Search results for: polymer impregnation and pyrolysis

Authors: R. Sharma, A. Sil, S. Ray

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Nanocomposites gel polymer electrolytes are gaining more and more attention among the researchers worldwide due to their possible applications in various electrochemical devices particularly in solid-state Li-ion batteries. In this work we have investigated the effect of nanofibers on the electrical properties of PVDF-HFP based gel electrolytes. The nanocomposites polymer electrolytes have been synthesized by solution casting technique with 10wt% of ZrO2. By analysis of impedance spectroscopy it has been demonstrated that the incorporation of ZrO2 into PVDF-HFP–(PC+DEC)–LiClO4 gel polymer electrolyte system significantly enhances the ionic conductivity of the electrolyte. The enhancement of ionic conductivity seems to be correlated with the fact that the dispersion of ZrO2 to PVDF-HFP prevents polymer chain reorganization due to the high aspect ratio of ZrO2, resulting in reduction in polymer crystallinity, which gives rise to an increase in ionic conductivity. The decrease of crystallinity of PVDF-HFP due the addition of ZrO2 has been confirmed by XRD. The interaction of ZrO2 with various constituents of polymer electrolytes has been studied by FTIR spectroscopy. TEM results show that the fillers (ZrO2) has distributed uniformly in the polymer electrolytes. Moreover, ZrO2 added gel polymer electrolytes offer better thermal stability as compared to that of ZrO2 free electrolytes as confirmed by TGA analysis.

Keywords: polymer electrolytes, ZrO2, ionic conductivity, FTIR

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Authors: Kianoosh Shojae

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In recent years, the environmental challenges due to the excessive use of fossil fuels have led to heightened greenhouse gas production. In response, biodiesel has emerged as a cleaner alternative, offering reduced pollutant emissions compared to traditional fuels. The large-scale production of biodiesel, involving ester exchange of animal fats or vegetable oils, results in a surplus of crude glycerin. With environmental regulations on the rise and an increasing demand for biodiesel, glycerin production has seen a significant upswing. This paper focuses on the economic significance of glycerin through its pyrolysis as a raw material, particularly in the synthesis of metals. As industries pivoted towards cleaner fuels, glycerin, as a byproduct of biodiesel production, is poised to remain a cost-effective and surplus product. In this work, for evaluating the possible performance of using the gaseous products from the pyrolysis reaction of glycerol, we concerned the glycerin pyrolysis reactions, emphasizing the catalytic role of activated carbon, various reaction pathways and the impact of carrier gas flow rate on hydrogen production, providing valuable insights into the evolving landscape of sustainable fuel alternatives.

Keywords: biodiesel, glycerin pyrolysis, activated carbon catalysis, syngas

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Authors: Hiroyuki Aoki

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The physical properties of polymer materials are dependent on the conformation and molecular motion of a polymer chain. Therefore, the structure and dynamic behavior of the single polymer chain have been the most important concerns in the field of polymer physics. However, it has been impossible to directly observe the conformation of the single polymer chain in a bulk medium. In the current work, the novel techniques to study the conformation and dynamics of a single polymer chain are proposed. Since a fluorescence method is extremely sensitive, the fluorescence microscopy enables the direct detection of a single molecule. However, the structure of the polymer chain as large as 100 nm cannot be resolved by conventional fluorescence methods because of the diffraction limit of light. In order to observe the single chains, we developed the labeling method of polymer materials with a photo-switchable dye and the super-resolution microscopy. The real-space conformational analysis of single polymer chains with the spatial resolution of 15-20 nm was achieved. The super-resolution microscopy enables us to obtain the three-dimensional coordinates; therefore, we succeeded the conformational analysis in three dimensions. The direct observation by the nanometric optical microscopy would reveal the detailed information on the molecular processes in the various polymer systems.

Keywords: polymer materials, single molecule, super-resolution techniques, conformation

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Authors: Bhargav Baruah, Ali Shemsedin Reshad, Pankaj Tiwari

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This work presents a detailed study on the thermal degradation kinetics of co-pyrolysis of oil shale of Upper Assam, India with rubber seed shell, and lab-scale pyrolysis to investigate the influence of pyrolysis parameters on product yield and composition of products. The physicochemical characteristics of oil shale and rubber seed shell were studied by proximate analysis, elemental analysis, Fourier transform infrared spectroscopy and X-ray diffraction. The physicochemical study showed the mixture to be of low moisture, high ash, siliceous, sour with the presence of aliphatic, aromatic, and phenolic compounds. The thermal decomposition of the oil shale with rubber seed shell was studied using thermogravimetric analysis at heating rates of 5, 10, 20, 30, and 50 °C/min. The kinetic study of the oil shale pyrolysis process was performed on the thermogravimetric (TGA) data using three model-free isoconversional methods viz. Friedman, Flynn Wall Ozawa (FWO), and Kissinger Akahira Sunnose (KAS). The reaction mechanisms were determined using the Criado master plot. The understanding of the composition of Indian oil shale and rubber seed shell and pyrolysis process kinetics can help to establish the experimental parameters for the extraction of valuable products from the mixture. Response surface methodology (RSM) was employed usinf central composite design (CCD) model to setup the lab-scale experiment using TGA data, and optimization of process parameters viz. heating rate, temperature, and particle size. The samples were pre-dried at 115°C for 24 hours prior to pyrolysis. The pyrolysis temperatures were set from 450 to 650 °C, at heating rates of 2 to 20°C/min. The retention time was set between 2 to 8 hours. The optimum oil yield was observed at 5°C/min and 550°C with a retention time of 5 hours. The pyrolytic oil and gas obtained at optimum conditions were subjected to characterization using Fourier transform infrared spectroscopy (FT-IR) gas chromatography and mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (NMR).

