An assessment of creep deformation and fracture behavior of 2.25Cr-1Mo

The evaluation of the creep deformation and fracture behavior of a 2.25Cr-1Mo steel base metal, a 2.25Cr-1Mo/2.25Cr-1Mo similar weld joint, and a 2.25Cr-1Mo/Alloy 800 dissimilar weld joint at 823 K over a stress range of 90 to WO MPa has been carried out. The specimens for creep testing were taken from single-V weld pads fabricated by a shielded metal arc-welding process using 2.25Cr-1Mo steel (for similar-joint) and INCONEL 182 (for dissimilar-joint) electrodes. The weld pads were subsequently given a postweld hear treatment (PWHT) of 973 K for I hour. The microstructure and microhardness of the weld joints were evaluated in the as-welded, postweld heat-treated, and creep-tested conditions. The heat-affected zone (HAZ) of similar weld joint consisted of bainite in the coarse-prior-austenitic-grain (CPAG) region near the fusion line, followed by bainite in the fine-prior-austenitic-grain (FPAG) and intercritical regions merging with the unaffected base metal. In addition to the HAZ structures in the 2.25Cr-1Mo steel, the dissimilar weld joint displayed a definite INCONEL/2.25Cr-1Mo weld interface structure present either as a sharp line or as a diffuse region. A hardness trough was observed in the intercritical region of the HAZ in both weld joints, while a maxima in hardness was seen at the weld interface of the dissimilar weld joint. Both weld joints exhibited significantly lower rupture lives compared to the 2.25Cr-1Mo base metal. The dissimilar weld joint exhibited poor rupture life compared to the similar weld joint, at applied stresses lower than 130 MPa. In both weld joints, the strain distribution across the specimen gage length during creep testing varied significantly. During creep testing, localization of deformation occurred in the intercritical HAZ. In the similar weld joint, at all stress levels investigated, and in the dissimilar weld joint, at stresses greater than or equal to 150 MPa, the creep failure occulted in the intercritical HAZ. The fracture occurred by transgranular mode with a large number of dimples. At stresses below 150 MPa, the failure in the dissimilar weld joint occurred in the CPAG HAZ near to the weld interface. The failure occurred by extensive intergranular creep cavity formation.

Thermodynamic properties of Fe3O4 FeAl2O4 spinel solid solution

The Gibbs energy of mixing for the system Fe3O4-FeAl2O4 was determined at 1573 K using a gas-metal-oxide equilibration technique. Oxide solid solution samples were equilibrated with Pt foils under controlled CO+CO2 gas streams. The equilibrium iron concentration in the foil was determined by chemical analysis. The cation distribution between tetrahedral and octahedral sites in the spinel crystal can be calculated from site-preference energies and used as an alternate method of determining some thermodynamic properties, including the Gibbs energy of mixing. The solvus occurring at low temperatures in the system Fe3C4-FeAl2C4 was used to derive the effect of lattice distortion due to cation size difference on the enthalpy of mixing and to obtain a better approximation to the measured thermodynamic quantities.

Bimetallic olefin polymerization catalysis : mechanisms and applications of proximal effects

This dissertation covers progress with bimetallic polymerization catalysts. The complexes we have designed were aimed at expanding the capabilities of homogeneous polymerization catalysts by taking advantage of multimetallic effects. Such effects were examined in group 4 and group 10 bimetallic complexes; proximity and steric repulsion were determined to be major factors in the effects observed.

Chapters 2 and 3 introduce the rigid p-terphenyl dinucleating framework utilized in most of this thesis. The permethylation of the central arene allows for the separation of syn and anti atropisomers of the terphenyl compounds. Kinetic studies were carried out to examine the isomerization of the dinucleating bis(salicylaldimine) ligand precursors. Metallation of the syn and anti bis(salicylaldimine)s using Ni(Me)2(tmeda) and excess pyridine afforded dinickel bisphenoxyiminato complexes with a methyl and a pyridyl ligand on each nickel. The syn and anti atropisomers of the dinickel complexes were structurally characterized and utilized in ethylene and ethylene/α-olefin polymerizations. Monometallic analogues were also synthesized and tested for polymerization activity. Ethylene polymerizations were performed in the presence of primary, secondary, and tertiary amines – additives that generally deactivate nickel polymerization catalysts. Inhibition of this deactivation was observed with the syn atropisomer of the bimetallic species, but not with the anti or monometallic analogues. A mechanism was proposed wherein steric repulsion of the substituents on proximal nickel centers disfavors simultaneous ligation of base to both of the metal centers. The bimetallic effect has been explored with respect to size and binding ability of the added base.

