Analytische Chemie
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Imuno-histochemical staining (IHC) of cancer biomarker on tissue sections is one of the most important analytical techniques for cancer diagnosis although standardization and quality management is tedious and differ significantly from clinic to clinic. Combining established IHC staining strategies with modern quantitative methods would increase it`s potential. We used element mass spectrometry (ICP-MS) and a new ink-jet printed internal standardization approach in combination with IHC staining. The printing strategy was utilized to improve elemental image resolution and reproducibility of paraffin embedded breast cancer tissue sections in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) after conventional IHC staining as a model system to investigate the new capabilities of this technique.
Thermoresponsive polymers have shown great potential in applications such as bioseparation, drug delivery and diagnostic. Only few thermoresponsive polymers that present an upper critical solution temperature (UCST) in a relevant temperature range, i.e. phase separate from solution upon cooling, have been reported so far. Moreover, the most studied UCST type polymers namely polybetaines are difficult to use under physiological conditions, which significantly restricts their potential applications. Therefore, UCST polymers with sharp and robust phase transition in physiological conditions (in the presence of salts, ions etc.) are highly needed in order to extend the range of applications of this class of polymers. Herein, a robust UCST-type copolymer of acrylamide (AAm) and acrylonitrile (AN) (poly(AAm-co-AN)) was prepared by reversible addition fragmentation chain transfer (RAFT) polymerization and its thermo-induced aggregation behavior in aqueous media was studied. At temperature below the UCST, the copolymer chains were aggregated together. The aggregate size was found to be larger with increasing AN contents and became smaller upon dilution of the copolymer solutions. While above the UCST, the copolymer chains were expanded and weekly associated in solution. The association between the copolymer chains formed smaller aggregates with increasing the AN contents or the dilution of the solutions. A model is proposed to explain such aggregation-association behavior of the Fig. 1.
Figure 1. Schematic illustration of the proposed thermos-induced aggregation behavior of the poly(AAm-co-AN) in aqueous solution.
Imuno-histochemical staining (IHC) of cancer biomarker on tissue sections is one of the most important analytical techniques for cancer diagnosis although standardization and quality management is tedious and differ significantly from clinic to clinic. Combining established IHC staining strategies with modern quantitative methods would increase it`s potential. We used element mass spectrometry (ICP-MS) and a new ink-jet printed internal standardization approach in combination with IHC staining. The printing strategy was utilized to improve elemental image resolution and reproducibility of paraffin embedded breast cancer tissue sections in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) after conventional IHC staining as a model system to investigate the new capabilities of this technique.
The motivation to examine the influence of friction on surfaces of energetic materials (EM) has diverse backgrounds. On the one hand the very old hot spot theory predicts, that the size of such hot spot could be in the range of a molecule. The initiation of an EM could start by mechanical excitation, i.e. friction, and continues driven by an exothermal chemical reaction. Following such phenomena on the molecular scale with an imaging method such as AFM should enable us to separate several steps of ignition, if there are any. The experiments showed that HMX mainly undergoes a plastic deformation without further consequences. TNP however showed self healing in the wear track after scratching and simultaneously the destruction of a crystal edge outside the wear track. Additionally nanoparticles appear, tribologists call this "third body formation", which are proven to have a different chemical composition as the original TNP. The self healing effect on the surface is verified with experiments on self diffusion of TNP molecules to and fro the free edges of the crystal. The conclusion is that the formation of a hot spot can be shown to consist of several subsequent steps, separated temporally and locally. The goal to excite the thermal decomposition of a whole TNP crystal (nanoexplosion) was yet not reached due to unfavourable conditions related to thermal conductivity and build-up of pressure.
qNMR provides the most universally applicable form of direct purity determination without need for reference materials of impurities or the calculation of response factors but only exhibiting suitable NMR properties. The development of CRMs addressing qNMR specific measurement issues will give analysts compounds ideally suited for the analytical method and also provide full characterisation of qNMR related parameters to enable more realistic uncertainty budgets. These materials will give users the tools to exploit qNMR more easily and enable them to speed up analytical method development and reduce the time and financial burden of multiple analytical testing.
Inhalt des Vortrags sind die Einführung und Erläuterung der Ziele und Inhalte der Technologie-Roadmap „Prozesssensoren 4.0“, welche von der NAMUR im November 2015 veröffentlicht wurde. Dazu werden Beispiele von aktuellen und zukünftigen Anwendungen erläutert.
Derzeit finden gravierende Veränderungen im Umfeld der Informations- und Kommunikationstechnik statt, die eine große Chance für die optimierte Prozessführung und Wertschöpfung mit darauf abgestimmten vernetzt kommunizierenden Sensoren bieten. Diese Art „smarter“ Sensoren stellen Dienste innerhalb eines Netzwerks bereit und nutzen Informationen daraus. Dadurch ergibt sich aktuell die Notwendigkeit, die Anforderungen an Prozesssensoren sowie an deren Kommunikationsfähigkeiten detaillierter zu beschreiben.
