Bone response to biosilicates® with different crystal phases

The aim of this study was to investigate the histological and histomorphometrical bone response to three Biosilicates with different crystal phases comparing them to Bioglass®45S5 implants used as control. Ceramic glass Biosilicate and Bioglass®45S5 implants were bilaterally inserted in rabbit femurs and harvested after 8 and 12 weeks. Histological examination did not revealed persistent inflammation or foreign body reaction at implantation sites. Bone and a layer of soft tissue were observed in close contact with the implant surfaces in the medullary canal. The connective tissue presented few elongated cells and collagen fibers located parallel to implant surface. Cortical portion after 8 weeks was the only area that demonstrated significant difference between all tested materials, with Biosilicate 1F and Biosilicate 2F presenting higher bone formation than Bioglass®45S5 and Biosilicate® vitreo (p=0.02). All other areas and periods were statistically non-significant (p>0.05). In conclusion, all tested materials were considered biocompatible, demonstrating surface bone formation and a satisfactory behavior at biological environment.

Different coordination modes for disulfoxides towards diorganotin(IV) dichlorides. X-ray crystal structures of 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) and adducts [{Ph2SnCl2(meso-bpse)}n] and [{n-Bu2SnCl2(pdtd)}2]

The reactions of meso-1,2-bis(phenylsulfinyl)ethane (meso-bpse) with Ph2SnCl2, 2-phenyl-1,3-dithiane trans-1-trans-3-dioxide (pdtd) with n-Bu2SnCl2 and 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) with Ph2SnCl2, in 1:1 molar ratio, yielded [{Ph2SnCl2(meso-bpse)}n], [{n-Bu2SnCl2(pdtd)}2] and [{Ph2SnCl2(rac,cis-cbpse)}x] (x = 2 or n), respectively. All adducts were studied by IR, Mössbauer and 119Sn NMR spectroscopic methods, elemental analysis and single crystal X-ray diffractometry. The X-ray crystal structure of [{Ph2SnCl2(meso-bpse)}n] revealed the occurrence of infinite chains in which the tin(IV) atoms appear in a distorted octahedral geometry with Cl atoms in cis and Ph groups in trans positions. The X-ray crystal structure of [{n-Bu2SnCl2(pdtd)}2] revealed discrete centrosymmetric dimeric species in which the tin(IV) atoms possess a distorted octahedral geometry with bridging disulfoxides in cis and n-butyl moieties in trans positions. The spectroscopic data indicated that the adduct containing the rac,cis-cbpse ligand can be dimeric or polymeric. The X-ray structural analysis of the free rac-,cis-cbpse sulfoxide revealed that the crystals belong to the C2/c space group.

Nanostructured thin films obtained by electrodeposition over a colloidal crystal template: applications in electrochemical devices

Colloidal particles have been used to template the electrosynthesis of several materials, such as semiconductors, metals and alloys. The method allows good control over the thickness of the resulting material by choosing the appropriate charge applied to the system, and it is able to produce high density deposited materials without shrinkage. These materials are a true model of the template structure and, due to the high surface areas obtained, are very promising for use in electrochemical applications. In the present work, the assembly of monodisperse polystyrene templates was conduced over gold, platinum and glassy carbon substrates in order to show the electrodeposition of an oxide, a conducting polymer and a hybrid inorganic-organic material with applications in the supercapacitor and sensor fields. The performances of the resulting nanostructured films have been compared with the analogue bulk material and the results achieved are depicted in this paper.

