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Interactions between waste paper sludge ashes and superplasticizers based on polycarboxylates
(2016)
In many industrial nations, about two third of the paper demand is covered by recovered paper. A major process step within the treatment of waste paper is the de-inking. It is a floating process yielding paper sludge as a waste product. About 50 % of this residue is used as a fuel. In several cases it is burnt at temperature of about 850 °C and thereafter the accrued ashes are collected in the flue gas filter. During the combustion, kaolinite and calcium oxide generate gehlenite and larnite. Calcite is the main component of waste paper sludge ash (PA).The chemical and mineralogical composition of PA suggests using it as a supplementary cementitious material.
In modern construction materials technology, workability aspects gain importance, since for most modern materials the rheology and compaction ability are relevant for the operation at a hardened state. It was observed that PA significantly increases the water demand of powder systems, which can cause serious problems during the casting of mineral binder systems containing PA. It is therefore obvious that binder systems containing PA might demand for the use of superplasticizers. Superplasticizers are polymers with anionic backbone that cause electrostatic and steric repulsion effects upon adsorption on surfaces of particles and hydration phases.
In this paper interactions between superplasticizers and waste paper sludge ashes are discussed and analysed. Based on observations of changes in the zeta potential and the dispersion of the particle system, the influence of the charge density of superplasticizers is observed and time dependent effects are demonstrated.
Viscosity modifying agents: Key components of advanced cement-based materials with adapted rheology
(2022)
Viscosity modifying agents (VMAs) are essential ingredients for the production of flowable cement-based materials. This paper presents an overview of commonly used VMAs and attempts to shed some light on the underlying physics at the origin of their mechanisms of action. The main molecular parameters of VMA controlling the rheological properties of the cement pore solution are highlighted. As the mechanisms of action of VMAs in cement-based materials are closely related to their affinity with the surface of cement particles, the adsorption of the main VMA types is discussed. The effect of VMAs on flow properties and stability of cement-based materials is presented for VMAs added without any superplasticizer, and then in systems incorporating both VMAs and superplasticizers. Finally, the effect of VMAs in enhancing concrete properties to secure adequate performance of different construction applications, and perspectives for future developments of novel cement-based materials made with VMAs are showcased.
Chemical admixtures allow to the create a variety of fresh and hardened state properties in cementitious materials. In the case of self-compacting concrete, plasticizers or superplasticizers are introduced with the aim to decrease the yield stress and the viscosity of the materials. However, in order to prevent segregation and bleeding, and to improve the water retention of cement-based system, stabilizing agents or viscosity agents are often introduced in addition. Among these admixtures, polysaccharides are most commonly used.
The aim of this study is to provide an understanding of competitive or synergetic effects induced by the combination of hydroxypropyl guar stabilizing agents (HPG) and superplasticizers on cement pastes. Two polycarboxylate superplasticizers (PCE) exhibiting different charge densities and one HPG were studied. It was found that the combination of HPG with PCE superplasticizer strongly affects the rheological behavior of cement pastes. Despite the presence of HPG, the viscosity of the pastes strongly decreased with increasing dosage of PCE until it became close to the viscosity of a cement paste with PCE only. However, the use of HPG in combination with PCE allows maintaining a significant yield stress in the cement paste compared to PCE alone. The increase in the charge density of the PCE seemed to amplify the drop of the viscosity and to reduce the gain on the yield stress induced by HPG.
The results also highlight a delay in the setting-time of the cement paste by adding HPG and PCE. The delay induced by HPG is significantly lower than that generated by PCEs. However, the combination of the both kind of admixtures leads to a slightly shorter setting-time compared to the PCE alone.
Chemical admixtures allow to create a variety of fresh and hardened state properties in cementitious materials. In the case of self-compacting concrete, plasticizers or superplasticizers are introduced with the aim to decrease the yield stress and the viscosity of the materials.
However, in order to prevent segregation and bleeding, and to improve the water retention of cement-based system, stabilizing agents or viscosity agents are often introduced in addition.
