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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.
SCM potential in Africa
(2012)
South Africa and recently Nigeria are the only net exporter of cement in Africa, yet cements are imported into the country mainly on the basis of price competitiveness. This poses potential for scatter in the properties of the cements in the South African market as pricing seems to be the only determining factor that affects Portland cements imported. A survey of cements of grade 42.5N in the South African cement market was carried out to identify major players in the industry. The identified cements, which included four locally produced and one imported cement were then analysed for both chemical composition and physical properties in line with the Eurocode EN 196. Tests carried out include loss on ignition, chloride content, sulphate content, specific surface (Blaine), standard consistence, initial setting time, final setting time, soundness and flexural and compressive strength at 2, 7 and 28 days. The testing program was initiated as part of on-going Africa-wide cement testing competency program in partnership with BAM and PTB in Germany. The performance of the identified cements from the different local manufacturers and the imported cement were analysed and are presented in this paper. These results reveal some similarities and differences in the properties. Particularly of interest is the marked difference in the 28 days compressive strength of the cements. This paper shows that there is need for further tests across the cement industry as some of the cements failed to meet certain requirement as set by EN 196. The paper also recommends the use of proficiency testing schemes in the cement industry of the country to ensure the cement laboratories are providing results of high quality and at the same time act as a check to make sure these laboratories are not failing to meet standard requirements.
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.
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.
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 Produktionspausen können in Betonwerken nennenswerte Lagerungsintervalle entstehen. Auf Baustellen und in den Instandsetzungen werden Zement- und Trockenmörtelsäcke teilweise über längere Zeiträume gelagert. Auch im Zusammenhang mit Zementimporten und zunehmend filigran abgestimmten Betonrezepturen die bereits bei kleinen Änderungen der Ausgangsstoffe sensibel reagieren, nimmt die Relevanz der Zementlagerung zu. Aus diesem Grund wurde der Einfluss der Zementlagerung auf die Eigenschaften von Betonen in einer Versuchsreihe an der Bundesanstalt für Materialforschung und -prüfung (BAM) ermittelt.
Portland cement, as we know it today, has its origin in Great Britain approximately 170 years ago. Since then, concrete technology has spread out to Europe, the United States, and Japan, where it became a key component for rapid industrial development. Europe, the Unites States and many Asian countries today have developed a high level of technology regarding concrete construction.
However, each of them has a unique history and as a result, different “concrete philosophy” depending upon the social, environmental and financial boundary conditions, as well as their evolution throughout the years and local construction traditions. As a result, the word concrete may refer to rather different materials in America, Europe, and Asia.
Apart from South Africa, most sub-Saharan African countries cannot look back on a similarly long cement and concrete history. Cement and concrete are rather new materials and not yet well established. This gives African engineers the unique opportunity to learn from past mistakes and to develop a concrete technology, which refers to the best available practice. However, in many sub-Saharan African countries, standards and regulations are adopted (preferably from Europe or the US) without consideration of the historical background of these standards. Although this practice helps saving resources for the implementation, it does not necessarily yield the best result in the African environment, and also from an economic point of view it might come back disadvantageously due to unnecessary overdesigning.
By comparing the differing states-of-the-art in North America, Europe, and Asia, this paper emphasizes, how regional conditions determine the practice of concrete technology in the sub-Saharan area. It is therefore important for Africa to develop a unique African concrete technology, which is perfectly fitted to the specific local conditions, even if it may vary distinctively from the established practice elsewhere. The paper concludes that African nations should effort into adapting existing principles that have proved to function well rather than adopting existing standards.
Chemical admixtures like superplasticisers or stabilising agents are of ever increasing importance for modern concrete technology. They liberate the workability of concrete from its dependency on water content, and thus, open the gate towards innovative and future oriented concrete technologies such as self-compacting concrete. Today, admixture addition has become common practice in concrete technology, but the understanding of their highly complex mode of operation is extremely difficult and demands for understanding of processes within the range between nanometres and centimetres. Due to its complex time-dependent, multi-phase and multi-scale behaviour, flowable concrete systems are highly complicated and cannot be described comprehensively by simple models. It is therefore extremely challenging to identify the relevant parameters that predominantly control flow phenomena on different size scales, since these may occur on any scale between the nano scale (e.g. superplasticizer adsorption) and macro scale (e.g. grading of the aggregates). The present study discusses fundamental mechanisms at the interface between particle or hydrate surfaces and the fluid phase at a very early stage of concrete formation, and links these effects to macroscopic flow phenomena. Methods are discussed that appear promising interdisciplinary tools for enhancement of the understanding of the relevant interactions that are responsible for the macroscopic flow of flowable concrete.
