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Eingeladener Vortrag
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Results are reported from a pilot study under the Consultative Committee for Amount of Substance (CCQM) to compare measurements of and resolve any relevant measurement issues in, the amount of thermal SiO2 oxide on (100) and (111) orientation Si wafer substrates in the thickness range 1.5 - 8 nm. As a result of the invitation to participate in this activity, 45 sets of measurements have been made in different laboratories using 10 analytical methods: medium-energy ion scattering spectrometry (MEIS), nuclear reaction analysis (NRA), RBS, elastic backscattering spectrometry (EBS), XPS, SIMS, ellipsometry, grazing-incidence x-ray reflectrometry (GIXRR), neutron reflectometry and transmission electron microscopy (TEM). The measurements are made on separate sets of 10 carefully prepared samples, all of which have been characterised by a combination of ellipsometry and XPS using carefully established reference conditions and reference parameters.
The results have been assessed against the National Physical Laboratory (NPL) data and all show excellent linearity. The remaining data sets correlate with the NPL data with average root-mean-square scatters of 0.15 nm, half being better than 0.1 nm and a few at or better than 0.05 nm. Each set of data allows a relative scaling constant and a zero thickness offset to be determined. Each method has an inherent zero thickness offset between 0 nm and 1 nm and it is these offsets, measured here for the first time, that have caused many problems in the past. There are three basic classes of offset: water and carbonadeous contamination equivalent to ~1 nm as seen by ellipsometry; adsorbed oxygen mainly from water at an equivalent thickness of 0.5 nm as seen by MEIS, NRA, RBS and possibly GIXRR; and no offset as seen by XPS using the Si 2p peaks. Each technique has a different uncertainty for the scaling constant and consistent results have been achieved. X-Ray photoelectron spectroscopy has large uncertainties for the scaling constant but a high precision and, critically, if used correctly, has zero offset. Thus, a combination of XPS and the other methods allows the XPS scaling constant to be determined with low uncertainty, traceable via the other methods. XPS laboratories returning results early were invited to test a new reference procedure. All showed very significant improvements. The reference attenuation lengths thus need scaling by 0.986 ± 0.009 (at an expansion factor of 2) deduced from the data for the other methods. Several other methods have small offsets and, to the extent that these can be shown to be constant or measurable, then these methods will also show low uncertainty. Recommendations are provided for parameters for XPS, MEIS, RBS and NRA to improve their accuracy.
Geruchsintensität und Emissionen von Bauprodukten - Vorstellung des Verfahrens und Laborvergleich
(2007)
Measuring perceived air quality and intensity by a Sensor System, the European Project SysPAQ
(2008)
Die Bewertung von VOC-Emissionen aus Bauprodukten soll durch das AgBB-Schema vereinheitlicht werden und eine gesundheitsrelevante Komponente enthalten. Das Deutsche Institut für Bautechnik (DIBt) hat das AgBB-Schema in weiten Teilen für seine Grundsätze zur gesundheitlichen Bewertung von Bauprodukten in Innenräumen implementiert. Neben der üblichen chemischen Emissionsmessung soll auch der Geruch für die Bewertung des Produkts herangezogen werden. Um den Geruch als festen Bestandteil in die Produktprüfung zu integrieren, wurden vom Umweltbundesamt zwei Vorhaben initiiert. Erste Ergebnisse des zweiten Vorhabens (FKZ 37 07 62 300; Sensorische Bewertung der Emissionen aus Bauprodukten Integration in die Vergabegrundlagen für den Blauen Engel und das Bewertungsschema des Ausschusses zur gesundheitlichen Bewertung von Bauprodukten) werden hier dargestellt.
In this study 50 construction products were tested in emission test chambers according to the requirements of the AgBB-scheme: 7 acrylic and 6 silicone sealants, 6 paste-like synthetic resin plasters, 13 wood based products, 4 adhesives, 5 lacquers, 6 wall paints and 3 further construction products. VOC and odour emissions were tested on the 1st, 3rd, 10th, and 28th day. In addition to the VOC-measurements, a test procedure was developed to evaluate odour emission of construction products.This test is planned to be implemented into the AgBB-Scheme. A direct evaluation by a sensory panel in the emission test chamber was not possible. So the odour samples were collected in 300- litre tedlar bags which were evaluated later. Odour intensity of the samples was compared with different acetone concentrations. Within this study an interlaboratory comparison was conducted using the newly developed odour test method. Additionally, VVOC emissions, detection of carcinogenic compounds, repeatability of emission test chamber tests, and other issues are presented. This project has shown that construction products can be evaluated in accordance with the AgBB scheme. A sensory evaluation is intended to be introduced in the AgBB scheme. A method for this evaluation is described in this study. The test procedure should be enhanced and validated for practical utilisation.
