MIE determination and thermal degradation study of PA12 polymer powder used for laser sintering

Pulverized materials such as metallic or polymer powders play a considerable role in many industrial processes. Their use requires the introduction of preventive safeguards to control the plant's safety.PA12 polymer powder processing by laser sintering is characteristic of this tendency. The present work concerns PA12 powder (bimodal particle size distribution: 10 μm and 55 μm) and relates to explosion sensitivity and the thermal degradation of this powder, which can occur during laser sintering. Minimum Ignition Energy is determined using a modified Hartmann tube combined with the Langlie method developed in the PRISME Laboratory. This study shows the influence of parameters such as distance between the electrodes, powder concentration and arc power on MIE values. Theses parameters vary in the range of 3–6 A for the current intensity of the spark and the electrode gap in the range of 2.5–4 mm. The MIE is obtained for a spark gap of 3 mm and current intensity of the 4 A spark in our device. It shows that the MIE is less than 40 mJ for concentrations approaching 1000 g/m³. At lower concentrations (under 150 g/m³) the MIE increases but discrepancies in measurements appear, probably because of the static electricity that creates strong irregularities in dust dispersion. The second part of this study concerns the thermal degradation of the PA12 which is performed by thermogravimetric experiments coupled with mass spectrometric (MS) analysis for gas investigation. The mass loss measurement combined with the gas analysis allows the principal stages of degradation to be determined so as to calculate the kinetics parameter PA12. Experiments have been performed for different heating rates between 1 and 30 K min^?1 and the reproducibility of experiments has been verified. The activation energy is determined using two methods: Freidman and KAS. For a reaction rate of between 0.2 and 0.6, the activation energy is nearly constant. The KAS method gives a value of E_a = 250 kJ mol^?1 and the Friedman method gives E_a = 300 kJ mol^?1. The gas analysis by MS shows that oxidation begins at over 350 °C and finishes at under 650 °C with the formation of CO₂ and H₂O. Other major peaks with an m/z ratio of 29, 28 and 30 are noticed in this range of temperature. They show the presence of intermediate species such as C₂H₆, NO or CH₂O. The presence of HCN is also detected (m/z ratio of 27).     

Testing of dust clouds for the electrostatic-spark ignition hazard in industry. Need for a modified approach?

Current standard test methods for electric-spark minimum ignition energies (MIEs) of dust clouds in air require that a series inductance of at least 1–2 mH be included in the electric-spark discharge circuit. The reason is to prolong the spark discharge duration and thus minimize the spark energy required for ignition. However, when assessing the minimum electrostatic energy ½CU² for dust cloud ignition by accidental electrostatic-spark discharges, current testing standards require that the series inductance of at least 1–2 mH be removed from the spark discharge circuit. No other changes of apparatus and test procedure are required. The present paper questions whether this simple approach is always adequate. The reason is that in practice in industry accidental electrostatic-spark discharge circuits may contain large ohmic resistances due to corrosion, poor electrical grounding connections, poorly electrically conducting construction materials etc. The result is increased spark discharge durations and reduced mechanical disturbance of the dust cloud by the blast wave emitted by the spark. Therefore, testing for minimum ½CU² for ignition by accidental electrostatic spark discharges may not only require removal of the series inductance of 1–2 mH from the standard MIE spark discharge circuit. Additional tests may be needed with one or more quite large series resistances R_s inserted into the spark discharge circuit. The present paper proposes a modified standard test procedure for measurement of the minimum electrostatic-spark ignition energy of dust clouds that accounts for these effects.     

