TY - JOUR A1 - Malow, Marcus A1 - Krause, Ulrich A1 - Wehrstedt, Klaus-Dieter T1 - Some comments on the paper of H. Fierz: Influence of heat transport mechanisms on transport classification by SADT-measurement as measured by the Dewar-method PY - 2003 DO - https://doi.org/10.1016/S0304-3894(03)00221-8 SN - 0304-3894 VL - 103 SP - 169 EP - 173 PB - Elsevier CY - Amsterdam AN - OPUS4-2687 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Steensma, M. A1 - Schuurman, P. A1 - Malow, Marcus A1 - Krause, Ulrich A1 - Wehrstedt, Klaus-Dieter T1 - Evaluation of the validity of the UN SADT H.4 test for solid organic peroxides and self-reactive substances N2 - Many self-accelerating decomposition temperatures (SADTs) of solid organic peroxides and self-reactive substances have been determined with the UN test method H.4, which is a scaled down test in a small Dewar vessel. For solid organic peroxides and solid self-reactive substances Fierz has questioned this procedure in a recent paper. Fierz concluded that the Dewar test results should not be extrapolated to beyond 8 l packages, owing to the thermal insulation value of solids. On the other hand, long term experience with the test, with a great variety of solid organic peroxides and self-reactive substances show about equal critical temperatures in the small Dewar vessel and on 50 kg scale. In the present work, we first checked, by numerical simulations, the Dewar scale versus the larger scale, in a way comparable with Fierz’ method: both scales are simulated by spheres, consisting of a number of annular layers, for the large scale the usual external heat loss term is used but for the small scale the outside heat transfer is strongly limited. The outcome of these simulations, covering a variety of physical parameters, supports the concerns expressed by Fierz. After this, we performed accurate cooling and heating experiments with solid organic peroxide in the usual Dewar vessel, provided with a large set of thermocouples. The results of these experiments showed that the simulation model for the Dewar vessel has to be changed from a spherical analogue to a short cylinder of solid material with heat exchange mainly via its top (Utop 3.5 W/(m2 K), overall heat transfer coefficient) and some heat exchange (Uside 0.29 W/(m2 K)) through its cylindrical and bottom part. With this “modified cylinder” model (being neither an infinitely long cylinder nor a slab) of the Dewar vessel, we found that the UN method H.4 enables an accurate prediction of the SADT, with small deviations of 0 ± 2.5 °C. Further, by performing a truly three-dimensional (3D) finite element calculation in FEMLAB, the new heat characteristics of the Dewar vessel as well as a 50 kg package of dilauroyl peroxide, a solid organic peroxide, were checked. The outcome was compared with the critical ambient temperatures known for various package sizes, which agreed well. KW - SADT of solids KW - Transport regulations KW - UN H.4 test (HAST) KW - Numerical simulations KW - Scale-up procedure PY - 2005 DO - https://doi.org/10.1016/j.jhazmat.2004.09.028 SN - 0304-3894 VL - 117 IS - 2-3 SP - 89 EP - 102 PB - Elsevier CY - Amsterdam AN - OPUS4-5604 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmidt, Martin A1 - Malow, Marcus A1 - Lohrer, Christian A1 - Krause, Ulrich T1 - Selbstentzündung von Stäuben und Schüttgütern bei vermindertem Sauerstoffgehalt PY - 2002 UR - http://www3.interscience.wiley.com/journal/91014775/issue SN - 0009-286X SN - 1522-2640 VL - 74 IS - 12 SP - 1 EP - 6 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-5993 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Malow, Marcus A1 - Wehrstedt, Klaus-Dieter T1 - Prediction of the self-accelerating decomposition temperature (SADT) for liquid organic peroxides from differential scanning calorimetry (DSC) measurements N2 - We present a prediction (estimation, calculation, screening) method for the estimation of the self-accelerating decomposition temperature (SADT) for liquid organic peroxides from differential scanning calorimetry (DSC) measurements based on the concepts of thermal explosion theory originally introduced by Semonov which are adopted to our problem assuming nth-order reaction kinetics. For the peroxides under investigation, we demonstrate good agreement with the experimental SADT. This method can be used as a quick and easy applicable method for the estimation of the critical temperatures. KW - Organic peroxides KW - Differential scanning calorimetry (DSC) KW - Self-accelerating decomposition temperature (SADT) PY - 2005 DO - https://doi.org/10.1016/j.jhazmat.2004.12.040 SN - 0304-3894 VL - 120 IS - 1-3 SP - 21 EP - 24 PB - Elsevier CY - Amsterdam AN - OPUS4-7308 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lohrer, Christian A1 - Schmidt, Martin A1 - Malow, Marcus A1 - Krause, Ulrich A1 - Steinbach, J. T1 - Einfluss von Feuchte und Konvektionsströmung auf das Selbstentzündungsverhalten von Feststoffschüttungen KW - Selbstentzündung KW - Konvektion KW - Feuchte PY - 2005 DO - https://doi.org/10.1002/cite.200590078 SN - 0009-286X SN - 1522-2640 VL - 77 IS - 8 SP - 1141 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-10847 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Malow, Marcus