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- Acidity (2)
- Abbruch (1)
- Abbruchverfahren (1)
- Al substitution (1)
- Bauschuttaufbereitung (1)
- Bronsted acidity (1)
- Building waste (1)
- Catalysis (1)
- Clinoptilolite (1)
- Composite material (1)
Organisationseinheit der BAM
The supermolecular mechanism of the template-mediated oxidative polymerization of pyrrole is investigated in detail. It is shown for the first time that 2,5-bis(pyrrol-2-yl)pyrrolidyl complexes with aromatic sulfonic acids such as %#946;-naphtalenesulfonic acid or para-toluenesulfonic acid are formed in the early polymerization step. The crystalline acidbase complexes are isolated and their crystal structures are analyzed. A 2,5-bis(pyrrol-2-yl)pyrrolidyl cation is common to both complexes and forms an inner salt with the sulfonic acid anion. As concluded from NMR investigations the synthesis using sulfonic acids results in a high stereo selectivity with respect to the trans conformation of the pyrrolidyl ring compared with the classical synthesis routine of this compound using hydrochloric acid. The needle-like crystals of the complexes act as hard templates during the next step of the polymerization and result in tubular morphologies of the polypyrrole.
Aufgrund der großen Massenströme ist das Recycling von Baurestmassen von besonderer Bedeutung
für die Schonung von natürlichen Ressourcen. Eine wichtige Voraussetzung für ein hochwertiges
Recycling, wie z.B. eine Wiederverwertung von aufbereitetem Bauschutt/Altbeton als rezyklierte
Gesteinskörnung im Hochbau, ist die Einhaltung von Grenzwerten für Stör- und Schadstoffe. Dabei
steht der Sulfatgehalt im Eluat von Bauschutt besonders im Fokus. In der vorliegenden Studie wird
untersucht, wie durch die Optimierung von Abbrucharbeiten und Bauschuttaufbereitung hochwertige
Gesteinskörnungen aus Altbeton gewonnen werden können. Anhand von Literatur- und
Datenrecherchen werden zunächst Sulfatquellen in Gebäuden sowie verfügbare Abbruch- und
Aufbereitungstechniken zusammengestellt. Am Beispiel von unterschiedlichen Gebäudetypen werden
Szenarien für selektiven und nicht selektiven Abbruch (Schwerpunkt: Sulfatentfachtung) in Hinblick auf
ihre Umweltwirkungen ökobilanziell bewertet. Ergänzt werden diese Bewertungen durch
Untersuchungen an realen Bauschuttmaterialien und Abbruchprojekten. Auf dieser Basis werden
Handlungsempfehlungen für die Gewinnung von hochwertigen RC-Gesteinskörnungen erarbeitet und
diskutiert.-----------------------------------------------------------------------------------------
Due to the large-scale mass flow of construction and demolition wastes, the recycling of those
residues is of particular importance for the conservation of natural resources. An important
requirement for recycling on a high level, like the reuse of crushed concrete as recycled concrete
aggregate, is the observation of limits for hazardous substances and impurities. This study is focusing
on the reduction of sulphates in the eluate of crushed concrete. An investigation of possibilities to
optimize demolition and dismantling as well as treatment of crushed concrete with the objective of
gaining recycled concrete aggregates of high quality. Based on a literature research and a data review
the origins of sulfates in buildings and also the availability of techniques for demolition and treatment
of crushed concrete are listed and evaluated. Using the examples of different building types scenarios
for selective dismantling and non-selective demolition (focused on reducing suphates) are evaluated in
terms of affecting the environment. In addition samples from real demolition construction sites and
plants for treatment of construction rubble were investigated. Based on these results
recommendations for the production of high quality recycled concrete aggregates are worked out.
