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The dynamics of a series of soft colloids comprised of polystyrene cores with poly(N-isopropylacrylamide) (PNIPAM) coronas was investigated by diffusing wave spectroscopy (DWS). The modulus of the coronas was varied by changing the cross-link density and we were able to interpret the results within a hard-soft mapping framework. The soft, swellable particle properties were modeled using an extended Flory-Rehner theory and a Hertzian pair potential. Following volume fraction jumps, softness effects on the concentration dependence of dynamics were determined, with a ‘soft colloids make strong glass-forming liquid’-type of behavior observed close to the nominal glass transition volume fraction, φ g . Such behavior from the current systems cannot be fully explained by the osmotic deswelling model alone. However, inspired by the soft-hard mapping from Schmiedeberg et al, [Europhys. Lett. 2011, 96 (3) , 36010] we estimated effective hard-sphere diameters and achieved a successful mapping of the α-relaxation times to a master curve below φ g . Above φ g , the curves no longer collapse but show strong deviations from a Vogel-Fulcher type of divergence onto soft jamming plateaux. Our results provide evidence that osmotic deswelling itself cannot fully explain the observed dynamics. Softness also plays an important role in the dynamics of soft, concentrated colloids.

The glass transition temperature (Tg) of a binary miscible mixture of molecular glasses, termed a coamorphous glass, is often synergistically increased over that expected for an athermal mixture due to the strong interactions between the two components. This synergistic interaction is particularly important for the formulation of coamorphous pharmaceuticals since the molecular interactions and resulting Tg strongly impact stability against crystallization, dissolution kinetics, and bioavailability. Current models that describe the composition dependence of Tg for binary systems, including the Gordon-Taylor, Fox, Kwei, and Braun-Kovacs equations, fail to describe the behavior of coamorphous pharmaceuticals using parameters consistent with experimental ΔCP and Δα. Here, we develop a robust thermodynamic approach extending the Couchman and Karasz method through the use of activity coefficient models, including the two-parameter Margules, non-random-two-liquid (NRTL), and three-suffix Redlich-Kister models. We find that the models, using experimental values of ΔCP and fitting parameters related to the binary interactions, successfully describe observed synergistic elevations and inflections in the Tg versus composition response of coamorphous pharmaceuticals. Moreover, the predictions from the NRTL model are improved when the association-NRTL version of that model is used. Results are reported and discussed for four different coamorphous systems: indomethacin-glibenclamide, indomethacin-arginine, acetaminophen-indomethacin, and fenretinide-cholic acid.

Crystallization of active pharmaceutical ingredients (APIs) from the supercooled liquid state is an important issue in determining the stability of amorphous pharmaceutical dispersions. In the present study, the isothermal crystallization from the supercooled liquid state of the pharmaceutical compound nifedipine was investigated by both rheological and differential scanning calorimetry (DSC) measurements, and the crystallization kinetics was fitted to the Johnson-Mehl-Avrami (JMA) equation. Both the crystallization induction time and completion time from the two methods were used to construct the time-temperature-transformation (TTT) diagram for nifedipine. A model based on a modification of classical homogeneous nucleation and crystal growth theory was employed to fit the induction and completion time curves. Both DSC and rheological methods give similar results for the crystallization kinetics of the nifedipine. From the crystallization kinetics modeling, the solid-liquid interfacial surface tension σSL of nifedipine was estimated and the value was found to be consistent with prior results obtained from melting point depression measurements as a function of crystal size. Evidence is shown that for temperatures below 110 °C, at the early stage of nucleation, NIF first nucleates into the metastable β'-form and later converts into the stable α-form during the isothermal crystallization. We are also able to report the heat of fusion of the γ'-NIF based on the calorimetric experiments.

Agglomerates of polar molecules in nonpolar solvents are selectively heated by microwave radiation. The magnitude of the selective heating was directly measured by using the temperature dependence of the intensities of the Stokes and anti-Stokes bands in the Raman spectra of p-nitroanisole (pNA) and mesitylene. Under dynamic heating conditions, a large apparent temperature difference (ΔT) of over 100 °C was observed between the polar pNA solute and the nonpolar mesitylene solvent. This represents the first direct measurement of the selective microwave heating process. The magnitude of the selective microwave heating was affected by the properties of the agglomerated pNA. As the concentration of the pNA increases, the magnitude of the selective heating of the pNA was observed to decrease. This is explained by the tendency of the pNA dipoles to orient in an antiparallel fashion in the aggregates as measured by the Kirkwood g value, which decreased with increasing concentration. This effect reduces the net dipole moment of the agglomerates, which decreases the microwave absorption. After the radiation was terminated, the effective temperature of the dipolar molecules returned slowly to that of the medium. The slow heat transfer was modeled successfully by treating the solutions as a biphasic solvent/solute system. Based on modeling and the fact that the agglomerate can be heated above the boiling temperature of the solvent, an insulating layer of solvent vapor is suggested to form around the heated agglomerate, slowing convective heat transfer out of the agglomerate. This is an effect unique to microwave heating.

