COMPARATIVE EVALUATION OF THERMAL CONDUCTIVITY OF ZIRCONIA SOLID AND HONEYCOMB STRUCTURES

Porous zirconia ceramic monoliths have been extensively used in thermo-structural applications due to their inherent low thermal conductivity in combination with their adaptability to form complicated shapes through advanced ceramic processing techniques. However, extruded cellular honeycomb structures made from these materials have been less explored for thermal management applications. There exist large potential applications due to their unique configurations, resulting in better heat-management mechanisms. Some of the studies carried out on zirconia honeycombs are safeguarded through patents due to its technical importance, or the information is not in the public domain. In the present study, for the sake of comparison, honeycomb specimens with varying wall thicknesses and unit cell lengths maintaining almost same bulk density of around 90% theoretical and relative density of 0.34-0.37 were prepared and subjected to thermal conductivity evaluation along with the solid samples with relative density of 1.0 using monotonic heating regime methodology. In addition, the effect of channel shape was also evaluated using square and triangular channeled honeycombs with the same relative densities. The results obtained from these specimens were correlated with their configurations to bring out the advantages accrued by using the honeycomb with these configurations. It was observed that a significant decrease in thermal conductivity was achieved in honeycombs, which can be attributed to the behavior of various heat transfer mechanisms that are operative at high temperatures in combination with the considerable reduction in thermal mass and the consequent conduction through the solids.

The Relationship of Solid-State Plasticity to Mechanochromic Luminescence in Difluoroboron Avobenzone Polymorphs

In solid-state mechanochromic luminescence (ML) materials, it remains a challenge to establish the origin of fluorescence color changes upon mechanical action and to determine why only some fluorophores exhibit ML behavior. The study of mechanical properties by nanoindentation, followed by ML experiments on green- and cyan-emitting polymorphs of difluoroboron avobenzone reveals that upon smearing, the plastically deformable cyan form shows a prominent color change to yellow, while in the harder green form the redshifted emission is barely detectable. Crystal structure analysis reveals the presence of slip planes in the softer cyan form that can facilitate the formation of recoverable and low energy defects in the structure. Hence, the cyan form exhibits prominent and reversible ML behavior. This suggests a potential design strategy for efficient ML materials.

Synthon identification in co-crystals and polymorphs with IR spectroscopy. Primary amides as a case study

IR spectroscopy has been widely employed to distinguish between different crystal forms such as polymorphs, clathrates, hydrates and co-crystals. IR has been used to monitor co-crystal formation and single synthon detection. In this work, we have developed a strategy to identify multiple supramolecular synthons in polymorphs and co-crystals with this technique. The identification of multiple synthons in co-crystals with IR is difficult for several reasons. In this paper, a four step method involving well assigned IR spectral markers that correspond to bonds in a synthon is used. IR spectra of three forms of the co-crystal system, 4-hydroxybenzoic acid: 4,4'-bipyridine (2 : 1), show clear differences that may be attributed to differences in the synthon combinations existing in the forms (synthon polymorphism). These differences were picked out from the three IR spectra and the bands analysed and assigned to synthons. Our method first identifies IR marker bands corresponding to (covalent) bonds in known/model crystals and then the markers are mapped in known co-crystals having single synthons. Thereafter, the IR markers are queried in known co-crystals with multiple synthons. Finally they are queried in unknown co-crystals with multiple synthons. In the last part of the study, the N-H stretching absorptions of primary amides that crystallize with the amide dimers linked in a ladder like chain show two specific absorptions which are used as marker absorptions and all variations of this band structure have been used to provide details on the environment around the dimer. The extended dimer can accordingly be easily distinguished from the isolated dimer.

Nucleation of a Stable Solid from Melt in the Presence of Multiple Metastable Intermediate Phases: Wetting, Ostwald's Step Rule, and Vanishing Polymorphs