Messung der empfundenen Geruchsintensität mit Multigas-Sensorsystemen, das Forschungsvorhaben SysPAQ
(2007)
27Al nuclear magnetic resonance spectra of polycrystalline aluminium borate 9Al2O3 · 2B2O3 have been measured in double rotation at 11.7 and 7.0 T and high-speed magic-angle spinning at 7.0, 9.4, 11.7, 14.1 and 17.6 T. Spinning sidebands from the satellite transitions were observed at 7.0 and 14.1 T. Each of the four structural aluminium sites [Al(IV), Al(V)(1), Al(V)(2) and Al(VI)] are observed, characterised and assigned in the spectra. The obtained parameter set gives a fully consistent interpretation in agreement with the crystal structure of the compound.
VOC emissions from building materials accompanying sensory tests for different evaluation schemes
(2011)
Within a follow up project of a former study (Horn et al. 2005) emissions and odor from different types of construction products were investigated (financed by the German Federal Environmental Agency - FKZ 37 07 62 300).
The tested materials were mainly those used for construction of floors indoors. For this type of materials in Germany several labeling procedures exist which are based on Emission chamber testing. Two important labeling procedures in Germany are based on the AgBBevaluation scheme (Däumling et al. 2005). For some applications (flooring material) it is the mandatory Ü-mark of DIBt (German Institute for Construction Technology). Furthermore for carpets, adhesives and many other products, like sealants, mattresses, furniture and so on the voluntary blue angel mark exist. Within this scheme the volatile organic compounds (VOC) compounds are measured with well established procedures and are evaluated with LCI-values which were derived from health information.
Beyond that many complaints according to building products are caused by odors. Therefore an evaluation procedure for the odor is very important and should be implemented into all of the mentioned labeling schemes.
Indoor air pollutants influence the health and comfort of building occupants and consequently the energy consumption of the building. The pollutants are emitted by various sources.
Among these sources, building products are of particular importance. To control the emission of pollutants from building materials, a few different voluntary labelling Systems have been introduced in Europe. In Germany also mandatory “Principles for the health assessment of construction products used in interiors” have been applied for the technical approval of floor coverings since 2004. This procedure is based on the assessment scheine of the Committee for Health-related
Evaluation of Building Products (AgBBScheme). The sensory-limit settings for building-material label Blue Angel offer consumer to differ not only low-emission but also low-odour Building materials from another building materials.
Um eine gute Luftqualität in Gebäuden zu erreichen, müssen Reinigungslasten durch Lüften aus Räumen abgeführt bzw. vermieden oder verringert werden. Wird der Luftwechsel verringert, verschlechtert sich die Raumluftqualität, und die Zufriedenheit der Nutzer nimmt ab. An Arbeitsplätzen kann es bei schlechter Luftqualität und der daraus resultierenden Unzufriedenheit zu einer geringeren Produktivität der Beschäftigten kommen. Um die Reinigungslasten und deren Wirkung auf den Raumnutzer überdas Geruchsempfinden zu verringern, ist neben einer messtechnischen Erfassung der Verunreinigungen auch eine sensorische Prüfung in Innenräumen und von Bauprodukten notwendig. In diesem Artikel wird die Entwicklung der Bewertungsmethodik von Gerüchen im Innenraum erläutert und auf Anwendungen eingegangen.
For absorption processes with fluctuating feed gas compositions it is vital to continuously adjust
the operation point to achieve energy efficiency. In this contribution a Raman-based advanced
process control (APC) is introduced for the absorption of carbon dioxide (CO2) using an aqueous
solution of monoethanolamine (MEA). The APC is based on a Raman spectroscopic analysis of
the composition and CO2 load of the scrubbing liquid and a non-linear model predictive control
(NMPC) to adjust the scrubbing liquid cycle. In addition, an outer real-time optimization loop is
set in place to update the set points for the absorption process depending on the current feed gas composition minimizing the energy consumption of the process. Implementation and testing of the APC have been carried out in a mini-plant at TU Berlin. During a plant operation of more than 160 hours robustness and stability of the APC were shown.
