Measurements Of Bulk Properties Research Articles

Magnetic order in holmium and erbium formate: Parent frameworks for a potential random spin chain paramagnet

This work uses a combination of neutron diffraction and bulk property measurements to establish the low temperature magnetic states in the dense metal-organic frameworks Ho(HCO2)3 and Er(HCO2)3; whose structures feature chains of face-sharing LnO9 polyhedra packed into a triangular lattice. Below 0.7 K Ho(HCO2)3 is found to adopt a state in which the magnetic moment on its ferromagnetic chains vary from neighbouring chains but the sum around each triangle is constant. Er(HCO2)3 is found to be the first lanthanide formate to adopt an ordered magnetic state with antiferromagnetic coupling within its chains near 50 mK. The potential to combine the ferromagnetic and antiferromagnetic coupling within chains associated with Ho and Er cations, respectively, in the same compound has also been explored via the series Ho1-xErx(HCO2)3. Ho0.5Er0.5(HCO2)3 remains paramagnetic to 0.4 K, suggesting it may be a starting point to search for a random spin chain paramagnet.

Application of Machine Learning for Predicting Bulk Behaviour of Active Pharmaceutical Ingredients

The aim of this study was to develop models for predicting powder bulk behaviour from particle properties using machine learning methods. The data consisted of various measurements of particle size, shape, and bulk properties for different active pharmaceutical ingredients. Python libraries were used to pre-process the data, select input features, and train. The models were evaluated using leave-one-out cross-validation and r2 scores. The results showed that the models could predict the flow function coefficient (FFC), bulk density, porosity, and tap density with moderate to high accuracy. However, the models exhibited low prediction accuracy for FT-4 rheometer descriptors. The study demonstrated the feasibility and limitations of using machine learning for powder bulk behaviour prediction.

Evaluation of particle models of corn kernels for discrete element method simulation of shelled corn mass flow

Bulk handling behavior of grains can be studied experimentally, but large-scale investigations of grain flow especially at the commercial scale are expensive, time consuming, and are therefore limited in the treatment factors that can be evaluated in any one study. Recent research has demonstrated the potential of discrete element method (DEM) in simulating grain flow in handling operations. However, application of DEM for simulating grain flow, requires development of appropriate particle models for each grain type. In this study, particle models comprised of one to four overlapping spheres were developed for shelled corn and tested. With these models, measurement of bulk properties, namely bulk density and angle of repose, both involving bulk flow were simulated using EDEM™ software with published data of material and interaction properties of shelled corn as inputs associated with each particle shape. Predicted time for the complete outflow from the bulk density test hopper (hopper emptying time), designated as simulation time in the study, was also recorded as another discriminant for model selection. Variable inputs into the simulation modeling were material properties particle shape, particle size distribution, Poisson's ratio, shear modulus, and density and interaction properties particle coefficients of restitution, static friction, and rolling friction. Computation time is critical in DEM modeling so single sphere particle models were emphasized over multi-sphere particles in the research even though multi-sphere particles represent the corn kernel shape more precisely because their simplicity can provide markedly reduced computation times to complete simulations. Predicted results for hopper emptying time, bulk density, and angle of repose were compared to experimental results or published data to select the most appropriate particle models for simulating bulk behavior of corn kernels in free-flowing grain applications using DEM. From the study, the most appropriate particle model (particle shape/physical properties combination) for corn kernels involved a single-sphere shape particle shape with a particle coefficient of restitution of 0.30, particle coefficients of static friction of 0.30 for corn-corn contact and 0.20 for corn-steel contact, particle coefficient of rolling friction of 0.05, normal particle size distribution with a standard deviation factor of 0.4, and particle shear modulus of 20 MPa.

Low-Dimensional Metal-Organic Magnets as a Route toward the S = 2 Haldane Phase.

