High Pressure-Temperature Phase Diagram of 1,1-Diamino-2,2-dinitroethylene (FOX-7).

The pressure-temperature (P-T) phase diagram of 1,1-diamino-2,2-dinitroethylene (FOX-7) was determined by in situ synchrotron infrared radiation spectroscopy with the resistively heated diamond anvil cell (DAC) technique. The stability of high-P-T FOX-7 polymorphs is established from ambient pressure up to 10 GPa and temperatures until decomposition. The phase diagram indicates two near isobaric phase boundaries at ∼2 GPa (α → I) and ∼5 GPa (I → II) that persists from 25 °C until the onset of decomposition at ∼300 °C. In addition, the ambient pressure, high-temperature α → ß phase transition (∼111 °C) lies along a steep boundary (∼100 °C/GPa) with a α-ß-δ triple point at ∼1 GPa and 300 °C. A 0.9 GPa isobaric temperature ramping measurement indicates a limited stability range for the γ-phase between 0.5 and 0.9 GPa and 180 and 260 °C, terminating in a ß-γ-δ triple point. With increasing pressure, the δ-phase exhibited a small negative dT/dP slope (up to ∼0.2 GPa) before turning over to a positive 70 °C/GPa slope, at higher pressures. The decomposition boundary (∼55 °C/GPa) was identified through the emergence of spectroscopic signatures of the characteristic decomposition products as well as trapped inclusions within the solid KBr pressure media.

Polymorphism in paracetamol: evidence of additional forms IV and V at high pressure.

The structural phase stability of N-(4-hydroxyphenyl) acetamide (paracetamol) has been studied at ambient temperature up to 23 GPa using Raman spectroscopy. Spectral changes have provided further evidence for a highly kinetically driven Form I → II transition that occurs as a mixed phase from 4.8 to 6.5 GPa, and might complete as early as 7 GPa. Upon further compression to 8.1 GPa, a drastic shift in spectral signature was observed providing the first evidence for a previously undiscovered Form IV of paracetamol. Additional shifts in mode intensities were observed near 11 GPa indicating a potential restructuring of the hydrogen bonding network and/or structural modification to a potentially new Form V. Phase boundaries at 7 and 8 GPa were confirmed under hydrostatic conditions using Raman spectroscopy. Spectral changes indicate that the transition Form IV → V occurs near 11 GPa. Multiple ab initio harmonic frequency calculations at different levels of theory were performed with a B3LYP/6-31G** being used to provide a more robust mode assignment to our experimentally obtained Raman modes. High pressure X-ray diffraction (XRD) was performed up to 21 GPa, which provided further evidence for a highly kinetically driven Form I → II transition in agreement with our Raman measurements. In addition, the XRD provided further evidence for the existence of Form IV near 8 GPa and Form V near 11 GPa with Form V persisting up to 21 GPa.

First-principles calculation of HubbardUfor Terbium metal under high pressure.

Using density functional theory (DFT) and linear response approaches, we compute the on-site Hubbard interactionUof elemental Terbium (Tb) metal in the pressure range ∼ 0-65 GPa. The resulting first-principlesUvalues with experimental crystal structures enable us to examine the magnetic properties of Tb using a DFT+U method. The lowest-energy magnetic states in our calculations for different high-pressure Tb phases-including hcp,α-Sm, and dhcp-are found to be compatible with the corresponding magnetic ordering vectors reported in experiments. The result shows that the inclusion of HubbardUsubstantially improves the accuracy and efficiency in modeling correlated rare-earth materials. Our study also provides the necessaryUinformation for other quantum many-body techniques to study Tb under extreme pressure conditions.

High-pressure phase transition in 3-D printed nanolamellar high-entropy alloy by imaging and simulation insights.