Clearing the way
(2012)
The existing cement and concrete standards are not capable of making full use of the current technology capacity due to strong focus on conventional concrete and thus they are not fit for the current and future challenges of construction industry. The paper highlights shortcomings with regard to the implementation of the existing standards. It can be seen that future-oriented standards are generally required to contribute to a lower-carbon footprint of the industry. These changes are significantly more relevant in sub-Saharan Africa, due to the rapidly increasing urbanisation challenge and the enormous potentials to develop lower-carbon technologies than elsewhere in the world.
Sub-Saharan Africa is populated by more than half a billion people,
and rapid urbanization is creating challenges in the areas of housing,
roads, railways, power supply, dams and water pipelines —
aspects of infrastructure that are critical to the well being of the
population. This situation indicates that cement and concrete will
play a major role in the future construction technology in Africa, despite
the fact that it does not have a long-lasting tradition over most
of the continent. Although the continent is rich in natural resources
for the production of mineral binder systems, many sub-Saharan
African countries exhibit challenging boundary conditions, that have
to be well understood in order to use cement and concrete technologies
in a sustainable and reasonable way.
Polysaccharides provide high potential to be used as rheology modifying admixtures in mineral binder systems for the construction industry such as concrete or mortar. Since superplasticizers have become state of technology, today, concrete is more and more adjusted to flowable consistencies. This often goes along with the risk of segregation, which can be effectively avoided by adding stabilising agents supplementary to superplasticizers. Stabilising agents are typically based on polysaccharides such as cellulose, sphingan gum, or starch. Starch clearly distinguishes in its effect on rheology from other polysaccharides, mainly due to the strong influence of amylopectin on the dispersion and stabilisation of particles. Based on rheometric investigations on cementitious and limestone based dispersions with different volumetric water to solid ratios, the mode of operation of modified potato starch is explained in comparison to a sphingan gum. It is shown that the stabilising effect of starch in a coarsely dispersed system is mainly depending upon the water to solid ratio and that above a certain particle volume threshold starch mainly affects the dynamic yield stress of dispersions, while plastic viscosity is affected only to a minor degree. Sphingans operate more independent of the particle volume in a coarsely dispersed system and show significantly higher effect on the plastic viscosity than on the yield stress. In systems incorporating superplasticizers, influences of both stabilising agents on yield stress retreat into the background, while both observed polysaccharides maintain their effect on the plastic viscosity.
Structural design and application have always been linked to the compressive strength of concrete as the main relevant criterion. This was justifiable in the past, where concrete consisted of water, ordinary Portland cement and aggregates, but this concept is no longer relevant for modern and more sustainable cement and concrete.
Despite these new developments, existing standards, guidelines and academic curricula have not been much updated and are still used worldwide. There is a need to change this situation by proper education of the users.
This overview describes the challenges that arise at a user Level from the higher complexity of modern concrete, and defines needs and requirements for enhanced applicability of sustainable concrete concepts.
Furthermore, recommendations are given on how better concrete practice can be communicated to all the involved parties, from civil and design engineers to constructors and site-appliers on the construction site.
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.
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.
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.
Why Africa can spearhead innovative and sustainable cement and concrete technologies globally
(2016)
The perception of concrete in the society as well as in the politics is rather negative. This becomes obvious in the fact that the phrase “concrete jungle” has become synonym for hapless living with no perspectives. In politics and research funding, it is also not easy to create a broader audience, since concrete is falsely considered as old-fashioned material that is sufficiently understood today and does not need further considerations, particularly compared to allegedly newer materials. However, particularly since the last two decades the technology has completely changed. Binders of today are no more the same binders as used before, and concrete mixture compositions of today diverge quite significantly from compositions in the past. There is little understanding world-wide about that. This causes that potentials the concrete technology bears are wasted.
In the broadly found opinion that concrete is old-fashioned and ugly, it is ignored that architectural sins are not inherent to the material, which actually is extremely versatile and CO2-friendly compared to all other construction materials available. It is also ignored that 98% of the outer Earth’s crust are made of the elements cement and concrete are made from, and therefore it will be an illusion to believe that the complementary 2% can create materials to develop regions and infrastructures in less developed areas in the world.
