Ingenieurwissenschaften und zugeordnete Tätigkeiten
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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 talk presents experimental results about the influence of delayed addition of PCEs on the Hydration of alite and C3A-gypsum pastes investigated by isothermal heat flow calorimetry. Complementary in-situ XRD was carried out on C3S and C3A-gypsum 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 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 flowability of cement paste is of great importance in today’s construction industry and is influenced by additives such as superplasticizers (SP). One type of SPs are polycarboxylate ether type SPs. These additives electrostatically bind with the negatively charged carboxylic groups at the backbone to the positively charged clinker phases.
To model positively charged clinker phases with adsorbed SP, silicon Wafers are pre-coated with cationic polyethylenimine (PEI) and SP is adsorbed onto the coated surface (Si/PEI/SP). Two different polycarboxylate ether type (PCE) SP are compared – one for ready-mix concrete and one for precast concrete. In this preliminary study the interaction forces between Si/PEI/SP surface and a silica microsphere (colloidal probe) are investigated under mild physico-chemical conditions (pH *6, ion concentration <10−5 M) using Colloidal Probe Atomic Force Microscopy (CP-AFM).
The interaction force between the model surfaces is attractive for low concentration of SP. The force changes from attractive to repulsive by increasing amount of SP. The force upon approach reveals a biexponential behavior. The exponential decay at large and short surface separations are attributed to electrostatic and steric interactions, respectively. The steric forces of the SP for ready-mix concrete show a steeper onset than the SP for precast concrete.
The quantification of these interaction forces will be compared to rheological measurements of similar systems. Furthermore, the parameters will be changed to better approach the conditions in real systems, i.e. higher pH and ionic strength. This helps to understand how the forces on the nanoscale influence the macroscopic rheology.
Properties of interstitial liquid phase in cement paste, including the species and concentrations of polymers and ion etc., play an important role for the rheological properties of cementitious materials. In order to better understand their effect, an inert model substance, spherical silica beads (SBs) with defined surface and granulometry were used in the presence of electrolytes (CaCl2) and/or different polymers, including polycarboxylate superplasticizer (PCE) and polyethylene glycol (PEG). It was found the presence of Ca2+ greatly increases the viscosity and yield stress of silica beads paste (SBP), which is proportional to the [Ca2+]. For the effect of PCE, the addition of PCE is beneficial to the flowability of SBP, but a high dosage of PCE leads to a reversal effect. Furthermore, the yield stress firstly increases and then decreases with increasing [Ca2+] under the same dosage of PCE. The addition of PEG always increases the yield stress of SBP, regardless of the ion concentration and the presence or not of PCE.
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).
Additive manufacturing of alkali-activated materials currently attracts a lot of attention, because of the possibility to produce customized high-performance elements for a range of applications, potentially being more resource-efficient than conventionally produced parts. Here, we describe a new additive manufacturing process for alkali-activated materials that is based on selective laser-heating of lithium aluminate/microsilica slurries. The new process-material combination allows to manufacture elements with complex geometries at high building rates and high accuracy. The process is versatile and transferrable to structures of sizes differing by orders of magnitude. The mechanical strength of the obtained materials was in the range of values reported for conventional metakaolin-based geopolymers, and superior to what has been hitherto reported for alkali-activated materials produced by additive manufacturing. This mechanical performance was obtained despite the fact that the degree of reaction of the lithium aluminate and the microsilica was low, suggesting that significant reactions took place only at the surface of the microsilica particles.
Viscosity-modifying agent (VMA) are used in several applications of concrete, such as underwater concrete, Self-Compacting Concrete (SCC) or Self-Levelling Underlayments (SLU) in order to improve the washout resistance and the stability. The study focuses on the modifications of cement pastes properties implied when a VMA (hydroxypropyl guars or HPG) and a superplasticizer are introduced together. For reaching this objective, two chemically different polycarboxylate-based superplasticizers (PCE) and two HPGs exhibiting different molar substitution ratios (MSHP), were studied. A method, combining total organic carbon and size exclusion chromatography, was developed in order to quantify the adsorption of the both admixtures. The adsorption of HPGs appears being significantly lowered by the presence of PCE, while only the adsorption of the less charged PCE is slightly affected by the HPG. As consequence, strong modifications of the rheological properties of cement pastes were noticed when HPG and PCE are combined. The desorption of HPG leads to higher yield stress and residual viscosity than with PCE alone.
