883 resultados para solid-state structure
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Water-based latices, used in the production of internal liners for beer/beverage cans, were investigated using a number of analytical techniques. The epoxy-graft-acrylic polymers, used to prepare the latices, and films, produced from those latices, were also examined. It was confirmed that acrylic polymer preferentially grafts onto higher molecular weight portions of the epoxy polymer. The amount of epoxy remaining ungrafted was determined to be 80%. This figure is higher than was previously thought. Molecular weight distribution studies were carried out on the epoxy and epoxy-g-acrylic resins. A quantitative method for determining copolymer composition using GPC was evaluated. The GPC method was also used to determine polymer composition as a function of molecular weight. IR spectroscopy was used to determine the total level of acrylic modification of the polymers and NMR was used to determine the level of grafting. Particle size determinations were carried out using transmission electron microscopy and dynamic light scattering. Levels of stabilising amine greatly affected the viscosity of the latex, particle size and amount of soluble polymer but the core particle size, as determined using TEM, was unaffected. NMR spectra of the latices produced spectra only from solvents and amine modifiers. Using solid-state CP/MAS/freezing techniques spectra from the epoxy component could be observed. FT-IR spectra of the latices were obtained after special subtraction of water. The only difference between the spectra of the latices and those of the dry film were due to the presence of the solvents in the former. A distinctive morphology in the films produced from the latices was observed. This suggested that the micelle structure of the latex survives the film forming process. If insufficient acrylic is present, large epoxy domains are produced which gives rise to poor film characteristics. Casting the polymers from organic solutions failed to produce similar morphology.
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Mõssbauer spectroscopy and X-ray diffraction of five coals revealed the presence of pyrite, illite, kaolinite and Quartz, together with other minor phases. Analysis of the coal ashes indicated the formation of hematite and an Fe (3+) paramagnetic phase, the latter resulting from .the dehydroxylation of the clay minerals during ashing at 700 to 750 C. By using a combination of several physicochemical methods, different successive stages of dehydroxylation, structural consolidation, and recrystallisation of illite, montmorillonite and hectorite upon thermal treatment to 1300 C were investigated. Dehydroxylation of the clay minerals occurred between 450 and 750 C, the X-ray crysdallinity of illite and montmorillonite remaining until 800 C. Hectorite gradually recrystallises to enstatite at temperatures above 700°C. At 900 C the crystalline structure of all three clay minerals had totally collapsed. Solid state reactions occurred above 900 C producing such phases as spinel, hematite, enstatite, cristobalite and mullite. Illite and montmorillonite started to melt between 1200 and 1300°C, producing a silicate glass that contained Fe(3+) and Fe(2+) ions. Ortho-pnstatite, clino-enstatite and proto-enstatite were identified in the thermal products of hectorite, their relative proportions varying with temperature. Protoenstatite was stabilised with respect to metastable clinoenstatite upon cooling from 12000 C by the presence of exchanged transition metal cations. Solid state Nuclear Magnetic Resonance spectroscopy of thermally treated transition metal exchanged hectorite indicated the levels at which paramagnetic cations could be loaded on to the clay before spectral resolution is significantly diminished.
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Single crystal X-ray structure determinations are reported for eleven compounds all of which are either biologically active or potentially biologically important. The compounds fall into two distinct classes:- 1. Substituted diaminopyrimidines 2. Substituted aminopyrimidinones The first class of compounds were all selected on the basis of their common diaminopyrimidine nucleus which has been demonstrated to be a vital requirement for antifolate activity. They may all be described as non-classical or small molecule lipophilic dihydrofolate reductase (DHFR) inhibitors, as opposed to the classical folate analogues, having the ability to cross the blood-brain barrier, enter cells via a rapid passive diffusion process, and achieve high intracellular concentrations. Thus they are an excellent choice in the search for crystallography in the solid state, providing geometrical and distance data not available from any other analytical techniques to date; supporting and enhancing data obtained in the lower resolution studies of protein crystallography. The biological importance of these compounds is discussed and an attempt is made to relate/predict their pharmacological activity to observed structural features in the crystalline environment. Special attention is focussed on hydrogen bonding, confirmational flexibility and hydrophobicity of substituents; each of which appear to make contributions to tight binding in the enzyme active site. Chapter 9 describes the use of data from the literature and the solid state modelling of an observed enzyme-substrate interaction in an attempt to define it more accurately in terms of its geometric flexibility. Of the second class, one compound (ABPP) is reported; studies in two different crystal forms. In demonstrating both antiviral and high interferon inducing activity it is possible that this compound could be useful against cancer and also viral infections.
