The effect of ceramic surface treatment on bonding to densely sintered alumina ceramic

Statement of problem. Ceramic surface treatment is crucial for bonding to resin. High crystalline ceramics are poorly conditioned using traditional procedures.Purpose. The purpose of this study was to evaluate the effect of silica coating on a densely sintered alumina ceramic relative to its bond strength to composite, using a resin luting agent.Material and methods. Blocks (6 X 6 X 5 mm) of ceramic and composite were made. The ceramic (Procera AllCeram) surfaces were polished, and the blocks were divided into 3 groups (n = 5): SB, airborne-particle abrasion with 110-mu m Al(2)O(3); RS, silica coating using Rocatec System; and CS, silica coating using CoJet System. The treated ceramic blocks were luted to the composite (W3D Master) blocks using a resin luting agent (Panavia F). Specimens were stored in distilled water at 37 degrees C for 7 days and then Cut in 2 axes, x and y, to obtain specimens with a bonding area of approximately 0.6 mm(2) (n = 30). The specimens were loaded to failure in tension in a universal testing machine, and data were statistically analyzed using a randomized complete block design analysis of variance and Tukey's test (alpha=.05). Fractured surfaces were examined using light microscopy and scanning electron microscopy to determine the type of failure. Energy-dispersive spectroscopy was used for surface compositional analysis.Results. Mean bond strength values (MPa) of Groups RS (17.1 +/- 3.9) (P = .00015) and CS (18.5 +/- 4.7) (P=.00012) were significantly higher than the values of Group SB (12.7 +/- 2.6). There was no statistical difference between Groups RS and CS. All failures occurred at the adhesive zone.Conclusion. Tribochemical silica coating systems increased the tensile bond strength values between Panavia F and Procera AllCeram ceramic.

Microtensile bond strength of composite resin to glass-infiltrated alumina composite conditioned with Er,Cr:YSGG laser

Tribochemical silica-coating is the recommended conditioning method for improving glass-infiltrated alumina composite adhesion to resin cement. High-intensity lasers have been considered as an alternative for this purpose. This study evaluated the morphological effects of Er,Cr:YSGG laser irradiation on aluminous ceramic, and verified the microtensile bond strength of composite resin to ceramic following silica coating or laser irradiation. In-Ceram Alumina ceramic blocks were polished, submitted to airborne particle abrasion (110 mu m Al(2)O(3)), and conditioned with: (CG) tribochemical silica coating (110 mu m SiO(2)) + silanization (control group); (L1-L10) Er,Cr:YSGG laser (2.78 mu m, 20 Hz, 0.5 to 5.0 W) + silanization. Composite resin blocks were cemented to the ceramic blocks with resin cement. These sets were stored in 37A degrees C distilled water (24 h), embedded in acrylic resin, and sectioned to produce bar specimens that were submitted to microtensile testing. Bond strength values (MPa) were statistically analyzed (alpha a parts per thousand currency sign0.05), and failure modes were determined. Additional ceramic blocks were conditioned for qualitative analysis of the topography under SEM. There were no significant differences among silicatization and laser treatments (p > 0.05). Microtensile bond strength ranged from 19.2 to 27.9 MPa, and coefficients of variation ranged from 30 to 55%. Mixed failure of adhesive interface was predominant in all groups (75-96%). No chromatic alteration, cracks or melting were observed after laser irradiation with all parameters tested. Surface conditioning of glass-infiltrated alumina composite with Er,Cr:YSGG laser should be considered an innovative alternative for promoting adhesion of ceramics to resin cement, since it resulted in similar bond strength values compared to the tribochemical treatment.

Supported Cu(II) polymer catalysts for aqueous phenol oxidation

Supported Cu(II) polymer catalysts were used for the catalytic oxidation of phenol at 30 degrees C and atmospheric pressure using air and H(2)O(2) as oxidants. Heterogenisation of homogeneous Cu(II) catalysts was achieved by adsorption of Cu(II) salts onto polymeric matrices (poly(4-vinylpyridine), Chitosan). The catalytic active sites were represented by Cu(II) ions and showed to conserve their oxidative activity in heterogeneous catalysis as well as in homogeneous systems. The catalytic deactivation was evaluated by quantifying released Cu(II) ions in solution during oxidation, from where Cu-PVP(25) showed the best leaching levels no more than 5 mg L(-1). Results also indicated that Cu-PVP(25) had a catalytic activity (56% of phenol conversion when initial Cu(II) catalytic content was 200 mg L(Reaction)(-1)) comparable to that of commercial catalysts (59% of phenol conversion). Finally, the balance between activity and copper leaching was better represented by Cu-PVP(25) due to the heterogeneous catalytic activity had 86% performance in the heterogeneous phase, and the rest on the homogeneous phase, while Cu-PVP(2) had 59% and CuO/gamma-Al(2)O(3) 68%.

