A photophysical study of excited state dynamics in donor-acceptor copolymer photovoltaic blends

This thesis deals with the investigation of charge generation and recombination processes in three different polymer:fullerene photovoltaic blends by means of ultrafast time-resolved optical spectroscopy. The first donor polymer, namely poly[N-11"-henicosanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT), is a mid-bandgap polymer, the other two materials are the low-bandgap donor polymers poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole) (PCPDTBT) and poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (PSBTBT). Despite their broader absorption, the low-bandgap polymers do not show enhanced photovoltaic efficiencies compared to the mid-bandgap system.rnrnTransient absorption spectroscopy revealed that energetic disorder plays an important role in the photophysics of PCDTBT, and that in a blend with PCBM geminate losses are small. The photophysics of the low-bandgap system PCPDTBT were strongly altered by adding a high boiling point cosolvent to the polymer:fullerene blend due to a partial demixing of the materials. We observed an increase in device performance together with a reduction of geminate recombination upon addition of the cosolvent. By applying model-free multi-variate curve resolution to the spectroscopic data, we found that fast non-geminate recombination due to polymer triplet state formation is a limiting loss channel in the low-bandgap material system PCPDTBT, whereas in PSBTBT triplet formation has a smaller impact on device performance, and thus higher efficiencies are obtained.rn

Solid-State Compatibilization of Immiscible Polymer Blends: Cryogenic Milling and Solid-State Shear Pulverization

The blending of common polymers allows for the rapid and facile synthesis of new materials with highly tunable properties at a fraction of the costs of new monomer development and synthesis. Most blends of polymers, however, are completely immiscible and separate into distinct phases with minimal phase interaction, severelydegrading the performance of the material. Cross-phase interactions and property enhancement can be achieved with these blends through reactive processing or compatibilizer addition. A new class of blend compatibilization relies on the mechanochemical reactions between polymer chains via solid-state, high energy processing. Two contrasting mechanochemical processing techniques are explored in this thesis: cryogenic milling and solid-state shear pulverization (SSSP). Cryogenic milling is a batch process where a milling rod rapidly impacts the blend sample while submerged within a bath of liquid nitrogen. In contrast, SSSP is a continuous process where blend components are subjected to high shear and compressive forces while progressing down a chilled twin-screw barrel. In the cryogenic milling study, through the application of a synthesized labeledpolymer, in situ formation of copolymers was observed for the first time. The microstructures of polystyrene/high-density polyethylene (PS/HDPE) blends fabricated via cryomilling followed by intimate melt-state mixing and static annealing were found to be morphologically stable over time. PS/HDPE blends fabricated via SSSP also showed compatibilization by way of ideal blend morphology through growth mechanisms with slightly different behavior compared to the cryomilled blends. The new Bucknell University SSSP instrument was carefully analyzed and optimized to produce compatibilized polymer blends through a full-factorial experiment. Finally, blends of varying levels of compatibilization were subjected to common material tests to determine alternative means of measuring and quantifying compatibilization,

Performance and emissions testing of a small two stroke engine using mid-level ethanol blends

With the introduction of the mid-level ethanol blend gasoline fuel for commercial sale, the compatibility of different off-road engines is needed. This report details the test study of using one mid-level ethanol fuel in a two stroke hand held gasoline engine used to power line trimmers. The study sponsored by E3 is to test the effectiveness of an aftermarket spark plug from E3 Spark Plug when using a mid-level ethanol blend gasoline. A 15% ethanol by volume (E15) is the test mid-level ethanol used and the 10% ethanol by volume (E10) was used as the baseline fuel. The testing comprises running the engine at different load points and throttle positions to evaluate the cylinder head temperature, exhaust temperature and engine speed. Raw gas emissions were also measured to determine the impact of the performance spark plug. The low calorific value of the E15 fuel decreased the speed of the engine along with reduction in the fuel consumption and exhaust gas temperature. The HC emissions for E15 fuel and E3 spark plug increased when compared to the base line in most of the cases and NO formation was dependent on the cylinder head temperature. The E3 spark plug had a tendency to increase the temperature of the cylinder head irrespective of fuel type while reducing engine speed.

Technique to measure heats of reaction of Ti-B, Al-Ti-B, and Al-Ti-B4C powder blends

In this research, a modification to initiation aid ignition in bomb calorimetry that involves systemically blending levels of boron and potassium nitrate initiation aids with a bulk structural energetic elemental power blend is developed. A regression is used to estimate the nominal heat of reaction for the primary reaction. The technique is first applied to the synthesis of TiB2 as a validation study to see if close proximity to literature values can be achieved. The technique is then applied to two systems of interest, Al-Ti-B, and Al-Ti-B4C. In all three investigations, x-ray diffraction is used to characterize the product phases of the reactions to determine the extent and identity of the product phases and any by-products that may have formed as a result of adding the initiation aid. The experimental data indicates the technique approximates the heat of reaction value for the synthesis of TiB2 from Ti-B powder blends and the formation of TiB2 is supported by volume fraction analysis by x-ray diffraction. Application to the Al-Ti-B and Al-Ti-B4C blends show some correlation with variation of the initiation aid, with x-ray diffraction showing the formation of equilibrium products. However, these blends require further investigation to resolve more complex interactions and rule out extraneous variables.