A1 - Krause, Ulrich T1 - The overall activation energy of the exothermic reactions of thermally unstable materials N2 - The exothermic reactions of thermally unstable materials have been studied using self-heating methods in a wire-mesh-reactor as well as temperature-programmed methods utilizing a differential scanning calorimeter (DSC). Samples of lignite coal dust, cork dust, detergent powder and riboflavin (vitamin B2) were investigated. The overall activation energy E could be determined for each method. For lignite coal and cork dust all techniques show very nice agreement in E. For the detergent powder, the values are comparable except for the heat-release (HR) rate method value which is about 50–60 kJ/mol higher. Riboflavin on the other hand shows a different behaviour. The DSC-experiments lead to values being significantly higher compared to the self-heating values. The existing differences are clearly worked out. KW - Overall activation energy KW - Decomposition reactions KW - Self-heating KW - DSC PY - 2004 DO - https://doi.org/10.1016/j.jlp.2003.09.002 SN - 0950-4230 SN - 1873-3352 VL - 17 IS - 1 SP - 51 EP - 58 PB - Butterworth CY - Guildford, Surrey AN - OPUS4-4973 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - The overall activation energy of the exothermic rections of thrmally unstable materials T2 - 4th International Seminar on Fire and Explosion Hazards CY - Londonderry, Northern Ireland DA - 2003-09-08 PY - 2003 AN - OPUS4-3935 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Is the UN H.4 test a suitable test to determine the SADT for solids in a 50 kg packaging or not? T2 - Meeting TNO/BAM CY - Rijswijk, Netherlands DA - 2003-09-18 PY - 2003 AN - OPUS4-3936 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Malow, Marcus A1 - Wehrstedt, Klaus-Dieter A1 - Krause, Ulrich T1 - Anwendbarkeit des UN SADT H.4-Tests für feste organische Peroxide KW - Selbstentzündung KW - Peroxide PY - 2005 DO - https://doi.org/10.1002/cite.200590196 SN - 0009-286X SN - 1522-2640 VL - 77 IS - 8 SP - 1122 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-11572 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Anwendbarkeit des UN SADT H.4-Tests für feste organische Peroxide T2 - GVC/DECHEMA-Jahrestagung 2005 CY - Wiesbaden, Germany DA - 2005-09-06 PY - 2005 AN - OPUS4-11461 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Malow, Marcus A1 - Schulze, A. A1 - Krause, Ulrich T1 - The main gaseous products and the mass loss during the self-ignition of combustible materials T2 - 6th International Symposium on Hazards, Prevention, and Mitigation of Industrial Explosions CY - Halifax, Canada DA - 2006-08-27 KW - Self-ignition KW - Combustion KW - Biomass KW - FTIR-gas-measurements KW - Macro-thermal balance PY - 2006 SN - 0950-4230 SN - 1873-3352 SP - 825 EP - 836 PB - Butterworth CY - Guildford, Surrey AN - OPUS4-12892 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Malow, Marcus A1 - Wehrstedt, Klaus-Dieter A1 - Neuenfeld, S. T1 - On the explosive properties of 1H-benzotriazole and 1H-1,2,3-triazole N2 - For 1H-benzotriazole, no explosive properties are observable, but the relative high exothermic decomposition energy of 1590 J/g should be kept in mind. Nevertheless, an endothermic melting barrier at 100 °C ensures safe handling at lower temperatures. For 1H-1,2,3-triazole, the exothermic decomposition energy is as high as 2600 J/g, but explosive properties are also not detectable. Therefore, both reagents are hazardous with regard to the exothermic decomposition potential and can be handled safely with precautions. KW - 1H-Benzotriazole KW - 1H-1,2,3-Triazole KW - Explosive properties KW - DSC PY - 2007 SN - 0040-4039 SN - 1873-3581 VL - 48 IS - 7 SP - 1233 EP - 1235 PB - Elsevier CY - Amsterdam AN - OPUS4-14476 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schmidt, Martin A1 - Malow, Marcus A1 - Krause, Ulrich A1 - Neumann, F. T1 - Untersuchung des Verhaltens von Steinkohlen unter dem Gesichtspunkt des Ex-Schutzes N2 - Die Kenntnis des Brenn- und Explosionsverhaltens von Stäuben ermöglicht die Festlegung geeig-neter Explosionsschutzmaßnahmen. Am Beispiel von Steinkohle- Mahlanlagen werden Untersu-chungen zur Bestimmung sicherheitstechnischer Kenngrößen (STK) von Stäuben vorgestellt. Hier-bei erfolgt zunächst die auf den Anwendungsfall abgestimmte Auswahl geeigneter Untersuchungs-verfahren und deren Anpassung an vorliegende Randbedingungen. Aufbauend auf die gewonnenen Erkenntnisse werden Schlussfolgerungen für den sicheren Betrieb von Steinkohle- Mahlanlagen getroffen. T2 - VGB-Konferenz "Kraftwerke im Wettbewerb 2007, Neue Kraftwerke - mit Erfahrung und Innovation die Zukunft gestalten" CY - Hamburg, Deutschland DA - 2007-04-25 KW - Explosionsschutz KW - Steinkohle KW - Mahlanlagen KW - Selbstentzündung PY - 2007 IS - CD-ROM SP - 15 Seiten PB - VGB PowerTech e.V. CY - Hamburg AN - OPUS4-14785 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - The ISTC-Project - a suitable approach to revise the UN-Test Series H? T2 - OECD - IGUS - EOS - working group meeting CY - Rijswijk, Netherlands DA - 2007-05-09 PY - 2007 AN - OPUS4-14847 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Explosive properties of Triazole derivatives - A case study