Spherulitic Grains Research Articles

Seismic faulting and CO2-rich fluid interactions: Evidence from carbonate spherulitic grains in ultramafic fault damage zones

Faults and shear zones in the metamorphic ultramafic rocks of the Voltri Massif (Ligurian Alps, NW Italy) are often accompanied by intense or complete carbonation of the host rocks. One of these fault zones, hosted in peridotite and serpentinite, is characterized by distinctive structural features that can be related to a fluid-assisted multistage brittle deformation, indicative of paleoseismic activity. The fault rocks contain cataclasite and breccias with layers of coseismic spherulitic grains of dolomitic composition, silica/calchedony veins and cement, and saponite bearing gouge. The fault is part of a system of regional structures associated with gold mineralization in quartz veins and various stages of hydrothermal alterations.Here we present a multiscale study of this fault zone combining field observations, microstructural analysis, SEM-EDS, and electron backscattered diffraction (EBSD). Focus is on the microstructures of the fault core and the significance of the characteristic carbonate spherulite layers in association with silica/chalcedony cement and veins. Our results show that these structures are indicative of the interaction between CO2-rich fluids released during coseismic and interseismic phases of faulting, i.e., during cycles of fluid pressure build-ups, faulting, fluid flushing, and mineral precipitation and sealing during seismic failure of the fault.

Solution‐Processed, Highly Crystalline, and Oriented MAPbI3 Thin Films by Engineering Crystal‐Growth Kinetics

Growing oriented and monocrystalline layers of lead halide perovskites over device substrates helps to harness their outstanding optoelectronic properties. Epitaxial growth of lead halide perovskites for device fabrication is limited by the lack of lattice‐matched substrates and the requirement of compact pinhole‐free films. Most optoelectronic devices use amorphous substrates, hindering oriented epitaxial growth. Herein, highly crystalline methylammonium lead iodide (MAPbI3) thin films over amorphous substrates are demonstrated by meticulously optimizing the nucleation and growth kinetics in spin‐coating. The “epitaxial‐like” films enable large‐area crystalline layer fabrication, with larger than 100 μm spherulitic grains oriented along [200] and [224] planes. The compact, highly crystalline, and oriented films of MAPbI3 formed over indium tin oxide/SnO2 are used to fabricate perovskite solar cells (PSCs) with an area of 1 cm2. Despite the perovskite films being highly oriented and crystalline, the PSCs’ performances highlight the critical role the interfaces play in photovoltaic cells.

From Amorphous to Polycrystalline Rubrene: Charge Transport in Organic Semiconductors Paralleled with Silicon

AbstractWhile progress has been made in the design of organic semiconductors (OSCs) with improved transport properties, the understanding of the mechanisms involved is still limited, hindering further development. In this study, the interplay between structural order and transport considering one single OSC, analogous to past research on silicon is investigated. Rubrene (C42H28) is selected as it spans transport mechanisms from thermally activated hopping in its amorphous form to band‐like in highly ordered crystals in the orthorhombic polymorph. Transport characterizations including variable temperature conductivity, advanced Hall effect, and magnetoresistance measurements are performed on rubrene films with varying levels of order (polycrystalline vs amorphous), crystal phase (orthorhombic vs triclinic), and morphologies (platelet‐like vs spherulitic grains). A conductivity tuning range over four orders of magnitude between polycrystalline (platelet‐like) orthorhombic and amorphous films is reported. As observed in silicon, transport in polycrystalline orthorhombic rubrene is limited by energy barriers at grain boundaries. Additionally, a gradual transition from predominantly band‐like to predominantly hopping transport with increasing disorder, reminiscent of observations in silicon is shown. Nevertheless, OSCs differ from covalently bonded silicon by their weak intermolecular interaction. This study highlights that molecular packing must be optimized in OSCs to favor advantageous π‐orbital overlap and optimized transport properties.

