Calcined kaolinitic clays are known to be very reactive pozzolans, and combined with limestone can enable significant clinker substitution in cementitious systems. Thermal activation of kaolinitic clays takes place when the hydroxyl groups are removed, leading to formation of an amorphous reactive structure. There are several technologies for clay activation, but the most used at industrial scale are flash and stationary calcination. The objective of this paper is to investigate the impact of the calcination regime on the properties of the calcined product. It presents the results of an experimental program carried out with a kaolinitic clay calcined at a flash calciner and at a laboratory furnace. Calcination brings about a drop in specific surface, and an increase of average diameter due to agglomeration, an effect more pronounced in stationary calcination. No major differences were found at the heat of hydration, CH consumption and phase assemblage for the fully dehydroxylated material. The flash calcined material had slightly better results mainly due to a finer PSD compared with the one stationary calcined. No major difference was found in water demand and compressive strength for both regimes. As expected, the main impact of the calcination regime is the agglomeration.

RILEM TC 267-TRM is studying tests for the reactivity supplementary cementitious materials (SCMs). In the first phase, the lime reactivity (LR) test, which is standardised in Indian standard (IS)-1727, gave promising correlations with 90-days cement mortar strength. In Phase 2, working group 1 has looked at further optimisation and robustness study of the LR test. A parameter screening approach for improving the mix design to use fixed mass proportions targeting enhanced reproducibility and robustness was focused. The parameters studied include mixture properties such as the effects of lime (hydrated lime/calcium hydroxide-CH) to SCM ratio, water to binder (binder = CH + SCM) ratio (w/b), activators, curing temperature, and testing age as well as the impact of factors from different national standards (IS and European Committee for Standardisation-EN) such as mould size, shape & type of sand. The modified mixture recommended by the TC uses a fixed CH to SCM mass ratio of 1:1 and the addition of activators. Also, a higher curing temperature of 50 °C in comparison to the 27 °C specified in IS 1727, for the first 2 days is proposed to accelerate the early hydration especially for slowly reacting SCMs. It is also recommended that, the minimum purity and fineness of the CH need to be specified to obtain reproducible results.

A primary aim of RILEM TC 267-TRM: “Tests for Reactivity of Supplementary Cementitious Materials (SCMs)” is to compare and evaluate the performance of conventional and novel SCM reactivity test methods across a wide range of SCMs. To this purpose, a round robin campaign was organized to investigate 10 different tests for reactivity and 11 SCMs covering the main classes of materials in use, such as granulated blast furnace slag, fly ash, natural pozzolan and calcined clays. The methods were evaluated based on the correlation to the 28 days relative compressive strength of standard mortar bars containing 30% of SCM as cement replacement and the interlaboratory reproducibility of the test results. It was found that only a few test methods showed acceptable correlation to the 28 days relative strength over the whole range of SCMs. The methods that showed the best reproducibility and gave good correlations used the R 3 model system of the SCM and Ca(OH) 2 , supplemented with alkali sulfate/carbonate. The use of this simplified model system isolates the reaction of the SCM and the reactivity can be easily quantified from the heat release or bound water content. Later age (90 days) strength results also correlated well with the results of the IS 1727 (Indian standard) reactivity test, an accelerated strength test using an SCM/Ca(OH) 2 -based model system. The current standardized tests did not show acceptable correlations across all SCMs, although they performed better when latently hydraulic materials (blast furnace slag) were excluded. However, the Frattini test, Chapelle and modified Chapelle test showed poor interlaboratory reproducibility, demonstrating experimental difficulties. The TC 267-TRM will pursue the development of test protocols based on the R 3 model systems. Acceleration and improvement of the reproducibility of the IS 1727 test will be attempted as well.

The goal of this study was to understand the behavior of clays from Iza, Boyaca, Colombia and their potential to be used in blended cement after calcination as pozzolan. The materials were characterized before and after thermal treatment by XRF, XRD, TGA and SEM. The performance in mortar was evaluated by compressive strength of mortar.

