Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “crystallization”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Crystal Growth of Quaternary RE 2 EuSi 2 S 8 ( RE = Ce–Nd, Sm, Gd, Tb) Using Flux-Assisted Boron Chalcogen Mixture (BCM) Method: Investigation of Magnetic and Luminescence Properties

A series of quaternary rare-earth containing thiosilicates with the general formula RE 2 EuSi 2 S 8 (RE = Ce–Nd, Sm, Gd, Tb) has been synthesized via the flux-assisted boron chalcogen mixture (BCM) crystal growth method. High-quality single crystals were obtained, and their crystal structures were determined by single-crystal X-ray diffraction. The RE 2 EuSi 2 S 8 series crystallizes in the trigonal system, adopting the space group R-3c. Polycrystalline samples were employed for physical property measurements, including magnetic susceptibility measurements, UV–visible diffuse reflectance, and photoluminescent response. Magnetic data of RE 2 EuSi 2 S 8 ( RE = Ce, Nd, and Gd) were collected over the 2–300 K temperature range. The samples were paramagnetic behavior with negative Weiss constants (θ W = −11.05, −10.55, and −1.35 K respectively). Their thermal stability was investigated using thermogravimetric analysis (TGA). Optical band gaps, estimated from diffuse reflectance spectra, were determined to be 2.2(1) eV for Ce 2 EuSi 2 S 8 , 1.8(1) eV for Nd 2 EuSi 2 S 8 , and 1.7(1) eV for Gd 2 EuSi 2 S 8 respectively. Finally, photoluminescence measurements were collected on Ce 2 EuSi 2 S 8 and Tb 2 EuSi 2 S 8 single crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Identifying Order and Disorder in Double Four-Membered Rings via Raman Spectroscopy during Crystallization of LTA Zeolite

Fluoride (F – ) has been essential for the synthesis of low-defect siliceous zeolites. It has been hypothesized that F – balances the positive charges from organic structure-directing agents (OSDAs) and stabilizes key building units during zeolite crystallization such as the double four-membered ring (D4R). However, due to the lack of characterization techniques for investigating medium-range structures, including rings and cages formed during zeolite crystallization, the roles of F – in stabilizing building units and maintaining local charge balance during zeolite assembly are not yet fully understood. Here, the crystallization of siliceous Linde type A (LTA) zeolite in the presence of F – was investigated using Raman spectroscopy and periodic density functional theory (DFT) calculations. We have discovered that the F – -filled double four-membered ring (F – /D4R) and the empty D4R exhibit rather distinct Raman features. Both the F – /D4R and empty D4R are formed in the LTA zeolite synthesized in the presence of F – using 1,2-dimethyl-3-(4-methylbenzyl) imidazolium as the OSDA. Observed Raman bands of the F – /D4R and empty D4R, along with predictive DFT calculations on LTA supercells, reveal an ordered distribution of these two D4R units in the final as-made LTA zeolite. The discovery of these distinct Raman signatures of F – /D4R and empty D4R units opens an interesting new window for studying defects in the D4R during zeolite formation. In particular, we have observed variation in Raman intensities of F – /D4R and empty D4R bands during LTA crystallization; periodic DFT calculations indicate that the observed Raman behavior is consistent with empty D4R units containing one or two Si vacancies surrounded by Q 3 Si—consistent also with solid-state nuclear magnetic resonance measurement. These defects appear to heal during further crystallization, leading to the formation of defect-free LTA zeolite crystals. Altogether, our results provide deeper understanding on the roles of F – in charge balancing and stabilizing intact D4R units during zeolite formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Spatiotemporal Route to Understanding Metal Halide Perovskitoid Crystallization

