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Organisationseinheit der BAM
- 6 Materialchemie (4)
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- 2.1 Sicherheit von Energieträgern (3)
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- 6.1 Oberflächen- und Dünnschichtanalyse (2)
- 1.4 Prozessanalytik (1)
- 3 Gefahrgutumschließungen; Energiespeicher (1)
- 3.1 Sicherheit von Gefahrgutverpackungen und Batterien (1)
Safety concerns on cable tray fires in urban utility tunnels, which may further trigger huge casualties, ceiling structure damages, power failures and other domino effects, attract increasing attention in recent years. Determining the maximum excess ceiling gas temperature (MECT) induced by cable tray fires in urban utility tunnels is crucial to evaluate the fire risks. A series of one-layer horizontal cable tray fire experiments to explore the MECT were carried out in a large-scale utility tunnel without mechanical ventilations. The number of cables on the tray was varied from 8 to 18 in the experiments. The experimental results showed that the cable tray fire burning could be divided into three distinct stages, including ignition, self-sustaining and decaying stages. In the self-sustaining combustion stage, the cable tray was found to burn relatively steady. The mean MECT was also investigated since it represents one of the main characteristics of the cable tray fire. By redefining two parameters (the heat release rate and the effective ceiling height) in three classical MECT models proposed originally based on pool-fire, these three models could be extended to be able to predict the mean MECT generated from the cable tray fire (solid combustible) within 20% deviations. Consequently, two novel models were respectively proposed to predict the mean MECT at the self-sustaining burning period and the instantaneous MECT of one-layer horizontal cable tray fire in utility tunnel, which would be useful in the field of fire protection engineering.
Our ability to produce and transform engineered materials over the past 150 years is responsible for our high standards of living today, especially in the developed economies. Yet, we must carefully think of the effects our addiction to creating and using materials at this fast rate will have on the future generations. The way we currently make and use materials detrimentally affects the planet Earth, creating many severe environmental problems. It affects the next generations by putting in danger the future of economy, energy, and climate. We are at the point where something must drastically change, and it must change NOW. We must create more sustainable materials alternatives using natural raw materials and inspiration from Nature while making sure not to deplete important resources, i.e. in competition with the food chain supply. We must use less materials, eliminate the use of toxic materials and create a circular materials economy where reuse and recycle are priorities. We must develop sustainable methods for materials recycling and encourage design for disassembly. We must look across the whole materials life cycle from raw resources till end of life and apply thorough life cycle assessments based on reliable and relevant data to quantify sustainability.
KEY COMPARISON
Under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) a key comparison, CCQM K55.c, was coordinated by the Bureau International des Poids et Mesures (BIPM) in 2012. Twenty National Measurement Institutes or Designated Institutes and the BIPM participated. Participants were required to assign the mass fraction of valine present as the main component in the comparison sample for CCQM-K55.c. The comparison samples were prepared from analytical grade L-valine purchased from a commercial supplier and used as provided without further treatment or purification.
Valine was selected to be representative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of low structural complexity [molecular weight range 100300] and high polarity (pKOW > –2).
The KCRV for the valine content of the material was 992.0 mg/g with a combined standard uncertainty of 0.3 mg/g. The key comparison reference value (KCRV) was assigned by combination of KCRVs assigned from participant results for each orthogonal impurity class. The relative expanded uncertainties reported by laboratories having results consistent with the KCRV ranged from 1 mg/g to 6 mg/g when using mass balance based approaches alone, 2 mg/g to 7 mg/g using quantitative 1H NMR (qNMR) based approaches and from 1 mg/g to 2.5 mg/g when a result obtained by a mass balance method was combined with a separate qNMR result.
The material provided several analytical challenges. In addition to the need to identify and quantify various related amino acid impurities including leucine, isoleucine, alanine and a-amino butyrate, care was required to select appropriate conditions for performing Karl Fischer titration assay for water content to avoid bias due to in situ formation of water by self-condensation under the assay conditions. It also proved to be a challenging compound for purity assignment by qNMR techniques.
There was overall excellent agreement between participants in the identification and the quantification of the total and individual related structure impurities, water content, residual solvent and total non-volatile content of the sample. Appropriate technical justifications were developed to rationalise observed discrepancies in the limited cases where methodology differences led to inconsistent results.