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Salt formation has extensively been studied as a strategy to improve drug solubility but it has not been explored as a strategy to improve mechanical properties. A better understanding of which factors of the solid state can have an influence in the mechanical properties of pharmaceutical powders can help to optimise and reduce cost of tablet manufacturing. The aim of this study was to form different series of amine salts of flurbiprofen, gemfibrozil and diclofenac and to establish predictive relationships between architectural characteristics and physicochemical and mechanical properties of the salts. For this purpose, three different carboxylic acid drugs were selected: flurbiprofen, gemfibrozil and diclofenac, similar in size but varying in flexibility and shape and three different series of counterions were also chosen: one with increasing bulk and no hydroxyl groups to limit the hydrogen bonding potential; a second one with increasing number of hydroxyl groups and finally a third series, related to the latter in number of hydroxyl groups but with different molecular shape and flexibility. Physico-chemical characterization was performed (DSC, TGA, solubility, intrinsic dissolution rate, particle size, true density) and mechanical properties measured using a compaction replicator. Strained molecular conformations produce weaker compacts as they have higher energy than preferred conformations that usually lie close to energy minimums and oppose plastic deformation. It was observed that slip planes, which correspond to regions of weakest interaction between the planes, were associated with improved plasticity and stronger compacts. Apart from hydrogen bonds, profuse van der Waals forces can result in ineffective slip planes. Salts displaying two-dimensional densely hydrogen bonded layers produced stronger compacts than salts showing one-dimensional networks of non-bonded columns, probably by reducing the attachment energy between layers. When hydrogen bonds are created intramolecularly, it is possible that the mechanical properties are compromised as they do not contribute so much to create twodimensional densely bonded layers and they can force molecules into strained conformations. Some types of hydrogen bonding network may be associated with improved mechanical properties, such as type II, or R (10) 3 4 using graph-set notation, versus type III, or R (12) 4 8 , columns. This work clearly demonstrates the potential of investigating crystal structure-mechanical property relationship in pharmaceutical materials.
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Objective: Biomedical events extraction concerns about events describing changes on the state of bio-molecules from literature. Comparing to the protein-protein interactions (PPIs) extraction task which often only involves the extraction of binary relations between two proteins, biomedical events extraction is much harder since it needs to deal with complex events consisting of embedded or hierarchical relations among proteins, events, and their textual triggers. In this paper, we propose an information extraction system based on the hidden vector state (HVS) model, called HVS-BioEvent, for biomedical events extraction, and investigate its capability in extracting complex events. Methods and material: HVS has been previously employed for extracting PPIs. In HVS-BioEvent, we propose an automated way to generate abstract annotations for HVS training and further propose novel machine learning approaches for event trigger words identification, and for biomedical events extraction from the HVS parse results. Results: Our proposed system achieves an F-score of 49.57% on the corpus used in the BioNLP'09 shared task, which is only 2.38% lower than the best performing system by UTurku in the BioNLP'09 shared task. Nevertheless, HVS-BioEvent outperforms UTurku's system on complex events extraction with 36.57% vs. 30.52% being achieved for extracting regulation events, and 40.61% vs. 38.99% for negative regulation events. Conclusions: The results suggest that the HVS model with the hierarchical hidden state structure is indeed more suitable for complex event extraction since it could naturally model embedded structural context in sentences.
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Melt quenched silicate glasses containing calcium, phosphorus and alkali metals have the ability to promote bone regeneration and to fuse to living bone. Of these glasses 45S5 Bioglass® is the most widely used being sold in over 35 countries as a bone graft product for medical and dental applications; particulate 45S5 is also incorporated into toothpastes to help remineralize the surface of teeth. Recently it has been suggested that adding titanium dioxide can increase the bioactivity of these materials. This work investigates the structural consequences of incorporating 4 mol% TiO2 into Bioglass® using isotopic substitution (of the Ti) applied to neutron diffraction and X-ray Absorption Near Edge Structure (XANES). We present the first isotopic substitution data applied to melt quench derived Bioglass or its derivatives. Results show that titanium is on average surrounded by 5.2(1) nearest neighbor oxygen atoms. This implies an upper limit of 40% four-fold coordinated titanium and shows that the network connectivity is reduced from 2.11 to 1.97 for small quantities of titanium. Titanium XANES micro-fluorescence confirms the titanium environment is homogenous on the micron length scale within these glasses. Solid state magic angle spinning (MAS) NMR confirms the network connectivity model proposed. Furthermore, the results show the intermediate range order containing Na-O, Ca-O, O-P-O and O-Si-O correlations are unaffected by the addition of small quantities of TiO2 into these systems.
