Thermal stability of the martensitic transformation of Cu-Al-Ni-Mn-Ti

The development of new shape memory alloys with high martensitic transformation temperature increases the potential for applications. The development and use of these new alloys depends on the stability of the structure during cycling at high temperatures. If it is possible to guarantee that on alloys keeps the structure during cycling, then the alloy can be used because of the shape memory properties. The aim of this work is to obtain a kinetic model of the forward and backward martensitic transformation of two Cu-Al-Ni-Mn-Ti alloys. Differential scanning calorimetry has been performed in order to establish the kinetic stability of the martensite and the beta transformation. (c) 2006 Elsevier B.V. All rights reserved.

On non-ideal simple portal frame structural model: Experimental results under a non-ideal excitation

We present measurements of the non-linear oscillations of a portal frame foundation for a non-ideal motor. We consider a three-time redundant structure with two columns, clamped in their bases and a horizontal beam. An electrical unbalanced motor is mounted at mid span of the beam. Two non-linear phenomena are studied: a) mode saturation and energy transfer between modes; b) interaction between high amplitude motions of the structure and the rotation regime of a real limited power motor. The dynamic characteristics of the structure were chosen to have one-to-two internal resonance between the anti-symmetrical mode (sway motions) and the first symmetrical mode natural frequencies. As the excitation frequency reaches near resonance conditions with the 2nd natural frequency, the amplitude of this mode grows up to a certain level and then it saturates. The surplus energy pumped into the system is transferred to the sway mode, which experiences a sudden increase in its amplitude. Energy is transformed from low amplitude high frequency motion into high amplitude low frequency motion. Such a transformation is potentially dangerous.We consider the fact that real motors, such as the one used in this study, have limited power output. In this case, this energy source is said to be non-ideal, in contrast to the ideal source whose amplitude and frequency are independent of the motion of the structure. Our experimental research detected the Sommerfeld Effect: as the motor accelerates to reach near resonant conditions, a considerable part of its output energy is consumed to generate large amplitude motions of the structure and not to increase its own angular speed. For certain parameters of the system, the motor can get stuck at resonance not having enough power to reach higher rotation regimes. If some more power is available, jump phenomena may occur from near resonance to considerably higher motor speed regimes, no stable motions being possible between these two.

Structural features of phosphate and sulfate modified zirconia prepared by sol-gel route

This paper describes the effect of sulfate, phosphate and nitrate complexing ligands on the structural features of amorphous xerogels and on the crystallization of metastable zirconia phases during the xerogel-ceramic conversion. Powdered samples were prepared by a sol-gel route using zirconyl chloride precursors chemically modified by complexing ligands. The structural evolution of ZrO2 phases as function of firing temperature was analyzed by XRPD, EXAFS and P-13 NMR/MAS. The experimental results show the formation of metastable t-ZrO2 during the low firing temperature of xerogels modified by sulfate or phosphate groups. The martensitic tetragonal-monoclinic transformation occurs during desorption of sulfate groups. The largest temperature interval of stability of metastable tetragonal zirconia was observed for phosphate-modified xerogels.

Structural and phenomenological characterization of the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The thermoreversible sol-gel transition is well-known in biological and organic polymeric systems but has not been reported for inorganic systems. In this paper we put in evidence a thermoreversible sol-gel transition for zirconyl chloride aqueous solutions modified by sulfuric acid in the ratio 3:1 Zr:SO4. The synthesis conditions are detailed and a variety of experimental techniques (turbidimetry, dynamic rheology, and EXAFS) have been employed for investigating the thermal reversibility and the chemical structure of this new material. Turbidimetric measurements performed for solutions containing different concentrations of precursor have evidenced that the sol-gel transformation temperature increases from 50 to 80 degrees C as the concentration of zirconyl chloride decreases from 0.22 to 0.018 mol L-1. A more detailed study has been done for the sample with [Zr] = 0.156 mol L-1, in which the sol-gel-sol transformation has been repeated several times by a cyclic variation of the temperature. The mechanical properties of this sample, evaluated by measuring the storage and the loss moduli, show a change from liquid like to viscoelastic to elastic behavior during the sol-gel transition and vice versa during the gel-sol one. In situ EXAFS measurements performed at the Zr K-edge show that no change of the local order around Zr occurs during the sol-gel-sol transition, in agreement with the concept of physical gel formation. We have proposed for the structure of the precursor an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded in surface by complexing sulfate ligands, the sulfate groups act as a protective layer, playing a key role in the linking propagation among primary particles during sol-gel-sol transition.

