Pozzolanic activity of oil-refining catalyst: evaluation by electron and atomic microscopy

The reuse of waste fluid catalytic cracking (FCC) catalyst as partial surrogate for cement can reduce the environmental impact of both the oil-refinery and cement production industries [1,2]. FCC catalysts can be considered as pozzolanic materials since in the presence of water they tend to chemically react with calcium hydroxide to produce compounds possessing cementitious properties [3,4]. In addition, partial replacement of cement with FCC catalysts can enhance the performance of pastes and mortars, namely by improving their compressive strength [5,6]. In the present work the reaction of waste FCC catalyst with Ca(OH)2 has been investigated after a curing time of 28 days by scanning electron microscopy (SEM) with electron backscattered signal (BSE) combined with X-ray energy dispersive spectroscopy (EDS) carried out with a JEOL JSM 7001F instrument operated at 15 kV coupled to an INCA pentaFetx3 Oxford spectrometer. The polished cross-sections of FCC particles embedded in resin have also been evaluated by atomic force microscopy (AFM) in contact mode (CM) using a NanoSurf EasyScan 2 instrument. The SEM/EDS results revealed that an inward migration of Ca occurred during the reaction. A weaker outward migration of Si and Al was also apparent (Fig. 1). The migration of Ca was not homogeneous and tended to follow high-diffusivity paths within the porous waste FCC catalyst particles. The present study suggests that the porosity of waste FCC catalysts is key for the migration/reaction of Ca from the surrounding matrix, playing an important role in the pozzolanic activity of the system. The topography images and surface roughness parameters obtained by atomic force microscopy can be used to infer the local porosity in waste FCC catalyst particles (Fig. 2).

Produção de biodiesel a partir de pastas de gordura e resíduo de glicerol

O principal objectivo deste trabalho consistiu na produção de biodiesel a partir de resíduos fornecidos pela Empresa SOCIPOLE, S.A. Esta, forneceu, pastas de gordura (depósito formado nos óleos usados), só aproveitadas pela empresa para a produção de sabões, e resíduo de glicerol proveniente da produção de biodiesel. Com as pastas de gordura, foi feito um estudo onde se variaram alguns parâmetros, tais como: o tipo de reactor, catalisador, temperatura, agitação, tempo de reacção, razão molar gordura:metanol e condições de secagem. O estudo mais pormenorizado foi efectuado com o NaOH, como catalisador. Foram feitos vários ensaios para os tempos de reacção de 30minutos, 1hora e 2horas, a 65ºC e razão molar gordura:metanol 1:6, tendo-se obtido respectivamente 86,7; 88,1 e 87,5% para o teor de ésteres. No caso da resina catiónica forte como catalisador, aparentemente não houve reacção ao fim de 12h, enquanto no ensaio que utilizou o ácido sulfúrico, o teor de ésteres foi de 82,6%, ao fim de 12h com razão molar gordura:metanol igual a 1:11. Quanto à produção de biodiesel a partir do resíduo de ácidos gordos resultante da purificação do resíduo de glicerol, foi feito um estudo preliminar usando diferentes catalisadores, uma resina catiónica forte, ácido sulfúrico e zircónia sulfatada. Este resíduo continha cerca de 60% de ácidos gordos e aproximadamente 39% de ésteres metílicos. Dos três catalisadores usados, o que permitiu obter maior teor de ésteres foi a zircónia sulfatada, tendo-se obtido 82,9% trabalhando a 60ºC durante 18horas com agitação de 230rpm e razão molar ácidos gordos:metanol de 1:12 . O ensaio em que se obteve menor percentagem de ésteres (56,4%) foi com resina catiónica. Com as duas matérias-primas obteve-se sempre um teor de ésteres, no produto final, abaixo dos 96,5% estabelecidos pela Norma Europeia EN 14103. Estes resultados reflectem provavelmente a composição complexa das matérias-primas. As pastas de gordura podem conter compostos não esterificáveis, solúveis no biodiesel, ou mais dificilmente esterificáveis nas condições operacionais usadas. Já o resíduo de ácidos gordos apresenta uma cor escura o que indica a existência de compostos corados, talvez polímeros. Portanto, para se tirar conclusões fundamentadas é necessário fazer análises mais completas das pastas de gordura e do resíduo de ácidos gordos, assim como ao biodiesel produzido de forma a identificar as possíveis contaminações existentes nos produtos com esta proveniência.

