Application of Molecular Materials in the Manufacture of Flexible and Organic Devices for Photovoltaic Applications

Many sustainable approaches to generate electric energy have emerged in the last few decades; one of them is through solar cells. Yet, this also has the disadvantage of highly polluting inorganic semiconductor manufacturing processes. Therefore, the use of molecular semiconductors must be considered. In this work, allene compounds C24H26O4 and C24H26O5 were used as dopants to manufacture semiconductor films based on PbPc by high-vacuum evaporation technique. IR spectroscopy was carried out to determine the phase and any significant chemical changes which may occur during the thermal evaporation. According to UV-visible spectroscopy and Tauc’s model, the deposition process generated thin films with an activation energy range of 1.47 eV to 1.55 eV for direct transitions and 1.29 eV to 1.33 eV for indirect transitions. These values place the manufactured films within the range of low bandgap semiconductors. The flexible devices were manufactured: polyethylene terephthalate (PET), Indium tin oxide (ITO)/organic semiconductor/Cubic Close Packed (CCP). The characterization of the devices was carried out by evaluating electrical conductivity using the four-probe collinear method. I-V curves were obtained under different lighting conditions at room temperature. OS1 (PbPc/C24H26O4) showed an Ohmic behavior, while OS2 (PbPc/C24H26O5) reached higher current values at lower voltages. The results obtained show that the semiconductor devices doped with allene compounds can be used in the manufacture of optoelectronic devices.

Catalytic Pyrolysis of Sewage Sludge for Upgrading Bio-Oil Quality Using Sludge-Based Activated Char as an Alternative to HZSM5

Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contain four obvious stages and the main decomposition reaction occurred in the range of 200-600 °C. Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2 and 3 were in the range of 6.67-20.37 kJ/mol for SS; 1.51-6.87 kJ/mol for HZSM5; and 2.29-9.17 kJ/mol for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1 and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with HZSM5 and AC were in the total range of C4-C17 with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds while the presence of HZSM5 and AC dropped to 7.3% and 13.02%, respectively. Meanwhile, generation of value-added chemicals such as light aromatic compounds were significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR and TGA techniques. Overall, this research demonstrated that AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

Kinetic Parameter Estimation from Thermogravimetry and Microscale Combustion Calorimetry

Flammability analysis of extruded polystyrene (XPS) has become crucial due to its utilization as insulation material for energy efficient buildings. Using the Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa methods, the degradation kinetics of two pure XPS from the local market, red and grey ones, were obtained from the results of thermogravity analysis (TG) and microscale combustion calorimetry (MCC) experiments performed under the same heating rates. From the experiments, it was discovered that red XPS released more heat than grey XPS and both materials showed two mass loss stages. Consequently, the kinetic parameters for red XPS were higher than grey XPS. A comparative evaluation of activation energies from MCC and TG showed an insignificant degree of deviation signifying an equivalent apparent activation energy from both methods. However, different activation energy profiles as a result of the different chemical pathways were presented when the dependencies of the activation energies on extent of conversion for TG and MCC were compared.

Influence of Moringa Leaves Extract on the Response of Hb Molecule to Dose Rates’ Changes: II. Relaxation Time and Its Thermodynamic Driven State Functions

Irradiation deposits energy through ionisation changing the bio-system’s net dipole, allowing the use of dielectric parameters and thermodynamic state functions related to these parameters as biophysical detectors to electrical inhomogeneity within the biosystem. This part is concerned with the effect of Moringa leaves extract, natural supplement, on the response of the biosystem to two different dose rates of irradiation. Having Hb molecule as a representative to the biosystem to be least invasive to the biosystem, dielectric measurements were used to extract the relaxation time of certain process found in the Hb spectrum within the indicated frequency window and the interrelated thermodynamic state functions were calculated from the deduced relaxation time. The results showed that relaxation time was decreased for both dose rates indicating a strong influence of Moringa on the response of biosystem and consequently Hb molecule. This influence was presented in the relaxation time and other parameters as well.