Effect of lithium doping on the evolution of rheological and structural properties during gelation of siloxane-poly(oxypropylene) nanocomposites

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

The transformation of collective action in Latin America

Includes bibliography

Employment and structural mobility. Revisiting a Prebischian theme

Includes bibliography

Air-particle abrasion on zirconia ceramic using different protocols: Effects on biaxial flexural strength after cyclic loading, phase transformation and surface topography

This study evaluated the effect of different air-particle abrasion protocols on the biaxial flexural strength and structural stability of zirconia ceramics. Zirconia ceramic specimens (ISO 6872) (Lava, 3M ESPE) were obtained (N=336). The specimens (N=118, n=20 per group) were randomly assigned to one of the air-abrasion protocols: Gr1: Control (as-sintered); Gr2: 50 μm Al2O3 (2.5 bar); Gr3: 50 μm Al2O3 (3.5 bar); Gr4: 110 μm Al2O3(2.5 bar); Gr5: 110 μm Al2O3 (3.5 bar); Gr6: 30 μm SiO2 (2.5 bar) (CoJet); Gr7: 30 μm SiO2(3.5 bar); Gr8: 110 μm SiO2 (2.5 bar) (Rocatec Plus); and Gr9: 110 μm SiO2 (3.5 bar) (duration: 20 s, distance: 10 mm). While half of the specimens were tested immediately, the other half was subjected to cyclic loading in water (100,000 cycles; 50 N, 4 Hz, 37 °°C) prior to biaxial flexural strength test (ISO 6872). Phase transformation (t→m), relative amount of transformed monoclinic zirconia (FM), transformed zone depth (TZD) and surface roughness were measured. Particle type (p=0.2746), pressure (p=0.5084) and cyclic loading (p=0.1610) did not influence the flexural strength. Except for the air-abraded group with 110 μm Al2O3 at 3.5 bar, all air-abrasion protocols increased the biaxial flexural strength (MPa) (Controlnon-aged: 1030±153, Controlaged: 1138±138; Experimentalnon-aged: 1307±184-1554±124; Experimentalaged: 1308±118-1451±135) in both non-aged and aged conditions, respectively. Surface roughness (Ra) was the highest with 110 μm Al2O3(0.84 μm. FM values ranged from 0% to 27.21%, higher value for the Rocatec Plus (110 μm SiO2) and 110 μm Al2O3 groups at 3.5 bar pressure. TZD ranged between 0 and 1.43 μm, with the highest values for Rocatec Plus and 110 μm Al2O3 groups at 3.5 bar pressure. © 2013 Elsevier Ltd.

Titanate nanotubes produced from microwave-assisted hydrothermal synthesis: Photocatalytic and structural properties

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effects of aging procedures on the topographic surface, structural stability, and mechanical strength of a ZrO2-based dental ceramic