Vernetzte Sensoren sind die Voraussetzung für die Realisierung von Cyberphysischen Produktionssystemen (CPPS) und zukünftiger Automatisierungskonzepte für die Prozess-industrie.
Wesentliche Ziele der Roadmap sind das Zusammenbringen von Technologie- und Marktsicht, Analyse und Priorisierung des (zukünftigen) Informationsbedarfs in verfahrenstechnischen Prozessen, das Erarbeiten von Entwicklungszielen für neue Sensorik sowie das Aufzeigen möglicher Lösungsansätze und ihres Realisierungszeitraums. Darüber hinaus liefert sie Perspektiven für Forschungs- und Entwicklungsförderung und gibt Ansätze für die Normungsarbeit.
Silver nanoparticles (Ag NPs) are widely used in consumer products due to their excellent antibacterial properties. Their broad application has led to a variety of recent regulation on their use and labelling. Thus, a highly specific analytical method for their characterization and quantification is needed.
Due to their large separation range, field-flow fractionation (FFF) techniques are repeatedly applied for the analysis of NP. Limitations of FFF include quantification, sample loss and insufficient recovery rates. Another challenge can be non-ideal elution behavior of particles in complex and unknown matrices.
The possible sources for sample losses of Ag NP have been studied using an asymmetric flow FFF (AF4) in combination with inductively coupled plasma mass spectrometry (ICP-MS). The influence of different parameters, for example the sample concentration, on the recovery rates and sample loss has been investigated. Using laser ablation ICP-MS, the Ag deposition on the membrane was located and quantified. Our results identified ionic silver as the main sources of sample loss. These results can be useful for further method improvement.
However, when a Ag NP sample containing an unknown complex matrix is analyzed, FFF method optimization is challenging as the sample might show a shift in the retention times and lower recovery rates. In this case, ICP-MS experiment in the single particle mode (sp-ICP-MS) can be a useful addition to the FFF measurement. Here, upon assumption of spherical particles, the geometric diameters can be calculated. This fast and easy approach can be helpful in order to interpret the FFF fractograms and advice the FFF method optimization process.
Recent technical developments of NMR instruments such as in acquisition electronics and probe design allow detection limits of components in liquid mixtures in the lower ppm range (approx.. 5–10 ppm amount of substance). The major advantage of quantitative NMR spectroscopy (qNMR) is that it is a direct ratio method of analysis without the need of calibration. This means that the signal for a specific NMR-active nucleus (e.g., a proton) in an analyte can be compared and quantified by reference to a different nucleus of a separate compound, comparable to a counting of spins in the active volume of the spectrometer.
Technical mixtures can be investigated online directly next to a process setup by using flow probes. This makes it a promising method for process analytical applications, especially during process development in laboratory and pilot plant scale. With the growing market of Benchtop devices based on permanent magnets nowadays an integration of NMR spectroscopy in an industrial environment becomes reasonable.
A special application of qNMR in technical mixtures is the observation in the gas phase, which is rarely applied compared to liquid and solid NMR studies. Because of the low density it results in a reduced sensitivity, which can be improved by applying pressure. Therefore a high-pressure NMR setup was developed based on a commercially available NMR tube made of zirconia. This is currently tested up to 20 MPa, but can be extended up to 100 MPa with regard to pressure rating of its components. This work shows results of gas-phase application on natural-gas like reference gas mixtures produced at BAM, as well as investigations on liquefied gas mixtures with high accuracy provided in piston cylinders.
Besides that amine gas treatment and hydroformylation in a microemulsion represent two other examples of applications in process analytical technology. These show the potential of combination of online NMR spectroscopy with other spectroscopic methods, especially during model development for data evaluation.
Since the advent of industrial computed tomography (CT), this new analysis method has been used also for the investigation of objects of cultural heritage and art. CT provides the possibility to determine the inner and outer surfaces and to investigate the material structure without causing damage to the valuable objects.
In this talk I will present examples of measurements performed at BAM, which demonstrate what CT can do for objects of diverse materials and for different objectives.
Due to recent advances in technical developments of NMR instruments such as acquisition electronics and probe design, detection limits of components in liquid mixtures were improved into the lower ppm range (approx. 5–10 ppm amount of substance). This showed that modern NMR equipment is also suitable for the observation of hydrocarbon samples in the expanded fluid phase or gas phase. Since Quantitative NMR spectroscopy (qNMR) is a direct ratio method of analysis without the need of calibration it was used to determine impurities in appropriate liquid and liquefied hydrocarbon isomers up to C6, which are used for preparation of primary gas standards, e.g., natural gas or exhaust gas standards. At the same time it is possible to yield structural information with a minimum of sample preparation. Thus, cross contaminations between different isomers of the observed hydrocarbons and their (NMR-active) impurities can be identified and quantified.
