Ingenieurwissenschaften und zugeordnete Tätigkeiten
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Paper des Monats
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Sample functions, i.e., stochastic process realizations, are used to define cumulative damage phenomena which end into an observable terminal state or failure. The complexity inherent to such phenomena justifies the use of phenomenological models associated with the evolution of a physical magnitude feasible to be monitored during the test. Sample functions representing the damage evolution may be identified, once normalized to the interval [0,1], with cumulative distribution functions (cdfs), generally, of the generalized extreme value (GEV) family. Though usually only a fraction of the whole damage evolution, according to the specific problem handled, is available from the test record, the phenomenological models proposed allow the whole damage process to be recovered. In this way, down- and upwards extrapolations of the whole damage process beyond the scope of the experimental program are provided as a fundamental tool for failure prediction in the practical design. The proposed methodology is detailed and its utility and generality confirmed by its successive application to representative well-known problems in fatigue and fracture characterization. The excellent fittings, the physical interpretation of the model parameters and the good expectations to achieve a complete probabilistic analysis of these phenomena justify the interest of the proposed phenomenological approach with possible applications to other cumulative damage processes.
The aim of this study is to develop polymeric thin films for corrosion protection of magnesium alloy AZ31. As polymer matrix, poly(4-vinyl pyridine) (P4VP) is selected due to its semiconducting properties and protonic conductivity. Polyacrylic acid is tested as crosslinking layers to improve interfacial adhesion. The macroscopic corrosion properties of the multilayer coatings are investigated by means of electrochemical methods, such as linear sweep voltammetry and electrochemical impedance spectroscopy (EIS), in corrosive media simulating technical and biomedical applications. It is demonstrated that thin multilayer coatings can suppress the corrosion rates of magnesium alloys. To our best knowledge, this is the first demonstration of the use of P4VP as a conducting polymer film with protonic conductivity for corrosion protection of magnesium alloys.
Um die zunehmenden AKR-Schäden an Betonfahrbahnen im deutschen Autobahnnetz zukünftig zu vermeiden, wurden mit dem ARS 04/2013 verbindliche Eignungsprüfungen zum Ausschluss alkaliempfindlicher Gesteinskörnungen bei Neubau- und Erhaltungsmaßnahmen eingeführt. Dies führte zu einer deutlichen Reduzierung der geeigneten Gesteinskörnungen. Vor diesem Hintergrund soll durch die Zugabe eines Innenhydrophobierungsmittels während der Betonherstellung grenzwertig alkaliempfindliche Gesteinskörnung nutzbar gemacht werden.
Die AKR-Vermeidungsstrategie basiert dabei auf der signifikanten Reduzierung des Eindringens von Wasser und Tausalzlösung in den Fahrbahndeckenbeton. In einem im Aufträge der BASt an der BAM durchgeführten Forschungsvorhaben wurde die Leistungsfähigkeit verschiedener Hydrophobierungsmittel für diesen Einsatzzweck
grundhaft untersucht. In dem Beitrag wird exemplarisch die Leistungsfähigkeit eines geeigneten Hydrophobierungsmittels in einem Waschbeton mit einer sehr alkaliempfindlichen Grauwacke aufgezeigt. Das Spektrum der Laboruntersuchungen reicht dabei von AKR-Betonversuchen mit Alkalizufuhr sowie den aufbauend durchgeführten mikroskopischen Untersuchungen zur Bewertung des AKR-Schädigungspotenzials über die Analyse des Feuchte- und Tausalzeintrags bis zur Ermittlung der mechanischen Eigenschaften und des Frost-Tausalz-Widerstands.
Abschließend wird der noch vorhandene Forschungsbedarf zur Überführung dieser neuen AKR-Vermeidungsstrategie in die Praxis aufgezeigt.
