Crescimento epitaxial e caracterização de filmes finos: óxidos condutores e ferroelétricos preparados por deposição de solução química

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

O efeito da ordenação e estrutura geométrica dos materiais PtSn/C e PdSn/C na eletrooxidação do glicerol em meio alcalino

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Pré-hidrólise ácida de bagaço de cana-de-açúcar e sua caracterização físico-química

The biomass resulting from processing sugarcane bagasse has been considered a source of cellulose with the potential production of bio-fuels. This lignocellulose can be processed into ethanol since is hydrolyzed by chemical processes (acids) or biotechnology (enzymes) which generate sugars suit for fermentation. This study had the objective to utilize physical and chemical pre-treatment processes for prehydrolysis of sugarcane bagasse. The experimental treatment was adjusted at a factor of 4 X 2, by the combination of pre-hydrolysis timing (15, 30, 45 and 60 minutes) and sulfuric acid concentrations (7.0% and 9.0%) which was incubated at a temperature of 121° C in an autoclave. The treatment data was subjected to analysis of the variance and averages which were compared using the Tukey test with a probability of 5%. The results obtained showed that through pretreatment acid applied on the lignocellulose material, there was a significant break from the substrate fibers like cellulose, hemicellulose and lignin.

Estrutura e algumas propriedades ópticas de difenilfosfinatos de terras-raras

Coordination compounds of trivalent lanthanides cations with diphenylphosphinate are originated from direct reaction between a lanthanide salt and diphenylphosphinic acid. These complexes have peculiar and intriguing features, as (i) quickly obtainment through wet process precipitation, (ii) appreciable thermal stability, similar to inorganic phosphates, (iii) polymeric structure, and consequently, (iv) low solubility in both polar and non-polar solvents. Nowadays, coordination polymers are classified as coordination networks or, in case of porous materials, as metal-organic frameworks (MOFs). By this study, we aim to determine some optical properties of rare-earth diphenylphosphinate (RE = La3+, Eu3+, Gd3+, Lu3+) and conduct an updated classification of these compounds, bringing more details of its structure and the possible proposal of new materials with applications in lighting, detection of ionizing radiation and magnetism. The complexes of trivalent rare-earth cation with diphenylphosphinate were prepared by direct mixture of diphenylphosphinic acid with rare-earth metal chloride, both in ethanolic solution. The solution of diphenylphosphinic acid was kept in a beaker under constant stirring with pH measurements of the solution and gadolinium chloride solution was then dripped slowly with the aid of a burette until its complete addition; the following metal:ligand molar ratios were tested: 1:1, 1:2, 1:3, 2:1 e 3:1. The compounds were characterized by spectroscopic and structural techniques. By Fourier Transform Infrared Spectroscopy (FT-IR), it was possible to check the total ionization of diphenylphosphinic acid in synthesized complexes, confirmed by the absence of the band type A, B, C related to ѵ(O-H) of the acid (2663 cm-1, 2168 cm-1, 1684 cm-1), as well as the disappearance of ѵ(P-OH)=961 cm-1. Furthermore, the occurrence of bands shifts of ѵ(POO-) [symmetrical and asymmetrical] of...

Estrutura e algumas propriedades ópticas de difenilfosfinatos de terras-raras

Coordination compounds of trivalent lanthanides cations with diphenylphosphinate are originated from direct reaction between a lanthanide salt and diphenylphosphinic acid. These complexes have peculiar and intriguing features, as (i) quickly obtainment through wet process precipitation, (ii) appreciable thermal stability, similar to inorganic phosphates, (iii) polymeric structure, and consequently, (iv) low solubility in both polar and non-polar solvents. Nowadays, coordination polymers are classified as coordination networks or, in case of porous materials, as metal-organic frameworks (MOFs). By this study, we aim to determine some optical properties of rare-earth diphenylphosphinate (RE = La3+, Eu3+, Gd3+, Lu3+) and conduct an updated classification of these compounds, bringing more details of its structure and the possible proposal of new materials with applications in lighting, detection of ionizing radiation and magnetism. The complexes of trivalent rare-earth cation with diphenylphosphinate were prepared by direct mixture of diphenylphosphinic acid with rare-earth metal chloride, both in ethanolic solution. The solution of diphenylphosphinic acid was kept in a beaker under constant stirring with pH measurements of the solution and gadolinium chloride solution was then dripped slowly with the aid of a burette until its complete addition; the following metal:ligand molar ratios were tested: 1:1, 1:2, 1:3, 2:1 e 3:1. The compounds were characterized by spectroscopic and structural techniques. By Fourier Transform Infrared Spectroscopy (FT-IR), it was possible to check the total ionization of diphenylphosphinic acid in synthesized complexes, confirmed by the absence of the band type A, B, C related to ѵ(O-H) of the acid (2663 cm-1, 2168 cm-1, 1684 cm-1), as well as the disappearance of ѵ(P-OH)=961 cm-1. Furthermore, the occurrence of bands shifts of ѵ(POO-) [symmetrical and asymmetrical] of...

