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The use of starch and its derivatives in concrete as an admixture to modify relevant properties of concrete is on the increase in recent times. It is known to modify the rheology, to affect the hydration kinetics of cement, and influence on initial and final setting time of cement. This paper examines the effect of cassava starch on concrete. shrinkage properties of concrete, with and without starch addition, were studied. Various percentages (0, 0.5, 1.0, 1.5 and 2 %) of starches by weight of cement were added to concrete mixes prepared in the laboratory. Shrinkage tests were conducted for duration of up to one year. The result show that concretes with starch additions exhibit lower shrinkage, which is an indication the addition of starch as admixture in concrete improves the ability of the concrete reduce shrinkage problems.
Interactions between waste paper sludge ashes and superplasticizers based on polycarboxylates
(2016)
In many industrial nations, about two third of the paper demand is covered by recovered paper. A major process step within the treatment of waste paper is the de-inking. It is a floating process yielding paper sludge as a waste product. About 50 % of this residue is used as a fuel. In several cases it is burnt at temperature of about 850 °C and thereafter the accrued ashes are collected in the flue gas filter. During the combustion, kaolinite and calcium oxide generate gehlenite and larnite. Calcite is the main component of waste paper sludge ash (PA).The chemical and mineralogical composition of PA suggests using it as a supplementary cementitious material.
In modern construction materials technology, workability aspects gain importance, since for most modern materials the rheology and compaction ability are relevant for the operation at a hardened state. It was observed that PA significantly increases the water demand of powder systems, which can cause serious problems during the casting of mineral binder systems containing PA. It is therefore obvious that binder systems containing PA might demand for the use of superplasticizers. Superplasticizers are polymers with anionic backbone that cause electrostatic and steric repulsion effects upon adsorption on surfaces of particles and hydration phases.
In this paper interactions between superplasticizers and waste paper sludge ashes are discussed and analysed. Based on observations of changes in the zeta potential and the dispersion of the particle system, the influence of the charge density of superplasticizers is observed and time dependent effects are demonstrated.
Viscosity modifying agents: Key components of advanced cement-based materials with adapted rheology
(2022)
Viscosity modifying agents (VMAs) are essential ingredients for the production of flowable cement-based materials. This paper presents an overview of commonly used VMAs and attempts to shed some light on the underlying physics at the origin of their mechanisms of action. The main molecular parameters of VMA controlling the rheological properties of the cement pore solution are highlighted. As the mechanisms of action of VMAs in cement-based materials are closely related to their affinity with the surface of cement particles, the adsorption of the main VMA types is discussed. The effect of VMAs on flow properties and stability of cement-based materials is presented for VMAs added without any superplasticizer, and then in systems incorporating both VMAs and superplasticizers. Finally, the effect of VMAs in enhancing concrete properties to secure adequate performance of different construction applications, and perspectives for future developments of novel cement-based materials made with VMAs are showcased.
The presence of polycarboxylate ether (PCE) based superplasticizers (SPs) has enormous influence on the early hydration of cement. C3A as the most reactive phase of Portland cement plays a significant role in early hydration reactions and affects the rheological performance. Therefore, this paper presents experimental results about the influence of delayed addition of PCEs on the Hydration of cement and C3A-gypsum pastes investigated by isothermal heat flow calorimetry. Complementary in-situ XRD was carried out on C3A pastes to analyze hydration and phase changes related to the addition of PCE.
Cement pastes with a delayed addition of PCE showed less Retardation compared to simultaneous addition. The alteration caused by PCE is much more pronounced for C3A-gypsum mixes. With a delayed addition of SP, the hydration of C3A is less retarded or even accelerated. It is obvious that there is less retardation the later the addition of SP. Furthermore, the PCE alter the hydration of C3A when added delayed and exhibit changes in kinetics and hydration rates. XRD results showed that more C3A is dissolved in the presence of PCE. Also, the gypsum depletion occurs earlier in the presence of PCE and even faster with delayed addition. Without PCE AFm starts to form just after the gypsum depletion. However, in the presence of PCE AFm already starts to form at the beginning of the hydration. Due to the faster gypsum depletion in the presence of PCE, also the transformation from ettringite into AFm begins earlier, but takes longer as without SP.