Objective. To determine the effects of different aging methods on the degradation and flexural strength of yttria-stabilized tetragonal zirconia (Y-TZP)Methods. Sixty disc-shaped specimens (0, 12 mm; thickness, 1.6 mm) of zirconia (Vita InCeram 2000 YZ Cubes, VITA Zahnfabrik) were prepared (ISO 6872) and randomly divided into five groups, according to the aging procedures (n=10): (C) control; (M) mechanical cycling (15,000,000 cycles/3.8 Hz/200N); (T) thermal cycling (6,000 cycles/5-55 degrees C/30 s); (TM) thermomechanical cycling (1,200,000 cycles/3.8 Hz/200N with temperature range from 5 C to 55 C for 60s each); (AUT) 12h in autoclave at 134 degrees C/2 bars; and (STO) storage in distilled water (37 degrees C/400 days). After the aging procedures, the monoclinic phase percentages were evaluated by X-ray diffraction (XRD), and topographic surface analysis was performed by 3D profilometry. The specimens were then subjected to biaxial flexure testing (1 mm/min, load 100 kgf, in water). The biaxial flexural strength data (MPa) were analyzed by 1-way ANOVA and Tukey's test (alpha = 0.05). The data for monoclinic phase percentage and profilometry (Ra) were analyzed by Kruskal-Wallis and Dunn's tests.Results. ANOVA revealed that flexural strength was affected by the aging procedures (p = 0.002). The M (781.6 MPa) and TM (771.3 MPa) groups presented lower values of flexural strength than did C (955 MPa), AUT (955.8 MPa), T (960.8 MPa) and STO (910.4 MPa). The monoclinic phase percentage was significantly higher only for STO (12.22%) and AUT (29.97%) when compared with that of the control group (Kruskal-Wallis test, p = 0.004). In addition, the surface roughnesses were similar among the groups (p = 0.165).Signcance. Water storage for 400 days and autoclave aging procedures induced higher phase transformation from tetragonal to monoclinic; however, they did not affect the flexural strength of Y-TZP ceramic, which decreased only after mechanical and thermomechanical cycling. (C) 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Key participants of the tumor microenvironment of the prostate: An approach of the structural dynamic of cellular elements and extracellular matrix components during epithelial-stromal transition

Cancer is a multistep process that begins with the transformation of normal epithelial cells and continues with tumor growth, stromal invasion and metastasis. The remodeling of the peritumoral environment is decisive for the onset of tumor invasiveness. This event is dependent on epithelial–stromal interactions, degradation of extracellular matrix components and reorganization of fibrillar components. Our research group has studied in a new proposed rodent model the participation of cellular and molecular components in the prostate microenvironment that contributes to cancer progression. Our group adopted the gerbil Meriones unguiculatus as an alternative experimental model for prostate cancer study. This model has presented significant responses to hormonal treatments and to development of spontaneous and induced neoplasias. The data obtained indicate reorganization of type I collagen fibers and reticular fibers, synthesis of new components such as tenascin and proteoglycans, degradation of basement membrane components and elastic fibers and increased expression of metalloproteinases. Fibroblasts that border the region, apparently participate in the stromal reaction. The roles of each of these events, as well as some signaling molecules, participants of neoplastic progression and factors that promote genetic reprogramming during epithelial–stromal transition are also discussed.

Photoluminescence of BaZrO3 explained by a order/disorded transformation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Fabrication and structural characterization of bismuth niobate thin films grown by chemical solution deposition

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Incorporation of PbF2 into Heavy Metal Oxide Borate Glasses. Structural Studies by Solid State NMR

A series of heavy metal oxide (HMO) glasses with composition 26.66B(2)O(3)-16GeO(2)-4 Bi2O3-(53.33-x)PbO-xPbF2 (0 <= x <= 40) were prepared and characterized with respect to their bulk (glass transition and crystallization temperatures, densities, molar volumes) and spectroscopic properties. Homogeneous glasses are formed up to x = 30, while crystallization of beta-PbF2 takes place at higher contents. Substitution of PbO by PbF2 shifts the optical band gap toward higher energies, thereby extending the UV transmission window significantly toward higher frequencies. Raman and infrared absorption spectra can be interpreted in conjunction with published reference data. Using B-11 and F-19 high-resolution solid state NMR as well as B-11/F-19 double resonance methodologies, we develop a quantitative structural description of this material. The fraction of four-coordinate boron is found to be moderately higher compared to that in glasses with the same PbO/B2O3 ratios, suggesting some participation of PbF2 in the network transformation process. This suggestion is confirmed by the F-19 NMR spectra. While the majority of the fluoride ions is present as ionic fluoride, similar to 20% of the fluorine inventory acts as a network modifier, resulting in the formation of four-coordinate BO3/2F- units. These units can be identified by F-19{B-11} rotational echo double resonance and B-11{F-19} cross-polarization magic angle spinning (CPMAS) data. These results provide the first unambiguous evidence of B-F bonding in a PbF2-modified glass system. The majority of the fluoride ions are found in a lead-dominated environment. F-19-F-19 homonuclear dipolar second moments measured by spin echo decay spectroscopy are quantitatively consistent with a model in which these ions are randomly distributed within the network modifier subdomain consisting of PbO, Bi2O3, and PbF2. This model, which implies both the features of atomic scale mixing with the network former borate species and some degree of fluoride ion clustering is consistent with all of the experimental data obtained on these glasses.