This paper presents the results of an industrial trial for the production of calcined clay to be used as pozzolan in cement manufacture. For the trial, a wet-process clinker rotary kiln was modified to process on dry basis the low grade kaolinitic clay used as raw material. The kaolinitic clay deposit was chosen through a screening based on geologic, chemical and mineralogical criteria, and a confirmation of reactivity with an experimental protocol at lab scale. During the calcination trial technological parameters such as rotation speed, fuel pressure and outer temperature of calcined clay were measured and coupled with the reactivity of the samples tested, thus, preliminary estimations of operational parameters can be made. The trial proved that it is possible to produce a reactive pozzolan at industrial scale by implementing small conversions on existing equipment of a typical clinker plant.

With cement production forecast to double by 2050, it is bound to increase pressure on the already fragile environment and the natural resource base. Critical analysis shows that the most viable option to improve the sustainability of cementitious materials are blends of Portland cement clinker with, so called, supplementary cementitious materials, SCMs. Based on previous experience we have shown that cements with good strengths at early ages may be obtained by substituting clinker with a combination of calcined clay and limestone. Such blends offer a very promising solution for cements with a lower environmental footprint, particularly in terms of associated CO2 emissions. In this paper, some initial results on chemistry, strength development and durability are presented. The calcination of clays was known to give pozzolanic reactive material. The most reactive clay mineral is kaolinite, obtained after calcination between 600 and 800 degrees C. Therefore, the blending with calcined clays containing kaolinite provides an extra source of alumina to react with limestone. It was found that even low grade clay containing only around 40% kaolin gave good results when used in combination with limestone. The low carbon cement developed is expected to reduce CO2 emissions by 20-50%. Experimentation is ongoing to explore the potential of using low quality clay, which are available in large quantities in various places in many countries. These studies are expected to produce localized cement without the need to transport materials over long distances. It is envisaged that low carbon cement will be a much sought after commodity contributing to a sustainable development.

Ternary cements made of clinker, limestone and metakaolin present a high potential to be used as general-use cement with decreased associated CO2 emissions and embodied energy. In this article a systematic investigation of the synergies in the ternary system containing up to 50 % limestone, metakaolin or slag was done following a DoE approach. Flow results and compressive strengths at 2, 7 and 28 days are reported as well as phase assemblage as obtained by Rietveld refinement. The results in the ternary system are compared with results that have been obtained with slag and limestone and the respective contributions of carboaluminates hydrates and C-A-S-H gel are assessed. The contribution of the reactive aluminates from the SCMs is decisive for 7 day strength, while strength at 28 days seems to be more dependent on the reactive silicate fraction. At early age (2 days), compressive strength depends more on the fineness of the mineral addition.

The results of an industrial trial for the production and applications of a low-clinker blended cement—also called low carbon cement (LCC)—based on the system clinker-calcined clay-limestone are presented. A low-purity kaolinitic clay was calcined in a rotatory kiln and used in the manufacture of the ternary blended cement. The produced cement contains 50 % of clinker, 41 % of the combined addition calcined clay-limestone in a 2:1 proportion and gypsum. The ternary blend accomplish with the requirements of Cuban standards for blended cements although it exceed the allowed additions limit in 10 %. Concrete prefabricated elements made with the LCC under industrial conditions exhibit nice mechanical and permeability properties. It is estimated that the massive production of this type of cements may contribute to the reduction of CO2 emission in more than 25 % related to daily practice.

This paper looks at the effect of fineness of the different components in a blend containing 55% Portland cement, 30% calcined clay and 15% limestone. The calcined clay originates from a natural deposit in Cuba and contains less than 50% kaolinite. The particle size distribution (PSD) of each of the three components was varied by using different grinding times, and the consequences on heat release, strength development, pore structure and phase assemblage development were investigated up to 28 d. Higher fineness of both clinker and calcined clay can considerably improve compressive strength at all ages, while limestone fineness only plays a role at early age. The formation of carboaluminate hydrates owing to the combined addition of calcined clays and limestone is confirmed for this case of a mixed clay with moderate kaolinite content.