The presence of polycarboxylate ether (PCE) based superplasticizers (SPs) has an enormous influence on the early hydration of cement. The hydration is retarded and the timing of formation and the morphology of hydrates is affected. This short paper presents experimental results about the influence of delayed addition time of PCE SPs on hydration of cement and alite pastes, investigated by isothermal heat flow calorimetry. For cement as well as for alite pastes the hydration is retarded with SP, whereby the high charge PCE has a stronger retarding effect than the low charge PCE. The retardation caused by PCE is much more pronounced for alite than for cement mixes. If PCE is added later to the mix, the induction period is shortened and the hydration is accelerated compared to simultaneous addition. This applies for cement and alite pastes. With delayed PCE addition the alite shows a clearly less retarded setting and main hydration than after simultaneous addition. It is obvious that for alite pastes there is less retardation the later the addition of SP.
Admixtures are important constituents to enhance the performance of concrete. They allow for more efficient use of binders which can mitigate negative environmental impacts from producing cement-based materials. Commonly used rheology modifying agents like polycarboxylate ethers or cellulose ethers are synthetic or semi-synthetic, respectively. This requires additional energy consumption for their production and global supply chains particularly for many developing regions, which will be large consumers of concrete in the future. However, many locally available bio-based polysaccharides could be effectively used instead. These polymers are often overlooked by engineers and scientists due to their limited distribution and inherent complexity, yet they represent an underleveraged source of precursors for admixtures. This study investigates the action mechanisms of some bio-based rheology modifying agents, i.e., acacia gum and miscanthus gum, and provides a comparison to a conventionally modified starch. The results show that the mechanism of action of these polymers is closely related to the composition of the mixture, mixing regime, and the composition of the aqueous phase. Depending on the agent, either plasticizing or stabilizing effects on rheology can be revealed.
Chemical admixtures allow to the create a variety of fresh and hardened state properties in cementitious materials. In the case of self-compacting concrete, plasticizers or superplasticizers are introduced with the aim to decrease the yield stress and the viscosity of the materials. However, in order to prevent segregation and bleeding, and to improve the water retention of cement-based system, stabilizing agents or viscosity agents are often introduced in addition. Among these admixtures, polysaccharides are most commonly used.
The aim of this study is to provide an understanding of competitive or synergetic effects induced by the combination of hydroxypropyl guar stabilizing agents (HPG) and superplasticizers on cement pastes. Two polycarboxylate superplasticizers (PCE) exhibiting different charge densities and one HPG were studied. It was found that the combination of HPG with PCE superplasticizer strongly affects the rheological behavior of cement pastes. Despite the presence of HPG, the viscosity of the pastes strongly decreased with increasing dosage of PCE until it became close to the viscosity of a cement paste with PCE only. However, the use of HPG in combination with PCE allows maintaining a significant yield stress in the cement paste compared to PCE alone. The increase in the charge density of the PCE seemed to amplify the drop of the viscosity and to reduce the gain on the yield stress induced by HPG.
The results also highlight a delay in the setting-time of the cement paste by adding HPG and PCE. The delay induced by HPG is significantly lower than that generated by PCEs. However, the combination of the both kind of admixtures leads to a slightly shorter setting-time compared to the PCE alone.
Chemical admixtures allow to create a variety of fresh and hardened state properties in cementitious materials. In the case of self-compacting concrete, plasticizers or superplasticizers are introduced with the aim to decrease the yield stress and the viscosity of the materials.
However, in order to prevent segregation and bleeding, and to improve the water retention of cement-based system, stabilizing agents or viscosity agents are often introduced in addition.
Among these admixtures, polysaccharides are most commonly used. The aim of this study is to provide an understanding of competitive or synergetic effects induced by the combination of hydroxypropyl guar stabilizing agents (HPG) and superplasticizers on cement pastes. Two polycarboxylate superplasticizers (PCE) exhibiting different charge densities and one HPG were studied. It was found that the combination of HPG with PCE superplasticizer strongly affects the rheological behavior of cement pastes. Despite the presence of HPG, the viscosity of the pastes strongly decreased with increasing dosage of PCE until it became close to the viscosity of a cement paste with PCE only. However, the use of HPG in combination with PCE allows maintaining a significant yield stress in the cement paste compared to PCE alone. The increase in the charge density of the PCE seemed to amplify the drop of the viscosity and to reduce the gain on the yield stress induced by HPG. The results also highlight a delay in the setting-time of the cement paste by adding HPG and PCE. The delay induced by HPG is significantly lower than that generated by PCEs. However, the combination of the both kind of admixtures leads to a slightly shorter setting-time compared to the PCE alone.