We report the first observation of electron spin resonance of the bulk charge carriers in 3D topological insulator Bi1.08Sn0.02Sb0.9Te2S. The observed spectra represent the overlay of two different signals from electrons and holes with the g-factors enormously enhanced due to strong spin–orbit coupling typical of topological insulators. The analysis of the ESR lines indicates that the current carriers responsible for the resonance may be organized in electron and hole nanodroplets. It is not excluded that such droplets when residing near the surface may give rise to nonzero back scattering of surface current carriers.

We demonstrate the application of mode-locked mid-infrared dual frequency comb spectroscopy for combustion analysis. With two settings of the same dual-comb system, the measurement spans 1500 cm−1 from 2.8 to 5 µm with 0.0067 cm−1 (200 MHz) point spacing, or almost a quarter-million discrete comb modes. Using this broadband spectrometer, we quantify the pyrolysis and smoldering combustion of wood samples. Specifically, we measure 20-second time-resolved mole fractions of CH4, H2O, two isotopologues of CO2 (12C16O2, 13C16O2), two isotopologues of CO (12C16O, 13C16O), ethane, formaldehyde, methanol, formic acid, as well as gas temperature directly above radiatively heated wood samples. The combination of the fine spectral resolution and the broad bandwidth of the dual-comb spectrometer allows for precise separation of absorption signatures of individual molecules from the congested spectra.

High-pressure gasification processes are important for conversion of solid materials into gaseous fuels and other chemicals. Laser absorption diagnostics are an important means to study these processes, but are challenging to implement due to the extreme temperatures and pressures present in the system. Here, we combine broadband high-resolution dual-comb spectroscopy with an advanced spectral absorption database and a new means for baseline-free absorption spectroscopy analysis to enable measurements of temperature and water vapor concentration in the core of an entrained flow gasifier operating at up to 1700 K and 15 bar. The dual-comb spectrometer measures the absorption of water vapor from 6800 to 7150 cm−1 with a point spacing of 0.0067 cm−1. The bandwidth is helpful for resolving the complex, congested absorption fingerprint of water vapor that is used to determine the species concentrations and temperature. We interpret the spectrum with absorption models based on a database measured under carefully controlled high-temperature conditions with the dual-comb spectrometer. The database includes the pressure broadening, shift, and temperature dependence of these parameters for water vapor in argon, which is the gasifier bath gas. Finally, fitting the absorption model to the data is enabled by modified free induction decay analysis, which is an approach for quantitatively obtaining species and temperature information without determining the baseline intensity of the spectrometer. The baseline-free approach is crucial to success in this environment, where there are no non-absorbing regions of the spectrum to anchor the normalization of the laser intensity as in traditional direct absorption spectroscopy. We demonstrate good agreement with temperatures measured on the reactor core via optical pyrometry, and show that water vapor concentrations in the reactor core did not reach the expected system set points during some experiments.

There has been much recent work investigating the reinforcement of glassy polymers with nanoparticles, and much excitement has been generated by some apparent synergies that suggest reinforcements greater than expected from elastic bound models. Here we show that it is necessary to consider the thermoviscoelastic response of the polymer matrix in nanocomposites (PNCs) to fully understand the reinforcement of the filler. This is especially so because polymer nanocomposites are frequently used at high fractions of the glass transition temperature Tg, where the time dependence of the polymer is significant. Therefore it is a conceptual error to examine the modulus behavior of PNCs via only elastic micromechanics. When the glass transition temperature increases due to the interactions between reinforcement and polymer, it is more reasonable to use a viscoelastic micromechanics approach to estimate the bounds on modulus behavior of PNCs. Here we use new results for grapheme oxide reinforced poly(ethyl methacry...

Grain boundary structures have long been known to depend on factors such as solutes and temperature. In this work, in-situ atomic scale imaging was used to observe the faceting of a Σ21a [1 1 1]-tilt-axis boundary at 600 ∘C and 800 ∘C in a Pt-5Au (at. %) nanocrystalline alloy. With an increase in temperature, we observe an evolution from many, shorter facets to fewer, longer facets. The preferred facets are shown to be symmetrically equivalent tilt boundaries, via the fundamental zone formalism. Simulation of Pt bicrystals reveals that these preferred facets do not lie in an energy minimum (of the tilt boundaries that the grain boundary misorientation could access); however, calculation of the segregation enthalpy of Au to these grain boundary lattice sites indicates a greater preference of Au, reducing the grain boundary energy, and explaining the facet stabilization observed.

Recently, Hor et al. [Hor, J. L., Wang, H., Fakhraai, Z., & Lee, D. (2018). Macromolecules 51 (14), 5069–5078] reported a set of interesting results for the viscosity of unentangled polystyrene of ...

