Prismatic Growth Research Articles

Trace element composition of beryl from spodumene pegmatite deposits of the Kunar Province, Afghanistan

The study of trace element composition of beryl from the Chambalak and Digal deposits of the Darai Pech pegmatite feld of the Kunar province (Afghanistan) using secondary ion mass spectrometry (SIMS) revealed the sectoriality of the beryl crystal from the Chambalak deposit. The inner and outer parts of the profle are identifed as the pinacoid (0001) and prism (10 1 0) growth zones, respectively. At the boundary of these two simple forms, the Cs, Na, Ca, Fe, Mg, and V content strongly increases. The prism growth zone exhibits the growth pyramids: a decrease in the Na, Fe, V, Ni, and Cr content during growth towards the edge of the beryl crystal. The H2O and Mg content increases in the prism growth zone. No boundary between the pinacoid and prism growth zones is observed in beryl from the Digal deposit. There is a reason to consider its profle as the prism growth zone. A comparison of beryl based on the content of indicative elements, the increase of which corresponds to the fractionation trend of pegmatite melt (Cs, Li, and Rb), from pegmatite deposits of the Kunar province with beryl from other objects showed that pegmatite melt in the studied deposits was moderately fractionated corresponding to the initial evolution stages. It is shown that the content of some elements of beryl from the prism and pinacoid growth zones can fundamentally differ.

Structural Variation Along the Southern Hikurangi Subduction Zone, Aotearoa New Zealand, From Seismic Reflection and Retro‐Deformation Analysis

AbstractThe southern Hikurangi subduction zone exhibits significant along‐strike variation in convergence rate and obliquity, sediment thickness and, uniquely, the increasing proximity of southern Hikurangi to, and impingement on, the incoming continental Chatham Rise, an ancient Gondwana accretionary complex. There are corresponding changes in the morphology and structure of the Hikurangi accretionary prism. We combine widely spaced multichannel seismic reflection profiles with high resolution bathymetry and previous interpretations to characterize the structure and the history of the accretionary prism since 2 Ma. The southern Hikurangi margin can be divided into three segments. A northeastern segment (A) characterized by a moderately wide (∼70 km), low taper (∼5°) prism recording uninhibited outward growth in the last ∼1 Myr. Deformation resolvable in seismic reflection data accounts for ∼20 % of plate convergence, comparable with the central Hikurangi margin further North. A central segment (B) characterized by a narrow (∼30 km), moderate taper (∼8°) prism, with earlier (∼2‐∼1 Ma) shortening than segment A. Outward prism growth ceased coincidentally with development of major strike‐slip faults in the prism interior, reduced margin‐normal convergence rate, and the onset of impingement on the incoming Chatham Rise to the south. A southwestern segment (C) marks the approximate southern termination of subduction but widens to ∼50 km due to rapid outward migration of the deformation front via fault reactivation within the now‐underthrusting corner of the Chatham Rise. Segment C exhibits minimal shortening as margin‐normal subduction velocity decreases and plate motion is increasingly taken up by interior thrusts and strike‐slip faults.

Evidence of a Scheduled End for Prism Growth in the Shell of Pinctada margaritifera: Closure of the Calcite Biomineralization Area by a Specific Organic Membrane

The shell of the pearl oyster Pinctada margaritifera is made up of two layers: an outer layer of calcite prisms and an inner layer of aragonite tablets. Recent studies have shown that the calcite layer develops in a series of steps. We found that the end of prism growth and the start of aragonite deposition are also complex processes. Contrary to the common belief that prism growth is interrupted by the expansion of the aragonite layer, we found that a specific membrane covers the calcite surface before aragonite deposition starts. The earliest aragonite depositions occur as granular spots located only on the surfaces covered by this organic membrane This membrane appears to be the final stage of the calcite biomineralization cycle. This new understanding of calcite development has implications for shell biomineralization research and the production of pearls.

Crystal Growth of Defect-Free Single-Crystalline Fibers in Super-High Supersaturation Solution.

