Disposal of hexachlorodisilane and its hydrolyzed deposits

Hexachlorodisilane (Si₂Cl₆, HCDS) is an important precursor used in semiconductor device manufacturing. It is a flammable as well as a water reactive liquid which hydrolyzes rapidly upon contact with water or moisture. The hydrolyzed deposits are also known to be shock-sensitive with explosion energy equivalent to trinitrotoluene (TNT). In this work, two phases of test program including disposal of HCDS and disposal of the shock sensitive HCDS hydrolyzed deposits were conducted. The first phase of the program was to find an agent that can completely dissolve/react the HCDS vapor without forming shock sensitive deposits. The second phase of the program attempted to find a suitable agent to suppress the Si–Si bonds, one of the essential roles of chemical functional groups in shock sensitivity of the HCDS hydrolyzed deposits to suppress the shock sensitivity. A variety of agents such as sulfuric acid solutions, aqueous sodium hydroxide (NaOH) solutions, aqueous potassium hydroxide (KOH) solutions, KOH/alcohol solutions were utilized as the suppressants in this work. Samples mixed with suppressants were not only tested for shock sensitivity by a Fall-hammer apparatus but also analyzed for chemical functional groups to identify the effect of each agent. Concentrated sulfuric acid was found to suppress the shock sensitivity of the liquid HCDS hydrolyzed deposits by acting as a medium that helps the hydrolyzed deposit to retain moisture. KOH/alcohol solutions can turn HCDS vapor into non-hazardous silica, so that, it provided a safe way to dispose HCDS. Finally, practical recommendations about handling and eliminating the risk of shock sensitivity are given for HCDS liquid spill, HCDS vapor vent and HCDS hydrolyzed deposits.     

Characterization and control of energetic deposits from hexachlorodisilane in process tool exhaust lines

This work aims to characterize and develop a disposal method for a gel-like deposit generated in a vacuum foreline of an atomic layer deposition (ALD) tool that is using hexachlorodisilane (Si₂Cl₆, HCDS) as a precursor. This ALD foreline gel was reproduced by replicating the ALD tool process conditions by using a benchtop system that was a 1/85 scale down of one user's process. All samples were tested for shock sensitivity using the Fall hammer apparatus. Extensive infrared studies were done for unhydrolyzed and hydrolyzed gel. Dissolution tests were conducted to develop a method for removing and disposing the gel off-site. Many different solutions such as solvent based solutions, water based alkaline solutions and alcohol based alkaline solutions were tested. It was found that alcohol based alkaline solutions produced only hydrogen as a byproduct and were considered satisfactory for off-site abatement of gel. Furthermore, in-situ cleaning gel of the foreline using a fluorine/N₂ mixture with a concentration of 1–10vol% was done. They were all effective in cleaning/removing the gel under the condition of ambient temperature and reduced pressure. Finally, recommended procedures were given for removing as well as disposing the ALD gel.     

Friction spark generation and incendivity of several metal alloys

When metal alloys are used as mechanical equipment or tools in explosive atmospheres, the occurrence and incendivity of mechanically generated sparks as ignition sources should be taken into consideration. The formation of mechanically generated sparks was investigated for seven metals, including Q235 steel, 304 stainless steel, TC4 titanium alloy, 6061 aluminum alloy, H62 bronze alloy, AMAK3 zinc alloy, and AZ31B magnesium alloy. The relationship between the physical-chemical properties and generation and incendivity of friction sparks was evaluated. For 6061 aluminum alloy, H62 bronze alloy, AMAK3 zinc alloy, and AZ31B magnesium alloy, no bright friction sparks were observed in the maximum friction velocity of 12 m/s and maximum surface pressure of 3.75 N/mm², because of low hardness, high thermal conductivity, low melting point, and the absence of carbon content. Ignition testing indicated that nano titanium dust layers with MIEL (minimum ignition energy of dust layer) of 1 mJ were not ignited by friction particles from the four metal alloys. However, bright particles were clearly observed for 304 stainless steel, Q235 steel, and TC4 titanium alloy. Friction sparks at the maximum power densities showed incendivity with micro titanium layers having an MIEL of 17.5–25 mJ but not with PMMA, corn starch, and wood dust having MIELs greater than 1 J. Two different particle burning behaviors with different fragmentation mechanisms during the friction process were determined, namely the micro explosion phenomenon for TC4 titanium alloy and particle burst for Q235 steel. Results indicate that the physical-chemical properties of friction metal rods are useful for preliminary evaluation of spark generation. Powder layers with known MIEL can be considered as indicator testing materials to evaluate spark incendivity.     