Aging Evaluation of Ammonium Perchlorate/Hydroxyl Terminated Polybutadiene-Based Solid Rocket Engine by Reactive Molecular Dynamics Simulation and Thermal Analysis

Propellants based on Hydroxyl Terminated Polybutadiene/Ammonium Perchlorate (HTPB/AP) are the most commonly used in most of the rocket engines used by the Brazilian Armed Forces. This work aimed at the possibility of extending its useful life (currently in 10 years) by performing kinetic-chemical analyzes of its energetic material via Differential Scanning Calorimetry (DSC) and also performing computer simulation of aging process using the software Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS). Thermal analysis via DSC was performed in triplicates and in three heating ratios (5 ºC, 10 ºC, and 15 ºC) of rocket motor with 11 years shelf-life, using the Arrhenius equation to obtain its activation energy, using Ozawa and Kissinger kinetic methods, allowing comparison with manufacturing period data (standard motor). In addition, the kinetic parameters of internal pressure of the combustion chamber in 08 rocket engines with 11 years of shelf-life were also acquired, for comparison purposes with the engine start-up data.

Activation Parameters of the Low Temperature Creep Controlling Mechanism in Martensitic Steels

Martensitic steels with an ultimate tensile strength beyond 2000 MPa are applied in the powertrain of vehicles due to their excellent fatigue strength and high creep resistance. However, the creep controlling mechanism in martensitic steels at ambient temperatures up to 423 K is not evident. The purpose of this study is to review the low temperature creep (LTC) behavior of martensitic steels at temperatures from 363 K to 523 K. Thus, the validity of a logarithmic creep law is reviewed and the stress and temperature dependence of the creep parameters α and β are revealed. Furthermore, creep tests are carried out, which include stepped changes in temperature or stress, respectively. On one hand, the change of the creep rate due to a temperature step provides information on the magnitude of the activation energy of the LTC controlling mechanism and on the other hand, the stress step approach provides information on the magnitude of the activation volume. The magnitude, the temperature dependency, and the stress dependency of both material specific activation parameters may deliver a significant contribution to the disclosure of the nature of the LTC rate controlling mechanism.

Molding Properties of Cobalt-Chrome-Based Feedstocks Used in Low-Pressure Powder Injection Molding

Low-pressure powder injection molding is an emerging technology for cost-effectively producing complex shape metallic parts with the proper dimensional tolerances, either in high or in low production volumes. In this study, the molding properties of cobalt-chrome-based feedstocks were evaluated for use in a low-pressure powder injection molding process. The rheological properties of feedstock formulations were obtained by mixing metallic powder with a proprietary wax-based binder system. Rheological parameters such as reference viscosity, shear rate sensitivity index, and activation energy for viscous flow, were extracted from the viscosity profiles and introduced into the Weir model to calculate the moldability index. Feedstocks were experimentally injected into a spiral mold cavity to validate the injection performance calculated with the model.

Formation of Volatile Iodine from Cesium Iodide Aerosols: A DFT Study

Periodic DFT calculations were performed to study the chemistry of CsI particles and the possible release of volatile iodine from CsI surfaces for nuclear safety interest. The results show that water adsorbs at low temperature associatively on the (011) surface of CsI, while water desorbs at higher temperatures. On the other hand, removing iodine species from the surface requires oxidizing the surface one time for each removed iodide atom. The activation energy of removing I2 from the surface in the presence of two OH is 1,2 eV.

Influence of Organic Modifier Loading on Particle Dispersion of Biodegradable Polycaprolactone/Montmorillonite Nanocomposites

Natural sodium montmorillonite (NaMMT), Cloisite Na+ and two organophilic montmorillonites (OMMTs), Cloisites 20A and 15A were used. Polycaprolactone (PCL)/MMT composites containing 1, 3, 5, and 10 wt% of Cloisite Na+ and PCL/OMMT nanocomposites containing 5 and 10 wt% of Cloisites 20A and 15A were prepared via solution intercalation technique to study the influence of organic modifier loading on particle dispersion of PCL/ NaMMT composites. Thermal stabilities of the obtained composites were characterized by thermal analysis using the thermogravimetric analyzer (TGA) which showed that in the presence of nitrogen flow the incorporation of 5 and 10 wt% of filler brings some decrease in PCL thermal stability in the sequence: Cloisite Na+>Cloisite 15A > Cloisite 20A, while in the presence of air flow these fillers scarcely influenced the thermoxidative stability of PCL by slightly accelerating the process. The interaction between PCL and silicate layers was studied by Fourier transform infrared (FTIR) spectroscopy which confirmed moderate interactions between nanometric silicate layers and PCL segments. The electrical conductivity (σ) which describes the ionic mobility of the systems was studied as a function of temperature and showed that σ of PCL was enhanced on increasing the modifier loading at filler content of 5 wt%, especially at higher temperatures in the sequence: Cloisite Na+

