Ab initio study of anharmonicity in high pressure Cmca-4 metallic hydrogen

Hydrogen is the only atom for which the Schr odinger equation is solvable. Consisting only of a proton and an electron, hydrogen is the lightest element and, nevertheless, is far from being simple. Under ambient conditions, it forms diatomic molecules H2 in gas phase, but di erent temperature and pressures lead to a complex phase diagram, which is not completely known yet. Solid hydrogen was rst documented in 1899 [1] and was found to be isolating. At higher pressures, however, hydrogen can be metallized. In 1935 Wigner and Huntington predicted that the metallization pressure would be 25 GPa [2], where molecules would disociate to form a monoatomic metal, as alkali metals that lie below hydrogen in the periodic table. The prediction of the metallization pressure turned out to be wrong: metallic hydrogen has not been found yet, even under a pressure as high as 320 GPa. Nevertheless, extrapolations based on optical measurements suggest that a metallic phase may be attained at 450 GPa [3]. The interest of material scientist in metallic hydrogen can be attributed, at least to a great extent, to Ashcroft, who in 1968 suggested that such a system could be a hightemperature superconductor [4]. The temperature at which this material would exhibit a transition from a superconducting to a non-superconducting state (Tc) was estimated to be around room temperature. The implications of such a statement are very interesting in the eld of astrophysics: in planets that contain a big quantity of hydrogen and whose temperature is below Tc, superconducting hydrogen may be found, specially at the center, where the gravitational pressure is high. This might be the case of Jupiter, whose proportion of hydrogen is about 90%. There are also speculations suggesting that the high magnetic eld of Jupiter is due to persistent currents related to the superconducting phase [5]. Metallization and superconductivity of hydrogen has puzzled scientists for decades, and the community is trying to answer several questions. For instance, what is the structure of hydrogen at very high pressures? Or a more general one: what is the maximum Tc a phonon-mediated superconductor can have [6]? A great experimental e ort has been carried out pursuing metallic hydrogen and trying to answer the questions above; however, the characterization of solid phases of hydrogen is a hard task. Achieving the high pressures needed to get the sought phases requires advanced technologies. Diamond anvil cells (DAC) are commonly used devices. These devices consist of two diamonds with a tip of small area; for this reason, when a force is applied, the pressure exerted is very big. This pressure is uniaxial, but it can be turned into hydrostatic pressure using transmitting media. Nowadays, this method makes it possible to reach pressures higher than 300 GPa, but even at this pressure hydrogen does not show metallic properties. A recently developed technique that is an improvement of DAC can reach pressures as high as 600 GPa [7], so it is a promising step forward in high pressure physics. Another drawback is that the electronic density of the structures is so low that X-ray di raction patterns have low resolution. For these reasons, ab initio studies are an important source of knowledge in this eld, within their limitations. When treating hydrogen, there are many subtleties in the calculations: as the atoms are so light, the ions forming the crystalline lattice have signi cant displacements even when temperatures are very low, and even at T=0 K, due to Heisenberg's uncertainty principle. Thus, the energy corresponding to this zero-point (ZP) motion is signi cant and has to be included in an accurate determination of the most stable phase. This has been done including ZP vibrational energies within the harmonic approximation for a range of pressures and at T=0 K, giving rise to a series of structures that are stable in their respective pressure ranges [8]. Very recently, a treatment of the phases of hydrogen that includes anharmonicity in ZP energies has suggested that relative stability of the phases may change with respect to the calculations within the harmonic approximation [9]. Many of the proposed structures for solid hydrogen have been investigated. Particularly, the Cmca-4 structure, which was found to be the stable one from 385-490 GPa [8], is metallic. Calculations for this structure, within the harmonic approximation for the ionic motion, predict a Tc up to 242 K at 450 GPa [10]. Nonetheless, due to the big ionic displacements, the harmonic approximation may not su ce to describe correctly the system. The aim of this work is to apply a recently developed method to treat anharmonicity, the stochastic self-consistent harmonic approximation (SSCHA) [11], to Cmca-4 metallic hydrogen. This way, we will be able to study the e ects of anharmonicity in the phonon spectrum and to try to understand the changes it may provoque in the value of Tc. The work is structured as follows. First we present the theoretical basis of the calculations: Density Functional Theory (DFT) for the electronic calculations, phonons in the harmonic approximation and the SSCHA. Then we apply these methods to Cmca-4 hydrogen and we discuss the results obtained. In the last chapter we draw some conclusions and propose possible future work.