In general, most quantitative organic chemical measurements rely on the availability of highly purified compounds to act as calibration standards. The traceability and providence of these standards is an essential component of any measurement uncertainty budget and provides the final link of the result to the units of measurement, ideally the SI. The more recent increase in the use of qNMR for the direct assessment of chemical purity however can potentially improve the traceability and reduce the uncertainty of the measured chemical purity at a reduced cost and with less material. For example the method has beneficially been used by National Measurement institutes for recent CCQM comparisons including the CCQM–K55 series of purity studies.
Traditional ‘indirect’ methods of purity analysis require that all impurities are identified and quantified, leading to a minimum of 4 individual analytical methods (organic impurities, water, solvents, inorganic residue). These multiple technique approaches measure an array of different chemical impurities normally present in purified organic chemical compounds. As many analytical methodologies have compound-specific response factors, the accuracy and traceability of the purity assessment is dependent on the availability of reference materials of the impurities being available.
qNMR provides the most universally applicable form of direct purity determination without need for reference materials of impurities or the calculation of response factors but only exhibiting suitable NMR properties. The development of CRMs addressing qNMR specific measurement issues will give analysts compounds ideally suited for the analytical method and also provide full characterisation of qNMR related parameters to enable more realistic uncertainty budgets. These materials will give users the tools to exploit qNMR more easily and enable them to speed up analytical method development and reduce the time and financial burden of multiple analytical testing.
Online NMR spectroscopy is an excellent tool to study complex reacting multicomponent mixtures and gain process insight and understanding. For online studies under process conditions, flow NMR probes can be used in a wide range of temperature and pressure. This paper compiles the most important aspects towards quantitative process NMR spectroscopy in complex multicomponent mixtures and provides examples. After NMR spectroscopy is introduced as an online method and for technical samples without sample preparation in deuterated solvents, influences of the residence time distribution, pre-magnetization, and cell design are discussed. NMR acquisition and processing parameters as well as data preparation methods are presented and the most practical data analysis strategies are introduced.
Troubleshooting Samples Analytics:
Impurities in products: unexpected & unwanted occurrence, unknown identity, analytical method unclear, often various analytical methods, necessary, short response time important (< 1 d), benefits: allocation of its source within hours safes cost
• Investigations planned, coordinated and documented by TSA team
• Variety of analytical methods available
Resolving overlapping peaks of multiple components. Relative primary analytical method - Fundamental relationship of qNMR.
CCQM has established a framework of comparisons to demonstrate the international comparability of chemical measurements. The key point is the establishment of comparable measurements, with traceability to internationally or nationally stated references. The Surface Analysis Working Group (SAWG) has been formally founded in 2003. CCQM ratified the group as a full working group of CCQM in April 2003 with these terms of reference:
- to develop pilot studies and carry out key comparisons of national measurement standards for surface and micro/nano-analysis;
- to assist in identifying and establishing inter-laboratory work to improve the traceability of surface and micro/nano-analysis;
- to establish and update a work plan to be adopted by CCQM;
- to discuss and review the scope of the working group and to liase with other working groups related to nanotechnology.
Following the 2015 meeting of the CCQM, the pilot study CCQM-P130 “WD and ED Electron Probe Micro Analysis on Au-Cu alloys” lead by BAM&NIST has been finalized. The Key Comparison K-129 “Measurement of atomic fractions in Cu(In,Ga)Se2 Films” lead by KRISS has made substantial progress and is about to be finalized. The new Key Comparison K-136 on “BET specific surface of ” lead by UNIIM&BAM has made strong progress in 2015 and will be finished in 2016.
Spray drying is a widely used process step in ceramic technology to
convert fine grained raw powders to free-flowing granules. Type and
amount of the organic additives (dispersants, binders and plasticizers)
define viscosity and stability of the slurry, the granulate structure and
the compaction behaviour.
Alumina and Zirconia powders were characterized with regard to
particle size, shape and specific surface area (BET). Zeta-potential
measurements by Stabino® were used to investigate the effect of
different dispersants on slurry stability. Unfortunately, this method is
restricted to suspensions with less than about 30% by weight of solid
content. The multi-sample analytical centrifuge LUMiSizer® overcomes
this problem. This device enables analysis of the separation behaviour
of suspensions over a wide range of solid content. On the basis of
position and time resolved photometric detection of transmitted light,
it is possible to determine the instability index, the sedimentation
velocity, and the sediment height in dependence of type and amount
of organic additives at various centrifugal accelerations. Additional
information is obtained from the shape of the transmission profiles.
Based on LUMiSizer® measurements, suitable additive concentrations
were derived. Thereby, the number of investigations by viscometry and
spray drying experiments can be significantly reduced.
Finally, it was possible to produce alumina, zirconia and ZTA aqueous
slurries with up to 80 weight-% of solid. The optimized suspensions
were successfully spray dried and the resulted granules show good
compaction behaviour.