Co–Mn Mineralisations in the Ni Laterite Deposits of Loma Caribe (Dominican Republic) and Loma de Hierro (Venezuela)

Cobalt demand is increasing due to its key role in the transition to clean energies. Although the main Co ores are the sediment-hosted stratiform copper deposits of the Democratic Republic of the Congo, Co is also a by-product of Ni–Co laterite deposits, where Co extraction efficiency depends, among other factors, on the correct identification of Co-bearing minerals. In this paper, we reported a detailed study of the Co mineralisation in the Ni–Co laterite profiles of Loma Caribe (Dominican Republic) and Loma de Hierro (Venezuela). Cobalt is mainly associated with Mn-oxyhydroxide minerals, with a composition between Ni asbolane and lithiophorite, although a Co association with phyllosilicates has also been recorded in a Loma de Hierro deposit. In Loma Caribe, Co-bearing Mn-oxyhydroxide minerals mainly developed colloform aggregates, and globular to spherulitic grains, while in Loma de Hierro, they displayed banded colloform, fibrous or tabular textures. Most of the compositional analyses of Mn-oxyhydroxides yielded 20 and 40 wt.% Mn, with Ni and Co up to 16 and 10 wt.%, respectively. In both profiles, Mn-bearing minerals were mainly found in the transition from the oxide horizon to the saprolite, as observed in other laterite profiles in the world, where the precipitation of Mn-bearing minerals is enhanced because of the pore solution saturation and pH increase.

Preparation, characterization, and electrochemical properties of PEO/PVDF blend films

This paper reports the electrochemical properties of PEO, PEO/PVDF10, and PEO/PVDF30 blend films, The XRD spectra reveal the structural properties of the blend and, FTIR spectra provide the chemical interaction between the blends, and observed FESEM images of PEO/PVDF blend film shows the porous with spherulite grain structure and AFM images gives the surface topology. The thermal stability, melting point, and decomposes of the polymer blend film were examined through TGA, DTA, and DSC. CV curve shows the proper oxidation and redox reaction involved in the blend film, these results provide the prepared polymer blend film is a good candidate for used to the separator in energy storage applications.

Mechanically treated vermiculite particles in PCL/vermiculite thin films

In this study, we investigated the influence of mechanically treated vermiculite particles obtained from ball (VB) and jet (VBj) milling on the structure, morphology, crystallinity, phase and thermal stability of a polycaprolactone (PCL)/vermiculite thin films prepared in CHCl3 environment. Three concentrations (1, 3 and 5 %) of the VB and VBj particles in the PCL matrix was evaluated by optical microscope, scanning electron microscope, X-ray diffraction, thermogravimetric analysis and Fourier transforms infrared spectroscopy. The wettability of PCL/vermiculite thin films was investigated by the water contact angle and the glycerol contact angle, which did not exceed 71°. The experimental results revealed that VBj particles showed high interaction with PCL matrix, when increasing concentration affected the PCL spherulite morphology, the spherulite grain size decreased to the 20 µm, as well as crystallinity decreased to the 48.2 % and at the same time the arrangement of VBj particles in PCL matrix increased. It was observed that VB and VBj particles does not affect the wettability of the PCL/vermiculite thin films. Likewise, the presence of these clay fillers has no effect on thermal stability of prepared PCL/vermiculite thin films.

