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Due to higher combustion chamber temperatures and pressures in efficient combustion engines, both the high-cycle and thermomechanical fatigue loads on service life-critical components, such as the cylinder head, are increasing. Material comparisons and analysis of damage behavior are very expensive and time-consuming using component tests. This study therefore develops a test method for cylinder head materials that takes into account the combined loading conditions from the above-mentioned loads and allows realistic temperature transients and gradients on near-component samples. The near-component cylinder head sample represents the failure-critical exhaust valve crosspiece and is tested in a test rig specially designed with the aid of conjugate heat transfer simulations. In the test rig, the sample is subjected to thermal stress by a hot gas burner and to mechanical stress by a high-frequency pulsator. Optical crack detection allows permanent observation of fatigue crack growth and crack closure during the test. Fractographic and metallo-graphic examinations of the fracture areas as well as analyses of the damage patterns show that loads close to engine operation can be set in this way and their influences on the damage can be monitored.
Governments have restricted public life during the COVID-19 pandemic, inter alia closing sports facilities and gyms. As regular exercise is essential for health, this study examined the effect of pandemic-related confinements on physical activity (PA) levels. A multinational survey was performed in 14 countries. Times spent in moderate-to-vigorous physical activity (MVPA) as well as in vigorous physical activity only (VPA) were assessed using the Nordic Physical Activity Questionnaire (short form). Data were obtained for leisure and occupational PA pre- and during restrictions. Compliance with PA guidelines was calculated based on the recommendations of the World Health Organization (WHO). In total, n = 13,503 respondents (39 ± 15 years, 59% females) were surveyed. Compared to pre-restrictions, overall self-reported PA declined by 41% (MVPA) and 42.2% (VPA). Reductions were higher for occupational vs. leisure time, young and old vs. middle-aged persons, previously more active vs. less active individuals, but similar between men and women. Compared to pre-pandemic, compliance with WHO guidelines decreased from 80.9% (95% CI: 80.3–81.7) to 62.5% (95% CI: 61.6–63.3). Results suggest PA levels have substantially decreased globally during the COVID-19 pandemic. Key stakeholders should consider strategies to mitigate loss in PA in order to preserve health during the pandemic.
The aim of this review was to determine whether smartphone applications are reliable and valid to measure range of motion (RoM) in lower extremity joints. A literature search was performed up to October 2020 in the databases PubMed and Cochrane Library. Studies that reported reliability or validity of smartphone applications for RoM measurements were included. The study quality was assessed with the QUADAS-2 tool and baseline information, validity and reliability were extracted. Twenty-five studies were included in the review. Eighteen studies examined knee RoM, whereof two apps were analysed as having good to excellent reliability and validity for knee flexion (“DrGoniometer”, “Angle”) and one app showed good results for knee extension (“DrGoniometer”). Eight studies analysed ankle RoM. One of these apps showed good intra-rater reliability and excellent validity for dorsiflexion RoM (“iHandy level”), another app showed excellent reliability and moderate validity for plantarflexion RoM (“Coach’s Eye”). All other apps concerning lower extremity RoM had either insufficient results, lacked study quality or were no longer available. Some apps are reliable and valid to measure RoM in the knee and ankle joint. No app can be recommended for hip RoM measurement without restrictions.
Uphill training is applied to induce specific overload on the musculoskeletal system to improve sprinting mechanics. This study aimed to identify unique kinematic features of uphill sprinting at different slopes and to suggest practical implications based on comparisons we early stance phase. At take-off, steeper slopes induced significantly more extended joint angles and higher ROMs during the late stance phase. Compared with moderate slopes, more anti-phase coordination patterns were detected at steeper slopes. Thus, uphill sprinting at steeper slopes shares essential kinematic features with the early acceleration phase of level sprinting. Moderate inclinations induce biomechanical adaptations similar to those in the late acceleration phase of level sprinting. Hence, the specific transfer of uphill sprinting to acceleration depends on the slope inclinations.
Quantifying the midsole material characteristics of athletic footwear is a standard task in footwear research and development. Current material testing protocols primarily focus on the determination of cushioning properties of the heel region or the quantification of the midsole properties as one assembly. However, midsoles possess different spatial material properties that have not been quantified from previous methodologies. Therefore, new material testing methods are required to quantify the local material response of athletic footwear. We developed a cyclical force-controlled material testing protocol for the determination of non-homogeneously distributed material stiffness with a high spatial resolution. In five prototype shoes varying in their stiffness distribution, we found that the material properties can be reliably measured across the midsole. Furthermore, we observed a characteristic non-linear material response regardless of the midsole location. We found that the material stiffness increased with an increase of the applied force and that this effect is further intensified by higher testing cycles. Additionally, the obtained midsole stiffness depends on the geometry of the midsole. We explored different approaches to reduce the measurement time of the testing protocol and found that the number of measurements can be reduced by 70% using 2 D-interpolation procedures. Determining the spatial material properties of midsoles needs to be considered to understand foot-shoe interactions. Furthermore, this measurement protocol can be used for quality control within the footwear and can be adapted for considering the effects of different running styles or speeds on ground force application characteristics.
Treadmills are essential to the study of human and animal locomotion as well as for applied diagnostics in both sports and medicine. The quantification of relevant biomechanical and physiological variables requires a precise regulation of treadmill belt velocity (TBV). Here, we present a novel method for time-efficient tracking of TBV using standard 3D motion capture technology. Further, we analyzed TBV fluctuations of four different treadmills as seven participants walked and ran at target speeds ranging from 1.0 to 4.5 m/s. Using the novel method, we show that TBV regulation differs between treadmill types, and that certain features of TBV regulation are affected by the subjects’ body mass and their locomotion speed. With higher body mass, the TBV reductions in the braking phase of stance became higher, even though this relationship differed between locomotion speeds and treadmill type (significant body mass × speed × treadmill type interaction). Average belt speeds varied between about 98 and 103% of the target speed. For three of the four treadmills, TBV reduction during the stance phase of running was more intense (> 5% target speed) and occurred earlier (before 50% of stance phase) unlike the typical overground center of mass velocity patterns reported in the literature. Overall, the results of this study emphasize the importance of monitoring TBV during locomotor research and applied diagnostics. We provide a novel method that is freely accessible on Matlab’s file exchange server (“getBeltVelocity.m”) allowing TBV tracking to become standard practice in locomotion research.
We present a densitometric quantification method for triclosan in toothpaste, separated by high-performance thin-layer chromatography (HPTLC) and using a 48-bit flatbed scanner as the detection system. The sample was band-wise applied to HPTLC plates (10 × 20 cm), with fluorescent dye, Merck, Germany (1.05554). The plates were developed in a vertical developing chamber with 20 min of chamber saturation over 70 mm, using n-heptane–methyl tert-butyl ether–acetic acid (92:8:0.1, V/V) as solvent. The RF value of triclosan is hRF = 22.4, and quantification is based on direct measurements using an inexpensive 48-bit flatbed scanner for color measurements (in red, green, and blue) after plate staining with 2,6-dichloroquinone-4-chloroimide (Gibbs' reagent). Evaluation of the red channel makes the measurements of triclosan very specific. For linearization, an extended Kubelka–Munk expression was used for data transformation. The range of linearity covers more than two orders of magnitude and is between 91 and 1000 ng. The separation method is inexpensive, fast and reliable.
We present a video-densitometric high-performance thin-layer chromatography (HPTLC) quantification method for patulin in apple juice, developed in a vertical chamber from the starting point to a distance of 50 mm, using MTBE, n-pentane (9 + 5, v/v) as mobile phase. After separation the plate is sprayed with methyl-benzothiazolinone hydrazone hydrochloride monohydrate (MBTH) solution (40 mg in 20 mL methanol) and heated at 105 °C for 15 min. Patulin zones are transformed into yellow spots. The quantification is based on direct measurements using an inexpensive 48-bit flatbed scanner for color measurements (in red, green, and blue). Evaluation of the blue channel makes the measurements very specific. Quantification in fluorescence was also done by use of a 16-bit CCD-camera and UV-366 nm illumination as well as using a HPTLC DAD-scanner. For linearization the extended Kubelka–Munk expression for data transformation was used. The range of linearity covers more than two magnitudes and lies between 5 and 800 ng patulin. The extraction of 20 g apple juice and an extract application on plate up to 50 µL allows statistically defined checking the limit of detection (LOD) of 50 ng patulin per track, which is equivalent to 50 µg patulin per kg apple juice.
In the present paper, the influence of locally varying microstructures in case of an AlSi12 cast aluminium alloy is investigated by means of extracting the test pieces from different removal positions and low cycle fatigue tests. The temperature-dependent damage mechanisms, the material specific defect types, sizes and their influence on the fatigue properties of two AlSi7 and AlSi12 cast aluminium alloys are studied. An extreme value statistics methodology is applied to predict maximum defect sizes expected in a critical surface volume from two-dimensional metallographic micrographs. A damage map for the AlSi12 cast aluminium alloy is presented explaining the influence of the temperature- and load-dependent damage mechanisms on the observed isothermal and thermomechanical lifetime behavior.
In this work, the influence of superimposed high cycle fatigue on the LCF/HCF and TMF/HCF lifetime is investigated for two cast aluminium alloys of the types AlSi7 and AlSi12. The replica technique is used to examine the short crack growth behavior under pure LCF and LCF/HCF loading. The observed short crack growth evolution explains the observed lifetime reduction with increasing HCF amplitudes.
Detailed material investigations of the fatigue behavior of two cast aluminium alloys used in combustion engines are presented. The network of intermetallic phases of both aluminium alloys is characterized by means of detailed energy dispersive X-ray spectroscopy. In order to investigate the temperature-dependent fatigue behavior of the materials, tensile, low cycle and thermomechanical fatigue tests are performed over a wide temperature and loading range. The influence of the temperature dependence on the experimental results is discussed.
In this paper, the Bauschinger effect and latent hardening of single crystals are assessed in finite element calculations using a single crystal plasticity model with kinematic hardening. To this end, results of cyclic micro-bending experiments on single crystal Alloy 718 in different crystal orientations (single slip and multi slip) with respect to the loading direction are used to determine the slip system related material properties of the single crystal plasticity model. Two kinematic hardening laws are considered: a kinematic hardening law describing latent hardening and a kinematic hardening law without latent hardening. For the determination of material properties for both hardening laws, a gradient-based optimization method is used. The results show that the different strength levels observed for micro-bending tests on different crystal orientations can only be described with latent kinematic hardening well, whereas the pronounced Bauschinger effect is described well by both kinematic hardening laws. It is concluded that cyclic micro-bending experiments on single crystals using different crystal orientations give an appropriate data base for the determination of the slip system related material properties of the single crystal plasticity model with latent kinematic hardening.
Cyclic micro-bending tests on fcc single crystal Ni-base Alloy 718 cantilevers with different crystal orientations were performed to analyze the influence of activated slip systems on dislocation plasticity, latent hardening and the Bauschinger effect. The investigations indicate that plasticity in single crystal micro-cantilevers is significantly influenced by two phenomena - dislocation interaction and dislocation pile-up at the neutral plane. Both phenomena occur at the same time. Their ratio seems to be determined by the activated slip systems. Slip trace analysis indicates that the activation of only one slip system leads to a strong localization of plasticity to a limited number of parallel slip bands. This results in low dislocation interaction and consequently pronounced pile-ups at the neutral plane. In multi slip orientation, the second slip system leads to activation of significantly more dislocation sources, causing a much earlier and more homogeneous elastic-plastic transition zone. In stress-strain hysteresis loops during bending, pronounced dislocation interaction in multi slip orientation leads to a more pronounced latent hardening. The results suggest that on a microstructural length scale, plasticity behavior is strongly affected by activated slip systems, which determine local dislocation phenomena. Based on the results presented in this paper, a finite element analysis of latent hardening and the Bauschinger effect using a single crystal plasticity model with latent kinematic hardening is presented in Part II.
