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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.
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.
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.
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.
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.
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.
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.
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.
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.
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.