Investigation of electrical conductivity as a function of dopant-ion radius in the systems Zr0.75Ce0.08M0.17O1.92 (M=Nd, Sm, Gd, Dy, Ho, Y, Er, Yb, Sc)

Electrical conductivity versus dopant ionic radius studies in zirconia- and ceria-based, solid oxide fuel cell (SOFC) electrolyte systems have shown that oxygen-ion conductivity is highest when the host and dopant ions are similar in size [J. Am. Ceram. Soc. 48 (1965) 286; Solid State Ionics 37 (1989) 67; Solid State Ionics 5 (1981) 547]. Under these conditions, it is thought that the conduction paths within the crystal lattice become less distorted [Solid State Ionics 8 (1983) 201]. In this study, binary ZrO2-M2O3 unit cells were expanded, via the partial substitution of Ce+4 for Zr+4 into the lattice, in an attempt to identify new, ternary, zirconia/ceria-based electrolyte systems with enhanced electrical conductivity. The compositions Zr0.75Ce0.08M0.17O1.92 (M = Nd, Sm, Gd, Dy, Ho, Y, Yb, Sc) were prepared using traditional solid state techniques. Bulk phase characterisation and precise lattice parameter measurements were performed with X-ray diffraction techniques. Four-probe DC conductivity measurements between 400 and 900 degreesC showed that the dopant-ion radius influenced electrical conductivity. The conductivity versus dopant-ion radius trends previously observed in zirconia-based, binary systems are clearly apparent in the ternary systems investigated in this study. The addition of ceria was found to have a negative influence on the electrical conductivity over the temperature range 400-900 degreesC. It is suggested that distortion of the oxygen-ion conduction path by the presence of the larger M+3 and Ce+4 species (relative to Zr+4) is the reason for the decreasing electrical conductivity as a function of increasing dopant size and ceria addition, respectively. (C) 2002 Elsevier Science B.V. All rights reserved.

Mineral inventory of continuously erupting basaltic andesites at Arenal volcano, Costa Rica: implications for interpreting monotonous, crystal-rich, mafic arc stratigraphies

Except for the first 2 years since July 29, 1968, Arenal volcano has continuously erupted compositionally monotonous and phenocryst-rich (similar to35%) basaltic andesites composed of plagioclase (plag), orthopyroxene (opx), clinopyroxene (cpx), spinel olivine. Detailed textural and compositional analyses of phenocrysts, mineral inclusions, and microlites reveal comparable complexities in any given sample and identify mineral components that require a minimum of four crystallization environments. We suggest three distinct crystallization environments crystallized low Mg# (<78) silicate phases from andesitic magma but at different physical conditions, such as variable pressure of crystallization and water conditions. The dominant environment, i.e., the one which accounts for the majority of minerals and overprinted all other assemblages near rims of phenocrysts, cocrystallized clinopyroxene (Mg# similar to71-78), orthopyroxene (Mg# similar to71-78), titanomagnetite and plagioclase (An(60) to An(85)). The second environment cocrystallized clinopyroxene (Mg# 71-78), olivine (<Fo(78)), titanomagnetite, and very high An (similar to90) plagioclase, while the third cocrystallized clinopyroxene (Mg# 71-78) with high (>7) Al/Ti and high (>4 wt.%) Al2O3, titanomagnetite with considerable Al2O3 (10-18 wt.%) and possibly olivine but appears to lack plagioclase. A fourth crystallization environment is characterized by clinopyroxene (e.g., Mg#=similar to78-85; Cr2O3=0.15-0.7 wt.%), Al-, Cr-rich spinel olivine (similar toFo(80)), and in some circumstances high-An (>80) plagioclase. This assemblage seems to record mafic inputs into the Arenal system and crystallization at high to low pressures. Single crystals cannot be completely classified as xenocrysts, antecrysts (cognate crystals), or phenocrysts, because they often contain different parts each representing a different crystallization environment and thus belong to different categories. Bulk compositions are mostly too mafic to have crystallized the bulk of ferromagnesian minerals and thus likely do not represent liquid compositions. On the other hand, they are the cumulative products of multiple mixing events assembling melts and minerals from a variety of sources. The driving force for this multistage mixing evolution to generate erupting basaltic andesites is thought to be the ascent of mafic magma from lower crustal levels to subvolcanic depths which at the same time may also go through compositional modification by fractionation and assimilation of country rocks. Thus, mafic magmas become basaltic andesite through mixing, fractionation and assimilation by the time they arrive at subvolcanic depths. We infer new increments of basaltic andesite are supplied nearly continuously to the subvolcanic reservoir concurrently to the current eruption and that these new increments are blended into the residing, subvolcanic magma. Thus, the compositional monotony is mostly the product of repetitious production of very similar basaltic andesite. Furthermore, we propose that this quasi-constant supply of small increments of magma is the fundamental cause for small-scale, decade-long continuous volcanic activity; that is, the current eruption of Arenal is flux-controlled by inputs of mantle magmas. (C) 2004 Elsevier B.V. All rights reserved.