By controlling the supersaturation and choosing high-quality seeds, we successfully suppress the prismatic growth of the tetragonal potassium dihydrogen phosphate (KDP) SCFs, realize the rapid growth along the [001] direction, and obtain SCFs less than 10 μm in width with lengths of centimeters. The experimental results show that there exist critical supersaturation points, 22.40% and 41.41% at 25 °C, for initiating the growth of KDP SCF on its pyramidal and prismatic faces, respectively, which are quite different from those of the bulk crystals. We use the mechanism of 2D nucleation on smooth faces to explain the peculiar phenomena, assuming that there is no 2D or 3D defect on the surfaces of the seed fiber crystal. The assumption is supported by AFM observation of the surface micromorphology of the SCFs. Our solution growth technique developed can be used to grow ultrafine SCFs unable to be achieved by existing melt growth techniques.

Does Zircon Shape Retain Petrogenetic Information?

AbstractZircon shape is commonly reported during geochronology and geochemistry analyses of igneous, metamorphic, and sedimentary rocks, but the relationship of zircon shape to primary growth environmental conditions remains poorly constrained. Current models for the control on igneous zircon shape focus on the relative growth of crystal prisms and pyramids, which are not discernible in the imaging techniques used for rapid quantification of zircon shape in geochronology sample mounts. We model the relationship between whole‐rock composition and zircon 2D shape in mineral separates from 45 mafic to felsic igneous samples, representative of Archean and Proterozoic crust in Western Australia. Shape parameters are derived from semi‐automated measurement of photomicrographs of polished zircon crystals in epoxy resin mounts. Whole‐rock composition shows a statistically significant relationship to median magmatic zircon crystal area and mathematically defined “roundness.” Zircon populations show reduced median area and increased median roundness as whole‐rock silica decreases. Phase equilibrium modeling based on whole‐rock composition, and automated electron microscopy mineral maps, indicates that the compositional predisposition of zircon shape is influenced by fundamentally different physical growth environments in mafic versus felsic melts. Specifically, influential factors that differ between mafic and felsic liquids include crystallization sequence and duration—which influence unconstrained growth space—and the potential for absorption/exsolution of zirconium from the accompanying mineral assemblage. We present quantitative, explanatory models for the relationship between zircon 2D shape and whole‐rock silica and demonstrate that the relationships are adhered to across a broad spectrum of whole‐rock compositions.

Extreme Abnormal Grain Growth: Connecting Mechanisms to Microstructural Outcomes

If variety is the spice of life, then abnormal grain growth (AGG) may be the materials processing equivalent of sriracha sauce. Abnormally growing grains can be prismatic, dendritic, or practically any shape in between. When they grow at least an order of magnitude larger than their neighbors in the matrix—a state we call extreme AGG—we can examine the abnormal/matrix interface for clues to the underlying mechanism. Simulating AGG for various formulations of the grain boundary (GB) equation of motion, we show that anisotropies in GB mobility and energy leave a characteristic fingerprint in the abnormal/matrix boundary. Except in the case of prismatic growth, the morphological signature of most reported instances of AGG is consistent with a certain degree of GB mobility variability. Open questions remain, however, concerning the mechanism by which the corresponding growth advantage is established and maintained as the GBs of abnormal grains advance through the matrix.

Salvage of ribose from uridine or RNA supports glycolysis in nutrient-limited conditions

Glucose is vital for life, serving as both a source of energy and carbon building block for growth. When glucose is limiting, alternative nutrients must be harnessed. To identify mechanisms by which cells can tolerate complete loss of glucose, we performed nutrient-sensitized genome-wide genetic screens and a PRISM growth assay across 482 cancer cell lines. We report that catabolism of uridine from the medium enables the growth of cells in the complete absence of glucose. While previous studies have shown that uridine can be salvaged to support pyrimidine synthesis in the setting of mitochondrial oxidative phosphorylation deficiency1, our work demonstrates that the ribose moiety of uridine or RNA can be salvaged to fulfil energy requirements via a pathway based on: (1) the phosphorylytic cleavage of uridine by uridine phosphorylase UPP1/UPP2 into uracil and ribose-1-phosphate (R1P), (2) the conversion of uridine-derived R1P into fructose-6-P and glyceraldehyde-3-P by the non-oxidative branch of the pentose phosphate pathway and (3) their glycolytic utilization to fuel ATP production, biosynthesis and gluconeogenesis. Capacity for glycolysis from uridine-derived ribose appears widespread, and we confirm its activity in cancer lineages, primary macrophages and mice in vivo. An interesting property of this pathway is that R1P enters downstream of the initial, highly regulated steps of glucose transport and upper glycolysis. We anticipate that ‘uridine bypass’ of upper glycolysis could be important in the context of disease and even exploited for therapeutic purposes.