Chapter 4 presents the optimization of the bisphenoxyimine ligand synthesis and synthesis of syn and anti m-terphenyl analogues. Metallation with NiClMe(PMe₃)₂ yielded phosphine-ligated dinickel complexes, which have been structurally characterized. Ethylene/1-hexene copolymerizations in the presence of amines using Ni(COD)₂ as a phosphine scavenger showed significantly improved activity relative to the pyridine-ligated analogues. Incorporation of amino olefins in copolymerizations with ethylene was accomplished, and a mechanism was proposed based on proximal effects. Copolymerization trials with a variety of amino olefins and ethylene/1-hexene/amino olefin terpolymerizations were completed.

Early transition metal complexes based on the rigid p-terphenyl framework were designed with a variety of donor sets (Chapter 5 and Appendix B). Chapter 5 details the use of syn dizirconium di[amine bis(phenolate)] complexes for isoselective 1-hexene and propylene homopolymerizations. Ligand variation and monometallic complexes were studied to determine the origin of tacticity control. A mechanistic proposal was presented based on the symmetry at zirconium and the steric effects of the proximal metal center. Appendix B covers additional studies of bimetallic early transition metal complexes based on the p-terphenyl. Dititanium, dizirconium, and asymmetric complexes with bisphenoxyiminato ligands and derivatives thereof were targeted. Progress toward the synthesis of these complexes is described along with preliminary polymerization data. 1-hexene/diene copolymerizations and attempted polymerizations in the presence of ethers and esters with the syn dizirconium di[amine bis(phenolate)] complexes demonstrate the potential for further applications of this system in catalysis.

Appendix A includes work toward palladium catalysts for insertion polymerization of polar monomers. These complexes were based on dioxime and diimine frameworks with the intent of binding Lewis acidic metals at the oxime oxygens, at pendant phenolic donors, or at pendant aminediol moieties. The synthesis and structural characterization of a number of palladium and Lewis acid complexes is presented. Due to the instability of the desired species, efforts toward isolation of the desired complexes proved unsuccessful, though preliminary ethylene/methyl acrylate copolymerizations using in situ activation of the palladium species were attempted.

Oxy anion-accelerated rearrangements

The alkali metal salts of 1,5-hexadien-3-ols undergo accelerated Cope rearrangements to the enolates of δ, ε-unsaturated carbonyl compounds. The generality of the rearrangement was investigated in numerous systems, particularly acyclic cases, and the effect of changes in substituents, counterions, solvents, and geometrical structures were noted and discussed. Applications of this methodology in synthesis included the synthesis of the insect pheromone frontalin, the preparation of selectively monoprotected 1,6-dicarbonyl compounds from 4-methoxy- and 4-phenylthio-1,5-hexadien-3-ols, and the construction of complex ring structures such as a D-homo-estratetraenone derivative.

Thermochemical estimates of the energetics of anionpromoted alkoxide fragmentations were made, and in all cases heterolytic cleavage was favored over hemolytic cleavage by 8.5-53 kcal/mol. The implication of these and other thermochemical estimates is that the anionic oxy-Cope rearrangement occurs via a concerted mechanism rather than a dissociation-recombination process. The concepts of anion-induced bond weakening were successfully applied to an accelerated [1,3]-shift of a dithiane fragment in a cyclohexenyl system. Trapping experiments demonstrated that > 85% of the [1,3]-shift occurred within a solvent cage. Attempts at promoting an intramolecular ene reaction using the potassium salts of 2,7-octadien-1-o1 and 2,8-nonadien-1-o1 were unsuccessful. A general review of anion-promoted bond reorganizations and anion substituent effects is also presented.