Core capability tables list the skills and experiences, which at least partially are needed to successfully carry out a specific analytical task within the IAWG. The required skills and experiences, so-called core capabilities (CC), are identified for each analytical procedure. The summarized CC tables are listed in the appendix of each report on the corresponding key comparison or pilot study. These CC tables enable us to demonstrate that we have the analytical procedure we claim under control by means of other Key Comparison, which do not exactly meet the claimed calibration and measurement capability. This is especially important for: a) fields where no Key Comparison is available, b) Revision of CMC claims or c) when a participation in a Key Comparison was not possible.
CCQM-P149 is an attempt to obtain a snapshot on actual procedures the NMIs and DIs within CCQM-IAWG applied to the purity characterization of their “fit for purpose” elemental Standards. This presentation describes how the results of CCQM-P149 may be used to underpin calibration and measurement capabilities being claimed in the BIPM database.
Hydroformylation represents an important homogeneous catalyzed process, which is widely used within chemical industry. Usually applied for short-chained alkenes like Propene and Butene aldehydes obtained from alkenes >C6 are relevant intermediates in production of plasticizers, surfactants and polymers. Today the active catalyst species is often based on valuable Rhodium complexes in aqueous solution. This implies the problem of limited water solubility of the reactants, which is acceptable for short chain lengths, but states a problem in case of higher alkenes. Along with that efficient separation and recycling of the catalyst becomes more complicated. There are different approaches tackling this problem, e.g., by using of salt formation in the BASF process or downstream distillation within the Shell process. Another promising approach is the processing within a microemulsion by using a suitable surfactant system. This maintains a large interface between catalyst and reactants, as well as the possibility of catalyst recycling via downstream phase separation in a settler. Optimized processing within the three-phase region in accordance with Kahlweit fish leads to an efficient product separation, while the valuable catalyst and surfactant can be recycled into the process. In this work we present reaction monitoring of Rh-catalyzed hydroformylation of 1 dodecene. Experiments were conducted on a specialized laboratory setup, which allows coupling of different online spectroscopic methods (Raman, HR-NMR, LF-NMR, UV/VIS) under process-similar conditions. The focus of this contribution lies on results of high-resolution Online-NMR obtained during calibration experiments for development of a multivariate model for Raman spectroscopy, which will be part of another contribution.
Resource Analytics with the help of process analytical technology and the use of online methods is becoming increasingly important for mining and processing technologies and for the recovery of raw materials from secondary raw materials. Current online analytical methods like laser-induced breakdown spectroscopy (LIBS), X-ray fluorescence analysis (RFA), or Raman spectroscopy for the characterization of primary and secondary raw materials are increasingly being used in close association with the technologies for exploration and extraction, mechanical and metallurgical processing, as well as for recycling. Because of the complex matrices such methods are a considerable challenge at the same time. The use of reference materials, which are derived from appropriate matrices, can considerably shorten calibration and method development times. As an example, the development of an online process control method for recovery of phosphorus from sewage sludge ashes is discussed. A combination of LIBS and RFA was developed for the determination of element contents in sewage sludge ashes and their products coming from a thermo-chemical reprocessing step, which removes pollutants.
To understand the metabolic fate of food relevant mycotoxins in vitro systems were mainly used as the method of choice, so far. Yet, in recent years coupling of electrochemistry mass spectrometry (EC-MS) gained increasing importance as promising technique for fast simulation of metabolic processes and was successfully applied in particular for drug metabolism [1].
The aim of our work was to investigate the potential of EC-MS to predict phase I metabolites of priority mycotoxins and to compare the results with in vitro experiments. Hence, the EU-regulated Fusarium mycotoxins zearalenone (ZEN) and patulin as well as dihydroergocristine (DHEC) as model compound of ergot alkaloids were electrochemically oxidized and analyzed by EC MS for the first time.
Electrochemical conditions were set-up individually for each of the three mycotoxins. By using a coulometric flow through cell with a diamond working electrode oxidation of the chosen mycotoxins was observed after applying potentials between 1.7 and 2.0 V vs. Pd/H2. The electrochemically generated reaction products were analyzed online by mass-spectrometric detection.
All of the three chosen mycotoxins were electrochemically converted to mono- and/or dihydroxylated products confirming the results of ZEN related metabolism studies [2, 3] and in case of DHEC own results from in vitro assays. Due to a lack of metabolism studies concerning the oxidative fate of patulin, interpretation of EC-MS data and performing microsomal studies is of particular relevance.
Beside the identified products from electrochemical oxidation of ZEN, patulin and DHEC there is still a number of yet unknown compounds. Additional structural characterization of detected compounds by NMR and X-ray analysis will be facilitated by their large-scale production using preparative EC cells.
Air-coupled ultrasound has been applied increasingly as a non-destructive testing method for lightweight construction in recent years. It is particularly appropriate for composite materials being used in automotive and aviation industry. Air-coupled ultrasound transducers mostly consist of piezoelectric materials and matching layers. However, their fabrication is challenging and their signal-to-noise ratio often not sufficient for many testing requirements. To enhance the efficiency, air-coupled ultrasound transducers made of cellular polypropylene have been developed. Because of its small density and sound velocity, this piezoelectric ferroelectret matches the small acoustic impedance of air much better than matching layers applied in conventional transducers. In our contribution, we present two different methods of spherical focusing of ferroelectret transducers for the further enhancement of their performance in NDT applications. Measurements on carbon-fiber-reinforced polymer (CFRP) samples and on metal adhesive joints performed with commercially available focused air-coupled ultrasound transducers are compared to measurements executed with self-developed focused ferroelectret transducers.