As PV enters the terawatt era, reliability, sustainability and low carbon footprint of solar modules are key requirements. The N.I.C.E.TM technology from Apollon Solar is a good candidate for significant improvements in these areas. As the second-generation pilot line is now functional with IEC certification underway, we present a holistic assessment of N.I.C.E.TM technology compared with conventional module technology with encapsulant. This includes electrical performance and cost/consumables, reliability, and degradation mechanisms as well as sustainability aspects. In addition, the new generation of N.I.C.E.-wire modules are presented that use thin round Cu wires instead of flat ribbons for interconnection. This candidate technology for an alternative to the Smart Wire Connection Technology (SWCT) is investigated experimentally as well as via numerical simulations.
Pure orbital blowout fractures occur within the confines of the internal orbital wall. Restoration of orbital form and volume is paramount to prevent functional and esthetic impairment. The anatomical peculiarity of the orbit has encouraged surgeons to develop implants with customized features to restore its architecture. This has resulted in worldwide clinical demand for patient-specific implants (PSIs) designed to fit precisely in the patient’s unique anatomy. Material extrusion or Fused filament fabrication (FFF) three-dimensional (3D) printing technology has enabled the fabrication of implant-grade polymers such as Polyetheretherketone (PEEK), paving the way for a more sophisticated generation of biomaterials. This study evaluates the FFF 3D printed PEEK orbital mesh customized implants with a metric considering the relevant design, biomechanical, and morphological parameters. The performance of the implants is studied as a function of varying thicknesses and porous design constructs through a finite element (FE) based computational model and a decision matrix based statistical approach. The maximum stress values achieved in our results predict the high durability of the implants, and the maximum deformation values were under one-tenth of a millimeter (mm) domain in all the implant profile configurations. The circular patterned implant (0.9 mm) had the best performance score. The study demonstrates that compounding multi-design computational analysis with 3D printing can be beneficial for the optimal restoration of the orbital floor.
The German government is aiming to increase the share of renewable energies in the electricity supply to 80% in 2050. To date, however, neither the technical requirements nor the market requirements to implement this aim are provided: Germany is struggling to establish the technical requirements and the market requirements to meet this goal. As an important incentive mechanism, the German government has used and continues to use support measures, such as guaranteed feed-in tariffs, and continuously adapts these to market developments and requirements of the European Union. The purpose of the study is to outline a concept for the implementation of regional flexibility markets in Europe based on a thorough review of technical solutions. The method of a comprehensive review of research in regional flexibility markets of electricity, distribution, and pricing from the study is applied to summarize and discuss the opportunities, risks, and future potentials of grid distribution technology. Based on the insights, a new market-based supply and distribution scheme for electricity, which is aimed to benefit of a fully regenerative, decentral and fairly priced electricity markets on the European level is presented. The study suggests a blockchain based pricing mechanism which shall allow equal market access for consumer, providers, and grid operators and rewards regenerative production and short-distance transmission.
Considering the literature for aqueous rechargeable Zn//MnO2 batteries with acidic electrolytes using the doctor blade coating of the active material (AM), carbon black (CB), and binder polymer (BP) for the positive electrode fabrication, different binder types with (non-)aqueous solvents were introduced so far. Furthermore, in most of the cases, relatively high passive material (CB+BP) shares ~30 wt% were applied. The first part of this work focuses on different selected BPs: polyacrylonitrile (PAN), carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), cellulose acetate (CA), and nitrile butadiene rubber (NBR). They were used together with (non-)aqueous solvents: DI-water, methyl ethyl ketone (MEK), and dimethyl sulfoxide (DMSO). By performing mechanical, electrochemical and optical characterizations, a better overall performance of the BPs using aqueous solvents was found in aqueous 2 M ZnSO4 + 0.1 M MnSO4 electrolyte (i.e., BP LA133: 150 mAh·g−1 and 189 mWh·g−1 @ 160 mA·g−1). The second part focuses on the mixing ratio of the electrode components, aiming at the decrease of the commonly used passive material share of ~30 wt% for an industrial-oriented electrode fabrication, while still maintaining the electrochemical performance. Here, the absolute CB share and the CB/BP ratio are found to be important parameters for an application-oriented electrode fabrication (i.e., high energy/power applications).
This paper shows the results of an in-depth techno-economic analysis of the public transport sector in a small to midsize city and its surrounding area. Public battery-electric and hydrogen fuel cell buses are comparatively evaluated by means of a total cost of ownership (TCO) model building on historical data and a projection of market prices. Additionally, a structural analysis of the public transport system of a specific city is performed, assessing best fitting bus lines for the use of electric or hydrogen busses, which is supported by a brief acceptance evaluation of the local citizens. The TCO results for electric buses show a strong cost decrease until the year 2030, reaching 23.5% lower TCOs compared to the conventional diesel bus. The optimal electric bus charging system will be the opportunity (pantograph) charging infrastructure. However, the opportunity charging method is applicable under the assumption that several buses share the same station and there is a “hotspot” where as many as possible bus lines converge. In the case of electric buses for the year 2020, the parameter which influenced the most on the TCO was the battery cost, opposite to the year 2030 in where the bus body cost and fuel cost parameters are the ones that dominate the TCO, due to the learning rate of the batteries. For H2 buses, finding a hotspot is not crucial because they have a similar range to the diesel ones as well as a similar refueling time. H2 buses until 2030 still have 15.4% higher TCO than the diesel bus system. Considering the benefits of a hypothetical scaling-up effect of hydrogen infrastructures in the region, the hydrogen cost could drop to 5 €/kg. In this case, the overall TCO of the hydrogen solution would drop to a slightly lower TCO than the diesel solution in 2030. Therefore, hydrogen buses can be competitive in small to midsize cities, even with limited routes. For hydrogen buses, the bus body and fuel cost make up a large part of the TCO. Reducing the fuel cost will be an important aspect to reduce the total TCO of the hydrogen bus.
This work presents the results of experimental operation of a solar-driven climate system using mixed-integer nonlinear model predictive control (MPC). The system is installed in a university building and consists of two solar thermal collector fields, an adsorption cooling machine with different operation modes, a stratified hot water storage with multiple inlets and outlets as well as a cold water storage. The system and the applied modeling approach is described and a parallelized algorithm for mixed-integer nonlinear MPC and a corresponding implementation for the system are presented. Finally, we show and discuss the results of experimental operation of the system and highlight the advantages of the mixed-integer nonlinear MPC application.
Lithium‐ion battery cells are multiscale and multiphysics systems. Design and material parameters influence the macroscopically observable cell performance in a complex and nonlinear way. Herein, the development and application of three methodologies for model‐based interpretation and visualization of these influences are presented: 1) deconvolution of overpotential contributions, including ohmic, concentration, and activation overpotentials of the various cell components; 2) partial electrochemical impedance spectroscopy, allowing a direct visualization of the origin of different impedance features; and 3) sensitivity analyses, allowing a systematic assessment of the influence of cell parameters on capacity, internal resistance, and impedance. The methods are applied to a previously developed and validated pseudo‐3D model of a high‐power lithium‐ion pouch cell. The cell features a blend cathode. The two blend components show strong coupling, which can be observed and interpreted using the results of overpotential deconvolution, partial impedance spectroscopy, and sensitivity analysis. The presented methods are useful tools for model‐supported lithium‐ion cell research and development.
This article presents a comparative experimental study of the electrical, structural and chemical properties of large‐format, 180 Ah prismatic lithium iron phosphate (LFP)/graphite lithium‐ion battery cells from two different manufacturers. These cells are particularly used in the field of stationary energy storage such as home‐storage systems. The investigations include (1) cell‐to‐cell performance assessment, for which a total of 28 cells was tested from each manufacturer, (2) electrical charge/discharge characteristics at different currents and ambient temperatures, (3) internal cell geometries, components, and weight analysis after cell opening, (4) microstructural analysis of the electrodes via light microscopy and scanning electron microscopy, (5) chemical analysis of the electrode materials using energy‐dispersive X‐ray spectroscopy, and (6) mathematical analysis of the electrode balances. The combined results give a detailed and comparative insight into the cell characteristics, providing essential information needed for system integration. The study also provides complete and self‐consistent parameter sets for the use in cells models needed for performance prediction or state diagnosis.
A Simple and Reliable HPTLC Method for the Quantification of the Intense Sweetener Sucralose®
(2003)
This paper describes a simple and fast thin layer chromatography (TLC) method for the monitoring of the relatively new intense sweetener Sucralose® in various food matrices. The method requires little or no sample preparation to isolate or concentrate the analyte. The Sucralose® extract is separated on amino‐TLC‐plates, and the analyte is derivatized “reagent‐free” by heating the developed plate for 20 min at 190°C. Spots can be measured either in the absorption or fluorescence mode. The method allows the determination of Sucralose® at the levels of interest regarding foreseen European legislation (>50 mg/kg) with excellent repeatability (RSD = 3.4%) and recovery data (95%).
Quantification of astaxanthin in salmons by chemiluminescence and absorption after TLC separation
(2018)
Astaxanthin is a keto-carotenoid, belongs to the chemical class of terpenes and is a yellow lipid soluble compound. The compound is present in marine animals like salmons and crustacean. Its colour is due to conjugated double bonds and these double bonds are responsible for its antioxidant effect. Its antioxidant activity is ten times stronger than other carotenoids and nearly 500 fold stronger than vitamin-E. We present a new thin layer chromatography (TLC) method to measure astaxanthin on TLC-plates (Merck, 1.05554) in the visible absorption range as well as by using chemiluminescence. For separation a solvent mixture of cyclohexane and acetone (10 + 2.4, v/v) was used. The RF-value of astaxanthin is 0.14.The limit of detection in vis-absorption is 64 ng / band and the limit of quantification is 92 ng/band. In chemiluminescence the values are 90 ng / band and 115 ng/band. The method offers two independently working measurement modes on a single plate which increase the accuracy of the quantification.
Experimental Investigation of the Air Exchange Effectiveness of Push-Pull Ventilation Devices
(2020)
The increasing installation numbers of ventilation units in residential buildings are driven by legal objectives to improve their energy efficiency. The dimensioning of a ventilation system for nearly zero energy buildings is usually based on the air flow rate desired by the clients or requested by technical regulations. However, this does not necessarily lead to a system actually able to renew the air volume of the living space effectively. In recent years decentralised systems with an alternating operation mode and fairly good energy efficiencies entered the market and following question was raised: “Does this operation mode allow an efficient air renewal?” This question can be answered experimentally by performing a tracer gas analysis. In the presented study, a total of 15 preliminary tests are carried out in a climatic chamber representing a single room equipped with two push-pull devices. The tests include summer, winter and isothermal supply air conditions since this parameter variation is missing till now for push-pull devices. Further investigations are dedicated to the effect of thermal convection due to human heat dissipation on the room air flow. In dependence on these boundary conditions, the determined air exchange efficiency varies, lagging behind the expected range 0.5 < εa < 1 in almost all cases, indicating insufficient air exchange including short-circuiting. Local air exchange values suggest inhomogeneous air renewal depending on the distance to the indoor apertures as well as the temperature gradients between in- and outdoor. The tested measurement set-up is applicable for field measurements.