The maximum strength of polycrystalline metals/alloys has been suggested to occur at nanoscale grain sizes where the governing deformation mechanism transitions from dislocation plasticity to grain boundary mediated deformation. Despite tremendous progress recently uncovering links between transitions in nanoscale mechanisms and peak strength, the scientific literature is mostly devoid of any quantitative support, owing to the difficulty in measuring the resolved contribution of individual mechanisms to microstructural strain accommodation. In this study, the contribution of individual nanoscale mechanisms to the overall deformation of nanocrystalline Ni is calculated from atomistic simulations leveraging continuum-based kinematic metrics to compute mechanistic contributions to microstructural strain. By employing such a quantitative approach to analyze deformation behavior, it is shown that the realization of maximum strength in nanocrystalline metals corresponds to a grain size regime where the operative nanoscale mechanisms transition, and are thus equally competing to accommodate strain. However, the transition occurs between intergranular and intragranular mediated mechanisms, as it is found that dislocation plasticity alone is not the governing mechanism at all grain sizes above the peak strength regime.

Ascertaining the mechanism(s) of nanocrystalline stability is a critical need in revealing how specific alloys retard grain growth. Often significant debate exists concerning such mechanisms, even in the same alloy. Here, we compare two processing methods—high-energy ball milling and thin film deposition—in the fabrication and subsequent two-step annealing (500 °C/24 h followed by a temperature ramp to 900 °C whereupon the sample was held for 1 min and quenched) for nanocrystalline Cu–Zr. Using precession electron diffraction (PED) and atom probe tomography (APT), the grain stability and secondary phase content was quantified. The milled powder sample revealed that the Zr solute was largely in an oxide/carbide state after milling with no significant change upon annealing. In contrast, the thin film sample showed nearly all elemental Zr upon deposition but significant oxidation after the vacuum anneal. The significant uptake of oxygen is contributed to the high surface area-to-volume ratio of the film coupled with columnar grains that were enriched in elemental Zr in the as-deposited state. Furthermore, upon sputter deposition, many of these boundaries were vitrified which was lost upon annealing. These glassy boundaries were not observed by PED of the powders. The consequence of when the solute reacts with contaminate species is discussed in relation to nanocrystalline and microstructural stability. The use of Zener pinning predicted grain sizes, based on the quantification of the secondary phase particulates measured by APT, are given to better ascertain their contribution to nanocrystalline stability.

This paper examines the residual stresses generated by laser-assisted cold spray deposition of an iron-based oxide dispersion strengthened alloy (Fe91Ni8Zr1 at.%) on an AISI 1018 mild steel substrate, as well as studies of the effect of the laser heating on the substrate alone. The in-plane residual stress values were determined by X-ray diffraction-based measurements. In the top section of the layers, established at a raster deposition rate of 25 mm/s and simultaneous surface heating temperatures of 650 and 950 °C, stresses were compressive ranging from − 170 to − 440 MPa. For the substrate only study, a larger span of surface temperatures from 350 to 950 °C and scan rates of 5 and 25 mm/s were investigated. Here, the stresses in the laser tracks were tensile, of the order of + 400 MPa, with both “W''- and “M”- shaped profiles about the laser centerline. It was found that the stress profile shape was influenced by the Gaussian power distribution across the laser spot diameter which correlated with microstructural changes (martensite formation) in the substrate.

Improving the properties of durable high-temperature alloys is based on the fundamental understanding of the link between microstructure and three-dimensional (3D) nanochemistry. Here we utilize a complementary approach of transmission electron microscopy and atom probe tomography to link microstructure and 3D nanochemistry of a ternary single crystal Ni83.9Si13Fe3.1 (at.%) model alloy. The formation of a γ/γ' microstructure is revealed, containing primary and secondary γ' precipitates analogous to Ni-based superalloys. Subsequently, microstructural hierarchy is created by the formation of γ particles inside primary γ' precipitates. The correlated supersaturation with γ forming elements (Ni, Fe) of primary γ' precipitates was identified as driving force for the formation of γ particles. The influence of aging on the mechanical properties is reported and peak hardness is achieved after 24 h of aging at 923 K. Thermo-Calc equilibrium phase concentrations based on the TTNi8 database where found to be closer to the APT data than the TCNi8 based values. Our results suggest that improved stability of γ particles can be achieved by tailoring the phase chemistry and the lattice misfit.

Nanocrystalline materials are known to possess excellent radiation resistance due to high fraction of grain boundaries that act as defect sinks, provided they are microstructurally stable at such extreme conditions. In this work, radiation response of a stable nanocrystalline Cu-Ta alloy is studied by irradiating with 4 MeV copper ions to doses (close to the surface) of 1 displacements per atom (dpa) at room temperature (RT); 10 dpa at RT, 573 and 723 K; 100 and 200 dpa at RT and 573 K. Nanoindentation results carried out for samples irradiated till 100 dpa at RT and 573 K show exceptionally low radiation hardening behavior compared to various candidate materials from literature. Results from microstructural characterization, using atom probe analysis and transmission electron microscopy, show a stable nanocrystalline microstructure with minimal grain growth and a meagre swelling in samples irradiated to 100 dpa (~0.2%) and 200 dpa at RT, while no voids in those at 573 K. This radiation tolerance is partly attributed to the stability of Ta nanoclusters due to phase separating nature of the alloy. Additionally, the larger tantalum particles are observed to undergo ballistic dissolution at doses greater than 100 dpa and are eventually precipitated as nanoclusters, replenishing the sink strength, which enhanced material's radiation tolerance when exposed to high irradiation doses and elevated temperatures.