We report on the high-resolution imaging and molecular dynamics simulations of a 3D-printed eutectic high-entropy alloy (EHEA) Ni40Co20Fe10Cr10Al18W2 consisting of nanolamellar BCC and FCC phases. The direct lattice imaging of 3D-printed samples shows the Kurdjumov-Sachs (K-S) orientation relation {111} FCC parallel to {110} BCC planes in the dual-phase lamellae. Unlike traditional iron and steels, this alloy shows an irreversible BCC-to-FCC phase transformation under high pressures. The nanolamellar morphology is maintained after pressure cycling to 30 GPa, and nano-diffraction studies show both layers to be in the FCC phase. The chemical compositions of the dual-phase lamellae after pressure recovery remain unchanged, suggesting a diffusion-less BCC-FCC transformation in this EHEA. The lattice imaging of the pressure-recovered sample does not show any specific orientation relation between the two resulting FCC phases, indicating that many grain orientations are produced during the BCC-FCC phase transformation. Molecular dynamics simulations on phase transformation in a nanolamellar BCC/FCC in K-S orientation show that phase transformation from BCC to FCC is completed under high pressures, and the FCC phase is retained on decompression aided by the stable interfaces. Our work elucidates the irreversible phase transformation under static compression, providing an understanding of the orientation relationships in 3-D printed EHEA under high pressures.

Synthesis and Thermal Oxidation Resistance of Boron-Rich Boron-Carbide Material.

A boron-rich boron-carbide material (B4+δC) was synthesized by spark plasma sintering of a ball-milled mixture of high-purity boron powder and graphitic carbon at a pressure of 7 MPa and a temperature of 1930 °C. This high-pressure, high-temperature synthesized material was recovered and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Vickers hardness measurements, and thermal oxidation studies. The X-ray diffraction studies revealed a single-phase rhombohedral structure (space group R-3m) with lattice parameters in hexagonal representation as a = 5.609 ± 0.007 Å and c = 12.082 ± 0.02 Å. The experimental lattice parameters result in a value of δ = 0.55, or the composition of the synthesized compound as B4.55C. The high-resolution scans of boron binding energy reveal the existence of a B-C bond at 188.5 eV. Raman spectroscopy reveals the existence of a 386 cm-1 vibrational mode representative of C-B-B linear chain formation due to excess boron in the lattice. The measured Vickers microhardness at a load of 200 gf shows a high hardness value of 33.8 ± 2.3 GPa. Thermal gravimetric studies on B4.55C were conducted at a temperature of 1300 °C in a compressed dry air environment, and its behavior is compared to other high-temperature ceramic materials such as high-entropy transition metal boride. The high neutron absorption cross section, high melting point, high mechanical strength, and thermal oxidation resistance make this material ideal for applications in extreme environments.

High Entropy Borides Synthesized by the Thermal Reduction of Metal Oxides in a Microwave Plasma.

Metal oxide thermal reduction, enabled by microwave-induced plasma, was used to synthesize high entropy borides (HEBs). This approach capitalized on the ability of a microwave (MW) plasma source to efficiently transfer thermal energy to drive chemical reactions in an argon-rich plasma. A predominantly single-phase hexagonal AlB2-type structural characteristic of HEBs was obtained by boro/carbothermal reduction as well as by borothermal reduction. We compare the microstructural, mechanical, and oxidation resistance properties using the two different thermal reduction approaches (i.e., with and without carbon as a reducing agent). The plasma-annealed HEB (Hf0.2, Zr0.2, Ti0.2, Ta0.2, Mo0.2)B2 made via boro/carbothermal reduction resulted in a higher measured hardness (38 ± 4 GPa) compared to the same HEB made via borothermal reduction (28 ± 3 GPa). These hardness values were consistent with the theoretical value of ~33 GPa obtained by first-principles simulations using special quasi-random structures. Sample cross-sections were evaluated to examine the effects of the plasma on structural, compositional, and mechanical homogeneity throughout the HEB thickness. MW-plasma-produced HEBs synthesized with carbon exhibit a reduced porosity, higher density, and higher average hardness when compared to HEBs made without carbon.

Synthesis and Ultrahigh Pressure Compression of High-Entropy Boride (Hf0.2Mo0.2Nb0.2Ta0.2Zr0.2)B2 to 220 GPa.