Keywords: ternary blends ; carboaluminates synergy ; calcined clays ; limestone ; durability ; STADIUM ; chloride penetration ; carbonation These Ecole polytechnique federale de Lausanne EPFL, n° 6001 (2013)Programme doctoral Sciences et Genie des materiauxFaculte des sciences et techniques de l'ingenieurInstitut des materiauxLaboratoire des materiaux de constructionJury: A. Fontcuberta i Morral (presidente), P. Bowen, D. Herfort, M. Thomas Public defense: 2013-12-3 Reference doi:10.5075/epfl-thesis-6001Print copy in library catalog Record created on 2013-11-27, modified on 2017-05-10

This study investigates the coupled substitution of metakaolin and limestone in Portland cement (PC). The mechanical properties were studied in mortars and the microstructural development in pastes by X-ray diffraction, thermogravimetry analysis, mercury intrusion porosimetry and isothermal calorimetry. We show that 45% of substitution by 30% of metakaolin and 15% of limestone gives better mechanical properties at 7 and 28days than the 100% PC reference. Our results show that calcium carbonate reacts with alumina from the metakaolin, forming supplementary AFm phases and stabilizing ettringite. Using simple mass balance calculations derived from thermogravimetry results, we also present the thermodynamic simulation for the system, which agrees fairly well with the experimental observations.It is shown that gypsum addition should be carefully balanced when using calcined clays because it considerably influences the early age strength by controlling the very rapid reaction of aluminates.

Actualmente son bien conocidas las ventajas económicas y medioambientales de la sustitución del clínker de cemento por otros materiales cementicios suplementarios. Las arcillas calcinadas en forma de metacaolín han recibido por ejemplo especial atención en años recientes. Se conoce que estas adiciones, cuando se añaden a morteros y hormigones, mejoran tanto su resistencia mecánica como su durabilidad. El objetivo de este trabajo es evaluar el comportamiento de las propiedades físico-mecánicas y la durabilidad en microhormigones, empleando arcillas calcinadas y molidas como material sustituyente del 30% en peso del cemento Pórtland ordinario (CPO). Para ello se utilizó una tierra arcillosa, compuesta principalmente por mineral caolín de bajo grado de pureza, para la obtención de arcillas calcinadas como minerales cementicios suplementarios. Los mejores resultados se resistencia a la compresión a los 28 días se obtuvieron para la arcilla sedimentada y calcinada, la cual posee mayor contenido de mineral caolín debido a un proceso de purificación por sedimentación de la materia prima acometido sólo para esta adición. Sin embargo, los ensayos de absorción de agua por capilaridad arrojaron los mejores resultados para el suelo arcilloso calcinado, el cual posee una elevada finura en comparación al resto de los materiales estudiados. Los menores valores mostrados por esta adición, tanto de porosidad capilar como de sorptividad, indican que existió un predominio del fenómeno de la compacidad e impermeabilidad, lograda en la matriz cementicia al usar un material tan fino, por encima del efecto de la reacción puzolánica. Estudios en la microestructura del gel de C-S-H, usando energía dispersiva por rayos-X (EDX), demostraron como el empleo de arcillas calcinadas en sustitución del CPO favorece la formación de productos de hidratación más estables, principalmente monosulfos del tipo hemicarbo y monocarbo, lo cual es conveniente para el hormigón ante la posible acción de diferentes mecanismos de degradación.

Actualmente son bien conocidas las ventajas económicas y medioambientales de la sustitución del clínker de cemento por otros materiales cementicios suplementarios. Las arcillas calcinadas en forma de metacaolín han recibido por ejemplo especial atención en años recientes. Se conoce que estas adiciones, cuando se añaden a morteros y hormigones, mejoran tanto su resistencia mecánica como su durabilidad. El objetivo de este trabajo es evaluar el comportamiento de las propiedades físico-mecánicas y la durabilidad en microhormigones, empleando arcillas calcinadas y molidas como material sustituyente del 30% en peso del cemento Pórtland ordinario (CPO). Para ello se utilizó una tierra arcillosa, compuesta principalmente por mineral caolín de bajo grado de pureza, para la obtención de arcillas calcinadas como minerales cementicios suplementarios. Los mejores resultados se resistencia a la compresión a los 28 días se obtuvieron para la arcilla sedimentada y calcinada, la cual posee mayor contenido de mineral caolín debido a un proceso de purificación por sedimentación de la materia prima acometido sólo para esta adición. Sin embargo, los ensayos de absorción de agua por capilaridad arrojaron los mejores resultados para el suelo arcilloso calcinado, el cual posee una elevada finura en comparación al resto de los materiales estudiados. Los menores valores mostrados por esta adición, tanto de porosidad capilar como de sorptividad, indican que existió un predominio del fenómeno de la compacidad e impermeabilidad, lograda en la matriz cementicia al usar un material tan fino, por encima del efecto de la reacción puzolánica. Estudios en la microestructura del gel de C-S-H, usando energía dispersiva por rayos-X (EDX), demostraron como el empleo de arcillas calcinadas en sustitución del CPO favorece la formación de productos de hidratación más estables, principalmente monosulfos del tipo hemicarbo y monocarbo, lo cual es conveniente para el hormigón ante la posible acción de diferentes mecanismos de degradación.Currently economical and environmental advantages of cement clinker replacement by other supplementary cementious materials are well known. For example calcined clays, such as metakaolin, have drawn special attention during recent years. It is well known that these admixtures added to mortars and concretes improve mechanical strength as well as durability. The purpose of this study is to evaluate the behavior of physical-mechanical properties and durability in micro-concretes, by employing calcinated and grinded clays as replacement material, by 30% of ordinary Portland cement (OPC). Therefore, clay soil was employed, which is mainly composed by low-purity-kaolin mineral, so as to obtain calcined clays to be used as supplementary cementious minerals. Best results for compressive strength at 28 days were obtained by sedimentary calcined clays, which have higher content of kaolin mineral thanks to a purification process by means of raw material sedimentation conducted on this admixture only. Nevertheless, capillary water absorption tests delivered best results for calcined clay soil, which finesse is quite high. Lower values showed by this admixture, as much for capillary porosity and sorptivity, revealed there was a predominance of compaction and impermeability phenomena achieved by cementious matrix using such fine material, over the effect of puzzolanic reaction. Micro-structure studies on C-S-H gel, employing energy dispersive x-ray (EDX) technique, demonstrated that the use of calcined clays as replacement of RPC favors the creation of quite stable hydration products, mainly monosulfos of hemicabo and monocarbo types, which is convenient for concrete against possible deterioration actions from different mechanisms.

Currently economical and environmental advantages of cement clinker replacement by other supplementary cementious materials are well known. For example calcined clays, such as metakaolin, have drawn special attention during recent years. It is well known that these admixtures added to mortars and concretes improve mechanical strength as well as durability. The purpose of this study is to evaluate the behavior of physical-mechanical properties and durability in micro-concretes, by employing calcinated and grinded clays as replacement material, by 30% of ordinary Portland cement (OPC). Therefore, clay soil was employed, which is mainly composed by low-purity-kaolin mineral, so as to obtain calcined clays to be used as supplementary cementious minerals. Best results for compressive strength at 28 days were obtained by sedimentary calcined clays, which have higher content of kaolin mineral thanks to a purification process by means of raw material sedimentation conducted on this admixture only. Nevertheless, capillary water absorption tests delivered best results for calcined clay soil, which finesse is quite high. Lower values showed by this admixture, as much for capillary porosity and sorptivity, revealed there was a predominance of compaction and impermeability phenomena achieved by cementious matrix using such fine material, over the effect of puzzolanic reaction. Micro-structure studies on C-S-H gel, employing energy dispersive x-ray (EDX) technique, demonstrated that the use of calcined clays as replacement of RPC favors the creation of quite stable hydration products, mainly monosulfos of hemicabo and monocarbo types, which is convenient for concrete against possible deterioration actions from different mechanisms.