T2 - IGUS-EOS-working group meeting CY - Rijswijk, Netherlands DA - 2007-05-09 PY - 2007 AN - OPUS4-14848 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmidt, Martin A1 - Malow, Marcus A1 - Krause, Ulrich A1 - Neumann, F. T1 - Untersuchung des Entzündungs- und Brandverhaltens von Steinkohlen unter dem Gesichtspunkt des Ex-Schutzes KW - Explosionsschutz KW - Steinkohle KW - Mahlanlagen KW - Selbstentzündung PY - 2007 SN - 1435-3199 VL - 87 IS - 7 SP - 67 EP - 72 PB - VGB PowerTech e.V. CY - Essen AN - OPUS4-15711 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - The ISTC project from the current point of view of BAM T2 - Meeting of the ISCT project collaborators CY - Pfinztal, Germany DA - 2007-09-04 PY - 2007 AN - OPUS4-16023 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Schmidt, Martin A1 - Malow, Marcus A1 - Krause, Ulrich ED - Thomas Stolz, ED - Heino Bothe, T1 - Vorhersage von Brandszenarien bei der Lagerung von Schüttgütern KW - Selbstentzündung KW - Schüttgüter KW - Kohle KW - Biomasse KW - Numerische Simulation PY - 2007 SN - 978-3-86509-700-2 SP - 90 EP - 101 PB - Wirtschaftsverl. NW, Verl. für Neue Wiss. CY - Braunschweig AN - OPUS4-16277 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Brandvermeidung bei der Lagerung von biogenen Brennstoffen T2 - Klimazwei Tagung, Umweltforum CY - Berlin, Germany DA - 2007-02-28 PY - 2007 AN - OPUS4-16509 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ferrero, Fabio A1 - Malow, Marcus A1 - Noll, Matthias T1 - Temperature and gas evolution during large scale outside storage of wood chips N2 - The temperature and gas concentrations in a newly established pine-wood debris pile of 20 m × 15 m × 6 m in dimensions (approximately 400 tons of fresh weight material) were monitored for 150 days. Temperature was measured at ten different positions within the pile, while concentrations of CO2, O2, CO and CH4 were taken at four different representative locations. The pile was characterized by a strong temperature increase within the first 10– 12 days of storage. Results of the gas analysis in this period suggest that the temperature increase was caused by microbial processes. In particular, reduced oxygen concentration and almost complete absence of methane indicate mainly aerobic respiration processes. Effects of weather conditions on the temperature/gas distribution and time evolution are also discussed in the paper. KW - Wood KW - Storage KW - Temperature KW - Gas concentration PY - 2011 DO - https://doi.org/10.1007/s00107-010-0512-0 SN - 0018-3768 VL - 69 IS - 4 SP - 587 EP - 595 PB - Springer CY - Berlin ; Heidelberg AN - OPUS4-23849 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Impact of Particle Size on the Oxidising Potential of Solids T2 - IGUS EOS Meeting CY - Berlin, Germany DA - 2012-05-07 PY - 2012 AN - OPUS4-26370 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Test results with different types of cellulose as reference material for the UN-Test O.1 T2 - IGUS EOS Meeting CY - Berlin, Germany DA - 2012-05-07 PY - 2012 AN - OPUS4-26371 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - New validation results on the UN-Test N.5 T2 - IGUS EOS Meeting CY - Berlin, Germany DA - 2012-05-07 PY - 2012 AN - OPUS4-26372 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Flammability of solids T2 - ECHA Trainig Course "Physical and Chemical Properties" CY - Berlin, Germany DA - 2011-10-24 PY - 2011 AN - OPUS4-25043 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Oxidizing properties for solids and liquids T2 - ECHA Trainig Course "Physical and Chemical Properties" CY - Berlin, Germany DA - 2011-10-24 PY - 2011 AN - OPUS4-25044 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Validierung der UN Test Methode N.5 zur Klassifizierung von Stoffen die bei Kontakt mit Wasser brennbare Gase entwickeln T2 - ProcessNet-Jahrestagung 2012 CY - Karlsruhe, Germany DA - 2012-09-10 PY - 2012 AN - OPUS4-26483 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Validation of the UN Test Method N.5 T2 - Mary Kay O`Connor Process Safety Center Symposium 2012 CY - College Station, TX, USA DA - 2012-10-23 PY - 2012 AN - OPUS4-26620 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schälike, Stefan A1 - Mishra, Kirti Bhushan A1 - Malow, Marcus A1 - Berger, Anka A1 - Wehrstedt, Klaus-Dieter A1 - Schönbucher, A. ED - Pierucci, S. ED - Klemes, J.J. ED - De Rademaeker, E. ED - Fabiano, B. ED - Buratti, S.S. T1 - Mass burning rate of a large TBPB pool fire - experimental study and modeling N2 - Data and prediction for the mass burning rate of a tert-butyl-peroxy-benzoat (TBPB) pool fire (pool diameter = 3 m) is presented. The mass burning rates of TBPB fires are up to six times higher and less dependent on pool diameter compared to hydrocarbon pool fires caused by an additional heat release rate due to exothermic decomposition reaction in the liquid phase. This heat release rate is calculated using a 1st order reaction kinetic obtained from micro calorimetric measurements. A new model is derived considering the heat release rate due to the decomposition reaction which is shown to be 100 % of the heat release rate radiated to the pool surface. With the presented model, including also physical quantities, especially