Chevkinite-Group Minerals from Granulite-Facies Metamorphic Rocks and Associated Pegmatites of East Antarctica and South India

Electron microprobe data are presented for chevkinite-group minerals from granulite-facies rocks and associated pegmatities of the Napier Complex and Mawson Station charnockite in East Antarctica and from the Eastern Ghats, South India. Their compositions conform to the general formula for this group, viz. A(4)BC(2)D(2)Si(4)O(22) where, in the analysed specimens A = (rare-earth elements (REE), Ca, Y, Th), B = Fe(2+) Mg, C = (Al, Mg, Ti, Fe(2+), Fe(3+), Zr) and D = Ti and plot within the perrierite field oftlic total Fe (as FeO) (wt.%) vs. CaO (wt.%) discriminator diagram of Macdonald and Belkin (2002). In contrast to most chevkinite-group minerals, the A site shows unusual enrichment in the MREE and HREE relative to the LREE and Ca. In one sample from the Napier Complex, Y is the dominant cation among the total REE + Y in the A site, the first reported case of Y-dominance in the chevkinite group. The minerals include the most Al-rich yet reported in the chevkinite group (<= 9.15 wt.% Al(2)O(3)), sufficient to fill the C site in two samples. Conversely, the amount of Ti in these samples does not fill the D site. and, thus, some of the Al could be making up the deficiency at D, a situation not previously reported in the chevkinite group. Fe abudances are low, requiring Mg to occupy up to 45% of the B site. The chevkinite-group minerals analysed originated from three distinct parageneses: (1) pegmatites containing hornblende and orthopyroxene or garnet; (2) orthopyroxene-bearing gneiss and granulite; (3) highly aluminous paragneisses in which the associated minerals are relatively magnesian or aluminous. Chevkinite-group minerals from the first two parageneses have relatively high FeO content and low MgO and Al(2)O(3) contents; their compositions plot in the field for mafic and intermediate igneous rocks. In contrast, chevkinite-group minerals from the third paragenesis are notably more aluminous and have greater Mg/Fe ratios.

Phase equilibria in high MgO ferro-manganese and silico-manganese smelting slags

Liquidus isotherms and phase equilibria have been determined experimentally for a pseudo-ternary section of the form MnO-(CaO+MgO)-(SiO2+Al2O3) with a fixed Al-2,O-3,/SiO2, weight ratio of 0.17 and MgO/CaO weight ratio of 0.17 for temperatures in the range 1473-1673 K. The primary phase fields present for the section investigated include manganosite (Mn,Mg,Ca)O; dicalcium silicate alpha-2(Ca,Mg,Mn)O (.) SiO2; merwinite 3CaO(.) ((Mg,Mn)O.2SiO(2); wollastonite [(Ca,Mg,Mn)(OSiO2)-Si-.]; ;tephroite [2(Mn,Mg)O.SiO2]; rhodonite [(Mn,Mg)O. diopside [(CaO,MgO,MnO,Al2O3)(SiO2)-Si-.]; tridymite (SiO2), SiO2] and melilite [2CaO (.) (MgO,MnO,Al2O3).2(SiO2,Al2O3)]. The liquidus temperatures relevant to ferro-manganese and silico-manganese smelting slags have been determined. The liquiclus temperature is shown to be principally dependent on the modified basicity weight ratio (CaO+Mgo)/(SiO2+Al2O3) at low MnO concentrations, and dependent on the mole ratio (CaO+ MgO+MnO)/(SiO2+Al2O3) at higher MnO concentrations.

