Synthesis and characterisation of interfacial layers in organic solar cells

The quest for renewable energy sources has led to growing attention in the research of organic photovoltaics (OPVs), as a promising alternative to fossil fuels, since these devices have low manufacturing costs and attractive end-user qualities, such as ease of installation and maintenance. Wide application of OPVs is majorly limited by the devices lifetime. With the development of new encapsulation materials, some degradation factors, such as water and oxygen ingress, can almost be excluded, whereas the thermal degradation of the devices remains a major issue. Two aspects have to be addressed to solve the problem of thermal instability: bulk effects in the photoactive layer and interfacial effects at the photoactive layer/charge-transporting layers. In this work, the interface between photoactive layer and electron-transporting zinc oxide (ZnO) in devices with inverted architecture was engineered by introducing polymeric interlayers, based on zinc-binding ligands, such as 3,4-dihydroxybenzene and 8-hydroxyquinoline. Also, a cross-linkable layer of poly(3,4-dimethoxystyrene) and its fullerene derivative were studied. At first, controlled reversible addition-fragmentation chain transfer (RAFT) polymerisation was employed to achieve well-defined polymers in a range of molar masses, all bearing a chain-end functionality for further modifications. Resulting polymers have been fully characterised, including their thermal and optical properties, and introduced as interlayers to study their effect on the initial device performance and thermal stability. Poly(3,4-dihydroxystyrene) and its fullerene derivative were found unsuitable for application in devices as they increased the work function of ZnO and created a barrier for electron extraction. On the other hand, their parental polymer, poly(3,4-dimethoxystyrene), and its fullerene derivative, upon cross-linking, resulted in enhanced efficiency and stability of devices, if compared to control. Polymers based on 8-hydroxyquinoline ligand had a negative effect on the initial stability of the devices, but increased the lifetime of the cells under accelerated thermal stress. Comprehensive studies of the key mechanisms, determining efficiency, such as charge generation and extraction, were performed by using time-resolved electrical and spectroscopic techniques, in order to understand in detail the effect of the interlayers on the device performance. Obtained results allow deeper insight into mechanisms of degradation that limit the lifetime of devices and prompt the design of better materials for the interface stabilisation.

Direct activation of microcrystalline zeolites

In this work a direct activation route of zeolites is assessed. It consists of NH4-exchanging the as-synthesized solids before removing the organic template. Calcination afterwards serves to combust the organic template and creates the Brønsted sites directly; thus applying merely a single thermal step. This method simplifies their activation and the material suffers less thermal stress. The approach was particularly effective for microcrystalline beta and ferrierite zeolites. Thorough investigation of the template content and materials' texture points out to three relevant effects that can explain the effective exchange process: partial removal of the template during exchange creates substantial microporosity (ferrierite), the remaining template is reorganized within the pores (ferrierite) and finally, void space can exist due to the non-perfect matching between the network and template (beta). This shorter method appears suited for microcrystalline zeolites; it was ineffective for crystalline MFI types. © 2013 Elsevier B.V. All rights reserved.

Impact of high pCO2 and warmer temperatures on the process of silica biomineralization in the sponge Mycale grandis

Siliceous sponges have survived pre-historical mass extinction events caused by ocean acidification and recent studies suggest that siliceous sponges will continue to resist predicted increases in ocean acidity. In this study, we monitored silica biomineralization in the Hawaiian sponge Mycale grandis under predicted pCO2 and sea surface temperature scenarios for 2100. Our goal was to determine if spicule biomineralization was enhanced or repressed by ocean acidification and thermal stress by monitoring silica uptake rates during short-term (48 h) experiments and comparing biomineralized tissue ratios before and after a long-term (26 d) experiment. In the short-term experiment, we found that silica uptake rates were not impacted by high pCO2 (1050 µatm), warmer temperatures (27°C), or combined high pCO2 with warmer temperature (1119 µatm; 27°C) treatments. The long-term exposure experiments revealed no effect on survival or growth rates of M. grandis to high pCO2 (1198 µatm), warmer temperatures (25.6°C), or combined high pCO2 with warmer temperature (1225 µatm, 25.7°C) treatments, indicating that M. grandis will continue to prosper under predicted increases in pCO2 and sea surface temperature. However, ash-free dry weight to dry weight ratios, subtylostyle lengths, and silicified weight to dry weight ratios decreased under conditions of high pCO2 and combined pCO2 warmer temperature treatments. Our results show that rising ocean acidity and temperature have marginal negative effects on spicule biomineralization and will not affect sponge survival rates of M. grandis.