Friction measurements on “anti-slip” floors under shoe sole,contamination, and inclination conditions

Friction measurements were conducted to study the effects of shoe sole, floor, contamination, and inclined angle of the floor surface on friction coefficient. The shoe sole samples included composite rubber outsole samples with and without V-shaped tread design. Unglazed ceramic tiles of both flat and tiles with molded profile design were tested. The contamination conditions included dry, wet, and glycerol-contaminated conditions. The inclined angles included 0°, 5°, and 10°. A Brungraber Mark II slipmeter was used. The results showed that all the four factors affected friction coefficient significantly (p < 0.0001). Flat rubber soles had higher friction coefficients than the soling samples with V-shaped tread design on all tested floors and inclined angles under wet conditions. Flat soles, however, had extremely low friction when tested on flat floors under glycerol-contaminated conditions. The floors with molded grooves perpendicular to friction measurement direction had the highest friction coefficients than all other floor conditions under both the wet and glycerol-contaminated conditions except the wet/flat sole/10° condition. A regression model with a cosine function was established to describe the relationship between friction coefficient and inclined angle of the floor under the experimental conditions. This model is statistically significant at p < 0.0001 with an R² of 0.97.     

A field assessment of floor slipperiness in a fish market in Taiwan

A field assessment of floor slipperiness in 10 fish stands in a fish market in Taiwan was conducted using both friction measurements and subjective ratings. The friction measurements were conducted using the Portable Skid Resistance Tester (PSRT). The subjective ratings of floor slipperiness of both the workers and the customers were collected. The friction measurement results showed that the sink areas had both the lowest friction values and subjective ratings. The overall friction measurement results and the subjective ratings were in fair agreement (r = 0.46 and ρ = 0.49). The customers perceived the walkways as somewhere between “very slippery” to “somewhat slippery” and the picking-up areas as “very slippery.” These were different from the perceptions of the workers where they perceived both areas as “somewhat slippery.”     

The influence of melt composition,liquidus temperature and solidus temperature on vapour explosions in melt droplet impingement experiments

For the investigation of vapour explosions, droplet impingement experiments were performed with the binary system Pb–Sn and the pseudo-binary system PbS–Cu₂S. The experiments were performed with a melt at 600 °C (Pb–Sn) or 700 °C (PbS–Cu₂S) and a water bath at ambient temperature and pressure. A hydrophone and a high-speed camera were used to study the interaction and from this data, the explosion probability and intensity were determined.The explosion probability had a single minimum around 70 wt% Sn, close to the eutectic composition. Moreover, the explosion probability increased approximately linearly with changing composition towards the pure melts, and was similar for pure tin and pure lead. On the other hand, the explosion intensity was comparable for tin and the eutectic alloy while clearly lower for lead. Almost all intermediate alloys had a reduced explosion intensity.Based on the variation in composition, the effects of the liquidus or solidus temperature and the liquidus-solidus gap on the explosion behaviour were also investigated. The explosion probability in both systems increased with increasing liquidus temperature. Also, the maximum explosion intensity in the Pb–Sn system increased with increasing liquidus temperature. Both could be related to easier triggering due to (partial) solidification. On the other hand, the explosion intensity was found to decrease with increasing gap between liquidus and solidus temperature, as was also found in literature. No significant trends for the explosion intensity were found for experiments with PbS–Cu₂S.     

Friction measurements on ramps using the Brungraber Mark II slipmeter

It is a common belief that a person is more likely to slip when walking on an inclined surface than when walking on a level surface. Reports of friction measurements were common on horizontal surfaces but were rare on inclined surfaces. A slip measurement device reports different readings on the same surface with different inclined angles if the effect of gravity comes into play. In this study, friction measurements were conducted on the same surface with 0°, 10° and 20° inclined angles under different footwear materials, floors, and surface conditions, using a Brungraber Mark II slipmeter. Statistically significant results were obtained for the measurement results under the inclined angle, footwear material, floor, and surface conditions. A regression model was established to describe the coefficients of friction on ramp floors under footwear material/floor/surface conditions. This model is significant at p < 0.0001 with an R² of 0.87. The cosine function of ramp angle, as suggested in the regression model, was recommended to be used as a correcting factor for friction measurement results using the Brungraber Mark II on ramps to report the corrected friction coefficient of the surfaces.     