Use of a Neural Network to Predict Strength and Optimum Compositions of Natural Alumina-Silica-Based Geopolymers

In order to predict compressive strength of geopolymers prepared from alumina-silica natural products, based on the effect of Al 2 O 3 /SiO 2, Na 2 O/Al 2 O 3, Na 2 O/H 2 O, and Na/[Na+K], more than 50 pieces of data were gathered from the literature. The data was utilized to train and test a multilayer artificial neural network (ANN). Therefore a multilayer feedforward network was designed with chemical compositions of alumina silicate and alkali activators as inputs and compressive strength as output. In this study, a feedforward network with various numbers of hidden layers and neurons were tested to select the optimum network architecture. The developed three-layer neural network simulator model used the feedforward back propagation architecture, demonstrated its ability in training the given input/output patterns. The cross-validation data was used to show the validity and high prediction accuracy of the network. This leads to the optimum chemical composition and the best paste can be made from activated alumina-silica natural products using alkaline hydroxide, and alkaline silicate. The research results are in agreement with mechanism of geopolymerization.


Read More: http://ascelibrary.org/doi/abs/10.1061/(ASCE)MT.1943-5533.0000829

Understanding the cation specific effects on the aqueous solubility of amino acids: from mono to polyvalent cations

The interactions established by mono and polyvalent cations in natural media have important implications on the structure formation, function and physico-chemical behavior of biomolecules, playing therefore a critical role in biochemical processes. In order to further elucidate the molecular phenomena behind the cation specific effects in biological environments, and clarify the influence of the charge of the ions, solubility measurements and molecular dynamics simulations were performed for aqueous solutions of three amino acids (alanine, valine and isoleucine), in the presence of a series of inorganic salts comprising mono-, di- and trivalent cations (LiCl, Li2SO4, K2SO4, CaCl2, AlCl3 and Al-2(SO4)(3)). The evidence gathered indicates that the mechanism by which (salting-in inducing) polyvalent cations affect the solubility of amino acids in aqueous solutions is different from that of monovalent cations. A consistent and refined molecular description of the effect of the cation on the solubility of amino acids based on specific interactions of the cations with the negatively charged moieties of the biomolecules is here proposed.

Eventos cardiovasculares en el Lupus eritematoso sistémico. Estudio del registro español Relesser

Objetivos: (1) Estudiar la frecuencia de eventos cardiovasculares (CV) que presentaron los pacientes de una gran cohorte española de lupus eritematoso sistémico (LES) tras el diagnóstico de la enfermedad, y (2) investigar los principales factores de riesgo implicados en la aterosclerosis. Material y métodos: Estudio transversal retrospectivo basado en RELESSER, un registro multicéntrico, nacional de pacientes diagnosticados de LES. Pacientes: sujetos con diagnóstico de LES (criterios ACR 1997), atendidos en 45 servicios de Reumatología españoles. Variables: demográficas, clínicas, factores de riesgo tradicionales y eventos CV. La variable de desenlace fue evento CV que se definió por la presencia de al menos uno de los siguientes tras el diagnóstico de LES: 1) Enfermedad cardiaca isquémica (infarto agudo de miocardio y/o angina por clínica y/o electrocardiograma y/o enzimas y/o coronariografía), 2) accidente cerebrovascular (ACV) basado en un diagnóstico previo o por clínica y/o imagen; y 3) enfermedad arterial periférica por diagnóstico previo o por imagen. Los pacientes con eventos CV previos al diagnóstico de LES se excluyeron del análisis. Protocolo: la información fue recogida a partir de las historias clínicas usando un protocolo específico en una plataforma web y con previo entrenamiento de los investigadores. Análisis estadístico: Descriptivo y comparaciones entre grupos utilizando χ2, T-Student o U Mann-Whitney. Análisis de regresión logística múltiple para analizar los posibles factores de riesgo CV asociados a aterosclerosis. Resultados: Desde el año 2.011 al 2.012, 3.658 pacientes con LES fueron reclutados en RELESSER y solo 9 se excluyeron por insuficiente información sobre eventos CV. De los 3.649 restantes, 374 (10,9%) presentaron al menos un evento CV. Doscientos sesenta y nueve (7,4%) pacientes tuvieron 318 eventos CV tras el diagnóstico de LES. El 86,2% de esos pacientes eran mujeres, mediana [RIQ] de edad de 54,9 años [43,2 ̶ 66,1] y una duración del LES de 212.0 meses [120,8 ̶ 289,0]. La media (DE) de edad al cuando sufrieron el primer evento CV fue 48,6 (17,1) años. Los ACV (5,7%), fueron los eventos más frecuentes seguidos de la cardiopatía isquémica (3,8%) y la enfermedad arterial periférica (2,2%). El análisis multivariante mostró una fuerte asociación (OR [IC 95%]) entre los eventos CV y la edad (1,03 [1,02 ̶ 1,04]), la hipertensión arterial (1,71 [1,20 ̶ 2,44]), el tabaquismo (1,48 [1,06 ̶ 2,07]), la diabetes (2,2 [1,32 ̶ 3,74]), la dislipemia (2.18 [1,54 ̶ 3,09], el lupus neuropsiquiátrico (2,42 [1,56 ̶ 3,75]), la presencia de valvulopatía (2,44[1,34 ̶ 4,26]), serositis (1,54 [1,09 ̶ 2.18]), anticuerpos antifosfolípidos (1,57 [1,13 ̶ 2,17]), disminución del complemento (1,81 [1,12 ̶ 2,93]) y la toma de azatioprina (1,47 [1,04 ̶ 2,07]). Conclusiones: Los pacientes con LES presentan una alta prevalencia de enfermedad CV prematura que se asocia con factores de riesgo CV tradicionales y relacionados con el LES. Aunque se necesitan futuros estudios que lo comprueben, nuestro trabajo demuestra, por primera vez, una asociación entre la diabetes y los eventos CV en pacientes con LES.