For betterment in Africa the infrastructural development should have highest priority, since poor connections between settlements are responsible for enormous Price increases [2], and urban traffic congestion is responsible for an incredible loss of productivity. It is not unrealistic to assume that earners that are dependent on a car get stuck in traffic about 3-4 hours per day in cities like Lagos, Nairobi or Dar es Salaam. However, the traffic congestions do not only affect the car owners negatively but the living of the entire urban population every day.
Besides infrastructure, housing should be the other priority, since a large part of the African population does not live in adequate condition. This is a societal problem, since unequal Distribution of wealth is a major driving force for instability in societies. The latter has a global impact, since 8 many phenomena that can be observed all over the world such as political radicalism, xenophobia, terrorism, and migration can often be linked to instable societies.
However, the importance of infrastructure has an even wider range. Most African countries go through a change process recently. In order to strengthen very positive perspectives, the focus in politics and research funding is put on issues such as agriculture, energy, and health, which are without doubt extremely important issues. However, it is typically overlooked that all enhancements in these areas can only become effective, when an infrastructure is created to support the implementation of better concepts. Mobility is the key to a prosperous future, and mobility can only be granted by infrastructural construction activities. Hence, compared to many other regions in the world, cement and concrete technologies have a significantly higher relevance in Africa.
Urbanisation, habitat, environment, infrastructure and sustainability are major global challenges of the 21st century. By planning, exploiting of resources, building, and maintaining, civil engineers and relevant adjacent disciplines have been carrying a large responsibility for the existing environmental problems. Civil engineers are responsible for 70% of all material uses in the world, and civil construction has been dominating the growth of the developing world for the next decades, with enormous impact on the global climate as well as the distribution of wealth and quality of living in the world.
Today a variety of sustainable construction concepts have been developed and discussed. Recently a UNEP report was published, which provides a comprehensive overview of the challenges and potentials in the future from a scientific and industrial point of view. Sustainable solutions based on abundantly available resources (pozzolana and clay) or on renewable instead of limited industrial by-products (e.g. agricultural waste ashes) and new construction echnologies do exist. By applying, promoting and developing the implementation of the existing knowledge into real life constructions, civil engineers also hold the key for the mitigation of the global challenges. Using best practice sustainable construction solutions is particularly of highest importance in the developing world, since the implementation at an early stage creates the highest leverage for positive effects.
Potentials for sustainable cement and concrete technologies - Comparison between Africa and Europe
(2017)
The fundamental knowledge about cement and concrete has made enormous progress over the last decades, and today it would be possible to find optimised sustainable concrete solutions tailored for every given boundary framework and raw material supply. However, this knowledge barely finds implementation into practice despite the urgent global need to minimise carbon emissions and energy consumption. A major reason is that most concrete developments were historically made in the northern hemisphere, where today over-regulations and stagnating market perspectives slow down innovation drive towards higher sustainability. In most African countries, however, sustainable building is simply an urgent real-life problem. The demand for building is enormous, Standard solutions are not an option, and the pool of innovative local raw materials and concrete concepts is enormous. The paper provides a comprehensive comparison between the boundary frameworks of Europe and Africa, and it is explained why local African solutions shall be given priority over imported solutions. Examples of local African concrete solutions are given, and ideas for a rapid implementation are developed. Most of the potentially useful materials such as agricultural ashes, natural and calcined pozzolans, polysaccharides, etc. have not yet been subject to intensive research to date. Therefore, it is not unlikely to assume that with an open mind for non-Standard solutions, combined with creativity and particularly knowledge and awareness, the next generation of innovative and sustainable concretes will be developed and applied on the African continent. Therefore, the conclusion is that particularly the African continent provides the best starting position to develop better and more sustainable concrete solutions than anywhere else in the world. Hence, Africa can become a global pioneer in green cement and concrete technology with impact to the entire world.
Today, concrete engineers can vary consistencies between very stiff and self-compacting. The possibility 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 of concrete systems 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 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, and particularly in Africa, the effective use of chemical admixtures for concrete could significantly contribute to solve problems induced by the challenging climatic conditions, but particularly in Africa it is difficult to use them, due to lacking local supply and supply infrastructure. For Africa, concrete admixtures are largely shipped or transported from Europe, the Arabian Peninsula, or Asia. The long distance transportation of chemicals is not very environmentally friendly and the economic consequences are dramatic: the agents are difficult to purchase, expensive, and there is not a large variety of products available in the market.
However, bio-based chemicals have been used in construction for ages effectively. Due to the enormous relevance of rheology modifying admixtures it is worthwhile to recollect that nature provides an enormous variety of chemicals 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 most countries in Africa. However, alternatives are available, which can be found in many regions.