Geopolymers as infill material for conservation of azulejos

The restoration materials currently used to fill gaps in architectural historical azulejos (e.g. lime or organic resin pastes) usually show serious drawbacks in terms of compatibility, effectiveness and durability. The existing solutions do not fully protect azulejos in outdoor conditions and frequently result in further deterioration. Geopolymers can be a potential solution for azulejo lacunae infill given the chemical-mineralogical similitude to the ceramic body, and also the durability and versatile range of physical properties that can be obtained through the manipulation of their formulation and curing conditions. This work presents and discusses the viability of the use of geopolymeric pastes to fill lacunae in azulejos or to act as “cold” cast ceramic tile surrogates reproducing missing azulejo fragments. The formulation of geopolymers, namely the type of activators, the aluminosilicate source, the amount of water (to meet adequate workability requirements) and curing conditions were studied. The need for post-curing desalination was also considered envisaging their application in the restoration of outdoor architectural historical azulejos frequently exposed to adverse environmental conditions. The possible advantages and disadvantages of the use of geopolymers in the conservation of azulejos are also discussed. Several techniques were used to study the chemical and physical behavior of geopolymers, namely FT-IR, XRD, MIP, SEM-EDS, WDXRF, electrical conductivity, open porosity, bending strength, adhesion strength, water vapour permeability, thermal expansion and hydric expansion. The results indicate that geopolymers are a promising material for restoration of azulejos, exhibiting some properties, such as adhesion to the ceramic substrate, higher than inorganic materials used nowadays, such as aerial lime based pastes.

Ureasilicate hybrid coatings for corrosion protection of galvanized steel in chloride-contaminated simulated concrete pore solution

Organic-inorganic hybrid (OIH) sol-gel coatings based on ureasilicates (U(X)) have promising properties for use as eco-friendly coatings on hot dip galvanized steel (HDGS) and may be considered potential substitutes for pre-treatment systems containing Cr(VI). These OIH coatings reduce corrosion activity during the initial stages of contact of the HDGS samples with highly alkaline environments (cementitious media) and allow the mitigation of harmful effects of an initial excessive reaction between cement pastes and the zinc layer. However, the behavior of HDGS coated with U(X) in the presence of chloride ions has never been reported. In this paper, the performance of HDGS coated with five different U(X) coatings was assessed by electrochemical measurements in chloride-contaminated simulated concrete pore solution (SCPS). U(X) sol-gel coatings were produced and deposited on HDGS by a dip coating method. The coatings performance was evaluated by electrochemical impedance spectroscopy, potentiodynamic polarization curves measurements, macrocell current density and polarization resistance in contact with chloride-contaminated SCPS. The SEM/EDS analyses of the coatings before and after the tests were also performed. The results showed that the HDGS samples coated with the OIH coatings exhibited enhanced corrosion resistance to chloride ions when compared to uncoated galvanized steel.