Numerical comparison between conventional dispersion compensating fibers and photonic crystal fibers as lumped Raman amplifiers

In this paper we discuss the use of photonic crystal fibers (PCFs) as discrete devices for simultaneous wideband dispersion compensation and Raman amplification. The performance of the PCFs in terms of gain, ripple, optical signal-to-noise ratio (OSNR) and required fiber length for complete dispersion compensation is compared with conventional dispersion compensating fibers (DCFs). The main goal is to determine the minimum PCF loss beyond which its performance surpasses a state-of-the-art DCF and justifies practical use in telecommunication systems. (C) 2009 Optical Society of America

Design methodology for multi-pumped discrete Raman amplifiers: case-study employing photonic crystal fibers

This paper proposes a new design methodology for discrete multi-pumped Raman amplifier. In a multi-objective optimization scenario, in a first step the whole solution-space is inspected by a CW analytical formulation. Then, the most promising solutions are fully investigated by a rigorous numerical treatment and the Raman amplification performance is thus determined by the combination of analytical and numerical approaches. As an application of our methodology we designed an photonic crystal fiber Raman amplifier configuration which provides low ripple, high gain, clear eye opening and a low power penalty. The amplifier configuration also enables to fully compensate the dispersion introduced by a 70-km singlemode fiber in a 10 Gbit/s system. We have successfully obtained a configuration with 8.5 dB average gain over the C-band and 0.71 dB ripple with almost zero eye-penalty using only two pump lasers with relatively low pump power. (C) 2009 Optical Society of America

Phase transformation and residual stress probed by Raman spectroscopy in diamond-turned single crystal silicon

Single-point diamond turning of monocrystalline semiconductors is an important field of research within brittle materials machining. Monocrystalline silicon samples with a (100) orientation have been diamond turned under different cutting conditions (feed rate and depth of cut). Micro-Raman spectroscopy and atomic force microscopy have been used to assess structural alterations and surface finish of the samples diamond turned under ductile and brittle modes. It was found that silicon undergoes a phase transformation when machined in the ductile mode. This phase transformation is evidenced by the creation of an amorphous surface layer after machining which has been probed by Raman scattering. Compressive residual stresses are estimated for the machined surface and it is observed that they decrease with an increase in the feed rate and depth of cut. This behaviour has been attributed to the formation of subsurface cracks when the feed rate is higher than or equal to 2.5 mu m/rev. The surface roughness was observed to vary with the feed rate and the depth of cut. An increase in the surface roughness was influenced by microcrack formation when the feed rate reached 5.0 mu m/rev. Furthermore, a high-pressure phase transformation induced by the tool/material interaction and responsible for the ductile response of this typical brittle material is discussed based upon the presented Raman spectra. The application of this machining technology finds use for a wide range of high quality components, for example the creation of a micrometre-range channel for microfluidic devices as well as microlenses used in the infrared spectrum range.

Frequency upconversion luminescence from Yb(+3)-Tm(+3) codoped PbO-GeO(2) glasses containing silver nanoparticles

Infrared-to-visible and infrared-to-infrared frequency upconversion processes in Yb(3+)-Tm(3+) doped PbO-GeO(2) glasses containing silver nanoparticles (NPs) were investigated. The experiments were performed by exciting the samples with a diode laser operating at 980 nm (in resonance with the Yb(3+) transition (2)F(7/2)->(2)F(5/2)) and observing the photoluminescence (PL) in the visible and infrared regions due to energy transfer from Yb(3+) to Tm(3+) ions followed by excited state absorption in the Tm3+ ions. The intensified local field in the vicinity of the metallic NPs contributes for enhancement in the PL intensity at 480 nm (Tm(3+) :(1)G(4)->(3)H(6)) and at 800 nm (Tm(3+) : (3)H(4) -> (3)H(6)). (C) 2009 American Institute of Physics. [doi:10.1063/1.3211300]

Mechanism of point-defect diffusion in a two-dimensional colloidal crystal

The dynamics and mechanism of migration of a vacancy point defect in a two-dimensional (2D) colloidal crystal are studied using numerical simulations. We find that the migration of a vacancy is always realized by topology switching between its different configurations. From the temperature dependence of the topology switch frequencies, we obtain the activation energies for possible topology transitions associated with the vacancy diffusion in the 2D crystal. (C) 2011 American Institute of Physics. [doi:10.1063/1.3615287]