Here, a spatiotemporal experimental route is reported for the antisolvent vapor diffusion crystal growth of metal halide perovskitoids. A computational analysis combining automated image capture and diffusion modeling enables the determination of the critical concentrations required for nucleation and crystal growth from a single experiment. Five different solvent systems and ten distinct organic ammonium iodide salts were investigated with lead iodide, from which nine previously unreported compounds were discovered. Automated image capture of the mother liquor and antisolvent vials was used to determine changes in solution meniscus positions and detect the nucleation event location. Matching the observations to a numerical solution of Fick's second law diffusion model enables the calculation of reactant, solvent, and antisolvent concentrations at both the time and position of the first stable nucleation and crystal growth. A machine learning model was trained on the resulting data, and it reveals solvent- and amine-specific crystallization tendencies. Solvent systems that interact more weakly with dissolved lead species promote crystallization, while those with stronger interactions can prevent crystallization through increased solubilities. Organic amines that interact more strongly with inorganic components and exhibit greater rigidity are more likely to be incorporated into crystalline products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Structural Transformation and Chemical Stability of a Shock-Compressed Insensitive High Explosive Single Crystal: Time-Resolved Raman Spectroscopy

Despite the considerable interest in insensitive high explosives (IHE) as a safer alternative to conventional high explosives, a good understanding of the low sensitivity of IHEs to shock initiation is lacking. In particular, real-time measurements to directly probe the molecular-level response of shock compressed IHE single crystals constitute an important need. To address this need, plate impact experiments were conducted to determine time-resolved changes in the Raman spectra of 1,1-diamino-2,2-dinitroethene (FOX-7) single crystals – a representative IHE crystal – shock compressed up to 20 GPa longitudinal stress. The Raman measurements examined vibrational frequencies from 800 cm-1 to 1500 cm-1 with 15 nanosecond time resolution and were conducted at several peak stresses. At 4 – 6 GPa, two new Raman peaks appeared, in addition to the original peaks, consistent with onset of the α' – ε structural transformation reported previously in static compression work. The measured spectra indicated completion of the transformation at 10 GPa. Raman data to 20 GPa showed neither additional transformations nor any indication of chemical decomposition. This finding, though consistent with recent continuum measurements, is in marked contrast to the chemical decomposition observed at lower stresses in shock compressed conventional high explosive single crystals. Our Raman results support the previous suggestion that strengthening of intra- and inter-molecular bonds, due to the α' – ε structural transformation, plays a significant role in the insensitivity of FOX-7 single crystals to shock initiation. In conclusion, the present work, in conjunction with previous static compression studies, provides the first experimental insight into the molecular-level response of a shock compressed IHE single crystal and can serve as a bench mark for theoretical studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

ReaxFF Parameter Set for Boron Clusters and Icosahedral Boron Crystals: Comparison with Density Functional Theory and Machine-Learning Potentials

Icosahedral boron materials, which include regular icosahedra of 12 boron atoms have gained increasing attention due to their potential applications as superhard materials, semiconductors, and energy storage media. However, the synthesis of high quality crystals of these materials has been a major barrier to the development of these applications. To enable computational prediction of synthesis conditions yielding high-quality icosahedral boron crystals, herein we tested and refined a set of ReaxFF parameters for the nucleation and growth of such crystals. We focused on matching the relative energies of small boron clusters obtained by density functional theory since such small clusters and similar motifs are likely present in crystal nuclei and at the interface of growing crystals. Using a training set of B 80 clusters, including a low-energy core–shell structure containing a B 12 icosahedron core and a high-energy single-shell structure produced in preliminary ReaxFF simulations, the ReaxFF parameter set was refined to better reproduce energies calculated by density functional theory (DFT). Among existing ReaxFF parameter sets and the machine-learning interatomic potentials MACE-MP-0, MACE-MP-0b3, MACE-MPA-0, PFP v7.0.0, and SevenNet-MF-ompa, only our new parameter set and PFP v7.0.0 correctly ranked these B 80 clusters. This refinement led to improved agreement with DFT for a test set of 58 clusters consisting of 8–103 boron atoms. Furthermore, our refined parameter set yielded greater local icosahedral structure than the previously existing ReaxFF parameter set for larger scale simulations of crystallization from supercooled liquid boron. Additionally, simulations of solid boron in contact with molten nickel using our refined ReaxFF parameters yielded a boron solubility value that agrees moderately well with experimental expectations, while the previous boron parameters gave a value that was much too low.

