Prediction of thermal hazard of liquid organic peroxides by non-isothermal and isothermal kinetic model of DSC tests

Liquid organic peroxides (LOPs) have been widely used as initiators of polymerization, hardening, or cross-linking agents. We evaluated a beneficial kinetic model to acquire accurate thermokinetic parameters to help preventing runaway reactions, fires or explosions in the process environment. Differential scanning calorimetry was used to assess the kinetic parameters, such as kinetic model, reaction order, heat of reaction (??H _d), activation energy (E _a), frequency factor (lnk ₀), etc. The non-isothermal and isothermal kinetic models were compared to determine the validity of the kinetic model, and then applied to the thermal hazard assessment of commercial package contaminated with LOPs. Simulations of a 0.5-L Dewar vessel and 25-kg commercial package were performed. We focused on the thermal stability of different liquid system properties for LOPs. From the results, the optimal conditions were determined for avoiding violent heat effects that can cause a runaway reaction in storage, transportation, and manufacturing.     

Thermal hazard studies for dicumyl peroxide by DSC and TAM

A differential scanning calorimetry (DSC) and thermal activity monitor (TAM) were used to study the thermo-kinetic parameters for dicumyl peroxide (DCPO) at various concentrations. The potential thermal hazards of intermediates and end products whose concentrations were at approximately 50, 70, 94 and 99.3 mass%, respectively, in the process of operating DCPO were investigated. Thermoanalytical curves indicate that the average heat of decomposition of various DCPO samples in a manufacturing process was 762 to 1200 J g ^-1 which made it an inherently hazardous material. In the incompatibilities study, significant thermal hazards appeared in the presence of H₂SO₄. From the TAM experiments, the synthetic process of DCPO could result in an unexpected reaction in the condition of batch addition with reactants and H₂SO₄.     

Evaluation of thermal hazard for lauroyl peroxide by VSP2 and TAM III

When above certain temperature limits, lauroyl peroxide is an unstable material. If the thermal source cannot be properly governed during any stage in the preparation, manufacturing process, storage or transport, runaway reactions may inevitably be induced immediately. In this study, the influence of runaway reactions on its basic thermal characteristic was assessed by evaluating thermokinetic parameters, such as activation energy (E _a) and frequency factor (A) by thermal activity monitor III (TAM III). This was achieved under five isothermal conditions of 50, 60, 70, 80, and 90?°C. Vent sizing package 2 (VSP2) was employed to determine the maximum pressure (P _max), maximum temperature (T _max ), maximum self-heating rate ((dT?dt ^?1)_max), maximum pressure rise rate ((dP?dt ^?1)_max), and isothermal time to maximum rate ((TMR)_iso) under the worst case. Results of this study will be provided to relevant plants for adopting best practices in emergency response or accident control.     

Exothermic behaviors in decomposition of three solid organic peroxides by DSC and VSP2

The new derivatives of 3,4-pyridinedicarboximide were synthesised. Experimental measurements were carried out using ¹H NMR spectra, IR spectra, elemental analyses and differential scanning calorimetry. The purpose of this study was to study the thermal stability of these four new compounds and to establish a solid-state polymorphism. Measurements were carried out for samples obtained from ethanol and n-hexane and after a long-time storage.     

Thermal hazard analyses of organic peroxides and inorganic peroxides by calorimetric approaches

Organic peroxides (OPs) and inorganic peroxides (IPs) are usually employed as an initiator for polymerization, a source of free radicals, a hardener, and a linking agent in low density polyethylene (LDPE), polyvinyl chloride (PVC), controlled-rheology polypropylene (CR-PP), and styrene industries. Worldwide, due to their unstably reactive natures, OPs and IPs have caused many serious thermal explosions and runaway reaction incidents. This study was conducted to elucidate its essentially hazardous characteristics. To analyze the runaway behavior of OPs and IPs in the traditional process, thermokinetic parameters including heat of decomposition (??H _d ), exothermic onset temperature (T ₀), self-accelerating decomposition temperature (SADT), time to maximum rate (TMR), critical temperature (T _c ), etc., were measured by calorimetric approaches involving differential scanning calorimetry (DSC), vent sizing package 2 (VSP2), and calculation method. Safety and health handling information of hazardous materials and toxic substances is noted in material safety data sheets (MSDS) and was applied to analyze in process safety management (PSM) in the chemical industries, but MSDS are not providing important handling indicators concerning the SADT, TMR, T _c , etc. In view of loss prevention, more useful indicators must be provided in the sheets or guide book.     