Structural and optical properties of rare earth-doped (Ba(0.77)Ca(0.23))(1-x)(Sm, Nd, Pr, Yb)(x)TiO(3)

The structural, dielectric, and vibrational properties of pure and rare earth (RE)-doped Ba(0.77) Ca(0.23)TiO(3) (BCT23; RE = Nd, Sm, Pr, Yb) ceramics obtained via solid-state reaction were investigated. The pure and RE-doped BCT23 ceramics sintered at 1450 degrees C in air for 4 h showed a dense microstructure in all ceramics. The use of RE ions as dopants introduced lattice-parameter changes that manifested in the reduction of the volume of the unit cell. RE-doped BCT23 samples exhibit a more homogenous microstructure due to the absence of a Ti-rich phase in the grain boundaries as demonstrated by scanning electron microscopy imaging. The incorporation of REs led to perturbations of the local symmetry of TiO(6) octahedra and the creation of a new Raman mode. The results of Raman scattering measurements indicated that the Curie temperature of the ferroelectric phase transition depends on the RE ion and ion content, with the Curie temperature shifting toward lower values as the RE content increases, with the exception of Yb(3+) doping, which did not affect the ferroelectric phase transition temperature. The phase transition behavior is explained using the standard soft mode model. Electronic paramagnetic resonance measurements showed the existence of Ti vacancies in the structure of RE-doped BCT23. Defects are created via charge compensation mechanisms due to the incorporation of elements with a different valence state relative to the ions of the pure BCT23 host. It is concluded that the Ti vacancies are responsible for the activation of the Raman mode at 840 cm(-1), which is in agreement with lattice dynamics calculations. (c) 2011 American Institute of Physics. [doi:10.1063/1.3594710]

Structural models for yttrium aluminium borate laser glasses: NMR and EPR studies of the system (Y(2)O(3))(0.2)-(Al(2)O(3))(x)-(B(2)O(3))(0.8-x)

The structure of laser glasses in the system (Y(2)O(3))(0.2){(Al(2)O(3))(x))(B(2)O(3))(0.8-x)} (0.15 <= x <= 0.40) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as electron spin echo envelope modulation (ESEEM) of Yb-doped samples. The latter technique has been applied for the first time to an aluminoborate glass system. (11)B magic-angle spinning (MAS)-NMR spectra reveal that, while the majority of the boron atoms are three-coordinated over the entire composition region, the fraction of three-coordinated boron atoms increases significantly with increasing x. Charge balance considerations as well as (11)B NMR lineshape analyses suggest that the dominant borate species are predominantly singly charged metaborate (BO(2/2)O(-)), doubly charged pyroborate (BO(1/2)(O(-))(2)), and (at x = 0.40) triply charged orthoborate groups. As x increases along this series, the average anionic charge per trigonal borate group increases from 1.38 to 2.91. (27)Al MAS-NMR spectra show that the alumina species are present in the coordination states four, five and six, and the fraction of four-coordinated Al increases markedly with increasing x. All of the Al coordination states are in intimate contact with both the three-and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, non-segregated glass structure. (89)Y solid state NMR spectra show a significant chemical shift trend, reflecting that the second coordination sphere becomes increasingly ""aluminate-like'' with increasing x. This conclusion is supported by electron spin echo envelope modulation (ESEEM) data of Yb-doped glasses, which indicate that both borate and aluminate species participate in the medium range structure of the rare-earth ions, consistent with a random spatial distribution of the glass components.