Metal-organic magnets (MOMs), modular magnetic materials where metal atoms are connected by organic linkers, are promising candidates for next-generation quantum technologies. MOMs readily form low-dimensional structures and so are ideal systems to realize physical examples of key quantum models, including the Haldane phase, where a topological excitation gap occurs in integer-spin antiferromagnetic (AFM) chains. Thus, far the Haldane phase has only been identified for S = 1, with S ≥ 2 still unrealized because the larger spin imposes more stringent requirements on the magnetic interactions. Here, we report the structure and magnetic properties of CrCl2(pym) (pym = pyrimidine), a new quasi-1D S = 2 AFM MOM. We show, using X-ray and neutron diffraction, bulk property measurements, density-functional theory calculations, and inelastic neutron spectroscopy (INS), that CrCl2(pym) consists of AFM CrCl2 spin chains (J1 = -1.13(4) meV) which are weakly ferromagnetically coupled through bridging pym (J2 = 0.10(2) meV), with easy-axis anisotropy (D = -0.15(3) meV). We find that, although small compared to J1, these additional interactions are sufficient to prevent observation of the Haldane phase in this material. Nevertheless, the proximity to the Haldane phase together with the modularity of MOMs suggests that layered Cr(II) MOMs are a promising family to search for the elusive S = 2 Haldane phase.

Production of pions, kaons, and (anti-)protons in Au+Au collisions at √SNN = 54.4 GeV at RHIC

We report systematic measurements of bulk properties of the system created in Au+Au collisions at √SNN = 54.4 GeV recorded by the STAR detector at the Relativistic Heavy Ion Collider (RHIC). The transverse momentum spectra of π±, K±, and p(p¯) are studied at mid-rapidity (|y| < 0.1) for different centrality classes. We also present mid-rapidity measurement of particle yields (dN/dy) and particle ratios in Au+Au collisions at √SNN = 54.4 GeV. The kinetic freeze-out parameters (Tkin and β>) are extracted from particle spectra using the blast-wave model, and all the results are compared with previously published experimental results.

Wettability-based ultrasensitive detection of amphiphiles through directed concentration at disordered regions in self-assembled monolayers

Various forms of ecological monitoring and disease diagnosis rely upon the detection of amphiphiles, including lipids, lipopolysaccharides, and lipoproteins, at ultralow concentrations in small droplets. Although assays based on droplets' wettability provide promising options in some cases, their reliance on the measurements of surface and bulk properties of whole droplets (e.g., contact angles, surface tensions) makes it difficult to monitor trace amounts of these amphiphiles within small-volume samples. Here, we report a design principle in which self-assembled monolayer-functionalized microstructured surfaces coated with silicone oil create locally disordered regions within a droplet's contact lines to effectively concentrate amphiphiles within the areas that dominate the droplet static friction. Remarkably, such surfaces enable the ultrasensitive, naked-eye detection of amphiphiles through changes in the droplets' sliding angles, even when the concentration is four to five orders of magnitude below their critical micelle concentration. We develop a thermodynamic model to explain the partitioning of amphiphiles at the contact line by their cooperative association within the disordered, loosely packed regions of the self-assembled monolayer. Based on this local analyte concentrating effect, we showcase laboratory-on-a-chip surfaces with positionally dependent pinning forces capable of both detecting industrially and biologically relevant amphiphiles (e.g., bacterial endotoxins), as well as sorting aqueous droplets into discrete groups based on their amphiphile concentrations. Furthermore, we demonstrate that the sliding behavior of amphiphile-laden aqueous droplets provides insight into the amphiphile's effective length, thereby allowing these surfaces to discriminate between analytes with highly disparate molecular sizes.

Enhanced Representation of Thermal Cracking Chemistry in the Context of Bitumen Partial Upgrading

A detailed modeling framework to describe thermal cracking reactions during bitumen partial upgrading on a molecular basis is put forward in this study. The first block of the framework describes the molecular composition of a whole bitumen feedstock using statistical distributions in conjunction with structural descriptors for hydrocarbon classes, including solubility parameters to distinguish asphaltene components. The creation of a molecular ensemble mimicking the bitumen feedstock is accomplished via Monte Carlo simulation using input information from bulk property measurements and advanced analytical methods. This ensemble of molecules forms the starting point of the conversion model, which is the second block. Thermal cracking chemistry is organized in terms of reaction families, such as carbon–carbon bond cracking, sulfur–carbon bond cracking, dehydrogenation, and condensation, and the reactivity parameters are approximated using structure–reactivity correlations. Because of its considerable size, the reaction network is generated on the fly by means of a kinetic Monte Carlo algorithm, whereby molecule cracking reactions progress one by one over time. Reactivity parameters are tuned against an experimental data set generated in a visbreaking pilot plant. Besides describing the evolution of yield structure under different cracking severities, the model is able to track changes in API gravity, asphaltene content, and molecular distributions. Most importantly, the model explains how the different molecular reaction pathways impact product properties relevant to bitumen partial upgrading and provides directional predictions into other aspects of these technologies, such as product solubility and formation of olefins.