Keywords: Indian oil shale, rubber seed shell, co-pyrolysis, isoconversional methods, gas chromatography, nuclear magnetic resonance, Fourier transform infrared spectroscopy

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Authors: María del Carmen Recio-Ruiz, Ramiro Ruiz-Rosas, Juana María Rosas, José Rodríguez-Mirasol, Tomás Cordero

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Nowadays, fossil resources are main precursors for fuel production. Due to their contribution to the greenhouse effect and their future depletion, there is a constant search for environmentally friendly feedstock alternatives. Biomass residues constitute an interesting replacement for fossil resources because of their zero net CO₂ emissions. One of the main routes to convert biomass into energy and chemicals is pyrolysis. In this work, conventional pyrolysis of different biomass residues highly available such as almond shells, hemp hurds, olive stones, and Kraft lignin, was studied. In a typical experiment, the biomass was crushed and loaded into a fixed bed reactor under continuous nitrogen flow. The influence of temperature (400-800 ºC) and heating rate (10 and 20 ºC/min) on the pyrolysis yield and composition of the different fractions has been studied. In every case, the mass yields revealed that the solid fraction decreased with temperature, while liquid and gas fractions increased due to depolymerization and cracking reactions at high temperatures. The composition of every pyrolysis fraction was studied in detail. The results showed that the composition of the gas fraction was mainly CO, CO₂ when working at low temperatures, and mostly CH₄ and H₂at high temperatures. The solid fraction developed an incipient microporosity, with narrow micropore volume of 0.21 cm³/g. Regarding the liquid fraction, pyrolysis of almond shell, hemp hurds, and olive stones led mainly to a high content in aliphatic acids and furans, due to the high volatile matter content of these biomass (>74 %wt.), and phenols to a lesser degree, which were formed due to the degradation of lignin at higher temperatures. However, when Kraft lignin was used as bio-oil precursor, the presence of phenols was very prominent, and aliphatic compounds were also detected in a lesser extent.

Keywords: Bio-oil, biomass, conventional pyrolysis, lignocellulosic

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Authors: Adilah Shariff, Nur Syairah Mohamad Aziz, Norsyahidah Md Saleh, Nur Syuhada Izzati Ruzali

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The first objective of this study is to investigate the suitability of coconut frond (CF) and coconut husk (CH) as feedstocks using a laboratory-scale slow pyrolysis experimental setup. The second objective is to investigate the effect of pyrolysis temperature on the biochar yield. The properties of CF and CH feedstocks were compared. The properties of the CF and CH feedstocks were investigated using proximate and elemental analysis, lignocellulosic determination, and also thermogravimetric analysis (TGA). The CF and CH feedstocks were pyrolysed at 300, 400, 500, 600 and 700 °C for 2 hours at 10 °C/min heating rate. The proximate analysis showed that CF feedstock has 89.96 mf wt% volatile matter, 4.67 mf wt% ash content and 5.37 mf wt% fixed carbon. The lignocelluloses analysis showed that CF feedstock contained 21.46% lignin, 39.05% cellulose and 22.49% hemicelluloses. The CH feedstock contained 84.13 mf wt% volatile matter, 0.33 mf wt% ash content, 15.54 mf wt% fixed carbon, 28.22% lignin, 33.61% cellulose and 22.03% hemicelluloses. Carbon and oxygen are the major component of the CF and CH feedstock compositions. Both of CF and CH feedstocks contained very low percentage of sulfur, 0.77% and 0.33%, respectively. TGA analysis indicated that coconut wastes are easily degraded. It may be due to their high volatile content. Between the temperature ranges of 300 and 800 °C, the TGA curves showed that the weight percentage of CF feedstock is lower than CH feedstock by 0.62%-5.88%. From the D TGA curves, most of the weight loss occurred between 210 and 400 °C for both feedstocks. The maximum weight loss for both CF and CH are 0.0074 wt%/min and 0.0061 wt%/min, respectively, which occurred at 324.5 °C. The yield percentage of both CF and CH biochars decreased significantly as the pyrolysis temperature was increased. For CF biochar, the yield decreased from 49.40 wt% to 28.12 wt% as the temperature increased from 300 to 700 °C. The yield for CH biochars also decreased from 52.18 wt% to 28.72 wt%. The findings of this study indicated that both CF and CH are suitable feedstock for slow pyrolysis of biochar.

Keywords: biochar, biomass, coconut wastes, slow pyrolysis

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Authors: Julius Ilawe Osayi, Peter Osifo

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Solid waste disposal, such as used tires is a global challenge as well as energy crisis due to rising energy demand amidst price uncertainty and depleting fossil fuel reserves. Therefore, the effectiveness of pyrolysis as a disposal method that can transform used tires into liquid fuel and other end-products has made the process attractive to researchers. Although used tires have been converted to liquid fuel using pyrolysis, there is the need to improve on the liquid fuel properties. Hence, this paper reports the investigation of zeolite NaY synthesized from kaolin, a locally abundant soil material in the Benin metropolis as a suitable catalyst and its effect on the properties of pyrolytic oil produced from used tires. The pyrolysis process was conducted for a range of 1 to 10 wt.% of catalyst concentration to used tire at a temperature of 600 oC, a heating rate of 15oC/min and particle size of 6mm. Although no significant increase in pyrolytic oil yield was observed compared to the previously investigated non-catalytic pyrolysis of a used tire. However, the Fourier transform infrared (FTIR), Nuclear Magnetic Resonance (NMR); and Gas chromatography-mass spectrometry (GC-MS) characterization results revealed the pyrolytic oil to possess an improved physicochemical and fuel properties alongside valuable industrial chemical species. This confirms the possibility of transforming kaolin into a catalyst suitable for improved fuel properties of the liquid fraction obtainable from thermal cracking of hydrocarbon materials.