In this paper, we describe the PALM model system 6.0. PALM (formerly an abbreviation for Parallelized Large-eddy Simulation Model and now an independent name) is a Fortran-based code and has been applied for studying a variety of atmospheric and oceanic boundary layers for about 20 years. The model is optimized for use on massively parallel computer architectures. This is a follow-up paper to the PALM 4.0 model description in Maronga et al. (2015). During the last years, PALM has been significantly improved and now offers a variety of new components. In particular, much effort was made to enhance the model with components needed for applications in urban environments, like fully interactive land surface and radiation schemes, chemistry, and an indoor model. This paper serves as an overview paper of the PALM 6.0 model system and we describe its current model core. The individual components for urban applications, case studies, validation runs, and issues with suitable input data are presented and discussed in a series of companion papers in this special issue.
Ecological concerns on the climatic effects of the emissions from electricity production stipulate the remuneration of electricity grids to accept growing amounts of intermittent regenerative electricity feed-in from wind and solar power. Germany’s eager political target to double regenerative electricity production by 2030 puts pressure on grid operators to adapt and restructure their transmission and distribution grids. The ability of local distribution grids to operate autonomous of transmission grid supply is essential to stabilize electricity supply at the level of German federal states. Although congestion management and collaboration at the distribution system operator (DSO) level are promising approaches, relatively few studies address this issue. This study presents a methodology to assess the electric energy balance for the low-voltage grids in the German federal state of Baden-Württemberg, assuming the typical load curves and the interchange potential among local distribution grids by means of linear programming of the supply function and for typical seasonal electricity demands. The model can make a statement about the performance and development requirements for grid architecture for scenarios in 2035 and 2050 when regenerative energies will—according to present legislation—account for more than half of Germany’s electricity supply. The study details the amendment to Baden-Württemberg’s electricity grid required to fit the system to the requirements of regenerative electricity production. The suggested model for grid analysis can be used in further German regions and internationally to systematically remunerate electricity grids for the acceptance of larger amounts of regenerative electricity inflows. This empirical study closes the research gap of assessing the interchange potential among DSO and considers usual power loads and simultaneously usual electricity inflows.
Optimisation based economic despatch of real-world complex energy systems demands reduced order and continuously differentiable component models that can represent their part-load behaviour and dynamic responses. A literature study of existing modelling methods and the necessary characteristics the models should meet for their successful application in model predictive control of a polygeneration system are presented. Deriving from that, a rational modelling procedure using engineering principles and assumptions to develop simplified component models is applied. The models are quantitatively and qualitatively evaluated against experimental data and their efficacy for application in a building automation and control architecture is established.
Cooling towers or recoolers are one of the major consumers of electricity in a HVAC plant. The implementation and analysis of advanced control methods in a practical application and its comparison with conventional controllers is necessary to establish a framework for their feasibility especially in the field of decentralised energy systems. A standard industrial controller, a PID and a model based controller were developed and tested in an experimental set-up using market-ready components. The characteristics of these controllers such as settling time, control difference, and frequency of control actions are compared based on the monitoring data. Modern controllers demonstrated clear advantages in terms of energy savings and higher accuracy and a model based controller was easier to set-up than a PID.
Passive hybridization refers to a parallel connection of photovoltaic and battery cells on the direct current level without any active controllers or inverters. We present the first study of a lithium-ion battery cell connected in parallel to a string of four or five serially-connected photovoltaic cells. Experimental investigations were performed using a modified commercial photovoltaic module and a lithium titanate battery pouch cell, representing an overall 41.7 W-peak (photovoltaic)/36.8 W-hour (battery) passive hybrid system. Systematic and detailed monitoring of this system over periods of several days with different load scenarios was carried out. A scaled dynamic synthetic load representing a typical profile of a single-family house was successfully supplied with 100 % self-sufficiency over a period of two days. The system shows dynamic, fully passive self-regulation without maximum power point tracking and without battery management system. The feasibility of a photovoltaic/lithium-ion battery passive hybrid system could therefore be demonstrated.
Mass transfer phenomena in membrane fuel cells are complex and diversified because of the presence of complex transport pathways including porous media of very different pore sizes and possible formation of liquid water. Electrochemical impedance spectroscopy, although allowing valuable information on ohmic phenomena, charge transfer and mass transfer phenomena, may nevertheless appear insufficient below 1 Hz. Use of another variable, that is, back pressure, as an excitation variable for electrochemical pressure impedance spectroscopy is shown here a promising tool for investigations and diagnosis of fuel cells.
Silicon (Si) has turned out to be a promising active material for next‐generation lithium‐ion battery anodes. Nevertheless, the issues known from Si as electrode material (pulverization effects, volume change etc.) are impeding the development of Si anodes to reach market maturity. In this study, we are investigating a possible application of Si anodes in low‐power printed electronic applications. Tailored Si inks are produced and the impact of carbon coating on the printability and their electrochemical behavior as printed Si anodes is investigated. The printed Si anodes contain active material loadings that are practical for powering printed electronic devices, like electrolyte gated transistors, and are able to show high capacity retentions. A capacity of 1754 mAh/gSi is achieved for a printed Si anode after 100 cycles. Additionally, the direct applicability of the printed Si anodes is shown by successfully powering an ink‐jet printed transistor.
Fast charging of lithium-ion batteries remains one of the most delicate challenges for the automotive industry, being seriously affected by the formation of lithium metal in the negative electrode. Here we present a physicochemical pseudo-3D model that explicitly includes the plating reaction as side reaction running in parallel to the main intercalation reaction. The thermodynamics of the plating reaction are modeled depending on temperature and ion concentration, which differs from the often-used assumption of a constant plating condition of 0 V anode potential. The reaction kinetics are described with an Arrhenius-type rate law parameterized from an extensive literature research. Re-intercalation of plated lithium was modeled to take place either via reverse plating (solution-mediated) or via an explicit interfacial reaction (surface-mediated). At low temperatures not only the main processes (intercalation and solid-state diffusion) become slow, but also the plating reaction itself becomes slower. Using this model, we are able to predict typical macroscopic experimental observables that are indicative of plating, that is, a voltage plateau during discharge and a voltage drop upon temperature increase. A spatiotemporal analysis of the internal cell states allows a quantitative insight into the competition between intercalation and plating. Finally, we calculate operation maps over a wide range of C-rates and temperatures that allow to assess plating propensity as function of operating condition.
The following contribution deals with the experimental investigation and theoretical evaluation of fatigue crack growth under isothermal and non-isothermal conditions at the nickel alloy 617. The microstructure and mechanical properties of alloy 617 are influenced significantly by the thermal heat treatment and the following thermal exposure in service. Hence, a solution annealed and a long-time service exposed material condition is studied. The crack growth measurement is carried out by using an alternate current potential drop system, which is integrated into a thermomechanical fatigue (TMF) test facility. The measured fatigue crack growth rates results in a function of material condition, temperature and load waveform. Furthermore, the results of the non-isothermal tests depend on the phase between thermal and mechanical load (in-phase, out-of-phase). A fracture mechanic based, time dependent model is upgraded by an approach to consider environmental effects, where almost all model parameters represent directly measureable values. A consistent description of all results and a good correlation with the experimental data can be achieved.
Thermisch angetriebene (Adsorptions-)Kältemaschinen können mit einem verhältnismäßig geringen elektrischen Energieaufwand bzw. mit einer hohen elektrischen Leistungszahl Kälte bereitstel-len. Wird die zum Antrieb erforderliche Wärme aus industrieller Abwärme bereitgestellt, ist diese Kältebereitstellung energetisch effizienter als die Kältebereitstellung über eine Kompressionskäl-temaschine. Wird die Wärme jedoch in Kraft-Wärme-Kopplung bereitgestellt, ist die primärenergetische Bewertung sowohl von mehreren Teilwirkungsgraden als auch den Primärenergiefaktoren für den eingesetzten Brennstoff und die erzeugte bzw. bezogene elektrische Energie abhängig. Eine umfangreiche Messkampagne im Sommer 2018 liefert unter realitätsnahen Randbedingungen in einer Labor umgebung detaillierte Energiekennzahlen für einen typischen Tagesgang des Kältebedarfs. Damit gelingt es, Teilenergiekennwerte für die Planungspraxis abzuleiten und das Gesamtsystem energetisch mit einer konventionellen Kompressionskältemaschine zu vergleichen.
In this article we outline the model development planned within the joint projectModel-based city planningand application in climate change (MOSAIK). The MOSAIK project is funded by the German FederalMinistry of Education and Research (BMBF) within the frameworkUrban Climate Under Change ([UC]2)since 2016. The aim of MOSAIK is to develop a highly-efficient, modern, and high-resolution urban climatemodel that allows to be applied for building-resolving simulations of large cities such as Berlin (Germany).The new urban climate model will be based on the well-established large-eddy simulation code PALM, whichalready has numerous features related to this goal, such as an option for prescribing Cartesian obstacles. Inthis article we will outline those components that will be added or modified in the framework of MOSAIK.Moreover, we will discuss the everlasting issue of acquisition of suitable geographical information as inputdata and the underlying requirements from the model's perspective.
We present a planar chromatographic separation method for the compounds caffeine, artemisinin, and equol, separated on high-performance thin-layer chromatography (HPTLC) silica gel plates. As solvents for separation, methyl t-butyl ether and cyclohexane (1:1, V/V) have been used for equol, cyclohexane and ethyl acetate (7:3, V/V) for artemisinin, and ethyl acetate and acetone (7:3, V/V) for caffeine. After separation, the plate was scanned with a very specific time of flight-direct analysis in real time-mass spectrometry (TOF-DART-MS) system using the (M + 1)+ signals of equol, artemisinin, and caffeine. The (M + 1) peak of artemisinin at 283.13 m/z is clearly detectable, which is the proof that DART-MS is applicable for the quantitative determination of rather instable molecules. The planar set-up of DART source, HPTLC plate and detector inlet in a line showed higher sensitivities compared to desorption at an angle. The optimal detector voltage increases with the molar mass of the analyte, thus an individual determination of optimal detector voltage setting for the different analyte is recommended to achieve the best possible measurement conditions. In conclusion, DART-MS detection in combination with an HPTLC separation allows very specific quantification of all three compounds.
Modeling and simulation play a key role in analyzing the complex electrochemical behavior of lithium-ion batteries. We present the development of a thermodynamic and kinetic modeling framework for intercalation electrochemistry within the open-source software Cantera. Instead of using equilibrium potentials and single-step Butler-Volmer kinetics, Cantera is based on molar thermodynamic data and mass-action kinetics, providing a physically-based and flexible means for complex reaction pathways. Herein, we introduce a new thermodynamic class for intercalation materials into the open-source software. We discuss the derivation of molar thermodynamic data from experimental half-cell potentials, and provide practical guidelines. We then demonstrate the new class using a single-particle model of a lithium cobalt oxide/graphite lithium-ion cell, implemented in MATLAB. With the present extensions, Cantera provides a platform for the lithium-ion battery modeling community both for consistent thermodynamic and kinetic models and for exchanging the required thermodynamic and kinetic parameters. We provide the full MATLAB code and parameter files as supplementary material to this article.