Evolution of microscopic strains, stresses, and dislocation density during in-situ tensile loading of additively manufactured AlSi10Mg alloy

The AlSi10Mg alloy produced by laser powder bed fusion (LPBF) possesses a novel microstructure and higher mechanical properties compared with its casting counterpart. So far, the crystallographic orientation-dependent lattice strains, average phase stresses, and dislocation density during the tensile loading of the LPBF AlSi10Mg are not well understood. This fact is impeding further optimization of microstructure and mechanical properties. High energy synchrotron X-ray diffraction providing deep penetration capability and phase-specific measurements of various bulk properties of crystal materials is applied to investigate the LPBF AlSi10Mg under loading. The crystallographic orientation-dependent lattice strains and elastoplastic properties of the Al matrix are assessed. The average phase stresses are calculated to quantify load partitioning between the Al and Si phases. The nano-sized Si particles that bear high-stress are efficient strengthening particles. The maximum value of the average phase stress of Si reaches up to ~2 GPa. Based on the modified Williamson-Hall and the modified Warren-Averbach methods, the dislocation density and its evolution during the plastic deformation are determined. A multistage strain hardening behavior is detected in the Al matrix, which is associated with the interactions between the dislocations and the cell boundary network.

Flocculation and magnetically-assisted sedimentation of size-sorted beidellite platelets mixed with maghemite nanoparticles

In this study, the flocculation and the subsequent decantation step of mixed suspensions of 10 nm-sized γ-Fe2O3 magnetic nanoparticles and 500 nm-sized beidellite clay platelets was investigated. This work may find application in the field of water treatment, specifically the flocculation processes with magnetically assisted sedimentation. After a short description of the preparation and characterization of the raw materials (nanoparticles and clays), the influence of several parameters (pH, concentrations of nanoparticles and clays etc.) on the amount of flocculated materials was examined, which gave information on the concentration ranges allowing a complete flocculation, together with a better understanding on the interactions between nanoparticles and clays responsible for flocculation. The optimal conditions for magnetically assisted settling were then determined by comparing for each sample sedimentation velocities under gravity and in the presence of a Nd-Fe-B magnet. Finally, the complex multiscale structure of the flocs in water was explored, through the measurement of several bulk properties (zeta-potential and volume measurements, laser granulometry), while the organization of the materials at a microscopic scale was investigated by cryo-transmission electron microscopy (cryo-TEM) and small-angle X-ray scattering (SAXS).

Simultaneous characterization of poly(acrylic acid) and polysaccharide polymers and copolymers.

Copolymer products that result from grafting acrylic acid and other hydrophilic monomers onto polysaccharides have recently gained significant interest in research and industry. Originating from renewable sources, these biodegradable, low toxicity, and polar copolymer products exhibit potential to replace polymers from fossil sources in several applications and industries. The methods usually employed to characterize these copolymers are, however, quite limited, especially for the measurement of bulk properties. With more sophisticated applications, for example, in pharmaceutics requiring a more detailed analysis of the chemical structure, we describe a new approach for this kind of complex polymers. Our approach utilizes chromatography in combination with several detection methods to separate and characterize reaction products of the copolymerization of acrylic acid and chemically hydrolyzed starch. These samples consisted of a mixture of homopolymer poly (acrylic acid), homopolymer hydrolyzed starch, and - in a lower amount - the formed copolymers. Several chromatographic methods exist that are capable of characterizing either poly (acrylic acid) or hydrolyzed starch. In contrast, our approach offers simultaneous characterization of both polymers. The combination of LC and UV/RI offered insight into the composition and copolymer content of the samples. Size exclusion chromatography experiments revealed the molar mass distribution of homopolymers and copolymers. FTIR investigations confirmed the formation of copolymers while ESI-MS gave more details on the end groups of hydrolyzed starches and poly (acrylic acids). Evidence of copolymer structures was obtained through NMR measurements. Finally, two-dimensional chromatography led to the separation of the copolymers from both homopolymers as well as the additional separation of sodium clusters. The methods described in this work are a powerful toolset to characterize copolymerization products of hydrolyzed starch and poly(acrylic acid). Together, our approach successfully correlates the physicochemical properties of such complex mixtures with their actual composition.