Charge and spin transport in graphene devices

170 p.

The spectroscopic properties of Er3(+)-doped TeO2-Nb2O5 glasses with high mechanical strength performance

(100 - x)TeO2 - xNb(2)O(5) (x=5-20) mobic tellurite glasses doped with 0.5 mol.% Er2O3 were synthesized, and their thermal, mechanical, and spectroscopic properties were measured and compared to the properties of the typical 75TeO(2)-20ZnO-5Na(2)O (TZN) tellurite glass. The refractive index (n(d)), density (p), and glass transition temperature (T-g) of bulk glasses increase with the Nb2O5 content. The Vickers microhardness (H-v) of bulk glass in niobic tellurite glasses also increases with the Nb2O5 content. The values (2.5-3.2 GPa) of H, in the niobic tellurite glasses are 47-88% larger than that (1.7 GPa) in TZN glass. The effect of Nb2O5 content on absorption spectra, the Judd-Ofelt parameters Omega(t) (t = 2, 4, 6), fluorescence spectra and the lifetimes of Er3+ :I-13/2 level were also investigated, and the stimulated emission crosssection was calculated from McCumber theory. With increasing Nb2O5 content in the glass composition, the Omega(t) (t = 2, 4, 6) parameters, fluorescence full width at half maximum (FWHM) Of I-13/2 of Er3+ increase, while the I-4(13/2) lifetimes of Er3+ decreases. Compared with TZN glass, the gain bandwidth properties of Er3+-doped TeO2-Nb2O5 glass is much larger than in tellurite glass based TeO2-ZnO-Na2O system, bismush-based glass, germanate, and silicate glasses, which indicates that TeO2-Nb2O5 glasses are better choice as a practical available host material for broadband Er3+-doped amplifier. (c) 2005 Elsevier B.V. All rights reserved.

Epitaxial growth of ZnO films on (100) and (001) gamma-LiAlO2 substrates by pulsed laser deposition

Structural and optical properties were investigated for ZnO films grown on (100) and (001) gamma-LiAlO2 (LAO) substrates by pulsed laser deposition method. According XRD results, it is intuitionistic that (100) LAO is suitable for fabricating high quality ZnO film, while (001) LAO is unsuitable. The FWHM of XRD, stress in film and FWHM of UV PL spectra for ZnO films on (100) LAO show a decreasing with increasing substrate temperature from 300 to 600 degrees C. ZnO film fabricated at 600 degrees C has the greatest grain size, the smallest stress (0.47 Gpa) and PL FWHM value (similar to 85 meV). This means that the substrate temperature of 600 degrees C is optimum for ZnO film deposited on (100) LAO. Moreover, it was found that the UV PL spectra intensity of ZnO film is not only related to the grain size and stoichiometric, but also depends on the stress in the film.

Caracterização mecânica e tribológica de dois glazeadores disponíveis comercialmente e uma composição experimental