We report the sputter deposition of Cu-7V and Cu-27V (at.%) alloy films in an attempt to yield a “clean” alloy to investigate nanocrystalline stability. Films grown in high vacuum chambers can mitigate processing contaminates which convolute the identification of nanocrystalline stability mechanism(s). The initial films were very clean with carbon and oxygen contents ranging between ~0.01 and 0.38 at.%. Annealing at 400 °C/1 h facilitated the clustering of vanadium at high-angle grain boundary triple junctions. At 800 °C/1 h annealing, the Cu-7V film lost its nanocrystalline grain sizes with the vanadium partitioned to the free surface; the Cu-27V retained its nanocrystalline grains with vanadium clusters in the matrix, but surface solute segregation was present. Though the initial alloy and vacuum annealing retained the low contamination levels sought, the high surface area-to-volume ratio of the film, coupled with high segregation tendencies, enabled this system to phase separate in such a manner that the stability mechanisms that were to be studied were lost at high temperatures. This illustrates obstacles in using thin films to address nanocrystalline stability.

Laser induced chemical vapor deposition (LCVD) of freestanding carbon fibers from ethylene at hyperbaric pressures was investigated. Relationships between processing conditions, growth behavior, microstructure, and mechanical properties of the carbon fibers were established. It is found that the fiber growth rates are limited by surface reaction kinetics at low temperatures and limited by gas phase nucleation at high temperatures. At higher pressures and intermediate temperatures, growth becomes mass transport limited whereupon the fibers exhibit drastic changes in morphology and microstructure from a core-shell, smooth appearance to nodular formations. The tensile strengths of the carbon fibers grown by LCVD are generally poor due to the nature of graphitic carbon deposits. However, the Weibull modulus among the LCVD grown carbon fibers was found to be very high. Effects of processing conditions and microstructure on the fiber strengths are observed and discussed.

The microstructures of materials typically undergo significant changes during shock loading, causing failure when higher shock pressures are reached. However, preservation of microstructural and mechanical integrity during shock loading are essential in situations such as space travel, nuclear energy, protection systems, extreme geological events, and transportation. Here, we report ex situ shock behavior of a chemically optimized and microstructurally stable, bulk nanocrystalline copper–tantalum alloy that shows a relatively unchanged microstructure or properties when shock compressed up to 15 GPa. The absence of shock-hardening indicates that the grains and grain boundaries that make up the stabilized nanocrystalline microstructure act as stable sinks, thereby annihilating deformation-induced defects during shock loading. This study helps to advance the possibility of developing advanced structural materials for extreme applications where shock loading occurs. Shock loading of materials alters the microstructure and considerably degrades mechanical performance. Here, shock loading of a nanocrystalline Cu–Ta alloy is found to induce minor changes to microstructure and mechanical performance, attributed to the annihilation of defects during deformation.

A particulate molecular model in which the solvent particles are considered explicitly is developed for studying the linear viscoelasticity of nanocolloidal suspensions using molecular dynamics simulations. Nanocolloidal systems of volume fractions ranging from 0.10 to 0.49 are studied. The hydrodynamics in these model systems are governed by interparticle interactions. The volume fraction dependence of the relative zero shear viscosity exhibited by this molecular model is consistent with that reported in the literature experiments and simulations. Over the range of frequencies studied, the relative dynamic viscosity values follow the same qualitative trend as that seen in the literature experiments. The time-concentration superposition (TCS) principle is successfully applied to construct the viscoelastic master curves that span nine decades of frequency in the case of the elastic modulus and more than four decades of frequency in the case of the loss modulus. The TCS principle was observed to fail at high volume fractions that are near the glass transition concentration; this finding is consistent with the literature experimental and simulation observations. The volume fraction dependence of the shift factors used in the construction of the viscoelastic master curves is in good quantitative agreement with that of the viscosity of the nanocolloidal systems. Our results demonstrate that molecular simulations in conjunction with an explicit solvent model can be used to quantitatively represent the viscosity and the viscoelastic properties of nanocolloidal suspensions. Such particulate models will be useful for studying the rheology of systems whose properties are governed by specific chemical interactions.

Interfacial solute segregation behavior of P in nanocrystalline (NC) Ni alloys is investigated at the atomic scale using cross-correlative PED-APT measurements and atomistic simulations. Inhomogeneous P-segregation in grain boundaries (GBs) of NC Ni is observed from both experimental measurements and simulation calculations. Interfacial excess (IE) of the solute within GBs is further studied as function of GB misorientation. Significant scatter is detected in the IE of boundaries with similar misorientation angles and even within special boundaries with identical Σ values. From atomistic simulations, a general trend of increasing IE with initial GB energy and volume is observed but with poor correlation, indicating that the segregation behavior cannot be captured with a single average measure of the entire GB character. Rather the results suggest that the extent of interfacial solute segregation correlates better with fraction of high energy atomic sites in the boundary. By comparing IE values with thermodynamic model predictions, it is shown that the interfacial segregation behavior is strongly influenced by the energy distribution of atomic sites in the GBs. However, in order to predict the extent of solute segregation, the evolution of the atomic energy landscape in the GB with continuous solute segregation must be considered.