Preparation and Conductivity Measurements of LSM/YSZ Composite Solid Oxide Electrolysis Cell Anode Materials

One of the most promising anode materials for solid oxide electrolysis cell (SOEC) application is the Sr-doped LaMnO3 (LSM) which is known to have a high electronic conductivity but low ionic conductivity. To increase the ionic conductivity or diffusion of ions through the anode, Yttria-stabilized Zirconia (YSZ), which has good ionic conductivity, is proposed to be combined with LSM to create a composite electrode and to obtain a high mixed ionic and electronic conducting anode. In this study, composite of lanthanum strontium manganite and YSZ oxide, La0.8Sr0.2MnO3/Zr0.92Y0.08O2 (LSM/YSZ), with different wt.% compositions of LSM and YSZ were synthesized using solid-state reaction. The obtained prepared composite samples of 60, 50, and 40 wt.% LSM with remaining wt.% of 40, 50, and 60, respectively for YSZ were fully characterized for its microstructure by using powder X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), and Scanning electron microscope/Energy dispersive spectroscopy (SEM/EDS) analyses. Surface morphology of the samples via SEM analysis revealed a well-sintered and densified pure LSM, while a more porous composite sample of LSM/YSZ was obtained. Electrochemical impedance measurements at intermediate temperature range (500-700 °C) of the synthesized samples were also performed which revealed that the 50 wt.% LSM with 50 wt.% YSZ (L50Y50) sample showed the highest total conductivity of 8.27x10-1 S/cm at 600 oC with 0.22 eV activation energy.

Dissolution Leaching Kinetics of Ulexite in Sodium Dihydrogen Phosphate Solutions

The aim of the present study was to investigate the dissolution kinetics of ulexite in sodium dihydrogen phosphate in a mechanical agitation system and also to declare an alternative reactant to produce the boric acid. Reaction temperature, concentration of sodium dihydrogen phosphate, stirring speed, solid-liquid ratio, and ulexite particle size were selected as parameters. The experimental results were successfully correlated by using linear regression and a statistical program. Dissolution curves were evaluated in order to test the shrinking core models for solid-fluid systems. It was observed that increase in the reaction temperature and decrease in the solid/liquid ratio causes an increase in the dissolution rate of ulexite. The activation energy was found to be 36.4 kJ/mol. The leaching of ulexite was controlled by diffusion through the ash (or product) layer.

Reaction Kinetics of Biodiesel Production from Refined Cottonseed Oil Using Calcium Oxide

Power law approximation was used in this study to evaluate the reaction orders of calcium oxide, CaO catalyzed transesterification of refined cottonseed oil and methanol. The kinetics study was carried out at temperatures of 45, 55 and 65 oC. The kinetic parameters such as reaction order 2.02 and rate constant 2.8 hr-1g-1cat, obtained at the temperature of 65 oC best fitted the kinetic model. The activation energy, Ea obtained was 127.744 KJ/mol. The results indicate that the transesterification reaction of the refined cottonseed oil using calcium oxide catalyst is approximately second order reaction.

