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The thermal gravimetric analysis (TG) is a common method for the examination of the carbonation progress of cement-based materials. Unfortunately, the thermal properties of some components complicate the evaluation of TG results. Various hydrate phases, like ettringite (AFt), C-S-H and AFm decompose almost simultaneously in the temperature range up to 200 °C. Additionally, physical bound water is released in the same temperature range. In the temperature range between 450 °C and 600 °C the decomposition of calcium hydroxide and amorphous or weakly bound carbonates takes place simultaneously. Carbonates, like calcite, from limestone powder or other additives may be already contained in the noncarbonated sample material. For this research an attempt was made to minimise the influence of these effects. Therefore, differential curves from DTG-results of non-carbonated areas and areas with various states of carbonation of the same sample material were calculated and evaluated. Concretes based on three different types of cement were produced and stored under accelerated carbonation conditions (1 % CO2 in air). The required sample material was obtained by cutting slices from various depth of previously CO2-treated specimen and subsequent grinding. During the sample preparation, a special attention was paid that no additional carbonation processes took place. As reference method for the determination of the carbonation depth the sprayed application of phenolphthalein solution was carried out. Microscopic analysis where examined to confirm the assumptions made previously. Furthermore, the observed effect of encapsulation of calcium hydroxide by carbonates caused by the accelerated carbonation conditions was examined more closely.
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.
Innovative admixture technology has significantly widened up the ränge of possibilities of concrete engineers. For many decades the water to cement ratio (w/c) was the major influencing factor for the performance of concrete. Due to the need to adjust a consistency, which still allowed reasonable workability, the w/c was typically significantly higher than technologically reasonable. Rheology modifying admixtures Support adjusting the concrete consistency largely independent of the w/c. It was only after the invention of the first superplasticizers that modern concrete technology significantly evolved in terms of flowability, strength, and durability, and only due to the steady evolution of the technology modern innovations, such as Self-Compacting Concrete, Ultra-High-Performance Concrete, or Engineered Cementitious Composites were made possible. Today’s superplasticizers are extremely versatile and can be adjusted to individual technologicalspecifications. However, the other side of the coin of versatility is that cementitious Systems incorporating superplasticizers have become more sensitive against environmental influences, such as the environmental temperature, which may cause unwanted effects or demand for supplementary admixture use such as stabilizing admixtures. Hence, concrete mixture composition with admixtures demands for a high level of expertise and offen there is lack of awareness about the mode of Operation of rheology modifying admixtures among concrete technologists. The paper gives a comprehensive overview about rheology modifying admixtures such as superplasticizers or stabilizing agents, and how they can be used depending upon the application in the most favourable way. Based on experiences with the sub-Saharan African concreting boundary conditions, which exhibit many challenges in terms of environmental boundary conditions and construction site logistics, conclusions are finally drawn, how admixtures can be used in the most beneficial way to improve the concrete casting Situation.
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.
The most common method for determination of the carbonation depth is the sprayed application of indicator solutions, Phenolphthalein in particular. Since the aerosols of Phenolphthalein are suspected to be carcinogenic, efforts have been intensified to use alternative indicators for the determination of carbonation depth. The subject and aim of this research paper are to examine indicator solutions from Alizarin Yellow R, Thymol Blue and a Mixed Indicator. These indicator solutions are commercially available and are not suspected to be carcinogenic.
For the purpose of this research, samples previously stored under accelerated carbonation conditions (1% CO2) were examined by thermogravimetric analysis (TGA) and examination of the pH value. Additionally, the electrolytic back-titration for determination of total CO2 amount was carried out comparatively to TGA.
Polysaccharides are important rheology modifying admixtures in the building material sector.
The use of starch is becoming increasingly important, due to many ecological and economic advantages. In the construction sector, starch ethers are being used as thickeners and as means to increase the yield stress. The starch ethers that are available on the market differ in
their behaviour, which can vary greatly depending upon the binder system and mortar composition, e.g. solid volume content, binder type, additional admixtures. In view of the limited knowledge about the influence of molecular modifications associated with cement based systems, some fundamental rheological functional mechanisms were analysed in this study. The differently modified starch ethers used were derived from potatoes. They varied in their charges and degrees of hydroxypropylation. The setting and the flow behaviour of all examined variations
of starch ethers were analysed in cement pastes. In order to illustrate the effects of the starch ethers that were used, the water-cement ratio (w/c) was held constant in all the mixtures [Schmidt 2012]. The results indicated significant differences in setting and flow behaviour.
Alkali-activated materials such as geopolymers are currently receiving a lot of attention because of their potential to be used as binders for concrete with advantageous engineering properties and reduced manufacturing CO2 emissions. Knowledge of the durability of steel in these concretes and related properties of alkali-activated materials is a prerequisite for their application as building materials, if they are to be used for steel reinforced elements. However, to date only limited data exists on this topic. The present contribution focuses on durability-related transport properties of geopolymer-based mortars (as model systems for concrete). We report results of accelerated carbonation, rapid chloride migration (RCM) and air permeability measurements as well as porosity data for fly ash-based geopolymer mortars, including mixes containing ground granulated blast furnace slag (GGBFS). In addition, we report polarization resistance data and corrosion potential vs. time curves for carbon steel bars embedded in two of the fly ash-based geopolymer mortars and a CEM I-based mortar (as reference).
Despite comparable total porosities, the carbonation depths, the chloride migration coefficients and the air permeabilities of the mortars differed significantly. In general, the addition of GGBFS to the binders improved the performance (decreased transport coefficients); however, this was not found to be true for the air permeability in all cases. This latter effect can be explained by drying damage of the C-(A-)S-H gel in GGBFS-containing binders. On the other hand, low transport coefficients can also be achieved by optimization of the binder formulation without the addition of GGBFS, which is also reflected in the material’s air permeability. Thus, there exists no simple correlation between air permeability (of harshly dried mortars) and durability-related transport coefficients for the studied alkali-activated materials.
The corrosion potential vs. time curves in combination with polarization resistance values reveal that the steel reinforcement in geopolymer mortars assumed a passive state. However, this happened considerably later than for steel in CEM I-based mortars. The free corrosion potential of carbon steel reinforcement in the geopolymer mortars had different values than the free corrosion potential values for the CEM I-based mortar for both the active and the passive state; possible reasons for this behavior are discussed.
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.