Crystal-field Hamiltonian and anisotropy in KErSe2 and CsErSe2

We use neutron scattering and bulk property measurements to determine the single-ion crystal-field Hamiltonians of delafossites $\rm KErSe_2$ and $\rm CsErSe_2$. These two systems contains planar equilateral triangular Er lattices arranged in two stacking variants: rhombohedral (for K) or hexagonal (Cs). Our analysis shows that regardless the stacking order both compound exhibit an easy-plane ground state doublet with large $J_z=1/2$ terms and the potential for significant quantum effects, making them candidates for quantum spin liquid or other exotic ground states.

Bulk properties of the system formed in Au+Au collisions at sNN=14.5 GeV at the BNL STAR detector

We report systematic measurements of bulk properties of the system created in Au+Au collisions at $\sqrt{s_{\mathrm{NN}}}$ = 14.5 GeV recorded by the STAR detector at the Relativistic Heavy Ion Collider (RHIC).The transverse momentum spectra of $\pi^{\pm}$, $K^{\pm}$ and $p(\bar{p})$ are studied at mid-rapidity ($|y| < 0.1$) for nine centrality intervals. The centrality, transverse momentum ($p_T$),and pseudorapidity ($\eta$) dependence of inclusive charged particle elliptic flow ($v_2$), and rapidity-odd charged particles directed flow ($v_{1}$) results near mid-rapidity are also presented. These measurements are compared with the published results from Au+Au collisions at other energies, and from Pb+Pb collisions at $\sqrt{s_{\mathrm{NN}}}$ = 2.76 TeV. The results at $\sqrt{s_{\mathrm{NN}}}$ = 14.5 GeV show similar behavior as established at other energies and fit well in the energy dependence trend. These results are important as the 14.5 GeV energy fills the gap in $\mu_B$, which is of the order of 100 MeV,between $\sqrt{s_{\mathrm{NN}}}$ =11.5 and 19.6 GeV. Comparisons of the data with UrQMD and AMPT models show poor agreement in general.

Ultrasensitive Three-Dimensional Orientation Imaging of Single Molecules on Plasmonic Nanohole Arrays Using Second Harmonic Generation.

Recently, fluorescence-based super-resolution techniques such as stimulated emission depletion (STED) and stochastic optical reconstruction microscopy (STORM) have been developed to achieve near molecular-scale resolution. However, such a super-resolution technique for nonlinear label-free microscopy based on second harmonic generation (SHG) is lacking. Since SHG is label-free and does not involve real-energy level transitions, fluorescence-based super-resolution techniques such as STED cannot be applied to improve the resolution. In addition, due to the coherent and non-isotropic emission nature of SHG, single-molecule localization techniques based on isotropic emission of fluorescent molecule such as STORM will not be appropriate. Single molecule SHG microscopy is largely hindered due to the very weak nonlinear optical scattering cross sections of SHG scattering processes. Thus, enhancing SHG using plasmonic nanostructures and nanoantennas has recently gained much attention owing to the potential of various nanoscale geometries to tightly confine electromagnetic fields into small volumes. This confinement provides substantial enhancement of electromagnetic field in nanoscale regions of interest, which can significantly boost the nonlinear signal produced by molecules located in the plasmonic hotspots. However, to date, plasmon-enhanced SHG has been primarily applied for the measurement of bulk properties of the materials/molecules, and single molecule SHG imaging along with its orientation information has not been realized yet. Herein, we achieved simultaneous visualization and three-dimensional (3D) orientation imaging of individual rhodamine 6G (R6G) molecules in the presence of plasmonic silver nanohole arrays. SHG and two-photon fluorescence microscopy experiments together with finite-difference time-domain (FDTD) simulations revealed a ∼106-fold nonlinear enhancement factor at the hot spots on the plasmonic silver nanohole substrate, enabling detection of single molecules using SHG. The position and 3D orientation of R6G molecules were determined using the template matching algorithm by comparing the experimental data with the calculated dipole emission images. These findings could enable SHG-based single molecule detection and orientation imaging of molecules which could lead to a wide range of applications from nanophotonics to super-resolution SHG imaging of biological cells and tissues.