Hybrid Advanced Oxidative Pretreatment of Complex Industrial Effluent for Biodegradability Enhancement

The study explores the hybrid combination of Hydrodynamic Cavitation (HC) and Subcritical Wet Air Oxidation-based pretreatment of complex industrial effluent to enhance the biodegradability selectively (without major COD destruction) to facilitate subsequent enhanced downstream processing via anaerobic or aerobic biological treatment. Advanced oxidation based techniques can be less efficient as standalone options and a hybrid approach by combining Hydrodynamic Cavitation (HC), and Wet Air Oxidation (WAO) can lead to a synergistic effect since both the options are based on common free radical mechanism. The HC can be used for initial turbulence and generation of hotspots which can begin the free radical attack and this agitating mixture then can be subjected to less intense WAO since initial heat (to raise the activation energy) can be taken care by HC alone. Lab-scale venturi-based hydrodynamic cavitation and wet air oxidation reactor with biomethanated distillery wastewater (BMDWW) as a model effluent was examined for establishing the proof-of-concept. The results indicated that for a desirable biodegradability index (BOD: COD - BI) enhancement (up to 0.4), the Cavitation (standalone) pretreatment condition was: 5 bar and 88 min reaction time with a COD reduction of 36 % and BI enhancement of up to 0.27 (initial BI - 0.17). The optimum WAO condition (standalone) was: 150oC, 6 bar and 30 minutes with 31% COD reduction and 0.33 BI. The hybrid pretreatment (combined Cavitation + WAO) worked out to be 23.18 min HC (at 5 bar) followed by 30 min WAO at 150oC, 6 bar, at which around 50% COD was retained yielding a BI of 0.55. FTIR & NMR analysis of pretreated effluent indicated dissociation and/or reorientation of complex organic compounds in untreated effluent to simpler organic compounds post-pretreatment.

Effects of Cerium Oxide Nanoparticle Addition in Diesel and Diesel-Biodiesel Blends on the Performance Characteristics of a CI Engine

An experimental investigation is carried out to establish the performance characteristics of a compression ignition engine while using cerium oxide nanoparticles as additive in neat diesel and diesel-biodiesel blends. In the first phase of the experiments, stability of neat diesel and diesel-biodiesel fuel blends with the addition of cerium oxide nanoparticles is analyzed. After series of experiments, it is found that the blends subjected to high speed blending followed by ultrasonic bath stabilization improves the stability. In the second phase, performance characteristics are studied using the stable fuel blends in a single cylinder four stroke engine coupled with an electrical dynamometer and a data acquisition system. The cerium oxide acts as an oxygen donating catalyst and provides oxygen for combustion. The activation energy of cerium oxide acts to burn off carbon deposits within the engine cylinder at the wall temperature and prevents the deposition of non-polar compounds on the cylinder wall results reduction in HC emissions. The tests revealed that cerium oxide nanoparticles can be used as additive in diesel and diesel-biodiesel blends to improve complete combustion of the fuel significantly.

Kinetics Study for the Recombinant Cellulosome to the Degradation of Chlorella Cell Residuals

In this study, lipid-deprived residuals of microalgae were hydrolyzed for the production of reducing sugars by using the recombinant Bacillus cellulosome, carrying eight genes from the Clostridium thermocellum ATCC27405. The obtained cellulosome was found to exist mostly in the broth supernatant with a cellulosome activity of 2.4 U/mL. Furthermore, the Michaelis-Menten constant (Km) and Vmax of cellulosome were found to be 14.832 g/L and 3.522 U/mL. The activation energy of the cellulosome to hydrolyze microalgae LDRs was calculated as 32.804 kJ/mol.

Porous Ni Electrodes Modified with Au Nanoparticles for Hydrogen Production

In this work new macroporous Ni electrodes modified with Au nanoparticles for hydrogen production have been developed. The supporting macroporous Ni electrodes have been obtained by means of the electrodeposition at high current densities. Then, the Au nanoparticles were synthesized and added to the electrode surface. The electrocatalytic behaviour of the developed electrocatalysts was studied by means of pseudo-steady-state polarization curves, electrochemical impedance spectroscopy (EIS) and hydrogen discharge curves. The size of the Au synthetized nanoparticles shows a monomodal distribution, with a very sharp band between 10 and 50 nm. The characteristic parameters d10, d50 and d90 were 14, 20 and 31 nm respectively. From Tafel polarization data has been concluded that the Au nanoparticles improve the catalytic activity of the developed electrodes towards the HER respect to the macroporous Ni electrodes. EIS permits to obtain the electrochemically active area by means of the roughness factor value. All the developed electrodes show roughness factor values in the same order of magnitude. From the activation energy results it can be concluded that the Au nanoparticles improve the intrinsic catalytic activity of the macroporous Ni electrodes.