The high-entropy boride (Hf0.2Mo0.2Nb0.2Ta0.2Zr0.2)B2 material was synthesized under high-pressures and high-temperatures in a large-volume Paris-Edinburgh (PE) press from a ball-milled powder mix of HfO2, MoO3, Nb2O5, Ta2O5, ZrO2, carbon black, and boron carbide. The transformation process was monitored in situ by energy-dispersive x-ray diffraction with conversion starting at 1100 °C and completed by 2000 °C with the formation of a single hexagonal AlB2-type phase. The synthesized sample was recovered, powdered, and mixed with platinum pressure marker and studied under high pressure by angle-dispersive x-ray diffraction in a diamond anvil cell. The hexagonal AlB2-type phase of (Hf0.2Mo0.2Nb0.2Ta0.2Zr0.2)B2 was found to be stable up to the highest pressure of 220 GPa reached in this study (volume compression V/V0 = 0.70). The third order Birch-Murnaghan equation of state fit to the high-pressure data up to 220 GPa results in an ambient pressure unit cell volume V0=28.16±0.04 Å3, bulk modulusKo = 407 ± 6 GPa, pressure derivative of bulk-modulus K0' = 2.73 ± 0.045 GPa. Our study indicates that this high-entropy boride (Hf0.2Mo0.2Nb0.2Ta0.2Zr0.2)B2 material is stable to ultrahigh pressures and temperatures and exhibit high bulk modulus similar to other incompressible transition metal borides like ReB2 and Os2B3.

Discovering Superhard B-N-O Compounds by Iterative Machine Learning and Evolutionary Structure Predictions.

We searched for new superhard B-N-O compounds with an iterative machine learning (ML) procedure, where ML models are trained using sample crystal structures from an evolutionary algorithm. We first used cohesive energy to evaluate the thermodynamic stability of varying B x N y O z compositions and then gradually focused on compositional regions with high cohesive energy and high hardness. The results converged quickly after a few iterations. Our resulting ML models show that B x+2N x O3 compounds with x ≥ 3 (like B5N3O3, B6N4O3, etc.) are potentially superhard and thermodynamically favorable. Our meta-GGA density functional theory calculations indicate that these materials are also wide bandgap (≥4.4 eV) insulators, with the valence band maximum related to the p-orbitals of nitrogen atoms near vacant sites. This study demonstrates that an iterative method combining ML and ab initio simulations provides a powerful tool for discovering novel materials.

Experimental and Computational Studies of Compression and Deformation Behavior of Hafnium Diboride to 208 GPa.

The compression behavior of the hexagonal AlB2 phase of Hafnium Diboride (HfB2) was studied in a diamond anvil cell to a pressure of 208 GPa by axial X-ray diffraction employing platinum as an internal pressure standard. The deformation behavior of HfB2 was studied by radial X-ray diffraction technique to 50 GPa, which allows for measurement of maximum differential stress or compressive yield strength at high pressures. The hydrostatic compression curve deduced from radial X-ray diffraction measurements yielded an ambient-pressure volume V0 = 29.73 Å3/atom and a bulk modulus K0 = 282 GPa. Density functional theory calculations showed ambient-pressure volume V0 = 29.84 Å3/atom and bulk modulus K0 = 262 GPa, which are in good agreement with the hydrostatic experimental values. The measured compressive yield strength approaches 3% of the shear modulus at a pressure of 50 GPa. The theoretical strain-stress calculation shows a maximum shear stress τmax~39 GPa along the (1-10) [110] direction of the hexagonal lattice of HfB2, which thereby can be an incompressible high strength material for extreme-environment applications.

Plasma Electroless Reduction: A Green Process for Designing Metallic Nanostructure Interfaces onto Polymeric Surfaces and 3D Scaffolds.