Halogen-bonded tris (2,4-Bis(trichloromethyl)-1,3,5,triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

One-pot template condensation of CCl3C=N with ammonia on a metal source [MnCl2 center dot 4H(2)O, FeCl3 center dot 6H(2)O or Co(CH3COO)(2)center dot 4H(2)O] in DMSO led to the formation of tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) complexes, [M(NH=C(CCl3)NC(CCl3)=-NH}(3)]center dot n(CH3)(2)SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)1, which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1-3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl center dot center dot center dot Cl distances [3.178 (3) > 3.155 (2) > 3.133 (1) Al. Compounds 1-3 and the related di(triazapentadienato)-Cu(v) complex [Cu(NH=C(CCl3)NC(CCl3)=NH}2]center dot 2(CH3)(2)SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 x 10(3) after 1 h of low power (10 W) MW irradiation.

Mu-Chlorido-Bridged Dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

Orientation of Non-Native 2-Monosubstituted and 2,3-Disubstituted 1,4-Naphthoquinones in the A1 binding site of PSI and the effect on the rate of electron transfer : an electron paramagnetic resonance spectroscopy study

The proce-ss ofoxygenic photosynthesis is vital to life on Earth. the central event in photosynthesis is light induced electron transfer that converts light into energy for growth. Ofparticular significance is the membrane bound multisubunit protein known as Photosystem I (PSI). PSI is a reaction centre that is responsible for the transfer of electrons across the membrane to reduce NADP+ to NADPH. The recent publication ofa high resolution X-ray structure of PSI has shown new information about the structure, in particular the electron transfer cofactors, which allows us to study it in more detail. In PSI, the secondary acceptor is crucial for forward electron transfer. In this thesis, the effect of removing the native acceptor phylloquinone and replacing it with a series of structurally related quinones was investigated via transient electron paramagnetic resonance (EPR) experiments. The orientation of non native quinones in the binding site and their ability to function in the electron transfer process was determined. It was found that PSI will readily accept alkyl naphthoquinones and anthraquinone. Q band EPR experiments revealed that the non-native quinones are incorporated into the binding site with the same orientation of the headgroup as in the native system. X band EPR spectra and deuteration experiments indicate that monosubstituted naphthoquinones are bound to the Al site with their side group in the position occupied by the methyl group in native PSI (meta to the hydrogen bonded carbonyl oxygen). X band EPR experiments show that 2, 3- disubstituted methyl naphthoquinones are also incorporated into the Al site in the same orientation as phylloquinone, even with the presence of a halogen- or sulfur-containing side chain in the position normally occupied by the phytyl tail ofphylloquinone. The exception to this is 2-bromo-3-methyl --.- _. -. - -- - - 4 _._ _ _ - _ _ naphthoquinone which has a poorly resolved spectrum, making determination of the orientation difficuh. All of the non-native quinones studied act as efficient electron acceptors. However, forward electron transfer past the quinone could only be demonstrated for anthraquinone, which has a more negative midpoint potential than phylloquinone. In the case of anthraquinone, an increased rate of forward electron transfer compared to native PSI was found. From these results we can conclude that the rate ofelectron transfer from Al to Fx in native PSI lies in the normal region ofthe Marcus Curve.

