A furação é um processo caracterizado por apresentar dificuldades em relação à formação e remoção do cavaco da região de corte, e à geração de altas temperaturas devido ao cisalhamento e encruamento do material no fundo do furo, principalmente, na usinagem do aço inoxidável austenítico. Com isso a presença do fluido de corte com boas propriedades de refrigeração e lubrificação faz-se necessária para preservar a vida da broca e garantir um acabamento satisfatório do furo. Contudo, com a tendência mundial de diminuição da quantidade de fluido de corte dispendido, tem-se buscado técnicas diferentes de aplicação que utilize o lubrirrefrigerante em quantidades reduzidas. Associado a essas novas técnicas, vem sendo empregado cada vez mais o uso de partículas sólidas adicionadas ao fluido com o intuito de aumentar sua eficiência. Um tipo de partícula, que vem sendo aplicada em diversos setores produtivos devido a suas ótimas propriedades mecânicas, químicas e elétricas, é o grafeno. Sendo assim, pretende-se analisar o comportamento da furação do aço inoxidável austenítico AISI 304 utilizando flocos de multicamadas de grafeno dispersos em fluido de corte empregando o projeto de experimentos Box-Behnken A aplicação do fluido é feita externamente utilizando a técnica de quantidade reduzida com três vazões: 1,5 l/h; 2,0 l/h e 2,5 l/h. O comportamento do processo é avaliado pelos esforços de corte (força de avanço e momento torsor), pela rugosidade (média e total), e pelos desvios (dimensional e de circularidade) na entrada e na saída do furo. O desempenho do grafeno é avaliado pela comparação dos resultados da sua utilização com os de outras duas condições de aplicação do fluido de corte sem adições: em quantidade reduzida e em abundância. Teve-se como resultado que todas as variáveis respostas analisadas sofreram alguma influência da velocidade de corte e/ou da vazão do fluido aplicado em quantidades reduzidas. Os benefícios da lubrificação e refrigeração do grafeno são sentidos em alguns resultados, como nos menores valores médios de rugosidade e de desvio dimensional. Mas, na análise do processo como um todo, não se afirma que o fluido de corte com flocos de multicamadas de grafeno aplicado externamente em quantidade reduzida traz mais benefícios que o sem adições. / Drilling is a machining process characterized by difficulties in the formation and removal of the chip from the cutting region and the generation of high temperatures due to shearing and hardening of the material at the bottom of the hole, especially in the machining of austenitic stainless steel. Thus the presence of cutting fluid with good cooling and lubrication properties is necessary to preserve the drill life and ensure a satisfactory hole finish. However, with the worldwide trend of decreasing the amount of cutting fluid expended, different application systems have been sought which use the coolant in reduced amounts. Associated with these new techniques, the presence of solid particles added to the fluid has been increasingly used in order to enhance its efficiency. One of these particles, which have been applied in several productive sectors due to its excellent mechanical, chemical and electrical properties, is graphene. Therefore, it is intended to analyze the drilling behavior of AISI 304 austenitic stainless steel using multilayer graphene flakes dispersed in the cutting fluid using the Box- Behnken Design The application of the fluid is done externally by means of reduced quantity lubricant with three flows: 1.5 l/h, 2.0 l/h and 2.5 l/h. The behavior of the process is evaluated via thrust force and torque, average and total roughness, and dimensional and circularity deviations at the input and output holes. The performance of graphene is evaluated by comparing the results of its use with two other cutting fluid conditions: quantity reduced and abundance. It was found that all the analyzed responses variables had some influence of the cutting speed and/or the flow of the applied fluid in reduced quantities. The benefits of graphene lubrication and cooling are felt in some results, such as the lower values of average roughness and dimensional deviation. However, in the analysis of the process as a whole, it is not possible to state that the multilayer graphene flakes cutting fluid externally applied brings more benefits than without additions.