In Deutschland fallen jährlich 20 Millionen Tonnen Altpapier an. 75 % davon werden dem Recyclingprozess zugeführt. Dabei bleiben Prozessrückstände wie Deinkingschlämme, Sortierrückstände und Faserreststoffe übrig. Zusammengefasst als Papierschlamm verwerten die Recycler diesen Reststoff thermisch in dezentralen Heizkraftwerken. Die dabei anfallende Papierasche hat mit den Anteilen der Hauptoxide von 59 M.-% CaO, 22 M.-% SiO2 und 13 M.-% Al2O3 eine ähnliche chemische Zusammensetzung wie Portlandzement, wobei sich die Mineralphasen unterscheiden. Durch eine Aktivierung der Papierasche können jedoch hydraulisch aktive Phasen wie Mayenit (C7A12) und Belit (C2S) erzeugt werden. Die Mineralphase Mayenit reagiert schnell mit Wasser zu Calciumaluminathydraten, wodurch der Bindemittelleim schnell ansteift. Die festigkeitsbildenden Calciumsilicathydrate (CSH) in Bindemittelleimen entstehen bei einer späteren Reaktion von Belit mit Wasser.
Zur Aktivierung dient eine hydrothermale Calcinierung. Dabei wird Papierasche mit einer Aktivatorlösung (Wasser oder KOH) gemischt und bei 200 °C hydrothermal behandelt, wobei sich Hydratphasen ausbilden. Diese Zwischenprodukte dehydratisieren durch eine anschließende Calcinierung zu reaktiven Calciumsilicaten und Calciumaluminaten. Wie sich die Parameter des Aktivierungsprozesses auf die Mineralphasen auswirken, war Fokus der Untersuchungen. Mit thermogravimetrischen Analysen der Zwischenprodukte konnten die Reaktionsprodukte nach dem hydrothermalen Prozessschritt bestimmt werden. Den größten Einfluss auf den Mineralphasenbestand hat hierbei die Alkalität der Aktivatorlösung. Im zweiten Prozessschritt, der Calcinierung, ist die Temperatur der wesentliche Faktor für die Ausbildung reaktiver Phasen. Die Ergebnisse kalorimetrischer Untersuchungen an Leimen aus den calcinierten Proben dienten der Auswahl der optimalen Calcinierungstemperatur. Die gesamte Reaktionswärme war für die Proben, welche bei einer Calcinierungstemperatur zwischen 700-800 °C hergestellt wurden, am höchsten.
A thorough characterization of starting materials is the precondition for further research, especially for cement, which contains various phases and presents quite a complex material for fundamental scientific investigation. In the paper at hand, the characterization data of the reference cement CEM I 42.5 R used within the priority program 2005 of the German Research Foundation (DFG SPP 2005) are presented from the aspects of chemical and mineralogical compositions as well as physical and chemical properties. The data were collected based on tests conducted by nine research groups involved in this cooperative program. For all data received, the mean values and the corresponding errors were calculated. The results shall be used for the ongoing research within the priority program.
Tuff ist in vielen historischen Objekten in Deutschland verbaut, hat aber wegen seiner Porosität und hygrischen Eigenschaften eine schlechte Verwitterungsresistenz. Ziel des Vorhabens ist die Entwicklung eines gesteinsmehlmodifizierten Schutzsystems auf Kieselsäurebasis (GEMOSK) zur Konservierung verbauter Tuffe. Für die Schutzmittelherstellung wird eine geeignete Mischung aus Kieselsol und feinen Gesteinsmehlen aus Steinbruchrückständen und Tuffabfällen verwendet. Bei erfolgreichem Abschluss des Projektes kann GEMOSK im Denkmalpflegebereich eingesetzt werden. Dadurch werden die Bausubstanz besser erhalten, Tuffsteinressourcen eingespart und Tuffabfälle wiederverwertet.