The design of metal nanoparticle-modified polymer surfaces in a green and scalable way is both desirable and highly challenging. Herein, a new green low-temperature plasma-based in situ surface reduction strategy termed plasma electroless reduction (PER) is reported for achieving in situ metallic nanostructuring on polymer surfaces. Proof of concept for this new method was first demonstrated on hydrophilic cellulose papers. Cellulose papers were dip-coated with different metal ion (Ag+ and Au3+) solutions and then subjected to hydrogen plasma treatment for this PER process. Transmission electron microscopy (TEM) analysis has revealed that this PER process caused anisotropic growth of either gold or silver nanoparticles, resulting in the time-dependent formation of both distinct spherical nanoparticles (∼20 nm) and anisotropic 2D nanosheets. Furthermore, we have demonstrated the adaptability of this process by applying it to hydrophobic fibrous and 3D printed polymeric materials such as surgical face masks and 3D printed polylactic acid scaffolds. The PER process on these hydrophobic polymer surfaces was accomplished via a sequential combination of air plasma and hydrogen plasma treatment. The metallic nanostructuring caused by the PER process on these hydrophobic surfaces was systematically studied using different surface imaging techniques including 3D confocal laser surface scanning microscopy and scanning electron microscopy. We have also systematically optimized the PER process on the surface of 3D scaffolds via varying the concentration of the silver ion precursor and by different postprocessing methods such as sonication and medium soaking. These optimization processes were found to be very important in generating uniform metallic nanoparticle-modified 3D printed scaffolds while simultaneously improving cytocompatibility. Through joint disk diffusion and inhibitory concentration testing, the antibacterial efficacy of silver coatings on face masks and 3D scaffolds was established. Altogether, these results clearly suggest the excellent futuristic potential of this new PER method for designing metallic nanostructured interfaces for different biomedical applications.

Pressure effect on magnetism and valence in ferromagnetic superconductor Eu(Fe0.75Ru0.25)2As2.

Eu(Fe0.75Ru0.25)2As2is an intriguing system with unusual coexistence of superconductivity and ferromagnetism, providing a unique platform to study the nature of such coexistence. To establish a magnetic phase diagram, time-domain synchrotron Mössbauer experiments in151Eu have been performed on a single crystalline Eu(Fe0.75Ru0.25)2As2sample under hydrostatic pressures and at low temperatures. Upon compression the magnetic ordering temperature increases sharply from 20 K at ambient pressure, reaching ∼49 K at 10.1 GPa. With further compression, the magnetic order is suppressed and eventually collapses. Isomer shift values from Mössbauer measurements and x-ray absorption spectroscopy data at EuL3edge show that pressure drives Eu ions to a homogeneous intermediate valence state with mean valence of ∼2.4 at 27.4 GPa, possibly responsible for the suppression of magnetism. Synchrotron powder x-ray diffraction experiment reveals a tetragonal to collapsed-tetragonal structural transition around 5 GPa, a lower transition pressure than in the parent compound. These results provide guidance to further work investigating the interplay of superconductivity and magnetism.

Improved adhesion of ultra-hard carbon films on cobalt-chromium orthopaedic implant alloy.

While interfacial graphite formation and subsequent poor film adhesion is commonly reported for chemical vapor deposited hard carbon films on cobalt-based materials, we find the presence of O(2) in the feedgas mixture to be useful in achieving adhesion on a CoCrMo alloy. Nucleation studies of surface structure before formation of fully coalesced hard carbon films reveal that O(2) feedgas helps mask the catalytic effect of cobalt with carbon through early formation of chromium oxides and carbides. The chromium oxides, in particular, act as a diffusion barrier to cobalt, minimizing its migration to the surface where it would otherwise interact deleteriously with carbon to form graphite. When O(2) is not used, graphitic soot forms and films delaminate readily upon cooling to room temperature. Continuous 1 µm-thick nanostructured carbon films grown with O(2) remain adhered with measured hardness of 60 GPa and show stable, non-catastrophic circumferential micro-cracks near the edges of indent craters made using Rockwell indentation.

Selective Deposition of Hard Boron-Carbon Microstructures on Silicon.

Boron-rich B-C compounds with high hardness have been recently synthesized by the chemical vapor deposition (CVD) method. In this paper, we present our successful efforts in the selective growth of microstructures of boron-carbon compounds on silicon substrates. This was achieved by combining microfabrication techniques such as maskless lithography and sputter deposition with the CVD technique. Our characterization studies on these B-C microstructures showed that they maintain structural and mechanical properties similar to that of their thin-film counterparts. The methodology presented here paves the way for the development of microstructures for microelectromechanical system (MEMS) applications which require custom hardness and strength properties. These hard B-C microstructures are an excellent choice as support structures in MEMS-based devices.

Two ply tubular scaffolds comprised of proteins/poliglecaprone/polycaprolactone fibers.