In many systems, nucleation of a stable solid may occur in the presence of other (often more than one) metastable phases. These may be polymorphic solids or even liquid phases. Sometimes, the metastable phase might have a lower free energy minimum than the liquid but higher than the stable-solid-phase minimum and have characteristics in between the parent liquid and the globally stable solid phase. In such cases, nucleation of the solid phase from the melt may be facilitated by the metastable phase because the latter can ``wet'' the interface between the parent and the daughter phases, even though there may be no signature of the existence of metastable phase in the thermodynamic properties of the parent liquid and the stable solid phase. Straightforward application of classical nucleation theory (CNT) is flawed here as it overestimates the nucleation barrier because surface tension is overestimated (by neglecting the metastable phases of intermediate order) while the thermodynamic free energy gap between daughter and parent phases remains unchanged. In this work, we discuss a density functional theory (DFT)-based statistical mechanical approach to explore and quantify such facilitation. We construct a simple order-parameter-dependent free energy surface that we then use in DFT to calculate (i) the order parameter profile, (ii) the overall nucleation free energy barrier, and (iii) the surface tension between the parent liquid and the metastable solid and also parent liquid and stable solid phases. The theory indeed finds that the nucleation free energy barrier can decrease significantly in the presence of wetting. This approach can provide a microscopic explanation of the Ostwald step rule and the well-known phenomenon of ``disappearing polymorphs'' that depends on temperature and other thermodynamic conditions. Theory reveals a diverse scenario for phase transformation kinetics, some of which may be explored via modem nanoscopic synthetic methods.

The Role of Weak Interactions in the Phase Transition and Distinct Mechanical Behavior of Two Structurally Similar Caffeine Co-crystal Polymorphs Studied by Nanoindentation

Although weak interactions, such as C-H center dot center dot center dot O and pi-stacking, are generally considered to be insignificant, it is their reorganization that holds the key for many a solid-state phenomenon, such as phase transitions, plastic deformation, elastic flexibility, and mechanochromic luminescence in solid-state fluorophores. Despite this, the role of weak interactions in these dynamic phenomena is poorly understood. In this study, we investigate two co-crystal polymorphs of caffeine:4-chloro-3-nitrobenzoic acid, which have close structural similarity (2D layered structures), but surprisingly show distinct mechanical behavior. Form I is brittle, but shows shear-induced phase instability and, upon grinding, converts to Form II, which is soft and plastically shearable. This observation is in contrast to those reported in earlier studies on aspirin, wherein the metastable drug forms are softer and convert to stable and harder forms upon stressing To establish a molecular level understanding, have investigated the two co-crystal polymorphs I and II by single crystal X-ray diffraction, nanoindentation to quantify mechanical properties, and theoretical calculations. The lower hardness (from nanoindentation) and smooth potential surfaces (from theoretical studies) for shearing of layers in Form II allowed us to rationalize the role of stronger intralayer (sp(2))C-H center dot center dot center dot O and nonspecific interlayer pi-stacking interactions in the structure of II. Although the Form I also possesses the same type of interactions, its strength is clearly opposite, that is, weaker intralayer (sp(3))C-H center dot center dot center dot O and specific interlayer pi-stacking interactions. Hence, Form I is harder than Form IL Theoretical calculations and indentation on (111) of Form I suggested the low resistance of this face to mechanical stress; thus, Form I converts to II upon mechanical action. Hence, our approach demonstrates the usefulness of multiple techniques for establishing the role of weak noncovalent interactions in solid-state dynamic phenomena, such as stress induced phase transformation, and hence is important in the context of solid-state pharmaceutical chemistry and crystal engineering.

Solubility-Hardness Correlation in Molecular Crystals: Curcumin and Sulfathiazole Polymorphs

Curcumin and sulfathiazole exist as three and five polymorphs, respectively. We correlate solubility and mechanical properties in these polymorphic systems. It is seen that hardness (H) is inversely proportional to the solubility of a polymorph. H of the polymorphs is explained on the basis of slip planes in the crystal structure, the Schmid factor (m), and the relative orientation of molecules with respect to the nanoindenter direction. Effectively, H is a useful parameter (compared to melting point, T-m, and density, rho) that correlates well with the solubility of a polymorph. Such a correlation is helpful in systems like curcumin and sulfathiazole in which the Gibbs free energy of the polymorphs are close to one another. To summarize, a softer polymorph is more soluble.

Creep in nanocrystalline zirconia

Grain boundary sliding remains a dominant deformation process during creep in both nanocrystalline and submicron-grained zirconia. The level of segregation of Y to grain boundaries is reduced by a factor of similar to 2 in nanocrystals. However, a scaling relationship for compression creep was valid in a 3 mol.% yttria-stabilized tetragonal zirconia with grain sizes in the range of similar to 65-400 nm, indicating the same deformation mechanism over this range of grain sizes. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Ligand 5,10,15,20-Tetra(N-methyl-4-pyridyl)porphine (TMPyP4) Prefers the Parallel Propeller-Type Human Telomeric G-Quadruplex DNA over Its Other Polymorphs