Declining European natural gas resources and increasing legislation mean that diversification towards ‘non-conventional gases’ is essential. Accurate and traceable measurements of the composition of non- conventional gases are required to ensure gases can be transported in existing pipeline networks, and used with existing appliances. The EMRP ‘Characterisation of energy gases’ project is successfully developing a metrology infrastructure to underpin these measurements. New standards and methods have been developed for biogas composition, biogas impurities, coal mine gases, refinery gases and environmentally-friendly odorants. The project is set to conclude in 2013 with the challenging analysis of a series of real non-conventional gas samples.
Titanium dioxide is one of the most studied metal oxides due to its interesting chemical, surface, electronic and (photo)catalytic properties. These properties provide this material of multisectorial applications, ranging from healthcare, photocatalysis, smart materials with self cleaning and self sterilizing properties and solar energy harvesting (photovoltaics and water photosplitting). However it is difficult to correlate the functional properties of TiO₂ nanomaterials to the properties at single nanoparticle level due to the high polydispersity in shape, size and surface properties of the currently available TiO₂ nanoparticles (NPs) Although intensive experimental and theoretical studies have been conducted on the reactivity of different surfaces of metal oxides such as TiO₂ [1,2] much less attention is paid on the dependence of functional properties, like photocatalytic activity, dye adsorption, open circuit potential and fill factor in dye sensitized solar cells, on crystal facets in different orientations [3]. One of the goal of SETNanoMetro is the development of design rules to tune crystal facets of TiO₂ NPs in order to optimize and control functional properties. By tuning the ratio of different facets, the functional properties would be correspondingly changed. In the present work we have developed a series of design rules in order to obtain sets of anatase TiO₂ NPs with low polydispersity and to tune their shape and their size though hydrothermal processing of Ti(IV)-Triethanolamine complex in presence of different shape controllers (OH-, triethanolamine, fluoride). Through a careful experimental design the influence of many process parameters (pH, temperature, shape controller type and concentration) on the synthesis outcome (size, shape and polydispersity), a predictive soft model was developed. The model is able to predict reasonably well the synthesis outcome allowing to tune the shape factor from 5 (prisms) to 1.5 (bipyramids) to 0.2 (platelets). This allows to control the main crystal facets exposed ranging from (100) to (001).
In this contribution the particle sizing techniques evaluated in NanoDefine are presented together with recommendations for their application/implementation on real-world materials. The experimental evaluation is discussed based on examples on NanoDefine materials. A systematic study on volume specific surface area as derived from BET measurements versus electron microscopy on powdered materials is also presented.
Influence of the of dealumination and porosity on the acid sites of natural zeolite clinoptilolite
(2016)
Heavy feedstock from crude and bio oil is a widely available and renewable resource for production of fuel and starting materials for other organic valuables by cracking or hydrocracking. Catalytic processing of heavy feedstock can meet the increased demand of energy up to a great extent. It requires the application of acidic catalysts like zeolites. However, the used synthetic catalysts are difficult to recover and reuse and are mostly spent.
The use of natural zeolite as spent catalysts may open new perspectives in the chemical use of heavy feed feedstock by chemical conversion. Natural zeolites are not expensive, widely available and environment friendly. Clinoptilolite is the most abundant natural zeolite. Clinoptilolite has a crystalline structure with a defined micropore system of medium size showing unique ion exchange and sorption properties. However, it is catalytically active only in the H-form. Also certain porosity is required for improvement of the accessibility of active sites.
This paper deals with the tuning of acid properties and of the mesoporosity of the clinoptilolite by variation of the Si/Al framework ratio, extra-framework aluminum and modification of the porosity by specific acid and water vapor treatment. The preparation of hierarchical pore structures containing interconnected micro-meso-macropores is an important factor influencing the catalytic performance.
The obtained materials have been characterized by XRD, TEM, FTIR, Raman, TG/DSC. The chemical composition has been determined by ICP-AES. The porosity have been investigated by nitrogen adsorption desorption measurements. The acidity has been measured by Ammonia-TPD. The extent of dealumination, stability of the clinoptilolite against acid treatment and the change in the nature of acid sites and their local structure has been studied by solid state 29Si and 27Al MAS NMR spectroscopy in detail. The catalytic activity has been investigated in the acetalization of benzaldehyde with 1,3-butanediol. The impact of the porosity, change of the Si/Al ratio as well as present Al species on catalytic properties will be discussed.
We aim at preparing, characterising, and applying SURMOFs incorporating electro-active and -switchable mechanically interlocked molecules such as rotaxanes as the basis of functional devices.
