Resumo A sonicação é amplamente utilizada para dispersão de nanomateriais em matrizes cimentícias. Aditivos superplastificantes à base de policarboxilato (SP) são geralmente incorporados na suspensão aquosa de nanomateriais antes da sonicação para melhorar a dispersão desses materiais. No entanto, o efeito da sonicação na estrutura molecular e no desempenho de dispersão do SP não foi totalmente investigado. Este trabalho avaliou o efeito da sonicação de um SP comercial a 20 kHz, potência de 750 W, amplitude de 50 e 80%, durante 15 e 30 min. Inicialmente, o efeito de sonicação foi avaliado em suspensão aquosa, determinando a distribuição de tamanho do SP (através de espalhamento dinâmico de luz – DLS) e potencial zeta. Posteriormente, as suspensões aquosas de SP foram utilizadas para a produção de pastas de cimento Portland. Foram realizados ensaios reológicos durante os primeiros 120 minutos de hidratação e a resistência à compressão foi avaliada aos 14 e 28 dias. Os resultados do potencial zeta e DLS sugeriram que a sonicação reduz o tamanho das cadeias de SP. Como resultado, a sonicação do SP aumentou a tensão de escoamento dinâmica inicial, a viscosidade e a área de histerese das pastas de cimento. Em contraste, a sonicação SP melhorou seu desempenho de dispersão ao longo do tempo, resultando em pastas com viscosidade reduzida a partir de 80 minutos. Finalmente, a sonicação SP não afetou a resistência à compressão das pastas de cimento aos 14 e 28 dias de hidratação. Em geral, quando o SP é disperso via sonicação juntamente com nanopartículas para aplicação em matrizes cimentícias, o efeito de sonicação do aditivo químico deve ser levado em consideração quando as propriedades de estado fresco do compósito são avaliadas.

Abstract Sonication is widely used for nanomaterials dispersion in cementitious matrices. Polycarboxylate-based superplasticizer (SP) admixtures are usually incorporated in the aqueous nanomaterials suspension before sonication to improve the dispersion of these materials. Nevertheless, the effect of sonicating SP on its molecular structure or dispersing performance has not been fully investigated. This work assessed the effect of sonicating a commercial SP at 20 kHz, 750 W power, 50 or 80% amplitude, during 15 and 30 min. Initially, the sonication effect was evaluated in aqueous suspension by determining the SP size distribution (through dynamic light scattering – DLS) and zeta potential. Subsequently, the aqueous SP suspensions were used for Portland cement paste production. Rheological tests up to 120 minutes and compressive strength at 14 and 28 days were conducted. DLS and zeta potential results suggested that sonication reduce the size of SP chains. As a result, SP sonication increased the initial dynamic yield stress, viscosity, and hysteresis area of cement pastes. In contrast, SP sonication improved its time-dependent dispersing performance, resulting in pastes with reduced viscosity from 80 minutes onwards. Finally, SP sonication did not affect the compressive strength of cement pastes at 14 and 28 days of hydration. Overall, when SP is sonicated together with nanoparticles for application in cementitious matrices, the effect of sonicating the chemical admixture must be considered when the fresh-state properties of the composite are evaluated.

RESUMO A construção civil tende a exigir a otimização dos processos, com prazos de entrega reduzidos. Logo, tornase necessária a busca por alternativas que forneçam as propriedades necessárias ao concreto em períodos de tempo mais curtos. O objetivo deste trabalho é avaliar a influência de um aditivo acelerador de resistência baseado em nitrato de cálcio na resistência à compressão e em propriedades físicas de argamassas de cimento Portland, com diferentes teores de cinza volante (CV), visando analisar se a incorporação do aditivo compensaria a baixa contribuição desta adição nas resistências nas primeiras idades. Foram realizados ensaios de calorimetria isotérmica, absorção de água por capilaridade, índice de consistência e resistência à compressão em misturas com teores de aditivo de 0%, 0,33%, 0,66% e 1,00%. No que se refere ao tempo de pega final, nas amostras sem CV, o aditivo reduziu este período. Nas amostras com 40% e 60% de CV, verificou-se um aumento deste tempo. Para as resistências à compressão de 1 dia, o teor de aditivo que gerou os maiores valores foi de 1,00% para as argamassas com 0% e 40% CV, não existindo diferenças estatisticamente significativas para os sistemas com 60%. Já em idades superiores, o aditivo ocasionou reduções na resistência das amostras sem CV e aumentos proporcionais ao teor de aditivo nas amostras com 40% e 60% de CV. Constatou-se que as argamassas com aditivo e sem adição de CV apresentaram uma redução no índice de absorção por capilaridade. Já para as amostras com 40% e 60% de CV os menores índices de absorção foram obtidos nos traços sem aditivo. Portanto, é possível concluir que o aditivo avaliado nesta pesquisa acelerou as reações de hidratação, gerando um aumento nas resistências em idades iniciais, mas com um acréscimo insuficiente para compensar a queda de resistência pela incorporação de CV na composição das amostras. Levando em consideração as diferentes propriedades avaliadas, observou-se não ser possível estabelecer um teor ótimo de aditivo para cada teor de CV estabelecido. Sendo necessário avaliar qual propriedade é de maior interesse ao usuário.

