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- F. A. Finger-Institut für Baustoffkunde (FIB) (6) (remove)
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- 2015 (6) (remove)
The aim of this study was to investigate the optimization of the strength development of quaternary cements with 50 % clinker by a variation of the particle size distribution of the components GGBFS, fly ash and limestone powder.
By balancing the overall PSD of the cement by using unprocessed fly ash and coarse limestone powder in combination with a very fine GGBFS, the water demand of the resulting quaternary cements remained unaltered, while the compressive strength of the cements was increased significantly after 7d, 28 and 56d. As can be expected, the quaternary cement with 30 wt.% of the fine slag exhibited a stronger strength increase (about 18 % after 28 d) than the cements with only 20 wt.% slag (about 10% after 28d).
In der vorliegenden Studie wurde der Einfluss der Klinkerzusammensetzung sowie der Sulfatträgerart auf die Leistungsfähigkeit eines Spritzzementes untersucht. Um eine Untersulfatisierung im System mit einen Aluminiumsulfat / -hydroxid Beschleuniger zu vermeiden, sollte ein anhydritbasierter Sulfatträger eingesetzt werden. Dies führt zu einer besseren Festigkeitsentwicklung im jungen Alter.
Gemäß dem Regelwerk für Betonstraßen muss für zweischichtige Betonfahrbahndecken derselbe Zement in Ober- und Unterbeton verwendet werden. Weiterhin ist die Anrechnung von Flugasche auf den w/z-Wert nicht gestattet. Durch eine flexiblere Handhabung der Bindemittel könnten sich Vorteile für die Betonbauweise ergeben. So könnte z.B. der stärker durch Frost beanspruchte Oberbeton mit CEM I hergestellt werden, während Zemente mit höheren Hüttensandgehalten nur im Unterbeton angewendet werden. Im Unterbeton könnten dann Gesteinskörnungen eingesetzt werden, die in einer herkömmlichen CEM I-Rezeptur als AKR-kritisch eingestuft würden.
Anhand von AKR-Performance-Prüfungen konnte die hohe Wirksamkeit hüttensandhaltiger Zemente sowie auch von Flugasche auf die AKR-Verminderung aufgezeigt werden. Schon mit einem CEM II/B-S wurden AKR-kritische Rezepturen in den unkritischen Bereich verschoben. Der Frost-Tausalz-Widerstand der Betone wurde bei hohen Gehalten an Hüttensand bzw. Hüttensand + Flugasche verringert, bewegte sich aber in jedem Fall noch im günstigen Bereich. Um eine Beeinträchtigung der baupraktischen Umsetzbarkeit zu vermeiden, sollte sich die Festigkeitsentwicklung von Ober- und Unterbeton im jungen Alter nicht zu stark unterscheiden. Modellberechnungen zur Festlegung einer Mindestfestigkeit für die frühe Belastung sind derzeit noch in Bearbeitung.
The main objective of this thesis is to investigate the characteristics of rice husk ash RHA) and then its behaviour in self-compacting high performance concrete (SCHPC) with respects to rheological properties, hydration and microstructure development and alkali silica reaction, in comparison with silica fume (SF). The main results show that the RHA is a macro-mesoporous amorphous siliceous material with a very high silica content comparable with SF. The pore size distribution is the most important parameter of RHA besides amorphous silica content. This parameter affects pore volume, specific surface area, and thus the water demand and the pozzolanic reactivity of RHA and its behaviour in SCHPC. The incorporation of RHA decreases filling and passing abilities, but significantly increases plastic viscosity and segregation resistance of SCHPC. Therefore, RHA can be used as a viscosity modifying admixture for SCHPC. The incorporation of RHA increases the superplasticizer adsorption, the superplasticizer saturation dosage, yield stress and plastic viscosity of mortar. Fresh mortar formulated from SCHPC is a shear-thickening material. The incorporation of RHA/SF ecreases the shearthickening degree. The incorporation of RHA/SF increases the degree of cement hydration. SF appears more effective at 3 days possibly due to the better nucleation site effect, whereas RHA dominates at the later ages possibly due to the internal water curing effect. The incorporation of RHA/SF increases the degree of C3S hydration, particularly the C3S hydration rate from 3 to 14 days. The pozzolanic reaction takes place outside and inside RHA particles.
The internal pozzolanic eaction products consolidate the pores inside RHA particles rather than contribute to the pore refinement in the cement matrix. In the presence of the high alkali concentration, RHA particles act as microreactive aggregates and react with alkali hydroxide to generate the expansive alkali silica reaction products. Increasing the particle size and temperature increases the alkali silica reactivity of RHA. The mechanism for the successive pozzolanic and alkali silica reactions of RHA is theorized. Additionally, a new simple
mix design method is proposed for SCHPC containing various supplementary cementitious materials, i.e. RHA, SF, fly ash and limestone powder.