Imaging the local electronic and magnetic properties of intrinsically phase separated RbxFe2–ySe2 superconductor using scanning microscopy techniques

The discovery in 2008 of the iron-based superconducting pnictide and chalcogenide compounds has provided an entirely new family of materials for studying the crucial interplay between superconductivity and magnetism in unconventional superconductors. The alkali-metal-intercalated iron selenide (AxFe2−ySe2, A = alkali metal) superconductors are of particular interest owing to their relatively high transition temperatures over 30 K and the co-existence of the superconducting state with antiferromagnetic ordering. Intrinsic phase separation on the mesoscopic scale is known to occur in ‘single crystals’ of these compounds, adding to the complexity of interpretation of bulk property measurements. In this study, we investigate the local electronic structure and chemistry of RbxFe2−ySe2 crystals using scanning microscopy techniques. Nano-focussed angle-resolved photoemission spectroscopy has enabled the band structure of the minority superconducting phase and the non-superconducting matrix to be measured independently and linked to the surface chemistry from the same regions using core level spectroscopy. Valence band mapping reveals the characteristic microstructure of these crystals, but does not have sufficient spatial resolution to enable the precise morphology of the superconducting phase to be elucidated. Cryogenic magnetic force microscopy has shown that the superconducting phase has a fine-scale stripey morphology that was not resolved in the scanning photoemission spectroscopy experiment. The correlation of these findings with previous microstructural studies, bulk measurements and first-principles density functional theory calculations paves the way for understanding the intriguing electronic and magnetic properties of these compounds.

Retention of a Paramagnetic Ground State at Low Temperatures in a Family of Structurally Related UIV Phosphates.

A new uranium fluoride phosphate, UFPO4, was synthesized via a mild hydrothermal route and characterized optically, thermally, and magnetically. Two thermal transformation products, U2O(PO4)2 and UIVUVIO2(PO4)2, were discovered to be structurally related, and were subsequently synthesized for bulk property measurements. All three materials failed to follow Curie-Weiss behavior at low temperatures, attributed to the nearly ubiquitous singlet ground state of U(IV), transitioning into a Curie-Weiss paramagnetic regime at high temperatures. Neutron diffraction experiments were performed on UFPO4 and UIVUVIO2(PO4)2 in order to characterize this unusual magnetic behavior.

Probing Intercell Variability Using Bulk Measurements.

The measurement of noise is critical when assessing the design and function of synthetic biological systems. Cell-to-cell variability can be quantified experimentally using single-cell measurement techniques such as flow cytometry and fluorescent microscopy. However, these approaches are costly and impractical for high-throughput parallelized experiments, which are frequently conducted using plate-reader devices. In this paper we describe reporter systems that allow estimation of the cell-to-cell variability in a biological system's output using only measurements of a cell culture's bulk properties. We analyze one potential implementation of such a system that is based upon a fluorescent protein FRET reporter pair, finding that with typical parameters from the literature it is able to reliably estimate variability. We also briefly describe an alternate implementation based upon an activating sRNA circuit. The feasible region of parameter values for which the reporter system can function is assessed, and the dependence of its performance on both extrinsic and intrinsic noise is investigated. Experimental realization of these constructs can yield novel reporter systems that allow measurement of a synthetic gene circuit's output, as well as the intrapopulation variability of this output, at little added cost.

