102 resultados para Nucleação


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Este trabalho apresenta um estudo da solidificação de metais puros utilizando o modelo de campo de fases. O modelo é utilizado para simular a solidificação com o intuito de obter a morfologia da interface sólido-líquido sob diversas condições de transferência de calor. Foram realizados testes de validação comparando as morfologias da interface sólido-líquido obtida com as morfologias apresentadas em trabalhos anteriores para os casos bi e tridimensionais. O modelo do campo de fases adotado consiste principalmente de duas equações diferenciais: uma para calcular a variável de campo de fases e outra para calcular o campo de temperaturas. As equações foram solucionadas numericamente para um oitavo do domínio devido a simetria do problema. Os cálculos do modelo indicam que um sólido esférico com um raio inicial menor que o raio crítico de nucleação refunde. Entretanto uma esfera de raio maior cresce. Quando o sólido inicial cresce em uma malha numérica relativamente grosseira, a forma do sólido desvia da forma esférica devido perturbações na interface sólido-líquido. Quando a malha é refinada, as perturbações não são detectadas; contudo, quando introduzidas artificialmente as perturbações crescem e distorcem o formato esférico.

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No presente trabalho foram avaliados processos alternativos de dessalinização visando a recuperação e reuso da água contida em salmouras concentradas, sendo o processo de cristalização assistida por destilação por membranas (MDC) investigado com profundidade. Foi desenvolvido um modelo diferencial para o processo de destilação por membranas por contato direto (DCMD), contemplando métodos termodinâmicos rigorosos para sistemas aquosos de eletrólitos fortes, bem como mecanismos de transferência de calor e massa e efeitos de polarização de temperatura e concentração característicos deste processo de separação. Com base em simulações realizadas a partir do modelo matemático assim desenvolvido, foram investigados os principais parâmetros que influenciam o projeto de um módulo de membranas para DCMD. O modelo foi posteriormente estendido com equações de balanço de massa e energia adicionais para incluir a operação de cristalização e desta forma representar o processo de MDC. De posse dos resultados das simulações e do modelo estendido, foi desenvolvido um método hierárquico para o projeto de processos de MDC, com o objetivo de conferir características de rastreabilidade e repetibilidade a esta atividade. Ainda a partir do modelo MDC foram discutidos aspectos importantes em MDC como a possibilidade de nucleação e crescimento de cristais sobre a superfície das membranas, bem como o comportamento do processo com sais com diferentes características de solubilidade e largura da zona metaestável. Verificou-se que para sais cuja solubilidade varia muito pouco com a temperatura e que possuem zona metaestável com pequena largura, caso do NaCl, a operação com resfriamento no cristalizador não é viável pois aumenta excessivamente o consumo energético do processo, sendo nesses casos preferível a operação \"isotérmica\" - sem resfriamento no cristalizador - e o convívio com a possibilidade de nucleação no interior do módulo. No extremo oposto, observou-se que para sais com grande variabilidade da solubilidade com a temperatura, um pequeno resfriamento no cristalizador é suficiente para garantir condições de subsaturação no interior do módulo, sem grande ônus energético para o processo. No caso de sais com pequena variabilidade da solubilidade com a temperatura, mas com largura da zona metaestável elevada, existe certo ônus energético para a operação com resfriamento do cristalizador, porém não tão acentuado como no caso de sais com zona metaestável estreita. Foi proposto um fluxograma alternativo para o processo de MDC, onde foi introduzido um circuito de pré-concentração da alimentação antes do circuito de cristalização, para o caso de alimentação com soluções muito diluídas. Este esquema proporcionou um aumento do fluxo permeado global do processo e consequentemente uma redução na área total de membrana requerida. Verificou-se que através do processo com préconcentração da alimentação de 5% até 10% em massa - no caso de dessalinização de uma solução de NaCl - foi possível reduzir-se a área total da membrana em 27,1% e o consumo energético específico do processo em 10,6%, quando comparado ao processo sem pré-concentração. Foram desenvolvidas ferramentas úteis para o projeto de processos de dessalinização por MDC em escala industrial.