Flammability of methane,propane, and hydrogen gases

This paper reports the results of flammability studies for methane, propane, hydrogen, and deuterium gases in air conducted by the Pittsburgh Research Laboratory. Knowledge of the explosion hazards of these gases is important to the coal mining industry and to other industries that produce or use flammable gases. The experimental research was conducted in 20 L and 120 L closed explosion chambers under both quiescent and turbulent conditions, using both electric spark and pyrotechnic ignition sources. The data reported here generally confirm the data of previous investigators, but they are more comprehensive than those reported previously. The results illustrate the complications associated with buoyancy, turbulence, selective diffusion, and ignitor strength versus chamber size. Although the lower flammable limits (LFLs) are well defined for methane (CH₄) and propane (C₃H₈), the LFLs for hydrogen (H₂) and its heavier isotope deuterium (D₂) are much more dependent on the limit criterion chosen. A similar behavior is observed for the upper flammable limit of propane. The data presented include lower and upper flammable limits, maximum pressures, and maximum rates of pressure rise. The rates of pressure rise, even when normalized by the cube root of the chamber volume (V^1/3), are shown to be sensitive to chamber size.     

Comparison of explosion parameters for Methane–Air mixture in different cylindrical flameproof enclosures

Flameproof enclosures having internal electrical components are generally used in classified hazardous areas such as underground coalmines, refineries and places where explosive gas atmosphere may be formed. Flameproof enclosure can withstand the pressure developed during an internal explosion of an explosive mixture due to electrical arc, spark or hot surface of internal electrical components. The internal electrical component of a flameproof enclosure can form ignition source and also work as an obstacle in the explosion wave propagation. The ignition source position and obstacle in a flameproof enclosure have significant effect on explosion pressure development and rate of explosion pressure rise. To study this effect three cylindrical flameproof enclosures with different diameters and heights are chosen to perform the experiment. The explosive mixture used for the experiment is stoichiometric composition of methane in air at normal atmospheric pressure and temperature.It is observed that the development of maximum explosion pressure (P_max) and maximum rate of explosion pressure rise (dp/dt)_ex in a cylindrical flameproof enclosure are influenced by the position of ignition source, presence of internal metal or non-metal obstacles (component). The severity index, K_G is also calculated for the cylindrical enclosures and found that it is influenced by position of ignition source as well as blockage ratios (BR) of the obstacles in the enclosures.     

Preoptimal analysis of phase characteristic indicators in the entire process of coal spontaneous combustion

To accurately predict the development degree of coal spontaneous combustion (CSC), the CSC process was investigated using a programmed high-temperature-heating experimental system, and the variation law of index gas concentration in the holistic process of CSC and oxidation is formulated. Additionally, the accuracy of the experimental system was evaluated using experimental design for thermal analysis, and the correlation between gas index and apparent activation energy was determined using grey correlation analysis. The results indicated the following. In the critical temperature stage (0–100 °C), φ(CO)/φ(CO₂) should serve as the main index and C₂H₄ should serve as the auxiliary index; in the crack-active-speedup temperature stage (100–260 °C), CO and φ(C₂H₄)/φ(C₂H₆) should serve as the main index and R₁, the Graham index, and φ(C₂H₄)/φ(CH₄) should serve as auxiliary indexes; in the speedup-ignition temperature stage (260–370 °C), R₂ and the Graham index should serve as main indexes and φ(CO)/φ(CO₂), C₂H₄, and R₁ should serve as auxiliary indexes; in the ignition temperature (370–500 °C), R₃ should serve as the main index and R₂, the Graham index and C₂H₄ should serve as auxiliary indexes. Among them, the grey correlation degrees among the Graham index, Grignard fire coefficient, and apparent activation energy were the highest, reaching 0.91.     

Initiation of dust explosions by electric spark discharges triggered by the explosive dust cloud itself

An investigation of ignition of dust clouds by the use of electric spark discharges triggered by the explosive dust cloud itself has been conducted. This method of triggering capacitive sparks probably represents a realistic mechanism for initiating accidental dust explosions in industrial practice. Unlike the conventional method for determining the minimum ignition energy (MIE) in the laboratory, the delay between dust dispersion and spark discharge is not a degree of freedom. In stead, the transient dust cloud itself is used to initiate spark breakdown between electrodes set at a high voltage lower than breakdown in pure air. In the present study, different kinds of dusts were tested as ‘spark triggers’, and they exhibited quite different abilities to trigger breakdown. Large particles were found to initiate breakdown at lower voltages than smaller ones. In general, conductive particles were not found to initiate breakdown at lower voltages than dielectric ones when using the same dust concentration.Minimum ignition energies (MIE) of three dusts (Lycopodium clavatum, sulphur and maize starch) were determined using the authors' method of study. The MIEs were somewhat higher than those obtained using conventional methods, but relatively close to the values obtained through conventional methods.     

