Ingenieurwissenschaften und zugeordnete Tätigkeiten
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- 2022 (23) (entfernen)
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- Corrosion (2)
- Earth block masonry (2)
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Viscosity modifying agents: Key components of advanced cement-based materials with adapted rheology
(2022)
Viscosity modifying agents (VMAs) are essential ingredients for the production of flowable cement-based materials. This paper presents an overview of commonly used VMAs and attempts to shed some light on the underlying physics at the origin of their mechanisms of action. The main molecular parameters of VMA controlling the rheological properties of the cement pore solution are highlighted. As the mechanisms of action of VMAs in cement-based materials are closely related to their affinity with the surface of cement particles, the adsorption of the main VMA types is discussed. The effect of VMAs on flow properties and stability of cement-based materials is presented for VMAs added without any superplasticizer, and then in systems incorporating both VMAs and superplasticizers. Finally, the effect of VMAs in enhancing concrete properties to secure adequate performance of different construction applications, and perspectives for future developments of novel cement-based materials made with VMAs are showcased.
The current paper develops a novel accelerated corrosion test method based on Faraday’s law to investigate the performance of different inhibitors in reinforced concrete elements under electrical voltage. Using the proposed method two commercially available and three lab-made inhibitors were tested. Lab-made inhibitors based on potassium fluorosilicate and amine carboxylate showed the best performance over others. Furthermore, it is found that under an electrical potential environment beyond 3.6 V, the higher the concrete strength, the more efficient is the corrosion inhibition. Based on experimental results, a novel model describing the corrosion evolution in reinforced concrete was proposed.
The structural build-up of fresh cement paste is often considered as a purely thixotropic phenomenon in literature even though cementitious materials undergo a non-reversible hydration process that can have an influence on the structuration process. In the current paper a method is proposed to validate the impact of the non-reversible structural build-up. It is shown that fresh cement paste samples lose their structural gain almost completely due to thixotropy while the structural build-up due to hydration can be observed but occurs in a significantly lower order of magnitude over the course of the first hours of hydration. In addition, it is shown, that the chemical component of the structural build-up accelerates with the onset of the acceleration period of hydration, while its contribution in the entire structural build-up remains constant.
The retardation mechanism of cement hydration as imparted by the addition of polyphosphate comb superplasticizer to model cement containing C3S, C3A and calcium sulfate hemihydrate is studied using XRD, ss NMR and calorimetry. Our findings show the retardation effect caused by the direct addition of polyphosphate comb superplasticizer differs significantly to that of conventional polycarboxylate superplasticizers. Conversely to polycarboxylates, polyphosphates, at a low dosage, inhibits the silicate reaction without affecting the aluminate reaction and formation of ettringite. Yet, at high doses, both reactions are hampered, and the induction period extended, followed by accelerated aluminate and silicate reactions.
The corrosivity of atmospheres in Europe has changed significantly in recent decades. For the Federal Republic of Germany, no current values for the corrosion rate based on 1‐year atmospheric exposure of standard specimens can be found in the scientific literature after 2000. This paper presents results from a field exposure study in the Berlin metropolitan area and Helgoland in 2016. Based on standard specimens, values for the corrosion rate and the corresponding atmospheric corrosivity category are determined for open exposure and indirect weathering in a ventilated enclosure as sheltering after 1 year of exposure. The results prove that determined corrosivity categories are material‐specific. Sheltered exposure is a typical atmospheric situation for many building components. It allows statements on the effect of the concentration of airborne substances on the corrosivity beyond the normative requirements.
Investigation of the Thermal Stability of Proteinase K for the Melt Processing of Poly(L‑lactide)
(2022)
The enzymatic degradation of aliphatic polyesters offers unique opportunities for various use cases in materials science. Although evidently desirable, the implementation of enzymes in technical applications of polyesters is generally challenging due to the thermal lability of enzymes. To prospectively overcome this intrinsic limitation, we here explored the thermal stability of proteinase K at conditions applicable for polymer melt processing, given that this hydrolytic enzyme is well established for its ability to degrade poly(L-lactide) (PLLA). Using assorted spectroscopic methods and enzymatic assays, we investigated the effects of high temperatures on the structure and specific activity of proteinase K. Whereas in solution, irreversible unfolding occurred at temperatures above 75−80 °C, in the dry, bulk state, proteinase K withstood prolonged incubation at elevated temperatures. Unexpectedly little activity loss occurred during incubation at up to 130 °C, and intermediate levels of catalytic activity were preserved at up to 150 °C. The resistance of bulk proteinase K to thermal treatment was slightly enhanced by absorption into polyacrylamide (PAM) particles. Under these conditions, after 5 min at a temperature of 200 °C, which is required for the melt processing of PLLA, proteinase K was not completely denatured but retained around 2% enzymatic activity. Our findings reveal that the thermal processing of proteinase K in the dry state is principally feasible, but equally, they also identify needs and prospects for improvement. The experimental pipeline we establish for proteinase K analysis stands to benefit efforts directed to this end. More broadly, our work sheds light on enzymatically degradable polymers and the thermal processing of enzymes, which are of increasing economical and societal relevance.