Development of a calcium aluminate cement from steelmaking slag by altering its mineralogical composition

Strict environmental norms and increasing awareness of the need to recycle solid wastes generated during ironmaking and steelmaking processes are the key driving force for the development of various new materials and manufacturing technologies. In this study, a calcium aluminate clinker was prepared from steel ladle slag by modifying its mineral composition. The slag paste, prepared by mixing slag with water, exhibited flash setting behaviour due to the presence of C12A7 and C3A phases. In contrast, the slag clinker, developed by sintering a mixture of a pre-determined quantity of slag and aluminium oxide at 1400°C for 2 h and 4 h, contained CA, CA2, gehlenite and ‘Q’ phases. Hydrated slag clinker contained stable C3AH6, AH3 and stratlingite with preferential growth of calcium aluminate hydrate prisms along the c-axis, which provided a well-defined raceme-like morphology with an interlinked structure. This improved the setting time and crushing strength of the clinkers after 6 h and 24 h of curing at room temperature. Additionally, the presence of the Q phase, with lamellar prismatic crystals, also helped to enhance strength. The developed clinker also exhibited superior crushing strength as compared with commercially available calcium aluminate cement of medium purity. The slag, used as a source of calcium oxide, could replace calcium carbonate completely and thus contribute to reductions in carbon dioxide emissions during the clinker-making process.

Bioinspired Compartmentalization Strategy for Coating Polymers with Self-Organized Prismatic Films

Biomineralization provides load-bearing and protective functions to living organisms by reinforcing soft tissues. Translation of biomineralization principles to materials science in a controlled and self-organized fashion is highly desirable but challenging. A major lesson from natural systems is that crystallization may be controlled by compartmentalization and templating. Here, we develop a crystallization technique based on graphene oxide-mediated compartmentalization and on templating prismatic growth of calcite nanocoatings via control of ionic diffusivity into the microcompartments, which results in a multistage, self-organized crystallization and represents an effective strategy for providing continuous nanocoatings and enhancing the tribological performance of polymeric surfaces under contact stresses. The present research offers a bottom-up approach of using very basic biomineralization principles for the protection of polymeric surfaces, which are of interest for biomedical applications and the fabrication of high-performance functional materials in a sustainable manner.

Plastic deformation of ZnO thin films through edge and screw dislocation movements

AbstractColumnar wurtzite grains were formed in sputtered ZnO thin films deposited on a plastic polyethylene terephthalate substrate. Selected‐area diffraction patterns reveal that the columnar grains in the sputtered films present two preferred growth planes, namely, the basal (0002) and prismatic (100) growth planes. The diffraction patterns obtained also confirm that the microstructure of sputtered indium tin oxide thin films is amorphous in nature. Tensile tests indicate that the fracture strain of the ZnO thin film occurs between 1.73% and 2.14%, while the fracture strain of the indium tin oxide thin film occurs between 0.24% and 0.67%. Thus, the fracture toughness of the sputtered ZnO thin film is greater than that of the sputtered indium tin oxide thin film. High‐resolution transmission electron microscopic images demonstrate that edge and screw dislocations could be identified in the sputtered ZnO thin films. Moreover, edge and screw dislocation movements may, respectively, be observed in the basal‐ and prismatic‐oriented ZnO columnar grains of the sputtered ZnO thin films. Our results indicate that movements of the edge and screw dislocations in the basal‐ and prismatic‐oriented ZnO columnar grains account for the plastic deformation of the investigated ZnO thin films under tensile stress.