Keywords: catalytic pyrolysis, fossil fuel, kaolin, pyrolytic oil, used tyres, Zeolite NaY

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Authors: Maryam Kiani

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In order to enhance the efficiency and stability of an electrocatalyst for formic acid electro-oxidation reaction (FAOR), we developed a method to create Pt/Ni nanoparticles with carbon black. These nanoparticles were prepared using a simple impregnation reduction technique. During the observation, it was found that the nanoparticles had a spherical shape. Additionally, the average particle size remained consistent, falling within the range of about 4 nm. This approach aimed to obtain a loaded Pt-based electrocatalyst that would exhibit improved performance and stability when used in FAOR applications. By utilizing the impregnation reduction method and incorporating Ni nanoparticles along with Pt, we sought to enhance the catalytic properties of the material. By incorporating Ni atoms into the Pt structure, the electronic properties of Pt are modified, resulting in a delay in the chemisorption of harmful CO intermediate species. This modification also promotes the dehydrogenation pathway of the formic acid oxidation reaction (FAOR). Through electrochemical analysis, it has been observed that the Pt3Ni-C catalyst exhibits enhanced performance in FAOR compared to traditional Pt catalysts. This means that the addition of Ni atoms improves the efficiency and effectiveness of the Pt3Ni-C catalyst in facilitating the FAOR process. Overall, the utilization of these alloy nanoparticles as electrocatalysts represents a significant advancement in fuel cell technology.

Keywords: electrocatalyst, impregnation reduction method, formic acid electro-oxidation reaction, fuel cells

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Authors: Sukruthai Sapniwat, Falan Srisuriyachai

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Polymer Flooding is one of the most well-known methods in Enhanced Oil Recovery (EOR) technology which can be implemented after either primary or secondary recovery, resulting in favorable conditions for the displacement mechanism in order to lower the residual oil in the reservoir. Polymer substances can lower the mobility ratio of the whole process by increasing the viscosity of injected water. Therefore, polymer flooding can increase volumetric sweep efficiency, which leads to a better recovery factor. Moreover, polymer adsorption onto rock surface can help decrease reservoir permeability contrast with high heterogeneity. Due to the reduction of the absolute permeability, effective permeability to water, representing flow ability of the injected fluid, is also reduced. Once polymer is adsorbed onto rock surface, polymer molecule can be desorbed when different fluids are injected. This study is performed to evaluate the effects of the adsorption and desorption process of polymer solutions to yield benefits on the oil recovery mechanism. A reservoir model is constructed by reservoir simulation program called STAR® commercialized by the Computer Modeling Group (CMG). Various polymer concentrations, starting times of polymer flooding process and polymer injection rates were evaluated with selected values of polymer desorption degrees including 0, 25, 50, 75 and 100%. The higher the value, the more adsorbed polymer molecules to return back to flowing fluid. According to the results, polymer desorption lowers polymer consumption, especially at low concentrations. Furthermore, starting time of polymer flooding and injection rate affect the oil production. The results show that waterflooding followed by earlier polymer flooding can increase the oil recovery factor while the higher injection rate also enhances the recovery. Polymer concentration is related to polymer consumption due to the two main benefits of polymer flooding control described above. Therefore, polymer slug size should be optimized based on polymer concentration. Polymer desorption causes polymer re-employment that is previously adsorbed onto rock surface, resulting in an increase of sweep efficiency in the further period of polymer flooding process. Even though waterflooding supports polymer injectivity, water cut at the producer can prematurely terminate the oil production. The injection rate decreases polymer adsorption due to decreased retention time of polymer flooding process.

Keywords: enhanced oil recovery technology, polymer adsorption and desorption, polymer flooding, reservoir simulation

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Authors: Yahya Asanoglu, Celaletdin Ergun

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Ceramic-matrix composites (CMC) have significant prominence in various engineering applications because of their heat resistance associated with an ability to withstand the brittle type of catastrophic failure. In this study, specific raw materials have been chosen for the purpose of having suitable CMC material for high-temperature dielectric applications. CMC material will be manufactured through the polymer infiltration and pyrolysis (PIP) method. During the manufacturing process, vacuum infiltration and autoclave will be applied so as to decrease porosity and obtain higher mechanical properties, although this advantage leads to a decrease in the electrical performance of the material. Time and temperature adjustment in pyrolysis parameters provide a significant difference in the properties of the resulting material. The mechanical and thermal properties will be investigated in addition to the measurement of dielectric constant and tangent loss values within the spectrum of Ku-band (12 to 18 GHz). Also, XRD, TGA/PTA analyses will be employed to prove the transition of precursor to ceramic phases and to detect critical transition temperatures. Additionally, SEM analysis on the fracture surfaces will be performed to see failure mechanism whether there is fiber pull-out, crack deflection and others which lead to ductility and toughness in the material. In this research, the cost-effectiveness and applicability of the PIP method will be proven in the manufacture of CMC materials while optimization of pyrolysis time, temperature and cycle for specific materials is detected by experiment. Also, several resins will be shown to be a potential raw material for CMC radome and antenna applications. This research will be distinguished from previous related papers due to the fact that in this research, the combination of different precursors and fabrics will be experimented with to specify the unique cons and pros of each combination. In this way, this is an experimental sum of previous works with unique PIP parameters and a guide to the manufacture of CMC radome and antenna.