Preparation and Positioning
Synthesis, purification and analytical characterization of electro-switchable rotaxanes suitable for SURMOF-formation as well as Layer-by-Layer assembly on surfaces.
Controlled deposition of electro-active SURMOFs and Layer-by-Layer self-assembled multilayers based on these switchable rotaxanes.
Construction of SURMOFs on micro-patterned surfaces.
Structural Characterisation and Physico-Chemical Properties
Electrochemical characterization of these rotaxanes in solution with cyclic voltammetry, chronoamperometry and impedance spectroscopy.
Surface characterization of SURMOFs and multilayers with XPS, NEXAFS, AFM, contact-angle measurements, transmission UV/Vis, ToF-SIMS and – in cooperation with partners from SPP – XRD.
Development of ToF-SIMS (also assisted by Principle Component Analysis of the fragment-ion data) as a method for imaging and depth-profiling.
Development of an appropriate electrochemical cell to perform cyclic voltammetry, chronoamperometry and impedance spectroscopy with SURMOFS and multilayers as working electrodes in a three-electrode cell.
Comparison of the structural and electrochemical properties of the redox-active unit in solution, multilayers and SURMOF focusing on the advantages of SURMOFs.
System Integration and Function Demonstration
Examination of the usability of the electroactive SURMOFS as optoelectronic switch or data storage device with a focus on the robustness of the system.
Usage of the SURMOFs as functional electrodes for electrochemical application.
Selective switching of ordered nanostructures to translate molecular motion to macroscopic property changes.
The implementation of new 2-D materials based technologies in production processes requires the development of quality management tools. These have to be underpinned by appropriate measurements. Consequently there is a need for the development of the metrology for measurement methods, the development of certified reference materials (CRM) and finally standardization. This chain represents the ideal way to practically useful standards. The presentation will give an overview on the main players in the field and summarize the recent status of activities. At the highest level the metrology of chemical characterization of 2D materials is in the scope of the International Meter Convention, specifically the Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology (CCQM). Pre-standardization is an activity field of the Versailles Project on Advanced Materials and Standards (VAMAS). Standardization is mainly addressed by addressed ISO Technical Committees. A summary on available CRMs relevant to the characterization of nano materials has been prepared by BAM. Examples from the work of BAM’s Division 6.1 “Surface Analysis and Interfacial Chemistry” showcasing the characterization of chemically modified graphene surfaces are given and specific needs for the development of metrology are addressed.
In the discussion the audience is invited to define specific needs which will be streamlined to the respective bodies!
Milling reactions often result in 100% yields of single products, making purifying procedures obsolete. Mech-anochemistry is also a sustainable and eco-friendly method. The ever increasing interest in this method is contrasted by a lack in mechanistic understanding of the mechanochemical reactivity and selectivity. Recent in situ investigations provided direct insight into formation pathways. However, the currently available theories do not predict temperature T as an influential factor. Here, we report the first determination of an activation energy for a mechanochemical reaction. In a temperature-dependent in situ study the cocrystallisation of ibuprofen and nicotinamide was investigated as a model system. These experiments provide a pivotal step towards a comprehensive understanding of milling reaction mechanisms.
Mechanochemistry is a convenient way to form metal phosphonates with neutral and/or monodeprotonated phosphonates, controlled by the stoichiometric. In situ investigation of reactions helps understanding mechanisms and formation of intermediates. The knowledge of intermediates helps to find metastable structures.The diffusion mechanism is most probable for the mechanochemical synthesis of metal phosphonates.
k-values (k-ratio, K-value) is defined as ratio of the X-ray photon intensity I measured for a particular characteristic peak from the unknown sample to the value measured for the same X-ray peak from a reference material of known composition under identical conditions of beam energy, spectrometer efficiency and electron dose.
Coating, stabilization layers, functionalization of particles or simple contamination are common variants of a core-shell system. For smaller nanoparticles this is of major importance. A particle with 16 nm diameter and a usual surface layer of 2 nm will have the same volume for the core as for the shell. In this case the material of the particle doesn’t have a clear definition. It is a common case that a particle consists of four different layers: Core, shell, stabilization layer and contamination. The properties of the particles differ according to this structure. For example silver particles might have a different dissolution rate for pure particles and for particles which are grown on top of a core.
Different solubility or defined other properties of materials is a common reason for producing core-shell systems. Gold cores are surrounded by silica to stabilize them or to get a defined distance between the cores. Silica might be surrounded by gold and the silica dissolved afterwards. This delivers hollow shells. Another important example for core-shell systems are quantum dots. A small core is surrounded by a different material for increasing the photoluminescence. Furthermore there a stabilization layer is needed. The smallest part of the final particles is the initial core. The photoluminescence is based on this core, but the shells contain much more material. Categorization should address this.
