Flammability of hydrocarbon and carbon dioxide mixtures

The effect of carbon dioxide (CO₂) concentration on the ignition behaviour of hydrocarbon and CO₂ gas mixtures is examined in both jets and confined explosions. Results from explosion tests are presented using a 20 l explosion sphere and an 8 m long section of 1.04 m diameter pipeline. Experiments to assess the flame stability and ignition probability in free-jets are reported for a range of different release velocities. An empirically-based flammability factor model for free-jets is also presented and results are compared to ignition probability measurements previously reported in the literature and those resulting from the present tests.The results help to understand how CO₂ changes the severity of fires and explosions resulting from hydrocarbon releases. They also demonstrate that it is possible to ignite gas mixtures when the mean concentration is outside the flammable range. This information may be useful for risk assessments of offshore platforms involved in carbon sequestration or enhanced oil recovery, or in assessing the hazards posed by poorly-inerted hydrocarbon processing plant.     

A novel way to upgrade the coarse part of a high calcium fly ash for reuse into cement systems

Reject fly ash (rFA) represents a significant portion of the fly ashes produced from coal-fired power plants. Due to the high carbon content and large particle mean diameter, rFA is not utilized in the construction sector (for example, as supplementary cementing material) and is currently dumped into landfills, thus representing an additional environmental burden. Recently, the feasibility of using rFA in a relatively small number of applications, like solidification/stabilization of other wastes, has been investigated by different researchers. However, as the overall amount of fly ash utilized in such applications is still limited, there is a need to investigate other possibilities for rFA utilization starting from a deeper understanding of its properties. In the work presented herein, mechanical and hydration properties of cementitious materials prepared by blending the coarse fraction of a lignite high-calcium fly ash with ordinary cement were monitored and compared with the respective ones of a good quality fly ash-cement mixture. The results of this work reveal that a relatively cheap, bilateral classification-grinding method is able to promote the pozzolanic behavior of the rFAs, so that the overall performances of rFA containing cements are drastically improved. The evaluation of these results supports the belief that appropriate utilization of non-standardized materials may lead to new environmental-friendly products of superior quality.     

Multiple use of waste catalysts with and without regeneration for waste polymer cracking

Waste plastics contain a substantial number of valuable chemicals. The wastes from post-consumer as well as from industrial production can be recycled to valuable chemical feedstock, which can be used in refineries and/or petrochemical industries. This chemical recycling process is an ideal approach in recycling the waste for a better environment. Polymer cracking using a laboratory fluidised bed reactor concentrated on the used highly contaminated catalyst, E-Cat 2. Even though E-Cat 2 had low activity due to fewer acid sites, the products yielded were similar with amorphous ASA and were far better than thermal cracking. The high levels of heavy metals, namely nickel and vanadium, deposited during their lifetime as an FCC catalyst, did not greatly affect on the catalyst activity. It was also shown that E-Cat 2 could be used with and without regeneration. Although there was more deactivation when there was no regeneration step, the yield of gases (C₂-C₇) remained fairly constant. For the first time, these results indicate that “waste” FCC catalyst (E-Cat) is a good candidate for future feedstock recycling of polymer waste. The major benefits of using E-Cat are a low market price, the ability to tolerate reuse and regeneration capacity.     

Recycling of high purity selenium from CIGS solar cell waste materials

Copper indium gallium diselenide (CIGS) is a promising material in thin film solar cell production. To make CIGS solar cells more competitive, both economically and environmentally, in comparison to other energy sources, methods for recycling are needed. In addition to the generally high price of the material, significant amounts of the metals are lost in the manufacturing process. The feasibility of recycling selenium from CIGS through oxidation at elevated temperatures was therefore examined. During oxidation gaseous selenium dioxide was formed and could be separated from the other elements, which remained in solid state. Upon cooling, the selenium dioxide sublimes and can be collected as crystals. After oxidation for 1 h at 800 °C all of the selenium was separated from the CIGS material. Two different reduction methods for reduction of the selenium dioxide to selenium were tested. In the first reduction method an organic molecule was used as the reducing agent in a Riley reaction. In the second reduction method sulphur dioxide gas was used. Both methods resulted in high purity selenium. This proves that the studied selenium separation method could be the first step in a recycling process aimed at the complete separation and recovery of high purity elements from CIGS.     

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), ¹H and ¹³C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, ¹³C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.     

