Preparo de óxido de nióbio suportado em alumina por deposição química em fase vapor: caracterização por espectroscopia vibracional e termogravimetria

Alumina supported niobium oxide was prepared by chemical vapor deposition (CVD) of NbCl5. The alumina was calcined and pretreated at differents temperatures in order to vary the density of OH groups on the surface which was determined by thermogravimetric analysis. A good correlation was found between the amount of anchored niobium and the total number of anionic sites (oxide and hydroxyl groups) on the surface of the alumina. The infrared spectra on the OH stretching region indicate that OH groups coordinated to at least one tetrahedral aluminum were more reactive towards NbCl5.

Influência da adição de defloculante, ligante e partículas de alumina no comportamento reológico de suspensões a base de frita e caulim

Enamel suspensions were characterized according to their rheological behavior. The suspensions presented a pseudoplastic behavior, yield stress and thixotropy, with or without the presence of deffloculant. Added carboxymethylcellulose increases the apparent viscosity of enamel suspensions and interacts complexly with the deffloculant, here sodium silicate. Addition of crystalline particles of two types of alumina, used to improve the wear resistance of ceramic glazes, also change strongly the rheological behavior of the suspensions. Added high specific area, irregular alumina particles produce a higher increase of the apparent viscosity of enamel suspensions compared to rounded ones.

Influência do pH sobre a estabilidade de suspensões de alumina estabilizadas eletroestericamente

In this work, aqueous suspensions of aluminas with different particle sizes were evaluated. The effect of pH on the electrosteric stabilization using PMAA-NH4 (ammonium polymethacrylate) as deflocculant was studied. The amount of deflocculant was optimized and rheologic properties were determined at four different pH values. Sedimentation was also evaluated. For suspensions with pH 4, an electrostatic mechanism of stabilization was observed, probably due to a flat adsorption of PMMA- on the alumina surface, leading to a small efficiency in relation to steric stabilization. For a suspension with pH 12, the steric mechanism of stabilization prevails. Suspensions with pH 7 and 9 present a higher flocculation degree. In relation to particle size, A-1000 samples present a smaller particle size, leading to a smaller interparticle distance (IPS), making stabilization more difficult.

A monolithic glass chip for active single-cell sorting based on mechanical phenotyping

The mechanical properties of biological cells have long been considered as inherent markers of biological function and disease. However, the screening and active sorting of heterogeneous populations based on serial single-cell mechanical measurements has not been demonstrated. Here we present a novel monolithic glass chip for combined fluorescence detection and mechanical phenotyping using an optical stretcher. A new design and manufacturing process, involving the bonding of two asymmetrically etched glass plates, combines exact optical fiber alignment, low laser damage threshold and high imaging quality with the possibility of several microfluidic inlet and outlet channels. We show the utility of such a custombuilt optical stretcher glass chip by measuring and sorting single cells in a heterogeneous population based on their different mechanical properties and verify sorting accuracy by simultaneous fluorescence detection. This offers new possibilities of exact characterization and sorting of small populations based on rheological properties for biological and biomedical applications.

On-line preconcentration system using a microcolumn packed with Alizarin Red S-modified alumina for zinc determination by flame atomic absorption spectrometry

A simple and sensitive on-line flow injection system for determination of zinc with FAAS has been described. The method is based on the separation and preconcentration of zinc on a microcolumn of immobilized Alizarin Red S on alumina. The adsorbed analyte is then eluted with 250 µL of nitric acid (1 mol L-1) and is transported to flame atomic absorption spectrometer for quantification. The effect of pH, sample and eluent flow rates and presence of various cations and anions on the retention of zinc was investigated. The sorption of zinc was quantitative in the pH range of 5.5-8.5. For a sample volume of 25 mL an enrichment factor of 144 and a detection limit (3S) of 0.2 µg L-1 was obtained. The precision (RSD, n=7) was 3.0% at the 20 µg L-1 level. The developed system was successfully applied to the determination of zinc in water samples, hair, urine and saliva.

