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- Rheology (10)
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- Adsorption (2)
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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.
Since its invention in the early 1990’s, self-consolidating concrete has never become well established in the ready-mix sectors worldwide. The reason for this can be mainly found in the fact that the sophisticated compositions are sensitive against changing environments. This lack of robustness can be attributed to the interaction between cement hydration reaction and high range water reducing agent (HRWRA). Understanding the relevant mechanisms that control the initial flow performance as well as the flow retention helps optimizing SCC mixtures that perform either steadily in one specific environment or that perform largely similarly at steadily changing environments.
This paper depicts how HRWRAs interact with clinker and hydration phases and discusses the important role of the charge density of a polycarboxylic HRWRA in the way the rheology is affected. Based on rheometric results and observations of the Vicat setting times, it is shown that increasing charge densities of the HRWRA and decreasing water to powder ratios (w/p) reduce the flow retention and have lesser retarding effect on the setting. Based on the discussion, optimization procedures for the mixture composition and the HRWRA modification are suggested to achieve optimized performance for varying environmental situations or highest robustness for specific conditions.
Today polycarboxylate ether based superplasticizer (PCE) is commonly used in concrete technology when high flow properties and water reduction are specified. The ionic strength of the polymers’ backbones determines the adsorption behaviour of polymers on clinker and early hydration products. The amount of required polymers for specified flow properties and the performance over the time of casting is thus determined by the molecular structure of the superplasticizer. The time depending consumption of polycarboxylate ether polymers strongly affects the reaction of aluminates and sulphate ions as well as the hydration process in general. Hence, the choice of polymers for particular flow properties greatly affects the very early properties of cementitious materials such as setting, heat evolution and autogenous deformations.
In order to better understand how PCEs influence the early properties, mixes from cement, limestone filler, viscosity modifying agent and water were varied with a high and a low charge density superplasticizer in differing amounts. Results are presented from measurements with an automatic Vicat device, an isothermal heat flow calorimeter, and shrinkage cones. Tests were conducted at 5, 20, and 30 °C.
It is shown that in presence of PCE the final set correlates well with the inflexion point of the heat flow curve, which emphasises the interrelation between C-S-H formation and setting. No such clear correlation can be found for the initial set, which is attributed to the fact that the initial set is rather a rheological than a structural phenomenon, so that other effects overlap with C-S-H formation. The results demonstrate that for a given polymer concentration low charge density polymers yield earlier setting than high charge polymers. However, this influence is overridden by the influence of the total amount of polymers in a cementitious system. Since PCE is typically added according to rheological specifications, and low charge PCE typically requires higher amounts of polymers than high charge PCE for comparable flow performance, low charge PCE retards setting more than high charge PCE.
The paper furthermore points out that there is no significant influence of the polymer type or amount on the early deformations. Since type and amount strongly affect the hydration, it is demonstrated that early setting causes higher strain after the final set. It is hence concluded that higher PCE solid contents reduce the risk of early cracks that occur at time of setting, when a solid structure has already been formed but without resistance against cracks yet.
To design robust self-consolidating concrete (SCC) for various environmental conditions, it is essential to understand the relevant mechanisms that control the flow performance. This paper depicts how high range water reducing agents (HRWRAs) interact with clinker and hydration phases, and it discusses the important role of the charge density of polycarboxylic HRWRAs in the way the rheology is affected. Based on the rheometric investigations on SCC mixture compositions with different water to powder ratios (w/p) and observations of their pastes' Vicat setting times, the study shows that increasing charge densities of the HRWRA and decreasing w/p reduce the flow retention and have lesser retarding effect on the setting. Based on the test results and discussions optimization procedures for the mixture composition and the HRWRA modification are suggested to achieve optimized performance for varying environmental situations and highest robustness for specific conditions.
Stabilising admixtures are commonly used additives in repair mortars and grouts. Beyond this, such type of admixture is increasingly used in concrete and other cementitious materials. In particular when fresh mortar or concrete properties have to be adjusted reliably, stabilising agents can be beneficially used to improve workability and robustness of the mixture. The mode of operation of these admixtures varies, rather affecting either the liquid phase or the solid particles in the dispersion, both causing strong interactions with the mortar or concrete system, and significant changes in their rheological behaviour. Furthermore, these are strongly affected by the environmental temperature during the casting process. In the paper the effect of temperature on the performance of stabilising agents in cementitious systems is presented and how performance changes affect fresh and hardening mortar or concrete properties. Particular attention is placed on interactions between stabilising agents and superplasticizers. Results are discussed with special focus on self-compacting concrete.