The binding of ligand 5,10,15,20-tetra(N-methyl-4-pyridyl)porphine (TMPyP4) with telomeric and genomic G-quadruplex DNA has been extensively studied. However, a comparative study of interactions of TMPyP4 with different conformations of human telomeric G-quadruplex DNA, namely, parallel propeller-type (PP), antiparallel basket-type (AB), and mixed hybrid-type (MH) G-quadruplex DNA, has not been done. We considered all the possible binding sites in each of the G-quadruplex DNA structures and docked TMPyP4 to each one of them. The resultant most potent sites for binding were analyzed from the mean binding free energy of the complexes. Molecular dynamics simulations were then carried out, and analysis of the binding free energy of the TMPyP4-G-quadruplex complex showed that the binding of TMPyP4 with parallel propeller-type G-quadruplex DNA is preferred over the other two G-quadruplex DNA conformations. The results obtained from the change in solvent excluded surface area (SESA) and solvent accessible surface area (SASA) also support the more pronounced binding of the ligand with the parallel propeller-type G-quadruplex DNA.

Inductively coupled reactive ion etching studies on sputtered yttria stabilized zirconia thin films in SF6, Cl-2, and BCl3 chemistries

Downscaling of yttria stabilized zirconia (YSZ) based electrochemical devices and gate oxide layers requires successful pattern transfer on YSZ thin films. Among a number of techniques available to transfer patterns to a material, reactive ion etching has the capability to offer high resolution, easily controllable, tunable anisotropic/isotropic pattern transfer for batch processing. This work reports inductively coupled reactive ion etching studies on sputtered YSZ thin films in fluorine and chlorine based plasmas and their etch chemistry analyses using x-ray photoelectron spectroscopy. Etching in SF6 plasma gives an etch rate of 7 nm/min chiefly through physical etching process. For same process parameters, in Cl-2 and BCl3 plasmas, YSZ etch rate is 17 nm/min and 45 nm/min, respectively. Increased etch rate in BCl3 plasma is attributed to its oxygen scavenging property synergetic with other chemical and physical etch pathways. BCl3 etched YSZ films show residue-free and smooth surface. The surface atomic concentration ratio of Zr/Y in BCl3 etched films is closer to as-annealed YSZ thin films. On the other hand, Cl-2 etched films show surface yttrium enrichment. Selectivity ratio of YSZ over silicon (Si), silicon dioxide (SiO2) and silicon nitride (Si3N4) are 1:2.7, 1:1, and 1:0.75, respectively, in BCl3 plasma. YSZ etch rate increases to 53 nm/min when nonoxygen supplying carrier wafer like Si3N4 is used. (C) 2015 American Vacuum Society.

Influence of yttria and zirconia additions on spark plasma sintering of alumina composites

The mechanisms of densification and creep were examined during spark plasma sintering (SPS) of alumina doped with a low and high level of zirconia or yttria, over a temperature range of 1173-1573 K and stresses between 25 and 100 MPa. Large additions of yttria led clearly to in situ reactions during SPS and the formation of a yttrium-aluminum garnet phase. Dopants generally lead to a reduction in the densification rate, with substantial reductions noted in samples with similar to 5.5 vol% second phase. In contrast to a stress exponent of n similar to 1 for pure alumina, the doped aluminas displayed n similar to 2 corresponding to an interface-controlled diffusion process. The higher activation energies in the composites are consistent with previous data on creep and changes in the interfacial energies. The results reveal a compensation effect, such that an increase in the activation energy is accompanied by a corresponding increase in the pre-exponential term for diffusion.

Effect of Manganese (II) Oxide on microstructure and ionic transport properties of nanostructured cubic zirconia

Effect of MnO addition on microstructure and ionic transport properties of nanocrystalline cubic(c)-ZrO2 is reported. Monoclinic (m) ZrO2 powders with 10-30 mol% MnO powder are mechanically alloyed in a planetary ball mill at room temperature for 10 h and annealed at 550 degrees C for 6 h. In all compositions m-ZrO2 transforms completely to nanocrystalline c-ZrO2 phase and MnO is fully incorporated into c-ZrO2 lattice. Rietveld's refinement technique is employed for detailed microstructure analysis by analyzing XRD patterns. High resolution transmission electron microscopy (HRTEM) analysis confirms the complete formation of c-ZrO2 phase. Presence of stoichiometric Mn in c-ZrO2 powder is confirmed by Electron Probe Microscopy analysis. XPS analysis reveals that Mn is mostly in Mn2+ oxidation state. A correlation between lattice parameter and oxygen vacancy is established. A detailed ionic conductivity measurement in the 250 degrees-575 degrees C temperature range describes the effect of MnO on conductivity of c-ZrO2. The ionic conductivity (s) of 30 mol% MnO alloyed ZrO2 at 550 degrees C is 0.04 s cm(-1). Electrical relaxation studies are carried out by impedance and modulus spectroscopy. Relaxation frequency is found to increase with temperature and MnO mol fraction. Electrical characterization predicts that these compounds have potentials for use as solid oxide fuel cell electrolyte material. (C) 2015 Elsevier Ltd. All rights reserved.