3D printing enables a better control over the microstructure of bone restoring constructs, addresses the challenges seen in the preparation of patient-specific bone scaffolds, and overcomes the bottlenecks that can appear in delivering drugs/growth factors promoting bone regeneration. Here, 3D printing is employed for the fabrication of an osteogenic construct made of hydrogel nanocomposites. Alginate dialdehyde-gelatin (ADA-GEL) hydrogel is reinforced by the incorporation of bioactive glass nanoparticles, i.e. mesoporous silica-calcia nanoparticles (MSNs), in two types of drug (icariin) loading. The composites hydrogel is printed as superhydrated composite constructs in a grid structure. The MSNs not only improve the mechanical stiffness of the constructs but also induce formation of an apatite layer when the construct is immersed in simulated body fluid (SBF), thereby promoting cell adhesion and proliferation. The nanocomposite constructs can hold and deliver icariin efficiently, regardless of its incorporation mode, either as loaded into the MSNs or freely distributed within the hydrogel. Biocompatibility tests showed that the hydrogel nanocomposites assure enhanced osteoblast proliferation, adhesion, and differentiation. Such optimum biological properties stem from the superior biocompatibility of ADA-GEL, the bioactivity of the MSNs, and the supportive effect of icariin in relation to cell Proliferation and differentiation. Taken together, given the achieved structural and biological properties and effective drug delivery capability, the hydrogel nanocomposites show promising potential for bone tissue engineering.
The microscopic diffusion and the low frequency density of states (VDOS) of PIM-EATB(CH3) are investigated by inelastic and quasi-elastic neutron scattering where also the demethylated counterpart of PIM-EA-TB(H2) is considered. These intrinsic microporous polymers are characterized by large BET surface area values of several hundred m2/g and pore sizes between 0.5 and 2 nm. Detailed comparison is made to the archetype of polymers of intrinsic microporosity, PIM-1, and polynorbornenes also bearing a microporosity. Due to the wavelength of neutrons, the diffusion and vibrations can be addressed on microscopic length and time scales. From the inelastic neutron scattering experiments the low frequency density of states (VDOS) is estimated which shows excess contributions to the Debye-type VDOS known as Boson peak. It was found that the maximum frequency of the Boson peak decreases with increasing microporosity characterized by the BET surface area. However, besides the BET surface area, additional factors such as the backbone stiffness govern the maximum frequency of the Boson peak. Further the mean squared displacement related to microscopic motions was estimated from elastic fixed window scans. At temperatures above 175 K, the mean squared displacement PIM-EA-TB(CH3) is higher than that for the demethylated counterpart PIM-EA-TB(H2). The additional contribution found for PIM-EATB(CH3) is ascribed to the rotation of the methyl group in this polymer because the only difference between the two structures is that PIM-EA-TB(CH3) has methyl groups where PIM-EA-TB(H2) has none. A detailed comparison of the molecular dynamics is also made to that of PIM-1 and the microporous polynorbornene PTCNSi1. The manuscript focuses on the importance of vibrations and the localized molecular mobility characterized by the microscopic diffusion on the gas Transport in polymeric separation membranes. In the frame of the random gate model localized fluctuations can open or close bottlenecks between pores to enable the diffusion of gas molecules.
Lignosulfonates are industrial biorefinery products that are characterized by significant variability and heterogeneity in their structural composition. Typically, they exhibit high dispersities in molar mass (molar mass distribution-MMD) and in functionalities (functionality-type distribution - FTD), which crucially affect their material usage. In terms of FTD, state-of-the-art Lignin analytics still rely mainly on the determination of functional group contents, which are statistical averages with limited explanatory power. In contrast, our online hydrophobic interaction chromatography−size-exclusion chromatography 2D-LC approach combines the determination of both MMD and FTD in a single measurement to provide a comprehensive picture of the characteristic composition of industrial lignosulfonates information hitherto inaccessible by state-of-the-art lignin analytics. In this way, the complex inter - relationships between these two important structural parameters can be studied in an unprecedented manner. In this study, we reveal the considerable differences in terms of hydrophobic composition and its dispersity present in a range of different industrial lignosulfonates - data desperately needed in tailoring and refining of lignosulfonate composition for material usage.