Análisis de los grafismos conducentes al dibujo y a la escritura en las edades de 3, 4 y 5 años.

Abordar el nacimiento y desarrollo de los primeros trazados del niño, habitualmente conocidos como garabatos, dentro de los cuales es posible discernir aquellos que configurarán un lenguaje gráfico básico de comunicación, que se manifestará en los primeros dibujos infantiles y en la escritura, dentro del trazado de las letras manuscritas, tanto mayúsculas como minúsculas. Los sujetos de la investigación son niños y niñas del tramo de Educación Infantil, con edades medias de 3, 4 y 5 años. Su número por curso oscilaba entre 24-25. Las pruebas se agrupan en cinco grandes bloques: 1.- Grafismos 2.- Relaciones geométricas 3.- Relación garabato-escritura 4.-Dibujo 5.- Escritura. A lo largo de los dos años se realizan 25 pruebas con 79 aplicaciones y con un total de 1.715 láminas realizadas por los niños: 15 de ellas con criterios de tipo cuantitativo-estadístico y 10 con un enfoque de corte eminentemente cualitativo. El amplio número de pruebas responde, por un lado, a la necesidad de variar las actividades ante los niños de edades pequeñas y, por otro, a la de alcanzar con cierto rigor conclusiones que estén suficientemente fundamentadas tanto cualitativa como cuantitativamente. Las conclusiones responden a los tres bloques de los objetivos planteados como respuesta final a las interrogantes que han marcado este trabajo 1.- Grafismos 2.- Dibujo 3.- Escritura. Se llega a sólidas conclusiones referidas tanto a los aspectos psicomotores en la gestación de los garabatos, como en las formas de representación de los dibujos y de la escritura, sistemas expresivos y comunicativos fuertemente entrelazados en los inicios del aprendizaje infantil.

Novel electroluminescent devices containing Eu(3+)-(2-acyl-1,3-indandionate) complexes with TPPO ligand

Fabrication and electroluminescent properties of devices containing europium complexes of general formula [Eu(ACIND)(3)(TPPO)(2)], where ACIND, 2-acyl-1,3-indandionate ligands: and TPPO, triphenylphosphine oxide. as emitter layers are discussed. The double-layer devices based on these complexes present the following configurations: device 1: ITO/TPD/[Eu(AlND)(3)(TPPO)(2)]/Al: device 2: ITO/TPD/[Eu(ISOV-IND)(3)(TPPO)(2)]/Al and device 3: ITO/TPD/[Eu(BIND)(3)(TPPO)(2)]/Al, where AlND, 2-acetyl-1,3-indandionate; ISOVIND, 2-isovaleryl-1,3-indandionate; and BIND, 2-benzoyl-1,3-indandionate, respectively. These devices exhibited photo and electroluminescent emissions. An important characteristic presented by devices is that their electroluminescent (EL) spectra, in the region of (5)D(0) -> (7)F(J) (J = 0, 1, 2, 3 and 4) transitions of Eu(3+) ion, show profiles that are different from photoluminescent (PL) ones. In addition to narrow bands arising from intraconfigurational-4f(6) transitions, devices 1 and 2 also exhibited a broad band with maximum at around 500 nm which is assigned to electrophosphorescence from the indandionate ligands. On the other hand, EL spectra of device 3 present only narrow bands from (5)D(0) -> (7)F(J) transitions. [Eu(ACIND)(3)(TPPO)(2)] complexes are promising candidates to prepare efficient organic light-emitting devices (OLEDs) when compared with those containing Eu(3+)-complexes of aliphatic beta-diketonate anions. (C) 2009 Elsevier B.V. All rights reserved.