Keywords: CMC, PIP, precursor, quartz

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Authors: Qian Li, Zhaoping Zhong

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Sewage sludge, a typical solid waste, has inevitably been produced in enormous quantities in China. Still worse, the amount of sewage sludge produced has been increasing due to rapid economic development and urbanization. Compared to the conventional method to treat sewage sludge, pyrolysis has been considered an economic and ecological technology because it can significantly reduce the sludge volume, completely kill pathogens, and produce valuable solid, gas, and liquid products. However, the large-scale utilization of sludge biochar has been limited due to the considerable risk posed by heavy metals in the sludge. Heavy metals enriched in pyrolytic biochar could be divided into exchangeable, reducible, oxidizable, and residual forms. The residual form of heavy metals is the most stable and cannot be used by organisms. Kaolin and zeolite are environmentally friendly inorganic minerals with a high surface area and heat resistance characteristics. So, they exhibit the enormous potential to immobilize heavy metals. In order to reduce the risk of leaching heavy metals in the pyrolysis biochar, this study pyrolyzed sewage sludge mixed with kaolin/zeolite in a small rotary kiln. The influences of additives and pyrolysis temperature on the leaching concentration and morphological transformation of heavy metals in pyrolysis biochar were investigated. The potential mechanism of stabilizing heavy metals in the co-pyrolysis of sludge blended with kaolin/zeolite was explained by scanning electron microscopy, X-ray diffraction, and specific surface area and porosity analysis. The European Community Bureau of Reference sequential extraction procedure has been applied to analyze the forms of heavy metals in sludge and pyrolysis biochar. All the concentrations of heavy metals were examined by flame atomic absorption spectrophotometry. Compared with the proportions of heavy metals associated with the F4 fraction in pyrolytic carbon prepared without additional agents, those in carbon obtained by co-pyrolysis of sludge and kaolin/zeolite increased. Increasing the additive dosage could improve the proportions of the stable fraction of various heavy metals in biochar. Kaolin exhibited a better effect on stabilizing heavy metals than zeolite. Aluminosilicate additives with excellent adsorption performance could capture more released heavy metals during sludge pyrolysis. Then heavy metal ions would react with the oxygen ions of additives to form silicate and aluminate, causing the conversion of heavy metals from unstable fractions (sulfate, chloride, etc.) to stable fractions (silicate, aluminate, etc.). This study reveals that the efficiency of stabilizing heavy metals depends on the formation of stable mineral compounds containing heavy metals in pyrolysis biochar.

Keywords: co-pyrolysis, heavy metals, immobilization mechanism, sewage sludge

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Authors: Bourfaa Fouzia, Meryem Lamri Zeggar, Adjimi Amel, Mohammed Salah Aida, Nadir Attaf

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Semiconductor photocatalysts such as ZnO has attracted much attention in recent years due to their various applications for the degradation of organic pollutants in water, air and in dye sensitized photovoltaic solar cell. In the present work, ZnO thin films were prepared by ultrasonic spray pyrolysis by using different precursors namely: Acetate, chloride and zinc nitrate in order to investigate their influence on ZnO photocatalytic activity. The films crystalline structure was studied by mean of X-ray diffraction measurements (XRD) and the films surface morphology by Scanning Electron Microscopy (SEM). The films optical properties were studied by mean of UV–visible spectroscopy. The prepared films were tested for the degradation of the red reactive dye largely used in textile industry. As a result, we found that the zinc nitrate is the best precursor to prepare ZnO thin films suitable for a good photocatalytic activity.

Keywords: precursor, thins films, spray pyrolysis, zinc oxide

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Authors: Anjan Sil, Rajni Sharma, Subrata Ray

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The effect of carbon nanofibers (CNFs) on the electrical properties of Poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP)) based gel polymer electrolytes has been investigated in the present work. The length and diameter ranges of CNFs used in the present work are 5-50 µm and 200-600 nm, respectively. The nanocomposite gel polymer electrolytes have been synthesized by solution casting technique with varying CNFs content in terms of weight percentage. Electrochemical impedance analysis demonstrates that the reinforcement of carbon nanofibers significantly enhances the ionic conductivity of the polymer electrolyte. The decrease of crystallinity of P(VdF-HFP) due the addition of CNFs has been confirmed by X-ray diffraction (XRD). The interaction of CNFs with various constituents of nanocomposite gel polymer electrolytes has been assessed by Fourier Transform Infrared (FTIR) spectroscopy. Moreover, CNFs added gel polymer electrolytes offer superior thermal stability as compared to that of CNFs free electrolytes as confirmed by Thermogravimetric analysis (TGA).

Keywords: polymer electrolytes, CNFs, ionic conductivity, TGA

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Authors: Mohammad Javad Afroughi, Farjad Falahati, Larry W. Kostiuk, Jason S. Olfert

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This study investigates the physical characteristics of nanoparticles generated during pyrolysis of methane in hot products of a premixed propane-air flame. An inverted burner is designed to provide a laminar premixed propane-air flame (35 SLPM) then introduce methane co-flow to be pyrolyzed within a closed cylindrical chamber (20 cm in diameter and 68 cm in length). The formed products are discharged through an exhaust with a sampling branch to measure emission characteristics. Carbon particles are sampled with a preheated nitrogen dilution system, and the size distribution of particles formed by pyrolysis is measured by a scanning mobility particle sizer (SMPS). Dilution ratio is calculated using simultaneously measured CO2 concentrations in the exhaust products and diluted samples. Results show that particle size distribution (PSD) is strongly affected by dilution ratio and preheating temperature. PSD becomes unstable at high dilution ratios (typically above 700 times) and/or low preheating temperatures (below 40° C). At a suitable dilution ratio of 55 and preheating temperature up to 70° C, the median diameter of PSD increases from 20 to 220 nm following the introduction of 0.5 SLPM of methane to the propane-air premixed flame. Furthermore, with pyrolysis of methane, total particle number concentration and estimated total mass concentration of particles in the size range of 14 to 700 nm, increase from 1.12 to 3.90 *107 cm-3 and from 0.11 to 154 µg L-1, respectively.