Magnetic imaging of antiferromagnetic and superconducting phases in RbxFe2−ySe2 crystals

High-temperature superconducting (HTS) cuprate materials, with the ability to carry large electrical currents with no resistance at easily reachable temperatures, have stimulated enormous scientific and industrial interest since their discovery in the 1980's. However, technological applications of these promising compounds have been limited by their chemical and microstructural complexity and the challenging processing strategies required for the exploitation of their extraordinary properties. The lack of theoretical understanding of the mechanism for superconductivity in these HTS materials has also hindered the search for new superconducting systems with enhanced performance. The unexpected discovery in 2008 of HTS iron-based compounds has provided an entirely new family of materials for studying the crucial interplay between superconductivity and magnetism in unconventional superconductors. Alkali-metal-doped iron selenide (${A}_{x}\mathrm{F}{\mathrm{e}}_{2\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{2}, A=\mathrm{alkali}\phantom{\rule{0.28em}{0ex}}\mathrm{metal}$) compounds are of particular interest owing to the coexistence of superconductivity at relatively high temperatures with antiferromagnetism. Intrinsic phase separation on the mesoscopic scale is also known to occur in what were intended to be single crystals of these compounds, making it difficult to interpret bulk property measurements. Here, we use a combination of two advanced microscopy techniques to provide direct evidence of the magnetic properties of the individual phases. First, x-ray linear dichroism studies in a photoelectron emission microscope, and supporting multiplet calculations, indicate that the matrix (majority) phase is antiferromagnetic whereas the minority phase is nonmagnetic at room temperature. Second, cryogenic magnetic force microscopy demonstrates unambiguously that superconductivity occurs only in the minority phase. The correlation of these findings with previous microstructural studies and bulk measurements paves the way for understanding the intriguing electronic and magnetic properties of these compounds.

Bulk properties of the medium produced in relativistic heavy-ion collisions from the beam energy scan program

We present measurements of bulk properties of the matter produced in Au+Au collisions at sNN=7.7,11.5,19.6,27, and 39 GeV using identified hadrons (π±, K±, p, and p¯) from the STAR experiment in the Beam Energy Scan (BES) Program at the Relativistic Heavy Ion Collider (RHIC). Midrapidity (|y|<0.1) results for multiplicity densities dN/dy, average transverse momenta 〈pT〉, and particle ratios are presented. The chemical and kinetic freeze-out dynamics at these energies are discussed and presented as a function of collision centrality and energy. These results constitute the systematic measurements of bulk properties of matter formed in heavy-ion collisions over a broad range of energy (or baryon chemical potential) at RHIC.31 MoreReceived 25 January 2017DOI:https://doi.org/10.1103/PhysRevC.96.044904©2017 American Physical SocietyPhysics Subject Headings (PhySH)Research AreasParticle & resonance productionQCD phase transitionsQuark-gluon plasmaRelativistic heavy-ion collisionsThermal & statistical modelsNuclear Physics

Supercritical Fluid Extraction of Fluid Catalytic Cracking Slurry Oil: Bulk Property and Molecular Composition of Narrow Fractions

The supercritical fluid extraction and fractionation (SFEF) method has the capacity of separating heavy petroleum residue into fractions with different processabilities. Different from traditional heavy residue feedstock, slurry oil (SLO) is a heavy liquid product from the fluid catalytic cracking (FCC) process, and there is concern for its potential application in producing carbonaceous materials. The high-value utilization of FCC SLO depends upon the aromatic and contaminate contents in the feedstock. The present study aimed to extend the SFEF method to the FCC SLO system and investigate the property and molecular composition distribution of derived fractions. A FCC SLO was subject to the SFEF process and separated into 13 extract fractions with each 5 wt % yield and 1 unextracted end cut. Systematic bulk property measurements, including boiling point distribution, density, molecular weight, viscosity, and carbon residue, were performed on each fraction. Hydrocarbon molecules in different fractions were...

Magnetic Instabilities in Non-Fermi Liquid Ce&lt;sub&gt;3&lt;/sub&gt;Pd&lt;sub&gt;4&lt;/sub&gt;Si&lt;sub&gt;4&lt;/sub&gt; Driven by Magnetic Dilution

Materials which are close to a quantum critical point are rather prone to magnetic instabilities; even small modifications of relevant interaction mechanisms can be responsible for a magnetic phase transition to occur at finite temperatures. In this work it is demonstrated that actually a substitution of Ce by non-magnetic La in Ce3Pd4Si4 drives a magnetic instability, with ordering temperatures as high as 10 K. To trace the evolution of magnetism and the onset of long range magnetic order in Ce3-xLaxPd4Si4, various bulk property measurements were carried out.