Hydration of C3S, C2S and their Blends. Micro- and Nanoscale Characterization

This study forms part of wider research conducted under a EU 7 th Framework Programme (COmputationally Driven design of Innovative CEment-based materials or CODICE). The ultimate aim is the multi-scale modelling of the variations in mechanical performance in degraded and non-degraded cementitious matrices. The model is being experimentally validated by hydrating the main tri-calcium silicate (T1-C3S) and bi-calcium silicate (β-C2S), phases present in Portland cement and their blends. The present paper discusses micro- and nanoscale studies of the cementitious skeletons forming during the hydration of C3S, C2S and 70 % / 30 % blends of both C3S/C2S and C2S/C3S with a water/cement ratio of 0.4. The hydrated pastes were characterized at different curing ages with 29 Si NMR, SEM/TEM/EDS, BET, and nanoindentation. The findings served as a basis for the micro- and nanoscale characterization of the hydration products formed, especially C-S-H gels. Differences were identified in composition, structure and mechanical behaviour (nanoindentation), depending on whether the gels formed in C3S or C2S pastes. The C3S gels had more compact morphologies, smaller BET-N2 specific surface area and lesser porosity than the gels from C2S-rich pastes. The results of nanoindentation tests appear to indicate that the various C-S-H phases formed in hydrated C3S and C2S have the same mechanical properties as those formed in Portland cement paste. Compared to the C3S sample, the hydrated C2S specimen was dominated by the loose-packed (LP) and the low-density (LD) C-S-H phases, and had a much lower content of the high density (HD) C-S-H phase

Biokerosene from Babassu and Camelina Oils: production and properties of their blends with fossil kerosene

Babassu and camelina oils have been transesterified with methanol by the classical homogeneous basic catalysis method with good yields. The babassu fatty acid methyl ester (FAME) has been subjected to fractional distillation at vacuum, and the low boiling point fraction has been blended with two types of fossil kerosene, a straight-run atmospheric distillation cut (hydrotreated) and a commercial Jet-A1. The camelina FAME has been blended with the fossil kerosene without previous distillation. The blends of babassu biokerosene and Jet-A1 have met some of the specifications selected for study of the ASTM D1655 standard: smoke point, density, flash point, cloud point, kinematic viscosity, oxidative stability and lower heating value. On the other hand, the blends of babassu biokerosene and atmospheric distillation cut only have met the density parameter and the oxidative stability. The blends of camelina FAME and atmospheric distillation cut have met the following specifications: density, kinematic viscosity at −20 °C, and lower heating value. With these preliminary results, it can be concluded that it would be feasible to blend babassu and camelina biokerosenes prepared in this way with commercial Jet-A1 up to 10 vol % of the former, if these blends prove to accomplish all the ASTM D1655-09 standards.

Perspectives on the design and use of direct alcohol fuel cells fed by alcohol blends

The fast-growing power demand by portable electronic devices has promoted the increase of global production of portable PEM fuel cell, a quarter of them consist of direct methanol fuel cell (DMFC) units. These present the advantage of being fuelled directly with a liquid fuel, as well as direct ethanol fuel cells (DEFC) do.

Biokerosene from coconut, babassu, camelina and palm kernel oils: production and properties of their blends with fossil kerosene

On December 20th 2006 the European Commission approved a law proposal to include the civil aviation sector in the European market of carbon dioxide emission rights [European Union Emissions Trading System, EUETS). On July 8th 2009, the European Parliament and Conseil agreed that all flights leaving or landing in the EU airports starting from January 1st 2012 should be included in the EUETS. On November 19th 2008, the EU Directive 2008/101/CE [1] included the civil aviation activities in the EUETS, and this directive was transposed by the Spanish law 13/2010 of July 5th 2010 [2]. Thus, in 2012 the aviation sector should reduce their emissions to 97 % of the mean values registered in the period 2004-2006, and for 2013 these emission reductions should reach 95 % of the mean values for that same period. Trying to face this situation, the aviation companies are planning seriously the use of alternative jet fuels to reduce their greenhouse gas emissions and to lower their costs. However, some US airlines have issued a lawsuit before the European Court of Justice based in that this EU action violates a long standing worldwide aviation treaty, the Chicago convention of 1944, and also the Chinese aviation companies have rejected to pay any EU carbon dioxide tax [3]. Moreover, the USA Departments of Agriculture and Energy and the Navy will invest a total of up to $150 million over three years to spur production of aviation and marine biofuels for commercial and military applications [4]. However, the jet fuels should fulfill a set of extraordinarily sensitive properties to guarantee the safety of planes and passengers during all the flights.