Study of the explosion parameters of vapor–liquid diethyl ether/air mixtures

The knowledge of the vapor–liquid two-phase diethyl ether (DEE)/air mixtures (mist) on the explosion parameters was an important basis of accident prevention. Two sets of vapor–liquid two-phase DEE/air mixtures of various concentrations were obtained with Sauter mean diameters of 12.89 and 22.90 μm. Experiments were conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at an ignition energy of 40.32 J and at an initial room temperature and pressure of 21 °C and 0.10 MPa, respectively. The effects of the concentration and particle size of DEE on the explosion pressure, the explosion temperature, and the lower and upper flammability limits were analyzed. Finally, a series of experiments was conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at various ignition energies. The minimum ignition energies were determined, and the results were discussed. The results were also compared against our previous work on the explosion characteristics of vapor–liquid two-phase n-hexane/air mixtures.     

Effects of typical additives on the thermal stability of ammonium peroxydisulfate

Ammonium peroxydisulfate (APS), one of the most widely used inorganic peroxides in the process industries, is a thermally unstable peroxide and potent oxidizer due to the presence of peroxy bond in the molecule and is incompatible with most substances. To investigate the effect of typical additives on the thermal decomposition of APS, in this paper, diamine phosphate (DAP), monoamine phosphate (MAP), and aluminum hydroxide (AH) were selected as additives; pure APS and samples with 10 wt% and 20 wt% of additives were first tested by differential scanning calorimetry (DSC). The experiments and analysis showed that the samples with 10 wt% of additive had better thermal stability than those with 20 wt% of additive. After screening, the three groups of 10 wt% AH, 10 wt% MAP, and 20 wt% MAP additive conditions could be considered to have a better thermal stability effect on the thermal decomposition of APS. Four groups of samples were, in turn, tested by Phi-Tec II. The adiabatic results showed two discontinuous exothermic processes; 10 wt% AH promoted the weak exothermic effect in the first stage. In contrast, the three groups of additives in the main exothermic stage showed different degrees of inhibition, and the inhibiting effect was ranked as 10 wt% AH, 10 wt% MAP, and 20 wt% MAP in order. Finally, the self-accelerated decomposition temperature (SADT) was calculated under the 25 kg standard package. The adiabatic results, including SADT, were combined to render feasible recommendations for the use of additives, which provides references for the packaging and transportation of additives and their applications.     

Thermal characterization of fly ash from one municipal solid waste incinerator (MSWI) in Shanghai

This study aims to develop a methodology for the thermal characterization of MSWI fly ash. We performed TGA–DTA and component variation analysis, microstructure transfer of sintered fly ash, as well as leaching toxicity, volatilization ratio and specification transformation of heavy metals as a function of temperature. It is found that content of crystal phases first increases between room temperature and 800 °C and then decreases between 800 °C and 1200 °C, while that of glass phases registers a reverse trend. Fly ash registers a SiO₂–Al₂O₃–metal oxides system and its content of glass phases is around 57%. Increase of sintering temperature between 600 °C and 1200 °C is conducive to the reduction of soluble As, Cd, Cu, Hg, Pb, Ni and Zn, while content of soluble Cr increases as temperature rises from 800 °C to 1200 °C.     