Emission, kinetic and magnetic phenomena in rare-earth and transition metal doped ZnSe single crystals

In this work emission, optical, electrical and magnetic properties of the d- and f- elements doped zinc selenide crystals were investigated within a wide temperature range. Doping was performed in various technological processes: during the growth by chemical vapor transport method; by thermal diffusion from the Bi or Zn melt. Concentration of the doping impurity in the crystals was controlled by amount of the dopant in the source material or by its concentration in the doping media. Special interest in the work was paid to the influence of the different concentrations of Cr and Yb impurities on ZnSe crystals’ properties, correlations between observed effects and similarities with the Ni, Mn and Gd dopants are analysed. Possibility of formation of the excitons bound to the doping d-ions was shown. In contrast to this, it was observed that f-elements do not bound excitons, but prevent formation of excitons bound to some uncontrolled impurities. A mechanism of Cr doping impurity interaction with background impurities and zinc selenide structural defects was proposed based on experimental data. An assumption about resonant energy transfer between double charged chromium ions and complexes based on crystals’ vacancy defects was made. A correlation between emission and magnetic properties of the d- ions doped samples was established. Based on this correlation a mechanism explaining the concentration quench of the emission was proposed. It was found that f-ions bind electrically active shallow and deep donor and acceptor states of background impurity to electrically neutral complexes. This may be observed as “purification” of ZnSe crystals by doping with the rare-earth elements, resulting i tendency of the properties of f-ion doped crystals to the properties of intrinsic crystals, but with smaller concentration of uncontrolled native and impurity defects. A possible interpretation of this effect was proposed. It was shown that selenium substituting impurities decrease efficiency of the Yb doping. Based on this experimental results an attempt to determine ytterbium ion surroundings in the crystal lattice was made. It was shown that co-doping of zinc selenide crystals with the d- and f- ions leads to the combination of the impurities influence on the material’s properties. On the basis of obtained data an interaction mechanism of the d- and f-elements co-dopants was proposed. Guided by the model of the ytterbium ion incorporation in the selenide sublattice of the ZnSe crystals, an assumption about stabilization of single charged chromium ions in the zinc sublattice crystal nodes, by means of formation of the local charge compensating clusters, was made.

Electrical properties of some single crystal dodecaborides /|nby Jyoti Burte. -- 260 St. Catharines [Ont. : s. n.],