Profilaxia do tifo exantemático neotrópico no Brasil

A profilaxia racional de um doença decorre do melhor e mais profundo conhecimento dela. A do tifo exantematico neotrópico, apesar do que se sabe da doença, não e fácil no Brasil. Uma das maiores dificuldade encontramos nas distancias do nosso "hinterland" e na falta de cultura dos nossos agricultores. O homem se infecta certamente com as raças VB, VA e VA do virus brasileiro: 1.°) no campo, nas matas e nas macegas; 2.°) dentro dos domicílios ou nos arredores dêstes. Os primeiros constitúem de regra, os casos insulados do mal. Os segundos fazem parte, não raro, dos focos domiciliares macicos, com 2, 5, 7 e até 12 casos na mesma casa. São responsáveis, pelos primeiros, os carrapatos, principalmente o Amblyomma cayennense e o Amblyomma brasiliense, mormente quando no estado de ninfas, dada a herança habitual das infecções nesses artrópodos, que se infestam em animais silvestres, depositários do virus. São responsáveis pelos segundos, os "Cimex lectularius", percevejos dos leitos e as ninfas e larvas dos carrapatos, deixadas cair junto aos domicílios ou mesmo dentro deles. A profilaxia racional e completa da doença entre nós compreende: 1.°) Descarrapatização das zonas infestadas, por meio de leis apropriadas, coercitivas e aplicadas sem excepção; 2.°) Combate aos cães vadios, cabritos e outros animais portadores do virus; 3.°) Queima dos pastes, campos e macegas de fraco valor econômico, principalmente os que confinam com residências; 4.°) A propaganda racional contra esta grave doença exantemática: a) com palestras locais, acompanhadas de fotografias e gráficos expressivos e ao alcance de todos; b) pelo cinema; c) com artigos simples, claros e precisos sôbre a matéria; d) com folhetos apropriados; 5.°) Combater toda a vermina dentro e nas proximidades dos domicílios, 6.°) Demonstrar que é possível, com toda a certeza, evitar a doença, retirando os carrapatos que se prenderem ao corpo, dentro de 12 ou 14 horas após a fixação; 7.°) Aconselhar o emprego do DDT, “Gammexame" e “Toxafeno" para o expurgo das casas e animais, a fim de combater os carrapatos; 8.°) Vacinação preventiva contra a doença, quando possível, em zonas delimitadas e já civilizadas, feitas principalmente com raças de virus colhidas no Brasil e, se possível, com uma só dose. O autor trabalhou durante algum tempo com a vacina tipo Spencer-Parker. Hoje aconselha o trabalho com a vacina tipo Cox, original ou modificada.

Investigation into Shrinkage of High-Performance Concrete Used for Iowa Bridge Decks and Overlays, TR-633, 2013

High-performance concrete (HPC) overlays have been used increasingly as an effective and economical method for bridge decks in Iowa and other states. However, due to its high cementitious material content, HPC often displays high shrinkage cracking potential. This study investigated the shrinkage behavior and cracking potential of the HPC overlay mixes commonly used in Iowa. In the study, 11 HPC overlay mixes were studied. These mixes consisted of three types of cements (Type I, I/II, and IP) and various supplementary cementitious materials (Class C fly ash, slag and metakaolin). Limestone with two different gradations was used as coarse aggregates in 10 mixes and quartzite was used in one mix. Chemical shrinkage of pastes, free drying shrinkage, autogenous shrinkage of mortar and concrete, and restrained ring shrinkage of concrete were monitored over time. Mechanical properties (such as elastic modulus and compressive and splitting tensile strength) of these concrete mixes were measured at different ages. Creep coefficients of these concrete mixes were estimated using the RILEM B3 and NCHRP Report 496 models. Cracking potential of the concrete mixes was assessed based on both ASTM C 1581 and simple stress-to-strength ratio methods. The results indicate that among the 11 mixes studied, three mixes (4, 5, and 6) cracked at the age of 15, 11, and 17 days, respectively. Autogenous shrinkage of the HPC mixes ranges from 150 to 250 microstrain and free dying shrinkage of the concrete ranges from 700 to 1,200 microstrain at 56 days. Different concrete materials (cementitious type and admixtures) and mix proportions (cementitious material content) affect concrete shrinkage in different ways. Not all mixes having a high shrinkage value cracked first. The stresses in the concrete are associated primarily with the concrete shrinkage, elastic modulus, tensile strength, and creep. However, a good relationship is found between cementitious material content and total (autogenous and free drying) shrinkage of concrete.