Partial magnetic ordering and crystal structure of the ludwigites Co(2)FeO(2)BO(3) and Ni(2)FeO(2)BO(3)

We present an extensive study of the structural, magnetic, and thermodynamic properties of the two heterometallic oxyborates: Co(2)FeO(2)BO(3) and Ni(2)FeO(2)BO(3). This has been carried out through x-ray diffraction at room temperature (RT) and 150 K, dc and ac magnetic susceptibilities, and specific-heat experiments in single crystals above 2 K. The magnetic properties of these iron ludwigites are discussed in comparison with those of the other two known homometallic ludwigites: Fe(3)O(2)BO(3) and Co(3)O(2)BO(3). In both ludwigites now studied we have found that the magnetic ordering of the Fe(3+) ions occurs at temperatures very near to which they order in Fe(3)O(2)BO(3). A freezing of the divalent ions (Co and Ni) is observed at lower temperatures. Our x-ray diffraction study of both ludwigites at RT and 150 K showed very small ionic disorder in apparent contrast with the freezing of the divalent ion spins. The structural transition that occurs in homometallic Fe(3)O(2)BO(3) has not been found in the present mixed ludwigites in the temperature range investigated.

Nonlinear refraction and absorption through phase transition in a Nd:SBN laser crystal

Time-resolved Z-scan measurements were performed in a Nd(3+)-doped Sr(0.61)Ba(0.39)Nb(2)O(6) laser crystal through ferroelectric phase transition. Both the differences in electronic polarizability (Delta alpha(p)) and cross section (Delta sigma) of the neodymium ions have been found to be strongly modified in the surroundings of the transition temperature. This observed unusual behavior is concluded to be caused by the remarkable influence that the structural changes associated to the ferro-to-paraelectric phase transition has on the 4f -> 5d transition probabilities. The maximum polarizability change value Delta alpha(p)=1.2x10(-25) cm(3) obtained at room temperature is the largest ever measured for a Nd(3+)-doped transparent material.

Microstructuration induced differences in the thermo-optical and luminescence properties of Nd:YAG fine grain ceramics and crystals

The temperature and compositional dependences of thermo- optical properties of neodymium doped yttrium aluminum garnet (YAG) crystals and fine grain ceramics have been systematically investigated by means of time- resolved thermal lens spectrometry. We have found that Nd:YAG ceramics show a reduced thermal diffusivity compared to Nd:YAG single crystals in the complete temperature range investigated (80-300 K). The analysis of the time- resolved luminescent properties of Nd(3+) has revealed that the reduction in the phonon mean free path taking place in Nd:YAG ceramics cannot be associated with an increment in the density of lattice defects, indicating that phonon scattering at grain boundaries is the origin of the observed reduction in the thermal diffusivity of Nd: YAG ceramics. Finally, our results showed the ability of the time- resolved thermal lens to determine and optimize the thermo- optical properties of Nd: YAG ceramic based lasers. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.2975335]

A monohydrate pseudopolymorph of 3,4-dihydroxybenzophenone and the role of water in the crystal assembly of benzophenones

During a polymorphism screening of hydroxybenzophenone derivatives, a monohydrate pseudopolymorph of (3,4-dihydroxyphenyl)(phenyl)methanone, C(13)H(10)O(3)center dot H(2)O, (I), was obtained. Structural relationships and the role of water in crystal assembly were established on the basis of the known anhydrous form [Cox, Kechagias & Kelly (2008). Acta Cryst. B64, 206-216]. The crystal packing of (I) is stabilized by classical intermolecular O-H...O hydrogen bonds, generating a three-dimensional network.

Influence of Poly(Vinyl Alcohol) (PVA) on the Cyclic-Voltammetry Behavior of Single-Crystal Pt Surfaces in Aqueous H(2)SO(4)

In the present work we investigated the electrochemical behavior of PVA on polycrystalline Pt and single-crystal Pt electrodes. PVA hampered the characteristic hydrogen UPD and anion adsorption on all investigated surfaces, with the processes on Pt(110) being the most affected by the PVA presence. Several oxidation waves appeared as the potential was swept in the positive direction and the Pt(111) was found to be the most active for the oxidation processes. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3615965] All rights reserved.