boron↗
DOE OSTI2024

Crystallization of Bottlebrush Statistical Copolymers of Polystyrene and Poly(ethylene oxide)

Here, bottlebrush statistical copolymers (BSCPs) with poly(ethylene oxide) (PEO) and polystyrene (PS) side chains grafted to a polynorbornene (PNB) backbone were synthesized by ring-opening metathesis polymerization (ROMP). The impact of the glassy PS side chains on the crystallization of the PEO side chains as a function of the backbone length, grafting densities, and fraction of the PS and PEO side chains is described. The bottlebrush architecture, where the side chains are anchored to the backbone, inherently constrains the mobility of PEO. Compared with the bulk crystallization temperature of PEO, the higher glass transition temperature of PS places further constraints on PEO crystallization. The limited mobility of PEO leads to cold crystallization behavior during heating. Reduced grafting densities, in turn, reduce side-chain crowding, leading to less extended pendant structures. The degree of crystallinity of PEO was found to decrease at lower grafting densities to a point where crystallization was not observed. The average distance between bottlebrush backbones increased linearly with the backbone length, suggesting that the backbone forms a distinct mesodomain. For BSCPs with asymmetric volume fractions of PS and PEO side chains, the degree of crystallinity of PEO increases with a change from cold crystallization to normal nucleation and growth during cooling, as a result of reduced constraints on PEO mobility by the glassy PS side chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Crystallization Mechanisms of Poly(vinylidene Fluoride- co -chlorotrifluoroethylene): Nucleation Transitions, Growth Kinetics, and Microstructure Evolution

The crystallization kinetics of FK-800, a commercial semicrystalline copolymer of chlorotrifluoroethylene and vinylidene fluoride (poly(CTFE-co-VDF)), dictate its microstructure and functional performance. Crystallization occurs between the glass transition (T g ≈ 31 °C) and melting point (T m ≈ 110 °C), with grain boundaries playing a key role in applications such as memristors, where they regulate filament growth. This study integrates in situ atomic force microscopy (AFM), grazing-incidence wide-angle X-ray scattering (GIWAXS), and differential scanning calorimetry (DSC) to characterize nucleation, growth, and morphology across the full crystallization window. Hot-stage AFM reveals a transition from homogeneous to heterogeneous nucleation near 45 °C and a shift from reaction-limited to diffusion-limited growth above 60 °C. Kinetics are analyzed using Lauritzen–Hoffman, Turnbull–Fisher, and Avrami models to extract surface free energies and activation barriers. A multiscale modeling framework is developed in which nucleation densities and growth rates measured by AFM are used to reconstruct Avrami kinetics, which are then validated against coverage data, and extrapolated to predict bulk crystallization behavior observed by DSC. GIWAXS confirms a primarily flat-on chain orientation at all temperatures, linking orientation to domain morphology. This integrative approach quantitatively connects nanoscale crystallization dynamics with macroscopic phase evolution, establishing a quantitative framework for modeling crystallization across time, temperature, and length scales.

Crystallization↗
DOE OSTI2018

Random Copolymers Allow Control of Crystallization and Microphase Separation in Fully Conjugated Block Copolymers