This article presents the development, parameterization, and experimental validation of a pseudo-three-dimensional (P3D) multiphysics model of a 350 mAh high-power lithium-ion pouch cell with graphite anode and lithium cobalt oxide/lithium nickel cobalt aluminum oxide (LCO/NCA) blend cathode. The model describes transport processes on three different scales: Heat transport on the macroscopic scale (cell), mass and charge transport on the mesoscopic scale (electrode pair), and mass transport on the microscopic scale (active material particles). A generalized description of electrochemistry in blend electrodes is developed, using the open-source software Cantera for calculating species source terms. Very good agreement of model predictions with galvanostatic charge/discharge measurements, electrochemical impedance spectroscopy, and surface temperature measurements is observed over a wide range of operating conditions (0.05C to 10C charge and discharge, 5°C to 35°C). The behavior of internal states (concentrations, potentials, temperatures) is discussed. The blend materials show a complex behavior with both intra-particle and inter-particle non-equilibria during cycling.
Tryptamines can occur naturally in plants, mushrooms, microbes, and amphibians. Synthetic tryptamines are sold as new psychoactive substances (NPS) because of their hallucinogenic effects. When it comes to NPS, metabolism studies are of crucial importance, due to the lack of pharmacological and toxicological data. Different approaches can be taken to study in vitro and in vivo metabolism of xenobiotica. The zygomycete fungus Cunninghamella elegans (C. elegans) can be used as a microbial model for the study of drug metabolism. The current study investigated the biotransformation of four naturally occurring and synthetic tryptamines [N,N‐Dimethyltryptamine (DMT), 4‐hydroxy‐N‐methyl‐N‐ethyltryptamine (4‐HO‐MET), N,N‐di allyl‐5‐methoxy tryptamine (5‐MeO‐DALT) and 5‐methoxy‐N‐methyl‐N‐isoporpoyltryptamine (5‐MeO‐MiPT)] in C. elegans after incubation for 72 hours. Metabolites were identified using liquid chromatography–high resolution–tandem mass spectrometry (LC–HR–MS/MS) with a quadrupole time‐of‐flight (QqTOF) instrument. Results were compared to already published data on these substances. C. elegans was capable of producing all major biotransformation steps: hydroxylation, N‐oxide formation, carboxylation, deamination, and demethylation. On average 63% of phase I metabolites found in the literature could also be detected in C. elegans. Additionally, metabolites specific for C. elegans were identified. Therefore, C. elegans is a suitable complementary model to other in vitro or in vivo methods to study the metabolism of naturally occurring or synthetic tryptamines.
With the growing share of renewable energies in the electricity supply, transmission and distribution grids have to be adapted. A profound understanding of the structural characteristics of distribution grids is essential to define suitable strategies for grid expansion. Many countries have a large number of distribution system operators (DSOs) whose standards vary widely, which contributes to coordination problems during peak load hours. This study contributes to targeted distribution grid development by classifying DSOs according to their remuneration requirement. To examine the amendment potential, structural and grid development data from 109 distribution grids in South-Western Germany, are collected, referring to publications of the respective DSOs. The resulting data base is assessed statistically to identify clusters of DSOs according to the fit of demographic requirements and grid-construction status and thus identify development needs to enable a broader use of regenerative energy resources. Three alternative algorithms are explored to manage this task. The study finds the novel Gauss-Newton algorithm optimal to analyse the fit of grid conditions to regional requirements and successfully identifies grids with remuneration needs. It is superior to the so far used K-Means algorithm. The method developed here is transferable to other areas for grid analysis and targeted, cost-efficient development.
Cast aluminum alloys are frequently used as materials for cylinder head applications in internal combustion gasoline engines. These components must withstand severe cyclic mechanical and thermal loads throughout their lifetime. Reliable computational methods allow for accurate estimation of stresses, strains, and temperature fields and lead to more realistic Thermomechanical Fatigue (TMF) lifetime predictions. With accurate numerical methods, the components could be optimized via computer simulations and the number of required bench tests could be reduced significantly. These types of alloys are normally optimized for peak hardness from a quenched state that maximizes the strength of the material. However due to high temperature exposure, in service or under test conditions, the material would experience an over-ageing effect that leads to a significant reduction in the strength of the material. To numerically account for ageing effects, the Shercliff & Ashby ageing model is combined with a Chaboche-type viscoplasticity model available in the finite-element program ABAQUS by defining field variables. The constitutive model with ageing effects is correlated with uniaxial cyclic isothermal tests in the T6 state, the overaged state, as well as thermomechanical tests. On the other hand, the mechanism-based TMF damage model (DTMF) is calibrated for both T6 and over-aged state. Both the constitutive and the damage model are applied to a cylinder head component simulating several cycles on an engine dynamometer test. The effects of including ageing for both models are shown.
High temperature components in internal combustion engines and exhaust systems must withstand severe mechanical and thermal cyclic loads throughout their lifetime. The combination of thermal transients and mechanical load cycling results in a complex evolution of damage, leading to thermomechanical fatigue (TMF) of the material. Analytical tools are increasingly employed by designers and engineers for component durability assessment well before any hardware testing. The DTMF model for TMF life prediction, which assumes that micro-crack growth is the dominant damage mechanism, is capable of providing reliable predictions for a wide range of high-temperature components and materials in internal combustion engines. Thus far, the DTMF model has employed a local approach where surface stresses, strains, and temperatures are used to compute damage for estimating the number of cycles for a small initial defect or micro-crack to reach a critical length. In the presence of significant gradients of stresses, strains, and temperatures, the use of surface field values could lead to very conservative estimates of TMF life when compared with reported lives from hardware testing. As an approximation of gradient effects, a non-local approach of the DTMF model is applied. This approach considers through-thickness fields where the micro-crack growth law is integrated through the thickness considering these variable fields. With the help of software tools, this method is automated and applied to components with complex geometries and fields. It is shown, for the TMF life prediction of a turbocharger housing, that the gradient correction using the non-local approach leads to more realistic life predictions and can distinguish between surface cracks that may arrest or propagate through the thickness and lead to component failure.
Instabilities of the interface between two thin liquid films under DC electroosmotic flow are investigated using linear stability analysis followed by an asymptotic analysis in the long-wave limit. The two-liquid system is bounded by two rigid plates which act as substrates. The Boltzmann charge distribution is considered for the two electrolyte solutions and gives rise to a potential distribution in these liquids. The effect of van der Waals interactions in these thin films is incorporated in the momentum equations through the disjoining pressure. Marginal stability and growth rate curves are plotted in order to identify the thresholds for the control parameters when instabilities set in. If the upper liquid is a dielectric, the applied electric field can have stabilizing or destabilizing effects depending on the viscosity ratio due to the competition between viscous and electric forces. For viscosity ratio equal to unity, the stability of the system gets disconnected from the electric parameters like interface zeta potential and electric double-layer thickness. As expected, disjoining pressure has a destabilizing effect, and capillary forces have stabilizing effect. The overall stability trend depends on the complex contest between all the above-mentioned parameters. The present study can be used to tune these parameters according to the stability requirement.
DEM–FEA estimation of pores arrangement effect on the compressive Young’s modulus for Mg foams
(2015)
This work reports the study of the effect of the pore arrangement on the compressive behavior of Mg foams with regular pore size and porosities ranging from 25% to 45%. Pore arrangements were modeled using Finite Element Analysis (FEA), with random and ordered models, and compared to the estimations obtained for a previous work. The coordinates of the random pore arrangements were firstly generated using Discrete Element Method (DEM), and used in a second stage for modeling the pores by FEA. Estimations were also compared to the experimental results for Mg foams obtained by means of powder metallurgy. Results show important drops in the Young’s moduli as the porosity increases for both, experimental results and FEA estimations. Estimations obtained using ordered pore arrangements presented significant differences when compared to the estimations acquired from models with random arrangements. The randomly arranged models represent more accurately the real topologies of the experimental metallic foams. The Young’s moduli estimated using these models were in excellent agreement with the experiments, whilst the estimations obtained using ordered models presented relative errors significantly higher. The importance of the use of more realistic FEA models for improving the predicting ability of this method was probed, for the study of the mechanical properties of metallic foams.
The formation and analysis of ten microporous triazolyl isophthalate based MOFs, including nine isomorphous and one isostructural compound is presented. The compounds 1 M – 3 M with the general formula [ M ( R 1 - R 2 - trz - ia ) ] ∞ 3 ·x H 2 O (M 2+ = Co 2+ , Cu 2+ , Zn 2+ , Cd 2+ ; R 1 = H, Me; R 2 = 2py, 2pym, prz (2py = 2-pyridinyle; 2pym = 2-pyrimidinyle; prz = pyrazinyle)) crystallize with rtl topology. They are available as single crystals and also easily accessible in a multi-gram scale via refluxing the metal salts and the protonated ligands in a solvent. Their isomorphous structures facilitate the synthesis of heteronuclear MOFs; in case of 2 M , Co 2+ ions could be gradually substituted by Cu 2+ ions. The Co 2+ :Cu 2+ ratios were determined by ICP-OES spectroscopy, the distribution of Co 2+ and Cu 2+ in the crystalline samples are investigated by SEM-EDX analysis leading to the conclusions that Cu 2+ is more favorably incorporated into the framework compared to Co 2+ and, moreover, that the distribution of the two metal ions between the crystals and within the crystals is inhomogeneous if the crystals were grown slowly. The various compositions of the heteronuclear materials lead to different colors and the sorption properties for CO 2 and N 2 are dependent on the integrated metal ions.
We tested the MOF framework Cu-BTC for natural gas (NG) storage. Adsorption isotherms of C1–C4 alkanes were simulated applying the Grand Canonical ensemble and the Monte Carlo algorithm in a classical molecular mechanics approach. Experimental monocomponent isotherm of the alkanes was used to validate the force field. We performed multicomponent adsorptions calculations for three different quaternary mixtures of C1–C4 alkanes, matching typical NG streams composition, and predicted theoretical storage capacities, efficiency and accumulation of the NG within that composition. Despite being one of the frameworks with greatest storage capacity of methane, we found that Cu-BTC presented great sensitivity to the variation of the heavier alkanes in NG composition. When we increase the percentage of butane from 0.1% to 0.7% in the mixture, the mass of components retained in the discharge pressure (1 bar) increases from 35 to 60%. We also perform siting and interaction energy investigations and compare the NG storage performance of the Cu-BTC with that of activated carbons. To our knowledge, this is the first study regarding the efficiency of the NG storage in Cu-BTC.
Die Analyse von Engpässen im Güterverkehr ist eine wichtige Voraussetzung, um zukünftige Heraus-forderungen der Infrastrukturplanung und Logistik bewältigen zu können. Im Rahmen des EU-Projekts Code24 sollen Strategien für die Behandlung zukünftiger Herausforderungen im Schienengüterverkehr im wichtigsten europäischen Güterverkehrskorridor Rotterdam-Genua entwickelt werden. Hierfür sind Infor-mationen über Zugzahlen und die Kapazitätsauslastung auf einzelnen Streckenabschnitten eine wichtige Voraussetzung.
Raman spectra from three different binary gasoline-ethanol blends (with ratios 95:5, 90:10, and 85:15) have been obtained by using a low-cost, frequency precise Fourier-transform Raman spectrometer (FT-Raman) prototype. The spectral information is presented in the range of 0 to 3500 cm-1 with a resolution of 1.66 cm-1, which is greater than the required for most liquid and solid chemical samples. This set-up delivers spectral information about the sample with a reduced spectral deviation compared to theoretical values (less than 0.4 cm-1 without compensation for instrumental response). The robust and highly fexible FT-Raman prototype presented for the spectral analysis, consisting mainly of a Michelson interferometer and a self-designed photon counter, is able to deliver high resolution and frequency precise Raman spectra from the gasoline-ethanol blends comparable to the obtained by using commercial devices. This FT-Raman set-up does not need additional complex hardware or software control and relies on re-sampling and interpolation algorithms. The qualitative spectral information obtained has been used to calculate the proportion of gasoline and ethanol present in the used chemical samples without using extra calibrations methods or chemical markers.