Keywords: laminar premixed flame, methane pyrolysis, nanoparticle physical characteristics, particle mass concentration, particle number concentration, particle size distribution (PSD)

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Authors: Katya Milenova, Penko Nikolov, Irina Stambolova, Plamen Nikolov, Vladimir Blaskov

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In the recent article, a comparison was made between Cu and TiO2 supported catalysts on activated carbon for ozone decomposition reaction. The activated carbon support in the case of TiO2/AC sample was prepared by physicochemical pyrolysis and for Cu/AC samples the supports are chemically modified carbons. The prepared catalysts were synthesized by impregnation method. The samples were annealed in two different regimes-in air and under vacuum. To examine adsorption efficiency of the samples BET method was used. All investigated catalysts supported on chemically modified carbons have higher specific surface area compared to the specific surface area of TiO2 supported catalysts, varying in the range 590÷620 m2/g. The method of synthesis of the precursors had influenced catalytic activity.

Keywords: activated carbon, adsorption, copper, ozone decomposition, TiO2

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Authors: Praveen K. Khatri, Neha Karanwal, Savita Kaul, Suman L. Jain

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Conversion of biomass through green chemical routes is of great industrial importance as biomass is considered to be most widely available inexpensive renewable resource that can be used as a raw material for the production of bio fuel and value-added organic products. In this regard, acid catalyzed dehydration of biomass derived pentose sugar (mainly D-xylose) to furfural is a process of tremendous research interest in current scenario due to the wider industrial applications of furfural. Furfural is an excellent organic solvent for refinement of lubricants and separation of butadiene from butene mixture in synthetic rubber fabrication. In addition it also serve as a promising solvent for many organic materials, such as resins, polymers and also used as a building block for synthesis of various valuable chemicals such as furfuryl alcohol, furan, pharmaceutical, agrochemicals and THF. Here in a sulfonated polymer impregnated carbon composite solid acid catalyst (P-C-SO3H) was prepared by the pyrolysis of a polymer matrix impregnated with glucose followed by its sulfonation and used for the dehydration of xylose to furfural. The developed catalyst exhibited excellent activity and provided almost quantitative conversion of xylose with the selective synthesis of furfural. The higher catalytic activity of P-C-SO3H may be due to the more even distribution of polycyclic aromatic hydrocarbons generated from incomplete carbonization of glucose along the polymer matrix network, leading to more available sites for sulfonation which resulted in greater sulfonic acid density in P-C-SO3H as compared to sulfonated carbon catalyst (C-SO3H). In conclusion, we have demonstrated sulfonated polymer impregnated carbon composite (P-C-SO3H) as an efficient and selective solid acid catalyst for the dehydration of xylose to furfural. After completion of the reaction, the catalyst was easily recovered and reused for several runs without noticeable loss in its activity and selectivity.

Keywords: Solid acid , Biomass conversion, Xylose Dehydration, Heterogeneous catalyst

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Authors: M. Sarikanat, E. Akar, I. Şen, Y. Seki, O. C. Yılmaz, B. O. Gürses, L. Cetin, O. Özdemir, K. Sever

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Chitosan is a natural, nontoxic, polyelectrolyte, cheap polymer. In this study, chitosan based electroactive polymer (CBEAP) was fabricated. Electroactive properties of this polymer were investigated at different voltages. It exhibited excellent tip displacement at low voltages (1, 3, 5, 7 V). Tip displacement was increased as the applied voltage increased. Best tip displacement was investigated as 28 mm at 5V. Characterization of CBEAP was investigated by scanning electron microscope, X-ray diffraction and tensile testing. CBEAP exhibited desired electroactive properties at low voltages. It is suitable for using in artificial muscle and various robotic applications.

Keywords: chitosan, electroactive polymer, electroactive properties

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Authors: Samaneh Nabavi, Hadi Shirzad, Arash Ghoorchian, Maryam Shanesaz, Reza Naderi

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Morphine (MO), the most effective painkiller, is considered the reference by which analgesics are assessed. It is very necessary for the biomedical applications to detect and maintain the MO concentrations in the blood and urine with in safe ranges. To date, there are many expensive techniques for detecting MO. Recently, many electrochemical sensors for direct determination of MO were constructed. The molecularly imprinted polymer (MIP) is a polymeric material, which has a built-in functionality for the recognition of a particular chemical substance with its complementary cavity.This paper reports a sensor for MO using a combination of a molecularly imprinted polymer (MIP) and differential-pulse voltammetry (DPV). Electropolymerization of MO doped polypyrrole yielded poor quality, but a well-doped, nanostructure and increased impregnation has been obtained in the pH=12. Above a pH of 11, MO is in the anionic forms. The effect of various experimental parameters including pH, scan rate and accumulation time on the voltammetric response of MO was investigated. At the optimum conditions, the concentration of MO was determined using DPV in a linear range of 7.07 × 10−6 to 2.1 × 10−4 mol L−1 with a correlation coefficient of 0.999, and a detection limit of 13.3 × 10-8 mol L−1, respectively. The effect of common interferences on the current response of MO namely ascorbic acid (AA) and uric acid (UA) is studied. The modified electrode can be used for the determination of MO spiked into urine samples, and excellent recovery results were obtained. The nanostructured polypyrrole films were characterized by field emission scanning electron microscopy (FESEM) and furrier transforms infrared (FTIR).

Keywords: morphine detection, sensor, polypyrrole, nanostructure, molecularly imprinted polymer

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Authors: P. A. Broodryk, A. F. Van Der Merwe, H. W. J. P. Neomagus

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The production of the clear liquid fertilizer ammonium polyphosphate (APP) is best achieved by the pyrolysis of urea phosphate, as it produces a product that is free from any of the impurities present in the raw phosphoric acid it was made from. This is a multiphase, multi-step reaction that produces carbon dioxide and ammonia as gasses and ammonium polyphosphate as liquid products. The polyphosphate chain length affects the solubility and thus the applicability of the product as liquid fertiliser, thus proper control of the reaction conditions is thus required for the use of this reaction in the production of fertilisers. This study investigates the reaction kinetics of the aforementioned reaction, describing a mathematical model for the kinetics of the reaction along with the accompanying rate constants. The reaction is initially exothermic, producing only carbon dioxide as a gas product and ammonium diphosphate, at higher temperatures the reaction becomes endothermic, producing ammonia gas as an additional by-product and longer chain polyphosphates, which when condensed too far becomes highly water insoluble. The aim of this study was to (i) characterise the pyrolysis reaction of urea phosphate by determining the mechanisms and the associated kinetic constants, and (ii) to determine the optimum conditions for ammonium diphosphate production. A qualitative investigation was also done to find the rate of hydrolysis of APP as this provides an estimate of the shelf life of an APP clear liquid fertiliser solution.

