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Calcium cobaltite is one of the most promising oxide p-type thermoelectric materials. The solid-state reaction (or calcination, respectively), which is well known for large-scale powder synthesis of functional materials, can also be used for the synthesis of thermoelectric oxides. There are various calcination routines in literature for Ca3Co4O9 powder synthesis, but no systematic study has been done on the influence of calcination procedure on thermoelectric properties. Therefore, the influence of calcination conditions on the Seebeck coefficient and the electrical conductivity was studied by modifying calcination temperature, dwell time, particle size of raw materials and number of calcination cycles. This study shows that elevated temperatures, longer dwell times, or repeated calcinations during powder synthesis do not improve but deteriorate the thermoelectric properties of calcium cobaltite. Diffusion during calcination leads to idiomorphic grain growth, which lowers the driving force for sintering of the calcined powder. A lower driving force for sintering reduces the densification. The electrical conductivity increases linearly with densification. The calcination procedure barely influences the Seebeck coefficient. The calcination procedure has no influence on the phase formation of the sintered specimens.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, the vibrational density of states (VDOS) for PIM-1, the prototypical polymer with intrinsic microporosity, is investigated by means of inelastic neutron scattering. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid). The measured data show the characteristic low frequency excess contribution to VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers. For an annealed PIM-1 sample, the Boson peak shifts to higher frequencies in comparison to the un-annealed sample. These changes in the VDOS of the annealed PIM-1 sample are related to changes in the microporous structure as confirmed by X-ray scattering.
The authors are currently investigating the possibility to apply compaction grouting for offshore pile foundations (Jacket piles as well as monopiles) as a possible retrofitting technique for an optimised foundation concept. In this research project, we are developing a design approach aiming to predict the ideal amount and properties of a grout for a specific soil situation and desired improvement of pile bearing capacity after Installation and during service time. Both numerical and experimental tests have been carried out to investigate the injection process during which a highly viscous grout is injected into the soil under high pressure to displace and compact the surrounding soil without fracturing it. The implicit Material Point Method (MPM) based on a mixed formulation is the numerical technique chosen to deal with the expected large deformations and the arbitrary shape of the developing grout bulb. The usage of MPM prevents both the need of remeshing and the numerical instability induced by extensive mesh distortion. For validation with experimental results, we have constructed a testing chamber with one transparent sidewall. This chamber enables us to observe the injection process directly at the transparent vertical window and to measure the in-plane soil displacements and strains by means of the Digital Image Correlation (DIC) technique.
The results already reveal the interrelation of soil and grout properties for a successful usage of this common ground improvement technique.
The salinization and contamination of metal surfaces by chloride-containing aerosols is of great importance with regard to corrosion phenomena of damaged coated metal surfaces and stainless steels in the maritime sector and in offshore applications. Detailed questions have to be answered to clarify whether and to what extent salinization of the surface has an influence on the adhesion and durability of coatings in repairing applications and on pitting occurrence on stainless steels under atmospheric conditions. The questions arise which degree of salinization is reached after which period of time and how a defined and reproducible salinization can be simulated in the laboratory for further systematic investigations. The article is dedicated to these questions. Results of a field trial on the Island of Heligoland are presented and a simple procedure for a defined loading of metal surfaces with chlorides at a laboratory scale using a design of experiments (DoE) approach is introduced.
The research focus of this study was set on the corrosion process of condensate as droplets on the surface of carbon steels (X52, X70) martensitic steel UNS S41500, and super austenite UNS N08031 in CO2 atmosphere with impurities at 278 K (to simulate the offshore transportation condition in a buried pipeline). The possibility of dew/droplet formation on the steel surface and wetting behavior of corresponding materials were evaluated by contact angle measurement in dense CO2 at 278 K. To observe the effect of impurities (SO2 and O2) on droplet corrosion process, exposure tests were carried out in the mixed atmosphere with a drop, 1 ‑ 10 µL in volume, of CO2 saturated ultra-pure water on steel surface. Comparable exposure tests were carried out with the same gas mixture and the same volume of water, as vapor, to observe the droplet formation and the corrosion process that follows. Effects of surface roughness on the droplet formation and its corrosion process were further studied and showed no significant role upon long time exposure. The results from droplet experiments were compared to those from the bulk electrolyte for the further recommendation on the quality control of gas stream along with the use of carbon steels as transport pipelines in CCS - Carbon Capture and Storage system.
