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Minerals
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Blended Cements Incorporating Calcined Clay and Limestone
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Blended Cements Incorporating Calcined Clay and Limestone

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Clays and Engineered Mineral Materials".

Deadline for manuscript submissions: closed (31 January 2023) | Viewed by 16457

Special Issue Editor

Dr. Franco Zunino

E-Mail Website
Guest Editor
Laboratory of Construction Materials, EPFL STI IMX LMC, École Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland
Interests: cement hydration mechanisms; cement chemistry; thermodynamic modeling; analytical techniques; calcined clays; microstructural analysis; durability

Special Issue Information

Dear Colleagues,

Portland cement (PC), the largest manufactured product on Earth on a mass basis, is accountable for about 7% of anthropogenic CO2 emissions worldwide. The most effective strategy to reduce the carbon footprint of the cement industry is to reduce the clinker factor. The adoption of blended cements has increased in recent decades to fulfill this need for clinker reduction. Blended cements incorporate supplementary cementitious materials (SCMs), replacing part of the PC fraction. Among commonly used SCMs are fine limestone, granulated blast furnace slag, and fly ash. However, slag and fly ash are not available in the quantities required for a widespread reduction of the clinker factor beyond 15%. Blended cements incorporating calcined clays or combinations of calcined clays and limestone have emerged as a promising solution to address the SCM availability issues and enable a widespread reduction of the clinker factor.

This Special Issue will cover studies on cements blended with calcined clays (and limestone), from extraction of raw materials to long-term assessment of mechanical properties, microstructure, and durability. In this manner, it will constitute a relevant collection of scientific and technological developments in this area that will become a reference for future advancements in this topic. Articles should be related to one or more of the thematic areas of the Special Issue:

  • Raw material extraction, processing, and characterization;
  • Blend design and optimization;
  • Rheology;
  • Mechanical properties;
  • Microstructural characterization and hydration;
  • Reactivity assessment methods;
  • Durability;
  • Modeling;
  • Equipment for industrial production.

Dr. Franco Zunino
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • calcined clays
  • limestone
  • carboaluminate
  • hydration
  • microstructure
  • strength
  • durability
  • sulfate balance
  • grinding
  • workability
  • admixtures
  • reactivity
  • calcination
  • kaolinite
  • illite
  • montmorillonite
  • dehydroxylation

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Published Papers (6 papers)