The measurement of thin film mechanical properties free from substrate influence remains one of the outstanding challenges in nanomechanics. Here, a technique based on indentation of a supported film with a flat punch whose diameter is many times the initial film thickness is introduced. This geometry generates a state of confined uniaxial strain for material beneath the punch, allowing direct access to intrinsic stress versus strain response. For simple elastic–plastic materials, this enables material parameters such as elastic modulus, bulk modulus, Poisson’s ratio, and yield stress to be simultaneously determined from a single loading curve. The phenomenon of confined plastic yield has not been previously observed in thin films or homogeneous materials, which we demonstrate here for 170–470 nm thick polystyrene (PS), polymethyl-methacrylate (PMMA) and amorphous Selenium films on silicon. As well as performing full elastic-plastic parameter extraction for these materials at room temperature, we used the technique to study the variation of yield stress in PS to temperatures above the nominal glass transition of 100 °C.

While the advantageous mechanical properties of nanocrystalline (NC) materials have stimulated numerous studies over the past decade, fewer studies have looked at the onset of yielding and deformation and the role of grain boundaries (GBs) prior to plastic flow. In this computational study, Ni microstructures with grain size between 6 nm and 20 nm were studied to elucidate the role of GBs during yielding. Residual strain was quantified by relaxing to zero stress during loading and calculating the resulting evolution of strain accommodation. The results of this work reveal the accumulation of plastic strain in GBs and how microplasticity changes with grain size, leading to the initiation of macroscopic yielding. Microplasticity accumulates homogeneously within large grain microstructures, then becomes localized with decreasing grain size. The resulting microstructural strain accommodation helps understand changes in the onset of dislocation plasticity and yielding behavior in NC materials and may have broader implications for their continual plastic deformation.

A high-temperature retro-Diels-Alder reaction is accelerated by microwave (MW) heating to rates higher than expected based on Arrhenius kinetics and the measured temperature of the reaction mixture. Observations are consistent with selective MW heating of the polar reactant relative to other, less polar components of the reaction mixture.

Fabrication of microfluidic devices by photolithography generally requires specialized training and access to a cleanroom. As an alternative, 3D printing enables cost-effective fabrication of microdevices with complex features that would be suitable for many biomedical applications. However, commonly used resins are cytotoxic and unsuitable for devices involving cells. Furthermore, 3D prints are generally refractory to elastomer polymerization such that they cannot be used as master molds for fabricating devices from polymers (e.g. polydimethylsiloxane, or PDMS). Different post-print treatment strategies, such as heat curing, ultraviolet light exposure, and coating with silanes, have been explored to overcome these obstacles, but none have proven universally effective. Here, we show that deposition of a thin layer of parylene, a polymer commonly used for medical device applications, renders 3D prints biocompatible and allows them to be used as master molds for elastomeric device fabrication. When placed in culture dishes containing human neurons, regardless of resin type, uncoated 3D prints leached toxic material to yield complete cell death within 48 hours, whereas cells exhibited uniform viability and healthy morphology out to 21 days if the prints were coated with parylene. Diverse PDMS devices of different shapes and sizes were easily cast from parylene-coated 3D printed molds without any visible defects. As a proof-of-concept, we rapid prototyped and tested different types of PDMS devices, including triple chamber perfusion chips, droplet generators, and microwells. Overall, we suggest that the simplicity and reproducibility of this technique will make it attractive for fabricating traditional microdevices and rapid prototyping new designs. In particular, by minimizing user intervention on the fabrication and post-print treatment steps, our strategy could help make microfluidics more accessible to the biomedical research community.

The spin-spin relaxation in connective tissues is simulated using a model in which a connective tissue is represented by a set of nanocavities containing H(2)O-D(2)O liquid. Collagen fibrils in connective tissues form ordered hierarchical long structures of hydrated nano-cavities with characteristic diameter from 1 nm to several tens of nanometers and length of about 100 nm. We consider influence of the restricted Brownian motion of molecules inside a nano-cavity on spin-spin relaxation. The analytical expression for the transverse time T(2) for H(2)O-D(2)O liquid in contained a nanocavity was obtained. We show that the angular dependence of the transverse relaxation rate does not depend on the concentration of D(2)O. The theoretical results could explain the experimentally observed dependence of the degree of deuteration on the relaxation time T(2). Accounting the orientation distribution of the nanocavities well agreement with the experimental dependence of the relaxation for articular cartilage on the deuteration degree was obtained.