This paper presents investigation results of a process for defect-free hybrid laser arc welding (HLAW) of closed circumferential welds. The process aims to avoid weld imperfections in the overlap area of a HLAW circumferential weld. A process control strategy for closing the circumferential weld was developed to achieve a defect-free overlap region by controlling the solidification conditions at the end of the weld. The controlled heat flow is achieved by adjusting the parameters of both welding processes involved, the laser beam as well as gas metal arc welding (GMAW) process. Experimental investigations were carried out on 12 mm to 15 mm thick tube sections. The influence of process parameters such as the laser ramp time, the change in magnification scale and the defocusing of the laser beam on the solidifi-cation conditions at the end of the circumferential weld was investigated to find an optimum strategy for ramping out the process energy. Within the framework of the experimental studies, it was demonstrated that defocusing the laser beam in the range between 60 mm and 100 mm over a short run-out area of the weld of approximately 15 mm led to a significantly better weld formation in the overlap area. A favourable cup-shaped weld shape could be achieved without a tendency to crack. The laser optics with a motor-driven lens system made it possible to increase the laser beam diameter without changing the position of the GMAW arc relative to the component surface.
Spherical lignin nanoparticles (LNPs) fabricated via nanoprecipitation of dissolved lignin are among the most attractive biomass-derived nanomaterials. Despite various studies exploring the methods to improve the uniformity of LNPs or seeking more application opportunities for LNPs, little attention has been given to the fundamental aspects of the solvent effects on the intrinsic properties of LNPs. In this study, we employed a variety of experimental techniques and molecular dynamics (MD) simulations to investigate the solvent effects on the intrinsic properties of LNPs. The LNPs were prepared from softwood Kraft lignin (SKL) using the binary solvents of aqueous acetone or aqueous tetrahydrofuran (THF) via nanoprecipitation. The internal morphology, porosity, and mechanical properties of the LNPs were analyzed with electron tomography (ET), small-angle X-ray scattering (SAXS), atomic force microscopy (AFM), and intermodulation AFM (ImAFM). We found that aqueous acetone resulted in smaller LNPs with higher uniformity compared to aqueous THF, mainly ascribing to stronger solvent−lignin interactions as suggested by MD simulation results and confirmed with aqueous 1,4-dioxane (DXN) and aqueous dimethyl sulfoxide (DMSO).
More importantly, we report that both LNPs were compact particles with relatively homogeneous density distribution and very low porosity in the internal structure. The stiffness of the particles was independent of the size, and the Young’s modulus was in the range of 0.3−4 GPa. Overall, the fundamental understandings of LNPs gained in this study are essential for the design of LNPs with optimal performance in applications.
Carbamazepine Dihydroxybenzoic Acid Cocrystals: Exploring Packing Interactions and Reaction Kinetics
(2021)
Herein, we present the mechanochemical formation of three new cocrystals containing the active pharmaceutical ingredient carbamazepine and dihydroxybenzoic acids as coformers (CBZ:2,4-DHBA 1:1, CBZ:2,5-DHBA 1:1, and CBZ:2,6-DHBA 1:1). Rietveld methods were used for three different purposes: (i) refining all structures solved using powder X-ray diffraction, (ii) performing a quantitative phase analysis of the diffraction data collected from ex situ mechanochemical reactions at different milling times, and (iii) determining the cocrystallization kinetic profiles. The rate of cocrystallization was found to be higher for the formation of CBZ:2,4-DHBA and CBZ:2,6-DHBA, reaching an equilibrium after 600 s of milling. In the case of CBZ:2,5-DHBA a short induction period of 20 s was detected prior to the start of the reaction and an equilibrium was reached after 1200 s. An empirical trend between the rate of cocrystallization and the structural complexity of the cocrystal product was found. The slowest cocrystallization rate observed for CBZ:2,5-DHBA corresponds to the crystal structure deviating substantially from the hydrogen-bonding motif found in the reactants.
Recent progress has shown that using wavelengths between 1,000 and 2,000 nm, referred to as the shortwave-infrared or near-infrared (NIR)-II range, can enable high-resolution in vivo imaging at depths not possible with conventional optical wavelengths.
However, few bioconjugatable probes of the type that have proven invaluable for multiplexed imaging in the visible and NIR range are available for imaging these wavelengths. Using rational design, we have generated persulfonated indocyanine dyes with absorbance maxima at 872 and 1,072 nm through catechol-ring and aryl-ring fusion, respectively, onto the nonamethine scaffold. Multiplexed two-color and three-color in vivo imaging using monoclonal antibody and dextran conjugates in several tumor models illustrate the benefits of concurrent labeling of the tumor and healthy surrounding tissue and lymphatics.
These efforts are enabled by complementary advances in a custom-built NIR/shortwave-infrared imaging setup and software package for multicolor real-time imaging.