Die Zuverlässigkeit und Betriebssicherheit von Feldgeräten ist für den sicheren und wirtschaftlichen Betrieb prozesstechnischer Anlagen unerlässlich. Ein entscheidender Faktor ist die Widerstandskraft der Geräte gegen die herrschenden Umgebungsbedingungen. Durch Korrosionsschäden hervorgerufene Anlagenstillstände zeigen, dass diesem Thema nicht immer die notwendige Aufmerksamkeit gewidmet wird, obwohl die korrosionsbedingten wirtschaftlichen Schäden immens sind. Wie man mit dem Thema Korrosionsschutz ernsthaft umgehen kann, zeigt dieser Beitrag am Beispiel elektrischer Stellantriebe.
Im Eurocode 3 wird im Gegensatz zu DIN 18800 die Bemessung von Verbindungen nicht in der Grundnorm DIN EN 1993‐1‐1, sondern in anderen Normenteilen geregelt. Dieser Beitrag behandelt die Bemessung geschweißter Verbindungen nach DIN EN 1993‐1‐8, die auch Hohlprofile, aber weder dünnwandige Bauteile noch Stähle höherer Festigkeit als S460 einschließt, vergleicht diese Bemessung mit der nach DIN 18800‐1, erläutert sie an Beispielen und hebt die wesentlichen Änderungen hervor. Da diese Änderungen auch die im Vergleich zu DIN 18800 viel stärkere Verknüpfung der in der Tragwerksplanung ansetzbaren Beanspruchbarkeiten mit dem Aufwand der Prüfung und Qualitätsüberwachung bei der Herstellung betreffen, werden abschließend wichtige Regelungen der DIN EN 1090‐2 zur Ausführung und Prüfung von Schweißnähten beschrieben, die auch der Tragwerksplaner kennen muss.
Improved separation of highly toxic contact herbicides paraquat (1,1′-dimethyl-4-4′-bipyridinium), diquat (6,7-dihydrodipyridol[ 1,2-a:2′,1′-c]pyrazine-5,8-di-ium), difenzoquat (1,2-dimethyl-3,5-diphenyl-1H-pyrazolium-methyl sulfate), mepiquat (1,1-dimethyl-piperidinium), and chloromequat (2-chloroethyltrimethylammonium) were presented by high-performance thin-layer chromatography (HPTLC). The quantification is based on a derivatization reaction, using sodium tetraphenylborate. Measurements were made in the wavelength range from 500 to 535 nm, using a light-emitting diode (LED) for excitation purposes, which emits very dense light at 365 nm. For calculations, a new theory of standard addition method was used, thus leading to a minimal error if exactly the same amount of sample content is added as a standard. The method provides a fast and inexpensive approach to quantification of the five most important quats used for plant protection purposes. The method works reliably because it takes into account losses during pre-treatment procedure. The method meets the European legislation limits for paraquat and diquat in drinking water according to United States Environmental Protection Agency (US EPA) method 549.2 which are 680 ng L−1 for paraquat and 720 ng L−1 for diquat. The method of standard addition in planar chromatography can be beneficially used to reduce systematic errors. Although recovery rates of 33.7% to 65.2% are observed, calculated contents according to the method of standard addition lie between 69% and 127% of the theoretical amounts.
The CO2 uptake on nanoscale AlO(OH) hollow spheres (260 mg g−1) as a new material is comparable to that on many metal–organic frameworks although their specific surface area is much lower (530 m2 g¬1versus 1500–6000 m2g¬1). Suited temperature–pressure cycles allow for reversible storage and separation of CO2 while the CO2 uptake is 4.3-times higher as compared to N2.
Pure gas adsorption isotherms of CH4 and N2 and their binary mixtures were measured at 273 K, 298 K and 323 K and up to 2 MPa on two different microporous metal–organic frameworks (MOFs), i.e. the commercially available Basolite® A100 and the recently reported copper-based triazolyl benzoate MOF 3∞[Cu(Me-4py-trz-ia)] (1). The Tòth isotherm model and the vacancy solution model were used to describe the experimentally determined isotherms and proved to be well suited for this purpose. While 1 shows a more homogeneous surface with a nearly constant isosteric heat of adsorption of 18–18.5 kJ mol−1 for CH4 and 12–15 kJ mol−1 for N2, the isosteric heat of adsorption at zero coverage for Basolite® A100 is 19 kJ mol−1 for CH4 and 16.2 kJ mol−1 for N2, decreasing significantly with increasing loading. Binary adsorption isotherms were measured gravimetrically to determine the total adsorbed mass of CH4 and N2. The van Ness method was successfully applied to calculate partial loadings from gravimetrically measured binary adsorption isotherms. Further studies by volumetric–chromatographic experiments support the good correlation between experimental data and predictions by the vacancy solution model (VSM-Wilson) and the ideal adsorbed solution theory (IAST) from pure gas isotherms. The experimental selectivities were determined to be αCH4/N2 = 4.0–5.0 for 1, slightly higher than for Basolite® A100 with αCH4/N2 = 3.4–4.5. These values are in good agreement with predictions for ideal selectivities based on Henry's law constants. From the experimental selectivities the potential of both MOFs in gas separation of CH4 from N2 can be derived.
Limits of quantification of some neonicotinoid insecticides measured by thin-layer chromatography
(2012)
A simple method to quantify the neonicotinoid insecticides nitenpyram, thiamethoxam, acetamiprid, imidacloprid, thiacloprid and clothianidin directly on an HPTLC-plate is presented. As stationary phase silica gel 60 RP-18WF254 s plates were used and a mixture of methyl-t-butyl ether, 2-butanone, NH3 (25%) (5 + 2+0.1, v/v) was used as solvent. All neonicotinoid insecticides show light absorptions below 300 nm. The calculated limits of quantification (LOQ) by UV-detection are in the range from 12 ng to 26 ng on plate depending on the different insecticides.Nitenpyram can be stained using fast blue salt B, forming red zones. The observed LOQ is 25 ng on plate. Acetamiprid can be specifically stained using phenylglyoxylic acid forming a yellow/green fluorescent compound. The LOQ is 52 ng per spot.The compounds thiamethoxam, acetamiprid, thiacloprid and clothianidin can be transformed into blue fluorescing zones, using a relatively new staining solution. This consists of tetraphenylborate and HCl. This is the first publication mentioning that neonicotinoids undergo this reaction. The calculated limits of quantification are in the range from 10 ng to 27 ng on plate.A simple pre-treatment procedure using an acetonitrile extraction and a Chromabond SiOH clean up procedure leads to overall LOQs for bee samples of 48 to 108 µg/Kg. The method can be used to measure neonicotinoid contaminations of bees.
In this paper, the multiaxial formulation of a mechanism-based model for fatigue life prediction is presented whichcan be applied to low-cycle fatigue (LCF) and thermomechanical fatigue (TMF) problems in which high-cycle fa-tigue loadings are superimposed. The model assumes that crack growth is the lifetime limiting mechanism and thatthe crack advance in a loading cycleda/dNcorrelates with the cyclic crack-tip opening displacement ΔCTOD.The multiaxial formulation makes use of fracture mechanics solutions and thus, does not need additional modelparameters quantifying the effect of the multiaxiality. Furthermore, the model includes contributions of HCF on ΔCTODand assesses the effect of the direction of the HCF loadings with respect to LCF or TMF loadings inthe life prediction. The model is implemented into the finite-element program ABAQUS. It is applied to predictthe fatigue life of a thermomechanically loaded notched specimen that should represent the situation between theinlet and outlet bore holes of cylinder heads. A good correlation of the predicted and the measured fatigue lives isobtained.
The newly synthesized Zn4O-based MOF 3∞[Zn4(μ4-O){(Metrz-pba)2mPh}3]·8 DMF (1·8 DMF) of rare tungsten carbide (acs) topology exhibits a porosity of 43% and remarkably high thermal stability up to 430 °C. Single crystal X-ray structure analyses could be performed using as-synthesized as well as desolvated crystals. Besides the solvothermal synthesis of single crystals a scalable synthesis of microcrystalline material of the MOF is reported. Combined TG-MS and solid state NMR measurements reveal the presence of mobile DMF molecules in the pore system of the framework. Adsorption measurements confirm that the pore structure is fully accessible for nitrogen molecules at 77 K. The adsorptive pore volume of 0.41 cm3 g−1 correlates well with the pore volume of 0.43 cm3 g−1 estimated from the single crystal structure.
An isomorphous series of 10 microporous copper-based metal–organic frameworks (MOFs) with the general formulas ∞3[{Cu3(μ3-OH)(X)}4{Cu2(H2O)2}3(H-R-trz-ia)12] (R = H, CH3, Ph; X2– = SO42–, SeO42–, 2 NO32– (1–8)) and ∞3[{Cu3(μ3-OH)(X)}8{Cu2(H2O)2}6(H-3py-trz-ia)24Cu6]X3 (R = 3py; X2– = SO42–, SeO42– (9, 10)) is presented together with the closely related compounds ∞3[Cu6(μ4-O)(μ3-OH)2(H-Metrz-ia)4][Cu(H2O)6](NO3)2·10H2O (11) and ∞3[Cu2(H-3py-trz-ia)2(H2O)3] (12Cu), which are obtained under similar reaction conditions. The porosity of the series of cubic MOFs with twf-d topology reaches up to 66%. While the diameters of the spherical pores remain unaffected, adsorption measurements show that the pore volume can be fine-tuned by the substituents of the triazolyl isophthalate ligand and choice of the respective copper salt, that is, copper sulfate, selenate, or nitrate.
As a basis for the evaluation of hydrogen storage by physisorption, adsorption isotherms of H2 were experimentally determined for several porous materials at 77 K and 298 K at pressures up to 15 MPa. Activated carbons and MOFs were studied as the most promising materials for this purpose. A noble focus was given on how to determine whether a material is feasible for hydrogen storage or not, dealing with an assessment method and the pitfalls and problems of determining the viability. For a quantitative evaluation of the feasibility of sorptive hydrogen storage in a general analysis, it is suggested to compare the stored amount in a theoretical tank filled with adsorbents to the amount of hydrogen stored in the same tank without adsorbents. According to our results, an “ideal” sorbent for hydrogen storage at 77 K is calculated to exhibit a specific surface area of >2580 m2 g−1 and a micropore volume of >1.58 cm3 g−1.
In this work the adsorption of CO2 and CH4 on a series of isoreticular microporous metal–organic frameworks based on 2-substituted imidazolate-4-amide-5-imidates, IFP-1–IFP-6 (IFP = Imidazolate Framework Potsdam), is studied firstly by pure gas adsorption at 273 K. All experimental isotherms can be nicely described by using the Tòth isotherm model and show the preferred adsorption of CO2 over CH4. At low pressures the Tòth isotherm equation exhibits a Henry region, wherefore Henry's law constants for CO2 and CH4 uptake could be determined and ideal selectivity αCO2/CH4 has been calculated. Secondly, selectivities were calculated from mixture data by using nearly equimolar binary mixtures of both gases by a volumetric–chromatographic method to examine the IFPs. Results showed the reliability of the selectivity calculation. Values of αCO2/CH4 around 7.5 for IFP-5 indicate that this material shows much better selectivities than IFP-1, IFP-2, IFP-3, IFP-4 and IFP-6 with slightly lower selectivity αCO2/CH4 = 4–6. The preferred adsorption of CO2 over CH4 especially of IFP-5 and IFP-4 makes these materials suitable for gas separation application.