block and mortar types is analysed with particular regard to the influence of varying relative humidity. The uniaxial compressive strength and deformation characteristics of unstabilised earth blocks and mortars as well as of unstabilised earth block masonry are studied in detail and compared to conventional masonry to evaluate whether the structural design can be made accordingly. An increase of 30 % points in relative humidity leads to a reduction of the masonry´s compressive strength between 33 % and 35 % whereas the Young´s modulus is reduced by 24–29 %. However, the ratio between the Young´s modulus and the characteristic compressive strength of earth block masonry ranges between E33/fk = 283–583 but is largely independent of the relative humidity. The results show that the mechanical properties of the investigated unstabilised earth block masonry are sufficient for load-bearing structures, yielding a masonry compressive strength between 2.3 MPa and 3.7 MPa throughout the range of moisture contents
investigated. In general, the design concept of conventional masonry can be adapted for unstabilised earth masonry provided that the rather low Young´s modulus as well as the moisture dependence of both, compressive strength and Young´s modulus, are sufficiently taken into
account.
Tailored crosslinking in elastomers is crucial for their technical applications. The incorporation of nanoparticles with high surface-to-volume ratios not only leads to the formation of physical networks and influences the ultimate performance of nanocomposites, but it also affects the chemical crosslinking reactions. The influence of few-layer graphene (FLG) on the crosslinking behavior of natural rubber is investigated. Four different curing systems, two sulfur-based with different accelerator-to-sulfur ratios, and two peroxide-based with different peroxide concentrations, are combined with different FLG contents. Using differential scanning calorimetry (DSC), vulcametry (MDR) and swelling measurements, the results show an accelerating effect of FLG on the kinetics of the sulfur-based curing systems, with an exothermic reaction peak in DSC shifted to lower temperatures and lower scorch and curing times in the MDR. While a higher accelerator-to-sulfur ratio in combination with FLG leads to reduced crosslinking densities, the peroxide crosslinkers are hardly affected by the presence of FLG. The good agreement of crosslink densities obtained from the swelling behavior confirms the suitability of vulcameter measurements for monitoring the complex vulcanization process of such nanocomposite systems in a simple and efficient way. The reinforcing effect of FLG shows the highest relative improvements in weakly crosslinked nanocomposites.
Hydrous lithium aluminosilicate (L–A–S–H) and lithium aluminate (L–A–H) gels are candidate precursors for glass-ceramics and ceramics with potential advantages over conventional processing routes. However, their structure before calcination remained largely unknown, despite the importance of precursor structure on the properties of the resulting materials. In the present study, it is demonstrated that L–A–S–H and L–A–H gels with Li/Al ≤ 1 can be produced via an organic steric entrapment route, while higher Li/Al ratios lead to crystallization of gibbsite or nordstrandite. The composition and the structure of the gels was studied by thermogravimetric analysis, X-ray diffraction, 27Al and 29Si magic-angle spinning nuclear magnetic resonance, and Raman spectroscopy. Aluminium was found to be almost exclusively in six-fold coordination in both the L–A–H and the L–A–S–H gels. Silicon in the L–A–S–H gels was mainly in Q4 sites and to a lesser extent in Q3 sites (four-fold coordination with no Si–O–Al bonds). The results thus indicate that silica-rich and aluminium-rich domains formed in these gels.
The fracture surface of slow and continuous crack propagation during environmental stress cracking of a semicrystalline polyethylene exhibits isotropic roughness exponents at the local scale but resolved across the macroscopic fracture surface a clear position dependence is found. The spatially resolved roughness exponent admits values in the range between 0.1 and 0.4, demonstrating nontrivial exponents in the small length-scale regime. Instead, they vary across the fracture surface according to the stress-state distribution, which suggests that the exponents are intimately linked to the locally dominating dissipation processes during craze cracking.