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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.
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.
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.
While today, engineers can choose from a wide range of rheology modifying admixtures, in some parts of the world, these are difficult to access, due to their complex processing. However, alternatives can be bio-based polymers such as polysaccharides from various sources. These are easily accessible all over the world, do not demand for complicated processing, and typically they are more sustainable than many established materials, which are crude oil-based.
The paper presents the effects of acacia gum, cassava starch and the gum of triumfetta pendrata A. Rich on the rheological performance of cementitious systems. It is shown that acacia gum can be as efficient as polycarboxylate based superplasticisers, cassava starch can reduce the yield stress slightly with little effect on the plastic viscosity, and the gum of triumfetta pendrata A. Rich increases the thixotropy of cement pastes with plasticizing polymers significantly.
The African cement, concrete and construction business is growing at rapid pace. The cement sales are expected to grow rapidly 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. Newly built 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.
In order to observe the effect of the aggregate phases between 2 mm and 16 mm without overlap with rheological effects induced by the cement hy-dration and without interactions with a threshold fine sand particle size that affects both, paste and aggregates, rheological experiments were conducted on a limestone filler based paste mixed with aggregates up to 16 mm. Vari-ous aggregate fractions were blended and mixed with the replacement paste in different volumetric ratios.
The dry aggregates’ flow coefficients were determined and compared to yield stress and plastic viscosity values at different aggregate volume fractions. The results indicated that the flow coefficient is not a suitable parameter to predict the performance of the aggregates in the paste. It was shown that the yield stress of pastes is largely determined by the blend of different aggregate fractions, while the plastic viscosity to large extend depends upon the coars-est aggregate fraction.
Based on the results, ideal aggregate composition ranges for minimised yield stress are presented. For the plastic viscosity no such grading curves to achieve minimum values could be found, but high viscosity curves are identified.
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.
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.
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.
While today, engineers can choose from a wide range of rheology modifying admixtures, in some parts of the world, these are difficult to access, due to their complex processing. However, alternatives can be bio‐based polymers such as polysaccharides from various sources. These are easily accessible all over the world, do not demand for complicated processing, and typically they are more sustainable than many established materials, which are crude oil‐based.
The paper presents the effects of acacia gum, cassava starch and the gum of triumfetta pendrata A. Rich on the rheological performance of cementitious systems. It is shown that acacia gum can be as efficient as polycarboxylate based superplasticisers, cassava starch can reduce the yield stress slightly with little effect on the plastic viscosity, and the gum of triumfet ta pendrata A. Rich increases the thixotropy of cement pastes with plasticizing polymers significantly.
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.
The cement proficiency testing (PT) scheme was set up by the German Metrology Institute (PTB) and the Federal Institute for Materials Research and Testing (BAM) in 2012. The PT scheme was a spin-off from a European Commission and African, Caribbean and Pacific-Group of States funded project entitled SPIN – Spearhead Network for Innovative, Clean and Safe Cement and Concrete Technologies (www.spin.bam.de). The SPIN project aimed at crosslinking experts in industry and policy making bodies, with the prospect of establishing a sustainable cement and concrete construction capacity in Africa.
After a successful first pan-African proficiency testing scheme in 2012/2013, it was decided to establish the scheme permanently and independent of the SPIN project.
The main focus of setting up a testing scheme was to enable all cement testing laboratories in Africa to evaluate their competence and efficiency in cement testing and further enhance their capacity to obtain better quality products according to their environment. The acronym developed for the PT scheme is PACE-PTS (Pan-African Cement Proficiency Testing Scheme). The framework for the PT scheme was set up jointly among the organisers and the first participants. The first PT scheme was initiated in Dar Es Salaam in 2012 followed by a final workshop in Berlin in 2013. The second PT scheme began in 2014. A final workshop was organised in Dar es Salaam in 2015. The third and current scheme was started in 2016 and the final workshop is held in Yaoundé.
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.
Polysaccharides are important rheology modifying admixtures in the building material sector.
The use of starch is becoming increasingly important, due to many ecological and economic advantages. In the construction sector, starch ethers are being used as thickeners and as means to increase the yield stress. The starch ethers that are available on the market differ in
their behaviour, which can vary greatly depending upon the binder system and mortar composition, e.g. solid volume content, binder type, additional admixtures. In view of the limited knowledge about the influence of molecular modifications associated with cement based systems, some fundamental rheological functional mechanisms were analysed in this study. The differently modified starch ethers used were derived from potatoes. They varied in their charges and degrees of hydroxypropylation. The setting and the flow behaviour of all examined variations
of starch ethers were analysed in cement pastes. In order to illustrate the effects of the starch ethers that were used, the water-cement ratio (w/c) was held constant in all the mixtures [Schmidt 2012]. The results indicated significant differences in setting and flow behaviour.
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.
Today, concrete engineers can vary consistencies between very stiff and self-compacting. At the same time engineers can opt for a vast variety of binders. The possibility to use optimised mineral binders and to tailor rheological properties of concrete eventually opened up the path to multiple new technologies, where design criteria are no longer limited to the Young’s modulus and the compressive strength, but often comprise additional added value. It can therefore be concluded that the capability to control the rheology and the interactions particles can be considered as the catalyst for concrete innovations such as polymer modified cementitious composites (PCC) self-compacting concrete (SCC), high-performance concrete (HPC), ultra-high performance concrete (UHPC) or strain hardening cement based composites (SHCC). In the same way rheology modifying additions, SCMs and admixtures will become key parameters in mastering the challenges of the next decades such as:
- Additive manufacturing/3D-printing
- Overcoming pumping height limitations
- Casting at extreme temperatures
- Tailored rheology at delivery
In many regions in the Southern hemisphere the effective use of SCMs, additions and chemical admixtures for concrete could significantly contribute to solve problems induced by the challenging climatic conditions, but particularly in many countries with challenging climatic conditions, it is difficult to use them, due to lacking local supply and supply infrastructure, and often the awareness of the value of local mineral resources is missing. However, the long distance transportation of mineral resources and chemicals is not very environmentally friendly and the economic consequences are dramatic.
However, bio-based constituents and chemicals have been used in construction for ages effectively. Due to the enormous relevance of binders, fillers and rheology modifying admixtures it is worthwhile to recollect that nature provides an enormous variety of products that can be used readily or with low processing. Today, the use of petrol based polycarboxylate ether superplasticizers has become quite common in concrete technology due to their versatility, but their uncomplicated and cost efficient availability is limited in many countries in the world. However, alternatives are available, which can be found locally. In addition many agricultural wastes today are dumped, although they could be converted to reactive ashes easily.
Plant extracts have been used to modify the properties of concrete for long time. These plants are typically regionally abundantly available, cheap, and they are environmental friendly. They do not require special caring for seedlings, weeding or manuring to grow since they grow wildly.
The talk will present an overview of various options for binders, fillers and rheology modifying admixtures, that can be found in nature, and that may become a real alternative, once their interaction within the complex cementitious system is well understood.