Analytische Chemie
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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.
NMR is becoming increasingly popular for the investigation of building materials as it is a non-invasive technology that does not require any sample preparation nor causes damage to the material. Depending on the specific application it can offer insights into properties like porosity and spatial saturation degree as well as pore structure. Moreover it enables the determination of moisture transport properties and the (re-)distribution of internal moisture into different reservoirs or chemical phases upon damage and curing. However, as yet most investigations were carried out using devices originally either designed for geophysical applications or the analysis of rather homogeneous small scale (< 10 mL) samples. This paper describes the capabilities of an NMR tomograph, which has been specifically optimized for the investigation of larger, heterogeneous building material samples (diameters of up to 72 mm, length of up to 700 mm) with a high flexibility due to interchangeable coils allowing for a high SNR and short echo times (50 - 80 m s).
Control chart systems are used in quality management systems to keep production processes stable. In concrete production they are often applied for the control of the compressive strength. The most efficient control chart systems are cumulated sums (cusum), which help to observe deviations from a targeted value. Unlike alternative observation chart systems that focus on process data evaluation, cusum observations react very rapidly on systematic process changes in processes. Therefore, the cusum method is particularly suitable if immediate counteractions have to be taken, like in the case of fresh concrete properties of self-compacting concrete (SCC), which can have severe influences on the durability and mechanical strength of concrete. The rheology of SCC can be affected by an enormous variety of influencing factors, from raw material properties to handling or environmental temperature. The present study shows that regardless of the material based influencing parameter for a rheology change, a steady slump flow can be achieved only by adding supplementary superplasticizer in case of loss of flow and adding stabilising agent (ST) in case of increased flow if the respective V-mask indicates a systematic change. A reference SCC was artificially manipulated in order to achieve realistic experimental data for flowability and flowability changes due to changes in the raw material properties. The results point out that productions with applied cusum methods were capable of keeping the target slump flow deviation within approximately 1% only, while productions without applied cusum method deviated up to 14% and more from the target.
Structural design and application have always been linked to the compressive strength of concrete as the main relevant criterion. This was justifiable in the past, where concrete consisted of water, ordinary Portland cement and aggregates, but this concept is no longer relevant for modern and more sustainable cement and concrete.
Despite these new developments, existing standards, guidelines and academic curricula have not been much updated and are still used worldwide. There is a need to change this situation by proper education of the users.
This overview describes the challenges that arise at a user Level from the higher complexity of modern concrete, and defines needs and requirements for enhanced applicability of sustainable concrete concepts.
Furthermore, recommendations are given on how better concrete practice can be communicated to all the involved parties, from civil and design engineers to constructors and site-appliers on the construction site.
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.
Most factors acting on concrete rheology work at an extremely small-scale level. Influencing factors in the millimetre or centimetre area are essentially restricted to sand and aggregates. The latter, however, make up 50 to 70% of the total volume of most concretes – a fact often ignored in research on controlling concrete processing properties.
Whereas suitably chosen concrete admixtures and additives can influence rheology in a very targeted manner, sand and aggregates are less suitable for controlling rheology but nonetheless contribute to the rheology of the Overall system. The actions of sand and aggregate can impose themselves upon the actions of admixtures and additives
and, in unfavourable circumstances, even render them redundant. For this reason, any results concerning the processability of binding agent systems can only be transferred to concrete with great care. It is important to better understand the action of sand and aggregates in order to be able to harmonise them in such a way that they complement the action of superplasticisers positively, instead of
working against them. Savings on costs can also be made by this targeted fine-tuning.
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 such as self-compacting concrete. Today, admixture addition has become common practice in concrete technology, but the understanding of their highly complex mode of operation is extremely difficult and demands for understanding of processes within the range between nanometres and centimetres. 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. Methods are discussed that appear promising interdisciplinary tools for enhancement of the understanding of the relevant interactions that are responsible for the macroscopic flow of flowable concrete.