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- Combustion duration time (2)
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- 1 Analytische Chemie; Referenzmaterialien (2)
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- 2 Prozess- und Anlagensicherheit (2)
- 2.1 Sicherheit von Energieträgern (2)
- 1.4 Prozessanalytik (1)
- 3 Gefahrgutumschließungen; Energiespeicher (1)
- 3.1 Sicherheit von Gefahrgutverpackungen und Batterien (1)
- 6 Materialchemie (1)
- 6.3 Strukturanalytik (1)
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%
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)%.
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 explosion characteristics of anthracite and bituminous coals in O2/N2 ambience were experimentally studied via a 20-L spherical explosion chamber with various ignition energies of 2, 5 and 10 kJ. A novel method based on combustion duration time was proposed for the first time, with an emphasis on the determination of the limiting oxygen concentration (LOC). The values of LOC determined by the alternative method were almost consistent with those obtained by using the standardized overpressure method, where the LOCs were above 21.6%, 19.8%, and 13.2% for anthracite coal and 11.4%, 9.6%, and 9.0% for bituminous coal when the ignition energy is 2, 5, and 10 kJ, respectively. But the newly proposed method was found to be much less affected by the ignition energy compared with the standardized overpressure method, taking combustion duration time as an explosion criterion thus had a higher efficiency and required fewer experiments. The results also showed that as oxygen concentration decreases from 21.6% to 14.4%, the maximum explosion pressure decreases from 0.4334 MPa to 0.1034 MPa for anthracite coal and from 0.5664 MPa to 0.3981 MPa for bituminous coal, respectively. Moreover, the effect of ignition energy varied with varying volatile matter content and ignition mechanism of coal dusts. The higher the volatile content, the less sensitive it is to the ignition energy. The newly proposed method will provide a reference for the new standard development, hazard analysis, explosion prevention and suppression by involving the use of inert gases of combustible powder industries.
Iron dust explosion characteristics with small amount of nano-sized Fe2O3 and Fe3O4 particles
(2022)
Iron powder, as one of the most abundant metal fuels that can be used as recyclable carriers of clean energy, is a promising alternative to fossil fuels in a future low-carbon economy. It may pose a potential explosion hazard during the process of processing, storage, transport, and reduction/oxidation (redox). The explosion characteristics of iron dust in air were undertaken via a 20 L spherical explosion chamber with an emphasis on minimum explosion concentration (MEC) of iron dust. The alternative method of combustion duration time (tc) was used to determine MEC and compared with the standardized over pressure method. Two kinds of nano-sized iron oxides (Fe2O3 and Fe3O4) were used as inertants to determine the inhibition effect of different oxidation products. The iron dust explosion products with various shapes and sizes were found to be able to grow up 4–6 times of the iron dust for the first time. Adding small amount of Fe2O3 or Fe3O4 could reduce the explosion severity and sensitivity of iron dust. The MEC data determined by both methods were comparable. The addition of 5 % oxide has obvious inhibition effect under 1500 g/m3 concentration. With the increase of oxide concentration to 10 %, the inerting effect increases, and the MEC of iron dust increases more than 3 times. The increase of dust concentration will weaken the inerting effect. When the concentration increases from 500 g/m3 to 3000 g/m3, the weakening effect of 10 % Fe2O3 on the explosion pressure decreases from 38.45 % to 2.24 %, and 10 % Fe3O4 decreases from 46.21 % to 10.63 %. Unlike coal, biomass or aluminum dusts, the iron dust explosion was found to have a unique secondary acceleration of pressure rise rate for the first time. These results provide a fundamental basis to mitigate the iron dust explosion via solid inerting method without adding extra elements.
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)).
NbC has a relatively high hardness (19.6 GPa) and melting temperature (3600 °C) and is usually applied as a grain growth inhibitor in WC–Co hardmetals. The current study reports on the influence of the sintering technology and overall chemical composition on the microstructure and mechanical properties of NbC-based hardmetals, using Co as a binder. The partial replacement of NbC by 5 wt.% WC, Mo2C, VC or TiC allows one to significantly improve the hardness and toughness of the NbC–Co materials. The influence of different binders, i.e., Co, 316L stainless steel and Fe3Al on the microstructure and mechanical properties of NbC-based hardmetals was also investigated. The powder mixtures were sintered in the solid state by PECS and liquid state by conventional vacuum sintering. Detailed microstructural analysis was conducted by EPMA elemental mapping and WDS point analysis. Mechanical properties, including Vickers hardness and indentation toughness were assessed.
Lanthanide-doped upconversion nanoparticles (UCNPs) are of great interest for biomedical applications. Currently, the applicability of UCNP bionanotechnology is hampered by the generally low luminescence intensity of UCNPs and inefficient energy Transfer from UCNPs to surface-bound chromophores used e.g. for photodynamic therapy or analyte sensing. In this work, we address the low-Efficiency issue by developing versatile core-Shell nanostructures, where high-concentration sensitizers and activators are confined in the core and Shell Region of representative hexagonal NaYF2:Yb,Er UCNPs. After Doping concentration optimization, the sensitizer-rich core is able to harvest/accumulate more excitation energy and generate almost one order of Magnitude higher luminescence intesity than conventional homogeneously doped nanostructures. At the same time, the activator Ions located in the Shell enable a ~6 times more efficient resonant energy Transfer from UCNPs to surface-bound acceptor dye molecules due to the short distance between donor-acceptor pairs. Our work provides new insights into the rational design of UCNPs and will greatly encrease the General applicability of upconversion nanotechnologies.
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).