Effects of in situ CO2 enrichment on structural characteristics, photosynthesis, and growth of the Mediterranean seagrass Posidonia oceanica

Seagrass is expected to benefit from increased carbon availability under future ocean acidification. This hypothesis has been little tested by in situ manipulation. To test for ocean acidification effects on seagrass meadows under controlled CO2/pH conditions, we used a Free Ocean Carbon Dioxide Enrichment (FOCE) system which allows for the manipulation of pH as continuous offset from ambient. It was deployed in a Posidonia oceanica meadow at 11 m depth in the Northwestern Mediterranean Sea. It consisted of two benthic enclosures, an experimental and a control unit both 1.7 m**3, and an additional reference plot in the ambient environment (2 m**2) to account for structural artifacts. The meadow was monitored from April to November 2014. The pH of the experimental enclosure was lowered by 0.26 pH units for the second half of the 8-month study. The greatest magnitude of change in P. oceanica leaf biometrics, photosynthesis, and leaf growth accompanied seasonal changes recorded in the environment and values were similar between the two enclosures. Leaf thickness may change in response to lower pH but this requires further testing. Results are congruent with other short-term and natural studies that have investigated the response of P. oceanica over a wide range of pH. They suggest any benefit from ocean acidification, over the next century (at a pH of 7.7 on the total scale), on Posidonia physiology and growth may be minimal and difficult to detect without increased replication or longer experimental duration. The limited stimulation, which did not surpass any enclosure or seasonal effect, casts doubts on speculations that elevated CO2 would confer resistance to thermal stress and increase the buffering capacity of meadows.

Desempenho reprodutivo de varrões e matrizes suínas de diferentes linhagens durante as estações do ano

The industrial Brazilian pig farming despite of the constant advance in the genetic improvement, nutrition, and in handling, seasonality problems occur in the production of weaned piglet, mainly due to the stations of the year that can impact directly in the profitability. These problems can be deepen due to breed and line of decent used in Brazil are all source from tempered weather countries. To the pig farmer it's difficult to determine the relations between indoor temperature of the barns, relative humidity of the air and top thermal amplitude which can provide good reproductive rates for the boars and arrays lodged in conventional barns. The lack research to production of environmental indices of easy interpretation to pigs, which are not dependent of complicated handling machines and also which are not expensive is considered as a negative factor from the producers. the objective os this experiment is evaluate the effects of the stations of the year over the reproductive performance of the boars Agroceres PIC 425, Agroceres PIC 337 and D.B. Dambred LM 6200, and of arrays Agroceres Canborough 22, Penarlan Naima e DB90 Danbred, in addition develop an environmental index with easy interpretation and use to the pig farmers of the region of Uberlândia - MG, using the maxim temperatures, rainfall monthly accumulated and of the thermal amplitude of the barn. The features rated during the stations of the years 2013 and 2014 were the volume and spermatic quality of the boars and the mainly reproductive indexes of the arrays as the total number of piglets born alive and total number of weaned piglets/ array/ parturition. The station of the year which had the worst results in the reproductive feature of the boars and arrays was the spring. Boars from different line of decent are sensitive to the effects of stress of the heat of spring causing lowest volume, concentration and problems in the spermatic morphology (p<0,05). The spring prejudice the reproductive indexes of arrays from different line of decent (p<0,05) and the pig farmers of Uberlândia are subjected to operating losses and income evasion due to the thermal stress in the reproduction that added can reach $150.000,00 annual for each 1000 arrays lodged/year.

