Flammability properties of polymer nanocomposites with single-walled carbon nanotubes: effects of nanotube dispersion and concentration

The effects of the dispersion and concentration of single walled carbon nanotube (SWNT) on the flammability of polymer/SWNT nanocomposites were investigated. The polymer matrix was poly (methyl methacrylate) (PMMA) and the SWNT were dispersed using a phase separation (‘coagulation’) method. Dispersion of SWNTs in these nanocomposites was characterized by optical microscopy on a micrometer scale. Flammability properties were measured with a cone calorimeter in air and a gasification device in a nitrogen atmosphere. In the case where the nanotubes were relatively well-dispersed, a nanotube containing network structured layer was formed without any major cracks or openings during the burning tests and covered the entire sample surface of the nanocomposite. However, nanocomposites having a poor nanotube dispersion or a low concentration of the nanotubes (0.2% by mass or less) formed numerous black discrete islands with vigorous bubbling occurring between these islands. Importantly, the peak heat release rate of the nanocomposite that formed the network layer is about a half of those, which formed the discrete islands. It is proposed that the formation of the discrete islands is due to localized accumulation of the nanotubes as a result of fluid convection accompanying bubble formation and rise of the bubbles to the surface through the molten sample layer and bursting of the bubbles at the surface. The network layer acts as a heat shield to slow the thermal degradation of PMMA.     

浮法玻璃下开口泡形成机理研究

通过对某锡槽槽底温度升高时,玻璃板下开口泡的气体分析,发现该气泡组分主要是氢气;根据气泡形成相关理论计算结合生产实际情况,研究分析表明,浮法玻璃下开口氢气泡形成的主要机理是锡槽槽底温度升高,槽底气体空间中氢气通过耐火砖贯通孔扩散溶入锡液中,形成氢的过饱和溶液,过饱和的氢再向耐火砖表面易于形成气泡的开口孔处聚集、形成气泡并长大、上浮,最终导致玻璃板下开口泡缺陷.     

Visual observation and numerical studies of polymer foaming behavior of polypropylene/carbon dioxide system in a core‐back injection molding process

Thermoplastic foaming within a mold cavity was visualized as it was conducted in an 85‐ton core‐back injection‐molding machine. The core‐back molding process moved a section of the mold just after injecting a molten polymer into the cavity, quickly reducing the pressure to enhance the bubble nucleation. The foaming behavior during core‐back was observed directly through the glass windows of the mold. In the experiments, impact copolymer polypropylene was foamed with carbon dioxide. The effects of the gas concentration and the core‐back rate on bubble nucleation and growth were investigated. It was experimentally confirmed that the bubbles disappeared when the cavity was fully packed and that bubble nucleation occurred when the mold plate was moved and the cavity pressure dropped. Faster core‐back rates and higher gas concentrations increased the number of bubbles while decreasing their size. To analyze the experimental results, a bubble nucleation and growth model was employed that was based on batch foaming. The numerical results were a reasonable representation of the experiments, and this study demonstrated the applicability of the conventional free foaming model to the industrial core‐back molding process. Many aspects of the foaming in the core‐back molding aresimilar to the behaviors observed by batch foaming. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effect of polymer properties on bubble growth in polymer–paperboard composites

Foamed paperboard is a composite material used in thermally insulated food packaging and beverage containers. The paperboard is sandwiched between a layer of low‐density polyethylene and a barrier layer, and the low‐density film is foamed through heating. The moisture inside the paperboard vaporizes and serves as the driving force for creating the foam. The bubble growth on the paper surface has been tracked with high‐speed photography. The number of generated bubbles has been found to depend on the number of pores on the surface of the paperboard; there is little or no dependence on the properties of the polymer, at least across the range of properties studied. In contrast, the thickness of the foam is relatively insensitive to the paperboard properties but has a strong dependence on the thickness of the initial polymer film, the nature of the polymer, and the speed at which it is extruded onto the paperboard. It is believed that some of these variations arise from differences in the degree of adhesion between the polymer and the paperboard. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Temperature inside burning polymer specimens: Pyrolysis zone and shielding