In the last years flowable concrete has become increasingly important in applications such as, for systems with highly reinforced concrete with a complicated formwork, or sprayed concrete and 3D-printing of concrete. For all these applications it is necessary to have tailored rheological properties. Rheology can be described by values of yield stress and plastic viscosity, which can be determined for example by evaluation of rheometer measurements. But for different materials various rheometers with different geometries and stirrers are being used. To see the effects from paste in concrete, it is necessary to investigate mixes of paste, mortar and concrete, stepwise. But currently there exists no device, which is calibrated for these different systems at once. Due to this fact, conventional tests such as V-funnel efflux-time and flow diameter were determined, as well as rheometer data in different cell sizes and geometries.
In this study the assessment of rheological effects in the binder on the rheology of mortar and concrete was investigated by using combination of two rheometers.
The paper showed that the STA behave completely different in pastes with LSF and cement, respectively, as well as with or without PCE. While STA can affect plastic viscosity and yield stress in LSF and cement pastes, the addition of PCE causes that the STA have mainly an impact on plastic viscosity, except DGUM and ST-low. The performance of STA in LSF and cementitious systems can vary greatly due to different ionic strengths of the liquid phase. The charges due to modification of the starches have an intense influence on the rheological properties in pastes. The combined use of PCE and STA can lead to a significant increase of the plastic viscosity without a strong effect to the yield stress.
For the evaluation of the effectivity of STA the ionic strength of the liquid phase and the solid volume fraction of the binder have to be taken into account. Further influences can arise from grain size and aggregate content as well as the temperature, which were not discussed in this paper.
Organic admixtures are an indispensable component of modern concrete. Thus, their purposeful application is not only technically and economically viable but in addition an inevitable tool to make concrete more environmentally friendly. In this context, the use of polysaccharides has increasingly gained interest in the built environment as sustainable resource for performance enhancement. However, due to its origin, biopolymers possess a vast variety of molecular structures which can result in incompatibilities with other polymers present in concrete, such as superplasticizers. The present study highlights effects of the joint application of different types of starches and polycarboxylates with respect to their influence on cement hydration and structural build-up of cement pastes.
Today, chemical admixtures like superplasticisers and stabilising agents are extremely important for modern concrete technology. These agents have meanwhile become common practice in concrete technology, but the understanding within the entire system lags far behind their application. The macroscopic rheology of concrete in the presence of superplasticizers strongly depends upon effects on a much smaller scale such as the hydration of the cement, the adsorption of superplasticizers, and the pore solution chemistry.
As soon as cement is mixed with water, the hydration reaction starts to set of. The progression of the hydration process is governed by the amount and the availability of water and its possibility to access the unhydrated cement grain surfaces. For a total hydration cement theoretically requires water amounting approximately 0.38 of its own mass. Nevertheless, due to the cement’s highly hygroscopic nature, already the moisture in the ambient air can cause first hydration reactions to set in upon the cement grain surfaces. Such pre-hydration processes have an effect on the cement's properties. Dpending on the specific conditions during the storage the significance of the impact on certain properties can vary.
If cement is consumed soon after production and is transported only short distances in a silo wagon to its final destination for immediate use without further stock transfer, the effects are rather negligible. However, if cement is delivered in bags, transported over long distances, shifted serval times and stored for longer time periods until it is finally consumend, these effects can be quite severe. Due to the actual logistical situation with comparably few cement plants, large delivery distances and partially less developed infrastructures, the latter scenario pictures the situation for the most cases in Africa quite well.
In order to verify the relevance of the pre-hydation for practical application, a series of tests was conducted at the German Federal Institute for Materials Research and Testing (BAM). The influence of the cement storage on gresh and hardened concrete properties was investigated for different concrete and mortar types. The investigations show that the impact of the storage conditions is more pronounced for specialized concretes with high sophisticated optimized mixture compositions containing admixtures. Nevertheless, the effects also occur for ordinary concrete and should not be ignored.