(Table 1) Sample descriptions and results: Carbon, lipid, and kerogen analyses, at DSDP Leg 64 Holes

Pleistocene sediments in the Guaymas Basin, Gulf of California, have been intruded by sills and their organic matter thus subjected to thermal stress. Sediment samples from DSDP/IPOD Sites 477, 478, and 481, and samples of thermally unaltered materials from Sites 474 and 479 were analyzed to characterize the lipids and kerogens and to evaluate the effects of the intrusive thermal stresses. The lipids of the thermally unaltered samples are derived from microbial and terrestrial higher-plant detritus. The samples from the sill proximities contain the distillates, and those adjacent to the sills contain essentially no lipids. The pyrograms of the kerogens from the unaltered samples reflect their predominantly autochthonous microbial origin. When compared with the unaltered samples, the pyrograms of the altered kerogen samples reflect the thermal effects by a reduction in the complexity of the products. Kerogens adjacent to the sills produced little or no pyrolysis products. The effects of intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter, as confirmed by these data.

Analyses of hydrocarbon gases and sulphate in sediments from the King George Basin, Antarctica

Thermogenic hydrocarbons, formed by the thermal alteration of organic matter, are encountered in several piston core stations in the King George Basin, Anatarctica. These hemipelagic sediments are being deposited in an area of active hydrothermalism, associated with the back-arc spreading in the Bransfield Strait. The lateral extent of sediments infiltrated by the hydrothermally influenced interstitial fluids is characterized by basalt diapiric intrusions and is delineated by an acoustically turbid zone in the sediments of the eastern part of the basin. Iron-sulphide-bearing veins and fractures cut across the sediment in several cores; they appear to be conduits for flow of hydrothermally altered fluids. These zones have the highest C2+ and ethene contents. The thermogenic hydrocarbons have molecular C1/(C2 + C3) ratios typically < 50 and delta13CH4 values between -38? and -48?, indicating an organic source which has undergone strong thermal stress. Several sediment cores also have mixed gas signatures, which indicate the presence of substantial amounts of bacterial gas, predominantly methane. Hydrocarbon generation in the King George Basin is thought to be a local phenomenon, resulting from submarine volcanism with temperatures in the range 70-150°C. There are no apparent seepages of hydrocarbons into the water column, and it is not believed that significant accumulation of thermogenic hydrocarbons reside in the basin.

Investigation of escape response of Norwegian Pecten maximus

The ongoing process of ocean acidification already affects marine life and, according to the concept of oxygen- and capacity limitation of thermal tolerance (OCLTT), these effects may be exacerbated at the boarders of the thermal tolerance window. We studied the effects of elevated CO2 concentrations on clapping performance and energy metabolism of the commercially important scallop Pecten maximus. Individuals were exposed for at least 30 days to 4°C (winter) or to 10°C (spring/summer) at either ambient (0.04 kPa, normocapnia) or predicted future PCO2 levels (0.11 kPa, hypercapnia). Cold (4°C) exposed groups revealed thermal stress exacerbated by PCO2 indicated by a high mortality overall and its increase from 55% under normocapnia to 90% under hypercapnia. We therefore excluded the 4°C groups from further experimentation. Scallops at 10°C showed impaired clapping performance following hypercapnic exposure. Force production was significantly reduced although the number of claps was unchanged between normo- and hypercapnia exposed scallops. The difference between maximal and resting metabolic rate (aerobic scope) of the hypercapnic scallops was significantly reduced compared to normocapnic animals, indicating a reduction in net aerobic scope. Our data confirm that ocean acidification narrows the thermal tolerance range of scallops resulting in elevated vulnerability to temperature extremes and impairs the animal's performance capacity with potentially detrimental consequences for its fitness and survival in the ocean of tomorrow.