ABSTRACT Civil construction tends to require the optimization of processes with reduced times. Therefore, it is necessary to search for alternatives that provide the required properties to the concrete, in shorter periods of time. The objective of this work is to evaluate the influence of a calcium nitrate based accelerator admixture on the properties of Portland cement mortars with different fly ash (FA) contents, in order to analyze the effect in the incorporation of the admixture, mainly if the accelerator is able to compensate the low strength contribution of the FA at early ages. Tests were carried out using isothermal calorimetry, water absorption by capillarity, consistency index and compressive strength in mixtures with admixture contents of 0%, 0,33%, 0,66% and 1,00%. Regarding setting time results, as excepted the admixture accelerated the final setting time. By the other hand, in the samples with 40% and 60% of FA, an increase of the final setting time was verified. For the 1-day compressive strengths, the admixture content that have generated the highest values was 1.00% for mortars with 0% and 40% FA. At higher ages, the admixtures led to reduce the compressive strength values of the samples without FA. On the other hand, in the samples with 40% and 60% of FA with the use of the accelerator higher compressive strength were identified. It was verified that the mortars with admixture and without addition of FA showed a reduction in the absorption index by capillarity. For the samples with 40% and 60% of FA, the lower absorption index was obtained in the samples without admixture. Therefore, it is possible to conclude that the admixture evaluated in this research accelerated the hydration reactions, generating an increase in the compressive strength at early ages, but with an insufficient increase to compensate the lower reactivity of the FA. Taking into account the different properties evaluated, it was not possible to establish an optimum admixture content for each FA content. It is necessary to evaluate which property is of greater interest to the user.

Spent fluid catalytic cracking (sFCC) catalyst is a residue that is produced in high volumes by the petrochemical industry and has shown a high potential to be used as a supplementary cementitious material (SCM). This article assesses the sFCC effectiveness as a SCM in mortar based on ordinary Portland cement (OPC), as well as its chemical resistance when the materials are immersed in sulfuric (H3SO4), acetic (CH3COOH) and hydrochloric acid (HCl). The performance of the sFCC was compared to other commercially available mineral additions, such as silica fume (SF) and metakaolin (MK). The results show a mechanical strength increase of up to 17% when the sFCC was included, compared to a control mortar without mineral additions. Immersion in H2SO4 during 90 days led to the formation of gypsum and a loss of chemical resistance up to ~25% in mortars with MK and sFCC. In the samples immersed in HCl, and particularly those made with sFCC and MK, Friedel's salt was identified due to the ingress of Cl-and the subsequent reaction with the monosulfoaluminates formed during cement hydration. Immersion in acetic acid led to a loss of strength of up to 57% and 37% in mortars with OPC and sFCC, respectively. Immersion in HCl leads to a stronger attack for blended systems, followed by CH3COOH and H3SO4. The mortar with 20% of sFCC exhibits the best performance, especially in the presence of sulfuric acid.

El catalizador de craqueo catalítico gastado (sFCC) es un residuo producido por la industria petroquímica y ha demostrado una elevada potencialidad como adición puzolánica en mezclas de cemento Portland (OPC). El presente artículo evalúa la eficacia del sFCC como adición mineral activa en morteros de cemento Portland, así como la resistencia al ataque químico cuando los materiales producidos son inmersos en ácido sulfúrico (H2SO4), acético (CH3COOH) o clorhídrico (HCl). Se llevó a cabo una comparación del desempeño del sFCC como adición frente a adiciones comercialmente disponibles, tales como humo de sílice (SF) y metacaolín (MK). Los resultados revelan un incremento en las resistencias mecánicas de hasta un 17% en morteros con sFCC en comparación a un mortero referencia sin adición (OPC). La inmersión en H2SO4 durante 90 días condujo a la formación de yeso y pérdida de resistencias mecánicas de hasta un ~25% en las mezclas con MK y sFCC. Para las muestras inmersas en HCl y especialmente las constituidas con sFCC y MK, se identificó Sal de Friedel, como consecuencia del ingreso de Cl" y posterior reacción con los monosulfoaluminatos formados durante la hidratación del cemento. La inmersión en ácido acético condujo a pérdidas de resistencia de hasta un 57% para OPC y 37% para morteros adicionados con sFCC. De esta manera, la inmersión en HCl promueve el mayor ataque para los sistemas adicionados y posterior deterioro, seguido del CH3COOH y H2SO4. Se destaca el mejor desempeño del mortero con 20% sFCC, en particular en presencia de ácido sulfúrico.