Core-shell systems are not covered by most of the existing decision trees for grouping. They are either regarded as special case or a singular layer. This disqualifies core-shell systems for grouping within the common models. There might be a very easy way to avoid this problem and even to combine some of the different decision trees. Starting the decision tree with the solubility of the outer shell and subsequently addressing the inner layers will be a pragmatic approach to solve the problem. If there is no shell, the categorization can start with a tiered approach or with the proposed “stawman” chemical categorization. If a shell is covering the surface there is a need to check if the shell is stable. If it is stable, the particle can be categorized based on this shell. If it is soluble, the ions need to be addressed as in the classic case. Furthermore the shell might increase the uptake by the cells. If the ions and the uptake are not critical the categorization can continue with the next layer.
With this not perfect but pragmatic approach, the surface layers can be addressed with very limited additional efforts. Most criteria are based on classically tabulated data. Including a rating system like the precautionary matrix approach might even address the fact that some parameters are not always Yes/No, e.g. solubility, ion toxicity and uptake.
Derzeit finden gravierende Veränderungen im Umfeld der Informations- und Kommunikationstechnik statt, die eine große Chance für die optimierte Prozessführung und Wertschöpfung mit darauf abgestimmten vernetzt kommunizierenden Sensoren bieten. Diese Art „smarte“ Sensoren stellen Dienste innerhalb eines Netzwerks bereit und nutzen Informationen daraus. Dieses ist die Voraussetzung für die Realisierung von Cyber Physical Systems (CPS) innerhalb zukünftiger Automatisierungskonzepte für die Prozessindustrie, wie sie auch durch das Zukunftsprojekt „Industrie 4.0“ adressiert werden.
Initiiert von NAMUR und VDI/GMA und unter Mitwirkung der Unternehmen ABB, BASF, BTS, Bilfinger Maintenance, Endress+Hauser, Evonik, Festo, Krohne, Lanxess, Siemens, des Fraunhofer ICT, der HS Reutlingen und der BAM (Projektleitung) entstand jetzt die grundlegend aktualisierte und überarbeitete Technologie-Roadmap „Prozess-Sensoren 4.0“, die am 06. November 2015 auf der NAMUR-Hauptsitzung in Bad Neuenahr wurde.
Numerous case histories show evidence that geophysical methods are valuable tools for levee inspection and monitoring. National and international standards and recommendations recommend the use of geophysics for a variety of tasks. However, in some cases reported have been flaws missed or false indications given. Due to the larger variety in type, size and construction of levees and the even larger variety of potential tasks and targets the success of geophysical surveys still pretty much depends on the available budget and the experience and capabilities of the clients and contractors involved. It is strongly recommended that all relevant parties agree on the detailed objectives of the survey, required accuracy and reliability of the results and any follow up measures. For the most common tasks more research and practical work using techniques as POD (probability of detection), which are well established in other fields of non-destructive testing, would be of benefit.
Concrete is known to be a very useful, flexible and durable construction material. However, due to excess load, fatigue, chemical processes, freeze-thaw or reinforcement corrosion concrete may suffer from degradation. If detected too late, repair is difficult and expensive.
The propagation of ultrasonic waves is influenced by changes in the properties and structure of the material, including, but not limited to, stress, temperature, moisture content and microcracking. Ultrasonic velocieties thus may serve as indicators for structural health. Traditional ultrasonic methods as transmission time of flight measurements are used since decades, but are not sensible enough to show subtle changes. Coda Wave Interferometry (CWI), originally developed in seismology to detect stress changes in the earth's crust uses the information in the late part of ultrasonic signals originating from multiple reflections and scattering. Since a few years it is used by several researchers for lab experiments on concrete.
Meanwhile specialized sensors to be embedded in concrete have been developed. We have conducted several lab and a few field experiments, which will be reported here. The capabilities and limitations of CWI are summarized.
Innovative seismic and resistivity tools for determining the diameter of jet grouting columns
(2016)
Jet grouting is used for soil improvement, foundation support and groundwater low control all over the world. It is well accepted and subject of standardization in many countries. However, some issues with the method remain. As the grout columns are produced in the subsurface without visual control in an often inhomogeneous soil, the prediction of the column’s diameter is still a challenge. All methods applied so far have their limitations.
The approach presented in this study is twofold. At Colorado School of Mines a resistivity probe has been developed, which is pushed into the fresh grout directly after production. ERT sections are measured and inverted. Given some background information is available, the diameter of the columns can be evaluated.
At BAM the focus has been on post-production investigations using seismic borehole methods. After hardening of the concrete seismic waves are sent through the column downhole (sensors placed in a casing in the column’s axis, source on top) and crosshole (source and sensor in boreholes on opposite sides of the column). We have developed a scheme to evaluate the diameter of the column based on travel time measurements without calibration. As this method is eventually more time and cost intensive we assume its application mainly for test columns. These are casted and dug out for visual inspection to determine appropriate grouting parameters. Our method would replace the often very cost intensive visual inspection.
Both approaches have been tested at three test columns produced at BAM’s test site at Horstwalde, Germany and on an actual constructions site. Both methods have been in good agreement with the diameters predicted by the jet grouting contractors, which were confirmed in one case by mechanical measurements.
