Simultaneous solidification of two catalyst wastes and their effect on the early stages of cement hydration

Two catalyst wastes (RNi and RAI) from polyol production were considered as hazardous, due to their respective high concentration of nickel and aluminum contents. This article presents the study, done to avoid environmental impacts, of the simultaneous solidification/stabilization of both catalyst wastes with type II Portland cement (CP) by non-conventional differential thermal analysis (NCDTA). This technique allows one to monitor the initial stages of cement hydration to evaluate the accelerating and/or retarding effects on the process due to the presence of the wastes and to identify the steps where the changes occur. Pastes with water/cement ratio equal to 0.5 were prepared, into which different amounts of each waste were added. NCDTA has the same basic principle of Differential Thermal Analysis (DTA), but differs in the fact that there is no external heating or cooling system as in the case of DTA. The thermal effects of the cement paste hydration with and without waste presence were evaluated from the energy released during the process in real time by acquiring the temperature data of the sample and reference using thermistors with 0.03 A degrees C resolution, coupled to an analog-digital interface. In the early stages of cement hydration retarding and accelerating effects occur, respectively due to RNi and RAl presence, with significant thermal effects. During the simultaneous use of the two waste catalysts for their stabilization process by solidification in cement, there is a synergic resulting effect, which allows better hydration operating conditions than when each waste is solidified separately. Thermogravimetric (TG) and derivative thermogravimetric analysis (DTG) of 4 and 24 h pastes allow a quantitative information about the main cement hydrated phases and confirm the same accelerating or retarding effects due to the presence of wastes indicated from respective NCDTA curves.

The influence of the mixing time in the rheological behavior of cement pastes

Rheology has the purpose to study the flux and deformation of materials when submitted to some tension or outer mechanical solicitation. In practice, the effective scientific field broached by rheology is restricted only to the study of homogeneous fluids behavior, in which are included eminent liquids, particles suspensions, and emulsions. The viscosity (η) and the yield stress (τ 0) are the two basic values that define the fluids' behavior. The first one is the proportionality constant that relates the shear rate (γ) with the shear stress (τ) applied, while the second indicates the minimal tension for the flowage beginning. The fluids that obey the Newton's relation - Newtonians fluids - display the constant viscosity and the null yield stress. It's the case of diluted suspensions and grate amount of the pure liquids (water, acetone, alcohol, etc.) in which the viscosity is an intrinsic characteristic that depends on temperature and, in a less significant way, pressure. The suspension, titled Cement Paste, is defined as being a mixture of water and cement with, or without, a superplasticizer additive. The cement paste has a non-Newtonian fluid behavior (pseudoplastic), showing a viscosity that varies in accord to the applied shear stress and significant deformations are obtained from a delimited yield stress. In some cases, systems can also manifest the influence of chemical additives used to modify the interactions fluid/particles, besides the introduced modifications by the presence of incorporated air. To the cement paste the rheometric rehearsals were made using the rheometer R/S Brookfield that controls shear stress and shear rate in accord to the rheological model of Herschel-Bulkley that seems to better adapt to this kind of suspension's behavior. This paper shows the results of rheometrical rehearsals on the cement paste that were produced with cements HOLCIM MC-20 RS and CPV-ARI RS with the addition of superplasticizer additives based of napthaline and polycarboxilate, with and without a constant agitation of the mixture. The obtainment of dosages of superplasticizer additives, as well as the water/cement ratio, at the cement at the fluidify rate determination, was done in a total of 12 different mixtures. It's observed that the rheological parameters seem to vary according to the cement type, the superplasticizer type, and the methodology applied at the fluidity rate determination.

Investigação de compósitos cimentícios para preenchimento de juntas da interface e de nichos em ligações de estruturas pré- moldadas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Avaliação do comportamento reológico na retração plástica e na fissuração de argamassas de concreto auto-adensável

This paper investigated the influence of the amount of superplasticizer and mineral adding - silica fume and basaltic filer - in plastic shrinkage and cracking of self-compacting concrete (SCC) mortars. Initially analysis was performed of the rheological behavior of cement paste and mortars phases of the compositions of SCC. Then the deformations of mortars were measured by the effect of shrinkage and evaluation of cracking. On plastic shrinkage and cracking, the composition with silica fume showed superior results, independent of wind and superplasticizer content, relative to the composition with addition of basalt filler. However, the composition with silica fume showed superior results only in the tests with imposed ventilation at vertical plastic deformation. The rheological behavior affected directly the plastic shrinkage and cracking at early ages, fact confirmed by the analysis of capillary pressures of mortars tested.

Portland cement use in dental root perforations: a long term followup

Root canal and furcal perforations are causes of endodontic therapy failure and different materials that stimulate tissue mineralization have been proposed for perforation treatment. In the first case, a patient presented tooth 46 with unsatisfactory endodontic treatment and a periapical radiographic lesion. A radiolucent area compatible with a perforating internal resorption cavity was found in the mesial root. The granulation tissue was removed, and root canals were prepared. The intracanal medication was composed of calcium hydroxide and the perforation cavity was filled with Portland cement. The 11-year followup showed radiographic repair of the tissue adjacent to the perforation and absence of clinical signs and symptoms or periapical lesion. In the second case, a patient presented with edema on the buccal surface of tooth 46. The examination showed a radiolucent area in the furcation region compatible with an iatrogenic perforation cavity. The mesial root canals were calcified, and only the distal root canal was prepared. The cavity was filled with a calcium hydroxide-based paste and the distal root canal was obturated. In sequence, the perforation cavity was filled with Portland cement. The 9-year followup showed the tooth in masticatory function with radiographic and clinical aspects compatible with normality.