Lower explosion limit of hybrid mixtures of burnable gas and dust

Hybrid mixtures – mixtures of burnable dusts and burnable gases – pose special problems to industries, as their combined Lower Explosion Limit (LEL) can lie below the LEL of the single substances. Different mathematical relations have been proposed by various authors in literature to predict the Lower Explosion Limit of hybrid mixtures (LEL_hybrid). The aim of this work is to prove the validity or limitations of these formulas for various combinations of dusts and gases. The experiments were executed in a standard 20 L vessel apparatus used for dust explosion testing. Permanent spark with an ignition energy of 10 J was used as ignition source. The results obtained so far show that, there are some combinations of dust and gas where the proposed mathematical formulas to predict the lower explosible limits of hybrid mixtures are not safe enough.     

Effects of a carbon monoxide-dominant gas mixture on the explosion and flame propagation behaviors of methane in air

This work aimed to experimentally evaluate the effects of a carbon monoxide-dominant gas mixture on the explosion characteristics of methane in air and report the results of an experimental study on explosion pressure measurement in closed vessel deflagration for a carbon monoxide-dominant gas mixture over its entire flammable range. Experiments were performed in a 20-L spherical explosion tank with a quartz glass window 110 mm in diameter using an electric spark (1 J) as the ignition source. All experiments were conducted at room temperature and at ambient pressure, with a relative humidity ranging from 52 to 73%. The peak explosion pressure (P_max), maximum pressure rise rate ((dp/dt)_max), and gas deflagration index (K_G) were observed and analyzed. The flame propagation behavior in the initial stage was recorded using a high-speed camera. The spherical outward flame front was determined on the basis of a canny method, from which the maximum flame propagation speed (S_n) was calculated. The results indicated that the existence of the mixture had a significant effect on the flame propagation of CH₄-air and increased its explosion risk. As the volume fraction of the mixed gas increases, the P_max, (dp/dt)_max, K_G and S_n of the fuel-lean CH₄-air mixture (7% CH₄-air mixture) increase nonlinearly. In contrast, addition of the mixed gas negatively affected the fuel-rich mixture (11% CH₄-air mixture), exhibiting a decreasing trend. Under stoichiometric conditions (9.5% CH₄-air mixture), the mixed gas slightly lowered P_max, (dp/dt)_max, K_G, and S_n. The P_max of CH₄-air mixtures at volume fractions of 7%, 9.5%, and 11% were 5.4, 6.9, and 6.8 bar, respectively. The S_n of CH₄-air mixtures at volume fractions of 7%, 9.5%, and 11% were 1.2 m/s, 2.0 m/s, and 1.8 m/s, respectively. The outcome of the study is comprehensive data that quantify the dependency of explosion severity parameters on the gas concentration. In the storage and transportation of flammable gases, the information is required to quantify the potential severity of an explosion, design vessels able to withstand an explosion and design explosion safety measures for installations handling this gas.     