Thin films of fully conjugated donor–acceptor block copolymers composed of an electron donating block and an electron accepting block can be used as single component photoactive layers in organic photovoltaic (OPV) devices. In order to realize their full potential, control over microphase separation and thin-film morphology are critical. In conjugated block copolymer systems where one or more blocks can crystallize, the morphological evolution is governed by the competition between microphase separation and crystallization. In this work, we control crystallization of fully conjugated block copolymers with a random copolymer block. Additionally, we suppress the crystal packing of poly(3-hexylthiophene-2,5-diyl) (P3HT) through the insertion of a small number of 3-octylthiophene (3OT) units within the chains, yielding poly(3-hexylthiophene-2,5-diyl- random -3-octylthiophene-2,5-diyl) (P[3HT- r -3OT]). Furthermore, while crystallization of P3HT dominates the morphology and prevents microphase separation in poly(3-hexylthiophene-2,5-diyl)- block -poly((9,9-dioctylfluorene-2,7-diyl)- alt -(4,7-di(thiophene-2-yl)-2,1,3-benzothiadiazole)-5',5"-diyl) (P3HT- b -PFTBT), modest levels of 3OT suppress crystallization in P[3HT- r -3OT]- b -PFTBT, and permit microphase separation. Thus, we demonstrate that incorporating a random copolymer into a donor–acceptor block copolymer can increase control over microphase separation and lead to enhanced performance in OPV devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photonic Crystal Waveguides for >90% Light Trapping Efficiency in Luminescent Solar Concentrators

Luminescent solar concentrators are currently limited in their potential concentration factor and solar conversion efficiency by the inherent escape cone losses present in conventional planar dielectric waveguides. Here, we demonstrate that photonic crystal slab waveguides tailored for luminescent solar concentrator applications can exhibit >90% light trapping efficiency. This is achieved by use of quantum dot luminophores embedded within the waveguide that absorb light at photon energies corresponding to photonic crystal leaky modes that couple to incoming sunlight. The luminophores then emit at lower photon energies into photonic crystal bound modes that enable highly efficient light trapping in slab waveguides of wavelength-scale thickness. Photonic crystal waveguides thus nearly eliminate escape cone losses, and overcome the performance limitations of previously proposed wavelength-selective dielectric multilayer filters. We describe designs for hole-array and rod-array photonic crystals comprised of hydrogenated amorphous silicon carbide using CdSe/CdS quantum dots. Our analysis suggests that photonic crystal waveguide luminescent solar concentrators using these materials these can achieve light trapping efficiency above 92% and a concentration factor as high as 100.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Symmetry-Breaking Dendrimer Synthons in Colloidal Crystal Engineering with DNA

Breaking symmetry in colloidal crystals is challenging due to the inherent chemical and structural isotropy of many nanoscale building blocks. If a non-particle component could be used to anisotropically encode such building blocks with orthogonal recognition properties, one could expand the scope of structural and compositional possibilities of colloidal crystals beyond what is thus far possible with purely particle-based systems. In this work, we report the synthesis and characterization of novel DNA dendrimers that function as symmetry-breaking synthons, capable of programming anisotropic and orthogonal interactions within colloidal crystals. When the DNA dendrimers have identical sticky ends, they hybridize with DNA-functionalized nanoparticles to yield three distinct colloidal crystals, dictated by dendrimer size, including a structure not previously reported in the field of colloidal crystal engineering, Si 2 Sr. When used as symmetry-breaking synthons (when the sticky ends deliberately consist of orthogonal sequences), the synthesis of binary and ternary colloidal alloys with structures that can only be realized through directional interactions is possible. Furthermore, by modulating the extent of shape anisotropy within the DNA dendrimers, the local distribution of the nanoparticles within the crystals can be directed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Two-photon excited deep-red and near-infrared emissive organic co-crystals