Development of a Rational Characterization Method for Iowa Fly Ash, HR-286, 1988

This research project was conducted in an attempt to determine the cause of paste strength variability in Iowa fly ashes and to develop test methods to more adequately reflect fly ash physical and chemical characteristics. An extensive three year sampling and testing program was developed and initiated which incorporated fly ash from several Iowa power plants. Power plant design and operating data were collected. The variability was directly linked to power plant maintenance schedules and to sodium carbonate coal pretreatment. Fly ash physical and chemical properties can change drastically immediately before and after a maintenance outage. The concentrations of sulfate bearing minerals in the fly ash increases sharply during shutdown. Chemical, mineralogical, and physical testing indicated that the sodium, sulfate bearing minerals, lime and tricalcium aluminate contents of the fly ashes play important roles in the development of hydration reaction products in fly ash pastes. The weak pastes always contained ettringite as the major reaction product. The strong pastes contained straetlingite and monosulfoaluminate as the major reaction products along with minor amounts of ettringite. Recommendations for testing procedure changes and suggested interim test methods are presented.

Effects of Cement on Moisture Migration in Concrete, Phase A, Laboratory Study of Moisture Migration in Hardened Cement Paste, HR-141, 1972

The Columbus Laboratories of Battelle Memorial Institute is currently conducting a study of the effect of cement on moisture migration in concrete as related to the problem of D-cracking of portland cement concrete pavements. The study began on December 31, 1970, and is planned as a 3-year program. The work plan, approved by the policy committee of the members of the Iowa, Kansas, and Missouri highway departments and the Federal Highway Administration, is composed of four parts. The first phase (A) of the investigation concerned the movement of moisture into and from hardened cement pastes and the dimensional changes accompanying the moisture changes. Small slab specimens of hardened neat cement pastes were prepared from 32 different cements which were prepared at the same water/cement ratio and hydrated to the same maturity factor.

Improving Portland Cement Concrete Mix Consistency and Production Rate through Two-Stage Mixing, TR-505, 2007

A two-stage mixing process for concrete involves mixing a slurry of cementitious materials and water, then adding the slurry to coarse and fine aggregate to form concrete. Some research has indicated that this process might facilitate dispersion of cementitious materials and improve cement hydration, the characteristics of the interfacial transition zone (ITZ) between aggregate and paste, and concrete homogeneity. The goal of the study was to find optimal mixing procedures for production of a homogeneous and workable mixture and quality concrete using a two-stage mixing operation. The specific objectives of the study are as follows: (1) To achieve optimal mixing energy and time for a homogeneous cementitious material, (2) To characterize the homogeneity and flow property of the pastes, (3) To investigate effective methods for coating aggregate particles with cement slurry, (4) To study the effect of the two-stage mixing procedure on concrete properties, (5) To obtain the improved production rates. Parameters measured for Phase I included: heat of hydration, maturity, and rheology tests were performed on the fresh paste samples, and compressive strength, degree of hydration, and scanning electron microscope (SEM) imaging tests were conducted on the cured specimens. For Phases II and III tests included slump and air content on fresh concrete and compressive and tensile strengths, rapid air void analysis, and rapid chloride permeability on hardened concrete.

La ceràmica de Barcelona. Organització i producció entre els segles XIII i XVIII a través de la seva caracterització arqueomètrica

L"estudi sobre la producció ceràmica de Barcelona en època medieval i postmedieval s'està fent des del Museu d"Història de Barcelona i des de l"ARQUB en aquest darrers anys. Aquest estudi s"ha reforçat amb els treballdesenvolupats en el marc del projecte de recerca Tecnolonial, cosa que ha permès ampliar les classes ceràmiques i el marc cronològic d"estudi. Els resultats aconseguits fins ara mostren que per a un mateix moment cronològic es preparen diverses pastes segons el producte final que es vol obtenir. Finalment, el canvi d"ubicació dels tallers que segurament es va produïr cap a finals del segle XIII / inicis del segle XIV podria estar relacionat amb l"explotació d"un nou llit d"argiles, la qual cosa coincidiria amb el fet que la producció del segle XIII és completament diferent químicament a la del segle XIV en endavant.