Application fo pressure DTA (DSC) to thermal hazard evaluation

Any hazard evaluation program should necessarily include assessment of the thermal hazards of a material. To this end, differential thermal methods (DTA and DSC) are commonly employed. The utility of these methods in thermal hazard evaluation can be significantly extended if pressurized atmospheres are also employed. The characterization of volatile chemicals as much as 100°C beyond their atmospheric boiling temperature may be achieved with pressures under 1654 kPa (225 p.s.i.g.). The effective oxygen reactivity is enhanced with a pressurized air atmosphere. Also the confined conditions in a pressurized DTA (DSC) atmosphere produce results which can be used in many instances for the semi-quantative assessment of the pressure—temperature change to be expected in more time-consuming “heating under confinements tests”.     

Thermal hazard analyses and incompatible reaction evaluation of hydrogen peroxide by DSC

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions worldwide. Its thermal hazards may also be incurred by an incompatible reaction with other chemical materials, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to thermal accidents by incompatibility and to discuss what might be formed by the upset situations. In this study, the thermal hazard analyses were conducted with various solvents, propanone (CH₃COCH₃), Fe₂O₃, FeSO₄, H₂SO₄, HCl, HNO₃, H₃PO₄, NaOH, LiOH, and KOH which were deliberately selected to individually mix with H₂O₂ for investigating the degree of hazard. Differential scanning calorimetry (DSC) was employed to evaluate the thermal hazard of H₂O₂-mixed ten chemicals. The results indicated that H₂O₂ is highly hazardous while separately mixed with ten materials, as a potential contaminant. Fire and explosion hazards could be successfully reduced if the safety-related data are suitably imbedded into manufacturing processes.     

Thermal hazard evaluation of carbon nanotubes with sulfuric acid by DSC

Many concerns over unsafe or unknown properties of multi-walled carbon nanotubes (MWNTs) have been raised. The thermal characteristics regarding stability would represent potential hazards during the production or utilization stage and could be determined by calorimetric tests for various thermokinetic parameters. Differential scanning calorimetry (DSC) was employed to evaluate the thermokinetic parameters for MWNTs at various compositions. Thermoanalytical curves showed that the average heat of decomposition (ΔH _d) of the MWNTs samples in a manufacturing process was about 31,723 J g⁻¹, by identifying them as an inherently hazardous material. In this study, significant thermal analysis appeared in the presence of sulfuric acid (H₂SO₄). From the DSC experiments, the purification process of MWNTs could induce an unexpected reaction in the condition of batch addition with reactants of H₂SO₄. The results can be applied for designing emergency relief system and emergency rescue strategies during a perturbed situation or accident.     

Systematic process hazard assessment of three kinds of solid organic peroxides with kinetic analysis and heat transfer equilibrium

Journal of Thermal Analysis and Calorimetry - Organic peroxide (OP) has been applied in the industry for at least 40 years. Driven by significant investments in today’s high-profile...     

