in lens and retinal rod membranes: Borchman, D., Lamba, O. Deptartment of Ophthalmology & Visual Sciences, Univiversity of Louisville, Louisville KY 40292 U.S.A.

Study on the composition-structure relationship of lipophorins

High density lipophorin (HDLp is the main lipoprotein found in resting insect hemolymph. It has, in general, two molecules of apolipoproteins: apoLp-I (250 kDa) and apoLp-II (80 kDa) and a variable lipid content which ranges from 35% to 59% (w/w). Diacylglycerols (DG), phospholipids (PL), and hydrocarbons (HC) are the main lipid components, whereas cholesterol and triacylglycerols are minor components. DG content varies from 7 to 30%, PL from 11 to 24%, and HC from 0 to 15%. In order to determine the relationship between the lipid composition and the arrangement of lipid and protein components in the lipoprotein particle, a density-composition structural model was designed. The model was established by means of 12 sets of data on lipophorin density-composition relationships, and model validity was determined throughout lipoprotein space- and surface-filling conditions. Despite the differences among the lipid compositions of lipophorins, it is concluded that there are several unifying structural restrictions that govern the molecular organization of lipophorins. Quantitative treatment of the model indicates that lipophorin structure is consistent with the following. 1) Spherical particles with a protein-rich outer layer of approximately 20-21 A thickness, comprised of proteins, phospholipids, cholesterol, and small amounts of DG, and a lipid-rich core composed of HC, TG, and almost all the lipophorin DG. 2) Apolipophorins have a lipid-embedded localization within the lipoprotein particle. They might represent one of the few examples of proteins containing beta-shift structure, exerting strong hydrophobic interaction and having a lipid-embedded localization.(ABSTRACT TRUNCATED AT 250 WORDS)

Composition-structure relationships for multisource evaporated CuGaSe2 thin films

X-ray diffraction (XRD) analysis of doublet formation and peak shifts were used to observe the compositional dependence of the order–disorder transition in polycrystalline CuGaSe2 thin films deposited by multisource evaporation. Cu-poor material had a strong tendency to disorder as evidenced by the simultaneous presence of both the chalcopyrite and sphalerite phases. Stoichiometric and Cu-rich material contained only the tetragonal phase as observed by XRD. Comparison of Cu-poor XRD patterns with theoretical calculations reflecting probable defect chemistries (VCu, GaCu, VSe) suggests an interesting microstructure. The absence of higher index group (iii) reflections, notably the (103) and (211) peaks, in chalcopyrite material suggest that the tetragonal phase maintains a near-stoichiometric composition. Overall Cu-poor film compositions may therefore be obtained by adjustment within the cubic phase which implies compositional segregation between the phases.