O objetivo desse estudo, in vitro, foi avaliar através de testes mecânicos e tribológicos, a aplicação de dois glazeadores disponíveis comercialmente e uma composição experimental como material de cobertura em restaurações de resina composta com relação à rugosidade superficial, à dureza e à resistência ao desgaste. Foram confeccionados 24 corpos de prova (CP) do compósito Z350XT (3M/ESPE) e divididos em 4 grupos. O grupo controle (GC) não recebeu selamento, o grupo Biscover LV (GB) recebeu aplicação do Biscover LV (Bisco), o grupo Natural Glaze (GN) recebeu aplicação do Natural Glaze (Nova DFL) e o grupo Experimental (GE) recebeu aplicação de um glazeador experimental contendo nanopartículas (1% em peso). Posteriormente, os CP foram submetidos à análise da rugosidade superficial utilizando um perfilômetro e avaliação da dureza através de um nanoindentador, que fornece também o módulo elástico do material. Em seguida, os CP foram submetidos ao teste de desgaste linear alternado, durante 15.000 ciclos, com carga de 5N, em água destilada. A profundidade máxima de desgaste foi avaliada através de um perfilômetro. A análise dos dados relativos à rugosidade superficial (m) foi realizada utilizando ANOVA/Duncan (p-valor = 0,000). As médias e desvio padrão foram: GC-0,12(0,01); GB-0,06(0,01); GN-0,13(0,02); GE-0,13(0,01). A análise da dureza (GPa) e módulo elástico (GPa) foram avaliados aplicando o teste não-paramétrico de Kruskal-Wallis. As médias e desvio padrão para dureza foram: GC-1,10(0,24); GB-0,31(0,004); GN-0,08(0,004); GE-0,12(0,008) para carga de 1,25mN; GC-1,08(0,139); GB-0,32(0,004); GN-0,08(0,003); GE-0,13(0,006) para carga de 2,5mN; GC-1,10(0,101); GB-0,33(0,003); GN-0,09(0,002); GE-0,13(0,056) para carga de 5,0mN. As médias e desvio padrão para módulo elástico foram: GC-17,71(1,666); GB-5,44(0,084); GN-3,484(0,114); GE-4,55(0,178) para carga de 1,25mN; GC-17,5(1,449); GB-5,18(0,065); GN-3,38(0,078); GE-4,55(0,12) para carga de 2,5mN; GC-17,69(1,793); GB-5,04(0,041); GN-3,63(0,066); GE-4,85(0,104) para carga de 5,0mN. A análise dos dados relativos à profundidade de desgaste (m) foi realizada utilizando ANOVA/Dunnett (p-valor = 0,000). As médias e desvio padrão foram: GC-12,51(0,89); GB-0,59(0,07); GN-1,41(0,12); GE-1,84(0,18). A partir dos resultados apresentados pode-se concluir que apenas o Biscover LV foi capaz de reduzir a rugosidade superficial da resina composta testada. Os demais, Natural Glaze e Experimental, não alteraram a rugosidade superficial e foram estatisticamente semelhantes entre si e com o grupo controle. Todos os glazeadores testados reduziram a dureza e o módulo elástico da resina composta quando comparados com o grupo controle, diferindo entre si, apresentando uma ordem crescente de dureza e módulo elástico (Natural Glaze < Experimental < Biscover < Controle). Todos os glazeadores testados foram capazes de reduzir o desgaste da resina composta, quando comparados com o grupo controle, diferindo entre si, apresentado uma ordem crescente de desgaste (Biscover < Natural Glaze < Experimental < Controle).

Smooth thin film C/diamond membranes with controllable optical band gaps

Mixed phase carbon-diamond films which consist of small grain diamond in an a:C matrix were deposited on polished Si using a radio frequency CH4 Ar plasma CVD deposition process. Ellipsometry, surface profilometry, scanning electron microscopy (SEM) and spectrophotometry were used to analyse these films. Film thicknesses were typically 50-100 nm with a surface roughness of ± 30 A ̊ over centimetre length scans. SEM analysis showed the films were smooth and pinhole free. The Si substrate was etched using backside masking and a directional etch to give taut carbon-diamond membranes on a Si grid. Spectrophotometry was used to analyse the optical properties of these membranes. Band gap control was achieved by varying the dc bias of the deposition process. Band gaps of 1.2 eV to 4.0 eV were achieved in these membranes. A technique for controlling the compressive stress in the films, which can range from 0.02 to 7.5 GPa has been employed. This has allowed the fabrication of thin, low stress, high band gap membranes that are extremely tough and chemically inert. Such carbon-diamond membranes seem promising for applications as windows in analytical instruments. © 1992.

Wet-spinning of amyloid protein nanofibers into multifunctional high-performance biofibers.

Amyloid nanofibers derived from hen egg white lysozyme were processed into macroscopic fibers in a wet-spinning process based on interfacial polyion complexation using a polyanionic polysaccharide as cross-linker. As a result of their amyloid nanostructure, the hierarchically self-assembled protein fibers have a stiffness of up to 14 GPa and a tensile strength of up to 326 MPa. Fine-tuning of the polyelectrolytic interactions via pH allows to trigger the release of small molecules, as demonstrated with riboflavin-5'-phophate. The amyloid fibrils, highly oriented within the gellan gum matrix, were mineralized with calcium phosphate, mimicking the fibrolamellar structure of bone. The formed mineral crystals are highly oriented along the nanofibers, thus resulting in a 9-fold increase in fiber stiffness.

Measurement of forces during the modification of C60 islands

A UHV atomic force microscope with a conducting tip is used to measure the tip-sample conductance as a function of the applied force on well-ordered, monolayer islands of C60 on Cu(111). By imaging the sample before and after each force-distance experiment, it was possible to investigate the forces required for the removal of individual C60 molecules from the islands. The removal of C60 occurs near defects or edges of the C60 islands and requires an applied force of 5-20 nN, which corresponds to applied pressures of order 1 GPa. In addition, it was possible to investigate the strength of the C60 film on the molecular scale. It was found that the mechanical stiffness of a C60 molecule is of order 6 N/m and the islands appear to undergo a reversible yield process at an applied pressure of around 1.2 GPa.