Chemical and mineralogical alteration of ceramics from a Late Bronze Age kiln at Kommos, Crete: the effect on the formation of a reference group

The formation of reference groups comprises an important procedure in chemical provenance studies of archaeological pottery. Material from ancient kilns is thought to be especially suitable for reference groups, as it comprises a definite unit of past production. Pottery from the Late Minoan IA kiln excavated at Kommos, Crete was analysed in order to produce a reference group in this important area of Minoan ceramic production. The samples were characterized by a combination of techniques providing information on the chemistry, mineralogy and microstructure of the ceramic body. Initially, the study was unable to establish, in a straightforward manner, a chemical reference group. Different ceramic pastes and a range of selective alterations and contaminations, affected by variable firing temperatures and burial environment, were shown to be responsible for the compositional variability. Procedures are described to compensate for such alterations and the perturbations in the data that they produce.

Modificação química e física do amido de quirera de arroz para aproveitamento na indústria de alimentos

The study evaluated the efficiency of chemical (phosphorylation) and physical (extrusion) modifications of the starch of broken rice. Results demonstrated a reduction in the moisture content of extruded and phosphorylated broken rice and an increase in the ash content of phosphorylated broken rice. Both phosphorylation and extrusion increased cold water binding capacity, swelling power, and solubility. Extruded and phosphorylated pastes were stable under refrigeration, but only extruded paste was stable when submitted to freezing. Phosphorylated paste had the lowest viscosity and the highest stability during heating, while the extruded one gelatinized without heating, but had higher losses during heating.

Production of silica gel from residual rice husk ash

This paper presents a study on the production of silica gel in hydrothermal process using residual rice husk ash. Measurements of the chemical composition, X-ray diffraction, infrared spectroscopy, particle size distribution, and pozzolanic activity were carried out in order to characterize the obtained material, and the optimal silica gel was selected for use as a mineral additive in cement pastes. The compressive strengths were determined for cement pastes containing silica gel (0.0, 2.5 or 5% by mass) in different times. The results indicate that the mixtures containing silica gel showed improved mechanical behavior over all time periods evaluated.

Efeito da adição de serragem de couro tratada quimicamente nas propriedades do cimento Portland

The sheave leather was subjected to chemical treatment in an attempt to immobilize chromium ion in a matrix of cement. Cementitious pastes were obtained by adding different proportions of waste treated solutions (5 and 10% compared to the cement mass) and the pH and setting time (hardening) were measured. Aiming to check the leather influence in Portland cement pastes, the phases formation were observed by X-ray diffraction (XRD). The results showed that the pretreatment was effective for the waste dissolution and the pH of treated waste chemical solutions did not influence significantly the characteristics of cement paste, with a slight increase in setting time results.

High quality human immunoglobulin G purified from Cohn fractions by liquid chromatography

In order to obtain intravenous immunoglobulin G (iv IgG) of high quality from F-I+II+III or F-II+III pastes prepared by the Cohn method, we developed a chromatography process using ion exchange gels, Q-Sepharose FF and CM-Sepharose FF, and Sephacryl S-300 gel filtration. Viral inactivation was performed by incubating the preparation with pepsin at pH 4.0 at 35oC for 18 h. The characteristics of 28 batches produced by us were: yield 4.3 ± 0.2 g/l plasma, i.e., a recovery of 39.1 ± 1.8%; IgG subclasses distribution: IgG1 = 58.4%, IgG2 = 34.8%, IgG3 = 4.5% and IgG4 = 2.3%; IgG size distribution was 98.4% monomers, 1.2% dimers and 0.4% polymers and protein aggregates; anticomplement activity was less than 0.5 CH50/mg IgG, and prekallikrein activator activity (PKA) was less than 5 IU/ml. These characteristics satisfied the requirements of the European Pharmacopoea edition, and the regulations of the Brazilian Health Ministry (M.S. Portaria No. 2, 30/10/1998).