We present a video-densitometric quantification method for the pain killer known as diclofenac and ibuprofen. These non-steroidal anti-inflammatory drugs were separated on cyanopropyl bonded plates using CH2Cl2, methanol, cyclohexane (95 + 5 + 40, v/v) as mobile phase. The quantification is based on a bio-effective-linked analysis using Vibrio fisheri bacteria. Within 10 min a CCD-camera registered the white light of the light-emitting bacteria. Diclofenac and ibuprofen effectively suppressed the bacterial light emission which can be used for quantification within a linear range of 10 to 2000 ng. The detection limit for ibuprofen is 20 ng and the limit of quantification 26 ng per zone. Measurements were carried out using a 16-bit ST-1603ME CCD camera with 1.56 megapixels (from Santa Barbara Instrument Group, Inc., Santa Barbara, USA). The range of linearity covers more than two magnitudes because the extended Kubelka-Munk expression is used for data transformation. The separation method is inexpensive, fast, and reliable.
High pressure adsorption phenomena are discussed for different gases on HKUST-1 (Cu3(BTC)2, commercially available product BasoliteTM C300). Sorption isotherms for hydrogen, nitrogen, methane and carbon dioxide on HKUST-1 were measured in the temperature range of 273–343 K and at pressures up to 50 MPa. The calculated surface excess adsorption capacities for all four adsorptive are one of the highest reported in the literature for HKUST-1 samples. All surface excess data were further calculated from the experimental data by using the helium buoyancy correction. A detailed description was given.
Also a procedure to calculate the absolute amount adsorbed from the surface excess amount by using two different models is shown. Using one model, the density and the volume of the adsorbed phase can be calculated. The density of the adsorbed phase ρads corresponds to the liquid density of the adsorptive at its boiling point ρliq,BP. In case of hydrogen no excess maximum was found up to 50 MPa, so that one model could not be applied. Finally, the isosteric heat of adsorption for each gas was calculated by using the Clausius–Clapeyron equation.
In dem abgeschlossenen Vorhaben „Entwicklung von Rechenmodellen zur Lebensdauervorhersage von Motorbauteilen unter thermisch-mechanischer Ermüdungsbeanspruchung“ der Forschungsvereinigung Verbrennungskraftmaschinen e. V. (FVV) wurde am Fraunhofer Institut für Werkstoffmechanik IWM in Freiburg ein Materialmodell zur Lebensdauervorhersage thermomechanisch belasteter Komponenten entwickelt. Das Modell basiert auf einem viskoplastischen Verformungsmodell für Eisengusswerkstoffe und einem mechanismenbasierten Modell für Mikrorisswachstum zur Lebensdauervorhersage.
Crystal structures of two metal–organic frameworks (MFU‐1 and MFU‐2) are presented, both of which contain redox‐active CoII centres coordinated by linear 1,4‐bis[(3,5‐dimethyl)pyrazol‐4‐yl] ligands. In contrast to many MOFs reported previously, these compounds show excellent stability against hydrolytic decomposition. Catalytic turnover is achieved in oxidation reactions by employing tert‐butyl hydroperoxide and the solid catalysts are easily recovered from the reaction mixture. Whereas heterogeneous catalysis is unambiguously demonstrated for MFU‐1, MFU‐2 shows catalytic activity due to slow metal leaching, emphasising the need for a deeper understanding of structure–reactivity relationships in the future design of redox‐active metal–organic frameworks. Mechanistic details for oxidation reactions employing tert‐butyl hydroperoxide are studied by UV/Vis and IR spectroscopy and XRPD measurements. The catalytic process accompanying changes of redox states and structural changes were investigated by means of cobalt K‐edge X‐ray absorption spectroscopy. To probe the putative binding modes of molecular oxygen, the isosteric heats of adsorption of O2 were determined and compared with models from DFT calculations. The stabilities of the frameworks in an oxygen atmosphere as a reactive gas were examined by temperature‐programmed oxidation (TPO). Solution impregnation of MFU‐1 with a co‐catalyst (N‐hydroxyphthalimide) led to NHPI@MFU‐1, which oxidised a range of organic substrates under ambient conditions by employing molecular oxygen from air. The catalytic reaction involved a biomimetic reaction cascade based on free radicals. The concept of an entatic state of the cobalt centres is proposed and its relevance for sustained catalytic activity is briefly discussed.
Synthesis and crystal structure of a novel copper-based MOF material are presented. The tetragonal crystal structure of [ ∞ 3 ( Cu 4 ( μ 4 -O ) ( μ 2 -OH ) 2 ( Me 2 trz p ba ) 4 ] possesses a calculated solvent-accessible pore volume of 57%. Besides the preparation of single crystals, synthesis routes to microcrystalline materials are reported. While PXRD measurements ensure the phase purity of the as-synthesized material, TD-PXRD measurements and coupled DTA–TG–MS analysis confirm the stability of the network up to 230 °C. The pore volume of the microcrystalline material determined by nitrogen adsorption at 77 K depends on the synthetic conditions applied. After synthesis in DMF/H2O/MeOH the pores are blocked for nitrogen, whereas they are accessible for nitrogen after synthesis in H2O/EtOH and subsequent MeOH Soxhleth extraction. The corresponding experimental pore volume was determined by nitrogen adsorption to be V Pore = 0.58 cm 3 g - 1 . In order to characterize the new material and to show its adsorption potential, comprehensive adsorption studies with different adsorptives such as nitrogen, argon, carbon dioxide, methanol and methane at different temperatures were carried out. Unusual adsorption–desorption isotherms with one or two hysteresis loops are found – a remarkable feature of the new flexible MOF material.
Uptakes of 9.2 mmol g−1 (40.5 wt %) for CO2 at 273 K/0.1 MPa and 15.23 mmol g−1 (3.07 wt %) for H2 at 77 K/0.1 MPa are among the highest reported for metal–organic frameworks (MOFs) and are found for a novel, highly microporous copper‐based MOF (see picture; Cu turquoise, O red, N blue). Thermal analyses show a stability of the flexible framework up to 250 °C.
Metal–organic frameworks (MOFs) as highly porous materials have gained increasing interest because of their distinct adsorption properties.1–3 They exhibit a high potential for applications in gas separation and storage,4 as sensors5 as well as in heterogeneous catalysis.6 In the last few years, the H2 storage capacity of MOFs has been considerably increased. Mesoporous MOFs show high adsorption capacities for CH4, CO2, and H2 at high pressures.2, 3, 7–10 To increase the uptake of H2 and CO2 by physisorption at ambient pressure, adsorbents with small micropores as well as high specific surface areas and micropore volumes are required.11, 12 Such microporous materials seem to be more appropriate for gas‐mixture separation by physisorption than mesoporous materials. For gas separation in MOFs the interactions between the fluid adsorptive and “open metal sites” (coordinatively unsaturated binding sites) or the ligands are regarded as important.13 Industrial processes, such as natural‐gas purification or biogas upgrading, can be improved with those materials during a vapor‐pressure swing adsorption cycle (VPSA cycle) or a temperature swing adsorption cycle (TSA cycle).14 The microporous MOF series CPO‐27‐M (M=Mg, Co, Ni, Zn), for example, shows very high CO2 uptakes at low pressures (<0.1 MPa).15, 16 Concerning H2 adsorption, the microporous MOF PCN‐12 offers with 3.05 wt % the highest uptake at ambient pressure and 77 K reported to date.17
Herein, we present a novel microporous copper‐based MOF equation image[Cu(Me‐4py‐trz‐ia)] (1; Me‐4py‐trz‐ia2−=5‐(3‐methyl‐5‐(pyridin‐4‐yl)‐4H‐1,2,4‐triazol‐4‐yl)isophthalate) with extraordinarily high CO2 and H2 uptakes at ambient pressure, the H2 uptake being similar to that in PCN‐12. The ligand Me‐4py‐trz‐ia2−, which can be obtained from cheap starting materials by a three‐step synthesis in good yield, combines carboxylate, triazole, and pyridine functions and is adopted from a recently presented series of linkers,18 for which up to now only a few coordination polymers are known.
The present study describes medium-chain-length polyhydroxyalkanoates (mcl-PHAs) production by the Pseudomonas Gl01 strain isolated from mixed microbial communities utilized for PHAs synthesis. A two-step fedbatch fermentation was conducted with glucose and waste rapeseed oil as the main carbon source for obtaining cell growth and mcl-PHAs accumulation, respectively. The results show that the Pseudomonas Gl01 strain is capable of growing and accumulating mcl-PHAs using a waste oily carbon source. The biomass value reached 3.0 g/l of CDW with 20% of PHAs content within 48 h of cultivation. The polymer was purified from lyophilized cells and analyzed by gas chromatography (GC). The results revealed that the monomeric composition of the obtained polyesters depended on the available substrate. When glucose was used in the growth phase, 3-hydroxyundecanoate and 3- hydroxydodecanoate were found in the polymer composition, whereas in the PHAs-accumulating stage, the Pseudomonas Gl01 strain synthesized mcl-PHAs consisting mainly of 3- hydroxyoctanoate and 3-hydroxydecanoate. The transcriptional analysis using reverse-transcription real-time PCR reaction revealed that the phaC1 gene could be transcribed simultaneously to the phaZ gene.
An analytical and numerical study of the wobbling dynamics of friction disks is presented. Of particular interest is the excitation mechanism taking into account two contrarian effects both originating in dry friction: the circulatory terms describing the energy input due to the sliding contacts and the friction induced damping which stabilizes the system. Balance of these terms determines the instability domain in the parameter space. It is shown that there is a slip threshold so that, if the slip is under this limit, the system remains stable. If the slip is larger than this limit, then the criterion of stability is determined by the relation between the friction coefficient and the internal damping. The limit cycle appearing in the unstable domain is also investigated. It is shown that the limit cycle can be described as a kind of a regular reverse precession of the wobbling disc. Its amplitude is limited by the geometric nonlinearity and partial contact loss. Analytic results are compared with numeric simulations.
This work provides a series of methane adsorption isotherms and breakthrough curves on one 5A zeolite and one activated carbon. Breakthrough curves of CH4 were obtained from dynamic column measurements at different temperature and pressure conditions for concentrations of 4.4 – 17.3 mol.‐% in H2/CH4 mixtures. A simple model was developed to simulate the curves using measured and calculated data inputs. The results show that the model predictions agree very well with the experiments.
Regarding the importance of adsorptive removal of carbon monoxide from hydrogen-rich mixtures for novel applications (e.g. fuel cells), this work provides a series of experimental data on adsorption isotherms and breakthrough curves of carbon monoxide. Three recently developed 5A zeolites and one commercial activated carbon were used as adsorbents. Isotherms were measured gravimetrically at temperatures of 278–313 K and pressures up to 0.85 MPa. Breakthrough curves of CO were obtained from dynamic column measurements at temperatures of 298–301 K, pressures ranging from 0.1 MPa to ca. 6 MPa and concentrations of CO in H2/CO mixtures of 5–17.5 mol%. A simple mathematical model was developed to simulate breakthrough curves on adsorbent beds using measured and calculated data as inputs. The number of parameters and the use of correlations to evaluate them were restricted in order to focus the importance of measured values. For the given assumptions and simplifications, the results show that the model predictions agree satisfactorily with the experimental data at the different operating conditions applied.