Analysis of the chosen thermal and flammability parameters of dried sewage dust

The hazardous sludge disposal process in the form of landfills requires the determination inter alia of the flammable and explosion properties of dried sewage sludge dust, which has the ability to ignite and spontaneously combust when stored in silos. At a constant furnace surface temperature, the minimum ignition temperature of the sludge dust layer with a layer thickness of 5 mm is 270 °C, and for a layer thickness of 12.5 mm it is 250 °C. Two selected fire extinguishing powders for Class A, B, C and D fires were used in the study to determine the possibility of reducing the susceptibility of dried wastewater to ignition from heated surface, self-ignition and explosion parameters. The most effective extinguishing powder was ABC Favorit, which increased the value of the minimum ignition temperature of the layer (5 mm thick) to 360 °C and the spontaneous ignition temperature of the sludge with this powder increased by 22 °C at 169.6 cm³ in comparison to the sludge without extinguishing powder, respectively. The lowest self-ignition temperature of 136 °C was recorded for the largest tested volume (169.6 cm³) for dried sewage dust without any fire extinguishing powders. The biggest values of p_max and (dp/dt)_max dried sewage dust were recorded 4.8 bar and 113 bar/s respectively. By analysing the obtained test results, it can be assumed that dried sewage dust is a combustible material with properties similar to biomass.     

Limiting explosible concentration of hydrogen–oxygen–helium mixtures related to the practical operational case

This paper presents data on the limiting (minimum) concentrations of hydrogen in oxygen, in the presence of added helium, at elevated temperature and pressure related to the practical operational case. A 5 L explosion vessel, an ignition sub-system and a transient pressure measurement sub-system were used. Through a series of experiments carried out using this system, the limiting concentrations of hydrogen in oxygen and helium at different initial pressures and temperatures for the practical operational case were studied, and the influence of ignition energy and initial temperature on the limiting concentration of hydrogen in oxygen and helium was analyzed and discussed. The variation of ignition energy within the studied range is found to have a significant effect on the limiting concentration of hydrogen in oxygen and helium at lower initial temperature. However, when the ignition energy is higher than 32 mJ, the limiting hydrogen concentration remains almost changeless as the initial temperature increases from 21 °C to 90 °C. The limiting explosible concentration of hydrogen–oxygen–helium mixture decreases as the ignition energy increases when the initial temperature is lower. When the initial temperature is higher, the ignition energy has little effect on the limiting hydrogen concentration of hydrogen–oxygen–helium mixtures. When the initial temperature reaches 90 °C, the limiting hydrogen concentration remains almost changeless with an increase in ignition energy. The limiting explosible concentration of hydrogen in the mixtures, at the initial temperature of 21 °C and the ignition energy of 0.5 mJ, is 8.5% and that of oxygen is 11.25%.     

Research on the critical temperature of thermal decomposition for large cartridge emulsion explosives

Emulsion explosives are one type of main industrial explosives. The emergence of the large cartridge emulsion explosives has brought new security incidents. The differential scanning calorimeter (DSC) and the accelerating rate calorimeter (ARC) were selected for the preliminary investigation of the thermal stability of emulsion explosives. The results showed that the initial thermal decomposition temperatures were in the range of 232–239 °C in nitrogen atmosphere (220–232 °C in oxygen atmosphere) in DSC measurements and 216 °C in ARC measurements. The slow cook-off experiments were carried out to investigate the critical temperature of the thermal decomposition (T_c) of the large cartridge emulsion explosives. The results indicated that the larger the diameter of the emulsion explosives, the smaller the T_c is. For the large cartridge emulsion explosives with diameter of 70 mm, the T_c was 170 °C at the heating rate of 3 °C h⁻¹. It is a dangerous temperature for the production of the large cartridge emulsion explosives and it should cause our attention.     

Autoignition temperature data and scaling for amide solvents

Autoignition temperature tests using the ASTM E659 test method have been conducted for N,N-dimethylacetamide (DMAC) and N,N-dimethylformamide (DMF) in test vessels with volumes of 0.5 l, 5 l, and 12 l. Tests were conducted at three different laboratories yielded good agreement (standard deviation with 5 °C) in all cases except for DMAC in the 0.5 l test vessel (standard deviation of 23 °C). Scaling correlations have been developed for the decrease of autoignition temperature with increasing volume and for increasing values of the vessel volume to surface area ratio. The variations for DMAC are steeper than the literature values for almost all other combustible liquids. Cool flames were observed for DMAC at temperatures as much as 44 °C below the autoignition temperature and for DMF at temperatures as much as 171 °C below its autoignition temperature. The DMF cool flame temperatures in the 5-l and 12-l test vessels are approximately equal to the DMF autoignition temperature in a closed 12-l test vessel. Gas samples taken after the cool flame and hot flame tests reveal the presence of high concentrations of diamines and dimethylamino acetonitrile, and small concentrations of many other partial decomposition/oxidation components.     