Keywords: ammonium polyphosphate, kinetics, pyrolysis, urea phosphate

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Authors: Francesca Gullo, Paola Palmero, Massimo Messori

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Transparent wood is considered a promising structural material for the development of environmentally friendly, energy-efficient engineered components. To obtain transparent wood from natural wood materials two approaches can be used: i) bottom-up and ii) top-down. Through the second method, the color of natural wood samples is lightened through a chemical bleaching process that acts on chromophore groups of lignin, such as the benzene ring, quinonoid, vinyl, phenolics, and carbonyl groups. These chromophoric units form complex conjugate systems responsible for the brown color of wood. There are two strategies to remove color and increase the whiteness of wood: i) lignin removal and ii) lignin bleaching. In the lignin removal strategy, strong chemicals containing chlorine (chlorine, hypochlorite, and chlorine dioxide) and oxidizers (oxygen, ozone, and peroxide) are used to completely destroy and dissolve the lignin. In lignin bleaching methods, a moderate reductive (hydrosulfite) or oxidative (hydrogen peroxide) is commonly used to alter or remove the groups and chromophore systems of lignin, selectively discoloring the lignin while keeping the macrostructure intact. It is, therefore, essential to manipulate nanostructured wood by precisely controlling the nanopores in the cell walls by monitoring both chemical treatments and process conditions, for instance, the treatment time, the concentration of chemical solutions, the pH value, and the temperature. The elimination of wood light scattering is the second step in the fabrication of transparent wood materials, which can be achieved through two-step approaches: i) the polymer impregnation method and ii) the densification method. For the polymer impregnation method, the wood scaffold is treated with polymers having a corresponding refractive index (e.g., PMMA and epoxy resins) under vacuum to obtain the transparent composite material, which can finally be pressed to align the cellulose fibers and reduce interfacial defects in order to have a finished product with high transmittance (>90%) and excellent light-guiding. However, both the solution-based bleaching and the impregnation processes used to produce transparent wood generally consume large amounts of energy and chemicals, including some toxic or pollutant agents, and are difficult to scale up industrially. Here, we report a method to produce optically transparent wood by modifying the lignin structure with a chemical reaction at room temperature using small amounts of hydrogen peroxide in an alkaline environment. This method preserves the lignin, which results only deconjugated and acts as a binder, providing both a strong wood scaffold and suitable porosity for infiltration of biobased polymers while reducing chemical consumption, the toxicity of the reagents used, polluting waste, petroleum by-products, energy and processing time. The resulting transparent wood demonstrates high transmittance and low thermal conductivity. Through the combination of process efficiency and scalability, the obtained materials are promising candidates for application in the field of construction for modern energy-efficient buildings.

Keywords: bleached wood, energy-efficient components, hydrogen peroxide, transparent wood, wood composites

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Authors: M. A. Hannan, N. Matthias Neisius

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Organophosphorus compound diethyloxymethyl-9-oxa-10-phosphaphenanthrene-10-oxide (DOPAC) was applied on cotton cellulose to impart eco-friendly flame retardant property to it. Here acetal linkage was introduced rather than conventionally used ester linkage to rescue from the undurability problem of flame retardant compound. Some acidic catalysts, sodium dihydrogen phosphate (NaH2PO4), ammonium dihydrogen phosphate (NH4H2PO4) and phosphoric acid (H3PO4) were successfully used to form acetal linkage between the base material and flame retardant compound. Inspiring limiting oxygen index (LOI) value of 22.4 was found after exclusive washing treatment. A good outcome of total heat of combustion (THC) 6.05 KJ/g was found possible during pyrolysis combustion flow calorimetry (PCFC) test of the treated sample. Low temperature dehydration with sufficient amount of char residue (14.89%) was experienced in case of treated sample. In addition, the temperature of peak heat release rate (TPHRR) 343.061°C supported the expected low temperature pyrolysis in condensed phase mechanism. With the consequence of pyrolysis effects, thermogravimetric analysis (TGA) also reported inspiring weight retention% of the treated samples.

Keywords: acetal linkage, char residue, cotton cellulose, flame retardant, loi, low temperature pyrolysis, organophosphorus, THC, THRR

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Authors: Muhammed Ertuğrul Çeloğlu, Mehmet Yılmaz

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In this study, apricot seed shell, walnut shell, and sawdust were chosen as biomass sources. The materials were sorted by using a sieve No. 50 and the sieved materials were subjected to pyrolysis process at 400 °C, resulting in three different biochar products. The resulting biochar products were added to the bitumen at three different rates (5%, 10% and 15%), producing modified bitumen. Penetration, softening point, rotation viscometer and dynamic shear rheometer (DSR) tests were conducted on modified binders. Thus the modified bitumen, which was obtained by using additives at 3 different rates obtained from biochar produced at 400 °C temperatures of 3 different biomass sources were compared and the effects of pyrolysis temperature and additive rates were evaluated. As a result of the conducted tests, it was determined that the rheology of the pure bitumen improved significantly as a result of the modification of the bitumen with the biochar. Additionally, with biochar additive, it was determined that the rutting parameter values obtained from softening point, viscometer and DSR tests were increased while the values in terms of penetration and phase angle decreased. It was also observed that the most effective biomass is sawdust while the least effective was ground apricot seed shell.