Cost effectiveness of preventive screening programmes for type 2 diabetes mellitus in Germany
(2010)
As in several other industrialized countries, Germany’s statutory health insurance (SHI) is facing rising healthcare costs as well as the challenges caused by a double-aging society. The early detection and prevention of chronic diseases is considered a possible way to reduce the impact of these developments. However, controversy surrounds the costs and effects in terms of medical and financial outcomes of such programmes.
The engineering company Evomotiv GmbH and the University of Applied Sciences Offenburg have developed a drive concept for light city scooters since 2008. The electrical drive train's goal is the series production of the highly-integrated, non-transmission and non-ferrous wheel-hub motor. The German Federal Ministry of Economy and Technology (BMWi) supports this project. The concept of this wheel-hub motor was awarded with the Bosch-Innovation prize in 2006. In 2011 Evomotiv will test the first prototypes with its cooperation partners on the track.
Hydrogen chloride and sulphur dioxide are gaseous by-products of chloridization processes that employ thionyl chloride. Absorption would be a feasible method to clean the rich gas stream. Two serial connectable absorption columns were equipped with the latest generation of packings to effect product recovery. Therefore, several tests concerning the baffle properties had to be performed. In the first experimental section, the hydraulic parameters pressure drop and hold-up were investigated. The hold up value range of the new baffles Raschig Super Ring (RSR) and Raschig Super Pak (RSP) was clearly below that of the former installed packing, Raschig Ring (RR). However, due to the low maximal flow rate, the range of stagnation and flooding could not be measured. The maximal measured pressure drop value was, for RR, only 0.3 mbar/m, which is very low compared to the measurement error. Batch experiments, where the waste gases were produced by reaction of thionyl chloride in water, showed that for the steady state determination of the separation steps it is advisable to use just one column in simplex mode with a defined gas supply by a gas cylinder. The HTU determination for RSR and a HCl/H2O system delivered a value of HTUHCl,OG = 0.14 ± 0.01 m with a variation coefficient of 24.2%.
A diode array HPTLC method for dequalinium chloride in pharmaceutical preparations is presented. For separation a Nano TLC silica gel plate (Merck) is used with the mobile phase methanol-7.8% aqueous NH(4)(+)CH(3)COO(-) (17:3, v/v) over a distance of 6 cm. Dequalinium chloride shows an R(F) value of 0.58. Pure dequalinium chloride is measured in the wavelength range from 200 to 500 nm and shows several by-products, contour plot visualized in absorption, fluorescence and using the Kubelka-Munk transformation. Scanning of a single track in absorption and fluorescence measuring 600 spectra in the range from 200 to 1100 nm takes 30s. As a sample pre-treatment of an ointment it is simply dissolved in methanol and can be quantified in absorption from 315 to 340 nm. The same separation can also be quantified using fluorescence spectrometry in the range from 355 to 370 nm. A new staining method for dequalinium chloride, using sodium tetraphenyl borate/HCl in water allows a fluorescence quantification in the range from 445 to 485 nm. The linearity range of absorption and fluorescence measurements is from 10 to 2000 ng. Sugar-containing preparations like liquids or lozenges with a reduced sample pre-treatment can be reliably quantified only in fluorescence. The total for the quantification of an ointment sample (measuring four standards and five samples), including all sample pre-treatment steps takes less than 45 min!
We report improved separation of the highly toxic contact herbicides paraquat, diquat, difenzoquat, mepiquat, and chloromequat by HPTLC. Quantification was based on a new derivatization reaction using sodium tetraphenylborate. Measurements were in the wavelength range from 440 to 480 nm or from 440 to 590 nm. An LED emitting very intense light at 365 nm was used for excitation. The quantification limits of paraquat and diquat in water, using improved solid-phase extraction, was in the low ng L −1 range. The linear range covered more than two orders of magnitude. Recovery was investigated for all the compounds, and was insufficient, ranging from 11 to 92%, but the method is inexpensive, rapid, and works reliably.
Flows in nature and technology are often associated with specific structures and pattern. This paper deals with the development and behaviour of such flow pattern. Flow structures are important for the mass, momentum and energy transport. The behaviour of different flow pattern is used by engineers to obtain an efficient mass and energy consumption. Mechanical power is transmitted via the momentum of rotating machine parts. Therefore the physical and mathematical knowledge of these basic concepts is important. Theoretical and experimental investigations of principle experiments are described in the following. We start with the classical problem of the flow between two concentric cylinders where the inner cylinder rotates. Periodic instabilities occur which are called Taylor vortices. The analogy between the cylindrical gap flow, the heat transfer in a horizontal fluid layer exposed to the gravity field and the boundary layer flow along concave boundaries concerning their stability behaviour is addressed. The vortex breakdown phenomenon in a cylinder with rotating cover is also described. A generalization to spherical sectors leads then to investigations with different boundary conditions. The spherical gap flow exhibits interesting phenomena concerning the nonlinear character of the Navier-Stokes equations. Multiple solutions in the nonlinear regime give rise to different routes during the laminar-turbulent transition. The interaction of two rotating spheres results in flow structures with separation and stagnation lines. Experimental results are confirmed by numerical simulations.
The efficiency of a chromatographic analytical method is determined by the selectivity of the chromatographic separation and the specificity of the detection method. In high-performance thin-layer chromatography (HPTLC) the separated components can be detected and quantified directly on the plate by physical and chemical methods. By coupling high-performance thin-layer chromatography with biological or biochemical inhibition tests it is possible to detect toxic substances in situ.
We present an improved quantification method for urethane found in spirits. The quantification is based on a derivatization reaction using cinnamaldehyde in combination with phosphoric acid. Measurements were carried out in the wavelength range from 445 to 460 nm using a diode-TLC device. An LED was used for illumination purposes. It emits very dense light at 365 nm. The quantification range of urethane is in the lower ng range. By applying 20 µL of sprits, the urethane quantification range is from 320 µg/L to 8.1 mg urethane per litre of spirit. The range of linearity covers nearly two magnitudes. The method is cheap, fast and reliable, and is able to monitor all European legislation limits without time-consuming sample pre-treatments.
HPTLC on amino plates, with simple heating of the plates for derivatization, has been used for quantification of glucosamine in nutritional supplements. On heating the plate glucosamine reacts to form a compound which strongly absorbs light between 305 and 330 nm, with weak fluorescence. The reaction product can be detected sensitively either by absorption of light or by fluorescence detection. The detection limit in absorption mode is approximately 25 ng per spot. In fluorescence mode a detection limit of 15 ng is achievable. A calibration plot for absorption detection is linear in the range 25 to 4000 ng glucosamine. The derivative formed from glucosamine by heating is stable for months, and the relative standard deviation is 1.64% for 600 ng glucosamine. The amounts of glucosamine found in nutritional supplements were in agreement with the label declarations.
Soot particles emitted from a light duty (LD) Volkswagen diesel engine running at different operating points (speed and torque levels) are analyzed for mean size determination using a laser‐based three Wavelength Extinction Method (3‐WEM). For this reason, collected soot samples are suspended using an appropriate sample preparation technique with optimized conditions of sonication as it revealed its effect on the soot mean particle size measured by 3‐WEM.
An online Scanning Mobility Particle Analyzer (SMPS) is also used to measure soot emission at identical engine operating points. Size values obtained from SMPS are lower than those of suspended soot samples obtained from 3‐WEM. The size discrepancies are mainly related to the required sample preparation procedure employed for 3‐WEM measurements. The engine operating points affect, differently, the size measurements obtained from SMPS and 3‐WEM.
Sedimentation Field‐Flow Fractionation (SdFFF) is used for density determination of soot samples based on size measurements of fractions collected at peak maxima of fractograms using the off‐line hyphenation with 3‐WEM. It is assumed that a size dependent separation of soot particles occurred with a uniform particle density over the whole size distribution. An average density value is used for the conversion of soot fractograms to size distributions. Discrepancies are also found with size distribution profiles obtained from SMPS for the same engine operating points, due to the sample preparation procedure employed for SdFFF measurements.
The structure of the separation bubble that appears in the secondary meridional flow between two coaxially rotating spheres at low and finite Reynolds number (Re) is considered. The low Re analytical study was motivated by recognizing some errors in the analytical work on this problem by Arunachalam and Majhi (1987, Q. Jl Mech. Appl. Math., 40, 47) whilst the finite Re experimental study was motivated by the desire to observe the separation bubble in the laboratory. Though the finite Re experiments were performed in a confined apparatus, they exhibit the qualitative features of the low Re theoretical predictions for the axisymmetric separation bubble that encloses two toroidal vortices symmetrically disposed above and below the mid‐plane of sphere separation, but strong effects of confinement are apparent. The flows observed include (i) a wall‐attached bubble symmetric about the mid‐plane at low Re, (ii) symmetric free‐standing bubbles at moderate Re, and (iii) an asymmetric bubble with flow separating from one sphere and attaching to the support shaft between the spheres at sufficiently high Re.
The free convection in a vertical gap is generalized to realize new analytical solutions of the Boussinesq-equations. The steady and time-dependent solutions for the temperature and velocity distribution are discussed in detail depending on the mass flux in vertical direction. The range of existence for flows with and without back flow is obtained. The transient behaviour of the solutions during the time-dependent development displays interesting physical behaviour.
The use of a TLC scanner can be regarded as a key step in high performance thin layer chromatography (HPTLC). Densitometric measurements transform the substance distribution on a TLC plate into digital computer data. Systems that allow quantitative measurements have been available for many years for either fluorescence or ultraviolet absorption measurements, while lately the reflection analysis mode for both types is the most common application. New scanning approaches are designed to aid the analyst who has common demands for TLC-densitometry without using special data, such as scanned images. Two examples that have been developed lately in the laboratories of the authors are described in this paper. These approaches were developed on the basis of current needs for analysts who employ TLC as a tool in research, as well as in routine analysis. One approach is aimed to support analysts in economically disadvantaged areas, where cost intensive apparatus is unsuitable but trace analysis by simple means is required. The other system, allows the spectral determination of chromatographic spots on TLC plates covering the ultraviolet and visible range, thus, revealing highly desired information for the analyst.
The aim of this study was to develop a biomechanically validated finite element model to predict the biomechanical behaviour of the human lumbar spine in compression.
For validation of the finite element model, an in vitro study was performed: Twelve human lumbar cadaveric spinal segments (six segments L2/3 and six segments L4/5) were loaded in axial compression using 600 N in the intact state and following surgical treatment using two different internal stabilisation devices. Range of motion was measured and used to calculate stiffness.
A finite element model of a human spinal segment L3/4 was loaded with the same force in intact and surgically altered state, corresponding to the situation of biomechanical in vitro study.
The results of the cadaver biomechanical and finite element analysis were compared. As they were close together, the finite element model was used to predict: (1) load-sharing within human lumbar spine in compression, (2) load-sharing within osteoporotic human lumbar spine in compression and (3) the stabilising potential of the different spinal implants with respect to bone mineral density.
A finite element model as described here may be used to predict the biomechanical behaviour of the spine. Moreover, the influence of different spinal stabilisation systems may be predicted.