Breaking the long-standing morphological paradigm: Individual prisms in the pearl oyster shell grow perpendicular to the c-axis of calcite

Cross-sections of calcitic prismatic layers in mollusk shells, cut perpendicular to growth direction, reveal well-defined polygonal shapes of individual “grains” clearly visible by light and electron microscopy. For several kinds of shells, it was shown that the average number of edges in an individual prism approaches six during the growth process. Taking into account the rhombohedral symmetry of calcite, often presented in hexagonal axes, all this led to the long-standing opinion that calcitic prisms grow along the c-axis of calcite. In this paper, using X-ray diffraction and electron backscatter diffraction (EBSD), we unambiguously show that calcitic prisms in pearl oyster Pinctada margaritifera predominantly grow perpendicular to the c-axis. The obtained results imply that the hexagon-like habitus of growing crystallites may be not necessarily connected to calcite crystallography and, therefore, other factors should be taken into consideration. We analyze this phenomenon by comparing the organic contents in Pinctada margaritifera and Pinna nobilis shells, the later revealing regular growth of calcitic prisms along the c-axis.

KH2PO4 single crystals activated with the Ti4+ ions in the form of TiO2−x × nH2O nanoparticles: Structural peculiarities, point defects, and dielectric properties

Potassium dihydrogen phosphate KH2PO4 (KDP) single crystals activated with Ti4+ ions in the form of TiO2−x × nH2O nanoparticles in the η-phase, synthesized by the sulfate method using TiOSO4 × хH2SO4 × yH2O, have been first grown by the temperature lowering method and cut from pyramidal (P) and prismatic (Pr) growth sectors. The first-performed neutron powder diffraction investigation of P and Pr samples cut from the KDP:Ti4+ crystal allowed us to reveal vacancies in the K and H sites for both samples, their number being larger in the Pr structure compared to the P one. Taking into account the deficiency of the K and H sites, full occupation of the O site, presence of Ti4+ ions in the structure, and the electroneutrality condition, a partial substitution of (PO4)3− anion by the (SO4)2− one, larger for the Pr sample, was observed. The real compositions of P and Pr samples, correlated with the cation-anion internuclear distances, were refined. The dielectric permittivity of the Pr sample was significantly lower than that of the P one; it decreases with decreasing К–O, P–O, and O···H distances and increasing deficiency of the K and H sites.

Overexpression of constitutively active MAP3K7 in ameloblasts causes enamel defects of mouse teeth

ObjectiveCompelling evidence suggests that mitogen-activated protein kinases (Mapks) play an important role in amelogenesis. However, the role of transforming growth factor (TGF)-β-activating kinase 1 (Tak1, Map3k7), which is a known upstream kinase of Mapks, during amelogenesis remains to be determined. The aim of this study was to investigate the possible involvement of Map3k7 in amelogenesis. DesignWe generated transgenic mice that produced constitutively active human MAP3K7 (caMAP3K7) under the control of amelogenin (Amelx) gene promoter. Radiography and micro-computed tomography (μCT) analysis was used to detect the radio-opacity and density of the teeth. The enamel microstructure was observed with a scanning electron microscope. Histological analysis was used to observe the adhesion between ameloblasts and residual organic matrix of the enamel. Quantitative real-time polymerase chain reaction (qRT-PCR) was used to analyze the expression of enamel matrix protein. ResultsThe enamel of mandibular molars in caMAP3K7-overexpressing mice displayed pigmentation and a highly irregular structure compared with the wild type littermates. Teeth of transgenic animals underwent rapid attrition due to the brittleness of the enamel layer. The microstructure of enamel, normally a highly ordered arrangement of hydroxyapatite crystals, was completely disorganized. The gross histological appearances of ameloblasts and supporting cellular structures, as well as the expression of the enamel protein amelotin (Amtn) were altered by the overexpression of caMAP3K7. ConclusionsOur data demonstrated that protein expression, processing and secretion occurred abnormally in transgenic mice overexpressing caMAP3K7. The overexpression of caMAP3K7 had a profound effect on enamel structure by disrupting the orderly growth of enamel prisms.

Physical versus Biological Control in Bivalve Calcite Prisms: Comparison of Euheterodonts and Pteriomorphs.