The comparison demonstrated that to perform a qNMR purity assignment the selection of appropriate parameters and an understanding of their potential influence on the assigned value is critical for reliable implementation of the method, particularly when one or more of the peaks to be quantified consist of complex multiplet signals.
The CCQM-K148.a comparison was coordinated by the BIPM on behalf of the CCQM Organic Analysis Working Group for NMIs and DIs which provide measurement services in organic analysis under the CIPM MRA. It was undertaken as a "Track A" comparison within the OAWG strategic plan. CCQM-K148.a demonstrates capabilities for assigning the mass fraction content of a solid organic compound having moderate molecular complexity, where the compound has a molar mass in the range (75 - 500) g/mol and is non-polar (pKow < −2), when present as the primary organic component in a neat organic solid and where the mass fraction content of the primary component in the material is in excess of 950 mg/g.
Participants were required to report the mass fraction of Bisphenol A present in one supplied unit of the comparison material. Participants using a mass balance method for the assignment were also required to report their assignments of the impurity components present in the material. Methods used by the seventeen participating NMIs or DIs were predominantly based on either stand-alone mass balance (summation of impurities) or qNMR approaches, or the combination of data obtained using both methods. The results obtained using thermal methods based on freezing-point depression methods were also reported by a limited number of participants. There was excellent agreement between assignments obtained using all three approaches to assign the BPA content.
The assignment of the values for the mass fraction content of BPA consistent with the KCRV was achieved by most of the comparison participants with an associated relative standard uncertainty in the assigned value in the range (0.1 - 0.5)%.
Metal-Assisted and Solvent-Mediated Synthesis of Two-Dimensional Triazine Structures on Gram Scale
(2020)
Covalent triazine frameworks are an emerging material class that have shown promising performance for a range of applications. In this work, we report on a metal-assisted and solvent-mediated reaction between calcium carbide and cyanuric chloride, as cheap and commercially available precursors, to synthesize two-dimensional triazine structures (2DTSs). The reaction between the solvent, dimethylformamide, and cyanuric chloride was promoted by calcium carbide and resulted in dimethylamino-s-triazine intermediates, which in turn undergo nucleophilic substitutions. This reaction was directed into two dimensions by calcium ions derived from calcium carbide and induced the formation of 2DTSs. The role of calcium ions to direct the two-dimensionality of the final structure was simulated using DFT and further proven by synthesizing molecular intermediates. The water content of the reaction medium was found to be a crucial factor that affected the structure of the products dramatically. While 2DTSs were obtained under anhydrous conditions, a mixture of graphitic material/2DTSs or only graphitic material (GM) was obtained in aqueous solutions. Due to the straightforward and gram-scale synthesis of 2DTSs, as well as their photothermal and photodynamic properties, they are promising materials for a wide range of future applications, including bacteria and virus incapacitation.
Under the Comité Consultatif pour la Quantité de Matière (CCQM), a key comparison, CCQM-K104, was coordinated by the National Institute of Metrology (NIM). The comparison was designed to demonstrate a laboratory's performance in determining the mass fraction of the main component in a complex high purity organic material. Nine NMIs or DIs participated in the comparison. Eight participants reported their results. An additional impurity was resolved from the avermectin B1a peak and was tentatively identified as an unknown impurity by NMIA (National Measurement Institute (Australia)). It was subsequently identified by NIM as a diastereoisomer of avermectin B1a at the C-26 position. Final reference value (KCRV) = 924.63 mg/g, with uncertainty (k=1) = 3.89 mg/g, and expanded uncertainty = 8.97 mg/g. The degrees of equivalence with the avermectin B1a KCRV for each participant were reported. The measurement results and degrees of equivalence should be indicative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of high structural complexity (relative molecular mass range of 500 Da -1000 Da and low polarity (-log KOW ≤ -2).