Keywords: rheology, biomass, pyrolysis, biochar

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Authors: Maha A. Younus, Dhefaf H. Badri, Maha A. Al Abayaji, Taha M. Salih

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Polymer metal complexes of poly vinyl alcohol and Cu (II), Ni (II), Mn (II) and Co (III) were prepared from the reaction of PVA with three different percentages of urea. The compound was characterized by fourier transform infrared spectrometry (FTIR) analysis and differential scanning calorimetric (DSC) Analysis. It has been established that the polymer and its metal complexes showed good activities against nine pathogenic bacteria (Escherichia coli, Klebsiellapneumonae, Staphylococcusaureus, Staphylococcus Albus, Salmonella Typhoid, Pseudomonas Aeruginosa, Shigella Dysentery, Proteus Morgani, Brucella Militensis). The polymer metal complexes show activity higher than that of the free polymer. The increasing activities were in the order (polymer < pol-Mn< pol-Co < pol-Ni ˂ pol-Cu). The ability of these compounds to show antimicrobial properties suggests that they can be further evaluated for medicinal and/or environmental applications.

Keywords: antimicrobial activity, PVA, polymer-metal complex, urea

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Authors: Panupong Lohrattanarungrot, Falan Srisuriyachai

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Polymer flooding is a well-known technique used for controlling mobility ratio in heterogeneous reservoirs, leading to improvement of sweep efficiency as well as wellbore profile. However, low injectivity of viscous polymer solution attenuates oil recovery rate and consecutively adds extra operating cost. An attempt of this study is to improve injectivity of polymer solution while maintaining recovery factor, enhancing effectiveness of polymer flooding method. This study is performed by using reservoir simulation program to modify conventional single polymer slug into sequential polymer flooding, emphasizing on increasing of injectivity and also reduction of polymer amount. Selection of operating conditions for single slug polymer including pre-injected water, polymer concentration and polymer slug size is firstly performed for a layered-heterogeneous reservoir with Lorenz coefficient (Lk) of 0.32. A selected single slug polymer flooding scheme is modified into sequential polymer flooding with reduction of polymer concentration in two different modes: Constant polymer mass and reduction of polymer mass. Effects of Residual Resistance Factor (RRF) is also evaluated. From simulation results, it is observed that first polymer slug with the highest concentration has the main function to buffer between displacing phase and reservoir oil. Moreover, part of polymer from this slug is also sacrificed for adsorption. Reduction of polymer concentration in the following slug prevents bypassing due to unfavorable mobility ratio. At the same time, following slugs with lower viscosity can be injected easily through formation, improving injectivity of the whole process. A sequential polymer flooding with reduction of polymer mass shows great benefit by reducing total production time and amount of polymer consumed up to 10% without any downside effect. The only advantage of using constant polymer mass is slightly increment of recovery factor (up to 1.4%) while total production time is almost the same. Increasing of residual resistance factor of polymer solution yields a benefit on mobility control by reducing effective permeability to water. Nevertheless, higher adsorption results in low injectivity, extending total production time. Modifying single polymer slug into sequence of reduced polymer concentration yields major benefits on reducing production time as well as polymer mass. With certain design of polymer flooding scheme, recovery factor can even be further increased. This study shows that application of sequential polymer flooding can be certainly applied to reservoir with high value of heterogeneity since it requires nothing complex for real implementation but just a proper design of polymer slug size and concentration.

Keywords: polymer flooding, sequential, heterogeneous reservoir, residual resistance factor

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Authors: Sy-Wei Lo, Chi-Heng Yu

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A new design of aerostatic thrust bearing is proposed for high static stiffness. The bearing body, which is mead of polymer covered with metallic membrane, is held by a circular ring. Such a support helps form a concave air gap to grasp the air pressure. The polymer body, which can be made rapidly by either injection or molding is able to provide extra damping under dynamic loading. The smooth membrane not only serves as the bearing surface but also protects the polymer body. The restrictor is a capillary inside a silicone tube. It can passively compensate the variation of load by expanding the capillary diameter for more air flux. In the present example, the stiffness soars from 15.85 N/µm of typical bearing to 349.85 N/µm at bearing elevation 9.5 µm; meanwhile the load capacity also enhances from 346.86 N to 704.18 N.

Keywords: aerostatic, bearing, polymer, static stiffness

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Authors: María Graciela Aguayo, Laura Reyes, Claudia Oviedo, José Navarrete, Liset Gómez, Hugo Torres

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Most wood species used in construction deteriorate when exposed to environmental conditions that favor wood-degrading organisms’ growth. Therefore, chemical protection by impregnation allows more efficient use of forest resources extending the wood useful life. A wood protection treatment which has attracted considerable interest in the scientific community during the last decade is wood impregnation with nano compounds. Radiata pine is the main wood species used in the Chilean construction industry, with total availability of 8 million m³ sawn timber. According to the requirements of the American Wood Protection Association (AWPA) and the Chilean Standards (NCh) radiata pine timber used in construction must be protected due to its low natural durability. In this work, the impregnation with copper nanoparticles (CuNP) was studied in terms of penetration and its protective effect against wood rot fungi. Two concentrations: 1 and 3 g/L of NPCu were applied by impregnation on radiata pine sapwood. Test penetration under AWPA A3-91 standard was carried out, and wood decay tests were performed according to EN 113, with slight modifications. The results of penetration for 1 g/L CuNP showed an irregular total penetration, and the samples impregnated with 3 g/L showed a total penetration with uniform concentration (blue color in all cross sections). The impregnation wood mass losses due to fungal exposure were significantly reduced, regardless of the concentration of the solution or the fungus. In impregnated wood samples, exposure to G. trabeum resulted ML values of 2.70% and 1.19% for 1 g/L and 3 g/L CuNP, respectively, and exposure to P. placenta resulted in 4.02% and 0.70%-ML values for 1 g/L and 3 g/L CuNP, respectively. In this study, the penetration analysis confirmed a uniform distribution inside the wood, and both concentrations were effective against the tested fungi, giving mass loss values lower than 5%. Therefore, future research in wood preservatives should focus on new nanomaterials that are more efficient and environmentally friendly. Acknowledgments: CONICYT FONDEF IDeA I+D 2019, grant number ID19I10122.