Preparation of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Tetrahedrally bonded amorphous carbon (ta-C) and nitrogen doped (ta-C:N) films were obtained at room temperature in a filtered cathodic vacuum arc (FCVA) system incorporating an off-plane double bend (S-bend) magnetic filter. The influence of the negative bias voltage applied to substrates (from -20 to -350 V) and the nitrogen background pressure (up to 10-3 Torr) on film properties was studied by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-ray photoemission spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and X-ray reflectivity (XRR). The ta-C films showed sp3 fractions between 84% and 88%, and mass densities around 3.2 g/cm3 in the wide range of bias voltage studied. In contrast, the compressive stress showed a maximum value of 11 GPa for bias voltages around -90 V, whereas for lower and higher bias voltages the stress decreased to 6 GPa. As for the ta-C:N films grown at bias voltages below -200 V and with N contents up to 7%, it has been found that the N atoms were preferentially sp3 bonded to the carbon network with a reduction in stress below 8 GPa. Further increase in bias voltage or N content increased the sp2 fraction, leading to a reduction in film density to 2.7 g/cm3.

Ultrastructural mechanical and material characterization of fossilized bone

Bone plays a key role in the paleontological and archeological records and can provide insight into the biology, ecology and the environment of ancient vertebrates. Examination of bone at the tissue level reveals a definitive relationship between nanomechanical properties and the local organic content, mineral content, and microstructural organization. However, it is unclear as to how these properties change following fossilization, or diagenesis, where the organic phase is rapidly removed and the remaining mineral phase is reinforced by the deposition of apatites, calcites, and other minerals. While the process of diagenesis is poorly understood, its outcome clearly results in the potential for dramatic alteration of the mechanical response of biological tissues. In this study, fossilized specimens of mammalian long bones, collected from Colorado and Wyoming, were studied for mechanical variations. Nanoindentation performed in both longitudinal and transverse directions revealed preservation of bone's natural anisotropy as transverse modulus values were consistently smaller than longitudinal values. Additionally, modulus values of fossilized bone from 35.0 to 89.1 GPa increased linearly with logarithm of the sample's age. Future studies will aim to clarify what mechanical and material elements of bone are retained during diagenesis as bone becomes part of the geologic milieu. © 2007 Materials Research Society.

Insight into differences in nanoindentation properties of bone.

Nanoindentation provides the ideal framework to determine mechanical properties of bone at the tissue scale without being affected by the size, shape, and porosity of the bone. However, the values of tissue level mechanical properties vary significantly between studies. Since the differences in the bone sample, hydration state, and test parameters complicate direct comparisons across the various studies, these discrepancies in values cannot be compared directly. The objective of the current study is to evaluate and compare mechanical properties of the same bones using a broad range of testing parameters. Wild type C56BL6 mice tibiae were embedded following different processes and tested in dry and rehydrated conditions. Spherical and Berkovich indenter probes were used, and data analysis was considered within the elasto-plastic (Oliver-Pharr), viscoelastic and visco-elastic-plastic frameworks. The mean values of plane strain modulus varied significantly depending on the hydration state, probe geometry and analysis method. Indentations in dry bone analyzed using a visco-elastic-plastic approach gave values of 34 GPa. After rehydrating the same bones and indenting them with a spherical tip and utilizing a viscoelastic analysis, the mean modulus value was 4 GPa, nearly an order of magnitude smaller. Results suggest that the hydration state, probe geometry and the limitations and assumptions of each analysis method influence significantly the measured mechanical properties. This is the first time that such a systematic study has been carried out and it has been concluded that the discrepancies in the mechanical properties of bone measured by nanoindentation found in the literature should not be attributed only to the differences between the bones themselves, but also to the testing and analysis protocols.