Applications for nanomaterials in critical technologies

This thesis is devoted to the development, synthesis, properties, and applications of nano materials for critical technologies, including three areas: (1) Microbial contamination of drinking water is a serious problem of global significance. About 51% of the waterborne disease outbreaks in the United States can be attributed to contaminated ground water. Development of metal oxide nanoparticles, as viricidal materials is of technological and fundamental scientific importance. Nanoparticles with high surface areas and ultra small particle sizes have dramatically enhanced efficiency and capacity of virus inactivation, which cannot be achieved by their bulk counterparts. A series of metal oxide nanoparticles, such as iron oxide nanoparticles, zinc oxide nanoparticles and iron oxide-silver nanoparticles, coated on fiber substrates was developed in this research for evaluation of their viricidal activity. We also carried out XRD, TEM, SEM, XPS, surface area measurements, and zeta potential of these nanoparticles. MS2 virus inactivation experiments showed that these metal oxide nanoparticle coated fibers were extremely powerful viricidal materials. Results from this research suggest that zinc oxide nanoparticles with diameter of 3.5 nm, showing an isoelectric point (IEP) at 9.0, were well dispersed on fiberglass. These fibers offer an increase in capacity by orders of magnitude over all other materials. Compared to iron oxide nanoparticles, zinc oxide nanoparticles didn’t show an improvement in inactivation kinetics but inactivation capacities did increase by two orders of magnitude to 99.99%. Furthermore, zinc oxide nanoparticles have higher affinity to viruses than the iron oxide nanoparticles in presence of competing ions. The advantages of zinc oxide depend on high surface charge density, small nanoparticle sizes and capabilities of generating reactive oxygen species. The research at its present stage of development appears to offer the best avenue to remove viruses from water. Without additional chemicals and energy input, this system can be implemented by both points of use (POU) and large-scale use water treatment technology, which will have a significant impact on the water purification industry. (2) A new family of aliphatic polyester lubricants has been developed for use in micro-electromechanical systems (MEMS), specifically for hard disk drives that operate at high spindle speeds (>15000rpm). Our program was initiated to address current problems with spin-off of the perfluoroether (PFPE) lubricants. The new polyester lubricant appears to alleviate spin-off problems and at the same time improves the chemical and thermal stability. This new system provides a low cost alternative to PFPE along with improved adhesion to the substrates. In addition, it displays a much lower viscosity, which may be of importance to stiction related problems. The synthetic route is readily scalable in case additional interest emerges in other areas including small motors. (3) The demand for increased signal transmission speed and device density for the next generation of multilevel integrated circuits has placed stringent demands on materials performance. Currently, integration of the ultra low-k materials in dual Damascene processing requires chemical mechanical polishing (CMP) to planarize the copper. Unfortunately, none of the commercially proposed dielectric candidates display the desired mechanical and thermal properties for successful CMP. A new polydiacetylene thermosetting polymer (DEB-TEB), which displays a low dielectric constant (low-k) of 2.7, was recently developed. This novel material appears to offer the only avenue for designing an ultra low k dielectric (1.85k), which can still display the desired modulus (7.7Gpa) and hardness (2.0Gpa) sufficient to withstand the process of CMP. We focused on further characterization of the thermal properties of spin-on poly (DEB-TEB) ultra-thin film. These include the coefficient of thermal expansion (CTE), biaxial thermal stress, and thermal conductivity. Thus the CTE is 2.0*10-5K-1 in the perpendicular direction and 8.0*10-6 K-1 in the planar direction. The low CTE provides a better match to the Si substrate which minimizes interfacial stress and greatly enhances the reliability of the microprocessors. Initial experiments with oxygen plasma etching suggest a high probability of success for achieving vertical profiles.

Small pelagics in a changing ocean : Biological responses of sardine early stages to warming

Small pelagic fishes are known to respond rapidly to changes in ocean climate. In this study, we evaluate the effects of future environmental warming (+2°C) during the early ontogeny of the European sardine, Sardina pilchardus. Warming reduced the survival of 30-day-old larvae by half. Length at hatching increased with temperature as expected, but no significant effect was observed on the length and growth at 30 days post-hatching. Warming did not significantly affect the thermal tolerance of sardine larvae, even though the mean lethal temperature increased by 1°C. In the warm conditions, sardine larvae showed signs of thermal stress, indicated by a pronounced increase in larval metabolism (Q 10 = 7.9) and a 45% increase in the heat shock response. Lipid peroxidation was not significantly affected by the higher temperature, even though the mean value doubled. Warming did not affect the time larvae spent swimming, but decreased by 36% the frequency of prey attacks. Given the key role of these small pelagics in the trophic dynamics off the Western Iberian upwelling ecosystem, the negative effects of warming on the early stages may have important implications for fish recruitment and ecosystem structure.