On the basis of two examples, temperature measurements are proposed within burning polymer specimen during the cone calorimeter test; especially to gain deeper insight into the actual pyrolysis conditions and flame retardancy mechanism. The heating and pyrolysis within a poly(methyl methacrylate) specimen were characterized, discussing the characteristic maximum heating rates (165−90°Cmin⁻¹ decreasing with depth within the specimen and >275°Cmin⁻¹ at the initial surface), pyrolysis temperature (454−432°C decreasing in accordance with decreasing heating rates), thickness of the pyrolysis zone (0.5–1.3 mm) and its velocity (1.2−2.1 mm min⁻¹) as a function of sample depth and burning time. Thermally thick behaviour corresponds to a pyrolysis zone thickness of 0.74 mm and a velocity of 1.51 mm min⁻¹ and occurs until the remaining specimen thickness is less than 8 mm. The shielding effect against radiation occurring in a layered silicate epoxy resin nanocomposite was investigated. It is the main flame retardancy effect of the silicate‐carbon surface layer formed under fire. The reradiation from the hot surface is increased by a factor of around 4–5 when an irradiance of 70kWm⁻² is applied. The energy impact into the pyrolysis zone is crucially reduced, resulting in a reduction of fuel production and thus heat release rate. Copyright © 2009 John Wiley & Sons, Ltd.     

Influence of bubbles characteristics on the skin friction and velocity gradient on solid sphere

A detailed study of the effects of individual bubbles at high gas flow‐rate has shown, that the dominant influence on skin friction over a solid sphere is the bubble volume in compared to bubble frequency. Nevertheless the bubble frequency is very important in case of low gas flow‐rate. Referring to bubbles produced by a gas distributor, statistical and spectral analyses were performed to study the influence of bubbling on exposure time and magnitude of fluctuations. Referring to a calibrated bubble train, the existence of critical frequency is demonstrated. A bubble with larger volume and a mobile, oscillatory surface generates larger velocity gradient. In the case of gas distribution, histograms of the velocity gradient for a 2 mm glass sphere creating bubble coalescence reveal the maximum exceeds 48 000 s^?1 in the front zone and 2000 s^?1 in the rear zone (θ = 180°). For 5 mm plastic spheres creating bubble break‐up, the maximum of the velocity gradient is only 8100 s^?1 for the front part of the sphere and 2000 s^?1 in the rear zone.     

Studies on structural foam processing I. The rheology of foam extrusion

An experimental study was carried out to investigate the flow behavior of gas-charged molten polymers in foam extrusion. For the study, a rectangular slit die with glass windows was constructed to permit visual observations, from the direction perpendicular to flow, of the dynamic behavior of gas bubbles when a gas-charged molten polymer flows between two parallel planes. Pictures were taken of gas bubbles in the flow channel with the aid of a camera attached to a microscope, and these were later used to determine the position at which gas bubbles start to grow. Using three melt pressure transducers mounted on the short side of the rectangular slot, pressure distributions were measured along the longitudinal centerline of the die. The polymeric materials used were high-density polyethylene and polystyrene, and the chemical blowing agents used were a proprietary hydrazide which generates nitrogen, and sodium bicarbonate which generates carbon dioxide. It was observed that the gas-charged molten polymer shows a curved pressure profile as the melt approaches the die exit, whereas the polymer without a blowing agent shows a linear pressure profile. The visual observations of the bubble growth in the flow channel, together with the pressure measurements, permitted us to determine the bubble inflation pressure, often referred to as the critical pressure for bubble inflation. It was found that the critical pressure decreases with increasing melt extrusion temperature, and increases with increasing blowing agent concentration. It was also found that the bulk viscosity of gas-charged molten polymers decreases with increasing blowing agent concentration and with increasing melt temperature. A general remark is made concerning the precaution one should take when an Instron rheometer is used for determining the bulk viscosity of gas-charged molten polymers.     