A micromechanics model was developed to evaluate the elastic binding energy between carbide precipitates and hydrogen interstitials using Eshelby's equivalent inclusion method. Density functional theory (DFT) simulations were performed to obtain the material-specific quantities, e.g., lattice constants and the elastic constants, for the continuum model. Using this model, we find that for coherent carbide precipitates, hydrogen atoms are more likely to bind on the broad surfaces of the disk-like precipitates, which is consistent with experimental observations. For semicoherent and incoherent precipitates, our model suggests that it is possible for semicoherent precipitates to have significant hydrogen binding capability while there is no hydrogen-binding capability of incoherent precipitates, which also agrees with experimental findings. In addition, several factors that influence the binding energies between hydrogen atoms and carbide precipitates were quantitatively analyzed, including the precipitate size, morphology, orientation, and interface. These collective results include both the position and the value of the strongest hydrogen-binding interaction for a wide range of carbide stoichiometries, which contributes to our understanding of hydrogen trapping in steel-based materials.

There is increasing experimental evidence that suggests that the dynamics of glass forming liquids do not diverge at finite temperature above zero Kelvin, at the same time there has been recent progress in the development of non-diverging glass transition models. In this work we examine two non-diverging models: the elastically collective nonlinear Langevin equation theory (ECNLE) and the shoving model, both of which relate an energy barrier in the glass formation process with elastic motion at small scales. The models are evaluated in comparison with the non-diverging dynamic data obtained in the deep glassy state (very stable) for a 20-million-year-old (20 Ma) ancient amber and for a vapor deposited amorphous Teflon obtained previously. We find that although both models are in qualitative agreement with the dynamic data for the two stable glasses, they still overestimate the actual relaxation times for the deep glassy state below the nominal glass transition temperature and for conditions corresponding to the equilibrium state or in a state in which the glass relaxation times are upper bounds to the equilibrium values.

We studied the anisotropy of 1H NMR spin–lattice and spin–spin relaxations in a fresh celery stem experimentally and modeled the sample theoretically as the water-containing nano- and micro-cavities. The angular dependence of the spin–lattice and the spin–spin relaxation times was obtained, which clearly shows the presence of water-filled nano- and micro-cavities in the celery stem, which have elongated shapes and are related to non-spherical vascular cells in the stem. To explain the experimental data, we applied the relaxation theory developed by us and used previously to interpret similar effects in liquids in nanocavities located in biological tissues such as cartilages and tendons. Good agreement between the experimental data and theoretical results was obtained by adjusting the fitting parameters. The obtained values of standard deviations (0.33 for the mean polar angle and 0.1 for the mean azimuthal angle) indicate a noticeable ordering of the water-filled nano- and micro-cavities in the celery stem. Our approach allows the use of the NMR technique to experimentally determine the order parameters of the microscopic vascular structures in plants.

Fabrication of microfluidic devices by photolithography generally requires specialized training and access to a cleanroom. As an alternative, 3D printing enables cost-effective fabrication of microdevices with complex features that would be suitable for many biomedical applications. However, commonly used resins are cytotoxic and unsuitable for devices involving cells. Furthermore, 3D prints are generally refractory to elastomer polymerization such that they cannot be used as master molds for fabricating devices from polymers (e.g. polydimethylsiloxane, or PDMS). Different post-print treatment strategies, such as heat curing, ultraviolet light exposure, and coating with silanes, have been explored to overcome these obstacles, but none have proven universally effective. Here, we show that deposition of a thin layer of parylene, a polymer commonly used for medical device applications, renders 3D prints biocompatible and allows them to be used as master molds for elastomeric device fabrication. When placed in culture dishes containing human neurons, regardless of resin type, uncoated 3D prints leached toxic material to yield complete cell death within 48 hours, whereas cells exhibited uniform viability and healthy morphology out to 21 days if the prints were coated with parylene. Diverse PDMS devices of different shapes and sizes were easily casted from parylene-coated 3D printed molds without any visible defects. As a proof-of-concept, we rapid prototyped and tested different types of PDMS devices, including triple chamber perfusion chips, droplet generators, and microwells. Overall, we suggest that the simplicity and reproducibility of this technique will make it attractive for fabricating traditional microdevices and rapid prototyping new designs. In particular, by minimizing user intervention on the fabrication and post-print treatment steps, our strategy could help make microfluidics more accessible to the biomedical research community.

Underlying electrical propagation in the heart and potentially fatal arrhythmia is the cardiac microstructure. Despite the critical role of muscle architecture, a non-destructive approach to examine not only myocyte orientation, but cellular arrangement in to laminar organization is lacking in hearts from translational animal models and humans. X-ray micro computed tomography using contrast enhancing agents achieves three-dimensional images at near-histological resolutions. However, imaging large mammalian hearts presents challenges including X-ray over-attenuation and loss of image contrast. The goal of this study was to rethink tissue pre-treatment to optimize, and benefit from micro computed tomography imaging resolution in large tissues. Whole pig and human hearts were dehydrated and perfused with a tissue reinforcing agent, hexamethyldisilazane, and slowly air-dried. Heart morphology was conserved and temporally stable. This enabled direct air-mounting for micro computed tomography imaging. Moreover, the desiccated tissue density was significantly reduced compared to the initial hydrated state (P=0.04). Three-dimensional image reconstructions of air-dried hearts segmented using a single intensity threshold revealed detailed microstructural architecture of myolaminae. Conversely, one-step segmentation of hearts loaded with contrast agents poorly estimated the gross anatomical morphology of the heart and lacked identification of tissue microarchitecture. Air-drying large mammalian hearts optimizes X-ray imaging of cardiac microstructure.