the limiting fuel concentration for upward flame propagation, it is possible to predict the mass burning rates of large TBPB pool fires. The predicted values are in very good agreement with the experiments. T2 - 14th International symposium on loss prevention and safety promotion in the process industries CY - Florence, Italy DA - 12.05.2013 KW - Mass burning rate KW - TBPB (tert-butyl-peroxy benzoat) KW - Pool fire KW - Experimental study KW - Modeling PY - 2013 SN - 978-88-95608-22-8 DO - https://doi.org/10.3303/CET1331143 SN - 1974-9791 N1 - Serientitel: Chemical engineering transactions – Series title: Chemical engineering transactions IS - 31 SP - 853 EP - 858 PB - AIDIC, Associazione Italiana di Ingegneria Chimica CY - Milano AN - OPUS4-28501 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Oxidizing properties of NH4NO3 in relation to its particle size T2 - IGUS EOS Meeting CY - Verneuil en Halatte, France DA - 2013-04-17 PY - 2013 AN - OPUS4-28542 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Classification of polymerizing substances T2 - IGUS EOS Meeting CY - Verneuil en Halatte, France DA - 2013-04-17 PY - 2013 AN - OPUS4-28543 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krösche, C. A1 - Malow, Marcus A1 - Budde, K. T1 - False-Positive Results of UN Test O.2 Liquid Oxidizer Test of Polychlorosilanes N2 - According to UN Test O.2, surprisingly, the polychlorosilanes hexachlorodisilane (HCDS), octachlorotrisilane (OCTS) and decachlorotetrasilane (DCTS) formally fulfill the criteria of the “test for oxidizing liquids”. This result is in contrast to the properties of polychlorosilanes that are described in the literature and those we have experienced in our own production. By investigating the reaction products from the UN O.2 test reactor, using IR, Raman and XPS spectroscopy, it was shown that the results are not due to oxidizing properties of HCDS, OCTS or DCTS, but are caused by the specified test substance cellulose. To our knowledge, this is the very first substance class in which the reference substance oxidizes the test sample, instead of vice versa. This represents an important limitation of the internationally used UN Test O.2 for this substance class. The cause for this false-positive result is the known high degree of affinity of oxygen to silicon. It is shown that the correctly executed UN Test O.2 produces false-positive results and that the polychlorosilanes do not have an oxidizing effect and, therefore, do not have to be classified as “oxidizing substances”. KW - Polychlorosilanes KW - UN Test O.2 KW - Hexachlorodisilane KW - Octachlortrisilane KW - Decachlorotetrasilane KW - False-positive results PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-523989 DO - https://doi.org/10.1016/j.jlp.2021.104434 VL - 70 SP - 104434 PB - Elsevier Ltd. AN - OPUS4-52398 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lüth, Peter A1 - Uhlig, S. A1 - Frost, K. A1 - Malow, Marcus A1 - Michael-Schulz, Heike A1 - Schmidt, Martin A1 - Zakel, Sabine T1 - CEQAT-DGHS interlaboratory tests for chemical safety: Validation of laboratory test methods by determining the measurement uncertainty and probability of incorrect classification including so-called “Shark profiles” N2 - Laboratory test results are of vital importance for correctly classifying and labelling chemicals as “hazardous” as defined in the UN Globally Harmonized System (GHS) / EC CLP Regulation or as “dangerous goods” as defined in the UN Recommendations on the Transport of Dangerous Goods. Interlaboratory tests play a decisive role in assessing the reliability of laboratory test results. Interlaboratory tests performed over the last 10 years have examined different laboratory test methods. After analysing the results of these interlaboratory tests, the following conclusions can be drawn: 1. There is a need for improvement and validation for all laboratory test methods examined. 2. To avoid any discrepancy concerning the classification and labelling of chemicals, the use of validated laboratory test methods should be state of the art, with the results accompanied by the measurement uncertainty and (if applicable) the probability of incorrect classification. This paper addresses the probability of correct/incorrect classification (for example, as dangerous goods) on the basis of the measurement deviation obtained from interlaboratory tests performed by the Centre for quality assurance for testing of dangerous goods and hazardous substances (CEQAT-DGHS) to validate laboratory test methods. This paper outlines typical results (e.g. so-called “Shark profiles” – the probability of incorrect classification as a function of the true value estimated from interlaboratory test data) as well as general conclusions and steps to be taken to guarantee that laboratory test results are fit for purpose and of high quality. T2 - 13th International Symposium on Hazards, Prevention and Mitigation of Industrial Explosions (ISHPMIE 2020) CY - Brunswick, Germany DA - 27.07.2020 KW - Dangerous goods KW - Hazardous substances KW - Interlaboratory test KW - Test method KW - Validation KW - Quality assurance KW - Measurement uncertainty KW - Incorrect classification KW - Shark profiles PY - 2021 DO - https://doi.org/10.1016/j.jlp.2021.104532 SN - 0950-4230/ VL - 72 SP - 104532 PB - Elsevier Ltd. AN - OPUS4-52751 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Lüth, Peter A1 - Malow, Marcus T1 - CEQAT-DGHS Interlaboratory tests for chemical safety – A new gravimetric procedure for the gas flow measurement for flammable and toxic gases N2 - Testing of hazardous materials and evaluating their hazardous properties concerning transport, handling or use is essential for the prevention of incidents. For this purpose, test methods have been developed and published that are used worldwide today (European Union, 2008, United Nations, 2019). For the evaluation of test results their correct measurement is of importance. On basis of the interlaboratory tests carried out by BAM and PTB within the framework of the CEQAT-DGHS in the last years, it is shown that there is a need for improvement in all the test methods examined so far. In addition to the interlaboratory tests further quality measures are mandatory (ISO, 2017). For example, methods for verifying the test equipment used in the laboratories should be developed. The development of a verification method is demonstrated using the test method UN Test N.5 as an example. This test method is used to evaluate substances which in contact with water emit flammable gases. The basic principle of the verification method is demonstrated by Lüth et al. (2019). Requirements and difficulties during this development are discussed. This test procedure UN Test N.5 has now been modified at BAM so that it is possible to measure very small or large amounts of both flammable and/or toxic gases over a long period of time in a validated and verified test apparatus, utilizing the principle of a gas collector. This allows us to determine slow as well as fast gas evolution rates. The determination of the evolution rates (e.g. total gas amount or flow rate) of toxic gases is of special interest because of the ongoing discussion how to evaluate and quantify toxic gases which are formed from a substance due to contact with water. Up today no validated test procedure for the measurement of evolution rates for toxic gases is described. It is shown that the newly modified test method could help to solve this problem. T2 - 13th International Symposium on Hazards, Prevention, and Mitigation of Industrial Explosions CY - Online meeting DA - 27.07.2020 KW - Hazardous materials KW - Transport regulations KW - Flammable gases KW - Toxic gases PY - 2020 SP - Paper 1002 AN - OPUS4-51271 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Schoßig, Jörg A1 - Berger, Anka A1 - Malow, Marcus A1 - Krause, Ulrich T1 - Beurteilung und Verhinderung von Selbstentzündung und Brandgasemission bei der Lagerung von Massenschüttgütern und Deponiestoffen N2 - Im Ergebnis des Vorhabens steht für die praktische Anwendung eine wissenschaftlich fundierte Methode der Gefahrenbewertung für Selbstentzündungsvorgänge bei der Lagerung von Massenschüttgütern, Deponiestoffen und Recyclingmaterialien zur Verfügung. Diese Methode besteht aus drei Bestandteilen: - Experimentelle Bestimmung der relevanten physiko-chemischen Eigenschaften des Materials, - Experimentelle Bestimmung des Reaktionsverhalten mittels thermischer Analyseverfahren, - Vorhersage der Selbstentzündung und des Brandverlaufes durch numerische Simulation anhand der realen Geometrie der Lageranordnung. Eine solche Methode wurde bisher nicht systematisch angewendet, weshalb sowohl bei der Erstellung von Brandschutzkonzepten durch die Betreiber von Deponien oder Recyclinglagern als auch bei der Genehmigung solcher Anlagen durch die Behörden große Unsicherheit bezüglich des vorbeugenden Brandschutzes bestehen. Diese Unsicherheiten können mit den Ergebnissen des Vorhabens ausgeräumt werden. Den Nutzen hieraus ziehen vor allem KMU, die den Hauptteil der Betreiberfirmen von Deponien und Recyclinglagern stellen. Darüber hinaus erwuchsen aus dem Vorhaben auch grundlegende Erkenntnisse zum thermischen und Reaktionsverhalten solcher Lager: - Gemische von Kunststoffen mit zellulosehaltigen oder faserartigen Stoffen sowie Gemische von Kunststoffen mit inerten Stoffen zeigen eine stärkere Selbstentzündungsgefahr als reine Kunststoffe. - Auch bei sehr geringen Anteilen brennbarer Stoffe kommt es noch zu gefährlicher Wärmefreisetzung. - Bei heterogener Verteilung der brennbaren Komponente (brennbare Einschlüsse in nicht-brennbarem Material) kann eine „Übertragung“ der Zündung zwischen brennbaren Einschlüssen erfolgen. Dies spiegelt z.B. die Situation in Lagern für Baumischabfälle wieder. Mit dem im Vorhaben entwickelten mathematischen Modell können Selbstentzündungsprozesse in beliebigen Lageranordnungen vorhergesagt werden. Die Ziele des Vorhabens wurden erreicht. Weiterer Forschungsbedarf wurde zu folgenden Teilaspekten erkannt: - Selbstentzündungsverhalten von Abfällen, die als sogenannte Ersatzbrennstoffe aufbereitet werden (Pressballen mit und ohne Folieumwicklung), - tiefer gehende Klärung der Reaktionsmechanismen beim Abbrand von Abfallgemischen. T3 - BAM Forschungsberichtreihe - 291 PY - 2010 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-1600 SN - 978-3-9813346-6-1 SN - 0938-5533 VL - 291 SP - 1 EP - 56 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-160 