Thermal runaway analyses for two organic peroxides with H2O and dry fire-extinguishing chemicals by DSC and VSP2

In recent years, organic peroxides, including methyl ethyl ketone peroxide (MEKPO) and cumene hydroperoxide (CHP), have often caused thermal runaway reactions, fires, and thermal explosions worldwide. Under normal circumstances, H₂O and dry fire-extinguishing chemicals are often employed to eliminate fire situations. We evaluated the thermal runaway reaction for MEKPO and CHP mixed with H₂O and dry fire-extinguishing chemicals by differential scanning calorimetry, and thermal runaway reaction for CHP mixed with dry fire-extinguishing chemicals by vent sizing package 2. The results showed that ABC dry chemical, BC dry chemical, and XBC dry chemical all caused the decomposition of MEKPO to occur at lower onset temperature and H₂O caused the ΔH _d of MEKPO to become higher. On the other hand, H₂O and XBC dry chemical induced the decomposition of CHP to occur at lower onset temperature as well as lower thermal explosion temperature. The maximum of self-heating rate ((dT/dt)_max) and the maximum pressure-rise rate ((dP/dt)_max) of CHP mixed with dry fire-extinguishing chemicals were measured lower than CHP alone. The results indicated that MEKPO and CHP are highly hazardous when mixed with H₂O and some dry fire-extinguishing chemicals. In view of loss prevention, the results can be useful references for fire fighters dealing with thermal upsets in chemical plants.     

An evaluation on thermokinetic parameters for hydrogen peroxide at various concentrations by DSC

Information about the kinetics and thermal decomposition of hydrogen peroxide (H₂O₂) has been required for safety reasons, due to its broad applications in many chemical industries. To determine the inherent hazards during H₂O₂ manufacturing, transportation, disposal, usage, and so on, this study deliberately selected various H₂O₂ concentrations and analyzed them by differential scanning calorimetry (DSC). In addition, thermokinetic parameters were not only established for each of these reactions, but also aimed at comprehensive, kinetic models with various tests conducted at different heating rates. To build up a comprehensive kinetic model, various tests were conducted by heating rates of 1, 2, 4, 10°C min^–1, respectively. According to dynamic DSC tests, the experimental curves show that H₂O₂ decomposition has one exothermic peak and may start to decompose under 47–81°C. The total heat of decomposition is about 192–1079 J g^–1. Not only can these results prevent accidents caused by H₂O₂ during storage and transportation, but also assess its inherent hazards and thereby design procedures for emergency response while runaway reactions occurring.     

Effects of various fire-extinguishing reagents for thermal hazard of triacetone triperoxide (TATP) by DSC/TG

Acetone, hydrogen peroxide (H₂O₂), and sulfuric acid (H₂SO₄) are easily to produce triacetone triperoxide (TATP), which is an organic peroxide and a hazardous material. The aim of this study was to analyze the thermal hazard of various fire-extinguishing reagents mixed with TATP. Various functions of fire-extinguishing reagents may have different extent of reactions with TATP. Differential scanning calorimetry (DSC) and thermogravimetric analyzer (TG) were used to detect the thermal hazard and to evaluate the effect of fire-extinguishing reagents mixed with TATP under fire condition. TATP decomposed rapidly and final decomposition was calculated before 200 °C. Therefore, heat of decomposition (ΔH _d) of TATP was evaluated to be 2,500 J g^?1 by DSC under 2 °C min^?1 of heating rate. H₂O₂, acetone, and H₂SO₄ should not be mixed in a wastewater drum. TATP decomposed at 50 °C by DSC using O₂ of reaction gas that is an exothermic reaction and can decompose a large amount of heat. Therefore, TATP was applied to assess thermal pyrolysis by DSC employing N₂ of reaction gas that can analyze an endothermic reaction. Mass loss percentage of TATP was evaluated to be 100 % when the ambient temperature exceeds 110 °C by TG using O₂ or N₂ of reaction gas.     

Thermokinetic model simulations for methyl ethyl ketone peroxide contaminated with H2SO4 OR NaOH by DSC and VSP2

In this study, a mixture of methyl ethyl ketone peroxide (MEKPO) with various contaminants, such as H₂SO₄ and NaOH, was prepared in order to elucidate the cause of these accidents and the results of upset conditions. Thermokinetic parameters were acquired by both differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2). In addition, we simulated the thermokinetic parameters and created kinetic models for the specific contaminants. The results indicate that the thermal hazard of MEKPO is less than that of the mixed MEKPO with the above-mentioned contaminants. Consequently, the evaluated parameters could be used to prevent any unexpected exothermic runaway reaction or to alleviate hazards to an acceptable extent, if such a reaction occurs.     