Se presenta una propuesta de producción de puzolanas artificiales a partir de activar arcillas de baja pureza, como alternativa de producción de Metacaolín. Se trabajó básicamente con tierra rica en minerales arcillosos, principalmente caolín. Este material fue sedimentado y luego calcinado a 900 grados Celsius. Igual proceso se realizó al material original sin sedimentar. Producto de la calcinación disminuyó considerablemente la superficie específica, y por ende la actividad puzolánica, que fue evaluada monitoreando el consumo de HC en pastas a varias edades, y la resistencia a compresión en morteros. El material calcinado, aparentemente inerte, fue molido hasta una alta finura. Se introdujo una serie experimental con ceniza de paja de caña, como referencia de puzolana anteriormente estudiada. Las arcillas calcinadas molidas incrementaron cuantiosamente su actividad puzolánica, caracterizado por un mayor consumo de HC en pastas, y una mayor resistencia a compresión en morteros. Aparentemente este cambio se debe al efecto del molido sobre la reactividad de los suelos arcillosos calcinados. Los mejores resultados se obtuvieron para las muestras sedimentadas antes de calcinar. La resistencia a compresión de morteros, sustituyendo un 30% del peso de cemento por dicho material, es similar al control (100% cemento) a 7 días, y mayor a 28 y 60 días. Aunque dicha sustitución no disminuye la porosidad total, se disminuye la sorptividad, principalmente en muestras producidas con material sedimentado calcinado y molido. Posiblemente este fenómeno ocurra por un proceso de refinación de poros capilares inducido por la precipitación de productos de la reacción puzolánica.This paper introduces a proposal to produce artificial pozzolans by means of activation of low grade clays, as an alternative to metakaolin production. Basically the work considered clay mineral enriched soils, mainly kaolin. Such material was sediment and later calcined at 900 Celsius degrees. The same process was conducted with non-sediment material. Due to calcinations, the specific surface decreased significantly, and therefore, its pozzolanic activity, which was assessed by monitoring the CH consumption in cement pastes of several ages, as well as compressive strength in cement mortars. Calcined material, apparently inert, was ground until achieving high finesse. An experimental series made of sugar cane straw ash was introduced, as a reference to the pozzolans previously studied. Ground calcined clays increased its pozzolanic activity at a huge extent, which is characterized by a higher consumption of CH in cement pastes and by a higher compressive strength in cement mortars. Apparently this change takes place due to grinding effect on the reactivity of calcined clayey soils. The best results were obtained from sediment samples before their calcinations. The compressive strength of cement mortars, replacing a 30% the cement weight by such material, is similar to the control (100% cement) at 7 days, and higher at 28 and 60 days. Although such replacement does not decrease total porosity, it does decrease sorptivity, mainly in samples produced with calcined and ground sedimented material. Probably this phenomenon occurs because of pores capillary refining process induced by the precipitation of products of pozzolanic reaction.

This paper introduces a proposal to produce artificial pozzolans by means of activation of low grade clays, as an alternative to metakaolin production. Basically the work considered clay mineral enriched soils, mainly kaolin. Such material was sediment and later calcined at 900 Celsius degrees. The same process was conducted with non-sediment material. Due to calcinations, the specific surface decreased significantly, and therefore, its pozzolanic activity, which was assessed by monitoring the CH consumption in cement pastes of several ages, as well as compressive strength in cement mortars. Calcined material, apparently inert, was ground until achieving high finesse. An experimental series made of sugar cane straw ash was introduced, as a reference to the pozzolans previously studied. Ground calcined clays increased its pozzolanic activity at a huge extent, which is characterized by a higher consumption of CH in cement pastes and by a higher compressive strength in cement mortars. Apparently this change takes place due to grinding effect on the reactivity of calcined clayey soils. The best results were obtained from sediment samples before their calcinations. The compressive strength of cement mortars, replacing a 30% the cement weight by such material, is similar to the control (100% cement) at 7 days, and higher at 28 and 60 days. Although such replacement does not decrease total porosity, it does decrease sorptivity, mainly in samples produced with calcined and ground sedimented material. Probably this phenomenon occurs because of pores capillary refining process induced by the precipitation of products of pozzolanic reaction.