一种改进型金属-半导体-金属光电探测器数学模型

以E. Sano的金属-半导体-金属光电探测器(MSM-PD)模型为基础,提出了一种改进型的模型。该模型以多个电流源和电容并联的形式构造,以吸收区过剩电子和空穴总数为研究对象,求解速率方程。另外计算了电容,给出了暗电流与端电压的非线性计算式,改进了传统模型中暗电流的线性计算方法。通过线性叠加给出了该模型光电流的数学解析解。通过在Matlab中的模拟计算,表明该模型具有计算量小、准确度高的特点,它不仅能反映一定偏压和光照下光电流的变化,而且能展示光电子在器件中的转化过程。这种模型也能较好地应用于微弱信号的检

The heavy metal content of skeletons from an ancient metalliferous polluted area in southern Jordan with particular reerence to bioaccumulation and human health

Pyatt, F.B., Pyatt, A.J., Walker, C., Sheen, T., Grattan, J.P, The heavy metal content of skeletons from an ancient metalliferous polluted area in southern Jordan with particular reerence to bioaccumulation and human health, Ecotoxicology & Environmental Safety 60, 13th August 2003, 295-300

Metal-directed assembly of large dinuclear copper(II) dithiocarbamate macrocyclic complexes

The synthesis of a range of dinuclear Cu(II) dithiocarbamate (dtc)-based macrocycles and their characterisation are described. By carefully tuning the size of the aromatic spacer, cavities of different dimensions can be designed. The length and flexibility of the chosen spacer group dictates the intermetallic distance and hence the degree of communication between the two metal centres as evidenced by electrochemical and EPR experiments. This is illustrated by crystallographic evidence that show the macrocycles can host guests (such as CH2Cl2) or can fold and form unexpected Cu(I) dtc clusters.

EFFECT of DIFFERENT AIRBORNE-PARTICLE ABRASION/BONDING AGENT COMBINATIONS on THE BOND STRENGTH of A RESIN CEMENT TO A BASE METAL ALLOY

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

THE EFFECT of DIFFERENT SURFACE TREATMENTS on THE SHEAR BOND STRENGTH of LUTING CEMENTS TO TITANIUM

Statement of problem. Although titanium presents attractive physical and mechanical properties, there is a need for improving the bond at the titanium/luting cement interface for the longevity of metal ceramic restorations.Purpose. The purpose of this study was to evaluate the effect of surface treatments on the shear bond strength (SBS) of resin-modified glass ionomer and resin cements to commercially pure titanium (CP Ti).Material and methods. Two hundred and forty CP Ti cast disks (9.0 x 3.0 mm) were divided into 8 surface treatment groups (n=30): 1) 50 mu m Al2O3 particles; 2) 120 mu m Al2O3 particles; 3) 250 mu m Al2O3 particles; 4) 50 mu m Al2O3 particles + silane (RelyX Ceramic Primer); 5) 120 mu m Al2O3 particles + silane; 6) 250 mu m Al2O3 particles + silane; 7) 30 mu m silica-modified Al2O3 particles (Cojet Sand) + silane; and 8) 120 mu m Al2O3 particles, followed by 110 mu m silica-modified Al2O3 particles (Rocatec). The luting cements 1) RelyX Luting 2; 2) RelyX ARC; or 3) RelyX U100 were applied to the treated CP Ti surfaces (n=10). Shear bond strength (SBS) was tested after thermal cycling (5000 cycles, 5 degrees C to 55 degrees C). Data were analyzed by 2-way analysis of variance (ANOVA) and the Tukey HSD post hoc test (alpha=.05). Failure mode was determined with a stereomicroscope (x20).Results. The surface treatments, cements, and their interaction significantly affected the SBS (P<.001). RelyX Luting 2 and RelyX U100 exhibited similar behavior for all surface treatments. For both cements, only the group abraded with 50 mu m Al2O3 particles had lower SBS than the other groups (P<.05). For RelyX ARC, regardless of silane application, abrasion with 50 mu m Al2O3 particles resulted in significantly lower SBS than abrasion with 120 mu m and 250 mu m particles, which exhibited statistically similar SBS values to each other. Rocatec + silane promoted the highest SBS for RelyX ARC. RelyX U100 presented the highest SBS mean values (P<.001). All groups showed a predominance of adhesive failure mode.Conclusions. The adhesive capability of RelyX Luting 2 and RelyX U100 on the SBS was decisive, while for RelyX ARC, mechanical and chemical factors were more influential. (J Prosthet Dent 2012;108:370-376)