PreVi011.3 ':i or~ : indicat e('. tk~t ho t~)rE's sed ~-Al B 12 1i~2, ~' a semiconductor. r:Toreove r , the s i mpl.(~ electronic t heory also indi cates that ~ -AIB1 2 should be a semico nductor, since thf're is one nonbonding e 'Le ctrofl per AlB12- uni t. JPor these reasons, we decided to measure t he electrical n ropert i ~ s of ~ -AlB1 2 single crystal s . Singl e crystal s of¥- AIB 12 ab ou t 1 x 1 r1n1 . size were grown from a copper mel t at 12500 C. The melt technique coupled. 1,vi th slow cooling vilas used because of i ts advantages such as : siTYInle set- up of the expe rimon t ; only e ;l.sil y available c hemi cals are required and it i s a c omparatively strair::bt forvvard y,le t hod still yielding crystal s big enouGh for OtU' purpose . Copper rms used as a solvent , i nst8ad of previOl.wly used aluminum , because it allows c.l.'ystal growth at hig he r t emneratures. HovlGver, the cry s tals of ] -AlB12 shm'red very hi gh res i s t ance a t r oom temperature . From our neasureJ'lents we conclude that the r esistivity of j3- Al B12 is, at least, given as ~ = 4. x 107 oblD .em •• Those results are inc ons i s t ent wi 'uh the ones .. reported by IIiss Khin fo r bot- pressed j3-AlB12 g i ven a s = 7600 ohm . em . or I e s s . ' Since tbe hot pressing was done at about 800 - ' 9000C i n ~ rap hi te moul ds 1,7i th 97% AlB12- p oVJder, vie thi nk there is pas s ib i 1 i ty th a.t lower borides or borot] carbide are , being formed, ':.Jhich are k11 own to be good semiconductors . v7e tried to ro-pe r-AlB12 by addi'J,'?: agents s uch as l:Ig , IG.-InO 4. ' HgS04 , KI12PO 4·' etc. to t he melt .. However , all these re age 11 t eel either reduced the yield and size of t lJe crystals or r;ave crystals of high r esis'can ce again. We think tba t molten copper keeps t he i mpurities off . There is also a pos s i bil i ty t hc:!,t these doping agents get oxidi~::;ed at '1 250°C • Hence, we co ~ clud e that J -AIB12 has v~ ry high r es i stance at r oom temperature . This was a l s o C011 - fi rmed by checki ng the siYlgle and. polycrystals of .~-AIB12 from Norton Co., Ontario and Cooper Nletallurgical Association. Boron carbide has been reported to be a semiconductor with ~ - 0.3 to 0.8 ohm . cm. for hotpres sed s araples. Boron carbide b e inq: struct urally related to ¥-AIB12 , we de cided to study the electrical prone rties of it~ Single crystals. These crystals were cut from a Single melt grovvn crystal a t Norton Co., Ontario. The resistivity of th," se crystal s was measured by the Van der Pam-v' s ~ nethod, which \vas very c onvenient fo r our crystal sha-pp.s. Some of the crystals showed resistivity ~ == 0.50 ob,Tn.cr] . i n agreement with the previously reported results . However , a few crystals showed lower resistivity e.g . 0 .13 and 0.20 ohm.cra • • The Hall mobility could .not be measured and th8reiore i s lower than 0 .16 em 2 v - 1 sec -1 • This is in agreement \vith t he re1)orted Hall mobility for pyrolytic boron . _ 2 -1 -1 carbide as 0.13 cm v sec • We also studied the orientation of the boron carbide crystals by the Jjaue-method. The inclination of c-axis with res pect to x-ray be81Il was det ermined . This was found to be 100 t o 20° f or normal resistivity sarnples (0.5 ohm . cm.) and 27 - 30° for t he lower r esistivity samples (0.1 ~5 to 0.20 ohm.cm .). This indica tes the possibility that th.e r es if.1tivity of B13C3 i s orientation dependent.

Nonlinear Dynamics of Nd:YAG lasers: Hopf bifurcation, Multistability and Chaotic Synchronization

In this thesis we have presented some aspects of the nonlinear dynamics of Nd:YAG lasers including synchronization, Hopf bifurcation, chaos control and delay induced multistability.We have chosen diode pumped Nd:YAG laser with intracavity KTP crystal operating with two mode and three mode output as our model system.Different types of orientation for the laser cavity modes were considered to carry out the studies. For laser operating with two mode output we have chosen the modes as having parallel polarization and perpendicular polarization. For laser having three mode output, we have chosen them as two modes polarized parallel to each other while the third mode polarized orthogonal to them.