Durability Enhancement of CaSO4 in Repetitive Operation of Chemical Heat Pump

An important problem for the CaSO4/CaSO4・1/2H2O Chemical heat pump (CHP) is that the material is deactivated through repetitive reaction between hydration and dehydration in which the crystal phase of the material is transformed from III-CaSO4 to II-CaSO4. We investigated suppression on the phase change by adding a sulfated compound. The most effective material was MgSO4. MgSO4 doping increased the durability of CaSO4 in the actual CHP repetitive cycle of hydration/dehydration to 3.6 times that of undoped CaSO4. The MgSO4-doped CaSO4 showed a higher phase transition temperature and activation energy for crystal transformation from III-CaSO4 to II-CaSO4. MgSO4 doping decreased the crystal lattice size of CaSO4・1/2H2O and II-CaSO4 to smaller than that of undoped CaSO4. Modification of the crystal structure is considered to be related to the durability change in CaSO4 resulting from MgSO4 doping.

Dissolution Leaching Kinetics of Ulexite in Disodium Hydrogen Phosphate Solutions

Ulexite (Na2O.2CaO.5B2O3.16H2O) is boron mineral that is found in large quantities in the Turkey and world. In this study, the dissolution of this mineral in the disodium hydrogen phosphate solutions has been studied. Temperature, concentration, stirring speed, solid liquid ratio and particle size were selected as parameters. The experimental results were successfully correlated by linear regression using Statistica program. Dissolution curves were evaluated shrinking core models for solid-fluid systems. It was observed that increase in the reaction temperature and decrease in the solid/liquid ratio causes an increase the dissolution rate of ulexite. The activation energy was found to be 63.4 kJ/mol. The leaching of ulexite was controlled by chemical reaction.

Investigation of Dissolution in Diammonium Hydrogen Phosphate Solutions of Gypsum

Gypsum (CaSO4.2H2O) is a mineral that is found in large quantities in the Turkey and in the World. In this study, the dissolution of this mineral in the diammonium hydrogen phosphate solutions has been studied. The dissolution and dissolution kinetics of gypsum in diammonium hydrogen phosphate solutions will be useful for evaluating of solid wastes containing gypsum. Parameters such as diammonium hydrogen phosphate concentration, temperature and stirring speed affecting on the dissolution rate of the gypsum in diammonium hydrogen phosphate solutions were investigated. In experimental studies have researched effectiveness of the selected parameters. The dissolution of gypsum were examined in two parts at low and high temperatures. The experimental results were successfully correlated by linear regression using Statistica program. Dissolution curves were evaluated shrinking core models for solidfluid systems. The activation energy was found to be 34.58 kJ/mol and 44.45 kJ/mol for the low and the high temperatures. The dissolution of gypsum was controlled by chemical reaction both low temperatures and high temperatures.

Properties of Bio-Phenol Formaldehyde Composites Filled with Empty Fruit Bunch Fiber

Bio-composites derived from plant fiber and/or bioderived polymer, are likely more ecofriendly and demonstrate competitive performance with petroleum based composites. In this research, the bio phenol-formaldehyde (bio-PF) was used as a matrix and oil palm empty fruit bunch fiber (EFB) as reinforcement. The matrix was synthesized via liquefaction and condensation to enhance the combination of phenol and formaldehyde, during the process. Then, the bio-PF was mixed with different percentage of EFB (5%, 10%, 15% and 20%) and molded at 180oC. The samples that viewed under scanning electron microscopy (SEM) showed an excellent wettability and interaction between EFB and matrix. Samples of 10% EFB gave the optimum properties of impact and hardness meanwhile sample 15% of EFB gave the highest reading of flexural modulus (MOE) and flexural strength (MOR). For thermal stability analysis, it was found that the weight loss and the activation energy (Ea) of the bio-composites samples were decreased as the filler content increased.