Avaliação da resistência ao desgaste abrasivo de revestimentos soldados do tipo Fe-C-Cr utilizados na indústria sucroalcooleira

Pós-graduação em Engenharia Mecânica - FEIS

Resistência de união de cimentos resinosos, ao cisalhamento, variando o substrato e o material restaurador

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of surface treatments on the shear bond strength of luting cements to Y-TZP ceramic

Statement of problem Because zirconia is a glass-free material, alternative surface treatments such as airborne-particle abrasion or silica coating should be used for long-term bonding. However, these surface treatments in combination with different bonding agents and luting cements have not yet been studied. Purpose The purpose of the study was to evaluate the effect of surface treatments on the shear bond strength (SBS) of luting cements to Y-TZP ceramic. Material and methods Zirconia disks (N=240) were airborne-particle abraded with the following particles (n=48): 50 μm Al2O3; 120 μm Al2O3; 30 μm silica-coated Al2O3 (Rocatec Soft); 120 μm Al2O3+110 μm silica-coated Al2O3 (Rocatec Plus); and Rocatec Plus. After silanization of the zirconia surface, composite resin disks were bonded with (n=12) RelyX Luting 2; RelyX ARC; RelyX U100; and Panavia F. The bonded specimens were thermocycled (10 000 cycles) and tested for SBS. Failure mode was determined with a stereomicroscope (×20). The morphology and elemental composition of airborne-particle abraded surfaces were evaluated with scanning electron microscopy (×500) and energy-dispersive x-ray spectroscopy (×50). Results Surface treatments, cements, and their interaction were significant (P<.001). For RelyX ARC, Rocatec Soft and Rocatec Plus provided the highest SBS. In general, surface treatments did not influence the SBS of RelyX U100 and Panavia F. Regardless of the cement, no significant difference was found between 50 μm and 120 μm Al2O3 particles, between Rocatec Soft and Rocatec Plus, or between Rocatec Plus and 120 μm Al2O3 particles+Rocatec Plus. All groups showed adhesive failures. Different particle sizes provided differences in morphological patterns. The elemental composition comprised Al and Al/Si for alumina and silica-abraded zirconia. Conclusions Particle size did not influence the SBS of the groups abraded exclusively with alumina or silica-coated particles. RelyX ARC was more surface-treatment dependent than RelyX U100 or Panavia F.

Biogenic calcium phosphate transformation in soils over millennial time scales

Changes in bioavailability of phosphorus (P) during pedogenesis and ecosystem development have been shown for geogenic calcium phosphate (Ca-P). However, very little is known about long-term changes of biogenic Ca-P in soil. Long-term transformation characteristics of biogenic Ca-P were examined using anthropogenic soils along a chronosequence from centennial to millennial time scales. Phosphorus fractionation of Anthrosols resulted in overall consistency with the Walker and Syers model of geogenic Ca-P transformation during pedogenesis. The biogenic Ca-P (e.g., animal and fish bones) disappeared to 3% of total P within the first ca. 2,000 years of soil development. This change concurred with increases in P adsorbed on metal-oxides surfaces, organic P, and occluded P at different pedogenic time. Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the crystalline and therefore thermodynamically most stable biogenic Ca-P was transformed into more soluble forms of Ca-P over time. While crystalline hydroxyapatite (34% of total P) dominated Ca-P species after about 600-1,000 years, beta-tricalcium phosphate increased to 16% of total P after 900-1,100 years, after which both Ca-P species disappeared. Iron-associated P was observable concurrently with Ca-P disappearance. Soluble P and organic P determined by XANES maintained relatively constant (58-65%) across the time scale studied. Disappearance of crystalline biogenic Ca-P on a time scale of a few thousand years appears to be ten times faster than that of geogenic Ca-P.