Characterization of Eocene flint

Eocene flint 48–56.0 million years old (mya) from the Negev desert (Israel) was characterized using a suite of analytical techniques. High-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) of the inorganic component showed the texture, morphology, size, and distribution of two silica polymorphs: α–quartz and moganite. While euhedral forms were attributed to α-quartz, moganite crystals were comprised of spherulitic grains. An electron less-dense amorphous material (no scattering under SAED) was found between the siliceous crystallites. Energy dispersive X-rays (EDS) and electron energy loss spectroscopy (EELS) demonstrated that this electron less-dense amorphous material is composed solely of carbon. Low vacuum, low energy backscattered environmental scanning electron microscopy (BSE-eSEM) imaging of flint surfaces showed the presence of micrometer-sized organic inclusions randomly distributed throughout the siliceous matrix. Energy-dispersive X-ray studies (EDS) demonstrated that these organic micro-inclusions were composed of carbon, sulfur, and nitrogen with a C/N ratio attributed to marine sources. These micro-inclusions were not directly associated with hard-shell fossils. BSE-eSEM imaging conditions allowed the identification of entrapped carbon-rich organic material, which is not possible when applying commonly used electron microscopy conditions that require carbon coating and high acceleration voltages, rendering carbon-rich features electron-transparent. Phase contrast-enhanced micro-computed tomography (PC-μCT) showed that these organic micro-inclusions were randomly distributed throughout the siliceous matrix.Time-of-flight secondary ion mass spectrometry (ToF-SIMS), nano-Fourier transform infrared spectroscopy (nano-FTIR), and scanning probe microscopy (SPM) were used to further characterize these organic micro-inclusions. These three in situ analytical techniques with nanometer resolution provided complementary information on the chemical composition and structure of the organic material. Specifically, ToF-SIMS analysis revealed amino acid and hydrocarbon mass spectra fingerprints inside the organic micro-inclusions. While the former were exclusively found in the organic micro-inclusions, the mass spectral fingerprints for hydrocarbons were also found in the siliceous matrix in agreement with the HR-TEM/EDS/EELS results, where pure carbon was found between the siliceous nanocrystals. While ToF-SIMS provides chemical information, it does not provide structural information. Nano-FTIR analysis showed the presence of amide I and II infrared vibrations exclusively on the organic micro-inclusions. The scanning probe microscopy (SPM) techniques Peak Force Quantitative Nanomechanics (PF-QNM) and Contact Resonance Atomic Force Microscopy (CR-AFM) were used to assess the mechanical properties. PF-QNM measurements on the organic micro-inclusions, under dry and liquid conditions, demonstrated that the organic micro-inclusions swell upon hydration and soften, pointing toward the presence of hydrophilic molecules in agreement with nano-FTIR and ToF-SIMS results. CR-AFM allows in situ determination of the mechanical properties of materials with high stiffness at nanometer resolution. This technique, rarely used in a geological context, revealed that the organic micro-inclusions had an unusually high stiffness atypical for modern organic material, which was attributed to molecular cross-linking promoted by diagenesis.This work provided a comprehensive view of the inorganic and organic components of Eocene flint from the Negev desert with implications for paleontology and archaeology. It offers a roadmap of novel complementary techniques that can be used in the exploration of entrapped organic material in flint.

Study of local structure at crystalline rubrene grain boundaries via scanning transmission X-ray microscopy

Abstract Rubrene is a promising and archetypal organic semiconductor owing to its high reported hole mobility. However, this high mobility only exists in its crystalline state, with orders of magnitude reduction in disordered films. Thus, as it pertains to thin film polycrystalline rubrene, it is important to understand structure and the presence of disordered regions at grain boundaries. Here, we use scanning transmission X-ray microscopy (STXM) to investigate polycrystalline rubrene thin films with either platelet or spherulite morphology. The STXM images allow us to distinguish and quantify the arrangement of the local structure in the crystal. The analysis suggests that the platelet film has more oriented molecules in the crystal than in the spherulite phase. Also, at spherulite grain boundaries, we reveal a high number of misaligned molecules compared to the smooth boundary in the platelet case, with grain boundary sinuosity of 0.045 ± 0.002 and 0.139 ± 0.002 μm for the platelet and spherulite cases, respectively, which help to explain the higher mobility in the former case.

Effects of walnut shell powders on the morphology and the thermal and mechanical properties of poly(lactic acid)

Poly(lactic acid) (PLA) has good environmental compatibility, however, its high brittleness, slow rate of crystallization, and low heat distortion temperature restrict its widespread use. To overcome these limitations, in this study, PLA was mixed with walnut shell (WS) powders. The effects of WS powders on the morphology and the thermal and mechanical properties of PLA were investigated. The products were characterized by differential scanning calorimetry (DSC), infrared (IR) spectroscopy, polarizing optical microscopy (POM), and various mechanical property testing techniques. The results showed that WS powders had a significant effect on the morphology and the thermal and mechanical properties of PLA. The tensile strength, impact strength, and elongation at break of the PLA/WS composites first increased and then decreased with the increasing addition of WS powders. When the addition of WS powders was about 0.5 wt%, they reached maximum values of 51.2 MPa, 23.3 MPa, and 19.0%, respectively. Compared with neat PLA, the spherulite grain size of the composites could be reduced and many irregular polygons were formed during crystallization. The melting, cold crystallization, and glass-transition temperatures of the composites were lower than those of neat PLA.