Measurement of minimum ignition energies (MIEs) of dust clouds – History,present, future

Nearly 130 years ago Holtzwart and von Meyer (1891) demonstrated by experiments that explosible dust clouds could be ignited by inductive electric sparks. Then more than half a century passed before the publication of the important quantitative research of Boyle and Llewellyn (1950) and Line et al. (1959). They worked with capacitive electric sparks and found that the minimum capacitor energies ½CU² required for ignition of various dust clouds in air decreased substantially when a large series resistance, in the range 10⁴–10⁷ Ω, was introduced in the discharge circuit. When considering that the net energies of the sparks themselves were only of the order of 10% of the ½CU² discharged, the minimum net spark energies required for ignition with a large series resistance were only a few per cent of the net energies required without such a resistance.Line et al. observed that the essential effect of increasing the series resistance, and hence increasing the discharge time of the sparks, was to reduce the disturbance of the dust cloud by the blast wave from the spark. This phenomenon was explored further by Eckhoff (1970, 2017), and subsequently by some simple experiments by Eckhoff and Enstad (1976). Franke (1974, 1977) and Laar (1980) confirmed the additional finding of Line et al. (1959) that the minimum ½CU² for ignition is also substantially reduced by including a series inductance in the discharge circuit, rather than a series resistance. The basic reason is the same as with a large series resistance, viz. increased spark discharge time and hence decreased disturbance of the dust cloud by blast wave from the spark. For this reason inclusion of an appreciable series inductance in the spark discharge circuit is an essential element in current standard MIE test methods.In experiments with spark ignition of transient dust clouds produced by a blast of air in a closed vessel, it is necessary to synchronize the occurrence of the spark with the formation of the dust cloud. The precision required from this type of synchronization is typically of the order of 10 ms, which can be obtained even by mechanical arrangements, such as rapid change of spark gap length, or of the distance between two capacitor plates. The present paper reviews some methods that have been/are being used for achieving adequate synchronization of dust cloud appearance and spark discharge. Some current standard experimental methods for determining MIEs of dust clouds experimentally have also been reviewed. The same applies to some theories of electric-spark ignition of dust clouds.At the end of paper some suggestions for possible future modifications of current standard methods for measuring MIEs of explosible dust clouds are presented. With regard to justifying significant modifications of existing standard methods, the “bottom line” is, as quite often in many connections, that any modifications should be based on realistic cost/benefit evaluations.     

Statistical method for the determination of the ignition energy of dust cloud-experimental validation

Powdery materials such as metallic or polymer powders play a considerable role in many industrial processes. Their use requires the introduction of preventive safeguard to control the plants safety. The mitigation of an explosion hazard, according to the ATEX 137 Directive (1999/92/EU), requires, among other things, the assessment of the dust ignition sensitivity. PRISME laboratory (University of Orléans) has developed an experimental set-up and methodology, using the Langlie test, for the quick determination of the explosion sensitivity of dusts. This method requires only 20 shots and ignition sensitivity is evaluated through the E₅₀ (energy with an ignition probability of 0.5). A Hartmann tube, with a volume of 1.3 l, was designed and built. Many results on the energy ignition thresholds of partially oxidised aluminium were obtained using this experimental device (Baudry, 2007) and compared to literature. E₅₀ evolution is the same as MIE but their respective values are different and MIE is lower than E₅₀ however the link between E₅₀ and MIE has not been elucidated.In this paper, the Langlie method is explained in detail for the determination of the parameters (mean value E₅₀ and standard deviation σ) of the associated statistic law. The ignition probability versus applied energy is firstly measured for Lycopodium in order to validate the method. A comparison between the normal and the lognormal law was achieved and the best fit was obtained with the lognormal law.In a second part, the Langlie test was performed on different dusts such as aluminium, cornstarch, lycopodium, coal, and PA12 in order to determine E₅₀ and σ for each dust. The energies E₀₅ and E₁₀ corresponding respectively to an ignition probability of 0.05 and 0.1 are determined with the lognormal law and compared to MIE find in literature. E₀₅ and E₁₀ values of ignition energy were found to be very close and were in good agreement with MIE in the literature.     