Electrospun bi-layer tubular hybrid scaffolds composed of poliglecaprone (PGC), polycaprolactone (PCL), elastin (E), and gelatin (G) were prepared and thereafter crosslinked by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). Scanning electron microscopic (SEM) images revealed a highly porous micro-structure comprising randomly distributed non-woven fibers with the majority of fibers in submicron diameters. The EDC-crosslinking yielded an average crosslinking degree of 40%. Uni-axial tensile test of hydrated scaffolds in both longitudinal and circumferential directions revealed tensile properties, comparable to those of native arteries. The graft (PGC:PCL = 1:3) did not demonstrate significant difference before and after EDC-crosslinking in tensile strength or % strain in either longitudinal or circumferential directions. However, crosslinking increased the Young's modulus of the graft along the longitudinal direction (from 5.84 to 8.67 MPa). On the contrary, the graft (3:1) demonstrated a significant decrease in maximum strain in both directions. Cyto-assay using human umbilical vein endothelial cells (HUVECs) showed excellent cell viability.

First-Principles Predictions and Synthesis of B50C2 by Chemical Vapor Deposition.

Density functional theory predictions have been combined with the microwave-plasma chemical vapor deposition technique to explore metastable synthesis of boron-rich boron-carbide materials. A thin film synthesis of high-hardness (up to 37 GPa) B50C2 via chemical vapor deposition was achieved. Characterization of the experimental crystal structure matches well with a new theoretical model structure, with carbon atoms inserted into the boron icosahedra and 2b sites in a α-tetragonal B52 base structure. Previously reported metallic B50C2 structures with carbons inserted only into the 2b or 4c sites are found to be dynamically unstable. The newly predicted structure is insulating and dynamically stable, with a computed hardness value and electrical properties in excellent agreement with the experiment. The present study thus validates the density functional theory calculations of stable crystal structures in boron-rich boron-carbide system and provides a pathway for large-area synthesis of novel materials by the chemical vapor deposition method.

Electronic structure and anisotropic compression of Os2B3 to 358 GPa.

High pressure study on ultra-hard transition-metal boride Os2B3 was carried out in a diamond anvil cell under isothermal and non-hydrostatic compression with platinum as an x-ray pressure standard. The ambient-pressure hexagonal phase of Os2B3 is found to be stable with a volume compression V/V 0 = 0.670 ± 0.009 at the maximum pressure of 358 ± 7 GPa. Anisotropic compression behavior is observed in Os2B3 to the highest pressure, with the c-axis being the least compressible. The measured equation of state using the 3rd-order Birch-Murnaghan fit reveals a bulk modulus K 0 = 397 GPa and its first pressure derivative [Formula: see text] = 4.0. The experimental lattice parameters and bulk modulus at ambient conditions also agree well with our density-functional-theory (DFT) calculations within an error margin of ∼1%. DFT results indicate that Os2B3 becomes more ductile under compression, with a strong anisotropy in the axial bulk modulus persisting to the highest pressure. DFT further enables the studies of charge distribution and electronic structure at high pressure. The pressure-enhanced electron density and repulsion along the Os and B bonds result in a high incompressibility along the crystal c-axis. Our work helps to elucidate the fundamental properties of Os2B3 under ultrahigh pressure for potential applications in extreme environments.

Experimental and Computational Studies on Superhard Material Rhenium Diboride under Ultrahigh Pressures.

An emerging class of superhard materials for extreme environment applications are compounds formed by heavy transition metals with light elements. In this work, ultrahigh pressure experiments on transition metal rhenium diboride (ReB2) were carried out in a diamond anvil cell under isothermal and non-hydrostatic compression. Two independent high-pressure experiments were carried out on ReB2 for the first time up to a pressure of 241 GPa (volume compression V/V0 = 0.731 ± 0.004), with platinum as an internal pressure standard in X-ray diffraction studies. The hexagonal phase of ReB2 was stable under highest pressure, and the anisotropy between the a-axis and c-axis compression increases with pressure to 241 GPa. The measured equation of state (EOS) above the yield stress of ReB2 is well represented by the bulk modulus K0 = 364 GPa and its first pressure derivative K0´ = 3.53. Corresponding density-functional-theory (DFT) simulations of the EOS and elastic constants agreed well with the experimental data. DFT results indicated that ReB2 becomes more ductile with enhanced tendency towards metallic bonding under compression. The DFT results also showed strong crystal anisotropy up to the maximum pressure under study. The pressure-enhanced electron density distribution along the Re and B bond direction renders the material highly incompressible along the c-axis. Our study helps to establish the fundamental basis for anisotropic compression of ReB2 under ultrahigh pressures.