A depositional model for spherulitic carbonates associated with alkaline, volcanic lakes

The South Atlantic Aptian ‘Pre-salt’ reservoirs are formed by a combination of spherulitic carbonates and Mg-rich clays accumulated in volcanic alkaline lake settings with exotic chemistries. So far, outcrop analogues characterised by metre-thick successions deposited in lacustrine scenarios are elusive so disentangling the genesis of spherulitic carbonates represents a major scientific challenge with business impact. In particular the controls on spatial distribution and the environment of spherulitic facies formation remain poorly constrained, little studied, and hotly debated. To shed light on this conundrum, a spherulitic carbonate-rich, alkaline volcanic lacustrine succession has been analysed at outcrop scale: the Carboniferous East Kirkton Limestone (Scotland). Despite clays being very scarce and limited to layers of amorphous Mg-Si minerals, a diverse array of spherulitic calcitic components were formed, including coated grains, crusts, and build-ups. This setting enables the mechanisms of spherulitic calcite development and the patterns of sediment accumulation to be explored in a geobiological and hydrochemical scenario similar to the ‘Pre-Salt’ subsurface occurrences but divorced from clay influence. The integration of logs, borehole data, outcrop photomosaics and petrographic observations collectively allowed the reconstruction of a depositional model for the East Kirkton lacustrine succession. In this model, calcite spherule nucleation took place at the sediment-water interface in the littoral zone, driven by the co-occurrence of 1) high alkalinity, 2) Ca-Mg rich hydrochemistry, and 3) microbial-derived colloidal exopolymeric substances. These environmental conditions permitted the coeval development of spherulitic cementstone build-ups and spherulitic grainstone-packstone within the wave-agitated zone, and the accumulation of floatstones and laminites of spherulitic grains in deeper lake regions by means of downslope reworking. This model is consistent with the previously documented microbial bloom occurrences and highlights the need to better understand the complex ‘microbe-solution’ interactions before any reliable facies model is envisaged.

Rotating lattice single crystal architecture on the surface of glass.

Defying the requirements of translational periodicity in 3D, rotation of the lattice orientation within an otherwise single crystal provides a new form of solid. Such rotating lattice single (RLS) crystals are found, but only as spherulitic grains too small for systematic characterization or practical application. Here we report a novel approach to fabricate RLS crystal lines and 2D layers of unlimited dimensions via a recently discovered solid-to-solid conversion process using a laser to heat a glass to its crystallization temperature but keeping it below the melting temperature. The proof-of-concept including key characteristics of RLS crystals is demonstrated using the example of Sb2S3 crystals within the Sb-S-I model glass system for which the rotation rate depends on the direction of laser scanning relative to the orientation of initially formed seed. Lattice rotation in this new mode of crystal growth occurs upon crystallization through a well-organized dislocation/disclination structure introduced at the glass/crystal interface. Implications of RLS growth on biomineralization and spherulitic crystal growth are noted.

Structure and Properties in Synthetic MSUM and the Corresponding Biomaterial

At the MRS Fall 2014 Meeting, Symposium E, we reported on morphologies, fragmentation, and hardness in synthetic hydrogen urate monohydrate (monosodium urate monohydrate, MSUM, or MSU) crystals. We are now presenting further characterization results, including some from the biomaterial that forms in humans with gout disease: The fanning of radiating blades (needles) in spherulitic grains of synthetic MSUM was examined by microscopy techniques. These and previous data are consistent with an interpretation in terms of the crystallographic parameters in the unit cell, and the presence of dislocation arrays at low angle boundaries. The kinetics of such branched growth is here related to thermodynamic properties and super-saturation levels. Secondary nucleation is an additional mechanism leading to more complex morphologies. Differences in overall growth rates, under conditions of either branched or single needle growth, are considered in relation to gout. Novel powder XRD and solid state NMR data show, respectively, preferred orientation in the biomaterial, and the potential of NMR for identifying and characterizing MSUM in specific environments, helping to resolve pending questions in gout. Present results are anticipated to be useful for designing bio-inspired and bio-mimetic materials, regarding morphologies, overall growth rates, and mechanical properties.