Influências do PIBID na representação social de licenciandos em química sobre ser \"professor de química\"

Esta Tese apresenta um estudo sobre a formação inicial de professores de Química em 10 diferentes universidades públicas brasileiras, estabelecidas em 7 diferentes estados e abrange 217 estudantes de licenciatura. Analisou-se a influência do \"Programa Institucional de Bolsas de Iniciação à Docência\" - PIBID - na composição do Núcleo Central (NC) da Representação Social (RS; (MOSCOVICI, 1978) desses Licenciandos sobre o ser \"professor de Química\". Para alocar um termo na zona de centralidade de uma RS é necessário identificar o valor simbólico do termo, refletido em sua saliência, a qual é indicada pela relação entre freqüência e Ordem Média de Evocação e, pelo poder associativo, refletido na conexidade e na categorização temática dos termos. Para a coleta de informações, empregou-se um questionário, com 20 questões, das quais apenas 5 fazem referência específica à tarefa de livre associação de palavras a partir do termo indutor \"professor de Química\", enquanto as demais se referem à caracterização do grupo social. As conclusões deste estudo emergiram da comparação entre o NC da RS de alunos participantes do PIBID (118) com aquele de licenciandos que jamais participaram do Programa (99). Para os alunos participantes dos sub-projetos PIBID-QUÍMICA, os termos do NC da RS investigada são: dedicado, experimentação, responsabilidade. Para o sub-grupo não/PIBID, os termos salientes e com conexidade suficiente para expressar sua centralidade na RS são: dedicado, experimentação, inteligente. Portanto, a zona de centralidade da RS dos dois sub-grupos é diferente, devido a dois termos: responsabilidade e inteligente. O primeiro termo destacado é exclusivo do NC do sub-grupo PIBID, enquanto o último ocorre apenas no NC do sub-grupo não/PIBID. Vale salientar que para o sub-grupo PIBID o termo experimentação apresenta saliência e conexidade expressivos e, para o outro sub-grupo, o termo mais saliente e conexo é dedicado, o que reflete uma diferença qualitativa na organização interna da estrutura das RS, resultado que os caracteriza como diferentes grupos sociais, cada um com uma RS para o ser \"professor de Química\". A presença de termos diferentes na zona de centralidade das RS indica que o processo de formação desenvolvido no âmbito do PIBID expressa a importância da vivência das diferentes práticas pedagógicas junto à Escola Básica durante a formação inicial para a docência em Química, o que não ocorre para o sub-grupo não/PIBID até o momento dos estágios docentes, que demoram muito para acontecer nas Licenciaturas convencionais. No caso do sub-grupo não/PIBID, é forte a presença de termos ligados à idéia de \"vocação\" na docência, expressando aspectos históricos resistentes à mudança no processo de formação de professores.

Avaliação da interação entre o persulfato de potássio com solos brasileiros para a utilização da tecnologia de remediação por oxidação química in situ.