Microwave plasma chemical vapor deposition (MPCVD) was used to diffuse boron into tantalum using plasma initiated from a feedgas mixture containing hydrogen and diborane. The role of substrate temperature and substrate bias in influencing surface chemical structure and hardness was investigated. X-ray diffraction shows that increased temperature results in increased TaB2 formation (relative to TaB) along with increased strain in the tantalum body-centered cubic lattice. Once the strained tantalum becomes locally supersaturated with boron, TaB and TaB2 precipitate. Additional boron remains in a solid solution within the tantalum. The combination of precipitation and solid solution hardening along with boron-induced lattice strain may help explain the 40 GPa average hardness measured by nanoindentation. Application of negative substrate bias did not further increase the hardness, possibly due to etching from increased ion bombardment. These results show that MPCVD is a viable method for synthesis of superhard borides based on plasma-assisted diffusion.

This paper explores the fracture behavior of niobium carbides of varying compositions between NbC1.0 and NbC0.5. The surface crack in flexure (SCF) method was used to evaluate the fracture toughness as a function of carbon concentration. Additionally, hardness measurements were conducted with a Knoop indenter, and X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to identify the phase content and microstructures. As the carbon content decreased, the hardness increased from 8 GPa for NbC1.0 to 12 GPa for NbC0.5 and the fracture toughness decreased from 2.5 MPa m to 0.44 MPa m . Notably, the NbC0.67 sample exhibited a secondary precipitate lath-like microstructure with the laths indexed to β-Nb2C and a KIC near 2 MPa m . Though similar lath like structures in tantalum carbides have been reported to yield a KIC of approximately 15 MPa m , the laths in these two materials have fundamentally different structures where bonding in the former is comprised of β-Nb2C and the latter of ζ-Ta4C3-x. This results in the observed different fracture properties, which can be explained through concepts of microstructural toughening.

Heart failure (HF) is one of the leading causes of death worldwide. HF is associated with substantial microstructural remodeling, which is linked to changes in left ventricular geometry and impaired cardiac function. The role of myocardial remodeling in altering the mechanics of failing hearts remains unclear. Structurally based constitutive modeling provides an approach to improve understanding of the relationship between biomechanical function and tissue organization in cardiac muscle during HF. In this study, we used cardiac magnetic resonance imaging and extended-volume confocal microscopy to quantify the remodeling of left ventricular geometry and myocardial microstructure of healthy and spontaneously hypertensive rat hearts at the ages of 12 and 24 months. Passive cardiac mechanical function was characterized using left ventricular pressure-volume compliance measurements. We have developed a, to our knowledge, new structurally based biomechanical constitutive equation built on parameters quantified directly from collagen distributions observed in confocal images of the myocardium. Three-dimensional left ventricular finite element models were constructed from subject-specific in vivo magnetic resonance imaging data. The structurally based constitutive equation was integrated into geometrically subject-specific finite element models of the hearts and used to investigate the underlying mechanisms of ventricular dysfunction during HF. Using a single pair of material parameters for all hearts, we were able to produce compliance curves that reproduced all of the experimental compliance measurements. The value of this study is not limited to reproducing the mechanical behavior of healthy and diseased hearts, but it also provides important insights into the structure-function relationship of diseased myocardium that will help pave the way toward more effective treatments for HF.

The thermal properties of CL-20 explosive in the bulk and confined in controlled pore glass matrices to nanoscale dimensions were studied using dynamic differential scanning calorimetry. The decomposition reaction of the CL-20 was found to be accelerated in 12-nm-diameter pores compared to the bulk CL-20 with the onset of the decomposition occurring 16–24 °C lower and a fourfold to sevenfold larger reaction rate constant. The total heat of decomposition was found to be independent of pore size and heating rate, and the average activation energy for all samples was found to be 160 ± 7 kJ mol−1.

The integrated computational materials engineering approach has been employed to design a series of four single-phase non-equimolar high entropy alloys (HEAs) with systematically varied compositions (Ni38Fe20CrxMn21–0.5xCo21–0.5x with x = 6, 10, 14, and 22) and corrosion behavior. The HEAs were successfully designed, synthesized and confirmed to possess a single-phase FCC structure. Preliminary electrochemical corrosion characterization was conducted to gain fundamental understanding of the effects of HEA composition on corrosion resistance, which will be utilized to develop mechanistic corrosion models that enable the optimal design of corrosion resistant HEA. HEA containing 6 at.% Cr showed indications of passivity at a relatively low Cr content.

Combustion-based processing of polymer films and other materials often requires temporal and spatial uniformity of the combustor. We characterize the temperature and H2O mole fraction of the buoyan...

Density functional theory (DFT) calculations including spin polarization were performed to obtain the energies for all end-member configurations of the μ phase, which were used to evaluate the Gibbs energies of the μ phase. The Co–W system was thermodynamically re-assessed in the present work. The present calculated phase diagram fits well with the experimental data. Applying the DFT results was essential for giving a better description of the μ phase.