Estimation of kinetic parameters for curing of epoxy-anhydride compositions by DSC

The kinetics of the curing process of epoxy resin (ED-22) in the presence of the anhydride hardeners (iso-methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and dodecylsuccinic anhydride) and accelerators (2-methyl imidazole and n-butyltriphenylphosphonium bromide) has been investigated by DSC method in the dynamic mode. Processing of experimental DSC thermograms recorded at different heating rates was carried out within the frameworks of isoconvertional analysis in two versions, namely "model-free" method of Friedman and the Ozawa—Flynn—Wall method. The possibility to describe the kinetics of epoxy compositions curing in the frameworks of one-step autocatalytic reaction model has been demonstrated. Obtained kinetic parameters were used to predict the curing kinetics under isothermal conditions and for comparative analysis of the compositions.     

Assessment of parameters for simulation of thermal ageing of materials in nuclear power plants using DSC

Summary Simulation of thermal ageing is an important part of qualification of materials designed for the use in nuclear power plants (NPP). According to standards, the simulation of long-term service thermal ageing is performed isothermally at elevated temperature using Arrhenius methodology. The samples or equipment are aged in thermal chamber, to bring them to the same state as after long-term service time. To proceed a reliable simulation, the testing parameters should be taken very carefully and the accelerator factors should not be too high. The testing temperature and time and the activation energy are the most important parameters. Determination of these factors and the limitations of their use in practice are discussed.     

Determination of some parameters to be utilized in correcting DSC curves for effects due to thermal lag

In many applications of differential scanning calorimetry (DSC), notably the determination of specific heat functions, the analysis of reaction kinetics and the determination of purity, the instantaneous differential heat flow and the instantaneous actual sample temperature are required. The measurement of both is influenced in DSC by thermal lag effects, i.e. signal filtering and thermal gradients. A procedure is proposed which permits, under certains experimental conditions, correction of thermal lag by means of characteristic time constants having material and instrumental components. The validity of the results is enhanced by the comparison with those obtained by other authors.

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Zusammenfassung Bei vielen Anwendungen der Differentialabtastkalorimetrie, besonders bei der Bestimmung der spezifischen WÄrme, der Analyse der Reaktionskinetik sowie bei der Reinheitsbestimmung werden die momentane differentiale WÄrmeströmung und die momentane Probentemperatur benötigt. Die Messung beider Grö\en wird bei der DSC durch thermische Verzögerungs-Effekte, d. h. Signalfiltrierung und thermische Gradienten beeinflu\t. Es wird ein Verfahren vorgeschlagen, das unter gewissen Versuchsbedingungen die Korrektur des thermischen Verzögerungs-Effekts durch charakteristische, aus Material- und Instrumentalkomponenten bestehende Zeitkonstanten, ermöglicht. Die Gültigkeit der Ergebnisse wird durch Vergleiche mit den von anderen Autoren erhaltenen besonders betont.

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Résumé Dans de nombreuses applications de l'analyse calorimétrique différentielle, par ex. les déterminations de chaleur spécifique, de cinétiques réactionnelles et de pureté, il est nécessaire de connaÎtre les valeurs instantanées du flux de chaleur différentiel ainsi que la température réelle de l'échantillon. En DSC, la mesure de ces deux valeurs est influencée par des effets d'inertie comme le filtrage du signal et les gradients thermiques. On propose un procédé qui permet, dans certaines conditions expérimentales, de corriger ce retard de transmission du signal thermique par des constantes de temps caractéristiques du matériau et de l'instrument. La validité des résultats est mise en valeur par comparaison avec ceux obtenus par d'autres méthodes.

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The author wishes to thank Prof. M. Piazzi for his helpful discussion with respect to this communication.