Organic/inorganic mixtures were prepared from ordinary Portland cement (OPC), water (w/c 0.22), a fluorescent dye in aqueous solution (stable at alkaline pH; BAM-I), and two different comb shape polycarboxylates (PCEs), i.e., high charge (PCE-HC) and low charge (PCE-LC), respectively. Rheological and calorimetric measurements were performed prior to optical studies in order to select PCE concentrations. Absorption and fluorescence spectroscopy of the system OPC + BAM-I (CBAM-I) revealed maxima of dye BAM-I located at 645 nm and 663 nm, respectively. In presence of PCE-HC and PCE-LC, these mixtures displayed a small red shift in reflectance and a faster decrease in intensity compared to studies with CBAM-I; however, only slight differences were observed between the different PCEs. With time, all systems exhibited a decrease in intensity of BAM-I in absorption/reflectance and emission. This could be caused by dye adsorption and possibly decomposition when in contact with cement particles or hydration products.
Nowadays, superplasticizers (SPs) are widely used to increase fluidity and reduce water content in concrete; thus, allowing better workability for final applications. The present study will focus on the hydration effect using comb shape polycarboxylates (PCEs), which are known to allow a very low water/cement ratio (w/c of 0.20) or less.Optical methods have been successfully used for the analysis and monitoring of the interactions between a broad variety of nanoscale and molecular systems like nanoparticles of various chemical composition and different types of organic ligands or biomolecules.This encouraged us to assess the potential of these methods, and particularly fluorescence, for the investigation of the interactions that occur at the interface between hydrate surfaces of cement particles and PCE at a very early stage of concrete formation and to differentiate between the impact of PCE’s molecular structures on such interactions.
Concrete technology was exposed to a rapid development during the last three decades. For the longest time in its history, concrete was considered as a three component System consisting of aggregates, which are bound by the hardened cement paste consisting of hydrated cement. Traditionally, the only way of adjusting the consistency of concrete was using well adjusted aggregates and grading curves and adding excess water to the concrete, accepting that the latter in return reduces strength and durability. During the last three decades, however, concrete has developed further from a three component System towards an (at least) five component system, since the use of mineral additions and Chemical admixtures has become state of the art. Both components are able to enhance the workability, the compactability, and the density of the microstructure with effects on strength, ductility and durability, while cement can be saved in parallel. Due to reasonable use of admixtures and additions, concrete can be designed to match mechanically high performance specifications. Traditionally, cement paste was considered the weakest component in concrete. Flowever, in modern concrete a good paste composition can yield highest performance, passing the role of the mechanical bottleneck towards the aggregates.
Potentials for sustainable cement and concrete technologies - Comparison between Africa and Europe
(2017)
Cement and concrete technologies in Africa provide vast potentials for sustainable future technologies as well as enormous challenges. The main focus of the symposium is to address existing challenges, possible solutions, and future potentials with all participants. This symposium also aims at offering a platform for networking with relevant players in science and industry.
The African cement, concrete and construction business are growing at rapid pace. The cement sales are expected to grow tremendously until 2050. The number of newly built cement plants increases dramatically and in addition more cements are being imported from outside the continent, e.g. from Turkey, Pakistan, Indonesia, and China, driven by overcapacities in the countries of origin. This causes a high number of potentials and challenges at the same time. New cement plants can operate directly at best technological state of the art and thus incorporate more sustainable technologies as well as produce new and more sustainable products such as cements blended with sustainable supplementary cementitious materials such as calcined clays, and industrial or agricultural by products. At the same time the new variety of binding agent as well as the international imports, which are driven by price considerations, make the cement market prone to quality scatter. This puts pressure on the quality control regulations and institutions to ensure safety of construction, healthy application, and environmental safety for the population.
The paper presents possible solutions to build up the rapidly increasing African cement production more sustainably than in the rest of the world as well as the related challenges and obstacles that need to be overcome. Based on experiences with a series of pan-African cement testing laboratory proficiency schemes conclusions are made on technical, regulative and political level.
After a brief introduction into past and modern concrete, the relevance of sustainable concrete technologies is emphasised from a global perspective. In order to minimise the environmental impact of cement and concrete in the world, solutions for alternative binder materials as well as rheology and performance modifying additives are presented based on local bio-based resources.
However, the perception of bio-based constituents is typically rather negative in construction materials and its application is often limited to low-end construction. In order to show that this is not inevitable, the lecture ends with a number of case studies for the use of bio-based materials for high performance concrete applications.