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In contrast to Se[CH2C(O)OH]2 versus S[CH2C(O)OH](2), the title compound, Se[CH(2)CH(2)C(O)OH]2 or C6H10O4Se, is structurally quite similar to its sulfur analogue. The molecule has twofold symmetry. The C-Se-C bond angle is 96.48 (8) degrees and the Se-C bond lengths are 1.9610 (14) Å. The shortest SeO intermolecular distance is 3.5410 (11) Å. The OO distances in the carboxylic acid dimers are 2.684 (2) Å. The temperature dependence of the IR spectrum suggests tautomerism in the solid state. Formula: C6H10O4Se
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The work investigates the adhesive/cohesive molecular and physical interactions together with nanoscopic features of commonly used orally disintegrating tablet (ODT) excipients microcrystalline cellulose (MCC) and D-mannitol. This helps to elucidate the underlying physico-chemical and mechanical mechanisms responsible for powder densification and optimum product functionality. Atomic force microscopy (AFM) contact mode analysis was performed to measure nano-adhesion forces and surface energies between excipient-drug particles (6-10 different particles per each pair). Moreover, surface topography images (100 nm2-10 μm2) and roughness data were acquired from AFM tapping mode. AFM data were related to ODT macro/microscopic properties obtained from SEM, FTIR, XRD, thermal analysis using DSC and TGA, disintegration testing, Heckel and tabletability profiles. The study results showed a good association between the adhesive molecular and physical forces of paired particles and the resultant densification mechanisms responsible for mechanical strength of tablets. MCC micro roughness was 3 times that of D-mannitol which explains the high hardness of MCC ODTs due to mechanical interlocking. Hydrogen bonding between MCC particles could not be established from both AFM and FTIR solid state investigation. On the contrary, D-mannitol produced fragile ODTs due to fragmentation of surface crystallites during compression attained from its weak crystal structure. Furthermore, AFM analysis has shown the presence of extensive micro fibril structures inhabiting nano pores which further supports the use of MCC as a disintegrant. Overall, excipients (and model drugs) showed mechanistic behaviour on the nano/micro scale that could be related to the functionality of materials on the macro scale. © 2014 Al-khattawi et al.
Resumo:
Grewia polysaccharide gum, a potential pharmaceutical excipient was extracted from the inner stem bark of Grewia mollis, thereupon drying was achieved by three techniques: air-drying, freeze-drying and spray-drying. Analysis of the monosaccharide composition including 1H and 13C NMR spectroscopic analysis of the polysaccharide gum was carried out. The effect of the drying methods on the physicochemical properties of the gum was evaluated by Fourier transformed infra-red (FT-IR) spectroscopy, solid-state 13C nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis, differential scanning calorimetry and gel permeation chromatography. Monosaccharide sugar analysis revealed that the gum is composed of glucose, rhamnose, galactose, arabinose and xylose as the main neutral sugars. These were supported by the results from 1H and 13C NMR spectroscopic analysis. FT-IR and solid-state NMR results indicated that drying technique has little effect on the structure of the polysaccharide gum but XPS showed that surface chemistry of the gum varied with drying methods. Thermogravimetric analyses showed that oxidation onset varied according to the drying method. The molecular weight was also dependent on the drying technique. For industrial extrapolation, air-drying may be preferable to spray-drying and freeze-drying when relative cost, product stability and powder flow are required, for example in tablet formulation. © 2010 Elsevier Ltd. All rights reserved.
Resumo:
Sol-gel-synthesized bioactive glasses may be formed via a hydrolysis condensation reaction, silica being introduced in the form of tetraethyl orthosilicate (TEOS), and calcium is typically added in the form of calcium nitrate. The synthesis reaction proceeds in an aqueous environment; the resultant gel is dried, before stabilization by heat treatment. These materials, being amorphous, are complex at the level of their atomic-scale structure, but their bulk properties may only be properly understood on the basis of that structural insight. Thus, a full understanding of their structure-property relationship may only be achieved through the application of a coherent suite of leading-edge experimental probes, coupled with the cogent use of advanced computer simulation methods. Using as an exemplar a calcia-silica sol-gel glass of the kind developed by Larry Hench, in the memory of whom this paper is dedicated, we illustrate the successful use of high-energy X-ray and neutron scattering (diffraction) methods, magic-angle spinning solid-state NMR, and molecular dynamics simulation as components to a powerful methodology for the study of amorphous materials.