Hopf bifurcation in parallel polarized Nd:YAG laser

Dynamics of Nd:YAG laser with intracavity KTP crystal operating in two parallel polarized modes is investigated analytically and numerically. System equilibrium points were found out and the stability of each of them was checked using Routh–Hurwitz criteria and also by calculating the eigen values of the Jacobian. It is found that the system possesses three equilibrium points for (Ij, Gj), where j = 1, 2. One of these equilibrium points undergoes Hopf bifurcation in output dynamics as the control parameter is increased. The other two remain unstable throughout the entire region of the parameter space. Our numerical analysis of the Hopf bifurcation phenomena is found to be in good agreement with the analytical results. Nature of energy transfer between the two modes is also studied numerically.

Eficacia del plasma rico en plaquetas en procedimientos médicos estéticos faciales . Evaluación en contorno de ojos.

Introducción: En la actualidad se están implementando nuevas técnicas, para el tratamiento de líneas de expresión facial. El Plasma Rico en Plaquetas (PRP) utiliza factores de crecimiento humano autólogos con fines médicos estéticos. El objetivo de este trabajo fue evaluar el tratamiento con plasma rico en plaquetas en el manejo del rejuvenecimiento periocular. Materiales y métodos: Estudio descriptivo retrospectivo en una cohorte de 27 pacientes entre 30 a 70 años de ambos sexos,tratados con PRP sin tratamientos médicos estéticos previos . Se compararon fotografías del sistema VISIA®, previo y posterior el PRP, para determinar los cambios del área periocular. Con análisis comparativo de medias utilizando pruebas t de student. Resultados: De 27 historias clínicas revisadas 96,3% eran mujeres, la edad promedio fue de 52.67 años. Se observaron cambios clínicos satisfactorios en el manejo del foto envejecimiento periocular con mejoría estadísticamente significativa entre el promedio inicial y el post tratamiento en arrugas, textura y porfirinas (p: 0.000). No se observaron diferencias estadísticamente significativas entre los grupos de edad (p = 0,62). Los pacientes analizados posterior al tratamiento se encuentran en mejor estado que el 63,78% de la población de su mismo sexo, edad y fototipo de piel. Los eventos adversos fueron disminuyendo en su frecuencia en cada una de las sesiones siguientes. Discusión: El PRP proporciona una mejoría global en los parámetros de envejecimiento periocular lo cual se correlaciono con los estudios previos in vitro. Conclusiones: El PRP es seguro y eficaz en contorno de ojos.

Structure determination, magnetic and optical properties of a new chromium(II) thioantimonate, [Cr((NH2CH2CH2)(3)N)]Sb4S7

The chromium(II) antimony(III) sulphicle, [Cr((NH2CH2CH2)(3)N)]Sb4S7, was synthesised under solvothermal conditions from the reaction of Sb2S3. Cr and S dissolved in tris(2-aminoethyl)amine (tren) at 438 K. The products were characterised by single-crystal X-ray diffraction. elemental analysis, SQUID magnetometry and diffuse reflectance spectroscopy. The compound crystallises in the monoclinic space group P2(1)/n with a = 7.9756(7), b = 10.5191(9), c = 25.880(2) angstrom and beta = 90.864(5)degrees. Alternating SbS33- trigonal pyramids and Sb36 semi-cubes generate Sb4S72- chains which are directly bonded to Cr(tren pendant units. The effective magnetic moment of 4.94(6)mu(B) shows a negligible orbital contribution, in agreement with expectations for Cr(II):d(4) in a (5)A ground state. The measured band gap of 2.14(3) eV is consistent with a correlation between optical band gap and framework density that is established from analysis of a wide range of antimony sulphides. (C) 2007 Elsevier Ltd. All rights reserved.