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gödde, Markus A1 - Clemens, Jörg A1 - Malow, Marcus T1 - Screening Procedures for Self-Reactive Substances, Differential Scanning Calorimetry-Onset and Heat-Flux Criteria N2 - We present a newscreening procedure for the determination of the thermal stability of potential candidates for the class of self-reactive substances. For the classification of self-reactive substances, elaborate testing is necessary to determine the applicable type, according to the regulations. Annex 6 of the UNManual of Tests and Criteria permits that the classification procedure for self-reactive substances may be omitted, if the estimated self accelerating decomposition temperature (SADT) is greater than 75 °C for a 50 kg package using an appropriate calorimetric technique, but no technique is described. Based on stationary theories of thermal explosion, we developed a screening approach using differential scanning calorimetry (DSC) onset and heat-flux criteria, respectively, at relevant temperatures. The proposed approach is validated with experimental data. KW - Self-reactive substances KW - Classification KW - Differential scanning calorimetry KW - Self accelerating decomposition temperature KW - Screening-procedures PY - 2025 DO - https://doi.org/10.1002/ceat.12006 SN - 1521-4125 SP - 1 EP - 9 PB - Wiley-VCH GmbH AN - OPUS4-62678 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Ferrero, Fabio A1 - Malow, Marcus A1 - Schmidt, Martin A1 - Krause, Ulrich T1 - Leitfaden zur Brandvermeidung bei der Lagerung von Biomasse N2 - Die Menge an genutztem, verarbeitetem und gelagertem Holz steigt von Jahr zu Jahr. In der Folge konnte in den letzten fünf Jahren eine deutlich gestiegene Zahl von Bränden in Holzlagern und -halden festgestellt werden. Viele dieser Brände sind durch Selbstentzündung des Materials verursacht worden. Sind die Ursachen der Selbstentzündung bekannt, kann die Brandentstehung durch geeignete Maßnahmen vermieden werden. Die Fachgruppe II.2 „Reaktionsfähige Stoffe und Stoffsysteme“ der Bundesanstalt für Materialforschung und -prüfung hat in diesem Leitfaden das Thema aufgegriffen und die derzeit vorliegenden Erkenntnisse zusammenfassend dargestellt. Ziel des Leitfadens ist es, die Grundlagen der Selbstentzündung von Biomasse am Beispiel von Holz in übersichtlicher Form darzustellen und daraus praktische Hinweise zur Vermeidung der Selbstentzündung von Holzhalden abzuleiten, um so einen Weg für einen sicheren und nachhaltigen Umgang mit diesem Rohstoff zu ebnen. Dem Leitfaden liegen Ergebnisse des Forschungsvorhabens „Brandvermeidung bei der Lagerung von biogenen Brennstoffen“ zugrunde. Das Projekt wurde innerhalb der Fördermaßnahme „klimazwei – Forschung für den Klimaschutz und Schutz vor Klimawirkungen“ des Bundesministeriums für Bildung und Forschung finanziell gefördert (Förderkennzeichen 01LS05079). Für diese Förderung möchten die Autoren sich bedanken. T3 - BAM Forschungsberichtreihe - 284 PY - 2009 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-1678 SN - 978-3-9812354-1-8 SN - 0938-5533 VL - 284 SP - 1 EP - 22 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-167 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rosenberg, Marika A1 - Michael-Schulz, Heike A1 - Wehrstedt, Klaus-Dieter A1 - Malow, Marcus T1 - Validation of the UN test method N.5 N2 - Many substances react with water in such a way that flammable gases are formed. For transport issues this reaction may possess a considerable hazard especially if the cargo is wetted by rain or by water from other sources. In the UN Recommendations on the Transport of Dangerous Goods these kinds of problems are addressed. The UN test N.5 “Test method for substances which in contact with water emit flammable gases” corresponds to this hazard. Classification according to the test method is done by measurement of the gas evolution rate of the flammable gas by any suitable procedure. At BAM a gravimetric approach is used to measure the gas evolution rate. In this paper we present the evaluation of the apparatus by means of an absolute calibration routine utilizing a reaction where a known amount of gas is produced as well as the evaluation of important parameters influencing the gas evolution rate using different substances. It can be shown that the apparatus is capable of measuring absolute gas volumes as low as 6 mL with an acceptable error of about 17% as determined from the reaction of Mg with demineralized water. T2 - 15th Annual symposium, Mary Kay O'Connor process safety center CY - College Station, TX, USA DA - 23.10.2012 KW - UN test N.5 KW - Water-reactive substance KW - Flammable gas PY - 2012 SN - 978-0-615-53719-1 SP - 826 EP - 835 AN - OPUS4-26898 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Ferrero, Fabio A1 - Malow, Marcus A1 - Schmidt, Martin A1 - Krause, Ulrich ED - Böllinghaus, Thomas ED - Kitagawa, Masaki ED - Kishi, Teruo ED - Lexow, Jürgen T1 - Computational modelling of the self-ignition process to achieve safe storage of biomass T2 - 1st World Materials Research Institutes Forum (WMRIF) - Workshop for young materials scientists CY - Tsukuba, Ibaraki, Japan DA - 2008-07-22 KW - Self-ignition KW - Fire prevention KW - Storage KW - Biomass KW - Bulk materials PY - 2008 SN - 978-4-9900563-3-9 SP - XXII 1 EP - 16 CY - Tsukuba, Ibaraki, Japan AN - OPUS4-17861 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Notwendigkeiten und Möglichkeiten zur Verifizierung von Prüfapparaturen zur Bestimmung sicherheitstechnischer Kennzahlen N2 - Prüfapparaturen zur Bestimmung sicherheitstechnischer Kennzahlen müssen präzise messen, um verlässliche Ergebnisse zu produzieren. Oftmals gibt es in der Methodenbeschreibung allerdings keine Informationen zu Messunsicherheiten o.