Among these admixtures, polysaccharides are most commonly used. The aim of this study is to provide an understanding of competitive or synergetic effects induced by the combination of hydroxypropyl guar stabilizing agents (HPG) and superplasticizers on cement pastes. Two polycarboxylate superplasticizers (PCE) exhibiting different charge densities and one HPG were studied. It was found that the combination of HPG with PCE superplasticizer strongly affects the rheological behavior of cement pastes. Despite the presence of HPG, the viscosity of the pastes strongly decreased with increasing dosage of PCE until it became close to the viscosity of a cement paste with PCE only. However, the use of HPG in combination with PCE allows maintaining a significant yield stress in the cement paste compared to PCE alone. The increase in the charge density of the PCE seemed to amplify the drop of the viscosity and to reduce the gain on the yield stress induced by HPG. The results also highlight a delay in the setting-time of the cement paste by adding HPG and PCE. The delay induced by HPG is significantly lower than that generated by PCEs. However, the combination of the both kind of admixtures leads to a slightly shorter setting-time compared to the PCE alone.
Special applications like pumping, spraying or printing of concrete require the precise adjustment of very specific rheological properties at different time steps during the casting process. Superplasticizers such as polycarboxylate ethers (PCE) can be used to obtain the required flowability, which, possibly in combination with additional rheology modifying admixtures, generate the required specified consistency. However, after the application, the concrete should change the rheological properties immediately in order to avoid deformations at rest. Therefore, the use of accelerators can be effective. Accelerators influence the hydration of cementitious materials, and thus the rheological properties over the course of time and the setting.
In this paper, the influence of different accelerators on the rheology and early hydration of cement paste as well as the interaction of accelerator and PCE are presented. Methods like rheometry, needle penetration tests and practical Tests like spread flow were applied. The used accelerators showed accelerating behavior on the cement pastes without and in the presence of PCE. At the same time an influence on the rheology could be observed. This effect was less in the mixes with PCE, especially at the highest water/cement ratio (w/c).
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.
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.
There is a wide range of research worldwide on supplementary cementitious materials (SCMs) such as fly ash and slag for substituting pure cement. Such materials are suitable to be considered in a cementitious system with ordinary Portland cement (OPC) due to their high pozzolanic properties. In addition, majority of the SCMs are said to significantly improve concrete properties especially in terms of increased strength and durability. Unfortunately, the production of such SCMs is not entirely eco-friendly and also limited to certain parts of the world, hence one has to look at alternative options.
The issue of availability of resources is a strong concept that is ever-increasing, and the use of more eco-friendly SCMs in a cementitious system is furthermore attractive. Hence this paper addresses the use of eco-friendly SCMs in concrete such as rice husk ash (RHA). Despite the fact that extensive research has been done on this material, its application in a cementitious system to obtain sufficient concrete properties is still rather limited. In a country like Tanzania, high strength concrete construction is applicable in special construction cases but certainly not a high priority. Majority of construction is still undertaken using normal strength concrete. In a ternary cementitious system consisting of OPC, RHA and other readily available resources such as limestone filler (LSF), normal strength concrete can still be produced having good performance and suitable for regular on-site construction. This paper explains a possible application of obtaining sufficient concrete properties from the available resources.
Over the course of the last decades, concrete construction has significantly changed from mass application towards sophisticated more innovative, future oriented, and performance based materials technology. Today concrete no longer consists of cement, water, and aggregates, but can be enhanced significantly by using supplementary additions and chemical admixtures. Advancements in admixtures eventually facilitated the development of new concrete types such as self-compacting concrete (SCC) and high performance concrete (HPC) by uncoupling the workability from the water-cement ratio (w/c).
While for traditional concrete types the major mixture parameter for the workability and strength were the w/c and the grading of the aggregates, for SCC and HPC the performance parameters are more complicated and the performance depends highly on the powder components. This makes the system more sophisticated and in parallel more prone to scatter during the production. The complexity and difficulty to predict the effects of changes in the process and mixture makes it very difficult to identify the right potentials for savings.
Concrete of today has only little in common with the traditional concrete used a few decades ago. It has become a high performance material, which can be adjusted for high performance applications and according to ultimate user specifications. The reason for the rapid evolvement was the increasing awareness about how the rheology of concrete can be improved without negatively affecting the mechanical properties of concrete by chemical admixtures.
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.