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Research

20 pages, 3374 KiB  
Article
A Model Linking Compressive Strength and Porosity in Ternary System: Metakaolin, Limestone, Cement
by Pascal Gonnon and Didier Lootens
Minerals 2023, 13(4), 454; https://doi.org/10.3390/min13040454 - 23 Mar 2023
Viewed by 1790
Abstract
The replacement of traditional cement with high clinker content should be achieved quickly to lower the carbon footprint of mortar and concrete. Cement is responsible for about 70% of the carbon footprint of cementitious materials. Current research suggests that the use of limestone [...] Read more.
The replacement of traditional cement with high clinker content should be achieved quickly to lower the carbon footprint of mortar and concrete. Cement is responsible for about 70% of the carbon footprint of cementitious materials. Current research suggests that the use of limestone and metakaolin or calcined clay could replace the current four gigatons of clinker produced. Here, binary systems composed of limestone/cement and metakaolin/cement are first studied to determine the individual impact of fine limestone and diverse fine metakaolins on the flow and compressive strength of the material. The flow properties are correlated with the surface areas of clinker and metakaolin and are almost independent of the limestone content. A model based on a linear relationship between compressive strength and porosity is used to estimate the reactivity of cement, limestone and metakaolin. An excellent correlation is obtained with the two binary systems and confirmed with the ternary systems using the same reactivity factors. The presented model allows the determination of the impact of each of the three components on compressive strength development. Limestone and metakaolin accelerate the hydration of clinker, leading to higher early strength, proportionally to their surface area. The reactivity of metakaolin is also found to be directly related to its mean size or surface area. Full article
(This article belongs to the Special Issue Blended Cements Incorporating Calcined Clay and Limestone)
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18 pages, 5693 KiB  
Article
Performance of Composite Portland Cements with Calcined Illite Clay and Limestone Filler Produced by Industrial Intergrinding
by Edgardo F. Irassar, Viviana L. Bonavetti, Gisela P. Cordoba, Viviana F. Rahhal, Claudia Cristina Castellano and Horacio A. Donza
Minerals 2023, 13(2), 240; https://doi.org/10.3390/min13020240 - 8 Feb 2023
Cited by 3 | Viewed by 2095
Abstract
The performance of five composite Portland cements (CPCs) with limestone filler (LF = 10%–25% by mass) and calcined illite clay (CIC = 10%–25% by mass) elaborated by intergrinding was analyzed in paste, mortar, and concrete. Hydration was studied by isothermal calorimetry, bound water, [...] Read more.
The performance of five composite Portland cements (CPCs) with limestone filler (LF = 10%–25% by mass) and calcined illite clay (CIC = 10%–25% by mass) elaborated by intergrinding was analyzed in paste, mortar, and concrete. Hydration was studied by isothermal calorimetry, bound water, and XRD. Flow and compressive strength (2 to 90 days) were determined in standard mortar. Concretes (w/b = 0.45; binder content = 350 kg/m3; slump = 15 ± 3 cm) were elaborated to determine compressive and flexural strength, water penetration, and chloride migration. Intergrinding CPCs have a large specific surface area when LF + CIC increases, with a similar size range of clinker particles. Supplementary cementing material replacements decreased the heat rate, prolonged the dormant period, and decreased the acceleration rate at early ages. According to the Fratini test, all CPCs had positive pozzolanicity after 28 days, but XRD analysis showed Ca(OH)2 associated with monocarboaluminate phases. Mortar flow was slightly reduced when the proportion of CIC was increased. Mortar strength decreased when the sum of LF + CIC increased. CPC strength class was limited by compressive strength after 28 days. Concretes were workable, and the compressive strength after 28 days depended on the LF + CIC, and CIC contributed after 90 days. After 28 days, the water penetration depended mainly on the LF + CIC content. The chloride migration coefficient was also reduced when CPC contained more CIC and less LF. Full article
(This article belongs to the Special Issue Blended Cements Incorporating Calcined Clay and Limestone)
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15 pages, 4094 KiB  
Article
Evaluation of the Shrinkage Produced with the Use of Cements with Pozzolanic Additions in the Production of Concrete
by Maria Betania Diaz-Garcia, Yosvany Diaz-Cardenas, Juan Ribalta-Quesada and Fernando Martirena-Hernandez
Minerals 2022, 12(9), 1175; https://doi.org/10.3390/min12091175 - 19 Sep 2022
Cited by 1 | Viewed by 1751
Abstract
Early age cracking in concrete is caused by a combination of the chemical and autogenous shrinkage caused by the exhaustion of the water in the pores during the hydration of cement phases. Generally, this process takes place in the first 72 h of [...] Read more.
Early age cracking in concrete is caused by a combination of the chemical and autogenous shrinkage caused by the exhaustion of the water in the pores during the hydration of cement phases. Generally, this process takes place in the first 72 h of concrete casting. The use of supplementary cementitious materials (SCMs) can mitigate cracking due to several factors, among them: dilution effect, provision of extra nucleation sites due to the high specific surface of the SCMs, and the increased water retention associated with the presence of fine SCMs. This paper compares the impact of two SCMs systems on early age cracking of the following concretes: (i) pozzolanic cement with natural pozzolan (zeolite) and (ii) a ternary binder limestone-calcined clay cement (LC3). The study was Carried out on cement paste and concrete. The addition of calcined clay and limestone decreases early age cracking better than in any other system, including the Portland-pozzolan system. It is related to a lower clinker factor and improved hydration of the system, and a better-developed microstructure at early ages due to the energetic reaction of the alumina phase C3A, enhanced by the extra alumina (Al2O3) provided by the calcined clay. Full article