Polymers with intrinsic microporosity (PIMs) are gaining attention as gas separation membranes. Nevertheless, they face limitations due to pronounced physical aging. In this study a covalent organic framework containing λ5-phosphinine moieties, CPSF-EtO were incorporated as a nanofiller (concentration range 0-10 wt%) into a PIM-1 matrix forming dense films with a thickness of ca. 100 μm. The aim of the investigation was to investigate possible enhancements of gas transport properties and mitigating effects on physical aging. The incorporation of the nanofiller occurred on aggregate level with domains up to 100 nm as observed by T-SEM and confirmed by X-ray scattering. Moreover, the X-ray data show that the structure of the microporous network of the PIM-1 matrix is changed by the nanofiller.
As the molecular mobility is fundamental for gas transport as well as for physical aging, the study includes dielectric investigations of pure PIM-1 and PIM-1/CPSF-EtO mixed matrix membranes to establish a correlation between the molecular mobility and the gas transport properties. Using the time-lag method the gas permeability and the permselectivity were determined for N2, O2, CH4 and CO2 for samples with variation in filler content. A significant increase in the permeability of CH4 and CO2 (50 % increase compared to pure PIM-1) was observed for a concentration of 5 wt% of the nanofiller. Furthermore, the most pronounced change in the permselectivity was found for the gas pair CO2/N2 at a filler concentration of 7 wt%.
The comparison required the assignment of the mass fraction of folic acid present as the main component in the comparison sample. Performance in the comparison is representative of a laboratory's measurement capability for the purity assignment of organic compounds of medium structural complexity [molecular weight range 300–500] and high polarity (pKOW < −2).
Methods used by the eighteen participating NMIs or DIs were based on a mass balance (summation of impurities) or qNMR approach, or the combination of data obtained using both methods. The qNMR results tended to give slightly lower values for the content of folic acid, albeit with larger associated uncertainties, compared with the results obtained by mass balance procedures. Possible reasons for this divergence are discussed in the report, without reaching a definitive conclusion as to their origin.
The comparison demonstrates that for a structurally complex polar organic compound containing a high water content and presenting a number of additional analytical challenges, the assignment of the mass fraction content property value of the main component can reasonably be achieved with an associated relative standard uncertainty in the assigned value of 0.5%
Godbert-Greenwald furnace was used to investigate the minimum ignition temperature of dust clouds (MITC) in air with the presence of flammable gas which is lower than its lower explosion limit (LEL). Three flammable gases (CH4, H2 and CO) and three carbonaceous dusts (anthracite coal, bituminous coal and sweet potato starch) were tested. Results showed that all flammable gases have distinct effects on the MITC of the dust samples and volatile matter content of dust plays an important role during the ignition process. Specifically, the MITC of anthracite coal dust decreased from 610 °C to 560 °C, 580 °C and 570 °C with 3% CH4, 3% CO and 2.5% H2, respectively. Moreover, a heterogeneous ignition mechanism model was proposed to verify the equally global ignition characteristic between hybrid anthracite coal-CxHy mixture and bituminous coal. All three gases had an ignorable effect on the MITC of starch dust considering the experimental error. The presence of CO and H2 slightly promoted the ignition of bituminous coal dust, but the addition of CH4 showed a distinct concentration effect on the MITC of bituminous coal: the MITC decreased with 1% CH4 while increased with 2% and 3% CH4.
This negative-effect of flammable gases at such low concentrations on ignition temperature of bituminous coal dusts was found for the first time. Furthermore, the presence of the 2nd flammable gas had a smaller effect on the MITC of dust samples with a higher volatile content, resulted from the competition of heterogeneous and homogeneous ignition mechanisms.