Elastic properties of crystalline-amorphous core-shell silicon nanowires

The pressure behavior of Raman frequencies and line widths of crystalline core-amorphous shell silicon nanowires (SiNWs) with two different core-to-shell ratio thicknesses was studied at pressures up to 8 GPa. The obtained isothermal compressibility (bulk modulus) of SiNWs with a core-to-shell ratio of about 1.8 is ∼20% higher (lower) than reported values for bulk Si. For SiNWs with smaller core-to-shell ratios, a plastic deformation of the shell was observed together with a strain relaxation. A significant increase in the full width at half-maximum of the Raman LTO-peak due to phonon decay was used to determine the critical pressure at which LTO-phonons decay into LO + TA phonons. Our results reveal that this critical pressure in strained core-shell SiNWs (∼4 GPa) is different from the reported value for bulk Si (∼7 GPa), whereas no change is observed for relaxed core-shell SiNWs. © 2013 American Chemical Society.

Handbook of nanoindentation with biological applications

Nanoindentation is ideal for the characterization of inhomogeneous biological materials. However, the use of nanoindentation techniques in biological systems is associated with some distinctively different techniques and challenges. For example, engineering materials used in the microelectronics industry (e.g. ceramics and metals) for which the technique was developed, are relatively stiff and exhibit time-independent mechanical responses. Biological materials, on the other hand, exhibit time-dependent behavior, and can span a range of stiffness regimes from moduli of Pa to GPa - eight to nine orders of magnitude. As such, there are differences in the selection of instrumentation, tip geometry, and data analysis in comparison with the "black box" nanoindentation techniques as sold by commercial manufacturers. The use of scanning probe equipment (atomic force miscroscopy) is also common for small-scale indentation of soft materials in biology. The book is broadly divided into two parts. The first part presents the "basic science" of nanoindentation including the background of contact mechanics underlying indentation technique, and the instrumentation used to gather mechanical data. Both the mechanics background and the instrumentation overview provide perspectives that are optimized for biological applications, including discussions on hydrated materials and adaptations for low-stiffness materials. The second part of the book covers the applications of nanoindentation technique in biological materials. Included in the coverage are mineralized and nonmineralized tissues, wood and plant tissues, tissue-engineering substitute materials, cells and membranes, and cutting-edge applications at molecular level including the use of functionalized tips to probe specific molecular interactions (e.g. the ligand-receptor binding). The book concludes with a concise summary and an insightful forecast of the future highlighting the current challenges. © 2011 by Pan Stanford Publishing Pte. Ltd. All rights reserved.

Investigation of the Young's modulus and thermal expansion of amorphous titania-doped tantala films

The current generation of advanced gravitational wave detectors utilize titania-doped tantala/silica multilayer stacks for their mirror coatings. The properties of the low-refractive-index silica are well known; however, in the absence of detailed direct measurements, the material parameters of Young's modulus and coefficient of thermal expansion (CTE) of the high refractive index material, titania-doped tantala, have been assumed to be equal to values measured for pure tantala coatings. In order to ascertain the true values necessary for thermal noise calculations, we have undertaken measurements of Young's modulus and CTE through the use of nanoindentation and thermal-bending measurements. The measurements were designed to assess the effects of titania doping concentration and post-deposition heat-treatment on the measured values in order to evaluate the possibility of optimizing material parameters to further improve thermal noise in the detector. Young's modulus measurements on pure tantala and 25% and 55% titania-doped tantala show a wide range of values, from 132 to 177 GPa, dependent on both titania concentration and heat-treatment. Measurements of CTE give values of (3.9 +/- 0.1) x 10^-6 K^-1 and (4.9 +/- 0.3) x 10^-6 K^-1 for 25% and 55% titania-doped tantala, respectively, without dependence on post-deposition heat-treatment.

First-principles study of ground-state properties and high pressure behavior of ThO2

The mechanical properties, electronic structure and phonon dispersion of ground state ThO2 as well as the structure behavior up to 240 GPa are studied using first-principles density-functional theory. Our calculated elastic constants indicate that both the ground-state fluorite structure and high pressure cotunnite structure of ThO2 are mechanically stable. The bulk modulus, shear modulus, and Young's modulus of cotunnite ThO2 are all smaller by approximately 25% compared with those of fluorite ThO2. The Poisson's ratios of both structures are approximately equal to 0.3 and the hardness of fluorite ThO2 is 22.4 GPa. The electronic structure and bonding nature of fluorite ThO2 are fully analyzed, and show that the Th-O bond displays a mixed ionic/covalent character. The phase transition from the fluorite to cotunnite structure is calculated to occur at the pressure of 26.5 GPa, consistent with recent experimental measurement by ldiri et al. [1]. For the cotunnite phase it is further predicted that an isostructural transition takes place in the pressure region of 80-130 GPa.