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 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.
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.
Chemical admixtures like superplasticisers or stabilising agents are of ever increasing importance for modern concrete technology. They liberate the workability of concrete from its dependency on water content, and thus, open the gate towards innovative and future oriented concrete technologies. Meanwhile admixtures have become common practice in concrete technology, but the understanding of these highly complex polymers in the entire concrete system lags far behind their application. Due to its complex time-dependent, multi-phase and multi-scale behaviour, flowable concrete systems are highly complicated and cannot be described comprehensively by simple models. It is therefore extremely challenging to identify the relevant parameters that predominantly control flow phenomena on different size scales, since these may occur on any scale between the nano scale (e.g. superplasticizer adsorption) and macro scale (e.g. grading of the aggregates). The present study discusses fundamental mechanisms at the interface between particle or hydrate surfaces and the fluid phase at a very early stage of concrete formation, and links these effects to macroscopic flow phenomena.
Based on the observations of the nano scale effects, it seems that higher sensitivity against variations in the constituents, the handling, or the boundary condition are the inevitable price for higher performances. However, eventually a very effective method is introduced that helps to maintain stable processes regardless of the root cause for performance changes based on an efficient in-situ process control scheme and superplasticizer and stabilising agents as counter actions.
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.
Tricalcium aluminate (C3A) is found with less than 10% wt. of the total composition; however, during hydration, C3A plays an important role in the early hydration of cement in the presence of gypsum as a set retarder.
The aim of this investigation is to assess the suitability of optical spectroscopy and a dye-based optical probe to monitor early hydration of C3A in the presence of gypsum and hemihydrate. Optical evaluation was performed using steady-state fluorescence and diffuses reflectance spectroscopy (UV-VisDR). Phase characterization during hydration was done with in-situ X-ray diffraction. UV-VisDR with a cyanine dye probe was used to monitor the formation of metastable phases and was employed together with fluorescence spectroscopy, to follow the Aggregation and disaggregation of the dye during hydration. In conclusion, for the first time, a cyanine dye was identified as a feasible and stable probe to monitor C3A hydration changes in the presence of calcium sulfate.
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.
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.
Superplasticizers (SPs) have been employed in concrete technology for decades to improve the workability of concrete in its fresh state. The addition of SPs in cement-based systems affects the early properties. Although the interaction of the cement particles with various SPs has been extensively researched, there still exists limited research on the interaction of SPs with supplementary cementitious materials such as rice husk ash (RHA). This paper investigates the rheological properties and early hydration kinetics of RHA-blended systems with three types of SPs, a polycarboxylate ether (PCE) and two lignosulphonates (LS-acc and LS-ret). In rheological properties, the addition of SP causes an initial improvement of workability as the yield stress is significantly reduced. The pastes with PCE and LS-acc show a slight increase of yield stress over time whereas pastes with LS-ret tend to lower the yield stress slightly over time, further improving the workability. Without SP, pastes with RHA show a lower yield stress but an increase in plastic viscosity as cement is further replaced with RHA. The addition of the LS SPs is observed to lower the plastic viscosity but remains constant with further replacement of cement with RHA. This indicates that LS SPs further adsorbs on RHA particles and hydration products produced causing dispersion of the particles
within the system. In early hydration kinetics, pastes with PCE retard hydration and the degree of retardation is further increased with LS SPs. In the presence of RHA, the retardation of LS SP systems is significantly reduced. The pastes with PCE show more ettringite in the SEM micrographs, but is observed to be shorter needles. This indicates an initial good workability for PCE. However, C-S-H and CH were observed to be low in quantity, whereby the pastes with LS show more nucleation sites for C-S-H and CH. The ettringite needles in the LS systems were similar in quantity and more elongated in some cases but not abundant as in the PCE systems.
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.
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.
Two types of cements were selected as the reference cement in the priority program 2005 of the German Research Foundation (DFG SPP 2005). A thorough characterization of CEM I 42.5 R has been made in a recent publication. In this paper, the characterization data of the other reference cement CEM III/A 42.5 N are presented from the aspects of chemical and mineralogical compositions as well as physical and chemical properties. The characterization data of the slag, which is the second main constituent of this specific cement besides the clinker, are presented independently. For all data received, the mean values and the corresponding errors were calculated. The data shall be used for the ongoing research within the priority program. Also, researchers from outside this priority program can benefit from these data if the same materials are used.
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.
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.
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.
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.
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.
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.
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.
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.