A furação é um processo caracterizado por apresentar dificuldades em relação à formação e remoção do cavaco da região de corte, e à geração de altas temperaturas devido ao cisalhamento e encruamento do material no fundo do furo, principalmente, na usinagem do aço inoxidável austenítico. Com isso a presença do fluido de corte com boas propriedades de refrigeração e lubrificação faz-se necessária para preservar a vida da broca e garantir um acabamento satisfatório do furo. Contudo, com a tendência mundial de diminuição da quantidade de fluido de corte dispendido, tem-se buscado técnicas diferentes de aplicação que utilize o lubrirrefrigerante em quantidades reduzidas. Associado a essas novas técnicas, vem sendo empregado cada vez mais o uso de partículas sólidas adicionadas ao fluido com o intuito de aumentar sua eficiência. Um tipo de partícula, que vem sendo aplicada em diversos setores produtivos devido a suas ótimas propriedades mecânicas, químicas e elétricas, é o grafeno. Sendo assim, pretende-se analisar o comportamento da furação do aço inoxidável austenítico AISI 304 utilizando flocos de multicamadas de grafeno dispersos em fluido de corte empregando o projeto de experimentos Box-Behnken A aplicação do fluido é feita externamente utilizando a técnica de quantidade reduzida com três vazões: 1,5 l/h; 2,0 l/h e 2,5 l/h. O comportamento do processo é avaliado pelos esforços de corte (força de avanço e momento torsor), pela rugosidade (média e total), e pelos desvios (dimensional e de circularidade) na entrada e na saída do furo. O desempenho do grafeno é avaliado pela comparação dos resultados da sua utilização com os de outras duas condições de aplicação do fluido de corte sem adições: em quantidade reduzida e em abundância. Teve-se como resultado que todas as variáveis respostas analisadas sofreram alguma influência da velocidade de corte e/ou da vazão do fluido aplicado em quantidades reduzidas. Os benefícios da lubrificação e refrigeração do grafeno são sentidos em alguns resultados, como nos menores valores médios de rugosidade e de desvio dimensional. Mas, na análise do processo como um todo, não se afirma que o fluido de corte com flocos de multicamadas de grafeno aplicado externamente em quantidade reduzida traz mais benefícios que o sem adições. / Drilling is a machining process characterized by difficulties in the formation and removal of the chip from the cutting region and the generation of high temperatures due to shearing and hardening of the material at the bottom of the hole, especially in the machining of austenitic stainless steel. Thus the presence of cutting fluid with good cooling and lubrication properties is necessary to preserve the drill life and ensure a satisfactory hole finish. However, with the worldwide trend of decreasing the amount of cutting fluid expended, different application systems have been sought which use the coolant in reduced amounts. Associated with these new techniques, the presence of solid particles added to the fluid has been increasingly used in order to enhance its efficiency. One of these particles, which have been applied in several productive sectors due to its excellent mechanical, chemical and electrical properties, is graphene. Therefore, it is intended to analyze the drilling behavior of AISI 304 austenitic stainless steel using multilayer graphene flakes dispersed in the cutting fluid using the Box- Behnken Design The application of the fluid is done externally by means of reduced quantity lubricant with three flows: 1.5 l/h, 2.0 l/h and 2.5 l/h. The behavior of the process is evaluated via thrust force and torque, average and total roughness, and dimensional and circularity deviations at the input and output holes. The performance of graphene is evaluated by comparing the results of its use with two other cutting fluid conditions: quantity reduced and abundance. It was found that all the analyzed responses variables had some influence of the cutting speed and/or the flow of the applied fluid in reduced quantities. The benefits of graphene lubrication and cooling are felt in some results, such as the lower values of average roughness and dimensional deviation. However, in the analysis of the process as a whole, it is not possible to state that the multilayer graphene flakes cutting fluid externally applied brings more benefits than without additions.

A furação é um processo caracterizado por apresentar dificuldades em relação à formação e remoção do cavaco da região de corte, e à geração de altas temperaturas devido ao cisalhamento e encruamento do material no fundo do furo, principalmente, na usinagem do aço inoxidável austenítico. Com isso a presença do fluido de corte com boas propriedades de refrigeração e lubrificação faz-se necessária para preservar a vida da broca e garantir um acabamento satisfatório do furo. Contudo, com a tendência mundial de diminuição da quantidade de fluido de corte dispendido, tem-se buscado técnicas diferentes de aplicação que utilize o lubrirrefrigerante em quantidades reduzidas. Associado a essas novas técnicas, vem sendo empregado cada vez mais o uso de partículas sólidas adicionadas ao fluido com o intuito de aumentar sua eficiência. Um tipo de partícula, que vem sendo aplicada em diversos setores produtivos devido a suas ótimas propriedades mecânicas, químicas e elétricas, é o grafeno. Sendo assim, pretende-se analisar o comportamento da furação do aço inoxidável austenítico AISI 304 utilizando flocos de multicamadas de grafeno dispersos em fluido de corte empregando o projeto de experimentos Box-Behnken A aplicação do fluido é feita externamente utilizando a técnica de quantidade reduzida com três vazões: 1,5 l/h; 2,0 l/h e 2,5 l/h. O comportamento do processo é avaliado