Recentemente, o uso de persulfato em processo de oxidação química in situ em áreas contaminadas por compostos orgânicos ganhou notoriedade. Contudo, a matriz sólida do solo pode interagir com o persulfato, favorecendo a formação de radicais livres, evitando o acesso do oxidante até o contaminante devido a oxidação de compostos reduzidos presentes no solo ou ainda pela alteração das propriedades hidráulicas do solo. Essa pesquisa teve como objetivos avaliar se as interações entre a solução de persulfato com três solos brasileiros poderiam eventualmente interferir sua capacidade de oxidação bem como se a interação entre eles poderia alterar as propriedades hidráulicas do solo. Para isso, foram realizados ensaios de oxidação do Latossolo Vermelho (LV), Latossolo Vermelho Amarelo (LVA) e Neossolo Quartzarênico (NQ) com solução de persulfato (1g/L e 14g/L) por meio de ensaios de batelada, bem como a oxidação do LV por solução de persulfato (9g/L e 14g/L) em colunas indeformadas. Os resultados mostraram que o decaimento do persulfato seguiu modelo de primeira ordem e o consumo do oxidante não foi finito. A maior constante da taxa de reação (kobs) foi observada para o reator com LV. Essa maior interação foi decorrente da diferença na composição mineralógica e área específica. A caulinita, a gibbsita e os óxidos de ferro apresentaram maior interação com o persulfato. A redução do pH da solução dos reatores causou a lixiviação do alumínio e do ferro devido a dissolução dos minerais. O ferro mobilizado pode ter participado como catalisador da reação, favorecendo a formação de radicais livres, mas foi o principal responsável pelo consumo do oxidante. Parte do ferro oxidado pode ter sido precipitado como óxido cristalino favorecendo a obstrução dos poros. Devido à maior relação entre massa de persulfato e massa de solo, a constante kobs obtida no ensaio com coluna foi 23 vezes maior do que a obtida no ensaio de batelada, mesmo utilizando concentração 1,5 vezes menor no ensaio com coluna. Houve redução na condutividade hidráulica do solo e o fluxo da água mostrou-se heterogêneo após a oxidação devido a mudanças na estrutura dos minerais. Para a remediação de áreas com predomínio de solos tropicais, especialmente do LV, pode ocorrer a formação de radicais livres, mas pode haver um consumo acentuado e não finito do oxidante. Verifica-se que o pH da solução não deve ser inferior a 5 afim de evitar a mobilização de metais para a água subterrânea e eventual obstrução dos poros por meio da desagregação dos grãos de argila.

Produção de estrutura com gradiente de porosidade a partir da sinterização por plasma da mistura de pós Ti-Nb-Sn

Porous structures are being widely investigated for use in biomedical implants, aiming to mechanically integrate and functionally the implant inside the bone tissue. Moreover, this structure is also important for drugs that can be stored and can induce and accelerate the process of osseointegration. With the purpose to investigate this effect, Ti, Nb and Sn metal powders, were sintered by plasma using a hollow cathode discharge. Sintering was performed in argon plasma set at 4 mbar pressure and temperatures of 500 ° C, 600 ° C and 700 ° C. Samples were also sintered in the electrical resistance furnace at 1200 ° C in order to compare plasma sintering with the conventional method. It was observed that plasma samples sintered with the hollow cathode configuration showed a gradient in porosity, while the samples sintered in the resistive furnace did not. Furthermore, differences in the microstructure of the samples were found, were a surface with higher porosity and ales porous core were obtained at different temperatures. The percolation profile of distilled water and the chemical compositions of the porous layers of the plasma treated samples were the main results obtained. Based on these results, we can conclude that this structure is particularly important for application in the biomedical field such as scaffolds for drug delivery and implants

Elaboração de uma unidade de ensino potencialmente significativa em Química para abordar a temática água