Explosibility of polyamide and polyester fibers

The current research is aimed at investigating the explosion behavior of hazardous materials in relation to aspects of particulate size. The materials of study are flocculent (fibrous) polyamide 6.6 (nylon) and polyester (polyethylene terephthalate). These materials may be termed nontraditional dusts due to their cylindrical shape which necessitates consideration of both particle diameter and length. The experimental work undertaken is divided into two main parts. The first deals with the determination of deflagration parameters for polyamide 6.6 (dtex 3.3) for different lengths: 0.3 mm, 0.5 mm, 0.75 mm, 0.9 mm and 1 mm; the second involves a study of the deflagration behavior of polyester and polyamide 6.6 samples, each having a length of 0.5 mm and two different values of dtex, namely 1.7 and 3.3. (Dtex or decitex is a unit of measure for the linear density of fibers. It is equivalent to the mass in grams per 10,000 m of a single filament, and can be converted to a particle diameter.) The explosibility parameters investigated for both flocculent materials include maximum explosion pressure (P_max), size-normalized maximum rate of pressure rise (K_St), minimum explosible concentration (MEC), minimum ignition energy (MIE) and minimum ignition temperature (MIT). ASTM protocols were followed using standard dust explosibility test equipment (Siwek 20-L explosion chamber, MIKE 3 apparatus and BAM oven). Both qualitative and quantitative analyses were undertaken as indicated by the following examples. Qualitative observation of the post-explosion residue for polyamide 6.6 indicated a complex interwoven structure, whereas the polyester residue showed a shiny, melt-type appearance. Quantitatively, the highest values of P_max and K_St were obtained at the shortest length and finest dtex for a given material. For a given length, polyester displayed a greater difference in P_max and K_St at different values of dtex than polyamide 6.6. Long ignition delay times were observed in the BAM oven (MIT measurements) for polyester, and video framing of explosions in the MIKE 3 apparatus (MIE measurements) enabled observation of secondary ignitions caused by flame propagation after the initial ignition occurring at the spark electrodes.     

Correlation of pmax and KSt to specific surface area and calorific value of a dust

The safety characteristics p_max and K_St of a flammable dust are usually determined in a closed apparatus (20 l- or 1 m³-vessel). The results are strongly influenced by the parameters of the apparatus (e.g. the volume, geometry, dispersion system). The aim of this project is to investigate whether there is a correlation between p_max and K_St on the one hand and the calorific value H_S and the specific surface area S_m of the dust on the other. In an experimental study, around 200 dust samples from different sectors of industry will be analysed. The analysis of around 102 dusts shows that the correlation may be described by a logarithmic function. Owing to differences in reaction mechanism it is reasonable to formulate different functions for different substance groups (e.g. metals, organic materials). This may lead to an algorithm which can predict p_max and K_St from H_S and S_m within a defined range of error.     

Validation of a new formula for predicting the lower flammability limit of hybrid mixtures

A correlation of the lower flammability limit for hybrid mixtures was recently proposed by us. The experimental conditions including ignition energy and turbulence which play a primary role in a gas or dust explosion were at fixed values. The sensitivity of such experimental conditions to the accuracy of the proposed formula was not thoroughly discussed in the previous work. Therefore, this work studied the effect of varying the ignition energy and turbulence intensity to the formula proposed in our previous paper. For ignition energy effect, results from methane/niacin mixture demonstrated that the MEC and LFL will not be affected by changing ignition energy. There is no distinguishable difference among gas explosion index (K_G) and dust explosion index (K_St) derived from tests with every ignition energy (2.5 kJ, 5 kJ and 10 kJ) in a 36 L vessel. The proposed formula is independent of ignition energy. For turbulence effect, the proposed formula can have a good prediction of the explosion and non-explosion zone if the ignition delay time is within a certain range. The formula prediction is good as the ignition delay time increases up to 100 ms in this work. Propane/niacin and propane/cornstarch mixtures are also tested to validate the proposed formula. It has been confirmed that the proposed formula predicts the explosion and non-explosion zone boundary of such mixtures.     