[Cr(C6H18N4)(SbS3)], a chromium complex containing an unusual bidentate SbS33- ligand

A new chromium-antimony-sulfide, [Cr(C6H18N4)(SbS3)], has been synthesised under solvothermal conditions from CrCl3. 6H(2)O, Sb2S3 and S in the presence of triethylenetetramine at 433 K and characterised by single-crystal X-ray diffraction, thermogravimetry, elemental analysis and SQUID magnetometry. The structure of [Cr(C6H18N4)(SbS3)] consists of neutral mononuclear chromium-centred complexes, in which the Cr3+ is chelated by one tetradentate triethylenetetramine molecule and a bidentate SbS33- ligand, yielding distorted octahedral coordination. Intermolecular hydrogen bonds link individual molecules into layers within the ac plane. Within a layer, molecules occur in pairs with each member related by a centre of inversion. The Cr...Cr separation within a pair is approximately 6.5 Angstrom. Magnetic susceptibility data reveal Curie-Weiss behaviour with mu(eff) = 3.819(3)/mu(B) and a negligible Weiss constant, indicative of non-interacting Cr3+ ions. (C) 2003 Elsevier Science Ltd. All rights reserved.

Synthesis, properties, and X-ray crystal and molecular structures of homoleptic alkenyls of tin and chromium

Reaction of Li(CPhCMe2) with SnCl4 or CrCl3·3thf (thf = tetrahydrofuran) affords the isoleptic compounds Sn(CPhCMe2)4 or [Cr(CPhCMe2)4] respectively. The mode of formation and chemical properties are reported for the chromium species, and the structures of the new compounds, both of which have been determined by single-crystal X-ray analysis, are described.

First-principles study of the inversion thermodynamics and electronic structure of FeM2X4 (thio)spinels (M = Cr, Mn, Co, Ni; X = O, S)

FeM2X4 spinels, where M is a transition metal and X is oxygen or sulfur, are candidate materials for spin filters, one of the key devices in spintronics. We present here a computational study of the inversion thermodynamics and the electronic structure of these (thio)spinels for M = Cr, Mn, Co, Ni, using calculations based on the density functional theory with on-site Hubbard corrections (DFT+U). The analysis of the configurational free energies shows that different behaviour is expected for the equilibrium cation distributions in these structures: FeCr2X4 and FeMn2S4 are fully normal, FeNi2X4 and FeCo2S4 are intermediate, and FeCo2O4 and FeMn2O4 are fully inverted. We have analyzed the role played by the size of the ions and by the crystal field stabilization effects in determining the equilibrium inversion degree. We also discuss how the electronic and magnetic structure of these spinels is modified by the degree of inversion, assuming that this could be varied from the equilibrium value. We have obtained electronic densities of states for the completely normal and completely inverse cation distribution of each compound. FeCr2X4, FeMn2X4, FeCo2O4 and FeNi2O4 are half-metals in the ferrimagnetic state when Fe is in tetrahedral positions. When M is filling the tetrahedral positions, the Cr-containing compounds and FeMn2O4 are half-metallic systems, while the Co and Ni spinels are insulators. The Co and Ni sulfide counterparts are metallic for any inversion degree together with the inverse FeMn2S4. Our calculations suggest that the spin filtering properties of the FeM2X4 (thio)spinels could be modified via the control of the cation distribution through variations in the synthesis conditions.

Influence of Er,Cr : YSGG laser treatment on the microtensile bond strength of adhesives to dentin

Purpose: In light of the concept of minimally invasive dentistry, erbium lasers have been considered as an alternative technique to the use of diamond burs for cavity preparation. The purpose of this study was to assess the bonding effectiveness of adhesives to Er,Cr:YSGG laser-irradiated dentin using irradiation settings specific for cavity preparation. Materials and Methods: Fifty-four midcoronal dentin surfaces, obtained from sound human molars, were irradiated with an Er,Cr:YSGG laser or prepared with a diamond bur using a high-speed turbine. One etch-and-rinse (Optibond FL/Kerr) and three self-etching adhesives (Adper Prompt L-Pop/3M ESPE, Clearfil SE Bond/Kuraray, and Clearfil S-3 Bond/Kuraray) were used to bond the composite to dentin. The microtensile bond strength (mu TBS) was determined after 24 h of storage in water at 37 degrees C. The Kruskal-Wallis test was used to determine pairwise statistical differences (p < 0.05). Prepared dentin surfaces, adhesive interfaces, and failure patterns were analyzed using a stereo microscope and Field-emission gun Scanning Electron Microscopy (Feg-SEM). Results: Significantly lower mu TBS was observed to laser-irradiated than to bur-cut dentin (p < 0.05), irrespective of the adhesive employed. Feg-SEM photomicrographs of lased dentin revealed an imbricate patterned substrate and the presence of microcracks at the dentin surface. Conclusion: Morphological alterations produced by Er,Cr:YSGG laser-irradiation adversely influence the bonding effectiveness of adhesives to dentin. Keywords: dentin, adhesion, adhesives, laser, ErCr:YSGG.