Abstract Two-photon excited near-infrared fluorescence materials have garnered considerable attention because of their superior optical penetration, higher spatial resolution, and lower optical scattering compared with other optical materials. Herein, a convenient and efficient supramolecular approach is used to synthesize a two-photon excited near-infrared emissive co-crystalline material. A naphthalenediimide-based triangular macrocycle and coronene form selectively two co-crystals. The triangle-shaped co-crystal emits deep-red fluorescence, while the quadrangle-shaped co-crystal displays deep-red and near-infrared emission centered on 668 nm, which represents a 162 nm red-shift compared with its precursors. Benefiting from intermolecular charge transfer interactions, the two co-crystals possess higher calculated two-photon absorption cross-sections than those of their individual constituents. Their two-photon absorption bands reach into the NIR-II region of the electromagnetic spectrum. The quadrangle-shaped co-crystal constitutes a unique material that exhibits two-photon absorption and near-infrared emission simultaneously. This co-crystallization strategy holds considerable promise for the future design and synthesis of more advanced optical materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Flower-shaped 2D crystals grown in curved fluid vesicle membranes

Abstract The morphologies of two-dimensional (2D) crystals, nucleated, grown, and integrated within 2D elastic fluids, for instance in giant vesicle membranes, are dictated by an interplay of mechanics, permeability, and thermal contraction. Mitigation of solid strain drives the formation of crystals with vanishing Gaussian curvature (i.e., developable domain shapes) and, correspondingly, enhanced Gaussian curvature in the surrounding 2D fluid. However, upon cooling to grow the crystals, large vesicles sustain greater inflation and tension because their small area-to-volume ratio slows water permeation. As a result, more elaborate shapes, for instance, flowers with bendable but inextensible petals, form on large vesicles despite their more gradual curvature, while small vesicles harbor compact planar crystals. This size dependence runs counter to the known cumulative growth of strain energy of 2D colloidal crystals on rigid spherical templates. This interplay of intra-membrane mechanics and processing points to the scalable production of flexible molecular crystals of controllable complex shape.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Novel ferroelectric single crystals of Bi(Zn{sub 1/2}Ti{sub 1/2})O{sub 3}-PbZrO{sub 3}-PbTiO{sub 3} ternary solid solution

Ferroelectric single crystals of a new lead-reduced Bi(Zn{sub 1/2}Ti{sub 1/2})O{sub 3}-PbZrO{sub 3}-PbTiO{sub 3} (BZT-PZ-PT) ternary solid solution system have been grown for the first time by three different methods, namely high temperature solution growth (HTSG, or flux method), top-cooled solution growth (TCSG), and top-seeded solution growth (TSSG). The chemical and thermodynamic parameters, including the flux concentration, the soaking temperature and the cooling rate, have been optimized, leading to the growth of good quality BZT-PZ-PT crystals of pseudo-cubic morphology. A large size crystal of the dimensions of 2 × 2 × 0.5 cm{sup 3} has been obtained by the TSSG technique. The crystal structure is analyzed by means of X-ray powder diffraction. The highest ferroelectric Curie temperature T{sub C} of the grown crystals is found to be 320 °C by means of dielectric measurements. A remnant polarization of 32 μC/cm{sup 2} is displayed with a coercive field of 15.4 kV/cm. The high T{sub C} and large coercive field of the BZT-PZ-PT single crystal make this material a promising candidate for applications in high power electromechanical transducers that can operate in a wider temperature range and at high fields.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Copper doping of ZnO crystals by transmutation of {sup 64}Zn to {sup 65}Cu: An electron paramagnetic resonance and gamma spectroscopy study