Natural zeolite clinoptilolite CLIN with a framework ratio of Si/Al ≥ 4 containing mainly potassium and calcium ions in its internal channel system was used as a starting material. The acidic HCLIN catalysts were prepared under soft conditions avoiding the use of environmental less benign mineral acids. The starting material was ion exchanged using a 0.2 M aqueous ammonium nitrate solution at a temperature 80 ◦C for 2 h. The obtained NH4CLIN was converted into the acid HCLIN catalyst by calcination at 300–600 ◦C. The obtained samples were characterized by XRD, FTIR, SEM/TEM, AAS, and EDX element mapping. The state of aluminium and silicon was studied by 27Al- and 29SiMAS NMR spectroscopy. The textural properties of the catalysts were investigated by nitrogen adsorption and desorption measurements. The Brønsted acidity of the HCLIN catalysts was studied by temperature-programmed decomposition of the exchanged ammonium ions releasing ammonia as well as 1H MAS NMR, {1H–27Al} Trapdor, and {1H–27Al}
Redor experiments. The strongly agglomerated samples were crystalline and thermally stable up to >500 ◦C. Although a part of the clinoptilolite framework is maintained up to 600 ◦C, a loss of crystallinity is already observed starting from 450 ◦C. The specific surface areas of the starting CLIN and ammonium exchanged NH4CLIN are low with ca. 26 m2/g. The pores are nearly blocked by the exchangeable cations located in the zeolite pores. The thermal decomposition of the ammonium ions by calcination at 400 ◦C causes an opening of the pore entrances and a markable increase in the specific micropore area and micropore volume to ca. 163 m2/g and 0.07 cm3/g, respectively. It decreases with further rising calcination temperature indicating some structural loss. The catalysts show a broad distribution of Brønsted acid sites (BS) ranging from weak to strong sites as indicated the
thermal decomposition of exchanged ammonium ions (TPDA). The ammonium ion decomposition leaving BS, i.e., H+ located at Al–O–Si framework bridges, starts at ≥250 ◦C. A part of the Brønsted sites is lost after calcination specifically at 500 ◦C. It is related to the formation of penta-coordinated aluminium at the expense of tetrahedral framework aluminium. The Brønsted sites are partially recreated after repeated ammonium ion exchange. The catalytic performance of the acidic HCLIN
catalysts was tested in the etherification of glycerol as a green renewable resource with different C1 -C4 alcohols. The catalysts are highly active in the etherification of glycerol, especially with alcohols containing the branched, tertiary alkyl groups. Highest activity is observed with the soft activated catalyst HCLIN300 (300 ◦C, temperature holding time: 1 min). A total of 78% conversion of glycerol to mono and di ether were achieved with tert-butanol at 140 ◦C after 4 h of reaction.
The mono- and di-ether selectivity were 75% and 25%, respectively. The catalyst can be reused.
Improved large mesoporous ordered molecular sieves - Stabilization and acid/base functionalization
(2010)
The preparation of nanoporous materials with enhanced stability using an improved synthesis route using reactive inorganic silica and alumina species is reported. This way improved mesoporous molecular sieves were obtained. The synthesized aluminum substituted mesoporous molecular materials (Al-MMS) contain very large pores of 50200 Å size combined with an improved pore wall thickness. Increased wall thickness and Al substitution lead to an improved chemical stability against alkaline solution. The textural, structural and acid properties are investigated by physico-chemical methods. The catalytic performance acidic materials was tested in the benzoylation reaction; amino functionalized materials were studied in the base catalyzed Michael addition.
For fully carbon fibre wrapped pressure vessels with load sharing metallic liner (Type III), it was recognized that the state of residual stress given after the autofrettage process can change even if the vessel is stored without pressure. This change is influenced by temperature and time and has a direct effect on the residual lifetime of the vessel. To study the influence of the temperature on the state of residual stress an analytical model was applied which is based on the Classical Laminate Theory (CLT). According to the model, the critical conditions leading to a decrease in lifetime were identified. To confirm the results of the model temperature cycle tests were carried out. The results of the tests are compared with the analytical model and a finite element model. To investigate the influence of time on the state of residual stress, tests on vessels were performed. The tested vessels were aged without any pressure for a longer period of time after the autofrettage process. During these tests, the strain of the vessels was monitored.