Isoconcentration surfaces are commonly used to delineate phases in atom probe datasets. These surfaces then provide the spatial and compositional reference for proximity histograms, the number density of particles, and the volume fraction of particles within a multiphase system. This paper discusses the influence of the isoconcentration surface selection value on these quantitative outputs, using a simple oxide dispersive strengthened alloy, Fe91Ni8Zr1, as the case system. Zirconium reacted with intrinsic oxygen impurities in a consolidated ball-milled powder to precipitate nanoscale zirconia particles. The zirconia particles were identified by varying the Zr-isoconcentration values as well as by the maximum separation data mining method. The associated outputs mentioned above are elaborated upon in reference to the variation in this Zr isosurface value. Considering the dataset as a whole, a 10.5 at.% Zr isosurface provided a compositional inflection point for Zr between the particles and matrix on the proximity histogram; however, this value was unable to delineate all of the secondary oxide particles identified using the maximum separation method. Consequently, variations in the number density and volume fraction were observed as the Zr isovalue was changed to capture these particles resulting in a loss of the compositional accuracy. This highlighted the need for particle-by-particle analysis.

Molecular Dynamics (MD) simulations have been employed to model the growth stresses of body-centered cubic (BCC) metal thin films, with tungsten being the primary case study, as a function of various embryonic island textures, grain sizes, grain morphologies, deposition rates, and deposition energies. Depending on the shape and size of the islands, the tensile stress varied as a function of the available contact area. If the adatoms were sufficiently confined to the surface, the tops of these islands initiated the elastic strain for coalescence. This was particularly relevant for island morphologies that had varied curvature gradients near the contact points. Depending on the texture of the film, the roughness changed, with the 〈1 1 1〉 orientation being the roughest and 〈0 0 1〉 orientation being the smoothest. These topologies are explained by differences in surface diffusivities. The injection energy of adatoms was found to have a dramatic effect on film stress. Species with injection energies in excess of 50 eV resulted in a notable increase in the structural disorder at the grain boundary-free surface intersection which corresponded to a reduction of the tensile stress. Upon ceasing deposition, these disordered regions experienced a recovery to the BCC structure with an increase in the tensile stress. Upon resuming deposition, at the same energies, the disordered structure re-developed and the stress became less tensile and matched the prior deposited stress evolution. Finally, reducing the grain size resulted in an increase in tensile stress up to a critical size, whereupon it decreased. This reversion is explained in terms of grain growth and grain boundary structure during deposition. Through these series of systemically controlled MD simulations, the paper addresses the significance of different microstructures on the evolution of thin film stress.

Thermodynamics-based predictive modeling for phase characteristics after the quench and partition (Q&P) process is key to the design of new alloys and processing cycles with the best combination of mechanical properties. The austenite carbon content influences its phase stability during mechanical deformation and thus determines the improvement to total elongation from transformation-induced plasticity. The current article describes a carbon partition model based on para-equilibrium simulations with the addition of a temperature-dependent effective stored energy model that predicts carbon enrichment in austenite after Q&P processing. A retained austenite stability model is also proposed that uses the predicted carbon in austenite to quantify the austenite stability in terms of the Msσ temperature. The developed models were calibrated and subsequently validated using measurements from advanced characterization techniques such as local electrode atom probe tomography, synchrotron-based x-ray diffraction and uniaxial tensile tests at varying test temperatures.

A series of second-generation dendronized wedge polymers were synthesized by ring-opening metathesis polymerization, and the linear viscoelastic response over a wide range of temperatures was investigated. From 0 to 90 °C the dynamic moduli (G′(ω) and G″(ω)) were determined, and frequency–temperature superposition was used to create master curves that showed behavior from the terminal zone to the glassy regime. An apparent extremely low rubbery plateau of ∼10 kPa was observed in both the dynamic response and in the corresponding van Gurp–Palmen plot. However, further investigation shows that the apparent rubbery plateau is related to the steady-state recoverable compliance, not the onset of entanglements. In addition, these wedge polymers exhibit an extremely low glassy modulus of ∼100 MPa at 0 °C, which is shown to increase at 1 Hz to ∼700 MPa at −80 °C for the wedge polymer 2G-EHW-311. In addition, both small- and wide-angle X-ray scattering patterns were obtained for all of the polymers investigated, and these showed that the polymer molecules adopt an extended cylinder conformation. Furthermore, based on calorimetric measurements, the polymers were found to exhibit two glass transition temperatures, with a 100 K difference between the higher (T_(g,hi) = 26.8 ± 0.7 °C) and lower glass transition temperatures (T_(g,lo) = −76.1 ± 1.1 °C) for the 2G-EHW-311 material. Hence, an intermediate regime extends to well below the T_(g,hi) to T_(g,lo), providing an explanation for the low glassy modulus of ∼100 MPa at 0 °C and its increase to ∼700 MPa when measured at T_(g,hi) – 100 °C and approaching the T_(g,lo).