Room-temperature compression and equation of state of body-centered cubic zirconium.

Zirconium (Zr) has properties conducive to nuclear applications and exhibits complex behavior at high pressure with respect to the effects of impurities, deviatoric stress, kinetics, and grain growth which makes it scientifically interesting. Here, we present experimental results on the 300 K equation of state of ultra-high purity Zr obtained using the diamond-anvil cell coupled with synchrotron-based x-ray diffraction and electrical resistance measurements. Based on quasi-hydrostatic room-temperature compression in helium to pressure P = 69.4(2) GPa, we constrain the bulk modulus and its pressure derivative of body-centered cubic (bcc) ß-Zr to be K = 224(2) GPa and K' = 2.6(1) at P = 37.0(1) GPa. A Monte Carlo approach was developed to accurately quantify the uncertainties in K and K'. In the Monte Carlo simulations, both the unit-cell volume and pressure vary according to their experimental uncertainty. Our high-pressure studies do not indicate additional isostructural volume collapse in the bcc phase of Zr in the 56-58 GPa pressure range.

Non-equilibrium organosilane plasma polymerization for modulating the surface of PTFE towards potential blood contact applications.

We report a novel and facile organosilane plasma polymerization method designed to improve the surface characteristics of poly(tetrafluoroethylene) (PTFE). We hypothesized that the polymerized silane coating would provide an adhesive surface for endothelial cell proliferation due to a large number of surface hydroxyl groups, while the large polymer networks on the surface of PTFE would hinder platelet attachment. The plasma polymerized PTFE surfaces were then systematically characterized via different analytical techniques such as FTIR, XPS, XRD, Contact angle, and SEM. The key finding of the characterization is the time-dependent deposition of an organosilane layer on the surface of PTFE. This layer was found to provide favorable surface properties to PTFE such as a very high surface oxygen content, high hydrophilicity and improved surface mechanics. Additionally, in vitro cellular studies were conducted to determine the bio-interface properties of the plasma-treated and untreated PTFE. The important results of these experiments were rapid endothelial cell growth and decreased platelet attachment on the plasma-treated PTFE compared to untreated PTFE. Thus, this new surface modification technique could potentially address the current challenges associated with PTFE for blood contact applications, specifically poor endothelial cell growth and risk of thrombosis.

A biomimetic tubular scaffold with spatially designed nanofibers of protein/PDS bio-blends.

Electrospun tubular conduit (4 mm inner diameter) based on blends of polydioxanone (PDS II(R)) and proteins such as gelatin and elastin having a spatially designed trilayer structure was prepared for arterial scaffolds. SEM analysis of scaffolds showed random nanofibrous morphology and well-interconnected pore network. Due to protein blending, the fiber diameter was reduced from 800-950 nm range to 300-500 nm range. Fourier-transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) results confirmed the blended composition and crystallinity of fibers. Pure PDS scaffold under hydrated state exhibited a tensile strength of 5.61 +/- 0.42 MPa and a modulus of 17.11 +/- 1.13 MPa with a failure strain of 216.7 +/- 13%. The blending of PDS with elastin and gelatin has decreased the tensile properties. A trilayer tubular scaffold was fabricated by sequential electrospinning of blends of elastin/gelatin, PDS/elastin/gelatin, and PDS/gelatin (EG/PEG/PG) to mimic the complex matrix structure of native arteries. Under hydrated state, the trilayer conduit exhibited tensile properties (tensile strength of 1.77 +/- 0.2 MPa and elastic modulus of 5.74 +/- 3 MPa with a failure strain of 75.08 +/- 10%) comparable to those of native arteries. In vitro degradation studies for up to 30 days showed about 40% mass loss and increase in crystallinity due to the removal of proteins and "cleavage-induced crystallization" of PDS.