Infrared emission and defect centres in Er and Yb codoped Y(3)Al(5)O(12) phosphors

YAG phosphor powders doped/codoped with Er(3+)/(Er(3+) + Yb(3+)) have been synthesised by using the solution combustion method. The effect of direct pumping into the (4)I(11/2) level under 980 nm excitation of doped/codoped Er(3+)/Yb(3+)-Er(3+) in Y(3)Al(5)O(12) (YAG) phosphor responsible for an infrared (IR) emission peaking at similar to 1.53 mu m corresponding to the (4)I(13/2)->(4)I(15/2) transition has been studied. YAG exhibits three thermally-stimulated luminescence (TSL) peaks at around 140A degrees C, 210A degrees C and 445A degrees C. Electron spin resonance (ESR) studies were carried out to identify the centres responsible for the TSL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0176 is identified as O(-) ion, while centre II with an isotropic g-factor 2.0020 is assigned to an F(+) centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal-annealing experiments and this centre (assigned to F(+) centre) seems to originate from an F-centre (oxygen vacancy with two electrons) and these two centres appear to correlate with the observed high-temperature TSL peak in YAG phosphor.

Pseudo-nonlinear and athermal lensing effects on transverse properties of Cr(3+) based solid-state lasers

Several experiments (time-resolved Z-scan experiments based on pulsed and CW pump lasers, time-resolved divergence diagnostics) have been performed to examine and clarify the question of the converging or diverging population lensing effect occurring in a Cr(3+):Al(2)O(3) ruby laser. The dynamics of the laser far-field divergence of such a laser indeed indicated initially a diverging effect while Z-scan measurements conclude to a converging one. The origin of this discrepancy is thus analysed and elucidated here by introducing the general concept of correlation collapse between the centre and the wings of a laser beam having some clipping. (C) 2010 Elsevier B.V. All rights reserved.

Bond strength of adhesive restorations to Er : YAG laser-treated dentin

Background and Objective: evaluate the adhesion of adhesive restorations with and without a base of resin-modified glass-ionomer cement (RMGIC) to dentin irradiated with Er:YAG laser.Study Design/Materials and Methods: Twenty-four human molar teeth were divided into 6 groups (n=4): G1) 37% Phosphoric acid (PA) + Adhesive system (Ad) + Composite resin (CR); G2) RMGIC + CR; G3) Laser (60mJ-5Hz-20s) + PA + Ad + CR; G4) Laser (60 mJ-5 Hz-20 s) + RMGIC + CR; G5) Laser (100mJ-5Hz-20s) + PA + Ad + CR; G6) Laser (100mJ-5Hz-20s) + RMGIC + CR. Teeth were prepared, restored and cut into specimens, according to the treatment proposed and to methodology for microtensile test. Data were submitted to ANOVA and Tukey statistical tests (alpha=5%).Results:. The mean values for adhesion (MPa) and standard deviation (+/- SD) were: G1) 26.30(+/- 4.50), G2) 5.34(+/- 2.87), G3) 21.16(+/- 6.01), G4) 5.22(+/- 1.52), G5) 22.23(+/- 4.98), G6) 5.25(+/- 3.08).Conclusion: the use of Er:YAG laser did not influence on the restorations adhesion.