Reaction monitoring in disperse systems, such as emulsions, is of significant technical importance in various disciplines like biotechnological engineering, chemical industry, food science, and a growing number other technical fields. These systems pose several challenges when it comes to process analytics, such as heterogeneity of mixtures, changes in optical behavior, and low optical activity. Concerning this, online nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for process monitoring in complex reaction mixtures due to its unique direct comparison abilities, while at the same time being non-invasive and independent of optical properties of the sample. In this study the applicability of online-spectroscopic methods on the homogeneously catalyzed hydroformylation system of 1-dodecene to tridecanal is investigated, which is operated in a mini-plant scale at Technische Universität Berlin. The design of a laboratory setup for process-like calibration experiments is presented, including a 500 MHz online NMR spectrometer, a benchtop NMR device with 43 MHz proton frequency as well as two Raman probes and a flow cell assembly for an ultraviolet and visible light (UV/VIS) spectrometer. Results of high-resolution online NMR spectroscopy are shown and technical as well as process-specific problems observed during the measurements are discussed.
Hydroformylation represents an important homogeneous catalyzed process, which is widely used within chemical industry. Usually applied with simple 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 reactands, 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
The Collaborative Research Center InPROMPT aims to establish a novel process concept for the hydroformylation of long-chained olefins, using a rhodium complex as catalyst in the presence of syngas. Recently, the hydroformylation in micro-emulsions, which allows for the efficient recycling of the expensive rhodium catalyst, was found to be feasible. However, the temperature and concentration sensitive multi-phase system demands a continuous observation of the reaction to achieve an operational and economically feasible plant operation. For that purpose, we tested the potential of both NMR and Raman spectroscopy for process control assistance. The lab-scale experiments were supported by sampling for off-line GC-analysis as reference analytics. The results of the NMR experiments will be part of another contribution.
A major industrial reaction based on homogeneous catalysis is hydroformylation for the production of aldehydes from alkenes and syngas. Hydroformylation in microemulsions, which is currently under investigation at Technische Universität Berlin on a mini-plant scale, was identified as a cost efficient approach which also enhances product selectivity. Herein, we present the application of online Raman spectroscopy on the reaction of 1-dodecene to 1-tridecanal within a microemulsion. To achieve a good representation of the operation range in the mini-plant with regard to concentrations of the reactants a design of experiments was used. Based on initial Raman spectra partial least squares regression (PLSR) models were calibrated for the prediction of 1-dodecene and 1-tridecanal. Limits of predictions arise from nonlinear correlations between Raman intensity and mass fractions of compounds in the microemulsion system. Furthermore, the prediction power of PLSR models becomes limited due to unexpected by-product formation. Application of the lab-scale derived calibration spectra and PLSR models on online spectra from a mini-plant operation yielded promising estimations of 1-tridecanal and acceptable predictions of 1-dodecene mass fractions suggesting Raman spectroscopy as a suitable technique for process analytics in microemulsions.
Die Abtrennung von CO2 aus industriellen Gasströmen ist eine großtechnisch wichtige Trennaufgabe. Neben der Aufarbeitung von Erdgas werden diese Verfahren zur Verminderung der CO2-Emission durch industrielle Rauchgase, insbesondere für alternativlose Prozesse wie die Stahl- und Zementproduktion diskutiert.
The project InPROMPT aims to establish a robust hydroformylation reaction process of the alkene n-dodecene to the aldehyde n-tridecanal using a rhodium complex as catalyst in the presence of syngas. This industrial relevant production process demands further research for optimization and expansion. For that purpose, the fiber optic coupled probe of a process Raman spectrometer is directly introduced in the product stream, which enables the recording of spectra within short control intervals.
Within the Collaborative Research Center InPROMPT a novel process concept for the hydroformylation of long-chained olefins is studied in a mini-plant, using a rhodium complex as catalyst in the presence of syngas. Recently, the hydroformylation in micro¬emulsions, which allows for the efficient recycling of the expensive rhodium catalyst, was found to be feasible. However, the high sensitivity of this multi-phase system with regard to changes in temperature and composition demands a continuous observation of the reaction to achieve a reliable and economic plant operation. For that purpose, we tested the potential of both online NMR and Raman spectroscopy for process control. The lab-scale experiments were supported by off-line GC-analysis as a reference method.