The evidence of the water theme in news reports is configured as an important topic of interest to contextualize, problematize and/or generate meaning in the midst of discussion of a content from different levels of education and/or disciplines of basic education. The possibilities to use this theme in classroom is also highlighted in Brazilian official documents that guide the practice of teachers of all Brazilian curricular components of this educational level. So, the theme water can be used as subsidy to teach chemistry, since contextualises the teaching of this discipline aiding in the discussion of different chemical concepts. In this perspective, the meaningful learning theory, developed by David Ausubel, has constructivist nature and says that an individual learns significantly when he can relate new information with a specific knowledge structure that integrates the prior knowledge of its structure. In this sense, the use of water as a theme for the approach prior knowledge of chemical concepts has already been characterized as an important topic that can give meaning to the content of education in chemistry. In this dissertation, a teaching unit potentially significant (TUPS) is presented based on meaningful learning theory of David Ausubel approaching the theme water. approaching the theme water. The unit was used in a class of thirty-five students of the 2nd year of high school, a public school in the city of Extremoz-RN, metropolitan region of Natal / RN. Through it was possible to discuss an issue of interest to students of the school to address the chemical contents, such as solutions, physicochemical aspects and stages of water treatment. At first, an initial questionnaire was used to identify the students' previous ideas on the topic under study to the concept of chemical solutions. It was subsequently developed and implemented a series of activities based on students' ideas. To subsidize the sequence, it was prepared four booklets that worked the content of chemical solutions, contextualizing the theme water. The results of this work showed that the alternative conceptions that students have about concepts related to the chemical solutions are similar to the ideas of other students presented in the literature and that the development of the TUPS, allied to the contextualization strategy with the theme water, not only motivated the students for the teaching of chemical content, as yet provided the learning of chemical concepts not in isolation, but making a connection between their ideas and experiences with scientific knowledge. To this, beyond of dialogued lectures, were also used strategies as experimental activities, problem solving, group discussions and construction of concept maps. The final evaluation of the unit was conducted by a questionnaire based on the Likert scale, answered individually by students, who approved the unit as conducive to teaching and learning of chemistry process

Transportadores sólidos de oxigênio à base de níquel e cobre suportados em aluminatos para combustão do metano pela tecnologia de recirculação química

In recent years, solid carriers suitable oxygen have been developed for use in different chemical processes recirculation. The success of this technology is directly related to the chemical reactivity and the oxygen storage capacity of the carrier. Thus, research into the development of new materials that can be applied to the process becomes extremely important. Possible candidates are the carriers based on nickel and copper for presenting favorable thermodynamic properties. In this work, aluminates type MAl2O4 (M = Mg and Ca) and M0,9B0,1Al2O4 (B = Ni and Cu) that are used as supports were synthesized by combustion reactions assisted by microwave and calcined at 900°C/2h. Then, the carriers were impregnated with 10% (m/m) of nickel or copper, and subsequently calcined at 600°C/2h to obtain the solid oxygen carriers, which were characterized by X-ray diffraction (XRD) Microscopy scanning electron microscopy (SEM) and temperature programmed reduction (TPR). Reactions simulating the combustion process by chemical recirculation were performed by cycles reduction/oxidation, in order to evaluate the reactivity of carriers. XRD analysis revealed diffraction peaks of the spinel type structures. In the doped substrates were verified the presence of secondary phases, suggesting that all the metal was incorporated into the spinel structure. In solid oxygen carriers, the NiO and CuO phases were observed after impregnation of active phases on different media. The results of evaluations of chemical cycles reduction/oxidation revealed that TSO's impregnated with nickel in various media were more active and are potential candidates for use in the chemical recirculation technology

Desenvolvimento de material BaCexPr1-xO3 (0 ≤ X ≤ 1) com estrutura perovskita para oxidação catalítica do CO a CO2 em reator de leito fixo

Barium Cerate (BaCeO3) is perovskite type structure of ABO3, wherein A and B are metal cations. These materials, or doped, have been studied by having characteristics that make them promising for the application in fuel cells solid oxide, hydrogen and oxygen permeation, as catalysts, etc .. However, as the ceramic materials mixed conductivity have been produced by different synthesis methods, some conditions directly influence the final properties, one of the most important doping Site B, which may have direct influence on the crystallite size, which in turn directly influences their catalytic activity. In this study, perovskite-type (BaCexO3) had cerium gradually replaced by praseodymium to obtain ternary type materials BaCexPr1-xO3 and BaPrO3 binaries. These materials were synthesized by EDTA/Citrate complexing method and the material characterized via XRD, SEM and BET for the identification of their structure, morphology and surface area. Moreover were performed on all materials, catalytic test in a fixed bed reactor for the identification of that person responsible for complete conversion of CO to CO2 at low operating temperature, which step can be used as the subsequent production of synthesis gas (CO + H2) from methane oxidation. In the present work the crystalline phase having the orthorhombic structure was obtained for all compositions, with a morphology consisting of agglomerated particles being more pronounced with increasing praseodymium in the crystal structure. The average crystal size was between 100 nm and 142,2 nm. The surface areas were 2,62 m²g-1 for the BaCeO3 composition, 3,03 m²g-1 to BaCe0,5Pr0,5O3 composition and 2,37 m²g-1 to BaPrO3 composition. Regarding the catalytic tests, we can conclude that the optimal flow reactor operation was 50 ml / min and the composition regarding the maximum rate of conversion to the lowest temperature was BaCeO3 to 400° C. Meanwhile, there was found that the partially replaced by praseodymium, cerium, there was a decrease in the catalytic activity of the material.