The fast identification and quantification of analytes in the field of food safety or environmental analysis is difficult. Surface enhanced Raman scattering (SERS) is an analytical method which can be used simultaneously for the rapid identification and concentration determination of trace analytes,[1,2] usually covering a large dynamic range from nanomolar up to molar concentrations. The identification of the molecules is accomplished through the specific fingerprint of a molecule’s Raman spectrum.
For facile and straightforward SERS measurements, we present here a combination of paper-based SERS test strips with microfluidic systems on paper as a microfluidic paper-based analytical device (μPAD). The SERS μPAD is thus principally suited for cheap, fast, non-destructive, label-free and portable detection of analytes. In this system basically, the use of the microfluidic structured paper increases the sensitivity and suppresses background signals of the SERS assay.
Deposition of the SERS substrate on the test strips is simple and relies on an inkjet printer. For the optimization of the reproducibility and intensity of the SERS signal, we tested different nanoparticles, different numbers of print cycles and different paper types. The nanoparticle solutions used in the μPAD preparation were gold and silver nanoparticle solutions. The paper types were cellulose and glass fiber. SERS arrays were prepared by printing and compared to arrays prepared by spraying. The optimized μPAD was used for the identification and quantification of pure analyte solutions (e.g., adenine) and mixtures of compounds, the concentration series following Langmuir isotherms.
Relevant analytes in the field of food safety are antibiotics and pesticides. We apply the SERS microfluidic paper-based analytical devices for the detection of antibiotics (enoxacin, enrofloxacin) and pesticides.
Due to its simplicity, speed and ability to obtain a particle number size distribution, single particle ICP-MS (spICP-MS) has emerged as an important tool for the analysis of nanoparticles (NPs). However, when NPs are suspended in a complex, unknown solution, matrix effects can occur affecting the instrument’s sensitivity. As a result, an over- or underestimation of the particle size is possible.
In this work, a proof-of-concept study of the combination of isotopic dilution analysis (IDA) and spICP-MS compensating for possible matrix effects is presented. As an example, an isotopically enriched 109Ag standard solution was added to silver NPs (Ag NP) suspensions. Different NP suspensions with mean particle diameters between 30 and 80 nm were chosen. The mixtures were analyzed using a quadrupole ICP-MS instrument. Both Ag isotopes (107Ag and 109Ag) were monitored during one experiment. The result show a good agreement with the diameters obtained using conventional spICP-MS.
In a second step, the Ag NPs were suspended in a simulated seawater matrix. Using conventional spICP-MS, a great reduction in the signal intensities and consequently in the particle sizes, was monitored. The application of the IDA-spICP-MS approach on these samples was able to obtain similar diameters compared to the samples without matrix.
Hydrogen can cause unexpected material failure under consideration of stresses (external/internal) during manufacturing, processing or service of the materials. This failure is mostly based on a certain degradation of the mechanical properties. Thus, the correlation of hydrogen trapping vs. a respective microstructure is necessary for high strength steels. Thus, the scope of this work is the improvement of existing hydrogen trap models by verification of activation energies for hydrogen traps as well as the influence of the determination method. In this scope, the thermal desorption method is appropriate to distinguish between different hydrogen traps. Nevertheless, the specimen temperature has to be accounted very carefully in case of calculating the necessary trap energy.
Mit dem KorroPad Verfahren ist es dem Anwender möglich den Zustand der Passivschicht nichtrostender Stähle auf sehr einfache und schnelle Weise einschätzen zu können. Das Verfahren eignet sich dazu, den Grad der Passivität in Abhängigkeit der Umgebungsbedingungen und der Zeit nachzuvollziehen. Dies ermöglicht dem Anwender und Verarbeiter von nichtrostenden Stählen, die Lagerungsbedingungen und –zeiten einer frisch bearbeiteten Stahloberfläche zu ermitteln, welche für die Ausbildung einer stabilen Passivschicht notwendig sind, bevor diese risikoarm eingesetzt werden kann. Wie die hier dargestellten Beispiele und auch weitere zahlreiche praktische Anwendungen gezeigt haben, eignet sich das KorroPad ebenfalls für die Identifikation kritischer Prozessparameter bei der Verarbeitung nichtrostender Stähle. Mit dem Verfahren lassen sich viele prozessbedingte Einflussfaktoren auf die Oberflächengüte wie auch auf den Werkstoff charakterisieren. Aufgrund der schnellen und einfachen Auswertung der Prüfergebnisse können positive wie auch negative Veränderungen hinsichtlich der Passivschichtstabilität zügig erkannt werden. Dies ermöglicht es dem Anwender schnell zu reagieren, um kritische Einflüsse zu korrigieren und um eine Optimierung von Inhouse-Prozessen durchzuführen. Weitere Einsatzgebiete sind im Bereich der Wareneingangs- und/oder Warenausgangskontrolle denkbar, überall wo es um die Frage der Passivschichtstabilität einer nichtrostenden Stahloberfläche geht.