Structure Elucidation and Characterization of Different Thyroxine Polymorphs

Thyroid hormones regulate almost every process in the body, including body temperature, growth, and heart rate. They influence carbohydrate metabolism, protein synthesis and breakdown, and cardiovascular, renal, and brain function. Two new polymorphs of synthetic L-thyroxine (T4) are reported and the effect of polymorphism on the solubility of this important hormone is shown. Conformational changes were also discovered to have a remarkable effect on the strength of halogen bonding and the reactivity of the CI bonds, which could have a significant effect on the hormone activity.

Investigation of Annealing Induced Yttria Segregation in Sputtered Yttria-Stabilized Zirconia Thin Films

8mol% yttria-stabilized zirconia (8YSZ) is an extensively studied solid electrolyte. But there is no consistency in the reported ionic conductivity values of 8YSZ thin films. Interfacial segregation in YSZ thin films can affect its ionic conductivity by locally altering the surface chemistry. This article presents the effects of annealing temperature and film thickness on free surface yttria segregation behavior in 8YSZ thin film by Angle Resolved XPS and its influence on the ionic conductivity of sputtered 8YSZ thin films. Surface yttria concentration of about 32, 20, and 9mol% have been found in 40nm 8YSZ films annealed at 1273, 1173, and 1073K, respectively. Yttria segregation is found to increase with increase in annealing temperature and film thickness. Ionic conductivities of 0.23, 0.16, and 0.08Scm(-1) are observed at 923K for 40nm 8YSZ films annealed at 1073, 1173, and 1273K, respectively. The decrease in conductivity with increase in annealing temperature is attributed to the increased yttria segregation with annealing. Neither segregation nor film thickness is found to affect the activation energy of oxygen ion conduction. Target purity is found to play a key role in determining free surface yttria segregation in 8YSZ thin films.

RF plasma enhanced MOCVD of yttria stabilized zirconia thin films using octanedionate precursors and their characterization

Yttria stabilized zirconia thin films have been deposited by RF plasma enhanced MOCVD technique on silicon substrates at substrate temperature of 400 degrees C. Plasma of precursor vapors of (2,7,7-trimethyl-3,5-octanedionate) yttrium (known as Y(tod)(3)), (2,7,7-trimethyl-3,5-octanedionate) zirconium (known as Zr(tod)(4)), oxygen and argon gases is used for deposition. To the best of our knowledge, plasma assisted MOCVD of YSZ films using octanediaonate precursors have not been reported in the literature so far. The deposited films have been characterized by GIXRD, FTIR, XPS, FESEM, AFM, XANES, EXAFS, EDAX and spectroscopic ellipsometry. Thickness of the films has been measured by stylus profilometer while tribological property measurement has been done to study mechanical behavior of the coatings. Characterization by different techniques indicates that properties of the films are dependent on the yttria content as well as on the structure of the films. (C) 2015 Elsevier B.V. All rights reserved.

Dimethyl 2,2 `-[(4-oxo-2-phenyl-4H-chromene 5,7-diyl)dioxy]diacetate: a more densely packed polymorph

The title molecule, C21H18O8, crystallizes in two crystal polymorphs, see also Nallasivam, Nethaji, Vembu & Jaswant [Acta Cryst. (2009), E65, o314-o315]. The molecules of both polymorphs differ by the conformation of the oxomethylacetate groups. The title molecules are rather planar compared to the molecules of the other polymorph. In the title molecule, one of the oxomethylacetate groups is disordered (occupancies of 0.6058/0.3942). The structures of both polymorphs are stabilized by C-H center dot center dot center dot O and C-H center dot center dot center dot pi interactions. Due to the planarity of the title molecules and similar intermolecular interactions, the title molecules are more densely packed than those of the other polymorph.