Comparação entre técnicas de aferição da temperatura corpórea em micos-estrela cativos (Callithrix penicillata) e sua relação com parâmetros hematológicos, peso corporal e umidade e temperatura do ambiente

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Ciências da Saúde, Programa de Pós-Graduação em Ciências da Saúde, 2015.

Comparação entre técnicas de aferição da temperatura corpórea em micos-estrela cativos (Callithrix penicillata) e sua relação com parâmetros hematológicos, peso corporal e umidade e temperatura do ambiente

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Ciências da Saúde, Programa de Pós-Graduação em Ciências da Saúde, 2015.

Physical Design Methodologies for Low Power and Reliable 3D ICs

As the semiconductor industry struggles to maintain its momentum down the path following the Moore's Law, three dimensional integrated circuit (3D IC) technology has emerged as a promising solution to achieve higher integration density, better performance, and lower power consumption. However, despite its significant improvement in electrical performance, 3D IC presents several serious physical design challenges. In this dissertation, we investigate physical design methodologies for 3D ICs with primary focus on two areas: low power 3D clock tree design, and reliability degradation modeling and management. Clock trees are essential parts for digital system which dissipate a large amount of power due to high capacitive loads. The majority of existing 3D clock tree designs focus on minimizing the total wire length, which produces sub-optimal results for power optimization. In this dissertation, we formulate a 3D clock tree design flow which directly optimizes for clock power. Besides, we also investigate the design methodology for clock gating a 3D clock tree, which uses shutdown gates to selectively turn off unnecessary clock activities. Different from the common assumption in 2D ICs that shutdown gates are cheap thus can be applied at every clock node, shutdown gates in 3D ICs introduce additional control TSVs, which compete with clock TSVs for placement resources. We explore the design methodologies to produce the optimal allocation and placement for clock and control TSVs so that the clock power is minimized. We show that the proposed synthesis flow saves significant clock power while accounting for available TSV placement area. Vertical integration also brings new reliability challenges including TSV's electromigration (EM) and several other reliability loss mechanisms caused by TSV-induced stress. These reliability loss models involve complex inter-dependencies between electrical and thermal conditions, which have not been investigated in the past. In this dissertation we set up an electrical/thermal/reliability co-simulation framework to capture the transient of reliability loss in 3D ICs. We further derive and validate an analytical reliability objective function that can be integrated into the 3D placement design flow. The reliability aware placement scheme enables co-design and co-optimization of both the electrical and reliability property, thus improves both the circuit's performance and its lifetime. Our electrical/reliability co-design scheme avoids unnecessary design cycles or application of ad-hoc fixes that lead to sub-optimal performance. Vertical integration also enables stacking DRAM on top of CPU, providing high bandwidth and short latency. However, non-uniform voltage fluctuation and local thermal hotspot in CPU layers are coupled into DRAM layers, causing a non-uniform bit-cell leakage (thereby bit flip) distribution. We propose a performance-power-resilience simulation framework to capture DRAM soft error in 3D multi-core CPU systems. In addition, a dynamic resilience management (DRM) scheme is investigated, which adaptively tunes CPU's operating points to adjust DRAM's voltage noise and thermal condition during runtime. The DRM uses dynamic frequency scaling to achieve a resilience borrow-in strategy, which effectively enhances DRAM's resilience without sacrificing performance. The proposed physical design methodologies should act as important building blocks for 3D ICs and push 3D ICs toward mainstream acceptance in the near future.