A sensitive and robust lc-ms/ms method with monolithic column and electrospray ionization for the quantitation of efavirenz in human plasma: application to a bioequivalence study

An LC-MS/MS method has been developed for the determination of efavirenz (EFZ) in human plasma using hydrochlorothiazide as internal standard (I.S.). An ESI negative mode with multiple reaction-monitoring was used monitoring the transitions m/z 313.88→69.24 (EFZ) and 296.02→204.76 (I.S.). Samples were extracted using liquid-liquid extraction. The total run time was 2.0 min. The separation was achieved with HPLC-RP using a monolithic column. The assay was linear in the concentration range of 100 - 5000 ng mL-1. The mean recovery was 83%. Intra- and inter-day precision were < 9.5% and < 8.9%, respectively and accuracy was in the range ± 8.33%. The method was successfully applied to a bioequivalence study.

Palladium-supported catalysts in methane combustion: comparison of alumina and zirconia supports

Palladium catalysts supported on alumina and zirconia were prepared by the impregnation method and calcined at 600 and 1000 ºC. Catalysts were characterized by BET measurements, XRD, XPS, O2-TPD and tested in methane combustion through temperature programmed surface reaction. Alumina supported catalysts were slightly more active than zirconia supported catalysts, but after initial heat treatment at 1000 ºC, zirconia supported palladium catalyst showed better performance above 500 ºC A pattern between temperature interval stability of PdOx species and activity was observed, where better PdOx stability was associated with more active catalysts.

Multi-component quantitation of loratadine, pseudoephedrine and paracetamol in plasma and pharmaceutical formulations with liquid chromatography-tandem mass spectrometry utilizing a monolithic column

The purpose of this study was to develop a rapid, simple and sensitive quantitation method for pseudoephedrine (PSE), paracetamol (PAR) and loratadine (LOR) in plasma and pharmaceuticals using liquid chromatography-tandem mass spectrometry with a monolithic column. Separation was achieved using a gradient composition of methanol-0.1% formic acid at a flow rate of 1.0 mL min-1. Mass spectral transitions were recorded in SRM mode. System validation was evaluated for precision, specificity and linearity. Limit of detection for pseudoephedrine, paracetamol, and loratadine were determined to be 3.14, 1.86 and 1.44 ng mL-1, respectively, allowing easy determination in plasma with % recovery of 93.12 to 101.56%.

Sodium dodecyl sulfate coated γ-alumina support modified by a new Schiff base for solid phase extraction and flame-AAS determination of lead and copper ions

A simple and fast approach for solid phase extraction is herein described, and used to determine trace amounts of Pb2+ and Cu2+ metal ions. The solid phase support is sodium dodecyl sulfate (SDS)-coated γ-alumina modified with bis(2-hydroxy acetophenone)-1,6-hexanediimine (BHAH) ligand. The adsorbed ions were stripped from the solid phase by 6 mL of 4 M nitric acid as eluent. The eluting solution was analyzed by flame atomic absorption spectrometry (FAAS). The sorption recovery of metal ions was investigated with regard to the effects of pH, amount of ligand, γ-alumina and surfactant and the amount and type of eluent. Complexation of BHAH with Pb2+ or Cu2+ ions was examined via spectrophotometry using the HypSpec program. The detection limit for Cu2+ was 7.9 µg L-1 with a relative standard deviation of 1.67%, while that for Pb2+ was 6.4 µg L-1 with a relative standard deviation of 1.64%. A preconcentration factor of 100 was achieved for these ions. The method was successfully applied to determine analyte concentrations in samples of liver, parsley, cabbage, and water.

Efeito da ativação mecânica de uma formulação de talco/caulim/alumina sobre o mecanismo e a cinética de formação de cordierita

In this study, the influence of mechanical activation by intensive ball milling of a stoichiometric mixture of talc, kaolin, and alumina on the mechanism and kinetics of cordierite (2MgO·2Al2O3·5SiO2) formation was evaluated. The raw materials were characterized by chemical analysis, X-ray diffraction (XRD), laser diffraction, and helium pycnometry. The kinetics and mechanism of cordierite formation were studied by XRD, differential thermal analysis, and dilatometry in order to describe the phase formation as a function of temperature (1000-1400 ºC), time of thermochemical treatment (0-4 h), and grinding time of the mixture (0-45 min). Finally, the optimal conditions of the thermochemical treatment that ensured the formation of cordierite were determined: milling time of 45 min and thermal treatment at 1280 ºC for 1 h.