Análisis experimental y computacional de modelos termofluidomecánicos para el diseño de ingeniería con metales líquidos

Es importante disponer de una herramienta con la cual diseñar dispositivos de uso industrial y comercial que trabajen con metales líquidos (fuentes de neutrones de alta intensidad, núcleos de sistemas de transmutación nuclear, reactores de fisión de nueva generación, instalaciones de irradiación de materiales o reactores de fusión nuclear). Los códigos CFD (Computational Fluid Dynamics) son una de esas herramientas, y la manera de llevar a cabo su validación es la simulación de experimentos existentes. La turbulencia y la presencia de dos o más fases, son los dos principales problemas a los que tiene que hacer frente un código CFD. La mayoría de los modelos de turbulencia presentes en los códigos CFD se basan en considerar la proporcionalidad directa entre el transporte de cantidad de movimiento turbulento y el transporte turbulento de calor. Precisamente, el coeficiente de difusión del calor turbulento, se asume que sea proporcional a la viscosidad turbulenta a través de una constante empírica, llamada número de Prandtl turbulento. El valor de este número, en los códigos comerciales está entre 0,9 y 0,85 dependiendo del modelo de turbulencia, lo cual significa que en los códigos se asume que el transporte turbulento tanto de cantidad de movimiento como de calor, son prácticamente equivalentes. Esta asunción no es cierta en los flujos de metales líquidos, donde se demuestra que la transmisión de calor por turbulencia es pequeña frente a la transmisión de calor molecular. La solución pasa por aumentar el número de Prandtl turbulento, o abandonar la analogía de Reynolds, en el tratamiento de la turbulencia. Por otro lado, en los metales líquidos la capa límite térmica es más ancha que la de velocidad, y las funciones de pared incluidas en los códigos no satisfacen adecuadamente los flujos turbulentos de los fluidos con bajo número de Prantdl (los metales líquidos). Sí serían adecuados, si el mallado es tal, que la celda más cercana a la pared, está dentro de la subcapa laminar, en la cual la propiedad dominante es la conductividad molecular. En la simulación de flujo multifase los códigos se encuentran con una serie de dificultades, que en el caso de que las densidades de los fluidos que intervienen sean muy diferentes entre sí (como ocurre con los metales líquidos y los gases), serán aún mayores. La modelización de la interfase gas metal líquido, así como el encontrar una correlación válida para los coeficientes de resistencia y sustentación para el movimiento de las burbujas en el seno del metal líquido, son dos de los principales retos en la simulación de este tipo de flujos. Las dificultades no se limitan sólo a la simulación mediante CFD, las medidas experimentales de velocidad de las burbujas y del metal líquido también son complicadas. Hay parámetros que no se pueden definir bien: la trayectoria y la forma de las burbujas entre ellos. En el campo de aplicación industrial de los metales líquidos, los altos valores de los coeficientes de expansión volumétrica y de conductividad térmica hacen que estos fluidos sean muy atractivos en la refrigeración por convección libre en dispositivos de alta densidad de potencia. Tomando como base uno de los diseños de ADS (Accelerator Driven System), y teniendo en cuenta la dificultad que conlleva el uso de múltiples modelos físicos, los cálculos realizados muestran cómo, en caso de fallo eléctrico, la operación de la instalación puede continuar de forma segura. Para la validación de los códigos CFD en su uso como herramienta de diseño, uno de los fenómenos donde cuantitativamente más dificultades encuentran los códigos es en los que aparecen en la modelización de las superficies libres. Un buen ajuste de los modelos multifase y de turbulencia es imprescindible en este tipo de simulaciones. Efectivamente, en la instalación de irradiación de materiales IFMIF, la formación de ondas en la superficie libre del flujo de Litio, es un fenómeno que hay que tratar de evitar, y además se requiere predecir las temperaturas, para ver si hay peligro de ebullición del metal líquido. La simulación llevada a cabo se enfoca al análisis termohidráulico. Variando la velocidad de inyección de Litio desde 10 hasta 20 m/s, se comprueba que las temperaturas máximas quedan alejadas del punto de ebullición del Litio, debido al aumento de presión producido por la fuerza centrífuga. Una de las cuestiones más críticas que se presentan en las fuentes de neutrones sería la refrigeración de la ventana metálica sobre la que incide el haz de protones. La simulación de experimentos como MEGAPIE y TS-1, permite la “visualización” de recirculación en el flujo, de los puntos de estancamiento, de los puntos calientes, etc, y da una fotografía de las zonas críticas del diseño.