Materiais zeolíticos de estrutura MWW: síntese e caracterização

In this paper a synthesis parameters study was conducted in order to optimize the obteinment of MCM-22 (MWW structure) and increase its accessibility, getting higher external surface and generating mesopores. Syntheses with Si / Al = 15 and Si / Al = 50 ratios were performed under static conditions at different temperatures and with seeds induction, which resulted in MCM-22 pure and crystalline (Si / Al ratio = 15) after 3 days and Si / Al = 50 after 11 days. The reduction of hexamethyleneimine content (HMI) was studied in the stirring synthesis and a HMI reduction of 47% was possible through the mother liquor reuse, in addition, a specific area of 481 m² / g has been obtained in the fourth synthesis day. Regarding the increase of accessibility of the MCM-22 zeolite skeins of MCM-22 plates with about 2 μm were obtained, through the use of dissolved silica, addition of seeds, increased temperature and synthesis time of 2 days. A significant value of specific area was found for this material, around 500 m² / g. Also with respect to the increase of MCM-22 accessibility, treatment with oxalic acid concentration of 0.5 mol / L and silanization of proto-zeolitic units resulted in the mesopores formation . Furthermore, silanization still favored reduction of 70 % in crystal size and a specific area of 566 m² / g.

Síntese, estrutura e propriedades de polímeros de coordenação à base de íons lantanídeos e ácidos benzenodicarboxílicos

Metal Organic Frameworks (MOFs) are hybrids materials, often crystalline, consisting of metal or metal clusters, connected by polytopic organic ligands repetitively, leading to structures, usually porous. In this work, MOFs based on lanthanide ions (La3+ and Gd3+) and dicarboxylate type of ligands (isophthalic and terephthalic acids), were synthesized by hydrothermal, solvothermal and hydro(solvo)thermal methods. The effects of the synthetic route as well as the type of heating, conventional or by microwave, on the structure and properties of MOFs were studied. The powder samples obtained were characterized by X-ray diffraction, infrared spectroscopy, thermal analysis and scanning electron microscopy. The results suggest that the addition of an organic or inorganic base is needed to promote the deprotonation of the ligand, since in the samples prepared by the hydrothermal method, without the use of a base, no formation of the metalorganic framework was observed. On the other hand, the presence of DMF as solvent or cosolvent, afforded the deprotonation of the ligand with the consequent formation of MOFs. At least two different crystalline structures were identified for the samples prepared with terephthalic acid. These samples are isostructural with those reported for phases Eu(1,3-BDC)DMF, Eu2(1,4-BDC)3 (DMF)2 and Tb(1,4-BDC)H2O. The presence of water in the reaction medium in the hydro(solvo)thermal method, provoked the growth of the structure different from that observed in the absence of water. This can be explained by the difference in the coordination mode of water and DMF to lanthanide ions. Although not identified by XRD, the samples prepared with isophthalic acid, also present metalorganic structures, which was confirmed by the presence of the characteristic displacement of the carbonyl group band in their infrared spectra, compared to the spectrum of the pure ligand. This shift was also observed in the samples prepared with terephthalic acid. Thermal analisys shows that the metal organic frameworks do not collapse occurs at a temperature below 430°C.The analysis of scanning electron microscopy suggests that the morphology of powders is highly dependent on the type of heating used, conventional or by microwave.