Photocrosslinking of an Acrylated Epoxidized Linseed Oil: Kinetics and its Application for Optimized Wood Coatings

Over the past few decades, the industry developed an increasing interest in using renewable, bio-based thermosetting polymers as matrix systems for composites and coating systems. In the present paper an acrylated epoxidized linseed oil (AELO) was synthesized from epoxidized linseed oil (ELO) through ring opening of the oxirane group using acrylic acid as the ring opening agent. The synthesized AELO was mixed with three different photoinitiators and cured under monochromatic conditions (???=?365?nm) at different light intensities and at different temperatures. The concentration of the initiators was aligned that all initiators absorb at 365?nm the same amount of light. The evolution of cure was monitored by using real-time infrared spectroscopy with a heated attenuated total reflection unit. The decrease of absorption in the measured spectra at 1,406?cm^?1 was used to calculate the conversion of acrylic double bonds with increasing time of UV light exposure to get information about the cure kinetics for each AELO mixture at different light intensities and different temperatures. Wood substrates were coated in a preliminary work with the AELO mixtures and after UV-curing some technological coating properties like gloss, scratch resistance, adhesion, and solvent resistance were tested. In combination with the information about the cure kinetics in the present work the coating properties were correlated with the cure evolution and the final degree of double bond conversion. The found correlation can be used in the future to find optimized coating conditions for the AELO mixtures on wood substrates.     

Real time alteration of a nuclear waste glass and remobilization of lanthanide into an interphase

The development of predictive models for the long term evolution of nuclear waste glass requires the complete knowledge of the glass dissolution at the laboratory scale. A new approach was developed to determine the initial reaction during the first steps of experience, a new concept was developed, based on the combination of dynamic leaching test and the characterization of the altered materials. With this experimental set-up it is possible to follow in real time the glass alteration process at a fine temporal scale. The results put in evidence a singular behaviour of the lanthanide, shown by a concentration peak of La, Nd and Ce after 2 h and a quick decrease of their concentration measured on line in the solution during the leaching test. This fact is directly linked to the development of an interphase (altered layer which differs from the initial solid by its texture, structure and chemical composition) at the interface of the glass surface and the leaching solution. This work is an attempt to integrate the formation of the alteration products (here the interphase) during leaching into the dissolution mechanisms of a nuclear waste glass. A model is proposed and discussed.     

Characterization of EVA/PLA Blends When Exposed to Different Environments

EVA/PLA blends compatibilized with EVA-g-PLA grafted copolymers synthesized by reactive extrusion, through transesterification reaction between ethylene-vinyl-acetate (EVA) and polylactide (PLA) using titanium propoxide (Ti(OPr)₄) as catalyst, were characterized when exposed to different environments. Stability to UV radiation was assessed exposing the samples to a Xenon lamp, which simulates the sun UV spectrum and the biodegradability was evaluated by biochemical oxygen demand (BOD) in a closed respirometer. Exposed samples were removed periodically and analyzed by several analytical techniques, such as, FTIR, DSC, rheology and tensile tests. The results obtained evidenced that UV radiation induces structural modifications, which affect substantially rheological and mechanical properties. Moreover, the blend with higher amount of copolymer exhibits lower photo durability and greater biodegradability. From the environmental point of view, these new materials are very promising for application with short lifetime, like packaging.     

Development of Thixotropic Coatings Using Dimerized Soybean Oil Fatty Acids: The Case of Polyamide of 1,2-Phenylene Diamine

Soybean oil (SBO) was dimerized and the crude dimer acid product reacted with 1,2-phenylene diamine at 210 ± 5 °C under inert atmosphere to obtain fatty polyamide (FPA). The FPA was used to modify a commercial alkyd resin by reacting a mixture of the alkyd resin with 5 wt% of FPA at 120 °C for 80 min under inert atmosphere. The FTIR spectrum of the FPA modified resin showed evidence of higher degree of H-bonding than was found for the unmodified alkyd. White gloss coatings of 15, 20, 25, and 30% solids were formulated from the modified and unmodified resins and examined for performance with respect to: leveling, sag resistance, drying time, pigment settling, skinning tendency and film hardness. Results showed that the unmodified alkyd coatings exhibited good leveling but poor sag resistance at all solid contents. In contrast, FPA modified alkyd coatings combined good leveling with high sag resistance indicating their thixotropic nature. A strong tendency to pigment settling was observed for unmodified alkyd coatings but was not observed in the FPA modified alkyd coatings. The modified alkyd coatings showed skinning while the unmodified alkyd coatings did not skin. A 30% solids coating formulation of the FPA modified resin showed shorter surface dry time but longer hard dry time than the unmodified alkyd resin coating.