Influence of Calcined Clay on Workability of Mortars with Low-carbon Cement

The second-largest industrial global emitter of CO2 (Carbon dioxide) is the cement sector. The technology roadmap of low carbon transition for cement industries includes the introduction of calcined clay (CC) as supplementary cementitious material. A new type of alternative binder, called Limestone Calcined Clay Cement (LC3), was recently proposed. This cement can reduce CO2 emissions of cement production by up to 40% and it is prepared using limestone (LS) and clay which are globally available. Many scientific studies aimed to investigate the hydration of LC3 to understand the contribution of CC to the development of the compressive strength. However, recent studies showed that other cement properties, like workability and water demand, are highly impacted by calcined clay. Despite some papers state that an increase in superplasticizer (SP) dosage compensate this effect, such concrete is usually sticky, and hard to handle and deal with. In this sense, a proper understanding of the mechanisms regulating rheology of LC3 is needed. The objective of this study is to analyze workability of CC-based cement pastes and mortar, specifically investigating the role of free water in particle suspensions. Preliminary results show that CC highly influences workability of mortars and pastes. The flow table test results highlight a need to increase SP dosage to achieve target workability with CC cements. Differential scanning calorimetry (DSC) and 1 H time domain-nuclear magnetic resonance (TD-NMR) results clarify that the capillary unbound water is rapidly consumed by CC, being thus unavailable to fluidify cement pastes. This multi-method approach provides a further step in understanding CC impact on workability of mortars with low-carbon cement and opens new ways to understand paste, mortar, and concrete workability

Freeze-Thaw Resistance of Concrete: Insight from Microstructural Properties

Composite cements offer low carbon alternatives to conventional CEM I. These binders also generally tend to perform better than CEM I in aggressive chemical environments. However, their freeze-thaw resistance, evident through surface scaling and internal damage is usually impaired. Postulated theories on freeze-thaw induced damage do not fully explain the origin of this weakness in composite cement concretes. This paper systematically presents the phase assemblage changes associated with the freeze-thaw of concrete specimen made from composite cements with and without limestone. The freeze-thaw test was performed on concrete according to CIF method based on CEN/TR 15177 and the corresponding cement pastes characterized by X-ray powder diffraction (XRD) and thermogravimetric analysis (TGA). In all investigated composite cements, portlandite was already depleted after the 7d capillary suction. The implications of this and other modified assemblages during the conditioning and the freeze-thaw test are consequently discussed

Relationship between cement composition and the freeze-thaw resistance of concretes

Concrete exposed to cyclic freezing and thawing may deteriorate by surface scaling, internally developed cracks or both in combination. The rate of deterioration tends to be accelerated in concretes containing higher levels of supplementary cementitious materials including slag and limestone. A fundamental insight into the relationship between cement composition and freeze–thaw resistance is therefore imperative for developing durable composite cement concretes. Concrete samples prepared from CEM I, binary slag cements and ternary limestone slag cement blends at 0·5 w/b ratio without air entrainment were investigated. The freeze–thaw test was based on the CIF method according to PD CEN/TR 15177. Additionally, phase assemblages in the concretes before and after freeze–thaw damage were evaluated. Before freeze–thaw testing, compressive strengths were similar but the composite cements were slightly more susceptible to carbonation. However, the scaling and internal damage resistance decreased in the order of CEM I, binary and limestone ternary blended cements. The composition of the scaled material differed from the bulk, revealing an absence of portlandite and a marked reduction in AFm and ettringite contents. A probable explanation for the reduced freeze–thaw resistance includes the porosity differences and the lower portlandite content compared to CEM I concrete

Effect of sulfate additions on hydration and performance of ternary slag-limestone composite cements

The global cement industry is striving to reduce its carbon footprint. Common approaches have included reduced clinker factors by blending cement clinker with supplementary cementitious materials (SCM). However supplies of SCMs are not sufficient to achieve replacement above about 30 %. Limestone ternary cements offer the opportunity to reduce the clinker factor of cements while maximizing the efficiency of SCMs. In these cements, calcite from limestone reacts with dissolved aluminates to form carboaluminate and in the process influence hydration of other constituents. However, sulfates which are conventionally added to regulate the early reactions in cement also compete for aluminates. Here we have used complementary techniques to investigate the effects of calcium sulfate additions on hydration, microstructure and performance of composite Portland clinker-slag-limestone cements. The results show that the presence of sulfate influenced the early-age reaction kinetics of the clinker phases and supplementary cementitious materials. However, even after sulfate depletion, the course of hydration and microstructures formed were significantly influenced. Increasing the sulfate level resulted in a gradual increase of the fraction of ettringite over AFm phases, coarser porosity and lower water content of the C-S-H. These microstructural changes impact the total porosity and hence cement strength in opposing ways, namely porosity is reduced with increasing ettringite fraction while the space filling capacity of the C-S-H is also reduced due to the lower water content of the C-S-H. These findings have important implications for optimizing the mechanical properties and durability of ternary blends

