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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.
Polysaccharides modify the rheological properties of cement based systems. Depending upon their chemistry, molecular architecture, and adsorption tendency, they have different modes of action. Some polysaccharides like diutan gum have strong effect on the fluid phase; others like starch strongly interact with particles. This paper presents effects of diutan gum and starches in presence of polycarboxylates. Rheometric investigations with varied particle volume fractions and increasing coarse aggregate diameters were conducted. The results show that starches have stronger influence on the rheology at high particle volume fractions than diutan gum. At lower particle volume fractions this trend is inverted. Experiments with aggregates sizes up to 16 mm (0.63 in.) indicate that stabilizing agent influences on the effects of aggregates on yield stress were small; however up to 1.0 mm (0.04 in.), a significant effect on the plastic viscosity could be observed, which levelled off at larger diameters.
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.
After a brief introduction into past and modern concrete, the relevance of sustainable concrete technologies is emphasised from a global perspective. In order to minimise the environmental impact of cement and concrete in the world, solutions for alternative binder materials as well as rheology and performance modifying additives are presented based on local bio-based resources.
However, the perception of bio-based constituents is typically rather negative in construction materials and its application is often limited to low-end construction. In order to show that this is not inevitable, the lecture ends with a number of case studies for the use of bio-based materials for high performance concrete applications.
Today, concrete engineers can vary consistencies between very stiff and self-compacting. The possibility to tailor rheological properties of concrete eventually opened up the path to multiple new technologies, where design criteria are no longer limited to the Young’s modulus and the compressive strength, but often comprise additional added value. It can therefore be concluded that the capability to control the rheology of concrete systems can be considered as the catalyst for concrete innovations such as polymer modified cementitious composites (PCC) self-compacting concrete (SCC), high-performance concrete (HPC), ultra-high performance concrete (UHPC) or strain hardening cement based composites (SHCC). In the same way rheology modifying admixtures will become key parameters in mastering the challenges of the next decades such as:
- Additive manufacturing/3D-printing
- Overcoming pumping height limitations
- Casting at extreme temperatures
- Tailored rheology at delivery
In many regions in the Southern hemisphere, and particularly in Africa, the effective use of chemical admixtures for concrete could significantly contribute to solve problems induced by the challenging climatic conditions, but particularly in Africa it is difficult to use them, due to lacking local supply and supply infrastructure. For Africa, concrete admixtures are largely shipped or transported from Europe, the Arabian Peninsula, or Asia. The long distance transportation of chemicals is not very environmentally friendly and the economic consequences are dramatic: the agents are difficult to purchase, expensive, and there is not a large variety of products available in the market.
However, bio-based chemicals have been used in construction for ages effectively. Due to the enormous relevance of rheology modifying admixtures it is worthwhile to recollect that nature provides an enormous variety of chemicals that can be used readily or with low processing. Today, the use of petrol based polycarboxylate ether superplasticizers has become quite common in concrete technology due to their versatility, but their uncomplicated and cost efficient availability is limited in most countries in Africa. However, alternatives are available, which can be found in many regions.
Plant extracts have been used to modify the properties of concrete for long time. These plants are typically regionally abundantly available, cheap, and they are environmental friendly. They do not require special caring for seedlings, weeding or manuring to grow since they grow wildly.
The talk will present an overview of various options for rheology modifying admixtures, that can be found in nature, and that may become a real alternative, once their interaction within the complex cementitious system is well understood.
Development and characterization of starch film and the incorporation of silver nanoparticles
(2020)
Starch is one of the biopolymers being used for bioplastic synthesis. For production, starch can be combined with different plasticizers, starches from different plant sources and even with nanomaterials to improve or to add film properties. The challenge of adding these, e.g. in the form of silver nanoparticles (AgNp) is to determine the concentration so as to avoid impairing the properties of the film, agglomeration or altering the visual characteristics of the film. In this study, a starch film synthesis route and the incorporation of silver nanoparticles has been proposed in order not to alter the properties of the film while maintaining the transparency and a clear colour of the starch film. The results showed that the proposed synthesis route is promising, efficient, reproducible, fast and the film has good mechanical properties.