The fresh behaviour of self-compacting concrete (SCC) at varying temperatures differs from that of normal vibrated concrete. This is because the rheology of SCC depends not only on degree of cement hydration, but also on the adsorption of superplasticizers – mostly polycarboxylate based polymers (PCE) -, which is affected by the time and hydration progress. Due to the variety of PCEs and mixture compositions for SCC a prediction of the rheology at varying temperatures is complicated. The charge densities of PCEs as well as the water to solid ratio in the paste are identified to be the main decisive parameters for robust fresh concrete properties.
Rheometric concrete investigations with different SCC mixture compositions and varied anionic charge densities of the PCE were conducted. SCC which is rich in powder components showed robust performance at low temperatures while SCC with low powder content was favourable at high temperatures. High charge density PCE pointed out to be very robust at low temperatures but at high temperatures it significantly reduced the flow retention. Low charge density PCE could not generate self-compacting properties at low temperatures but retained the flow performance over sufficiently long time. Based on considerations about particle interactions and adsorption mechanisms of PCEs, the relevant processes are explained and options for the development of robust mixture compositions for individual temperature ranges are itemised.
ln order to observe the influence of stabilising agents (STA) based on starch and diutan gum, rheometric experiments and setting tests were conducted on cement pastes with and without PCE superpiasticizers. The results show that with regard to yield stress both STAs show differing behaviours in Systems without PCE. In presence of PCE, yield stress infiuences of the STAs retreat into the background. The Vicat results exhibit that STAs can reduce the retard ing effect of PCE.
Polysaccharides are incorporated into cement based Systems in order to modify the rheological properties. Typically, cellulose ethers, sphingan gums, guar gum or starch ethers are applied. Depending upon their chemistry, molecular architecture, and adsorption tendency, polysaccharides interact differently with the entire cementitious system. Some stabilising agents like diutan gum mainly affect the cementitious paste; other stabilising agents like starch tend to interact with the sand fraction and even with the coarse aggregates. Cellulose and guar gum shows more diverse performances.
Typically stabilising admixtures like polysaccharides are used, when sophisticated rheological properties are adjusted. Therefore, polysaccharides are often used in combination with superplasticisers, which are added to reduce the yield stress of concrete. This can cause interactions, particularly when the stabilising Agent shows a strong tendency to adsorb on particle surfaces. Adsorptive stabilising agents may reduce the amount of adsorbed superplasticisers, thus affecting both viscosity and yield stress, while non-adsorptive stabilising agents mainly affect the plastic viscosity independently of the superplasticiser. Due to the strong influence of superplasticisers on the yield stress, influences of the stabilising agent on the yield stress retreat into the background, so that their major effect is an increase of the plastic viscosity.
The paper provides a comprehensive overview of how different polysaccharide superplasticisers affect cementitious flowable systems and points out the challenges of the combined use of polysaccharides and superplasticisers. Based on rheometric experiments and observations of the hydration process, time dependent effects on the workability as well as of the hydration of cement are presented and discussed.
Selbstverdichtender Beton verhält sich unter Temperatureinfluss anders als Normalbeton, da die Rheologie neben der fortschreitenden Hydratation zusätzlich durch die von der Zeit und dem Hydratationsfortschritt abhängige Adsorption von Fließmitteln beeinflusst wird. Anhand rheometrischer Betonversuche an SVB unterschiedlicher Entwurfskonzepte mit variierter anionischer Ladungsdichte im Fließmittel wird verdeutlicht, dass mehlkornreiche SVB bei niedrigen Temperaturen sehr robust sind, während bei hohen Temperaturen mehlkornärmere Entwürfe zu bevorzugen sind. Darüber hinaus wird gezeigt, wie sich unterschiedliche Fließmittelmodifikationen in bestimmten Temperaturbereichen verhalten. Anhand des Wasser-Feststoff-Verhältnisses und des Adsorptionsverhaltens von Fließmitteln werden die maßgeblichen Prozesse erläutert und Möglichkeiten für die Entwicklung robuster Mischungen für individuelle Temperaturbereiche aufgeführt.--------------------------------------------------------------------------------------------------------------------------------------------------------------
Regarding the temperature dependent performance, self-compacting concrete (SCC) distinguishes from normal concrete, since its rheology does not only depend upon the hydration itself but supplementary upon the adsorption of superplasticizers, which is affected by the time and the hydration progress. Based on rheometric concrete investigations with different SCC mixture compositions and varied anionic charge densities of the superplasticizers, it is shown that SCC, which is rich in powder components, shows robust performance at low temperatures, while compositions with lower powder contents are favourable at high temperatures. Furthermore, the performance of different superplasticizer modifications at different temperature ranges is demonstrated. The relevant processes are explained by means of the water to powder ratio as well as the adsorption behaviour of superplasticizers, and options for the development of robust mixture compositions for individual temperature ranges are itemised.