X-ray imaging of a high-temperature furnace applied to glass melting

The dynamics of soda-lime-silica glass grain melting is investigated experimentally using a nonintrusive technique. A cylindrical alumina crucible is filled with glass cullet and placed into a furnace illuminated by an X-ray source. This glass granular bed is gradually heated up to 1100°C, leading to its melting and the generation of a size-distributed population of bubbles rising in the molten glass. An image processing algorithm of X-ray images of the cullet bed during melting allows the characterization of bubbles size distribution in the crucible as well as their velocity. The introduction of tin dioxide μ-particles in the glass matrix before melting enhances the texture of the images and makes possible the determination of the bubble-induced molten glass velocity field by an optical flow technique. The bubble size distribution can be fitted by a log-normal law, suggesting that it is closely related to the initial size distribution in the cullet bed. The liquid motion induced by the bubbles in Stokes' regime is strongly affected by the flow confinement and the determination of bubble rising velocity along its trajectory unveils the existence of local tiny temperature fluctuations in the crucible. Overall, the measuring techniques developed in this work seem to be very promising for the improvement of models and optimization of industrial glass furnaces.     

Combustion Mechanism of Consolidated Mixtures of 5‐amino‐1H‐tetrazole with Potassium Nitrate or Sodium Nitrate

Recently, 5‐amino‐1H‐tetrazole is developed for practical use as a substitute for sodium azide, which is conventionally used as a fuel component of gas generating agents for automobile airbags. In this study, the combustion mechanisms of the mixtures 5‐amino‐1H‐tetrazole/potassium nitrate and 5‐amino‐1H‐tetrazole/sodium nitrate have been examined. It has been found that the Granular Diffusion Flame model is applicable to the tested samples even when a molten layer exists at the burning surface. In addition, it is shown that within the pressure range of 1–5 MPa, the greatest factor which affects the burning rate is the diffusion process. It is also demonstrated that the fuel component decomposes first, and the oxidizer decomposes next. Meanwhile, it has also been confirmed that the burning rate increases with an increase in pressure because the flame approaches the burning surface and the amount of heat transfer to the solid phase increases. In spite of a decrease in the amount of heat transfer from the gas phase to the solid phase and an increase in the thickness of the condensed phase reaction zone for a mixture with higher fuel content, there are little differences in the burning rates probably because of an increase in the rate of decomposition of the solid phase.     

Manganese as Fuel in Slow‐Burning Pyrotechnic Time Delay Compositions

Manganese metal was evaluated as a fuel for slow‐burning delay compositions press‐filled in aluminium or compaction‐rolled in lead tubes. Oxides of antimony, bismuth, copper, manganese and vanadium were considered as oxidants. Measured burn rates for binary mixtures varied between 5 and 22 mm s⁻¹ but slower burning ternary and quaternary compositions were also found. The addition of fumed silica to the Mn/MnO₂ system had little effect on the propagation rate but a low level addition of hollow glass sphere significantly reduced the burn rate. Mn MnO₂ mixtures showed reliable burning over a wide stoichiometric range. In this system the fuel and the oxidant share a common metal. They combine to form the more stable intermediate oxide (MnO) releasing considerable quantities of heat in the process.     

Visualization of bubble dynamics in foam injection molding

This article presents a visualization study on nonisothermal bubble growth and collapse in the foam injection molding process (FIM). Observation study can give more insight to the bubble growth in foaming process, especially in the challenging injection foaming process. In this study, besides the growth of bubbles, collapse of the bubbles was also observed which could provide knowledge to the final foam morphology. Cell growth vs. time was recorded and analyzed using a software‐equipped high speed camera. To investigate the cell collapse, various holding pressure was exerted on the gas‐charged molten polymer. The amount of holding pressure had noticeable effect on the rate of bubble collapse. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheology of simulated radioactive waste slurry and cold cap during vitrification

During the vitrification of radioactive waste in a Joule‐heated melter, aqueous melter feed slurry forms a cold cap, a reacting and melting material, which floats on the surface of the molten glass. The rheological behavior of the feed affects cold cap formation and shape, and is vital for modeling the feed‐to‐melt conversion process. We used slurry feed simulant and fast‐dried slurry solids representing the cold cap to investigate the rheological behavior of the feed as it transforms into glass. Both low‐temperature and high‐temperature rheometry were performed and a new scheme was applied to estimate the feed viscosity. This study shows that the conversion advances in four sequential stages that form distinct regions in the cold cap: (i) a fast‐spreading boiling slurry from which water evaporates, (ii) a porous solid region (viscosity > 10⁸ Pa s) containing reacting solids and molten salts, (iii) a plastic region in which glass‐forming melt connects the refractory solids (~10⁸ to ~10⁶ Pa s), and (iv) a viscous foam layer in which the viscosity drops from ~10⁵ to ~10¹ Pa s. The implications for the mathematical modeling of the cold cap are discussed.     