Ozon-Querempfindlichkeit bei der Immissionsmessung von schwebstaubakkumuliertem Benzo[a]pyren
(2002)
Für die Beschreibung der Belastung der Luft mit polycyclischen aromatischen Kohlenwasserstoffen (PAK) wird vorwiegend die Konzentration eines Vertreters, das auf Schwebstaub akkumulierte Benzo[a]pyren (BaP), analysiert. Hierbei stellt Benzo[a]pyren die Leit komponen te für die Stoffklasse der PAK dar. Auf europäischer Ebene ist vorgesehen, für diesen Luftinhaltsstoff einen Grenzwert als Jahresmittelwert festzulegen. Deshalb wird bei bei der Normungsbehörde CEN zurzeit eine Europäische Norm für diesen Stoff erarbeitet. Aus der Literatur ist bekannt, dass für Benzo[a]pyren eine Querempfindlichkeit gegen Ozon und NO2 besteht. Im Zuge der Neuentwicklung eines Probenahmekopfs (PNK) für PAK-Immissionsmessungen, der durch den Einsatz eines Ozon- Scrubbers eine ozonfreie Immissionsmessung der Benzo[a]pyren-Konzentration ermög licht, wurde in dieser Arbeit die prinzipielle Einsetzbarkeit dieses Probe nahmekopfs geprüft. Zu diesem Zweck wurden Voruntersuchungen und Feldversuche durchgeführt, mit dem Ziel, Kenntnisse über die Ozon-Querempfindlichkeit zu erhalten. Um die Ozon-Querempfindlichkeit bei der Benzo[a]pyren-Bestimmung zu studieren, wurde Ozon in den Ansaugbereich der Probenahme dosiert. Als Ergebnis der Untersuchungen kann festgehalten werden, dass für die Benzo[a]pyren-Immissionsmessung eine deutliche Ozon-Querempfindlichkeit besteht, die unter Einsatz des neuen Ozon- Scrubbers vermieden werden kann.
A systematic toxicological analysis procedure using high-performance thin layer chromatography in combination with fibre optical scanning densitometry for identification of drugs in biological samples is presented. Two examples illustrate the practicability of the technique. First, the identification of a multiple intake of analgesics: codeine, propyphenazone, tramadol, flupirtine and lidocaine, and second, the detection of the sedative diphenhydramine. In both cases, authentic urine specimens were used. The identifications were carried out by an automatic measurement and computer-based comparison of in situ UV spectra with data from a compiled library of reference spectra using the cross-correlation function. The technique allowed a parallel recording of chromatograms and in situ UV spectra in the range of 197–612 nm. Unlike the conventional densitometry, a dependency of UV spectra by concentration of substance in a range of 250–1000 ng/spot was not observed.
In-situ densitometry for qualitative or quantitative purposes is a key step in thin-layer chromatography (TLC). It is a simple means of quantification by measurement of the optical density of the separated spots directly on the plate. A new scanner has been developed which is capable of measuring TLC or HPTLC (high-performance thin-layer chromatography) plates simultaneously at different wavelengths without damaging the plate surface. Fiber optics and special fiber interfaces are used in combination with a diode-array detector. With this new scanner sophisticated plate evaluation is now possible, which enables use of chemometric methods in HPTLC. Different regression models have been introduced which enable appropriate evaluation of all analytical questions. Fluorescent measurements are possible without filters or special lamps and signal-to-noise ratios can be improved by wavelength bundling. Because of the richly structured spectra obtained from PAH, diode-array HPTLC enables quantification of all 16 EPA PAH on one track. Although the separation is incomplete all 16 compounds can be quantified by use of suitable wavelengths. All these aspects are enable substantial improvement of in-situ quantitative densitometric analysis.
Rotating flow systems are often used to study stability phenomena and structure developments. The closed spherical gap problem is generalized into an open flow system by superimposing a mass flux in meridional direction. The basic solutions at low Reynolds numbers are described by analytical methods. The nonlinear supercritical solutions are simulated numerically and realized in experiments. Novel steady and time-dependent modes of flows are obtained. The extensive results concern the stability behaviour, non-uniqueness of supercritical solutions, symmetry behaviour and transitions between steady and time-dependent solutions. The experimental investigations concern the visualization of the various instabilities and the quatitative description of the flow structures including the laminar-turbulent transition. A comparison between theoretical and experimental results shows good agreement within the limit of rotational symmetric solutions from the theory.
An algorithm is presented that has successfully been utilized in practice for several years. It improves data analysis in chromatography. The program runs in an extremely reliable way and evaluates chromatographic raw data with an acceptable error. The algorithm requires a minimum of preliminaries and integrates even unsmoothed noisy data correctly.
In this paper a high-performance thin-layer chromatography (HPTLC) scanner is presented in which a special fibre arrangement is used as HPTLC plate scanning interface. Measurements are taken with a set of 50 fibres at a distance of 400 to 500 μm above the HPTLC plate. Spatial resolutions on the HPTLC plate of better than 160 μm are possible. It takes less than 2 min to scan 450 spectra simultaneously in a range of 198 to 610 nm. The basic improvement of the item is the use of highly transparent glass fibres which provide excellent transmission at 200 nm and the use of a special fibre arrangement for plate illumination and detection.
Shapes and structures of vortex breakdown phenomena in rotating fluids are visualized. We investigate the flow in a cylindrical container and in a cone between two spherical surfaces. The primary swirling flow is induced by the rotating upper disk in the cylindrical case and by the lower boundary in the spherical case. The upper surface can be fixed with a no slip condition or can be a stress-free surface. Depending on these boundary conditions and on the Reynolds number novel structures of recirculation zones are realized. Experiments are done to visualize the topological structure of the flow and to determine their existence range as function of the geometry and rotation rate. A comparison between the experimental and theoretical approach shows a good agreement in respect to the topological structures of the flows.
Economic growth and ecological problems motivate industries to apply eco-friendly technologies and equipment. However, environmental impact, followed by energy and material consumption still remain the main negative implications of the technological progress in process engineering. Based on extensive patent analysis, this paper assigns more than 250 identified eco-innovation problems and requirements to 14 general eco-categories with energy consumption and losses, air pollution, and acidification as top issues. It defines primary eco-engineering contradictions, in case eco-problems appear as negative side effects of the new technologies, and secondary eco-engineering contradictions, if eco-friendly solutions have new environmental drawbacks. The study conceptualizes a correlation matrix between the eco-requirements for prediction of typical eco-contradictions on example of processes involving solids handling. Finally, it summarizes major eco-innovation approaches including Process Intensification in process engineering, and chronologically reviews 66 papers on eco-innovation adapting TRIZ methodology. Based on analysis of 100 eco-patents, 58 process intensification technologies, and literature, the study identifies 20 universal TRIZ inventive principles and sub-principles that have a higher value for environmental innovation.
The production of potable water in dry areas nowadays is mainly done by the desalination of seawater. State of the art desalination plants usually are built with high production capacities and consume a lot of electrical energy or energy from primary resources such as oil. This causes difficulties in rural areas, where no infrastructure is available neither for the plants’ energy supply nor the distribution of the produced potable water. To address this need, small, self-sustaining and locally operated desalination plants came into the focus of research. In this work, a novel flash evaporator design is proposed which can be driven either by solar power or by low temperature waste heat. It offers low operation costs as well as easy maintenance. The results of an experimental setup operated with water at a feed flow rate of up to 1,600 l/h are presented. It is shown that the proof of concept regarding efficient evaporation as well as efficient gas-liquid separation is provided successfully. The experimental evaporation yield counts for 98 % of the vapor content that is expected from the vapor pressure curve of water. Neither measurements of the electrical conductivity of the gained condensate, nor the analysis of the vapor flow by optical methods show significant droplet entrainment, so there are no concerns regarding the purity of the produced condensate for the use as drinking water.
Numerous 2,5-dimethoxy-N-benzylphenethylamines (NBOMe), carrying a variety of lipophilic substituents at the 4-position, are potent agonists at 5-hydroxytryptamine (5HT2A ) receptors and show hallucinogenic effects. The present study investigated the metabolism of 25D-NBOMe, 25E-NBOMe, and 25N-NBOMe using the microsomal model of pooled human liver microsomes (pHLM) and the microbial model of the fungi Cunninghamella elegans (C. elegans). Identification of metabolites was performed using liquid chromatography-high resolution-tandem mass spectrometry (LC-HR-MS/MS) with a quadrupole time-of-flight (QqToF) instrument. In total, 36 25D-NBOMe phase I metabolites, 26 25E-NBOMe phase I metabolites and 24 25N-NBOMe phase I metabolites were detected and identified in pHLM. Furthermore, 14 metabolites of 25D-NBOMe, 11 25E-NBOMe metabolites, and nine 25N-NBOMe metabolites could be found in C. elegans. The main biotransformation steps observed were oxidative deamination, oxidative N-dealkylation also in combination with hydroxylation, oxidative O-demethylation possibly combined with hydroxylation, oxidation of secondary alcohols, mono- and dihydroxylation, oxidation of primary alcohols, and carboxylation of primary alcohols. Additionally, oxidative di-O-demethylation for 25E-NBOMe and reduction of the aromatic nitro group and N-acetylation of the primary aromatic amine for 25N-NBOMe took place. The resulting 25N-NBOMe metabolites were unique for NBOMe compounds. For all NBOMes investigated, the corresponding 2,5-dimethoxyphenethylamine (2C-X) metabolite was detected. This study reports for the first time 25X-NBOMe N-oxide metabolites and hydroxylamine metabolites, which were identified for 25D-NBOMe and 25N-NBOMe and all three investigated NBOMes, respectively. C. elegans was capable of generating all main biotransformation steps observed in pHLM and might therefore be an interesting model for further studies of new psychoactive substances (NPS) metabolism.
We present an electrochemical model of a lithium iron phosphate/graphite (LFP/C6) cell that includes combined aging mechanisms: (i) Electrochemical formation of the solid electrolyte interphase (SEI) at the anode, leading to loss of lithium inventory, (ii) breaking of the SEI due to volume changes of the graphite particles, causing accelerated SEI growth, and (iii) loss of active material due to of loss percolation of the liquid electrolyte resulting from electrode dry-out. The latter requires the introduction of an activity-saturation relationship. A time-upscaling methodology is developed that allows to simulate large time spans (thousands of operating hours). The combined modeling and simulation framework is able to predict calendaric and cyclic aging up to the end of life of the battery cells. The aging parameters are adjusted to match literature calendaric and cyclic aging experiments, resulting in quantitative agreement of simulated nonlinear capacity loss with experimental data. The model predicts and provides an interpretation for the dependence of capacity loss on temperature, cycling depth, and average SOC. The introduction of a percolation threshold in the activity-saturation relationship allows to capture the strong nonlinearity of aging toward end of life (“sudden death”).
A Validated Quantification of Sudan Red Dyes in Spicery using TLC and a 16-bit Flatbed Scanner
(2018)
We present a video-densitometric quantification method for Sudan red dyes in spices and spice mixtures, separated by TLC. Application was done band-wise in small dots using a 5 μL glass pipette. For separation, the RP-18 plates (20 × 20 cm with fluorescent dye; Merck, Germany, 1.05559) were developed in a vertical developing chamber without vapor saturation from the starting point to a distance of 70 mm by using acetonitrile, methanol, and aqueous ammonia solution (25%; 8 + 1.8 + 0.2, v/v) as mobile phase. The quantification is based on direct measurements using an inexpensive 16-bit flatbed scanner for color measurements (in red, green, and blue). Evaluation of only the green channel makes the measurements very specific. For linearization, an extended Kubelka-Munk expression for data transformation was used. The range of linearity covers more than two magnitudes and lies between 20 and 500 ng. The extraction from a 2 g sample with acetonitrile, evaporation, and reconstitution to 200 μL with methanol and the band-wise application (7 mm) of a 10 μL sample allows a statistically defined LOD of less than 500 ppb of Sudan red dyes. To perform the analysis, a separation chamber, RP-18 plates, 5 μL glass pipettes, and a 16-bit flatbed scanner for 105 € are needed; therefore, the separation method is inexpensive, fast, and reliable.