Generalized Structural Description of Calcium–Sodium Aluminosilicate Hydrate Gels: The Cross-Linked Substituted Tobermorite Model

Structural models for the primary strength and durability-giving reaction product in modern cements, a calcium (alumino)silicate hydrate gel, have previously been based solely on non-cross-linked tobermorite structures. However, recent experimental studies of laboratory-synthesized and alkali-activated slag (AAS) binders have indicated that the calcium–sodium aluminosilicate hydrate [C-(N)-A-S-H] gel formed in these systems can be significantly cross-linked. Here, we propose a model that describes the C-(N)-A-S-H gel as a mixture of cross-linked and non-cross-linked tobermorite-based structures (the cross-linked substituted tobermorite model, CSTM), which can more appropriately describe the spectroscopic and density information available for this material. Analysis of the phase assemblage and Al coordination environments of AAS binders shows that it is not possible to fully account for the chemistry of AAS by use of the assumption that all of the tetrahedral Al is present in a tobermorite-type C-(N)-A-S-H gel, due to the structural constraints of the gel. Application of the CSTM can for the first time reconcile this information, indicating the presence of an additional activation product that contains highly connected four-coordinated silicate and aluminate species. The CSTM therefore provides a more advanced description of the chemistry and structure of calcium–sodium aluminosilicate gel structures than that previously established in the literature

Hydration and mixture design of calcined clay blended cements: review by the RILEM TC 282-CCL

The RILEM technical committee 282-CCL: Calcined Clays as Supplementary Cementitious Materials, investigates all the aspects related to calcined clays, from clay exploration and characterization to calcination process, hydration reactions and concrete properties. This white paper focuses on the hydration mechanisms of calcined clay-blended Portland cements, covering both 1:1 and 2:1 calcined clays. The pozzolanic reaction of calcined clay is detailed, and the main reaction products are described. The differences observed depending on the clay type are also discussed, as well as the potential influence of the secondary phases present in calcined clay. The factors controlling and limiting the reaction of calcined clay are investigated, evidencing the role of porosity saturation and refinement of the microstructure. The complete characterisation of the hydration of calcined clay cements is made possible by the determination of the reaction degree of calcined clay. Several methods are compared to estimate the extent of calcined clay reaction. The influence of clinker and limestone mineralogy are also discussed. Finally, guidelines for optimising the mixture design of calcined clay blended cements are provided, with special attention to sulphate adjustment and clinker factor

Clay calcination technology: state-of-the-art review by the RILEM TC 282-CCL

The use of calcined clays as supplementary cementitious materials provides the opportunity to significantly reduce the cement industry’s carbon burden; however, use at a global scale requires a deep understanding of the extraction and processing of the clays to be used, which will uncover routes to optimise their reactivity. This will enable increased usage of calcined clays as cement replacements, further improving the sustainability of concretes produced with them. Existing technologies can be adopted to produce calcined clays at an industrial scale in many regions around the world. This paper, produced by RILEM TC 282-CCL on calcined clays as supplementary cementitious materials (working group 2), focuses on the production of calcined clays, presents an overview of clay mining, and assesses the current state of the art in clay calcination technology, covering the most relevant aspects from the clay deposit to the factory gate. The energetics and associated carbon footprint of the calcination process are also discussed, and an outlook on clay calcination is presented, discussing the technological advancements required to fulfil future global demand for this material in sustainable infrastructure development

Reactivity tests for supplementary cementitious materials: RILEM TC 267-TRM phase 1

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 R3 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 R3 model systems. Acceleration and improvement of the reproducibility of the IS 1727 test will be attempted as well

Report of RILEM TC 267-TRM phase 3: validation of the R3 reactivity test across a wide range of materials

RILEM TC 267 TRM– “Tests for Reactivity of Supplementary Cementitious Materials” recommends the Rapid Reliable Relevant (R3) test as a method for determining the chemical reactivity of supplementary cementitious materials (SCMs) in Portland cement blends. In this paper, the R3 test was applied to 52 materials from a wide range of conventional and alternative SCMs with the aim to validate such test. An excellent correlation was found between the cumulative heat release and the bound water determined following the R3 test method. Comparison of the R3 test results to mortar compressive strength development showed that all conventional SCMs (e.g. blast furnace slag and fly ashes) followed the same trend, with the notable exception of very reactive calcined kaolinitic clays. It is discussed, through an in-depth statistical regression analysis of the R3 reactivity test results and the 28 days relative compressive strengths, how reactivity threshold values for classification of the chemical reactivity of SCMs could be proposed based on the R3 test results