pelos esforços de corte (força de avanço e momento torsor), pela rugosidade (média e total), e pelos desvios (dimensional e de circularidade) na entrada e na saída do furo. O desempenho do grafeno é avaliado pela comparação dos resultados da sua utilização com os de outras duas condições de aplicação do fluido de corte sem adições: em quantidade reduzida e em abundância. Teve-se como resultado que todas as variáveis respostas analisadas sofreram alguma influência da velocidade de corte e/ou da vazão do fluido aplicado em quantidades reduzidas. Os benefícios da lubrificação e refrigeração do grafeno são sentidos em alguns resultados, como nos menores valores médios de rugosidade e de desvio dimensional. Mas, na análise do processo como um todo, não se afirma que o fluido de corte com flocos de multicamadas de grafeno aplicado externamente em quantidade reduzida traz mais benefícios que o sem adições. / Drilling is a machining process characterized by difficulties in the formation and removal of the chip from the cutting region and the generation of high temperatures due to shearing and hardening of the material at the bottom of the hole, especially in the machining of austenitic stainless steel. Thus the presence of cutting fluid with good cooling and lubrication properties is necessary to preserve the drill life and ensure a satisfactory hole finish. However, with the worldwide trend of decreasing the amount of cutting fluid expended, different application systems have been sought which use the coolant in reduced amounts. Associated with these new techniques, the presence of solid particles added to the fluid has been increasingly used in order to enhance its efficiency. One of these particles, which have been applied in several productive sectors due to its excellent mechanical, chemical and electrical properties, is graphene. Therefore, it is intended to analyze the drilling behavior of AISI 304 austenitic stainless steel using multilayer graphene flakes dispersed in the cutting fluid using the Box- Behnken Design The application of the fluid is done externally by means of reduced quantity lubricant with three flows: 1.5 l/h, 2.0 l/h and 2.5 l/h. The behavior of the process is evaluated via thrust force and torque, average and total roughness, and dimensional and circularity deviations at the input and output holes. The performance of graphene is evaluated by comparing the results of its use with two other cutting fluid conditions: quantity reduced and abundance. It was found that all the analyzed responses variables had some influence of the cutting speed and/or the flow of the applied fluid in reduced quantities. The benefits of graphene lubrication and cooling are felt in some results, such as the lower values of average roughness and dimensional deviation. However, in the analysis of the process as a whole, it is not possible to state that the multilayer graphene flakes cutting fluid externally applied brings more benefits than without additions.

Transmission Electron Microscopy (TEM) on light element materials and soft matters is problematic due to electron irradiation damage and low contrast. In this doctoral thesis techniques were developed to address some of those issues and successfully characterize these materials at high resolution. These techniques were demonstrated on graphene flakes, DNA/magnetic beads and a number of water containing biomaterials. The details of these studies are given below. A TEM based method was presented for thickness characterization of graphene flakes. For the thickness characterization, the dynamical theory of electron diffraction is used to obtain an analytical expression for the intensity of the transmitted electron beam as a function of thickness. From JEMS simulations (experiments) the absorption constant λ in a low symmetry orientation was found to be ~ 208 nm (225 ± 9 nm). When compared to standard techniques for thickness determination of graphene/graphite, the method has the advantage of being relatively simple, fast and requiring only the acquisition of bright-field (BF) images. Using the proposed method, it is possible to measure the thickness change due to one monolayer of graphene if the flake has uniform thickness over a larger area. A real-space TEM study on magnetic bead-DNA coil interaction was conducted and a statistical analysis of the number of beads attached to the DNA-coils was performed. The average number of beads per DNA coil was calculated around 6 and slightly above 2 for samples with 40 nm and 130 nm beads, respectively. These results are in good agreement with magnetic measurements. In addition, the TEM analysis supported an earlier hypothesis that 40 nm beads are preferably attached interior of the DNA-coils while 130 nm beads closer to the exterior of the coils. A focused ion-beam in-situ lift-out technique for hydrated biological specimens was developed for cryo-TEM. The technique was demonstrated on frozen Aspergillus niger spores which were frozen with liquid nitrogen to preserve their cellular structures. A thin lamella was prepared, lifted out and welded to a TEM grid. Once the lamella was thinned to electron transparency, the grid was cryogenically transferred to the TEM using a cryo-transfer bath. The structure of the cells was revealed by BF imaging. Also, a series of energy filtered images was acquired and C, N and Mn elemental maps were produced. Furthermore, 3 Å lattice fringes of the underlying Al support were successfully resolved by high resolution imaging, confirming that the technique has the potential to extract structural information down to the atomic scale. The experimental protocol is ready now to be employed on a large variety of samples e.g. soft/hard matter interfaces.