With ongoing innovation in process technology, the challenges of concrete technology are more and more focused on the rheological optimisation for these processes, since improper mixture stability or poor compaction ability negatively affect the concrete homogeneity and quality. However, along with the increasing complexity of today’s concrete mixture compositions, concrete becomes more prone to failure regarding the casting process. Variable properties of the raw materials typically cause changing workability. The reasons can be found among others in scattering water contents, physical or chemical properties of the cement or varying environmental temperatures. Robustness in the delicately adjusted rheology, however, is of utmost importance for modern and future process technology, from sprayed concrete over pumpable concrete towards 3D-printing, with regard to the long-term strength, the function and the durability. Typically, material induced changes cannot be identified easily due to the complex interactions of concrete constituents. Therefore, a precise and prompt counteraction is impossible. However, it is known that the yield stress can be controlled by addition of supplementary superplasticizer or stabilising agent. In combination with computerized process observation tools that can rapidly interpret and react on changes in the rheology, it is therefore thinkable, that only these two admixture types can adjust the rheology steadily and permanently, regardless of the actual root cause for observed macroscopic rheology change. The presentation will firstly give a comprehensive overview of effects at the interface between pore solution, particles and hydrates, which affect the rheology of fresh concrete. Secondly, ways are recommended how the rheology can be actively manipulated before eventually computerized methods are demonstrated that help to actively and rapidly assess and counteract performance scatter during steady casting processes.
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.
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.
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.
Todays superplasticizers for self-compacting concrete and high Performance cementitious materials are very versatile. Typically superplasticizers are composed of a polycarboxylic backbone equipped with polyethylene oxide graft chains of variable length and grafting degree. The mode of operation of these admixtures is based on the steric repulsion of the particles upon adsorption. The adsorption is strongly depending upon the charge density of a superplasticizer and the time dependent Adsorption processes control the retention of the flow performance – an important issue particularly for ready-mix and construction site concrete. However, the properties of polycarboxylic superplasticizers typically remain a black box for users. The paper suggests a simple and rapid test method, which can be conducted without sophisticated equipment, to qualitatively distinguish between two types of superplasticizers based on the adsorption mechanism. Interpreting the results in the right way provides a powerful tool to choose the right admixture for individual time dependent flow specifications.
Varying ambient temperatures in plants or on construction sites during casting of SCC can cause serious problems affecting the fresh concrete performances, such as rheological properties and setting time, with consequences for the hardened properties in the structure. By sensible choices of the components, the robustness of SCC mixtures against temperature variations can be improved. However, this aspect has not been the focus of intensive research yet. In this study the effects of varied ambient temperatures on the early performance of differently composed SCC mixtures are investigated, with emphasis on changes in rheology, early deformations, heat evolution and setting. Focus is placed on the study of the influence of the polycarboxylate ether molecule type as well as different viscositymodifying agents on the temperature robustness. Effects on the relevance for practical concrete applications are evaluated, which will provide a reliable framework of possible actions on the appropriate use of admixtures for SCC.
With ongoing innovation in process technology, the challenges of concrete technology are more and more focused on the rheological optimisation for these processes, since improper mixture stability or poor compaction ability negatively affect the concrete homogeneity and quality. However, along with the increasing complexity of today’s concrete mixture compositions, concrete becomes more prone to failure regarding the casting process. Variable properties of the raw materials typically cause changing workability. The reasons can be found among others in scattering water contents, physical or chemical properties of the cement or varying environmental temperatures. Robustness in the delicately adjusted rheology, however, is of utmost importance for modern and future process technology, from sprayed concrete over pumpable concrete towards 3D-printing, with regard to the long-term strength, the function and the durability. Typically, material induced changes cannot be identified easily due to the complex interactions of concrete constituents. Therefore, a precise and prompt counteraction is impossible. However, it is known that the yield stress can be controlled by addition of supplementary superplasticizer or stabilising agent. In combination with computerized process observation tools that can rapidly interpret and react on changes in the rheology, it is therefore thinkable, that only these two admixture types can adjust the rheology steadily and permanently, regardless of the actual root cause for observed macroscopic rheology change. The presentation will firstly give a comprehensive overview of effects at the interface between pore solution, particles and hydrates, which affect the rheology of fresh concrete. Secondly, ways are recommended how the rheology can be actively manipulated before eventually computerized methods are demonstrated that help to actively and rapidly assess and counteract performance scatter during steady casting processes.