The use of coconut fiber (CF) agricultural waste was considered as an environmentally friendly and inexpensive alternative in flame retarded biocomposites. To decrease the high content of aluminum trihydrate (ATH) required, the thermal decomposition (thermogravimetry), flammability [oxygen index (LOI) and UL 94 test] and fire behavior (cone calorimeter) of a combination of CF and ATH were investigated in a commercial blend of thermoplastic starch (TPS) and cellulose derivatives. CF induced some charring activity, slightly decreasing the fire load and burning propensity in cone calorimeter test. ATH decomposes endothermically into water and inorganic residue. Significant fuel dilution as well as a pronounced residual protection layer reduces the fire hazards. Replacing a part of ATH with coconut fibers resulted in improved flame retardancy in terms of ignition, reaction to small flame, and flame-spread characteristics [heat release rate (HRR), fire growth rate (FIGRA), etc.]. The observed ATH and CF synergy opens the door to significant reduction of the ATH contents and thus to interesting flame retarded biocomposites.
Development and characterization of starch film and the incorporation of silver nanoparticles
(2020)
Starch is one of the biopolymers being used for bioplastic synthesis. For production, starch can be combined with different plasticizers, starches from different plant sources and even with nanomaterials to improve or to add film properties. The challenge of adding these, e.g. in the form of silver nanoparticles (AgNp) is to determine the concentration so as to avoid impairing the properties of the film, agglomeration or altering the visual characteristics of the film. In this study, a starch film synthesis route and the incorporation of silver nanoparticles has been proposed in order not to alter the properties of the film while maintaining the transparency and a clear colour of the starch film. The results showed that the proposed synthesis route is promising, efficient, reproducible, fast and the film has good mechanical properties.
The aim of this work was the synthesis of starch macroinitiators for cationic polymer grafted starches that: (i) are free of cationic homopolymer, and (ii) display a high degree of conversion of the cationic monomer. We show that this can be achieved by a free-radical polymerization reaction using the cationic monomer N-methacryloyloxyethyl-N,N-dimethyl-N-benzylammonium chloride (MADAM-BQ) and a new starch-based macroazoinitiator. For this purpose, the acid chloride of 4-tert-butylazo-4-cyanovaleric acid was synthesized and bound covalently to starch (predominantly in the C6 position) to form a nonsymmetrically substituted macroinitiator that was used to polymerize MADAM-BQ in aqueous media. Essentially no MADAM-BQ homopolymer was formed. The initiator decomposes thermally to starch radicals of high reactivity and low-molar mass radicals that do not initiate polymerization. The reason for the different reactivities of the radicals is presumably due to the nonsymmetric constitution of the starch-bound azo groups. The graft polymerization of MADAM-BQ in aqueous solution performs according to an ideal overall kinetic. The structure of the synthesized starch-graft-poly(MADAM-BQ) products is similar to that of block copolymers because of the low radical efficiency of the starch initiators in aqueous solution. Especially, starch substrates with a higher content of azo groups did not lead to graft products with shorter graft distances because the state of solution of these macroinitiators becomes worse and aggregation occurs with an increasing degree of substitution.
The use of starch and its derivatives in concrete as an admixture to modify relevant properties of concrete is on the increase in recent times. It is known to modify the rheology, to affect the hydration kinetics of cement, and influence on initial and final setting time of cement. This paper examines the effect of cassava starch on concrete. shrinkage properties of concrete, with and without starch addition, were studied. Various percentages (0, 0.5, 1.0, 1.5 and 2 %) of starches by weight of cement were added to concrete mixes prepared in the laboratory. Shrinkage tests were conducted for duration of up to one year. The result show that concretes with starch additions exhibit lower shrinkage, which is an indication the addition of starch as admixture in concrete improves the ability of the concrete reduce shrinkage problems.