A fiber optic coupled probe of a process Raman spectrometer was directly integrated into the reactor. 25 mixtures with varying concentrations of olefin (1-dodecene), product (n-tridecanal), water, n-dodecane, and technical surfactant (Marlipal 24/70) were prepared according to a D-optimal design. Online NMR spectroscopy was implemented by using a flow probe equipped with 1/16” PFA tubing serving as a flow cell. This was hyphenated to the reactor within a thermostated bypass to maintain process conditions in the transfer lines.
Partial least squares regression (PLSR) models were established based on the initial spectra after activation of the reaction with syngas for the prediction of unknown concentrations of 1-dodecene and n-tridecanal over the course of the reaction in the lab-scale system. The obtained Raman spectra do not only contain information on the chemical composition but are further affected by the emulsion properties of the mixtures, which depend on the phase state and the type of micelles. Based on the spectral signature of both Raman and NMR spectra, it could be deduced that especially in reaction mixtures with high 1-dodecene content the formation of isomers as a competitive reaction was dominating. Similar trends were also observed during some of the process runs in the mini-plant. The multivariate calibration allowed for the estimation of reactants and products of the hydroformylation reaction in both laboratory setup and mini-plant.
Emissionen aus Bauprodukten beeinträchtigen die Qualität der Innenraumluft erheblich. Mit Hilfe des AgBB-Schemas werden die Emissionen flüchtiger organischer Verbindungen (VOC) aus Bauprodukten bewertet. Die gesundheitliche Bewertung nach dem AgBB-Schema erfordert produktspezifische Messverfahren.
Diese gibt es mittlerweile für eine Reihe von Produkten. Sie wurden durch Beteiligung verschiedener Forschungseinrichtungen und Messinstitute validiert und u. a. in die Vergabekriterien des Umweltzeichens Blauer Engel übernommen. Die Bewertung ist allerdings mit zumeist niedrigeren Grenzwerten strenger. VOC-Emissionen und Gerüche können beide zu gesundheitlichen Belastungen führen. So ist die sensorische Prüfung ein weiteres wichtiges Element bei der Bewertung von Bauprodukten und vorsorglich auch im AgBB-Schema verankert.
Hauptziel des Projektes ist es, eine Methode der sensorischen Bewertung und Grenzen für die Vergabe des Blauen Engels und für das AgBB-Schema abzuleiten. Auf Grundlage der durchgeführten Untersuchungen (siehe Kapitel 5 Ergebnisse und Diskussion) wird als Bewertungsmethode die empfundene Intensität und die Hedonik vorgeschlagen. Die Ableitung der Grenzwerte für die sensorische Bewertung am 28. Tag erfolgt über die zusätzliche Befragung der Probanden im Rahmen der vorliegenden Studie nach der Zumutbarkeit einer Probe.
Für den Blauen Engel könnte es je Produktgruppe unterschiedliche Grenzen der empfundenen Intensität und der Hedonik geben. Ein erster Vorschlag für mögliche Grenzen, hier zunächst einheitlich für alle
Produktgruppen, ist für die empfundene Intensität 7 pi (5 pi + 2 pi als Sicherheit, Kapitel 5.1.5) und für die Hedonik -1 (0 +/-0,8, gerundet auf -1) (siehe dazu Abbildung 6-2).
Emissions from building products can considerably impair the quality of indoor air. The AgBB scheme is employed to evaluate the emissions of volatile organic compounds (VOC) from building products. The hygienic evaluation according to the AgBB scheme requires product-specific measuring procedures.
These are available for a range of products. They have been validated in co-operation with several research and testing institutes and have been included in the criteria for awarding the Blue Angel ecolabel.
The evaluation is, however, stricter and generally has lower limits. VOC emissions and odours can cause health problems so testing using sensors is an important element in the evaluation of building products and has – for reasons of precaution – been set down in the AgBB scheme. The main goal of the project was to derive a method of evaluation using sensors and limits for awarding the Blue Angel and for the AgBB scheme. Based on the research conducted (see Chapter 5 Results and Discussion), perceived intensity and hedonics were suggested as a suitable Evaluation method. The derivation of limits for the evaluation using sensors on the 28th day was effected in the present study through the additional questioning of the test subjects on the reasonability of a sample.
For the Blue Angel, there could be different limits of perceived intensity and hedonics for each group of products. A preliminary suggestion for possible limits – for all product groups – is a perceived intensity of 7 pi (5 pi + 2 pi as confidence coefficient, Chapter 5.1.5) and -1 (0+/-0.8, rounded to -1) for the hedonic value.