O ensino de química na educação de jovens e adultos do ensino médio no município de Itumbiara-GO

For this study, a research was conducted in order to answer the question "What chemistry teaching has been developed in the Youth and Adult Education (EJA) ?". The research provides an overview of the object to the proposed changes, leading students to live with different realities and investigating the issue of contextualization based on the daily lives of these students related to the subject of chemistry. The methodology focuses ethnographic research of the case study, in which a case is studied in depth using the participant observation. In the survey data a mixed qualitative and quantitative approach was used. The work involved 6 schools that offer adult education high school; 6 directors of these schools; 6 coordinators who work in adult education; 6 Chemistry teachers and 123 students of the EJA, level high school, enrolled in the 1st, 2nd, 3rd and 4th periods. The first stage of the research consisted of questionnaires in schools where everyone involved responded closed and open questions applied to each specific group. In the second stage two schools were selected in order to conduct a deeper knowledge of adult education through practical activities of Chemistry and subsequent interview conducted in groups with students. Three teachers were also interviewed to enable a deepening of issues relating to EJA and Chemistry Teaching. The interviews were analyzed by the technique of Discursive Textual Analysis (ATD). The main issues addressed in the questionnaires and interviews were on the school structure, reasons that lead students to drop out or remained in adult education and those who make the stay, the view of those involved of the importance of chemistry discipline for students of EJA and how this should be offered. It is necessary that we need to promote changes in the chemistry class and its activities, respecting the experiences and experience already gained by the student during his life story. Another factor to be highlighted is the need for ongoing training of teachers working in adult education. Note that your continued education is given more by the experience and the ways in which they try to overcome adverse situations. The Chemistry subject taught is not agree with the principles of EJA and practiced curriculum is just an adaptation or content reduction from the regular curriculum. The improvement in chemistry teaching of EJA will take place through a dialogue between those involved in the process, clearer educational policies and willingness to implement change. Thus the teaching of chemistry contribute to the students of the EJA are actually scientifically literate and integrated into society.

Acetilação do exopolissacarídeo (1→6)-β-D-glucana (lasiodiplodana): derivatização química e caracterização

Lasiodiplodan is an exocellular β-glucan with biological functionalities such as antioxidant, antiproliferative, hypocholesterolemic, protective activity against DNA damage induced by doxorubicin and hypoglycemic activity. Chemical derivatization of polysaccharide macromolecules has been considered as a potentiating mechanism for bioactivity. In this context, this work proposes the derivatization of lasiodiplodan by acetylation. Acetic anhydride was used as derivatizing agent and pyridine as catalyst and reaction medium. The derivatives obtained were evaluated by its water solubility, degree of substitution (DS), antioxidant potential, and characterized by infrared spectroscopy (FT-IR), thermal analysis, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. Acetylated derivatives with different degrees of substitution (1.26; 1.03; 0.66 and 0.48) were obtained, and there was correlation between the concentration of derivatizing agent and DS. FT-IR spectroscopy analysis confirmed the insertion of acetyl groups into derivatized macromolecules (LAS-AC) through of specific bands concerning to carbonyl group (C = O) and increase in C-O vibration. SEM analysis indicated that native lasiodiplodan presents morphological structure in the form of thin films with translucent appearance and folds along its length. Derivatization led to morphological changes in the polymer, including aspects thickness, translucency and agglomeration. Thermal analysis indicated the native sample and derivative with DS 0.48 presented three weight loss stages. The first stage occurred until 125 ° C (loss of water) and there were two consecutive events of weight loss (200 ° C - 400 ° C) attributed to molecule degradation. Samples with DS 1.26; 1.03 and 0.66 demonstrated four weight loss stages. The first stage occurred until 130 ° C (loss of water), following by two consecutive events of weight loss (200 ° C - 392 ° C) attributed to degradation of the biopolymer. The fourth stage was between 381 ° C and 532 ° C (final decomposition) with exothermic peaks between 472 ° C and 491 ° C. X-ray diffraction patterns showed that native and acetylated lasiodiplodan have amorphous structure with semicrystalline regions. Derivatization did not contribute to increased solubility of the macromolecule, but potentiated its antioxidant capacity. Acetylation of lasiodiplodan allowed to obtaining a new macromolecule with higher antioxidant potential than the native molecule and with technological properties applicable in various industrial sectors.