Effects of environmental temperature on the thermal runaway of lithium-ion batteries during charging process

Lithium-ion batteries with relatively narrow operating temperature range have provoked concerns regarding the safety of LIBs. In this work, a series of experiments were conducted to explore the thermal runaway (TR) behaviors of charging batteries in a high/low temperature test chamber. The effects of charging rates (0.5 C, 1 C, 2 C, and 3 C), and ambient temperature (2 °C, 32 °C and 56 °C) are comprehensively investigated.The results indicate that the cell exhibited greater thermal hazard at the high charging rate and ambient temperature conditions. As the charging rate increased from 0.5 C to 3 C, more lithium intercalated in the anode prompt the TR triggered in advance, the TR onset temperature decreased from 297.5 °C to 264.7 °C. In addition, the charging time decreased with the elevated ambient temperature, resulting in a relatively higher TR onset temperature and lower maximum temperature, and the average TR critical time declined by 115–143 s. Finally, the TR required less heat accumulation with increasing of charging rate and ambient temperature, and the heat generation of side reaction played a substantial role that accounted for approximately 54%∼63%. These results provide an insight into the charging cell thermal runaway behaviors in complex operation environments and deliver valuable guidance for improving the safety of cell operation.     

An Experimental Study on Pyrolysis of Biomass

In this study, pyrolysis of sugarcane bagasse was performed in fixed bed tubular reactor under the conditions of nitrogen atmosphere, by varying temperature and different particle sizes. The effect of final pyrolysis temperature from 400 to 500°C and the nitrogen flow rate from 50 to 200 cc min⁻¹ on the pyrolysis product yields from sugarcane bagasse have been investigated. The Maximum bio-oil yield obtained is 24.12 wt% at the final pyrolysis temperature of 450°C, N₂ flow rate of 50 cc min⁻¹ and particle size of mesh number −8 + 12. The yield of bio-oil decreases with increase in temperature from 450 to 550°C and N₂ flow rate from 50 to 200 cc min⁻¹. The various characteristics of pyrolysis oil obtained under these conditions were identified on the basis of standard test methods. The empirical formula of pyrolysis oil with a heating value of 37.01 MJ Kg⁻¹ was established as CH_1.434 O_0.555 N_0.004. The results from the pyrolysis show the potential of sugarcane bagasse as an important source of liquid hydrocarbon fuel.     

Explosion characteristics of micron- and nano-size magnesium powders

Explosion characteristics of micron- and nano-size magnesium powders were determined using CSIR-CBRI 20-L Sphere, Hartmann apparatus and Godbert-Greenwald furnace to study influence of particle size reduction to nano-range on these. The explosion parameters investigated are: maximum explosion pressure (P_max), maximum rate of pressure-rise (dP/dt)_max, dust explosibility index (K_St), minimum explosible concentration (MEC), minimum ignition energy (MIE), minimum ignition temperature (MIT), limiting oxygen concentration (LOC) and effect of reduced oxygen level on explosion severity. Magnesium particle sizes are: 125, 74, 38, 22, 10 and 1 μm; and 400, 200, 150, 100, 50 and 30 nm. Experimental results indicate significant increase in explosion severity (P_max: 7–14 bar, K_St: 98–510 bar·m/s) as particle size decreases from 125 to 1 μm, it is maximum for 400 nm (P_max: 14.6 bar, K_St: 528 bar·m/s) and decreases with further decrease of particle size to nano-range 200–30 nm (P_max: 12.4–9.4 bar, K_St: 460–262 bar·m/s) as it is affected by agglomeration of nano-particles. MEC decreases from 160 to 30 g/m³ on decreasing particle size from 125 to 1 μm, its value is 30 g/m³ for 400 and 200 nm and 20 g/m³ for further decrease in nano-range (150–30 nm). MIE reduces from 120 to 2 mJ on decreasing the particle size from 125 to 1 μm, its value is 1 mJ for 400, 200, 150 nm size and <1 mJ for 50 and 30 nm. Minimum ignition temperature is 600 °C for 125 μm magnesium, it varies between 570 and 450 °C for sizes 38–1 μm and 400–350 °C for size range 400–30 nm. Magnesium powders in nano-range (30–200 nm) explode less violently than micron-range powder. However, likelihood of explosion increases significantly for nano-range magnesium. LOC is 5% for magnesium size range 125–38 μm, 4% for 22–1 μm, 3% for 400 nm, 4% for 200, 150 and 100 nm, and 5% for 50 and 30 nm. Reduction in oxygen levels to 9% results in decrease in P_max and K_St by a factor of 2–3 and 4–5, respectively, for micron as well as nano-sizes. The experimental data presented will be useful for industries producing or handling similar size range micron- and nano-magnesium in order to evaluate explosibility of their magnesium powders and propose/design adequate safety measures.     