Ceramic materials more environment friendly and with similar or even better performance than traditional ones can be produced by alkali activation of natural minerals, wastes or industrial by-products. The present study assesses the effect of exposure at 600° and 1200°C of a MK-based geopolymers. Rice husk ash (RHA) and silica fume were modified chemically in order to obtain an alternative alkali activator. Exposure to elevated temperatures leads to dehydration of the reaction products and structural reorganization associated with the crystallization of the gel to leucite (KAlSi2O6) and kalsilite (KAlSiO4). The structural changes associated with the thermal treatment also promote a densification and reduction of porosity. The unreacted MK particles embedded into the geopolymeric gel lead to the formation of mullite (2Al2O3 · SiO2) after the thermal treatment at 1200°C.

Los geopolímeros se obtienen a partir de la activación alcalina de minerales naturales, desechos o subproductos industriales para generar un producto con características cerámicas que presentan ventajas a nivel ambiental y con propiedades similares y en algunos casos superiores frente a materiales tradicionales. El presente estudio evalúa el efecto de la exposición a 600° y 1200°C de sistemas geopoliméricos basados en metacaolín (MK) con la utilización de activadores basados en KOH. Se evaluó la utilización de una ceniza de cascarilla de arroz (RHA) y un humo de sílice comercial (SF) como fuentes alternativas de sílice para la preparación del activador alcalino. La exposición a las temperaturas elevadas conduce a la deshidratación de los productos formados durante la activación del MK y cambios estructurales asociados a la transformación del gel geopolimérico a estructuras cristalinas tipo leucita (KAlSi2O6) y kalsilita (KAlSiO4), lo cual promueve la densificación y reducción de la porosidad del material. La presencia de partículas de MK sin reaccionar en los materiales geopoliméricos condujo a la formación de mullita (2Al2O3 · SiO2), después del tratamiento a 1200°C.

Este artículo presenta la síntesis de materiales geopolimé-ricos a partir de una ceniza volante de origen colombiano (FA). Se evaluaron diferentes condiciones de activación de esta ceniza mediante el ajuste de los módulos totales de SiO2/Al2O3 y Na2O/SiO2, así como el efecto de la incorporación de dos fuentes de calcio: una escoria granulada de alto horno (GBFS) y un cemento Portland tipo I (OPC). La cinética de las reacciones desarrolladas después de la activación alcalina de la FA se evaluó realizando una calorimetría isotérmica, según la cual los sistemas de mayor alcalinidad exhiben una mayor liberación de calor y un mayor grado de disolución de la fuente primaria. La incorporación de la fuente de calcio modifica la cinética de reacción y el tipo y características de los productos formados tras la activación. El incremento en la relación molar SiO2/ Al2O3 del sistema condujo a obtener materiales con una resistencia a la compresión superior hasta en ∼77 %. En términos generales, la incorporación de una fuente de calcio al sistema contribuye a la adquisición de un mejor desempeño mecánico en todas las edades de curado en estudio. Los resultados evidencian el potencial aprovechamiento de esta FA para producir cementos no convencionales con resistencias a 28 días de curado superiores a los 50 MPa.

This article presents the synthesis of a geopolymeric material based on a Colombian fly ash (FA). Geopolymers with different total molar SiO2/Al2O3 and Na2O/SiO2 ratios and the inclusion of two source of calcium (a national granulated blast furnace slag and ordinary Portland cement) were evaluated. The reaction kinetic of FA alkali activation was monitored by isothermal calorimetry, which shows the systems with highest alkalinity exhibit higher release of heat and higher dissolution degree of FA. Replacing a percentage of FA by a calcium source (OPC or GBFS) modifies the kinetic and reaction products. A higher SiO2/ Al2O3 molar ratio leads to the production of materials with higher compressive strength up to ∼ 77 %. Overall, the addition of a calcium source contributes significantly to the acquisition of a higher mechanical performance. The results show the potential use of this FA with unprofitable physical and chemical characteristics as a raw material to produce non-conventional cementitious with compressive strength up to 50 MPa at 28 days of curing time.