Structural changes and dynamic behaviour of vanadium oxide-based catalysts for gas-phase selective oxidations

Selective oxidation is one of the simplest functionalization methods and essentially all monomers used in manufacturing artificial fibers and plastics are obtained by catalytic oxidation processes. Formally, oxidation is considered as an increase in the oxidation number of the carbon atoms, then reactions such as dehydrogenation, ammoxidation, cyclization or chlorination are all oxidation reactions. In this field, most of processes for the synthesis of important chemicals used vanadium oxide-based catalysts. These catalytic systems are used either in the form of multicomponent mixed oxides and oxysalts, e.g., in the oxidation of n-butane (V/P/O) and of benzene (supported V/Mo/O) to maleic anhydride, or in the form of supported metal oxide, e.g., in the manufacture of phthalic anhydride by o-xylene oxidation, of sulphuric acid by oxidation of SO2, in the reduction of NOx with ammonia and in the ammoxidation of alkyl aromatics. In addition, supported vanadia catalysts have also been investigated for the oxidative dehydrogenation of alkanes to olefins , oxidation of pentane to maleic anhydride and the selective oxidation of methanol to formaldehyde or methyl formate [1]. During my PhD I focused my work on two gas phase selective oxidation reactions. The work was done at the Department of Industrial Chemistry and Materials (University of Bologna) in collaboration with Polynt SpA. Polynt is a leader company in the development, production and marketing of catalysts for gas-phase oxidation. In particular, I studied the catalytic system for n-butane oxidation to maleic anhydride (fluid bed technology) and for o-xylene oxidation to phthalic anhydride. Both reactions are catalyzed by systems based on vanadium, but catalysts are completely different. Part A is dedicated to the study of V/P/O catalyst for n-butane selective oxidation, while in the Part B the results of an investigation on TiO2-supported V2O5, catalyst for o-xylene oxidation are showed. In Part A, a general introduction about the importance of maleic anhydride, its uses, the industrial processes and the catalytic system are reported. The reaction is the only industrial direct oxidation of paraffins to a chemical intermediate. It is produced by n-butane oxidation either using fixed bed and fluid bed technology; in both cases the catalyst is the vanadyl pyrophosphate (VPP). Notwithstanding the good performances, the yield value didn’t exceed 60% and the system is continuously studied to improve activity and selectivity. The main open problem is the understanding of the real active phase working under reaction conditions. Several articles deal with the role of different crystalline and/or amorphous vanadium/phosphorous (VPO) compounds. In all cases, bulk VPP is assumed to constitute the core of the active phase, while two different hypotheses have been formulated concerning the catalytic surface. In one case the development of surface amorphous layers that play a direct role in the reaction is described, in the second case specific planes of crystalline VPP are assumed to contribute to the reaction pattern, and the redox process occurs reversibly between VPP and VOPO4. Both hypotheses are supported also by in-situ characterization techniques, but the experiments were performed with different catalysts and probably under slightly different working conditions. Due to complexity of the system, these differences could be the cause of the contradictions present in literature. Supposing that a key role could be played by P/V ratio, I prepared, characterized and tested two samples with different P/V ratio. Transformation occurring on catalytic surfaces under different conditions of temperature and gas-phase composition were studied by means of in-situ Raman spectroscopy, trying to investigate the changes that VPP undergoes during reaction. The goal is to understand which kind of compound constituting the catalyst surface is the most active and selective for butane oxidation reaction, and also which features the catalyst should possess to ensure the development of this surface (e.g. catalyst composition). On the basis of results from this study, it could be possible to project a new catalyst more active and selective with respect to the present ones. In fact, the second topic investigated is the possibility to