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Devido à preocupação com o meio ambiente e o volume crescente de resíduos plástico em aterros sanitários, os polímeros biodegradáveis estão sendo estudados extensivamente. Um deles é o PLA. Apesar de possuir propriedades comparáveis a polímeros commodities e polímeros de engenharia, ainda é necessário melhorar certas características do PLA, como resistência ao impacto. Para isso, a nanocelulose (NC) pode ser usada sem alterações significativas na biodegradação polimérica. Este estudo teve como objetivo obter a nanocelulose, caracteriza-la e incorpora-la ao poli(ácido láctico) (PLA), assim como, estudar as propriedades térmicas, morfológicas e mecânicas do compósito obtido. A NC foi obtida por hidrólise ácida utilizando ácido fosfórico e posteriormente foi silanizada com três silanos distintos. As nanopartículas foram caracterizadas por Birrefringência, Microscopia Eletrônica de Transmissão (MET), Termogravimetria (TG), Potencial Zeta, Espectroscopia Vibracional de Absorção no Infravermelho com Transformada de Fourier (FTIR) e Difração de Raio X (DRX). Com as imagens obtidas pelo MET foi possível medir o tamanho das partículas de NC. E então obter a razão de aspecto de 82 e o limite de percolação de 1,1% em massa, confirmando a morfologia de nanofibra. De acordo as analises TG\'s, a presença de NC silanizada aumentou o início da degradação térmica. Os compósitos, contendo 3% em massa de NC, foram obtidos por fusão em câmara de mistura e moldados por injeção. Os compósitos foram caracterizados por FTIR, Cromatografia de Permeação em Gel (GPC), TG, Calorimetria Exploratória Diferencial (DSC), Microscopia Eletrônica de Varredura (MEV-FEG), Impacto e Tração. As análises dos compósitos mostraram que a NC atuou como agente de nucleação, facilitando a cristalização do PLA, além de a NC ter atuado como reforço na matriz polimérica melhorando as propriedades mecânicas.

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Micro cracking during service is a critical problem in polymer structures and polymer composite materials. Self-healing materials are able to repair micro cracks, thus their preventing propagation and catastrophic failure of structural components. One of the self-healing approaches presented in the literature involves the use of solvents which react with the polymer. The objective of this research is to investigate a procedure to encapsulate solvents in halloysite nanotubes to promote self-healing ability in epoxy. Healing is triggered by crack propagation through embedded nanotubes in the polymer, which then release the liquid sovent into the crack plane. Two solvents were considered in this work: dimethylsulfoxide (DMSO) and nitrobenzene. The nanotubes were coated using the layer-by-layer technique of oppositely charged polyelectrolytes: cetyltrimethylammonium bromide (CTAB) and sodium polyacrylate. Solvent encapsulation was verified by X-ray diffraction (XRD), Fourier transform infrared (FTIR), analysis thermogravimetry (TGA), adsorption and desorption of nitrogen and scanning electron microscopy (SEM). The introduction of the solvent DMSO into the cavity of the nanotubes was confirmed by the techniques employed. However, was not verified with nitrobenzene only promoted clay aggregation. The results suggest that the CTAB reacted with the halloystite to form a sealing layer on the surface of the nanotubes, thus encapsulating the solvent, while this was not verified using sodium polyacrylate.

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In the last decades, analogue modelling has been used in geology to improve the knowledge of how geological structures are nucleated, how they grow and what are the main important points in such processes. The use of this tool in the oil industry, to help seismic interpretations and mainly to search for structural traps contributed to disseminate the use of this tool in the literature. Nowadays, physical modelling has a large field of applications, since landslide to granite emplacement along shear zones. In this work, we deal with physical modelling to study the influence of mechanical stratifications in the nucleation and development of faults and fractures in a context of orthogonal and conjugated oblique basins. To simulate a mechanical stratigraphy we used different materials, with distinct physical proprieties, such as gypsum powder, glass beads, dry clay and quartz sand. Some experiments were run along with a PIV (Particle Image Velocimetry), an instrument that shows the movement of the particles to each deformation moment. Two series of experiments were studied: i) Series MO: We tested the development of normal faults in a context of an orthogonal (to the extension direction) basin. Experiments were run taking into account the change of materials and strata thickness. Some experiments were done with sintectonic sedimentation. We registered differences in the nucleation and growth of faults in layers with different rheological behavior. The gypsum powder layer behaves in a more competent mode, which generates a great number of high angle fractures. These fractures evolve to faults that exhibit a higher dip than when they cross less competent layers, like the one of quartz sand. This competent layer exhibits faulted blocks arranged in a typical domino-style. Cataclastic breccias developed along the faults affecting the competent layers and showed different evolutional history, depending on the deforming stratigraphic sequence; ii) Series MOS2: Normal faults were analyzed in conjugated sub-basins (oblique to the extension direction) developed in a sequence with and without rheological contrast. In experiments with rheological contrast, two important grabens developed along the faulted margins differing from the subbasins with mechanical stratigraphy. Both experiments developed oblique fault systems and, in the area of sub-basins intersection, faults traces became very curved.