Variações anátomo-fisiológicas face à aclimatação sazonal - estudo em vacas leiteiras com diferente potencial leiteiro

O presente estudo teve como objetivo a caracterização de variações anátomo-fisiológicas que decorrem do processo de aclimatação sazonal em bovinos leiteiros com alto (Altas) e baixo (Baixas) potencial leiteiro, com vista a selecionar animais que conciliem bons desempenhos produtivos e índices de adaptabilidade que possibilitem a mudança de homeostase face às condições climáticas presentes no clima mediterrânico. O estudo foi realizado numa herdade comercial, situada no Alentejo, utilizando 13 vacas multíparas (6 Baixas e 7 Altas), durante três períodos: P1 (animais aclimatados ao verão; presença de stresse térmico); P2 (animais aclimatados ao verão; termoneutralidade); P3 (animais aclimatados ao inverno; termoneutralidade). Em stresse térmico (P1), verificaram-se maiores esforços termolíticos e maiores armazenamentos de calor no grupo das Altas. Observou-se também que a produção de leite das Altas foi afetada pelo stresse térmico, evidênciando uma redução 24-48h após os valores de temperatura retal mais elevados. Nesta situação, as Baixas apresentaram uma variação na produção oposta à das Altas. Em P1, os valores de proteína e de gordura no leite foram significativamente mais baixos que em P3, em ambos os grupos. A ureia no leite foi significativamente mais elevada nas Altas durante o P1, revelando potencial como biomarcador de stresse térmico. Do P1 para o P3 obser-vou-se uma redução gradual do hematócrito, da hemoglobina e da triiodotironina (T3). As Altas apresentaram uma maior redução de triiodotironina (T3) que as Baixas, como consequência de uma maior intensidade de aclimatação. Nos pelos não se registaram diferenças entre os períodos, o que contrasta com alguma bibliografia. Porém, a ausência da insolação direta poderá ter sido um fator determinante; ABSTRACT: The main objective of the present study was the characterization of anatomical and physiological variations that occur in the seasonal acclimatization process of dairy cows with high (Altas) and low (Baixas) milk yield potential. In this way it should be possible to do a selection of animals with good productive traits and also with adaptability indexes that allow a change in homeostasis to cope with the climatic conditions of the mediterranean climate. Meteorological, clinical, productive, physiological and anatomical data were collected. The study was conducted in an Alentejo's dairy farm, using 13 multiparous cows (6 with low milk yield and 7 with high milk yield), during three periods: P1 (animals acclimated to summer, in heat stress); P2 (animals acclimated to summer, thermoneutrality); P3 (animals acclimated to winter; thermoneutrality). In thermal stress (P1), the high milk yield group (Altas) shown greater thermolytic efforts and also higher heat storage. The milk yield in this group was also affected by heat stress, showing a decrease in production when the rectal temperature increased, with a delay of 24-42 hours. In this situation the Baixas group showed an opposite milk production variation. In P1, the protein and fat milk content was lower than in P3, in both groups. Milk urea levels were significantly higher during P1 in the Altas group, revealing potential as an heat stress biomarker. Hematocrit, hemoglobin and triiodothyronine (T3) values gradualy decreased from P1 to P3. T3 values were lower in Altas than in Baixas group, as a consequence of a more intense acclimatization. The hair analysis didn’t show the standard seasonal acclimatization process, indicating the absence of direct solar radiation as a determinant factor.

Effect of different feed-rate in bone drilling: experimental and numerical study

The behaviour of bone tissue during drilling has been subject of recent studies due to its great importance. Because of thermal nature of the bone drilling, high temperatures and thermal mechanical stresses are developed during drilling that affect the process quality. However, there is still a lack information with regard to the distribution of mechanical and thermal stresses during bone drilling. The present paper describes a sequentially coupled thermal-stress analysis to assess the mechanical and thermal stress distribution during bone drilling. A three-dimensional thermo-mechanical model was developed using the ANSYS/LSDYNA finite element code under different drilling conditions. The model incorporates the dynamic characteristics of drilling process, as well as the thermo-mechanical properties of the involved materials. Experimental tests with polyurethane foam materials were also carried out. It was concluded that the use of higher feed-rates lead to a decrease of normal stresses and strains in the foam materials. The experimental and numerical results were compared and showed good agreement. The proposed numerical model could be used to predict the better drilling parameters and minimize the bone injuries.