Due to the great quantities of construction and demolition waste in Europe, the reuse of building material waste as secondary raw materials is of particular importance. A recycling of building materials can meet the requirements of sustainability in several aspects: the extended time availability of primary raw materials and the related protection of natural resources as well as the saving of landfill sites. In recent years sulphates originating from gypsum in secondary building materials, made of construction and demolition waste, received growing attention. Sulphates are unwanted in secondary building materials for concrete production as well as for other use e.g. in unbounded layers. The content of gypsum resp. sulphates in secondary aggregates can be reduced by different methods. Depending on the type of material different steps for selective dismantling can be used to separate gypsum containing residues from concrete rubble. Furthermore some steps for the processing of building rubble are suitable for the reduction of sulphates in the produced aggregates. An environmental evaluation of different ways for the production of recycled concrete aggregates was performed with regard to a reduction of sulphates in the secondary building material. The use of techniques for selective dismantling was environmentally advantegous for the deconstruction of three investigated model houses.
Entwickelt und validiert - Probengeometrie zur Untersuchung von gewickelten Faserverbundproben
(2012)
Durch die beschriebene, auf eine Umfangsbelastung ausgelegte Probengeometrie werden
Fertigung und Einsatz von Druckbehältern nachempfunden. Dafür wurden bereits bestehende
Probenformen überarbeitet, um im Probenkörper eine unidirektionale Zugbelastung zu
erzeugen. Da die endgültigen Eigenschaften von faserverstärktem Kunststoff erst in der
Fertigung entstehen, sind gleiche Fertigungsbedingungen von Proben und Bauteilen wichtig.
Die hier vorgestellte Probe verspricht dadurch eine gute Eignung für den Einsatz bei Untersuchungen
zum Zeitstandsverhalten.
The platinum group elements (PGEs) play an important role in reducing emissions from automotive vehicles through their use in catalytic convertors but also for catalysis in the pharmaceutical industry. The immense economic value of platinum (Pt), palladium (Pd) and rhodium (Rh) highlights the importance of highly accurate measurements. Therefore, there is a need for National Metrology Institutes (NMIs) and Designated Institutes (DIs) to demonstrate measurement capability in this space.
A pilot comparison (CCQM-P63) for precious metals in automotive catalyst took place in 2006, but with a limited number of institutes participating. Furthermore, this study was performed over 17 years ago. Therefore, there was a need to maintain existing capability and demonstrate new capability in a key comparison, in order to claim calibration and measurement capability claims (CMCs). With the core capability matrix, this study falls into the "Difficult to dissolve metals/metal oxides" which will support CMC categories 8 (Metal and metal alloys), 9 (Advanced materials) and 14 (Other materials).
Eleven NMIs and DIs participated in the Key Comparison CCQM-K160 Platinum Group Elements in Automotive Catalyst. Participants were requested to evaluate the mass fractions of Pt, Pd and Rh in mg/kg in an unused autocatalyst material (cordierite ceramic base). The Key Comparison Reference Values (KCRVs) and Degrees of Equivalence (DoEs) were calculated utilising the NIST Decision Tree for the measurands. The participants utilised a number of sample preparation and analytical methods including hot plate digestion, microwave digestion and sodium fusion, followed by either atomic absorption spectroscopy (AAS), inductively coupled plasma optical emission spectroscopy (ICP-OES) or inductively coupled plasma mass spectrometry (ICP-MS) detection. Several calibration techniques were used, namely external calibration, standard addition, isotope dilution mass spectrometry (IDMS) and an exact matching procedure. Additionally, one participant employed instrumental neutron activation analysis (INAA) with k0 standardisation which is a direct solid analysis method. The majority of participants claimed traceability to NIST primary calibrants or their own CRMs. Furthermore, several matrix CRMs were included or spiked samples for quality control. All institutes were required to determine the dry mass fraction using the stipulated protocol.
The NIST decision tree was implemented for the calculation of the KCRVs and DoEs. The participant results overall showed good agreement with the KCRV, despite the variety of dissolution procedures and measurement techniques for this highly complex matrix and challenging measurands. Successful participation in CCQM-K160 demonstrated measurement capabilities for the determination of mass fraction of Pt, Pd and Rh in the mg/kg range and will support broad scope CMC claims for a wide range of challenging matrices.
To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/.
The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).