reproduce the surface active layer of VPP onto a support. In general, supportation is a way to improve mechanical features of the catalysts and to overcome problems such as possible development of local hot spot temperatures, which could cause a decrease of selectivity at high conversion, and high costs of catalyst. In literature it is possible to find different works dealing with the development of supported catalysts, but in general intrinsic characteristics of VPP are worsened due to the chemical interaction between active phase and support. Moreover all these works deal with the supportation of VPP; on the contrary, my work is an attempt to build-up a V/P/O active layer on the surface of a zirconia support by thermal treatment of a precursor obtained by impregnation of a V5+ salt and of H3PO4. In-situ Raman analysis during the thermal treatment, as well as reactivity tests are used to investigate the parameters that may influence the generation of the active phase. Part B is devoted to the study of o-xylene oxidation of phthalic anhydride; industrially, the reaction is carried out in gas-phase using as catalysts a supported system formed by V2O5 on TiO2. The V/Ti/O system is quite complex; different vanadium species could be present on the titania surface, as a function of the vanadium content and of the titania surface area: (i) V species which is chemically bound to the support via oxo bridges (isolated V in octahedral or tetrahedral coordination, depending on the hydration degree), (ii) a polymeric species spread over titania, and (iii) bulk vanadium oxide, either amorphous or crystalline. The different species could have different catalytic properties therefore changing the relative amount of V species can be a way to optimize the catalytic performances of the system. For this reason, samples containing increasing amount of vanadium were prepared and tested in the oxidation of o-xylene, with the aim of find a correlations between V/Ti/O catalytic activity and the amount of the different vanadium species. The second part deals with the role of a gas-phase promoter. Catalytic surface can change under working conditions; the high temperatures and a different gas-phase composition could have an effect also on the formation of different V species. Furthermore, in the industrial practice, the vanadium oxide-based catalysts need the addition of gas-phase promoters in the feed stream, that although do not have a direct role in the reaction stoichiometry, when present leads to considerable improvement of catalytic performance. Starting point of my investigation is the possibility that steam, a component always present in oxidation reactions environment, could cause changes in the nature of catalytic surface under reaction conditions. For this reason, the dynamic phenomena occurring at the surface of a 7wt% V2O5 on TiO2 catalyst in the presence of steam is investigated by means of Raman spectroscopy. Moreover a correlation between the amount of the different vanadium species and catalytic performances have been searched. Finally, the role of dopants has been studied. The industrial V/Ti/O system contains several dopants; the nature and the relative amount of promoters may vary depending on catalyst supplier and on the technology employed for the process, either a single-bed or a multi-layer catalytic fixed-bed. Promoters have a quite remarkable effect on both activity and selectivity to phthalic anhydride. Their role is crucial, and the proper control of the relative amount of each component is fundamental for the process performance. Furthermore, it can not be excluded that the same promoter may play different role depending on reaction conditions (T, composition of gas phase..). The reaction network of phthalic anhydride formation is very complex and includes several parallel and consecutive reactions; for this reason a proper understanding of the role of each dopant cannot be separated from the analysis of the reaction scheme. One of the most important promoters at industrial level, which is always present in the catalytic formulations is Cs. It is known that Cs plays an important role on selectivity to phthalic anhydride, but the reasons of this phenomenon are not really clear. Therefore the effect of Cs on the reaction scheme has been investigated at two different temperature with the aim of evidencing in which step of the reaction network this promoter plays its role.