Multiple groups of bivalve molluscs produce calcitic shell layers, many of these broadly classified as "prismatic." Various pteriomorphian bivalves (such as oysters, pterioids, and mussels) secrete prismatic microstructures with high organic content and clear, strong biological control. However, we present the results of a detailed analysis by scanning electron microscopy (SEM), thermogravimetric analysis, and electron backscatter diffraction to characterize the calcitic prisms in two different clades within the euheterodont bivalves: the extant Chama arcana and the extinct rudists. These results show that the form of prisms constructed is both closely similar between the two taxa and significantly different from those of the pteriomorph bivalves. Most notably, C. arcana and the extinct rudists lack the clear organic outer envelopes and uniform polygonal, cross-sectional appearance. Instead, they form interdigitating crystals of very varied diameters, with some crystals encapsulating others. We advocate retaining the term "fibrillar prisms" to classify these euheterodont microstructures. These fibrillar prisms are more closely similar to abiotic speleothem deposits than to the calcitic prisms of pteriomorph bivalves. We argue that calcite prism growth in euheterodonts is dominated by abiotic constraints whereas, in pteriomorphs (such as oysters, pterioids, and mussels), it is under strong biological control.

Prismatic morphology of an ADP crystal grown in a defined crystallographic direction

The prismatic growth micro-morphologies of ADP and Cr3+-doped ADP in a defined crystallographic direction were explored by atomic microscopy (AFM) measurements.

Lateral epitaxial overgrowth of ZnO layers on hexagonally patterned buffer layers in low-temperature aqueous solution

Abstract In conjunction with lift-off patterning and thermal annealing, we have fabricated hexagonal arrays of epitaxial ZnAl2O4 buffer layers on sapphire substrates. Taking advantage of the small lattice mismatch between ZnO (0001) and ZnAl2O4 (111), site-controlled epitaxial growth of ZnO prisms occurred on the pre-patterned, lattice-matched buffer layers. Subsequently, using a continuous flow reactor, long-duration maskless lateral epitaxial overgrowth (LEO) of ZnO prisms led to coalescence into continuous, thick layers within aqueous solutions at low temperature. X-ray diffraction (XRD) confirmed that LEO on the hexagonally patterned buffer layers facilitated the fabrication of strain-relieved, wing-tilt-free, thick ZnO layers. The dislocation density at the coalesced LEO-grown ZnO layer was approximately 108 cm−2. The spatial variation in the micro-photoluminescence characteristics of the LEO-grown layer suggested that the improvement in crystalline quality occurred in the overgrown wings, originating from the decrease in dislocation in the ZnO layer during the LEO process.

Nonlinear optical response of nanocomposites based on KDP single crystal with incorporated Al2O3*nH2O nanofibriles under CW and pulsed laser irradiation at 532 nm

Optical properties and nonlinear optical response due to the CW and pulsed laser radiation self-action at 532nm were studied in composites based on KDP single crystals with incorporated nanofibriles of nanostructured oxyhydroxide of aluminum (NOA). It was shown a high optical quality and structural homogeneity of nanocomposites KDP:NOA by the transmittance spectra, elastic optical scattering and XRD analysis. It was observed manifestation of the second harmonic generation efficiency enhancement in the KDP:NOA versus the nominally pure KDP (λ=1064nm, τ=1ns) that is correlated with efficient refractive index self-modulation Δn∼10−4 (λ=532nm, τ=30ps). In the pyramidal and prismatic growth sectors of the nominally pure KDP crystal it was shown opposite signs of the photoinduced variations both of the refractive index and of the optical absorption/bleaching due to resonant excitation of the native defects at 532nm. It should be considered for the wide-aperture laser frequency KDP family based convertors fabrication.