Effects of metal ions on thermal hazard of tert-butyl peroxy-3,5,5-trimethylhexanoate

As a commonly used initiator for polyethylene, tert-butyl peroxide 3,5,5-trimethylhexanoate (TBPTMH), with the molecular formula of C₁₃H₂₆O₃, is more likely to decompose and cause fires and explosions. Understanding the thermal risks of TBPTMH mixed with common metal ions, potentially in containers and pipes, is important. In this work, by using differential scanning calorimetry (DSC) and Phi-Tec adiabatic calorimetry, the effects of CuCl₂, FeCl₃, CuBr_2, and FeBr₃ on the thermal decomposition of TBPTMH were investigated. Adiabatic kinetic analysis was performed and the apparent activation energy (E_a) was calculated by thermodynamic analysis. Time to maximum rise under adiabatic conditions (TMR_ad) and the self-accelerating decomposition temperature (SADT) under different packing qualities were reckoned. It was found that the thermal risk of TBPTMH was increased while mixing these metal ions, especially CuBr₂. To ensure the safety of the substance in process industry, the temperature of TBPTMH in the presence of metal should be governed below 39.48 °C. This work was expected to provide some guidance for improving the process safety of TBPTMH.     

Critical and transition conditions of gaseous explosion

The critical and transition conditions of a gaseous explosion at constant pressure and varying pressure is investigated. The study covered the solutions of the problem in pressure-time plane, temperature-time plane, as well as pressure-temperature plane. The explosion characteristics of combustible gases using the definition of criticality as an inflection point in critical trajectory. as well as other definitions of criticality are presented. The analytical study showed that the critical parameters for constant pressure explosion are lower than those for constant volumes where θ¹_tr is lowered from 0.5 to 0.29 and θ_atr is also lowered from 0.25 to 0.17. The sensitivity of the critical pressure to the ambient temperature and the boundary between ignition and non-ignition regions are also offered. It was also found that the critical parameters in the temperature–pressure plane were different from those obtained in the temperature-time plane or the pressure–time plane.     

Spill-over characteristics of peroxy-fuels: Two-phase CFD investigations

Two-phase CFD (Computational Fluid Dynamics) model for characterising the spill-over/dispersion of peroxy-fuels is presented. The model is independent of type and burning rate of the spilled/dispersed fuel and considers only overflow Reynolds number (Re) to characterise the spill/dispersion behaviour. Additional simulations are performed for LNG (Liquified Natural Gas) dispersion and it is found that the model can be used for different fuels within a defined range of Re. Different scenarios with Re = 100 to 3 × 10⁵ are investigated covering a wide range of mass flow rates, opening sizes and viscosities. Depending on Lower Flammability Limits (LFL) of the fuels spill/dispersion (vapour cloud) diameters (D_CFD) and heights (h_CFD) are predicted. A generalised correlation between D_CFD and Re is established to predict the dispersion occurring at varying scales. The model is validated by: (1) conducting an extensive grid independent study; (2) comparing the results with the existing analytical methods and (3) comparing against the standard field test data on LNG dispersions.     

Configuration predictions of large liquefied petroleum gas (LPG) pool fires using CFD method

Liquefied petroleum gas (LPG) has potential pool fire risks due to its flammability. The configuration of pool fires plays a significant role when applying the solid flame model or point source model to assess the risks from heat radiation. However, no existing correlations can precisely predict the configuration of large LPG (100% propane) pool fires. To enhance the fundamental understanding on how pool diameter and wind velocity can influence the configuration of large LPG pool fires, an experimentally validated Computational Fluid Dynamics (CFD) model is employed to simulate fires using different burning rate models. Fire temperature profiles, flame heights, and flame tilts predicted by the CFD model were compared with empirical models and experimental data. Accordingly, new correlations for flame height and flame tilt as functions of pool diameter D and wind velocity u_w have been developed. The comparisons demonstrate that the new correlations have the best overall accuracy in the prediction of flame height and tilt for large LPG pool fires under different conditions (10 m ≤ D ≤ 20 m, 0 ≤ u_w ≤ 3 m·s⁻¹).