Transmutation of {sup 64}Zn to {sup 65}Cu has been observed in a ZnO crystal irradiated with neutrons. The crystal was characterized with electron paramagnetic resonance (EPR) before and after the irradiation and with gamma spectroscopy after the irradiation. Major features in the gamma spectrum of the neutron-irradiated crystal included the primary 1115.5 keV gamma ray from the {sup 65}Zn decay and the positron annihilation peak at 511 keV. Their presence confirmed the successful transmutation of {sup 64}Zn nuclei to {sup 65}Cu. Additional direct evidence for transmutation was obtained from the EPR of Cu{sup 2+} ions (where {sup 63}Cu and {sup 65}Cu hyperfine lines are easily resolved). A spectrum from isolated Cu{sup 2+} (3d{sup 9}) ions acquired after the neutron irradiation showed only hyperfine lines from {sup 65}Cu nuclei. The absence of {sup 63}Cu lines in this Cu{sup 2+} spectrum left no doubt that the observed {sup 65}Cu signals were due to transmuted {sup 65}Cu nuclei created as a result of the neutron irradiation. Small concentrations of copper, in the form of Cu{sup +}-H complexes, were inadvertently present in our as-grown ZnO crystal. These Cu{sup +}-H complexes are not affected by the neutron irradiation, but they dissociate when a crystal is heated to 900 °C. This behavior allowed EPR to distinguish between the copper initially in the crystal and the copper subsequently produced by the neutron irradiation. In addition to transmutation, a second major effect of the neutron irradiation was the formation of zinc and oxygen vacancies by displacement. These vacancies were observed with EPR.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Electron microscopy study of Ni induced crystallization in amorphous Si thin films

The crystallization of amorphous silicon is studied by transmission electron microscopy. The effect of Ni on the crystallization is studied in a wide temperature range heating thinned samples in-situ inside the microscope. Two cases of limited Ni source and unlimited Ni source are studied and compared. NiSi{sub 2} phase started to form at a temperature as low as 250°C in the limited Ni source case. In-situ observation gives a clear view on the crystallization of silicon through small NiSi{sub 2} grain formation. The same phase is observed at the crystallization front in the unlimited Ni source case, where a second region is also observed with large grains of Ni{sub 3}Si{sub 2}. Low temperature experiments show, that long annealing of amorphous silicon at 410 °C already results in large crystallized Si regions due to the Ni induced crystallization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Growth and characterization of nonlinear optical single crystal: Nicotinic L-tartaric

Nonlinear optical single crystals were grown from Nicotinic and L-Tartaric acid by slow evaporation technique at room temperature. Structure of the grown crystal was confirmed by single crystal X-ray diffraction studies, The crystallinity of the Nicotinic L-Tartaric (NLT) crystals was confirmed from the powder XRD pattern. The transparent range and cut off wavelength of the grown crystal was studied by the UV–Vis spectroscopic analysis.The thermal stability of the crystal was studied by TG-DTA. The second harmonic generation (SHG) efficiency of NLT was confirmed by Kurtz Perry technique.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Growth and studies of cyclohexylammonium 4-methoxy benzoate single crystal for nonlinear optical applications

Cyclohexylammonium 4-Methoxy Benzoate (C4MB) was synthesised and the functional groups were confirmed by FTIR analysis. The purified C4MB (by repeated recrystallisation) was used for single crystal growth. Single crystal of cyclohexylammonium 4-methoxy benzoate was successfully grown by slow evaporation solution growth method at ambient temperature. Structural orientations were determined from single crystal X-ray diffractometer. Optical absorption and cut off wavelength were identified by UV-Visible spectroscopy. Thermal stability of the crystal was studied from thermogravimetric and differential thermal analyses curves. Mechanical stability of the grown crystal was analysed by Vicker’s microhardness tester. The Second Harmonic Generation (SHG) study revealed that the C4MB compound exhibits the SHG efficiency 3.3 times greater than KDP crystal.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Evaluation of DAST and zinc telluride nonlinear crystals for efficient terahertz generation

Terahertz (THz) signal is generated from 4-N, N-dimethylamino-4’-N’-methyl-stilbazolium tosylate (i.e. DAST Crystal) and Zinc telluride (ZnTe) nonlinear crystals by employing 140 fs laser pulses at 800 nm with 80 MHz repetition rate. The semi insulating gallium arsenide photoconductive stripline antennas (gap =5 µm, length = 20 µm) is used as a Terahertz detector. The detected temporal profile of Terahertz radiation generated from DAST crystal is high as compared to ZnTe crystal in terms of amplitude. THz effective bandwidths of these crystals are extended up to 1.1 THz range. The potential of THz generation of DAST and ZnTe crystals are evaluated with respect to incident laser power.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