Influence of the composition of natural gas-hydrogen blends (HCNG) on performance an CO2 emissions of a spark ignition engine

Addition of hydrogen to natural gas could be a short-term alternative to nowadays fossil fuels as the emissions of greenhouse gases may be reduced. The aim of this study is to evaluate the performance and emissions of a park ignition engine fuelled with pure natural gas, pure hydrogen and different blends of hydrogen and natural gas (HCNG). The increase of the hydrogen fraction leads to variations in the cylinder pressure and CO2 emissions. In this work, a combustion model based on thermodynamic equations is used considering separated zones for the burned and unburned gases. The results show that the maximum cylinder pressure gets higher as the fraction of hydrogen in the blend increases. The presence of hydrogen in the blend leads to a drecrease in the CO2 emissions. Due to hydrogen properties, leaner fuel-air mixtures can be used along with the appropiate spark timing, leading to an engine emissions improvement without a performance worsening.

Sensory and texture properties of mashed potato incorporated wigh inulin and olive oil blends

The effect of adding different ratios of inulin and extra virgin olive oil blends, formulated without (MPA) and with cryoprotectants (MPB), on texture properties of fresh mashed potatoes and frozen/thawed mashed potatoes was studied. Inulin and extra virgin olive oil behaved like soft ?llers, but inulin was associated with increased?brousness and extra virgin olive oil with increased creaminess. In the total dataset and frozen mashed potatoes, frozen/thawed mashed potatoes, and MPA subgroups, component 1 was a contrast between mechanical and surface textural attributes, whereas in MPB samples component 1 was determined by geometrical attributes. Addition of inulin at 30 g/kg and extra virgin olive oil at 45 g/kg is recommended.

CO2 emissions from a spark ignition engine operatin on natural-hydrogen blends (HCNG)

The addition of hydrogen to natural gas could be a short-term alternative to today’s fossil fuels, as greenhouse gas emissions may be reduced. The aim of this study is to evaluate the emissions and performance of a spark ignition engine fuelled by pure natural gas, pure hydrogen, and different blends of hydrogen and natural gas (HCNG). Increasing the hydrogen fraction leads to variations in cylinder pressure and CO2 emissions. In this study, a combustion model based on thermodynamic equations is used, considering separate zones for burned and unburned gases. The results show that the maximum cylinder pressure rises as the fraction of hydrogen in the blend increases. The presence of hydrogen in the blend leads to a decrease in CO2 emissions. Due to the properties of hydrogen, leaner fuel–air mixtures can be used along with the appropriate spark timing, leading to an improvement in engine emissions with no loss of performance.

Oxygen extended sooting index of FAME blends with aviation kerosene

The use of biofuels in the aviation sector has economic and environmental benefits. Among the options for the production of renewable jet fuels, hydroprocessed esters and fatty acids (HEFA) have received predominant attention in comparison with fatty acid methyl esters (FAME), which are not approved as additives for jet fuels. However, the presence of oxygen in methyl esters tends to reduce soot emissions and therefore particulate matter emissions. This sooting tendency is quantified in this work with an oxygen-extended sooting index, based on smoke point measurements. Results have shown considerable reduction in the sooting tendency for all biokerosenes (produced by transesterification and eventually distillation) with respect to fossil kerosenes. Among the tested biokerosenes, that made from palm kernel oil was the most effective one, and nondistilled methyl esters (from camelina and linseed oils) showed lower effectiveness than distilled biokerosenes to reduce the sooting tendency. These results may constitute an additional argument for the use of FAME’s as blend components of jet fuels. Other arguments were pointed out in previous publications, but some controversy has aroused over the use of these components. Some of the criticism was based on the fact that the methods used in our previous work are not approved for jet fuels in the standard methods and concluded that the use of FAME in any amount is, thus, inappropriate. However, some of the standard methods are not updated for considering oxygenated components (like the method for obtaining the lower heating value), and others are not precise enough (like the methods for measuring the freezing point), whereas some alternative methods may provide better reproducibility for oxygenated fuels.

Airplane materials compatibility with blends of fossil kerosene JET A1 with biokerosenes from babassu, palm kernel and coconut oils

The aviation companies are facing some problems that argue in favor of biofuels: Rising cost of traditional fuel: from 0.71 USD/gallon in May 2003 to 3.09 USD/gallon in January 2012. Environmental concerns: direct emissions from aviation account for about 3 % of the EU’s total greenhouse gas emissions. The International Civil Aviation Organization (ICAO) forecasts that by 2050 they could grow by a further 300-700 %. On December 20th 2006 the European Commission approved a law proposal to include the civil aviation sector in the European market of carbon dioxide emission rights (European Union Emissions Trading System, EUETS)

Blends of babassu, palm kernal and coconut mame with fossil kerosene: low carbon number methyl esters as a possible source for renewable jet fuel

Three different oils: babassu, coconut and palm kernel have been transesterified with methanol. The fatty acid methyl esters (FAME) have been subjected to vacuum fractional distillation, and the low boiling point fractions have been blended with fossil kerosene at three different proportions: 5, 10 and 20% vol.

Blends of babassu, palm kernel and coconut fame with fossil kerosene. Technical aspects of low carbon number methyl esters as a possible source for renewable jet fuel

State of the Art. Process and Distillation. Fuel Characterization. Fuel Compatibility Tests