El presente artículo muestra la modelación y optimización de la resistencia a la compresión de un conglomerante no convencional libre de cemento Portland, el cual fue producido a partir de la activación alcalina de una mezcla binaria de un metacaolín (MK) y una escoria siderúrgica de alto horno (GBFS). Como factores de estudio se consideró una relación GBFS/(GBFS/MK) entre 0,0-0,8 y una relación molar total SiO2⁄Al2O3 entre 2,8-4,2. La relación SiO2⁄Al2O3 fue ajustada a través de la contribución del precursor (MK+GBFS) y el activador alcalino. La evaluación estadística mediante la metodología de superficie de respuesta (MSR) mostró un efecto significativo entre la relación molar SiO2=Al2O3 y el contenido de GBFS sobre la resistencia a compresión. Complementariamente se desarrolló una caracterización microestructural a través de difracción de rayos X y microscopía electrónica de barrido. La incorporación de GBFS incrementó la cinética de reacción y la formación de una estructura más densa y compacta. Estos nuevos productos de reacción le otorgaron al material un mayor desempeño mecánico comparado con los constituidos con un 100% de MK.

The present article shows the compressive strength modeling and optimization for a non-conventional binder free of clinker, which was produced by the alkali activation of a binary mixture of metakaolin (MK) and a granulated blast furnace slag (GBFS). A GBFS/(GBFS+MK) ratio between 0,0 and 0,8; and the overall SiO2⁄Al2O3 molar ratio from 2,8 to 4,2 were considered as the main factor of this study. Sodium hydroxide and sodium silicate were used as alkali activator. The overall SiO2⁄Al2O3 molar ratio corresponds to the silica and alumina contribution from the precursor (MK+GBFS), as well as the alkali activator used. The statistical assessment through response surface methodology (MSR) showed a considerable effect between the SiO2⁄Al2O3 molar ratio, GBFS content and the compressive strength. Complementary, a microstructural characterization of the materials produced through X-ray diffraction (XRD) and scanning electron microscopy (SEM) was performed. The GBFS inclusion leads to an increasing of reaction kinetic and the formation of a more compact structure. These new reaction products gives to the material a higher mechanical performance than those based on a 100% of MK. The study shows the performance prediction in materials with 7 days of curing through the adjustment of some design criteria in order to obtain a binder with a particular mechanical performance.

En este documento se presenta una revisión de las propiedades microestructurales y macroestructurales de cementantes de activación alcalina basados en escorias granuladas de alto horno, metacaolín y sus mezclas, desarrollados por el Grupo Materiales Compuestos de la Universidad del Valle durante la última década. Resultados de durabilidad de cementos activados cuando son expuestos para agentes agresivos tales como cloruros y dióxido de carbono son reportados. Los resultados de esta investigación han elucidado la gran viabilidad de la adopción de la tecnología de activación alcalina en Colombia para la producción de concretos de alto desempeño basados en subproductos industriales, con un rango amplio de propiedades que puedan ser adecuadas para diferentes aplicaciones de infraestructura civil, y contribuye a la valorización de sub-productos industriales de bajo costo a través de la producción de materiales de construcción más amigables con el medio ambiente. Nuestros resultados resaltan el hecho que un entendimiento profundo de la química de estos sistemas permite la manipulación de la microestructura y por lo tanto el desempeño de los productos finales hacia la producción de materiales sostenibles y versátiles

This paper presents an overview examining the microstructural and macrostructural properties of alkali-activated binders based on granulated blast furnace slags, metakaolin and their blends, developed by the Composite Materials Group of Universidad del Valle over the past decade. Durability results of activated binders when exposed to aggressive agents such as chlorides, and carbon dioxide are reported. The results of this research have elucidated the great feasibility of adopting alkali-activation technology in Colombia for producing high strength concretes based on industrial by-products, with a wide range of properties that can be suitable for different civil infrastructure applications, and contribute to the valorization of low-cost industrial by products through production of more environmentally friendly building materials. Our research highlights the fact that a deep understanding of the chemistry of these systems allows the manipulation of the microstructure and therefore the performance of the final products, toward the production of sustainable and versatile materials