Growth, structure peculiarities, and dielectric properties of ferroelectric KDP/TiO2 single crystals

Potassium dihydrogen phosphate KH2PO4 (KDP) single crystals, both pure and with incorporated titanium dioxide TiO2 nanoparticles, are ferroelectric materials with dipole structure used in nonlinear optics, optoelectronics, and acoustooptics. To date, a comprehensive analysis of structural features and defect states in the KDP and KDP/TiO2 matrix is absent in literature data. Pure KH2PO4 (KDP) single crystals and KDP/TiO2 crystals with different TiO2 nanoparticles with anatase structure, synthesized by the sulfate and chloride methods, and with η-TiO2 structure, prepared by the sulfate method, grown by the temperature lowering method and cut from the pyramidal and prismatic growth sectors, have been investigated by the X-ray diffraction methods and by EDX spectroscopy. According to the energy-dispersive X-ray microanalysis, the sulfur content is higher in the sample with η-TiO2 and in the KDP/η-TiO2 crystal if compared with the samples with anatase and KDP/TiO2 (anatase). It was revealed that the sulfur content is higher in the prismatic growth sector if compared with the pyramidal one. Based on results of the X-ray single-crystal diffraction analysis, it is possible to assume the substitution of \( \text{PO}_{4}^{3 - } \) tetrahedra by \( \text{SO}_{4}^{2 - } \) ones in the KDP/TiO2 structures, which is greater in KDP/η-TiO2. The general composition of the KDP/η-TiO2 crystal from the prismatic growth sector with the highest titanium content can be written as \( (\text{K}_{0.950(1)} \square_{0.050} )\text{Ti}_{0.052\left( 2 \right)i} \left( {\text{H}_{2 - x}^{1 + } \square_{x} } \right)\left[ {\left( {\text{PO}_{4} } \right)_{y}^{3 - } \left( {\text{SO}_{4}^{2 - } } \right)_{1 - y} } \right] (\square \text{ - vacancies}). \) It was first found that the Ti4+ ions occupy the interstitial site (−0.048, 0.045, 0.550) in the KDP crystal matrix. Analysis of frequency-dependant dielectric characteristics revealed that the incorporation of TiO2 nanoparticles reduces the dielectric permittivity values of KDP/TiO2 samples compared with the pure KDP ones. It was found that the KDP/η-TiO2 sample has the smallest value of the dielectric permittivity.

Defects and Their Distribution in KH2PO4 Crystals with Embedded TiO2 Nanoparticles

ABSTRACTResults from the successful growth of high quality KH2PO4 (KDP) crystals with incorporated TiO2 anatase nanoparticles and the characterization of these crystals using several complementary methods are presented. Transmission and scanning electron microscopy have shown that the anatase nanoparticles were captured mainly by the pyramidal growth sector and, to a considerably lesser extent, by the prismatic growth sector. Energy dispersive x-ray analysis confirms that the growth layer stacks contain the TiO2 particles. Significant variation in the imaginary and real parts of the cubic nonlinear optical susceptibilities and refractive index changes at continuous wave excitation were found in prism and pyramid parts of pure KDP and KDP:TiO2 samples. The identified lines of electron paramagnetic resonance belong to four different centers FeA3+, FeB3+, CrR3+ and CrGB3+. From analysis of line intensities it was concluded that the concentration of non-controlled impurities in nominally pure KDP samples is several times larger than in KDP:TiO2, and that the concentration of non-controlled impurities in the prismatic part of the KDP:TiO2 boule is larger than in the pyramidal part.

Evidence of a Biological Control over Origin, Growth and End of the Calcite Prisms in the Shells of Pinctada margaritifera (Pelecypod, Pterioidea)

Consistently classified among the references for calcite simple prisms, the microstructural units that form the outer layer of the Pinctada margaritifera have been investigated through a series of morphological, crystallographical and biochemical characterizations. It is often said that the polygonal transverse shape of the prisms result from the competition for space between adjacent crystals. In contrast to this classical scheme the Pinctada prisms appear to be composed of four successive developmental stages from the concentrically growing disks on the internal side of the periostracum to the morphological, structural and compositional changes in both envelopes and mineral components at the end of the prisms. These latest structural and compositional changes predate nacre deposition, so that the end of prism growth is not caused by occurrence of nacre, but by metabolic changes in the secretory epithelium. This sequence makes obvious the permanent biological control exerted by the outer cell layer of the mantle in both organic envelopes and mineralizing organic phases.