The present thesis deals with a theoretical study of electronic structures in -conjugated molecular materials with focus on their application in organic elec-tronics. We also discuss a modified and efficient symmetrized DMRG algorithm for studying excited states in these systems. In recent times, organic conjugated systems have emerged as potential candidates in a wide range of fascinating fields by virtue of their tunable electronic properties, easy processability and low cost. Tunability in the electronic and optical properties primarily are centered on the or-dering and nature of the low-lying excited states. Probing these important excited states also demands development of efficient and adaptable techniques. Chapter 1 provides a basic overview of conjugated organic polymers which have been utilized over decades in diverse fields as in organic light emitting diodes (OLED), organic solar cells (OSC) and non-linear optical (NLO) devices. These systems also contribute significantly to theoretical understanding as they pro vide important insights of one and quasi-one dimensional systems. In this chapter, we have given basic description of the electronic processes in OLED and OSC along with a brief theoretical description of -conjugated organic systems. Chapter 2 gives an account of the numerical techniques which are necessary for the study of low-dimensional strongly correlated systems like -conjugated sys-tems. For this purpose, effective low-energy model Hamiltonians viz. Huckel,¨ Hubbard and Pariser-Parr-Pople Hamiltonians are discussed. Exact diagonalization technique within the diagrammatic valence bond (DVB) basis and density matrix renormalization group (DMRG) technique are discussed in details. We have also given brief accounts of the methods employed to study real-time dynamics. A short description of different computational techniques for the study of NLO properties in -conjugated systems is also provided. Engineering the position of the lowest triplet state (T1) relative to the first excited singlet state (S1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. In chapter 3, we have carried out model exact calculations of substituted polyene chains to understand the fac-tors that affect the energy gap between S1 and T1. The factors studied are backbone dimerization, different donor-acceptor substitutions and twisted backbone geome-try. The largest system studied is an eighteen carbon polyene which spans a Hilbert space of about 991 million in the triplet subspace. We show that for reverse inter-system crossing (RISC) process, the best choice involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. Singlet fission (SF) is a potential pathway for significant enhancement of efficiency in OSC. In chapter 4, we study singlet fission in a pair of polyene molecules in two different stacking arrangements employing exact many-body wave packet dy-namics. In the non-interacting model, SF is absent. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interac-tion between them involves transfer terms, intersite electron repulsions and site-charge—bond-charge repulsion terms. Initial wave packet is construc ted from ex-cited singlet state of one molecule and ground state of the other. Time develop-ment of this wave packet under the influence of intermolecular interactions is fol-lowed within the Schrodinger¨ picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, 21A state leads to significant SF yield while the 11B state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, the lowest excited state will have sufficient 2 1A char-acter and hence gives significant SF yield. Because of rapid internal c onversion, the nature of the lowest excited singlet will determine the SF contribution to OSC effi - ciency. Furthermore, we find the fission yield depends considerably on th e stacking arrangement of the polyene molecules. In chapter 5, we have given an account of a new modified algorithm for symmetry adaptation within symmetrized density matrix renormalization group (SDMRG) technique. SDMRG technique has been an efficient method for studying low-lying eigenstates in one and quasi-one dimensional electronic systems. However, SDMRG method until now, had bottlenecks involving construction of linearly in-dependent symmetry adapted basis states as the symmetry matrices in the DMRG basis were not sparse. Our modified algorithm overcomes this bottleneck. T he new method incorporates end-to-end interchange symmetry (C2), electron-hole symmetry (J) and parity or spin-flip symmetry (P) in these calculations. The one-to-one correspondence between direct-product basis states in the DMRG Hilbert space for these symmetry operations renders the symmetry matrices in the new ba-sis with maximum sparseness, just one non-zero matrix element per row. Using methods similar to those employed in exact diagonalization technique for Pariser-Parr-Pople (PPP) models, developed in the eighties, it is possible to construct or-thogonal SDMRG basis states while bypassing the slow step of Gram-Schmidt orthonormalization procedure. The method together with the PPP model which incorporates long-range electronic correlations is employed to study the correlated excited states of 1,12-benzoperylene. In chapter 6, we have studied the correlated excited states of coronene and ova-lene within Pariser-Parr-Pople (PPP) model employing symmetry adapted density matrix renormalization group technique. These polynuclear aromatic hydrocar-bons can be considered as graphene nanoflakes and study of their ele ctronic struc-tures will shed light on the electron correlation effects in these finite-size gr aphene analogues. The electron correlation effect usually diminishes on going from one-dimensional to higher-dimensional systems, yet, it is significant within these fin ite-size graphene derivatives where it depends on the molecular topology. We have characterized these low-lying energy states by calculating bond orders, spin den-sities in the lowest triplet state and two-photon absorption cross-sections for low-lying two-photon states. vi