De-vitrification of nanoscale phase-separated amorphous thin films in the immiscible copper–niobium system

Copper and niobium are mutually immiscible in the solid state and exhibit a large positive enthalpy of mixing in the liquid state. Using vapour quenching via magnetron co-sputter deposition, far-from equilibrium amorphous Cu–Nb films have been deposited which exhibit a nanoscale phase separation. Annealing these amorphous films at low temperatures (~200 °C) initiates crystallization via the nucleation and growth of primary nanocrystals of a face-centred cubic Cu-rich phase separated by the amorphous matrix. Interestingly, subsequent annealing at a higher temperature (>300 °C) leads to the polymorphic nucleation and growth of large spherulitic grains of a body-centred cubic Nb-rich phase within the retained amorphous matrix of the partially crystallized film. This sequential two-stage crystallization process has been investigated in detail by combining transmission electron microscopy [TEM] (including high-resolution TEM) and atom probe tomography studies. These results provide new insights into the crystallization behaviour of such unusual far-from equilibrium phase-separated metallic glasses in immiscible systems.

Fabrication and characterization of a biphasic scaffold for osteochondral tissue engineering

A biphasic scaffold with a stratified structure for osteochondral tissue engineering was developed. The chondral phase was a collagen–chitosan composite. The osseous phase was a composite of bioactive glass and collagen. Collagen integrated in the two respective phases was connected by cross-linking agents. Both layers of the scaffold showed interconnected porous structures. After being immersed into stimulated body fluid, precipitation of spherulitic grains could be found on the surface of the osseous phase and this precipitation was proved to be hydroxyapatite by X-ray diffraction and Fourier transform infrared spectroscopy. Inversion, fluorescence and scanning electron microscopy further confirmed that bone marrow stromal cells could anchor on this scaffold with healthy spreading. As the consequence, this biphasic scaffold may have significant potential as an alternative for osteochondral tissue engineering.

The Influence of Film Morphology in High‐Mobility Small‐Molecule:Polymer Blend Organic Transistors

AbstractOrganic field‐effect transistors (OFETs) based upon blends of small molecular semiconductors and polymers show promise for high performance organic electronics applications. Here the charge transport characteristics of high mobility p‐channel organic transistors based on 2,8‐difluoro‐5,11‐bis(triethylsilylethynyl) anthradithiophene:poly(triarylamine) blend films are investigated. By simple alteration of the film processing conditions two distinct film microstructures can be obtained: one characterized by small spherulitic grains (SG) and one by large grains (LG). Charge transport measurements reveal thermally activated hole transport in both SG and LG film microstructures with two distinct temperature regimes. For temperatures >115 K, gate voltage dependent activation energies (EA) in the range of 25–60 meV are derived. At temperatures <115 K, the activation energies are smaller and typically in the range 5–30 meV. For both film microstructures hole transport appears to be dominated by trapping at the grain boundaries. Estimates of the trap densities suggests that LG films with fewer grain boundaries are characterized by a reduced number of traps that are less energetically disordered but deeper in energy than for small SG films. The effects of source and drain electrode treatment with self‐assembled monolayers (SAMs) on current injection is also investigated. Fluorinated thiol SAMs were found to alter the work function of gold electrodes by up to ∼1 eV leading to a lower contact resistance. However, charge transport analysis suggests that electrode work function is not the only parameter to consider for efficient charge injection.

Competition between crystallization and dewetting fronts in thin polymer films

We investigate the competition between dewetting and crystallization fronts in thin polymer films where the velocities of these fronts are modulated by varying the temperature from a low temperature regime, where crystallization dominates, to a high temperature regime, where dewetting is more rapid and dominates the film structure. Specifically, thin films of poly(caprolactone) (PCL) on n-octyldimethylchlorosilane (ODS)-treated substrates are investigated as a model system exhibiting this general phenomenon. Structure formation at low temperatures is dominated by polycrystalline spherulitic structures that nucleate at random positions within the plane of the film, but at intermediate temperatures, where the crystallization and dewetting are strongly coupled, dewetting occurs preferentially at the grain boundaries between the spherulites. We term this phenomenon crystallization-induced dewetting (CID) and provide evidence that it arises from the high stresses at the spherulite grain boundaries that accompany local volume changes of the polymer material upon crystallization. CID is prevalent in a temperature range in which the angles between the grains are larger than a critical angle and this effect allows for considerable control over the resulting film morphology.