Se presenta una propuesta de producción de puzolanas artificiales a partir de activar arcillas de baja pureza, como alternativa de producción de Metacaolín. Se trabajó básicamente con tierra rica en minerales arcillosos, principalmente caolín. Este material fue sedimentado y luego calcinado a 900 grados Celsius. Igual proceso se realizó al material original sin sedimentar. Producto de la calcinación disminuyó considerablemente la superficie específica, y por ende la actividad puzolánica, que fue evaluada monitoreando el consumo de HC en pastas a varias edades, y la resistencia a compresión en morteros. El material calcinado, aparentemente inerte, fue molido hasta una alta finura. Se introdujo una serie experimental con ceniza de paja de caña, como referencia de puzolana anteriormente estudiada. Las arcillas calcinadas molidas incrementaron cuantiosamente su actividad puzolánica, caracterizado por un mayor consumo de HC en pastas, y una mayor resistencia a compresión en morteros. Aparentemente este cambio se debe al efecto del molido sobre la reactividad de los suelos arcillosos calcinados. Los mejores resultados se obtuvieron para las muestras sedimentadas antes de calcinar. La resistencia a compresión de morteros, sustituyendo un 30% del peso de cemento por dicho material, es similar al control (100% cemento) a 7 días, y mayor a 28 y 60 días. Aunque dicha sustitución no disminuye la porosidad total, se disminuye la sorptividad, principalmente en muestras producidas con material sedimentado calcinado y molido. Posiblemente este fenómeno ocurra por un proceso de refinación de poros capilares inducido por la precipitación de productos de la reacción puzolánica.

Low Temperature Co-fired Ceramics (LTCCs) are layered ceramic based components, which – in recent years - are increasingly used as high precision electronic devices (e.g. mobile and automotive technologies) in highly loaded (temperatures, inertia forces, etc.) environments. They consist of a complex three-dimensional micro-network of metal structures embedded within a glass-ceramic substrate. Even though LTCCs have been used for more than 20 years, there is insufficient understanding of the mechanical loads during processing. In this regard, different types of failure of the end component during service have been reported, coming from different parts within the part. In this work, the influence of the internal architectures in the fracture response of LTCC components during bending has been investigated. Strength has been determined in 10 × 10 mm2 specimens using the ball-on-three-balls test (biaxial loading) and evaluated using Weibull statistics. Fractography of broken specimens has been performed to determine the mode of fracture of the components and the role of the internal architecture in the crack path. Results show strength dependence as a function of the testing position within the part. The influence of the internal architecture and residual stresses is also discussed.

The use of nanoparticles for the fabrication of new functional ceramics and composites often requires the preparation of concentrated fluid suspensions. However, suspensions containing nanoparticles are limited in solids content because of the excluded volume formed by the dispersant adlayer around the particles. We investigated the effect of the adlayer thickness on the rheological behavior of suspensions containing model alumina nanoparticles, using dispersant molecules with deliberately tailored chain length. The apparent viscosity and yield stress of the particle suspensions were markedly decreased by increasing the dispersant length, mainly due to a reduction of the attractive forces among particles. Fluid suspensions with solids content up to 35 vol% were prepared in toluene using a dispersant length of 2.5 nm. Our experimental results and viscosity predictions based on a hard sphere model indicate that fluid suspensions with up to 43 vol% of 65 nm alumina particles could be prepared using an optimum dispersant length of about 3.6 nm.