(This article belongs to the Special Issue Blended Cements Incorporating Calcined Clay and Limestone)
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16 pages, 4112 KiB  
Article
The Challenge of Grinding Ternary Blends Containing Calcined Clays and Limestone
by Juan Francisco Garces-Vargas, Yosvany Díaz-Cardenas, Franco Zunino, Juan Ribalta-Quesada, Karen Scrivener and Fernando Martirena
Minerals 2022, 12(9), 1170; https://doi.org/10.3390/min12091170 - 16 Sep 2022
Cited by 4 | Viewed by 3139
Abstract
The inclusion of high specific surface materials such as calcined clays in cementitious systems enhances the hydration of clinker products at very early ages, but it may also increase water demand; thus, the pursuit of a flowing concrete may demand an increase in [...] Read more.
The inclusion of high specific surface materials such as calcined clays in cementitious systems enhances the hydration of clinker products at very early ages, but it may also increase water demand; thus, the pursuit of a flowing concrete may demand an increase in the dosage of superplasticizers. The grinding regime can have a major influence on the properties of the cementitious system and could help mitigate the problem of water demand. This paper discusses the impact of grinding alternatives for the production of a binder consisting of clinker, calcined clay, limestone and gypsum. Two main target products will be discussed: (i) LC3, a binder with a formulation of 50% clinker, 30% calcined clay, 15% limestone and 5% gypsum, co-ground all together, and (ii) LC2, a mineral addition with a formulation of 60% calcined clay, 35% limestone and 5% gypsum, ground separately and further blended with Portland cement on a 1:1 basis (mass). The experimental program is carried out in several stages: (i) the binder, (ii) cement pastes and (iii) standard mortars, and concrete grinding aids from the family TEA are used to enhance grinding, and their impact is also be assessed. Full article
(This article belongs to the Special Issue Blended Cements Incorporating Calcined Clay and Limestone)
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16 pages, 4547 KiB  
Article
Effect of Unhydrated Aminopropyl Triethoxysilane Modification on the Properties of Calcined Kaolin
by Jincai Zhang, Peng Zhang and Fangqin Cheng
Minerals 2022, 12(6), 705; https://doi.org/10.3390/min12060705 - 31 May 2022
Cited by 7 | Viewed by 2363
Abstract
Unhydrated aminopropyl triethoxysilane was used to modify calcined kaolin produced from coal-bearing kaolinite. The aim was to develop a simple and economic modification method without the need for solution immersion and subsequent wastewater treatment. The samples before and after modification were tested using [...] Read more.
Unhydrated aminopropyl triethoxysilane was used to modify calcined kaolin produced from coal-bearing kaolinite. The aim was to develop a simple and economic modification method without the need for solution immersion and subsequent wastewater treatment. The samples before and after modification were tested using multiple methods, such as XRD, MAS-NMR, FT-IR, XPS, and SEM. The study results indicate that this modification can effectively improve the surface property of calcined kaolin. The activity index increased to 76.7% when the modifier usage was 2%. With a further increase in the modifier content, the activity index decreased. Surface modification did not reduce the whiteness of calcined kaolin. Further, the modification reaction mechanism was elucidated. Based on the detailed analyses, it was found that the modification reaction took place between the NH2 groups in the modifier molecules and AlVI-OH in calcined kaolin, and hydrogen bonds were formed between the NH2 groups and the active sites on the calcined kaolin surface. Full article
(This article belongs to the Special Issue Blended Cements Incorporating Calcined Clay and Limestone)
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20 pages, 3127 KiB  
Article
Suitability of Clinker Replacement by a Calcined Common Clay in Self-Consolidating Mortar—Impact on Rheology and Early Age Properties
by Abubakar Muhammad, Karl-Christian Thienel and Ricarda Sposito
Minerals 2022, 12(5), 625; https://doi.org/10.3390/min12050625 - 14 May 2022
Cited by 5 | Viewed by 4299
Abstract
The use of a high amount of calcined clays as cement replacement presents a great challenge in designing self-consolidating concrete. This current attempt evaluates the influence of cement replacement with up to 40 vol.% by a calcined common clay (CC), dominated by 2:1 [...] Read more.
The use of a high amount of calcined clays as cement replacement presents a great challenge in designing self-consolidating concrete. This current attempt evaluates the influence of cement replacement with up to 40 vol.% by a calcined common clay (CC), dominated by 2:1 phyllosilicates in combination with a fixed limestone powder (LP) content on fresh and hardened properties of self-consolidating mortar (SC-M). The fresh properties of SC-M were investigated by mini-slump flow, V-funnel and rotational viscometer measurements. Setting and hardening behavior were observed via dynamic modulus of elasticity and plastic shrinkage. Hydration mechanisms were determined by isothermal calorimetry and thermal analysis. Hardened properties of SC-M were evaluated using compressive strength tests and mercury intrusion porosimetry (MIP). The results revealed a decreased rate of deformability in SC-M when cement is substituted increasingly by CC and a rising superplasticizer (SP) demand, but indicated an improved stability of SC-M even at a higher dosage of SP and hardly any impact on the setting behavior. CC enhanced the precipitation of monocarboaluminate phases and thereby refined the pore size distribution of the binder matrix. SC-M can be produced with up to 40 vol.% CC as cement replacement without having effect on its 28 days mechanical properties. Full article
(This article belongs to the Special Issue Blended Cements Incorporating Calcined Clay and Limestone)
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