Partial nitritation of landfill leachate with varying influent composition under intermittent aeration conditions

The start-up and operation of a partial nitritation sequencing batch reactor for the treatment of landfill leachate were carried out on intermittent aeration mode. Partial nitrite accumulation was established in 15 days after the mode was changed from continuous aeration to intermittent aeration. Despite the varying influent composition, partial nitritation could be maintained by adjusting the hydraulic retention time (HRT) and the air flow rate. An increase in the air flow rate together with a decrease in air off duration can improve the partial nitritation capacity and eventually result in the development of granular sludge with fine diameters. A nitrogen loading rate of 0.71 ± 0.14 kg/m³/d and a COD removal rate of 2.21 ± 0.13 kg/m³/d were achieved under the conditions of an air flow rate of 19.36 ± 1.71 m³ air/m³/h and an air on/off duration of 1.5 min/0.7 min. When the ratio of total air flux (TAF) to the influent loading rate (ILR) was controlled at the range of 163–256 m³ air/kg COD, a stable effluent NO₃^?–N/NO_x^?–N (NO₂^?–N plus NO₃^?–N) ratio below 13% was achieved. Interestingly, the effluent pH was found to be a good indicator of the effluent NO₂^?–N/NH₄⁺–N ratio, which is an essential parameter for a subsequent anaerobic ammonium oxidation (Anammox) reactor.     

Optimization of mixture ratio of electrolyte for reducing activation resistance of proton exchange membrane fuel cell

The purpose of this study is to find an optimal mixture ratio of the platinum-loaded carbon catalyst and the electrolyte in a membrane electrode assembly (MEA) of a proton exchange membrane fuel cell for reducing the activation resistance, which influences the electrochemical surface area, activation polarization, and maximum power density of the MEA. First, mixture ratios of 10, 20, 40, and 60 wt% platinum-loaded carbon catalysts and electrolyte were examined. The results indicated that the fuel cell performance improved for mixing weight ratios of 1.0:2.0 in 10 wt% Pt/C, 1.0:1.8 in 20 wt% Pt/C, 1.0:1.1 in 40 wt% Pt/C, and 1.0:0.5 in 60 wt% Pt/C. Next, we evaluated the activation resistances of the MEA from the AC impedance characteristics using the optimal mixing weight ratio of the platinum-loaded carbon catalyst and the electrolyte. It was found that the activation resistances of the anode and cathode decrease with an increase in the weight ratio of platinum-loaded carbon in the catalyst layer.     

Small-scale physical explosions in shock tubes in comparison with condensed high explosive detonations

A series of small-scale experiments involving physical explosions in a 1.6 l pressure vessel was carried out. Explosions were initiated by spontaneous rupture of an aluminium membrane on one side of the vessel at a pressure in the range 1–1.2 MPa. The pressure waves released were measured at different distances along two separate shock tubes, one 10 m long and 200 mm in diameter (closed at one end by the high pressure vessel) and the other 15 m long and 100 mm in diameter.TNT equivalency was used for predicting the blast wave characteristics after vessel rupture. TNT equivalency was used because equations for prediction of peak pressure and impulse of the blast wave in 1-D geometry after detonations of condensed explosives are known. Some experiments with an equivalent amount of real explosive were carried out for comparison with the theoretical and experimental data obtained. The applicability of the TNT equivalency method presented for calculations of maximum pressure and shock wave impulse generated after rupture of the pressure vessel in 1-D geometry is discussed.