Superplasticizers are utilized both to improve the fluidity during the placement and to reduce the water content of concretes. Both effects have also an impact on the properties of the hardened concrete. As a side effect the presence of superplasticizers affects the strength development of concretes that is strongly retarded. This may lead to an ecomomical drawback of the concrete manufacturing. The present work is aimed at gaining insights on the causes of the retarding effect of superplasticizers on the hydration of Portland cement. In order to simplify the complex interactions occurring during the hydration of Portland cement the majority of the work focuses on the interaction of superplasticizer and tricalcium silicate (Ca3SiO5 or C3S, the main compound of Portland cement clinker). The tests are performed in three main parts accompanied by methods as for example isothermal conduction calorimetry, electrical conductivity, Electron Microscopy, ICP-OES, TOC, as well as Analytical Ultracentrifugation.
In the first main part and based on the interaction of cations and anionic charges of polymers, the interactions between calcium ions and superplasticizers are investigated. As a main effect calcium ions are complexed by the functional groups of the polymers (carboxy, sulfonic). Calcium ions may be both dissolved in the aqueous phase and a constitute of particle interfaces. Besides these effects it is furthermore shown that superplasticizers induce the formation of nanoscaled particles which are dispersed in the aqueous phase (cluster formation). Analogous to recent findings in the field of biomineralization, it is reasonable to assume that these nanoparticles influence the crystal growth by their assembly process.
Based on the assumption that superplasticizers hinder either or both dissolution and precipitation and by that retard the cement hydration, the impact on separate reactions is investigated. On experiments that address the solubility of C-S-H phases and portlandite, it is shown that complexation of calcium ions in the aqueous phase by functional groups of polymers increases the solubility of portlandite. Contrary, in case of C-S-H solubility the complexation of calcium ions in solution leads to decrease of the calcium ion concentration in the aqueous phase. These effects are explained by differences in adsorption of polymers on C-S-H phases and portlandite. It is proposed that adsorption is stronger on C-S-H phases compared to portlandite due to the increased specific surface area of C-S-H phases. Following that, it is claimed that before polymers are able to adsorb on C-S-H phases the functional groups must be screened by calcium ions in the aqueous phase. It is further shown that data regarding the impact of superplasticizers on the unconstrained dissolution rate of C3S does not provide a clear relation to the overall retarding effect occurring during the hydration of C3S. Both increased and decreased dissolution rate with respect to the reference sample are detected. If the complexation capability of the superplasticizers is considered then also a reduced dissolution rate of C3S is determined. Despite the fact that the global hydration process is accelerated, the addition of calcite leads to a slower dissolution rate. Thus, a hindered unconstrained dissolution of C3S as possibly cause for the retarding effect still remains open for discussion. In the last section of this part, the pure crystallization of hydrate phases (C-S-H phases, portlandite) is fathomed. Results clearly show that superplasticizers prolong the induction time and modify the rate of crystal growth during pure crystallization in particular due to the complexation of ions in solution. But this effect is insufficient to account for the overall retarding effect. Further important factors are the blocking of crystal growth faces by adsorbed polymers and the dispersion of nanoscaled particles which hinders their agglomeration in order to build up crystals.
In the last main part of the work, the previously gathered results are utilized in order to investigate hydration kinetics. During hydration, dissolution and precipitation occur in parallel. Thereby, special attention is laid on the ion composition of the aqueous phase of C3S pastes and suspensions in order to determine the rate limiting step. All in all it is concluded that the retarding effect of superplasticizers on the hydration of tricalcium silicate is based on the retardation of crystallization of hydrate phases (C-S-H phases and portlandite). Thereby, the two effects complexation of calcium ions on surfaces and stabilization of nanoscaled particles are of major importance. These mechanisms may partly be compensated by template performance and increase in solubility by complexation of ions in solution. The decreased dissolution rate of C3S by the presence of superplasticizers during the in parallel occuring hydration process can only be assessed indirectly by means of the development of the ion concentrations in the aqueous phase (reaction path). Whether this observation is the cause or the consequence within the dissolution-precipitation process and therefore accounts for the retarding effect remains a topic for further investigations.
Besides these results it is shown that superplasticizers can be associated chemically with inhibitors because they reduce the frequency factor to end the induction period. Because the activation energy is widely unaffected it is shown that the basic reaction mechanism sustain. Furthermore, a method was developed which permits for the first time the determination of ion concentrations in the aqueous phase of C3S pastes in-situ. It is shown that during the C3S hydration the ion concentration in the aqueous phase is developed correspondingly to the heat release rate (calorimetry). The method permits the differentiation of the acceleration period in three stages. It is emphasized that crystallization of the product phases of C3S hydration, namely C-S-H phases and portlandite, are responsible for the end of the induction period.