COMPARAÇÃO E CONSTRUÇÃO DE REATORES DE "MILD" E "HARD ANODISATION" PARA FABRICAÇÃO DE ALUMINA ANÓDICA POROSA

The mild anodization (MA) reactor is exemplified for its operational simplicity and its excellent control over the experimental parameters that are involved in the anodization process. This method provides porous anodic alumina films with a regular cell-arrangement structure. This offers a better cost-benefit ratio than the other equipment configurations that are used to fabricate nanoporous structures (i.e., ion beam lithography). Conversely, the hard anodization (HA) reactor produces oxides at a rate that is 25 to 35 times faster than the MA reactor. The produced oxides also have greater layer thicknesses and interpore distance, and with a uniform nanopore spatial order (> 1000). In contrast to MA reactors, the construction of an HA reactor requires special components to maintain anodisation at a high potential regime. Herein, we describe and compare both reactors from a technical viewpoint.

Bonding of Composite Resin to Alumina and Zirconia Ceramics with Special Emphasis on Surface Conditioning and Use of Coupling Agents

Dental oxide ceramics have been inspired by their biocompability and mechanical properties which have made durable all-ceramic structures possible. Clinical longevity of the prosthetic structures is dependent on effective bonding with luting cements. As the initial shear bond strength values can be comparable with several materials and procedures, long-term durability is affected by ageing. Aims of the current study were: to measure the shear bond strength of resin composite-to-ceramics and to evaluate the longevity of the bond; to analyze factors affecting the bond, with special emphasis on: the form of silicatization of the ceramic surface; form of silanization; type of resin primer and the effect of the type of the resin composite luting cement; the effect of ageing in water was studied regarding its effect to the endurance of the bond. Ceramic substrates were alumina and yttrium stabilized zirconia. Ceramic conditioning methods included tribochemical silicatization and use of two silane couplings agents. A commercial silane primer was used as a control silane. Various combinations of conditioning methods, primers and resin cements were tested. Bond strengths were measured by shear bond strength method. The longevity of the bond was generally studied by thermocycling the materials in water. Additionally, in one of the studies thermal cycling was compared with long-term water storaging. Results were analysed statistically with ANOVA and Weibull analysis. Tribochemical treatment utilizing air pressure of 150 kPa resulted shear bond strengths of 11.2 MPa to 18.4 MPa and air pressure of 450 kPa 18.2 MPa to 30.5 MPa, respectively. Thermocycling of 8000 cycles or four years water storaging both decreased shear bond strength values to a range of 3.8 MPa to 7.2 MPa whereas initial situation varied from 16.8. Mpa to 23.0 MPa. The silane used in studies had no statistical significance. The use of primers without 10-MDP resulted spontaneous debonding during thermocycling or shear bond strengths below 5 MPa. As conclusion, the results showed superior long-term bonding with primers containing 10-MDP. Silicatization with silanizing showed improved initial shear bond strength values which considerably decreased with ageing in water. Thermal cycling and water storing for up to four years played the major role in reduction of bond strength, which could be due to thermal fatigue of the bonding interface and hydrolytic degradation of the silane coupled interface.

Bio-ethanol valorization towards C4s including 1-butanol over metal modified alumina and zeolite catalysts

Bio-ethanol has been used as a fuel additive in modern society aimed at reducing CO2-emissions and dependence on oil. However, ethanol is unsuitable as fuel supplement in higher proportions due to its physico-chemical properties. One option to counteract the negative effects is to upgrade ethanol in a continuous fixed bed reactor to more valuable C4 products such as 1-butanol providing chemical similarity with traditional gasoline components. Bio-ethanol based valorization products also have other end-uses than just fuel additives. E.g. 1-butanol and ethyl acetate are well characterised industrial solvents and platform chemicals providing greener alternatives. The modern approach is to apply heterogeneous catalysts in the investigated reactions. The research was concentrated on aluminium oxide (Al2O3) and zeolites that were used as catalysts and catalyst supports. The metals supported (Cu, Ni, Co) gave very different product profiles and, thus, a profound view of different catalyst preparation methods and characterisation techniques was necessary. Additionally, acidity and basicity of the catalyst surface have an important role in determining the product profile. It was observed that ordinary determination of acid strength was not enough to explain all the phenomena e.g. the reaction mechanism. One of the main findings of the thesis is based on the catalytically active site which originates from crystallite structure. As a consequence, the overall evaluation of different by-products and intermediates was carried out by combining the information. Further kinetic analysis was carried out on metal (Cu, Ni, Co) supported self-prepared alumina catalysts. The thesis gives information for further catalyst developments aimed to scale-up towards industrially feasible operations.