Repair is an indispensable part of the maintenance of structures over their lifetimes. Structural grouting is a widely used remediation technique for concrete components, trenches, mine subsidence, dam joints, restoration of masonry structures, and geological stabilizations. A structural grout system should be injectable in narrow spaces and hence include ingredients with finer particles. Ultrafine cements are ideal for these type of demanding grouts due to their superior properties compared to that of the less expensive, but coarser ordinary Portland cement (OPC). Supplementary cementitious materials (SCMs) are often used to replace OPC clinker based binder in order to modify certain properties and to reduce costs. The most commonly used SCMs are fly ash (FA), and ground granulated blast furnace slag (GGBS). For various special applications microsilica (MS), and metakaolin (MK) are also used. Identifying the optimum replacement contents of OPC by SCMs are a challenge during the design of such grouts. The aim of this experimental study is to investigate the effect of the selected SCMs (FA, MS and MK) on the slump flow, time of efflux, viscosity, shrinkage, and compressive and flexural strength of ultrafine cement based grouts with constant water-binder ratio and superplasticizer content. The test program was formulated using Box-Behnken design principles. Maximum percentages of replacement with ultrafine cement was 6% by volume of cement for MS and 16% for FA, and MK. The results suggest that most investigated grouts have the potential to be used for structural applications. The appropriate quadratic models are then formulated through statistical tools and presented as response surfaces. The trends indicate that fly ash improves the rheological properties, whereas microsilica and metakaolin positively affect shrinkage and mechanical properties to some extent. Based on the influence of SCMs and priorities among the properties, Decision Matrix Analysis (DMA) is carried out to select the most suitable ones among the SCMs. The analysis suggests that microsilica and fly ash are more suitable as SCMs than metakaolin without affecting the properties.
High-density polyethylene becomes optically transparent during tensile drawing when previously saturated with diesel fuel. This unusual phenomenon is investigated as it might allow conclusions with respect to the material behavior. Microscopy, differential scanning calorimetry, density measurements are applied together with two scanning X-ray scattering techniques: wide angle X-ray scattering (WAXS) and X-ray refraction, able to extract the spatially resolved crystal orientation and internal surface, respectively. The sorbed diesel softens the material and significantly alters the yielding characteristics. Although the crystallinity among stretched regions is similar, a virgin reference sample exhibits strain whitening during stretching, while the diesel-saturated sample becomes transparent. The WAXS results reveal a pronounced fiber texture in the tensile direction in the stretched region and an isotropic orientation in the unstretched region. This texture implies the formation of fibrils in the stretched region, while spherulites remain intact in the unstretched parts of the specimens. X-ray refraction reveals a preferred orientation of internal surfaces along the tensile direction in the stretched region of virgin samples, while the sample stretched in the diesel-saturated state shows no internal surfaces at all. Besides from stretching saturated samples, optical transparency is also obtained from sorbing samples in diesel after stretching.
Geothermal energy is an interesting alternative to polluting fossil energy sources. Therefore, in Belgium, two wells have been drilled for a deep geothermal power plant. However, the environment to which the installations are exposed is challenging. The geothermal brine has 165 g/l total dissolved solids (of which 90% are sodium and chlorine) and the production temperature can be up to 130 °C. To assess their suitability to be used in a geothermal power plant, the corrosivity of the artificial brine to three common construction materials was investigated with exposure and electrochemical tests. The metals under consideration are a low-alloyed carbon steel (S235JR), an austenitic stainless steel (UNS S31603) and a duplex stainless steel (UNS S31803). The carbon steel, that was found to corrode uniformly, could be considered as a constructional material if a sufficient wall thickness is chosen. The austenitic stainless steel and the duplex stainless steel demonstrate very low uniform
corrosion rates. They are however susceptible to pitting and crevice corrosion. To guarantee safe operation of the geothermal power plant, the susceptibility of the alloys to stress corrosion cracking should be tested and in situ experiments should be performed.
Polymers of Intrinsic Microporosity (PIMs) of high performance have developed as materials with a wide application range in gas separation and other energy-related fields. Further optimization and long-term behavior of devices with PIMs require an understanding of the structure-property relationships including physical aging. In this context the glass transi-tion plays a central role, but with conventional thermal analysis a glass transition is usually not detectable for PIMs be-fore their thermal decomposition. Fast scanning calorimetry provides evidence of the glass transition for a series of PIMs, as the time scales responsible for thermal degradation and for the glass transition are decoupled by employing ultrafast heating rates of tens of thousands K s-1. The investigated PIMs were chosen considering the chain rigidity. The estimated glass transition temperatures follow the order of the rigidity of the backbone of the PIMs.
The shaft bearing capacity often plays a dominant role for the overall structural behaviour of axially loaded piles in offshore deep foundations. Under cyclic loading, a narrow zone of soil at the pile-soil interface is subject to cyclic shearing solicitations. Thereby, the soil may densify and lead to a decrease of confining stress around the pile due to microphenomena such as particle crushing, migration and rearrangement. This reduction of radial stress has a direct impact on the shaft capacity, potentially leading in extreme cases to pile failure. An adequate interface model is needed in order to model this behaviour numerically. Different authors have proposed models that take typical Interface phenomena in account such as densification, grain breakage, normal pressure effect and roughness. However, as the models become more complex, a great number of material parameters need to be defined and calibrated. This paper proposes the adoption and transformation of an existing soil bulk model (Pastor- Zienkiewicz) into an interface model. To calibrate the new interface model, the results of an experimental campaign with the ring shear device under cyclic loading conditions are here presented. The constitutive model shows a good capability to reproduce typical features of sand behaviour such as cyclic compaction and dilatancy, which in saturated partially-drained conditions may lead to liquefaction and cyclic mobility phenomena.