En este artículo se analiza el efecto de las relaciones molares SiO2/Al2O3 (3,0 - 4,0) y Na2O/SiO2(0,25 - 0,40) en la resistencia a compresión y contracción autógena de sistemas geopoliméricos basados en metacaolín (MK) activado con una solución de silicato de sodio e hidróxido de sodio. Para tal efecto, se produjeron 16 tipos de mezclas geopoliméricas evaluándose en cada una la resistencia a la compresión a edad de 7 días de curado y el porcentaje de contracción autógena. Complementariamente, los materiales producidos se caracterizaron utilizando diferentes técnicas, tales como, difracción de rayos X (DRX), espectroscopia de infrarrojo por transformada de Fourier (IR) y termogravimetría (TGA). Los resultados revelan que las propiedades de los sistemas geopoliméricos son afectadas por las proporciones de Silicio (Si), Aluminio (Al) y Sodio (Na) disponibles en la reacción de geopolimerización, las cuales a su vez determinan la microestructura del material. El mejor desempeño mecánico a edades tempranas y la mínima contracción fue obtenida con una relación SiO2/Al2O3 de 3,0 y Na2O/SiO2 de 0,25.

In this work, the effects of the molar ratios SiO2/Al2O3 (3.0 - 4.0) and Na2O/ SiO2 (0.25 - 0.40) on the compression strength and the autogenous shrinkage of geopolymers based on Metakaolin (MK) were investigated. 16 types of geopolymeric mixtures activated with a solution of sodium silicate and sodium hydroxide were evaluated. Compressive strength and autogenous deformations were recorded. The materials produced were characterized by using different techniques X-ray diffraction (XRD), Fourier transform infrared (FTIR) and thermogravimetry (TG / DTG). The results show that the properties of the geopolymers systems are affected by the proportions of Silicon (Si), aluminum (Al) and Sodium (Na) available on the mix, which in turn determines the microstructure of the material. The best mechanical performance at early age and the minimal contraction were obtained with a ratio of SiO2/Al2O3 3.0 and Na2O/SiO(2)0.25.

El propósito de este artículo es presentar los resultados obtenidos en el estudio de mezclas de concreto producidas con un 90% de cemento Pórtland ordinario (OPC) y un 10% de adiciones de metacaolín (MK) y humo de sílice (SF). Se estudiaron cuatro tipos de MK, dos de ellos producidos a través de un tratamiento térmico de caolines colombianos y los dos restantes fueron obtenidos en el mercado internacional (Europa y Estados Unidos). Las propiedades evaluadas fueron resistencia a compresión, absorción de agua, volumen total de poros permeables, absorción capilar, resistencia a la carbonatación y resistencia a la penetración de iones cloruro. El estudio de carbonatación se realizó en especimenes de concreto a diferentes edades de curado en una cámara climática bajo condiciones controladas (30ºC, 70% H.R. y 2,25% CO2). Los concretos adicionados, a 28 días de curado, presentaron una mayor susceptibilidad frente a la carbonatación en comparación con los concretos de referencia (OPc sin adición), sin embargo, a mayor edad de curado la resistencia a carbonatación de las muestras de concreto con y sin adición incrementó. La permeabilidad a cloruros fue evaluada mediante la aplicación de la norma ASTM C1202. En general, los concretos con adición presentan la menor absorción capilar y la más alta resistencia a la penetración del ión cloruro en comparación a las mezclas de OPC sin adición.

The purpose of this paper is to present the results obtained in an experimental study that analyzed the performance of different concrete mixes. These mixes were produced with 90% of ordinary Portland cement (OPC) and the other 10% with the additions of metakaolin (MK) and silica fume (SF). Four types of MK were tested; two of these were produced by a thermal treatment on Colombian kaolin. The others two were imported from the international commercial market. The factors evaluated in all the concrete mixes were the following: compressive strength, water absorption and total volume of permeable porosity, capillary absorption, carbonation depth and chloride penetration. The concrete samples were submitted into an accelerated carbonation process inside a climatic chamber (30º C, 70% H.R. and 2.25% CO2). At 28 days of curing the carbonation depths for the blended concrete mixtures were greater than the one obtained in the OPC concrete without addition. With a prolonged curing age in all samples, with or without mineral additions, tend to slow the carbonation rate in the concrete. The resistance of the concrete to the chloride penetration was evaluated according to ASTM standard C1202. This study proved that blended concrete specimens have a lower capillary absorption and a higher chloride penetration resistance once these were compared with OPC concrete specimens without addition.