ä.. In dem Vortrag werden Ringversuchsprogramme das CEQAT-DGHS beschrieben und aktuelle Arbeiten zu Verifizierungsverfahren von Messmethoden beschrieben. T2 - 14. Fachtagung Anlagen-, Arbeits- und Umweltsicherheit CY - Köthen, Germany DA - 07.11.2019 KW - Gefahrgut KW - UN-Test N.5 KW - Verifizierung von Prüfapparaturen KW - Messunsicherheit PY - 2019 AN - OPUS4-50233 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - CEQAT-DGHS Development of procedures for the verification of test apparatuses (Example UN Test N.5) N2 - This presentation focuses on General aspects of development of verification methods. The development of verification methods is demonstrated using the test method UN Test N.5 as an example. T2 - EOS IGUS Meeting CY - Brussels, Belgium DA - 21.05.2019 KW - Dangerous Goods KW - UN-Test N.5 KW - Verification method KW - Measurement uncertainty PY - 2019 AN - OPUS4-49003 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Malow, Marcus T1 - Different methods for the determination of calcium peroxide N2 - The CaO2 Content ist analyzed using different titration methods. The results and the methods are compared. CaO2 is a reference material in the UN Test method O.3. T2 - EOS IGUS Meeting CY - Brussels, Belgium DA - 21.05.2019 KW - Dangerous Goods KW - UN-Test O.3 KW - Calcium peroxid KW - Content of calcium peroxide PY - 2019 AN - OPUS4-49001 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Lüth, Peter A1 - Frost, K. A1 - Kurth, Lutz A1 - Malow, Marcus A1 - Schmidt, Martin A1 - Michael-Schulz, Heike A1 - Uhlig, S. A1 - Zakel, S. T1 - CEQAT-DGHS Ringversuchsprogramm für die Chemikaliensicherheit - Schlussfolgerungen N2 - Die Ursachen für Chemikalienunfälle können vielfältig sein. Prävention beginnt bereits im Prüflabor, wenn Chemikalien auf ihre gefährlichen Eigenschaften getestet werden. Dazu sind Prüfmethoden entwickelt und veröffentlicht worden, die heute weltweit Anwendung finden. Auf die Validität der Prüfmethode und richtige Durchführung der Prüfung im Laboratorium müssen sich Sicherheitsfachkräfte, Transporteure oder Händler verlassen können. Anhand der in den letzten 10 Jahren im Rahmen des CEQAT-DGHS von BAM und PTB durchgeführten Ringversuche (RV) wird gezeigt, dass bei allen bisher untersuchten Prüfmethoden ein Verbesserungsbedarf besteht. Die RV müssen daher zunächst auf die Methodenverbesserung und -validierung abzielen und nicht auf Leistungstests. Das Labormanagement und die praktische Durchführung der Prüfung sind in vielen Laboratorien verbesserungsbedürftig. Der Begriff „Erfahrung der Prüfer“ ist kritisch zu sehen: Eine „lange Erfahrung mit vielen Prüfungen“ ist nicht unbedingt ein Garant für richtige Ergebnisse. T2 - 15. BAM-PTB-Kolloquium zur chemischen und physikalischen Sicherheitstechnik CY - Braunschweig, Germany DA - 21.05.2019 KW - Gefahrgut KW - Gefahrstoff KW - Ringversuch KW - Prüfmethode KW - Validierung KW - Qualitätssicherung PY - 2019 UR - https://www.ptb.de/cms/index.php?id=18763 DO - https://doi.org/10.7795/210.20190521M SP - 1 EP - 8 PB - Physikalisch-Technische Bundesanstalt (PTB) CY - Braunschweig AN - OPUS4-49489 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Lüth, Peter A1 - Frost, K. A1 - Kurth, Lutz A1 - Malow, Marcus A1 - Schmidt, Martin A1 - Michael-Schulz, Heike A1 - Uhlig, S. A1 - Zakel, S. T1 - CEQAT-DGHS Ringversuchsprogramm für die Chemikaliensicherheit – Entwicklung von Verfahren zur Verifizierung der Prüfapparatur am Beispiel der Prüfmethode UN Test N.5 N2 - Prävention beginnt im Prüflabor, wenn Chemikalien auf ihre gefährlichen Eigenschaften getestet werden. Dazu sind Prüfmethoden entwickelt und veröffentlicht worden, die heute weltweit Anwendung finden. Auf die Validität der Prüfmethode und richtige Durchführung der Prüfung im Laboratorium müssen sich Sicherheitsfachkräfte, Transporteure oder Händler verlassen können. Anhand der in den letzten 10 Jahren im Rahmen des CEQAT-DGHS von BAM und PTB durchgeführten Ringversuche (RV) wird gezeigt, dass bei allen bisher untersuchten Prüfmethoden ein Verbesserungsbedarf besteht. Die RV müssen daher zunächst auf die Methodenverbesserung und -validierung abzielen und nicht auf Leistungstests. Das Labormanagement und die praktische Durchführung der Prüfung sind in vielen Laboratorien verbesserungsbedürftig. Der Begriff „Erfahrung der Prüfer“ ist kritisch zu sehen: Eine „lange Erfahrung mit vielen Prüfungen“ ist nicht unbedingt ein Garant für richtige Ergebnisse. Bei der Prüfung der gefährlichen Eigenschaften von Chemikalien sind Referenzmaterialen auf Grund der Instabilität in der Regel nicht verfügbar. Für Prüflaboratorien sind RV daher eine Alternative bei der Qualitätssicherung. RV sind jedoch aufwendig und können nur in relativ großen Zeitabständen durchgeführt werden. Es sind deshalb Verfahren zur Verifizierung z. B. der in den Laboratorien verwendeten Prüfapparaturen zu entwickeln. Die Entwicklung von Verifizierungsverfahren wird am Bespiel der Prüfmethode UN Test N.5 demonstriert. T2 - 15. BAM-PTB-Kolloquium zur chemischen und physikalischen Sicherheitstechnik CY - Braunschweig, Germany DA - 21.05.2019 KW - Gefahrgut KW - Gefahrstoff KW - Ringversuch KW - Prüfmethode KW - Validierung KW - Qualitätssicherung KW - Verifizierung PY - 2019 UR - https://www.ptb.de/cms/index.php?id=18763 DO - https://doi.org/10.7795/210.20190521E SP - 1 EP - 10 CY - Braunschweig AN - OPUS4-49495 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lüth, Peter A1 - Frost, K. A1 - Kurth, Lutz A1 - Malow, Marcus A1 - Michael-Schulz, Heike A1 - Schmidt, Martin A1 - Schulte, Petra A1 - Uhlig, S. A1 - Zakel, S. T1 - CEQAT-DGHS Interlaboratory Test Programme for Chemical Safety - Need of Test Methods Validation N2 - Safety experts, manufacturers, suppliers, importers, employers or consumers must be able to rely on the validity of safety-related test methods and on correct test results and assessments in the laboratory. Via the eChemPortal lots of data from the REACH registration dossiers are available. However, the quality and correctness of the information remains in the responsibility of the data submitter. Unfortunately, we found more or less appropriate information on physicochemical properties and concluded that more quality or adequacy of any data submitted will be needed. Interlaboratory tests play a decisive role in assessing the reliability of test results. Interlaboratory tests on different test methods have been performed by Bundesanstalt für Materialforschung und –prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB) in collaboration with the QuoData GmbH during the last 10 years. Significant differences between the results of the participating laboratories were observed in all interlaboratory tests. The deviations of the test results were not caused only by laboratory faults but also by deficiencies of the test method. In view of the interlaboratory test results the following conclusions can be drawn: • To avoid any discrepancy on classification and labelling of chemicals it should become state of the art to use validated test methods and the results accompanied by the measurement uncertainty. • A need for improvement is demonstrated for all examined test methods. Thus, interlaboratory tests shall initially aim at the development, improvement and validation of the test methods and not on proficiency tests. • The laboratory management and the practical execution of the tests need to be improved in many laboratories. • The term "experience of the examiner" must be seen critically: A "long experience with many tests" is not necessarily a guarantee for correct results. T2 - 16th International Symposium on Loss Prevention and Safety Promotion in the Process Industries and accompanying exhibition. Loss prevention 2019 CY - Delft, The Netherlands DA - 16.06.2019 KW - Dangerous goods KW - Hazardous substances KW - Round robin test KW - Interlaboratory comparison KW - Test method KW - Validation KW - Quality assurance PY - 2019 UR - https://www.aidic.it/cet/19/77/001.pdf SN - 978-88-95608-74-7 DO - https://doi.org/10.3303/CET1977001 SN - 2283-9216 VL - 77 SP - 1 EP - 6 PB - Italian Association of Chemical Engineering AN - OPUS4-49496 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Léonard, Fabien A1 - Zhang, Zhen A1 - Malow, Marcus A1 - Bruno, Giovanni T1 - 3D characterisation of ammonium nitrate powders by X-ray computed tomography N2 - The mixture of ammonium nitrate (AN) prills and fuel oil (FO), usually called ANFO, is extensively used in the mining industry as a bulk industrial explosive. One of the major performance predictors of ANFO mixtures is the fuel oil retention, which is itself governed by the porosity of the AN prills. Standardised tests routinely used to assess oil retention face several important limitations; the first being the difficulty to cover the wide range of porosity contents and morphologies from different types of ammonium nitrate prills; the second being the inability to evaluate the closed porosity, which is an important factor regarding the sensitivity of the explosive to detonation. In this study, we present how X-ray computed tomography (XCT), and the associated advanced data processing workflow, can be used to fully characterise the structure and morphology of AN prills. We show that structural parameters such as volume fraction of the different phases and morphological parameters such as specific surface area and shape factor can be reliably extracted from the XCT data, and that there is a good agreement with the measured oil retention values. XCT can therefore be employed to non-destructively and accurately evaluate and characterise porosity in ammonium nitrate prills. T2 - 23rd Seminar on New Trends in Research of Energetic Materials CY - Meeting was canceled DA - 01.04.2020 KW - Ammonium nitrate KW - Prill KW - Non-destructive characterisation KW - Porosity KW - Specific surface area PY - 2020 SP - 163 EP - 171 AN - OPUS4-51272 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -