Comparing ignitability for in situ burning of oil spills for an asphaltenic,a waxy and a light crude oil as a function of weathering conditions under arctic conditions

In situ burning of oil spills in the Arctic is a promising countermeasure. In spite of the research already conducted more knowledge is needed especially regarding burning of weathered oils. This paper uses a new laboratory burning cell (100 mL sample) to test three Norwegian crude oils, Grane (asphalthenic), Kobbe (light oil) and Norne (waxy), for ignitability as a function of ice conditions and weathering degree. The crude oils (9 L) were weathered in a laboratory basin (4.8 m³) under simulated arctic conditions (0, 50 and 90% ice cover). The laboratory burning tests show that the ignitability is dependent on oil composition, ice conditions and weathering degree. In open water, oil spills rapidly become “not ignitable” due to the weathering e.g. high water content and low content of residual volatile components. The slower weathering of oil spills in ice (50 and 90% ice cover) results in longer time-windows for the oil to be ignitable. The composition of the oils is important for the window of opportunity. The asphalthenic Grane crude oil had a limited time-window for in situ burning (9 h or less), while the light Kobbe crude oil and the waxy Norne crude oil had the longest time-windows for in situ burning (from 18 h to more than 72 h). Such information regarding time windows for using in situ burning is very important for both contingency planning and operational use of in situ burning.     

Highly sensitive and selective ethanol sensor based on micron-sized zinc oxide porous-shell hollow spheres

Zinc oxide (ZnO) porous-shell hollow spheres (PHS) were prepared by thermally oxidizing high-purity zinc powder in an oxygen-containing atmosphere, and its ethanol gas sensing properties were measured in the concentration range of 10–400 ppm. At the optimum operating temperature of 350 °C, a sensitivity of 0.25/ppm was obtained and the response–concentration curve was of high linearity. The response and recovery times were measured to be ～5–12 s and 8–13 s, respectively. The sensor was proved to be highly selective to ethanol. Our results indicate that ZnO PHS might be a promising material for fabricating practical ethanol sensors.     

Physical and chemical characterization of Dead Sea mud

A laboratory analysis was performed to determine the physical and chemical properties of 24 Dead Sea mud samples collected from three different locations on the eastern shore of the Dead Sea. Several analytical techniques were used to determine the chemical and mineralogical compositions of those samples including atomic absorption spectrometry and X-ray diffraction. Physical parameters such as specific gravity, Atterberg limits, grain size, specific surface area, cation exchange capacity, pH and electrical conductivity were also studied. The main focus of the work was to document mud characteristics and to study the interrelation between physical and chemical properties. The mud samples were quite rich in minerals. Strontium was the most abundant trace element in the samples (range: 410–810 ppm) followed by barium (range: 155–380 ppm), vanadium (range: 209–264 ppm) and lead (range: 108–114 ppm). There were significant differences in the elemental contents of mud samples collected from different locations.     

Effect of processing methods on physicochemical properties of titania nanoparticles produced from natural rutile sand

Titania (TiO₂) nanoparticles were produced from natural rutile sand using different approaches such as sol–gel, sonication and spray pyrolysis. The inexpensive titanium sulphate precursor was extracted from rutile sand by employing simple chemical method and used for the production of TiO₂ nanoparticles. Particle size, crystalline structure, surface area, morphology and band gap of the produced nanoparticles are discussed and compared with the different production methods such as sol–gel, sonication and spray pyrolysis. Mean size distribution (d₅₀) of obtained particles is 76 ± 3, 68 ± 3 and 38 ± 3 nm, respectively, for sol–gel, sonication and spray pyrolysis techniques. The band gap (3.168 < 3.215 < 3.240 eV) and surface area (36 < 60 < 103 m² g^?1) of particles are increased with decreasing particle size (76 > 68 > 38 nm), when the process methodology is changed from sol–gel to sonication and sonication to the spray pyrolysis. Among the three methods, spray pyrolysis yields high-surface particles with active semiconductor bandgap energy. The effects of concentration of the precursor, pressure and working temperature are less significant for large-scale production of TiO₂ nanoparticles from natural minerals.     

The properties of ethanol gas sensor based on Ti doped ZnO nanotetrapods

An ethanol gas sensor was fabricated based on Ti doped ZnO nanotetrapods which were prepared by chemical vapor deposition (CVD) of ZnO nanotetrapods followed by co-annealing with TiO₂ powder. X-ray diffraction (XRD), Raman spectra and scanning electron microscopy (SEM) were used to characterize the morphology and structure of the as-obtained sample and the ethanol-sensing characteristics of the device were investigated. ZnO:Ti sensors show higher gas response than ZnO counterparts towards 100 ppm ethanol gas at a temperature of 260 °C. The recovery times of the devices are 3.1 min for ZnO:Ti and 10.1 min for ZnO, respectively. The enhancement of sensing properties of ZnO:Ti tetrapods indicates the potential application for fabricating low power and highly sensitive gas sensors.     

Application of waste heat powered absorption refrigeration system to the LNG recovery process

The recovery process of the liquefied natural gas requires low temperature cooling, which is typically provided by the vapor compression refrigeration systems. The usage of an absorption refrigeration system powered by waste heat from the electric power generating gas turbine could provide the necessary cooling at reduced overall energy consumption. In this study, a potential replacement of propane chillers with absorption refrigeration systems was theoretically analyzed. From the analysis, it was found that recovering waste heat from a 9 megawatts (MW) electricity generation process could provide 5.2 MW waste heat produced additional cooling to the LNG plant and save 1.9 MW of electricity consumption. Application of the integrated cooling, heating, and power is an excellent energy saving option for the oil and gas industry.     

Performance evaluation of ZnO–CuO hetero junction solid state room temperature ethanol sensor

A semiconductor ethanol sensor was developed using ZnO–CuO and its performance was evaluated at room temperature. Hetero-junction sensor was made of ZnO–CuO nanoparticles for sensing alcohol at room temperature. Nanoparticles were prepared by hydrothermal method and optimized with different weight ratios. Sensor characteristics were linear for the concentration range of 150–250 ppm. Composite materials of ZnO–CuO were characterized using X-ray diffraction (XRD), temperature-programmed reduction (TPR) and high-resolution transmission electron microscopy (HR-TEM). ZnO–CuO (1:1) material showed maximum sensor response (S = R_air/R_alcohol) of 3.32 ± 0.1 toward 200 ppm of alcohol vapor at room temperature. The response and recovery times were measured to be 62 and 83 s, respectively. The linearity R² of the sensor response was 0.9026. The sensing materials ZnO–CuO (1:1) provide a simple, rapid and highly sensitive alcohol gas sensor operating at room temperature.     

Direct synthesis of highly crystalline transparent conducting oxide nanoparticles by low pressure spray pyrolysis

In this article, we firstly reported a general preparation method for the production of highly crystallized and single crystalline transparent conducting oxide (TCO) nanoparticles: tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped zinc oxide (AZO), and gallium-doped zinc oxide (GZO). Low-pressure spray pyrolysis was applied by means of a modified-atomizer and preheated carrier gas. The effects of pyrolysis pressure, temperature and carrier gas temperature on the size and morphology of the synthesized TCO nanoparticles were systematically investigated. The synthesized TCO nanoparticles were 17 nm large with crystallite size of 8–11 nm. The resistivities of the formed pellets were measured and compared. These results showed that this method successfully produces various TCO nanoparticles using neither dispersing agents nor post-heating treatments, which allows rapid, continuous, single-step preparation.     

Synthesis and characterization of TiO2 powders by electrospray pyrolysis method

Electrospray pyrolysis, i.e. combination of electrospray and in-flight thermal treatment, has attracted much attention as a preparation method of functional ceramic particles. In this paper, we report the processing detail of spherical TiO₂ nano- and microparticles by the electrospray pyrolysis method as well as their photocatalytic activity for hydrogen evolution. Titanium(IV) bis(ammonium lactato)dihydroxide aqueous solutions (TALH aq., 0.2–20 wt%) were injected into a capillary nozzle by a syringe pump (0.15–0.59 mL/min), and were electrosprayed by using DC 4 kV voltage, followed by the pyrolysis at 300–500 °C. Spherical TiO₂ nano- and microparticles were successfully obtained. Effects of precursor-liquid concentration, liquid flow-rate, and pyrolysis temperature on the particle size, microstructure and functions were discussed.     

TG-FTIR study on urea-formaldehyde resin residue during pyrolysis and combustion

The pyrolysis and combustion characteristics of urea-formaldehyde resin (UFR) residue were investigated by using thermogravimetric analysis, coupled with Fourier transform infrared spectroscopy (TG-FTIR). It is indicated that the pyrolysis process can be subdivided into three stages: drying the sample, fast thermal decomposition and further cracking process. The total weight loss of 90 wt.% at 950 °C is found in pyrolysis, while 74 wt.% of the original mass lost in the second stage is between 195 °C and 430 °C. The emissions of carbon dioxide, isocyanic acid, ammonia, hydrocyanic acid and carbon monoxide are identified in UFR residue pyrolysis, moreover, isocyanic acid emitted at low temperature is found as the most important nitrogen-containing gaseous product in UFR residue pyrolysis, and there is a large amount of hydrocyanic acid emitted at high temperature. The similar TG and emission characteristics as the first two stages during pyrolysis are found in UFR residue combustion at low temperature. The combustion process almost finishes at 600 °C; moreover, carbon dioxide and water are identified as the main gaseous products at high temperature. It is indicated that the UFR residue should be pyrolyzed at low temperature to remove the initial nitrogen, and the gaseous products during pyrolysis should be burnt in high temperature furnace under oxygen-rich conditions for pollutant controlling.     

A study on the preparation of highly conductive graphene

The effects of the washing conditions of graphite oxide (GO) and pyrolysis times on the thermal reduction of graphene are discussed in this article. Graphene samples that had been pyrolyzed for 30 s and 5 min remained homogeneous in N,N-Dimethylformamide (DMF) for one month, whereas those samples that had been pyrolyzed for 20 and 40 min precipitated after one day. The conductivity of graphene increased with pyrolysis time. The resistivity of graphene thermally post-treated for 40 min reached 0.01 Ωcm. Whether or not GO was washed with deionized water had little effect on the structure and electric properties of graphene.     

Synthesis of nanoporous silicon carbide via the preceramic polymer route

Nanoporous silicon carbide materials were prepared by the pyrolysis of the preceramic polymer, polycarbosilane (PCS), with and without the addition of an inert filler (nano- and micron-sized silicon carbide powders). Hydrosilylation crosslinking of PCS with divinylbenzene prior to pyrolysis appeared to have little influence on the development of micro- and mesoporosity. Maximum micropore volumes were 0.28 cm³ g^?1 for non-crosslinked PCS and 0.25, 0.33 and 0.32 cm³ g^?1 for PCS crosslinked with 2, 6 and 10 wt.% DVB respectively. Micropore volumes decreased under hydrothermal conditions to 0.03 cm³ g^?1 for non-crosslinked and 0 cm³ g^?1 for crosslinked PCS. Porosity was also lost at temperatures above 700 °C. The addition of nano-sized SiC powders to PCS prior to pyrolysis maintained mesoporosity to temperatures of 1200 °C, however, micron-sized SiC powders did not maintain porosity above 800 °C. The modal pore size in pellets formed by compressing micron-sized powders with the preceramic polymer was 5 μm compared to 30 nm when nano-sized powders were used.     

Poly(furfuryl alcohol)-assisted pyrolysis synthesis of ceramic nanoparticles for solid oxide fuel cells

A pyrolysis synthesis method was developed to prepare ceramic nanoparticles for the fabrication of solid oxide fuel cells. Furfuryl alcohol was used as a polymerizable solvent to dissolve metal nitrates and then polymerized into poly(furfuryl alcohol) (PFA). During the pyrolysis at 600 °C, a mixture of nitrates/PFA was converted into ceramic nanoparticles/carbon networks nanocomposite, and the carbon networks act as a barrier to prevent the aggregation of newly formed nanoparticles during particle crystallization. Dispersible nanoparticles with particle sizes ranging from 40 nm to 200 nm were obtained after burning off carbon networks in air. As an example, Ce_0.8Sm_0.2O_1.9 nanoparticles were synthesized to prepare solid oxide fuel cells, and the fuel cells achieved maximum power densities of 444.5, 625.5 and 684 mW cm^?2 at 500 °C, 550 °C and 600 °C, respectively. Our study shows that the pyrolysis synthesis method described here is promising for the effective synthesis of high quality ceramic nanoparticles.     

Shear strength of palm oil clinker concrete beams

This paper presents experimental results on the shear behavior of reinforced concrete beams made of palm oil clinker concrete (POCC). Palm oil clinker (POC) is a by-product of palm oil industry and its utilization in concrete production not only solves the problem of disposing this solid waste but also helps to conserve natural resources. Seven reinforced POCC beams without shear reinforcement were fabricated and their shear behavior was tested. POCC has been classified as a lightweight structural concrete with air dry density less than 1850 kg/m³ and a 28-day compressive strength more than 20 MPa. The experimental variables which have been considered in this study were the POCC compressive strength, shear span–depth ratio (a/d) and the ratio of tensile reinforcement (ρ). The results show that the failure mode of the reinforced POCC beam is similar to that of conventional reinforced concrete beam. In addition, the shear equation of the Canadian Standard Association (CSA) can be used in designing reinforced POCC beam with ρ ⩾ 1. However, a 0.5 safety factor should be included in the formula for ρ < 1.     

Development of an instrumented and automated single mode cavity for ceramic microwave sintering: Application to an alpha pure alumina powder

This paper describes the development of an instrumented and automated single mode microwave cavity for sintering ceramic powders. This setup includes an optical dilatometer and a motorized plunger to control heating cycles in a wide range of heating rates (from 5 °C ∙ min^− 1 to 200 °C ∙ min^− 1) up to 1600 °C and to allow reliable comparison with conventional sintering. The cavity and the sintering cells for both hybrid and direct microwave sintering were designed using finite element simulation. For accurate temperature measurement, an optical pyrometer calibrated with a specific protocol has been used. Microwave sintering of fine grained (< 100 nm) alpha alumina compacts was thus investigated and compared to conventional sintering. This pure alumina powder has been sintered by direct microwave heating, without any susceptor nor doping element to initiate heating as often achieved in the literature. The comparison of the densification kinetics along an identical thermal cycle evidenced a significant enhancement of sintering under microwaves during the first and intermediate stages.     

Influence of oxygen on the processing maps for hot working of electrolytic tough pitch copper

Processing maps for the hot deformation of electrolytic tough pitch (ETP) copper (100 ppm oxygen) have been developed in the temperature range 600–950 °C and strain rate range 0.001–100 s^− 1, and compared with those published earlier on ETP copper with higher oxygen contents (180, 220 and 260 ppm). These reveal that dynamic recrystallization (DRX) occurs over a wide temperature and strain rate range and is controlled by different diffusion mechanisms. In ETP copper with 100 and 180 ppm oxygen, the apparent activation energy in the DRX domain occurring in the strain rate range 0.001–10 s^− 1 and temperature range 600–900 °C is about 198 kJ/mol which suggests lattice self-diffusion to be the rate-controlling mechanism. This DRX domain has moved to higher temperatures and lower strain rates in ETP copper with higher oxygen content. In the second domain occurring at strain rates in the range 10–100 s^− 1 and temperatures > 700 °C, the apparent activation energy is 91 kJ/mol and DRX is controlled by grain boundary self-diffusion. This domain is absent in the maps of ETP copper with oxygen content higher than 180 ppm and this is attributed to the pinning of the grain boundaries by the oxide particles preventing their migration.     

Effects of heat treatment on the microstructure of amorphous boron carbide coating deposited on graphite substrates by chemical vapor deposition

A two-layer boron carbide coating is deposited on a graphite substrate by chemical vapor deposition from a CH₄/BCl₃/H₂ precursor mixture at a low temperature of 950 °C and a reduced pressure of 10 KPa. Coated substrates are annealed at 1600 °C, 1700 °C, 1800 °C, 1900 °C and 2000 °C in high purity argon for 2 h, respectively. Structural evolution of the coatings is explored by electron microscopy and spectroscopy. Results demonstrate that the as-deposited coating is composed of pyrolytic carbon and amorphous boron carbide. A composition gradient of B and C is induced in each deposition. After annealing, B₄C crystallites precipitate out of the amorphous boron carbide and grow to several hundreds nanometers by receiving B and C from boron-doped pyrolytic carbon. Energy-dispersive spectroscopy proves that the crystallization is controlled by element diffusion activated by high temperature annealing, after that a larger concentration gradient of B and C is induced in the coating. Quantified Raman spectrum identifies a graphitization enhancement of pyrolytic carbon. Transmission electron microscopy exhibits an epitaxial growth of B₄C at layer/layer interface of the annealed coatings. Mechanism concerning the structural evolution on the basis of the experimental results is proposed.     

Synthesis of nanocrystalline GaN from Ga2O3 nanoparticles derived from salt-assisted spray pyrolysis

Gallium nitride (GaN) nanoparticles were successfully produced from nano-sized gallium oxide (Ga₂O₃) particles under a flow of ammonia gas. The gallium oxide nanoparticles were prepared by salt-assisted spray pyrolysis (SASP). Highly crystalline Ga₂O₃ nanoparticles with an average diameter of approximately 10 nm were obtained at various temperatures when a flux salt (LiCl, 5 mol/l) was added to the precursor solution. The effects of the crystallinity of the Ga₂O₃ particles and nitridation time on transformation to GaN were characterized using X-ray diffraction and scanning/transmission electron microscopy. Highly crystalline GaN nanoparticles with a mean size of 23.4 nm and a geometric standard deviation of 1.68 nm were obtained when Ga₂O₃ nanoparticles with relatively low crystallinity were used as the starting material. The resulting GaN nanoparticles showed a photoluminescence peak at 364 nm under UV excitation at 254 nm.     

Development of an inconel self powered neutron detector for in-core reactor monitoring

The paper describes the development and testing of an Inconel600 (2 mm diameter×21 cm long) self-powered neutron detector for in-core neutron monitoring. The detector has 3.5 mm overall diameter and 22 cm length and is integrally coupled to a 12 m long mineral insulated cable. The performance of the detector was compared with cobalt and platinum detectors of similar dimensions. Gamma sensitivity measurements performed at the ⁶⁰Co irradiation facility in 14 MR/h gamma field showed values of −4.4×10⁻¹⁸ A/R/h/cm (−9.3×10⁻²⁴ A/γ/cm²-s/cm), −5.2×10⁻¹⁸ A/R/h/cm (−1.133×10⁻²³ A/γ/cm²-s/cm) and 34×10⁻¹⁸ A/R/h/cm (7.14×10⁻²³ A/γ/cm²-s/cm) for the Inconel, Co and Pt detectors, respectively. The detectors together with a miniature gamma ion chamber and fission chamber were tested in the in-core Apsara Swimming Pool type reactor. The ion chambers were used to estimate the neutron and gamma fields. With an effective neutron cross-section of 4b, the Inconel detector has a total sensitivity of 6×10⁻²³ A/nv/cm while the corresponding sensitivities for the platinum and cobalt detectors were 1.69×10⁻²² and 2.64×10⁻²² A/nv/cm. The linearity of the detector responses at power levels ranging from 100 to 200 kW was within ±5%. The response of the detectors to reactor scram showed that the prompt response of the Inconel detector was 0.95 while it was 0.7 and 0.95 for the platinum and cobalt self-powered detectors, respectively. The detector was also installed in the horizontal flux unit of 540 MW Pressurised Heavy Water Reactor (PHWR). The neutron flux at the detector location was calculated by Triveni code. The detector response was measured from 0.02% to 0.07% of full power and showed good correlation between power level and detector signals. Long-term tests and the dynamic response of the detector to shut down in PHWR are in progress.     

Hydrodynamic behavior of binary mixture of solids in a triple-bed combined circulating fluidized bed with high mass flux

Flow behaviors of binary mixture of silica sand and nylonshot (coal char substitute) were investigated in a triple-bed circulating fluidized bed (TBCFB) as a cold model of coal gasifier. The TBCFB consisted of a downer (ϕ 0.1 m × 6.5 m), a bubbling fluidized bed (0.75 m × 0.27 m × 1.9 m), a riser (ϕ 0.1 m × 16.6 m) and a gas-sealing bed (GSB, ϕ 0.158 m × 5 m). The initial fraction of the nylonshot in the solid mixture (X_nylon,i) was 15.4 and 30% on mass and volume bases, respectively, or otherwise, 30.7 and 50%. The maximum solids mass flux (G_s) at X_nylon,i of 15.4 and 30.7 wt% were 394 and 349 kg/m² s, respectively, when the gas velocity in the riser (U_gr) was 10 m/s. Apparent solids holdups of silica sand and nylonshot were calculated separately from the static pressure gradient across the riser and the downer. The results showed possibility of large-mass-flux circulation of char in the gasifier, which plays a significant role in decomposition of tar from pyrolysis as the primary step of gasification. A newly developed pressure balance model successfully predicted G_s of the binary mixtures in TBCFB.