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This study makes an approach to the Morro Agudo Community (Cisterna) located in Catalão city(GO) rural area where stands the Maria Bárbara Sucena Municipal School. This school center is a result of getting together several small and isolated schools, which worked, scattered in many rural communities in the region. After this centralization in a single school, many students had to move along inconvenient distance to get their classes. Morro Agudo Community (Cisterna) was outstanding at garlic cultivation throughout the 1990`s when eventually this activity came to a decline. The region is constituted by properties of small tract of land. The landowners come from a Portuguese background and there are, in addit ion, migrant workers from the northeast region of Brazil. These northeasterners work for these local landowners, and that brings an additional meaning to the social relations in the region and to the rural schooling. The social and cultural diversity of the region has a feedback at the school arising tensions in many ways. In the teaching and learning process the school deals with this diversity, combined with rules and goals that, in the end, delivers a geography teaching not able to value the local knowledge accumulated in the region by its own inhabitants. New methodological approaches to rural school communities emerged out of the analysis of these unmet expectations. Furthermore, this study takes into consideration some “residues”, that means not all events are fit into programs; there are unintended consequences in an open process. All these are object of deep review in this doctoral dissertation. In this community, an analysis of the public policies implemented by Federal and municipal governments to rural schools communities in Brazil was conducted. The way in which public policies toward rural communities are implemented at the schools was reviewed; the goals they pursue and the role played by textbooks are also object of analysis. This study questions the relevance of this tools, mainly if they meet the real needs of the local people. The social representations of teachers and students are considered carefully based on their everyday lives and experiences.

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O presente trabalho incidiu sobre uma família de eletrólitos sólidos cerâmicos à base de óxido de zircónio, incluindo ainda óxido de magnésio como dopante, normalmente designados de Mg-PSZ (zircónia parcialmente estabilizada com magnésia). Dependendo da composição e condições de processamento (perfil de sinterização) estes materiais podem exibir interessantes combinações de propriedades mecânicas, térmicas e elétricas que permitem a sua utilização no fabrico de sensores de oxigénio para metais fundidos. O uso de sensores é hoje essencial numa lógica de controlo de processo e eficiência energética. No sentido de tentar compreender como influenciar estas propriedades, exploraram-se diversos níveis de dopante (de 2,5 até 10 mol%, com acréscimos de 2,5 mol% de MgO), diversas velocidades de arrefecimento (2, 3 e 5 °C.min-1) a partir de uma condição igual de patamar de sinterização (1700 °C, 3 horas), e ainda alguns ciclos de sinterização mais complexos, com patamares intermédios inseridos no processo de arrefecimento, com o objetivo de tentar alterar os processos de nucleação e crescimento de fases. Na realidade, as transformações de fases a que este tipo de materiais se encontra sujeito (cúbica  tetragonal  monoclínica, para temperaturas decrescentes), possuem diferentes velocidades características (uma é difusiva a outra displaciva), permitindo este tipo de condicionamento. Os materiais obtidos foram alvo de caracterização estrutural e microestrutural, complementada por um conjunto de outras técnicas de caracterização física como a espectroscopia de impedância, dilatometria e dureza. Os resultados obtidos confirmam a complexidade das relações entre processamento e comportamento mas permitiram identificar condições de potencial interesse prático para as aplicações em vista.