Messung und Bewertung von Gerüchen aus Bauprodukten für den Innenraum gewinnen vor allem durch den zunehmenden Bau energieeffizienter Gebäude an Bedeutung. Intensive und unangenehme Gerüche werden von Bewohnerinnen, Bewohnern und Angestellten nicht akzeptiert und können auf Dauer krank machen. Bislang stand noch kein allgemein anerkanntes Messverfahren zur Verfügung. Dieses wurde nun in Forschungsprojekten entwickelt, wobei auch konkrete Bewertungsvorschläge zur Zumutbarkeit von Gerüchen gemacht wurden. Das Verfahren ist an die Messung der Emissionen flüchtiger organischer Verbindungen aus Bauprodukten gekoppelt und nutzt Probanden, um die Geruchsstärke (Intensität) und den Geruchseindruck (Hedonik) zu ermitteln. In der Praxis wird das Verfahren nun an verschiedenen Stellen erprobt. Die Bewertung der Geruchsemissionen gibt der Industrie die Möglichkeit, geruchsarme Produkte zu gestalten. Die Kennzeichnung geruchsarmer Bauprodukte mit dem Umweltzeichen Blauer Engel erleichtert Verbraucherinnen und Verbrauchern die Orientierung beim Einkauf.
In this contribution a Raman spectrometer based control structure for the heating of a desorption column is proposed. For this purpose calibration experiments for the absorption of carbon dioxide using monoethanolamine solutions are carried out and calibration models are developed to measure both carbon dioxide liquid loads and monoethanolamine mass fractions. The calibration experiments are supported by online NMR spectroscopy to accurately measure the appearance of all species in the electrolyte system. Both models are tested during the plant operation of a mini-plant for the oxidative coupling of methane and the proof of concept for the control structure is given. The Raman spectroscopy implemented in the ATEX conform mini-plant shows a reliable and robust performance being even indifferent to impurities hindering the GC analysis.
Hydroformylation in microemulsions under mild reaction conditions is investigated using a Rhodium-based catalyst yields high selectivity of 98:2 of the desired linear product. A successful mini-plant operation for over 130 hours was performed. Online concentration monitoring of the system was done using 785nm Raman spectrometer.
Homogen katalysierte Reaktionen sind wichtige Werkzeuge der chemischen Industrie. Milde Reaktionsbedingungen und hohe Selektivitäten führen zu einer energie- und ressourcenschonenden Produktion. Ein bedeutender Prozessschritt ist die Hydroformylierung. Hier kommen Kobalt- und Rhodiumkomplexe mit mehrzähnigen Liganden zum Einsatz, die zumeist in wässriger Lösung vorliegen. Die Anwendbarkeit beschränkt sich demnach auf kurzkettige Edukte mit hinreichender Wasserlöslichkeit.
Normung und Standardisierung in der zerstörungsfreien Prüfung finden auf nationaler, europäischer und internationaler Ebene statt. Die Übernahme von Leitungsfunktionen in diesen Gremien erzeugt die Möglichkeit der Steuerung von Themen und Inhalten der relevanten Normen. Das persönliche Engagement der Fachexpert*innen in den nationalen Gremien und den europäischen und internationalen Arbeitsgruppen ist ein zusätzlicher Faktor für die inhaltliche Korrektheit und die inhaltliche Ausrichtung der Norm. Denn wer nicht normt, wird genormt und muss letztlich Normen anwenden, die andere entsprechend ihrer eigenen Interessen gestaltet haben. Voraussetzung für die Teilnahme in europäischen und internationalen Normungsgremien ist die Mitwirkung in den entsprechenden DINSpiegelgremien, welche die europäischen (CEN) und internationalen (ISO) Aktivitäten spiegeln und die Fachexpert*innen für die Mitarbeit autorisieren.
Auf internationaler Ebene findet die Normungsarbeit in den technischen Komitees ISO/TC 135 “Non-destructive testing” und ISO/TC 44/SC 5 “Testing and inspection of welds” und ihren Arbeitsgruppen statt. Das europäische Pendant ist das CEN/TC 138 “Zerstörungsfreie Prüfverfahren” mit seinen Arbeitsgremien. Die DINSpiegelgremien sind für die deutsche Mitarbeit in diesen Gremien und die inhaltliche Bewertung der Norm-Entwürfe zuständig.