Preparation of hafnium oxide thin films by sol–gel method

Hafnium oxide (HfO2) films were grown on SiO2/Si substrates by a sol–gel method, and their crystalline structure, microstructure and electrical properties were investigated. X-ray diffraction analysis indicated that the monoclinic HfO2 films could be obtained by annealing at 500 °C. A transmission electron microscopy (TEM) image showed that the films were grown as a spherulite grain structure with a mean grain size of approximately 15 nm. The dielectric constant of the HfO2 films of 300 nm was approximately 21.6, and the current–voltage measurements showed that the leakage current density of the HfO2 films was approximately 1.14 × 10−5 A/cm2 at an applied electric field of 100 kV/cm. The sol–gel method-fabricated HfO2 films are concluded to be feasible for MEMS applications, such as capacitive-type MEMS switches.

Crystalline phases, microstructures and electrical properties of hafnium oxide films deposited by sol–gel method

Hafnium oxide (HfO 2) films were grown on SiO 2/Si and Pt/Ti/SiO 2/Si substrates by a sol–gel method, and their crystalline structure, microstructure and electrical properties were investigated. XRD analysis indicated that the monoclinic HfO 2 films can be obtained by annealing at 500 °C. A transmission electron microscopy (TEM) image showed that the films were grown as a spherulite grain structure with a mean grain size of approximately 15 nm. The dielectric constant of the HfO 2 films of 300 nm was approximately 21.6, and the current–voltage measurements showed that the leakage current density of the HfO 2 films was approximately 1.14×10 −5 A/cm 2 at an applied electric field of 100 kV/cm.

Low-temperature growth of high-quality lead zirconate titanate thin films by 28 GHz microwave irradiation

Pb ( Zr x Ti 1 − x ) O 3 (PZT) thin films were coated on Pt/Ti/SiO2/Si substrates by a sol-gel method and then crystallized by 28 GHz microwave irradiation. The elevated temperature generated by microwave irradiation to obtain the perovskite phase is only 480 °C, which is significantly lower than that of conventional thermal processing. X-ray diffraction analysis indicated that the PZT films crystallized well in the perovskite phase. A scanning electron microscopy image showed that the film has a spherulite grain structure and most of the grains are approximately 2 μm in size. The average values of the remanent polarization, coercive field, dielectric constant, and loss of the PZT films are 40μC∕cm2, 50 kV/cm, 1100, and 004, respectively. It is clear that microwave irradiation is effective for obtaining well-crystallized PZT films with good properties at low temperatures.

Sequential growth of early diagenetic freshwater siderites in the Holocene coastal deposits, Korea

Spherulitic siderite grains ranging from 100 to 250 μm in diameter occur abundantly in a sediment layer, which is almost 8600 years old, in Namyang Bay, on the west coast of Korea. These large siderite grains consist predominantly of FeCO 3 (average 65%) and MnCO 3 (average 22%) and have low Mg/Ca and Mg/Fe ratios. Compositional scatter plots, together with the high Mn and low Mg contents, indicate that meteoric pore water was mainly involved in the siderite precipitation. Examination of the siderite grains with an electron microprobe reveals a systematic, micron-scale, center-to-margin compositional variation within individual grains. Three zones are recognized on the basis of the compositional variations: Zone I (center) in which Mn decreases and Fe increases, Zone II (intermediate) in which Mn increases and Fe decreases, and Zone III (outer) in which both Mn and Fe decrease and Mg increases. This zoning is interpreted as a result of depth-related early diagenetic reactions with different Fe, Mn, and Mg concentrations in the sediment pore waters. Meanwhile, compositional mapping of spherulitic grains implies that a siderite grain consists of numerous tiny siderite precipitates. Such dust-like tiny siderite precipitates appear to be adhered to the large spherulitic siderite grain. In some cases, large siderite grains are adjoined together and occurred as a siderite aggregate. We suggest that a spherulitic siderite grain is growing sequentially by adhering of numerous tiny siderite precipitates formed in each diagenetic zone onto the siderite grain like the formation of a snowball.