Friction factors and bubble dynamics in polymer solutions

This work reports on bubble dynamics in polymer solutions of various rheological character. Relations between the friction factor and the Reynolds number are discussed and master curves based on the results of Kawase and Moo-Young are presented and analyzed using two different viscosity expressions. The theoretical results overpredict the friction coefficient except at very high deformation rates. The surface tension is shown to affect the shape of the bubbles but not their velocity, except for bubble volumes smaller than 10^-7 m³.     

Studies on structural foam processing. III. Bubble dynamics in foam extrusion through a converging die

An experimental and theoretical study was carried out to achieve a better understanding of bubble dynamics in foam extrusion through a converging die. For the experimental study, a number of converging channels were constructed of aluminum, with glass windows on both sides. Bubble dynamics in the flow channel were recorded on movie film as a gas-charged molten polymer was extruded. The dies had various converging angles (30, 45, 60, 90, and 150 degrees), and the polymer was polystyrene. As blowing agent, sodium bicarbonate (generating CO₂) was used. It was found that the gas bubbles moving along the centerline of the channel grow initially at the upstream end of the die, and then start to collapse as the gas-charged molten polymer approaches the exit plane of the die. In order to help interpret the experimental results, a theoretical analysis was made of bubble dynamics in a converging channel, in which a thread-like bubble was assumed to flow along the centerline of the converging channel and the Coleman-Noll second-order fluid model was assumed to describe the rheological behavior of the polymer melt. Some mathematically convenient simplifying assumptions not-withstanding, the theoretical analysis corroborates the experimental observations. The practical significance of the present investigation is discussed in connection with controlling the cell structure in extruded foam products.     

Improving the stability of polylactic acid foams by interfacially adsorbed particles

Polymers such as poly(lactic acid) (PLA), which have poor melt strength, are difficult to foam due to severe cell coalescence during foaming. We show that addition of a few percent of polytetrafluoroethylene (PTFE) particles can stabilize PLA foams against bubble coalescence and collapse. The particles and a chemical blowing agent, were dispersed into the PLA by extrusion, and then foamed by heating. The PTFE‐containing foams remained stable even when the foams were held under molten conditions for extended periods. Foam stability is attributed to an interfacial mechanism: due to their low surface energy, the PTFE particles adsorb on the inner surface of the foam bubbles at a high surface coverage, and endow the bubbles with an interfacial “shell” that prevents coalescence. This mechanism resembles the particle‐stabilization of Pickering emulsions in oil/water systems. Particle adsorption at the interface is a necessary condition for using this approach, and hence this approach is most likely to be successful if the particles have a low surface energy and the polymer has a high surface tension. The approach of using interfacially adsorbed particles can be broadly generalized, and offers the opportunity of foaming various polymers with low melt strength, or for expanding the processing window within which foaming can be conducted. POLYM. ENG. SCI., 56:9–17, 2016. © 2015 Society of Plastics Engineers     

Bubble size in a forced circulation loop reactor

BACKGROUND: The bubble size distribution in gas‐liquid reactors influences gas holdup, residence time distribution, and gas‐liquid interfacial area for mass transfer. This work reports on the effects of independently varied gas and liquid flow rates on steady‐state bubble size distributions in a new design of forced circulation loop reactor operated with an air–water system. The reactor consisted of a cylindrical vessel (～26 L nominal volume, gas‐free aspect ratio ≈ 6, downcomer‐to‐riser cross‐sectional area ratio of 0.493) with a concentric draft tube and an annular riser zone. Both gas and liquid were in forced flow through a sparger that had been designed for minimizing the bubble size. RESULTS: Photographically measured bubble size distributions in the riser zone could be approximated as normal distributions for the combinations of gas and liquid flow rates used. This contrasted with other kinds of size distributions (e.g. bimodal, Gaussian) that have been reported for other types of gas‐liquid reactors. Most of the bubbles were in the 3 to 5 mm diameter range. At any fixed low value of aeration rate (≤1.8 × 10^?4 m³s^?1), increase in the liquid flow rate caused earlier detachment of bubbles from the sparger holes to reduce the Sauter mean bubble size in the riser region. CONCLUSION: Unlike in conventional bubble columns where bimodal and Gaussian bubble size distributions have been reported, a normal bubble size distribution is attained in forced circulation loop reactors with an air–water system over the entire range of operation. Copyright © 2007 Society of Chemical Industry     

Enhanced gas migration through permeable bubble networks within consolidated soft sediments

Many consolidated sediments experience in situ gas generation from methanogenesis, corrosion, or radiolysis reactions and can retain bubbles for long periods. Particular interest is motivated by the retention and acute release of flammable hydrogen from nuclear legacy waste sludge. X‐ray computed tomography was employed to observe 0.07–10 mm bubble populations within 30–1112 Pa yield strength Mg(OH)₂ sediments. High rates of partial coalescence were observed among sub‐millimeter microvoids, forming extensive bubble networks which spanned the 32 mm field of view. Lattice Boltzmann and Monte Carlo modeling demonstrated these networks to be highly pervious to gas, with effective diffusivities for hydrogen of 3.7–12.5 × 10^?5 m² s^?1. Continuous vessel‐spanning bubble networks, dynamic connectivity between ganglia of coalesced bubbles, Haines jumps, and composite diffusion through the gas and aqueous phase can account for enhanced gas migration over length‐scales of several meters, thus enabling chronic gas release from low‐intermediate strength sediments ( kPa) too strong for buoyant bubble ebullition and too weak for vertical channel formation. © 2018 The Authors. AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers. AIChE J, 64: 4131–4147, 2018     

Studies on structural foam processing. IV. Bubble growth during mold filling

An experimental and theoretical study was carried out to achieve a better understanding of bubble growth during the filling of gas-charged molten polymers into a rectangular mold cavity. For the experimental study, a rectangular mold cavity (15.24 × 4.55 × 0.64 cm) was constructed, with glass windows on both sides to permit recording on a movie film of the growth of gas bubbles in the mold cavity as a molten polymer containing inert gas was injected into it. Sodium bicarbonate (generating carbon dioxide) was used as a chemical blowing agent, and the polymer used was a general purpose clear polystyrene. All experimental runs were made at isothermal molding conditions, and the injection rate was varied. It was found that, at and above a certain injection rate, little bubble formation was observed in the mold cavity during injection except at and near the moving melt front. For the theoretical study, the growth of a single gas bubble in a viscoelastic medium (represented by the DeWitt model), subjected to high injection rates, was considered by including the effects of diffusion from the liquid phase to the gas phase, interfacial tension between the liquid and the gas phases, and stress relaxation of the melt upon ejection. It was found that the level of stresses, built up in the met during injection, has a profound influence on the formation and growth of gas bubbles during the initial stage of mold filling. Also, a multichannel mold cavity was employed in order to observe the effect of processing variables on the cell size and its distribution in molded specimens. A uniform cell structure was obtained at higher injection pressures, at an optimum injection melt temperature, and with an optimum combination of blowing agent and nucleating agent concentrations.     

被动式DMFC气泡行为的实验研究和数值模拟

在被动式直接甲醇燃料电池（DMFC）中,阳极催化层表面电化学反应生成的二氧化碳（CO2）通过扩散层及时排出阳极通道,对提高直接甲醇燃料电池的性能具有重要意义,因此研究阳极通道内的气液两相流对电池性能的优化具有非常重要的意义。利用计算流体力学模拟软件Fluent,采用VOF（volume of fluid）两相流模型追踪气液界面的方法对静止甲醇溶液中CO2气泡形成的过程进行模拟,利用可视化实验对部分结果进行验证,结果表明：气泡在浮力和表面张力作用下被拉长,受尾部液体剪切力作用脱离,倾斜的扩散层表面有利于气泡尽快的离开孔口,气速较大时气泡在脱离前会出现多次融合,气泡在高浓度甲醇溶液中以气泡链的方式产生。研究结果为扩散层的制备和优化提供了参考。