A boron dipyrromethene (BDP) unit and its monostyryl derivative (MSBDP) were introduced at the axial positions of a silicon(IV) phthalocyanine (SiPc) core. The absorption spectrum of this compound virtually covered the entire visible region (300-700 nm) and could be interpreted as a superposition of the spectra of individual components. The intramolecular photoinduced energy and charge transfer processes of this triad were studied using steady-state and time-resolved spectroscopic methods in polar and nonpolar solvents. Upon BDP-part excitation, a fast and highly efficient excitation energy transfer (EET) occurred resulting in strong quenching of its fluorescence and the formation of the first excited singlet state of SiPc or MSBDP. It was found that both EET and charge transfer (CT) processes competed with each other in the depopulation of the first excited singlet state of the MSBDP moiety. The former strongly superseded CT in nonpolar toluene, whereas the latter was dominant in a polar environment. Direct or indirect (via EET) excitation of the SiPc-part of the triad was followed by CT yielding the charge-separated (CS) species BDP-SiPc center dot--MSBDP center dot+. The energy gap between the CS state and the S-1-state of the SiPc moiety was found to be only 0.06 eV in toluene, which facilitated the back CT process and resulted in the appearance of thermally activated delayed fluorescence. With increasing solvent polarity, the energy of the CS state reduced resulting in the disappearance of the delayed fluorescence in CHCl3, tetrahydrofuran or N,N-dimethylformamide. The charge recombination rate, k(CR), was very fast in polar DMF (3.3 x 10(10) s(-1)), whereas this process was two-orders of magnitude slower in nonpolar toluene (k(CR) = 4.0 x 10(8) s(-1)).
Low cost, high-efficiency catalysts towards water splitting are urgently required to fulfil the increasing demand for energy. In this work, low-loading (<20 wt%) Ni-confined in layered metal oxide anode catalysts (birnessite and lepidocrocite titanate) have been synthesized by facile ion exchange methodology and subjected to systematic electrochemical studies. It was found that Ni-intercalated on K-rich birnessite (Ni-KMO) presents an onset overpotential (ηonset) as low as 100 mV and overpotential at 10 mA cm−2 (η10) of 206 mV in pH = 14 electrolyte. By combining electrochemical methods and X-ray absorption and emission spectroscopies (XAS and XES), we demonstrate Ni sites are the active sites for OER catalysis and that the Mn3+ sites facilitate Ni intercalation during the ion-exchange process, but display no observable contribution towards OER activity. The effect of the pH and the nature of the supporting electrolyte on the electrochemical performance was also evaluated.
Minimum explosion concentrations of coal dusts with CH4/H2/CO below the gas lower explosion limit
(2020)
A 20-L spherical explosion chamber was used to investigate the explosion characteristics of dust clouds in air with the presence of flammable gas which is lower than its lower explosion limit (LEL).
including minimum explosion concentration (MEC) of dust. Explosion pressure (Pex) and explosion pressure rise (dp/dt)ex). Two dust samples (anthracite coal, bituminous coal) and were three flammable gases (CH4, H2 and CO) were tested. Experimental results showed that the explosion of hybrid mixtures occurs when both dust and gas concentrations are lower than the LEL/MEC of the single substances.
Meanwhile. all flammable gases with different volume fractions have distinct effects on the MEC. Pex and (dp/dt)ex of the dust samples.
With the increase of the flammable gas concentration. either the Pex and (dp/dt)ex increase or the MEC decreases for all the hybrid mixtures of both two dust samples. At the same concentration of coal dusts. the addition of CH4 promotes higher explosion risks than the other two flammable gases. The distribution of (dp/dt)ex is quite different with the restricted area defined by empirical formulas.
These results improve our understanding of the explosion behaviour and the explosion risk of hybrid dust-gas mixtures in air.
Low-cost, high-efficient catalysts for water splitting can be potentially fulfilled by developing earthabundant metal oxides. In this work, surface galvanic formation of Co-OH on K0.45MnO2 (KMO) was achieved via the redox reaction of hydrated Co2+ with crystalline Mn4+. The synthesis method takes place at ambient temperature without using any surfactant agent or organic solvent, providing a clean, green route for the design of highly efficient catalysts. The redox reaction resulted in the formation of ultrathin Co-OH nanoflakes with high electrochemical surface area. X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) analysis confirmed the changes in the oxidation state of the bulk and
surface species on the Co-OH nanoflakes supported on the KMO. The effect of the anions, such as chloride, nitrate and sulfate, on the preparation of the catalyst was evaluated by electrochemical and spectrochemical means. XPS and Time of flight secondary ion mass spectrometry (ToF-SIMS) analysis demonstrated that the layer of CoOxHy deposited on the KMO and its electronic structure strongly depend on the anion of the precursor used during the synthesis of the catalyst. In particular, it was found that Cl- favors the formation of Co-OH, changing the rate-determining step of the reaction, which enhances the catalytic activity towards the OER, producing the most active OER catalyst in alkaline media.