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Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

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The goal of this study was to compare areas under different forest restoration technologies in relation to abundance, richness, diversity and composition of the present fauna in the litter and soil. The treatments evaluated were: natural regeneration (RN); high diversity tree plantations (L) and nucleation (N). An area of secondary forest was included in the study as a reference of soil conditions. The experimental design was in randomized block with four replications. Samples were collected for extraction of mesofauna (October/2012; July and October/2013) and macrofauna (June and October/2013) in six points of each plot, totaling 24 samples per treatment. For collecting soil macrofauna was used TSBF method. The mesofauna was collected with a metal cylinder and extracted by Berlese-Tüllgren funnel. Litter and soil were collected separately at each point and the fauna was identified level of class/taxonomic order. The springtails were classified using morphotypes. In total, considering the mesofauna, macrofauna and three times collected were accounted 28618 organisms. In relation soil mesofauna, the evaluated technologies did not differ, after three years of restoration, in relation to total abundance of organisms and community composition. The Shannon diversity index (H), in soil mesofauna, followed a human impact gradient. This index was higher in natural regeneration, which not was undergone technical interventions and showed higher moisture in the soil. The tree planting technology, under the control of volunteer plants in total area, showed lower H index. In the case of litter mesofauna, the technologies did not differ in relation the mean richness, total abundance of organisms and community composition. Considering edaphic macrofauna, technologies did not differ in relation to the abundance and richness, and in the evaluation of June/2013, RN showed higher H index and differed in relation to the community composition of other technologies. In October/2013 evaluation, the differences between the technologies in relation to H index were narrower and these did not differ in terms of composition of soil macrofauna community. In litter macrofauna, in June/2013, the RN presented greater richness and H index when compared to other technologies and in evaluation October/2013 technologies did not differ in relation to community composition, richness and mean abundance of organisms. In the case of springtails, technologies after three years in the restoration process, did not differ in relation to the abundance, richness and composition of Collembola community for different morphotypes. The secondary forest, in relation to forest restoration technologies, presented greater abundance of saprophages, predators and greater diversity of morphotypes of springtails. From these results it, we recommended to natural regeneration by to have the lowest cost of deployment, followed by nucleation and online planting. The animals should be monitored over time, in the restoration technologies, as well as the physical and chemical characteristics of the soil, in order to understand the possible changes in the composition and diversity of organisms.

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The replacement of native vegetation by other land uses is one of the main degrading ecosystem agents, being the most important component of terrestrial environments, natural or with different levels of human disturbance, besides being the main substrate used by plants to obtain conditions soil for its development. In this context, there is the need to adopt the use and sustainable management of land systems. The study aimed to evaluate what is forest restoration system more efficient degraded areas, based on the potential recovery of physical, chemical, carbon and biological activity in the soil. The work was conducted in a forest restoration area UTFPR- Campus two neighbors, whose experiment was established in October 2010. The experimental design is completely randomized, with four replications and experimental plot of 40 m wide by 54 m long ( 2160 m2) were collected and six sampling points per plot. The soil is classified as a Typic. The models evaluated are: 1 - natural or passive regeneration; 2 - Nucleation; 3 - Planting trees in the total area under lines fill and diversity (total planting); 4 - Reference area (forest). The collection of soil samples in layers of 0.0-0.05, 0.05-0.10, 0.10-0.20 and 0.20-0.40 m was carried out in October 2013 and evaluated physical attributes of texture, bulk density, total porosity, microporosity and soil macroporosity and stability of water in households, chemical properties, and total organic carbon (TOC) and physical particle size fractionation and soil biological activity. To find the best forest restoration model, we designed a Restoration Quality Weighted Index for each variable analyzed. Natural regeneration and total plantation showed generally better soil aggregation over 0.10 m and nucleation volume of similar porosity the forest for these layers. There were no differences between the models below 0.10 m for the variables aggregation and soil porosity. The nucleation template had the lowest bulk density, but being greater than the density in the layer forest 0.05-0.10 m, however, was similar to below 0.10 m above the ground. The models had chemical properties similar to or greater than the forest. The forest had the highest stock of COT and carbon associated with minerals (CAM), but natural regeneration was similar to the particulate organic carbon (POC) in the superficial layers of the soil (0-0.10 m), below 0, 10 m, the forest showed higher stock of COT and COP on the ground. The highest peak of C-CO2 emissions occurred in the 28-35 day range where the total plantation was similar to forest. After four years of experiments, it was found that the effect of restoration methods on physical attributes and soil carbon restricted to 0.10 m deep.

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Dissertação para obtenção do grau de Mestre no Instituto Superior de Ciências da Saúde Egas Moniz

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Dissertação (mestrado)—Universidade de Brasília, Departamento de Engenharia Florestal, Programa de Pós-Graduação em Ciências Florestasi, 2015.