Keywords: copper nanoparticles, fungal degradation, radiata pine wood, wood preservation

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Authors: Opeyemi Elujulo, Aderonke Okoya, Kehinde Awokoya

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Molecularly imprinted polymers (MIP) for the adsorption of pyridine (PYD) was obtained from PYD (the template), styrene (the functional monomer), divinyl benzene (the crosslinker), benzoyl peroxide (the initiator), and water (the porogen). When the template was removed by solvent extraction, imprinted binding sites were left in the polymer material that are capable of selectively rebinding the target molecule. The material was characterized by Fourier transform infrared spectroscopy and differential scanning calorimetry. Batch adsorption experiments were performed to study the adsorption of the material in terms of adsorption kinetics, isotherms, and thermodynamic parameters. The results showed that the imprinted polymer exhibited higher affinity for PYD compared to non-imprinted polymer (NIP).

Keywords: molecularly imprinted polymer, bulk polymerization, environmental pollutant, adsorption

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Authors: Khaled Benyounes, Abderrahmane Mellak

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The rheology of aqueous solutions of polyelectrolyte (polyanionic cellulose, PAC) at high molecular weight was investigated using a controlled stress rheometer. Several rheological measurements; viscosity measurements, creep compliance tests at a constant low shear stress and oscillation experiments have been performed. The concentrations ranged by weight from 0.01 to 2.5% of PAC. It was found that the aqueous solutions of PAC do not exhibit a yield stress, the flow curves of PAC over a wide range of shear rate (0 to 1000 s-1) could be described by the cross model and the Williamson models. The critical concentrations of polymer c* and c** have been estimated. The dynamic moduli, i.e., storage modulus (G’) and loss modulus (G’’) of the polymer have been determined at frequency sweep from 0.01 to 10 Hz. At polymer concentration above 1%, the modulus G’ is superior to G’’. The relationships between the dynamic modulus and concentration of polymer have been established. The creep-recovery experiments demonstrated that polymer solutions show important viscoelastic properties of system water-PAC when the concentration of the polymer increases.

Keywords: polyanionic cellulose, viscosity, creep, oscillation, cross model

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Authors: S. Said, Asmaa A. Abdulrahman

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MoOₓ/Al₂O₃ based catalyst has long been widely used as an active catalyst in oxidative desulfurization reaction due to its high stability under severe reaction conditions and high resistance to sulfur poisoning. In this context, 4 & 9wt.% MoO₃ grafted on mesoporous γ-Al₂O₃ has been synthesized using the modified atomic layer deposition (ALD) method. Another MoO₃/Al₂O₃ sample was prepared by the conventional wetness impregnation (IM) method, for comparison. The effect of the preparation methods on the metal-support interaction was evaluated using different characterization techniques, including X-ray diffraction, X-ray photoelectron spectroscopy (XPS), N₂-physisorption, transmission electron microscopy (TEM), H₂- temperature-programmed reduction and FT-IR. Oxidative desulfurization (ODS) reaction of the model fuel oil was used as a probe reaction to examine the catalytic efficiency of the prepared catalysts. ALD method led to samples with much better physicochemical properties than those of the prepared one via the impregnation method. However, the 9 wt.%MoO₃/Al₂O₃ (ALD) catalyst in the ODS reaction of model fuel oil shows enhanced catalytic performance with ~90%, which has been attributed to the more Mo⁶⁺ surface concentrations relative to Al³⁺ with large pore diameter and surface area. The kinetic study shows that the ODS of DBT follows a pseudo first-order rate reaction.

Keywords: mesoporous Al₂O₃, xMoO₃/Al₂O₃, atomic layer deposition, wetness impregnation, ODS, DBT

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Authors: Binod Shrestha, Sandrine Hoppe, Thierry Ghislain, Phillipe Marchal, Nicolas Brosse, Anthony Dufour

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The thermochemical conversion of lignin has received an increasing interest in the frame of different biorefinery concepts for the production of chemicals or energy. It is needed to better understand the physical and chemical conversion of lignin for feeder and reactor designs. In-situ rheology reveals the viscoelastic behaviour of lignin upon thermal conversion. The softening, re-solidification (char formation), swelling and shrinking behaviours are quantified during pyrolysis in real-time [1]. The in-situ rheology of an alkali lignin (Protobind 1000) was conducted in high torque controlled strain rheometer from 35°C to 400°C with a heating rate of 5°C.min-1. The swelling, through glass phase transition overlapped with depolymerization, and solidification (crosslinking and “char” formation) are two main phenomena observed during lignin pyrolysis. The onset of temperatures for softening and solidification for this lignin has been found to be 141°C and 248°C respectively. An ex-situ characterization of lignin/char residues obtained at different temperatures after quenching in the rheometer gives a clear understanding of the pathway of lignin degradation. The lignin residues were sampled from the mid-point temperatures of the softening range and solidification range to study the chemical transformations undergoing. Elemental analysis, FTIR and solid state NMR were conducted after quenching the solid residues (lignin/char). The quenched solid was also extracted by suitable solvent and followed by acetylation and GPC-UV analysis. The combination of 13C NMR and GPC-UV reveals the depolymerization followed by crosslinking of lignin/char. NMR and FTIR provide the evolution of functional moieties upon temperature. Physical and chemical mechanisms occurring during lignin pyrolysis are accounted in this study. Thanks to all these complementary methods.

Keywords: pyrolysis, bio-chemicals, valorization, mechanism, softening, solidification, cross linking, rheology, spectroscopic methods

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