Bonding ability of paste-paste glass ionomer systems to tooth structure: in vitro studies

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Voltammetric determination of isoprenaline in pharmaceutical preparations using a copper(II) hexacyanoferrate(III) modified carbon paste electrode

The electroanalytical determination of isoprenaline in pharmaceutical preparations of a homemade carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) was studied by cyclic voltammetry. Several parameters were studied for the optimization of the sensor such as electrode composition, electrolytic solution, pH effect, potential scan rate and interferences in potential. The optimum conditions were found in an electrode composition (in mass) of 15% CuHCF, 60% graphite and 25% mineral oil in 0.5 mol l(-1) acetate buffer solution at pH 6.0. The analytical curve for isoprenaline was linear in the concentration range from 1.96 x 10(-4) to 1.07 x 10(-3) mol l(-1) with a detection limit of 8.0 x 10(-5) mol l(-1). The relative standard deviation was 1.2% for 1.96 x 10(-4) mol l(-1) isoprenaline solution (n=5). The procedure was successfully applied to the determination of isoprenaline in pharmaceutical preparations; the CuHCF modified carbon paste electrode gave comparable results to those results obtained using a UV spectrophotometric method. (C) 2004 Elsevier B.V. All rights reserved.

Sensor for cysteine based on oxovanadium(IV) complex of Salen modified carbon paste electrode

The electrochemical behavior of a carbon paste electrode modified (CPEM) with N,N′-ethylenebis(salicylideneiminato)oxovanadium(IV) complex ([(VO)-O-IV(Salen)]) was investigated as a new sensor for cysteine. Cyclic voltammetry at the modified electrode in 0.1 mol L-1 KCl Solution (pH 5.0) showed a single-electron reduction/oxidation of the Couple VO3+/VO2+. The CPEM with [VO(Salen)] presented good electrochemical stability in a wide pH range (4.0-10.0) and an ability to electrooxidate cysteine at 0.65 V versus SCE. These results demonstrate the viability of the use of this modified electrode as an amperometric sensor for cysteine determination. © 2004 Elsevier B.V. All rights reserved.

Application of the Potentiometric Stripping Analysis with Constant Current for the Determination of Lithium Ions Using a Spinel-Type Manganese (IV) Oxide-Modified Carbon Paste Electrode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determination of Analgesics (Dipyrone and Acetaminophen) in Pharmaceutical Preparations by Cyclic Voltammetry at a Copper(II) Hexacyanoferrate(III) Modified Carbon Paste Electrode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrochemical characterization of the paste carbon modified electrode with KSr2Ni0.75Nb4.25O15-delta solid in catalytic oxidation of the dipyrone

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

Electrochemical evaluation of the a carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions for amperometric determination of lithium

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

Influência da adição no comportamento reológico da pasta autoadensável de alto desempenho

Influence of admixture on the rheological behavior of high performance self-compacting paste. This research proposes to study the influence of the specific area, mould and surface texture of admixtures on the rheological behavior of high performance self-compacting paste (HPSCP). The selected admixtures are calcareous filler and basalt filler, which are industrial residues, thus contributing to sustainable development. The paste is made up of cement, silica fume, calcareous filler or basalt filler, water and superplasticizer additive. For this study, the water/cement ratios are fixed = 0.40 L kg(-1); silica fume/cement = 0.10 kg kg(-1); the filler/cement and superplasticizer/cement ratios are determined through Marsh cone and mini-slump tests. The results show that for same filler/cement ratios, the ratios of superplasticizer to paste with calcareous filler are significantly lower than those of paste with basalt filler. The results show that the specific area, mould and surface texture of these admixtures significantly influence the rheological behavior of HPSCP.

Stripping voltammetry of mercury(II) with a chemically modified carbon paste electrode containing silica gel functionalized with 2,5-dimercapto-1,3,4-thiadiazole

The accumulation voltammetry of mercury(II) was investigated at a carbon paste electrode chemically modified with silica gel functionalized with 2,5-dimercapto-1,3,4-thiadiazole (DTTPSG-CPE). The repetitive cyclic voltammogram of mercury(II) solution in the potential range -0.2 to +0.8 V (vs. Ag/AgCl), (0.02 mol L-1 KNO3; nu=20 mV s(-1)) show two peaks one at about 0.0 V and other at 0.31 V. However, the cathodic wave peak, around 0.0 V, is irregular and changes its form in each cycle. This peak at about 0.0 V is the reduction current for mercury(II) accumulated in the DTTPSG-CPE. The anodic wave peak at 0.31 V is well-defined and does not change during the cycles. The resultant material was characterized by cyclic and differential pulse anodic stripping voltammetry performed with the electrode in differents supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. The precision for six determinations (n=6) of 0.05 and 0.20 mg (L)-(1) Hg(II) was 2.8 and 2.2% (relative standard deviation), respectively. The method was satisfactory and used to determine the concentration of mercury(II) in natural waters contaminated by this metal.

Open photoacoustic cell for thermal diffusivity measurements of a fast hardening cement used in dental restoring

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)