Monolithic zirconium dioxide as a full contour restorative material: With special emphasis on the optical and mechanical properties

Full contour monolithic zirconia restorations have shown an increased popularity in the dental field over the recent years, owing to its mechanical and acceptable optical properties. However, many features of the restoration are yet to be researched and supported by clinical studies to confirm its place among the other indirect restorative materials This series of in vitro studies aimed at evaluating and comparing the optical and mechanical properties, light cure irradiance, and cement polymerization of multiple monolithic zirconia material at variable thicknesses, environments, treatments, and stabilization. Five different monolithic zirconia materials, four of which were partially stabilized and one fully stabilized were investigated. The optical properties in terms of surface gloss, translucency parameter, and contrast ratio were determined via a reflection spectrophotometer at variable thicknesses, coloring, sintering method, and after immersion in an acidic environment. Light cure irradiance and radiant exposure were quantified through the specimens at variable thicknesses and the degree of conversion of two dual-cure cements was determined via Fourier Transform Infrared spectroscopy. Bi-axial flexural strength was evaluated to compare between the partially and fully stabilized zirconia prepared using different coloring and sintering methods. Surface characterization was performed using a scanning electron microscope and a spinning disk confocal microscope. The surface gloss and translucency of the zirconia investigated were brand and thickness dependent with the translucency values decreasing as the thickness increased. Staining decreased the translucency of the zirconia and enhanced surface gloss as well as the flexural strength of the fully stabilized zirconia but had no effect on partially stabilized zirconia. Immersion in a corrosive acid increased surface gloss and decreased the translucency of some zirconia brands. Zirconia thickness was inversely related to the amount of light irradiance, radiant exposure, and degree of monomer conversion. Type of sintering furnace had no effect on the optical and mechanical properties of zirconia. Monolithic zirconia maybe classified as a semi-translucent material that is well influenced by the thickness, limiting its use in the esthetic zones. Conventional acid-base reaction, autopolymerizing and dual-cure cements are recommended for its cementation. Its desirable mechanical properties give it a high potential as a restoration for posterior teeth. However, close monitoring with controlled clinical studies must be determined before any definite clinical recommendations can be drawn.

Bacterial adhesion and biofilm formation on monolithic zirconia

Tutkimuksen tavoitteena oli selvittää bakteerien kiinnittymistä ja bakteeribiofilmin muodostumista implanttimateriaalien pinnalla. Monoliittisen zirkonian ja lasikeramien käyttö implanttikruunujen materiaaleina kasvaa jatkuvasti. Zirkoniaa käytetään myös abutmenttien materiaalina esteettisillä alueilla. Tällä hetkellä on vain vähän tutkimustietoa näiden implanttikruunumateriaalien sekä implanttikruunujen sementoimiseen käytetyn sementin pinnalla tapahtuvasta bakteeriadheesiosta ja biofilmin muodostumisesta. Bakteerien adheesiota ja biofilmin muodistumista tutkittiin neljän eri materiaalin pinnalla. Tutkimuksessa käytetyt materiaalit olivat: (1) Litiumdisilikaatti (LDS; IPS e.max CAD, Ivoclar Vivadent,kontrolli), (2) Kokonaan stabiloitu zirkonia (FSZ; Prettau Anterior, Zirkonzahn), (3) Osittain stabiloitu zirkonia (PSZ; Katana, Noritake), ja (4) Kaksoiskovetteinen sementti (DCC; Multilink hybrid abutment cement, Ivoclar Vivadent). Kaikki tutkimuksessa käytetyt materiaalit valmisteltiin ja kiillotettiin valmistajien ohjeiden mukaisesti Tutkittavat pinnat inkuboitiin Streptococcus mutans-suspensiossa +37°C:ssä asteessa. Bakteeriadheesiotestissä inkubointiaika oli 30 minuuttia ja biofilmitestissä vastaava aika oli 24 tuntia. Materiaalien pintoja tarkasteltiin myös elektronimikroskooppia käyttäen. Tutkimuksessa todettiin, että bakteeriadheesiossa oli eroja eri materiaalien välillä. Biofilmin. muodostumisessa ei todettu tilastollisesti merkittäviä eroja tutkittavien materiaalien välillä.