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Aluminum oxide (Al2O3, or alumina) is a conventional ceramic known for applications such as wear resistant coatings, thermal liners, heaters, crucibles, dielectric systems, etc. However applications of Al 2O3 are limited owing to its inherent brittleness. Due to its excellent mechanical properties and bending strength, carbon nanotubes (CNT) is an ideal reinforcement for Al2O3 matrix to improve its fracture toughness. The role of CNT dispersion in the fracture toughening of the plasma sprayed Al2O3-CNT nanocomposite coating is discussed in the current work. Pretreatment of powder feedstock is required for dispersing CNTs in the matrix. Four coatings namely spray dried Al2O 3 (A-SD), Al2O3 blended with 4wt.% CNT (A4C-B), composite spray dried Al2O3-4wt.% CNT (A4C-SD) and composite spray dried A1203-8wt.% CNT (A8C-SD), are synthesized by plasma spraying. Owing to extreme temperatures and velocities involved in the plasma spraying of ceramics, retention of CNTs in the resulting coatings necessitates optimizing plasma processing parameters using an inflight particle diagnostic sensor. A bimodal microstructure was obtained in the matrix that consists of fully melted and resolidified structure and solid state sintered structure. CNTs are retained both in the fully melted region and solid-state sintered regions of processed coatings. Fracture toughness of A-SD, A4C-B, A4C-SD and A8C-SD coatings was 3.22, 3.86, 4.60 and 5.04 MPa m1/2 respectively. This affirms the improvement of fracture toughness from 20% (in A4C-B coating) to 43% (in A4C-SD coating) when compared to the A-SD coating because of the CNT dispersion. Fracture toughness improvement from 43% (in A4C-SD) to 57% (in A8C-SD) coating is evinced because of the CNT content. Reinforcement by CNTs is described by its bridging, anchoring, hook formation, impact alignment, fusion with splat, and mesh formation. The Al2O3/CNT interface is critical in assisting the stress transfer and utilizing excellent mechanical properties of CNTs. Mathematical and computational modeling using ab-initio principle is applied to understand the wetting behavior at the Al2O 3/CNT interface. Contrasting storage modulus was obtained by nanoindentation (∼210, 250, 250-350 and 325-420 GPa in A-SD, A4C-B, A4C-SD, and A8C-SD coatings respectively) depicting the toughening associated with CNT content and dispersion.
Resumo:
In this thesis, results of the investigation of a new low-dimensional cobaltates Ba2-xSrxCoO 4 are presented. The synthesis of both polycrystalline and single crystalline compounds using the methods of conventional solid state chemical reaction and floating-zone optical furnace is first introduced. Besides making polycrystalline powders, we successfully, for the first time, synthesized large single crystals of Ba2CoO4. Single crystals were also obtained for Sr doped Ba2-xSrxCoO 4. Powder and single crystal x-ray diffraction results indicate that pure Ba2CoO4 has a monoclinic structure at room temperature. With Sr doping, the lattice structure changes to orthorhombic when x ≥ 0.5 and to tetragonal when x = 2.0. In addition, Ba2CoO4 and Sr2CoO4, have completely different basic building blocks in the structure. One is CoO4 tetrahedron and the later is CoO6 octahedron, respectively. Electronic and magnetic properties were characterized and discussed. The magnetic susceptibility, specific heat and thermal conductivity show that Ba2CoO4 has an antiferromagnetic (AF) ground state with an AF ordering temperature TN = 25 K. However, the magnitude of the Néel temperature TN is significantly lower than the Curie-Weiss temperature (:&thetas;: ∼ 110 K), suggesting either reduced-dimensional magnetic interactions and/or the existence of magnetic frustration. The AF interaction persists in all the samples with different doping concentrations. The Néel temperature doesn't vary much in the monoclinic structure regime but decreases when the system enters orthorhombic. Magnetically, Ba2CoO4 has an AF insulating ground state while Sr2CoO4 has a ferromagnetic (FM) metallic ground state. Neutron powder refinement results indicate a magnetic structure with the spin mostly aligned along the a-axis. The result from a μ-spin rotation/relaxation (μ+SR) experiment agrees with our refinement. It confirms the AF order in the ab -plane. We also studied the spin dynamics and its anisotropy in the AF phase. The results from inelastic neutron scattering show that spin waves have a clear dispersion along a-axis but not along c-axis, indicating spin anisotropy. This work finds the strong spin-lattice coupling in this novel complex material. The interplay between the two degrees of freedom results an interesting phase diagram. Further research is needed when large single crystal samples are available.
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Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the "hydrogen economy" faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH 3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. ^ Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. ^ Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn2 1 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.^
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Aluminum oxide (A1203, or alumina) is a conventional ceramic known for applications such as wear resistant coatings, thermal liners, heaters, crucibles, dielectric systems, etc. However applications of A1203 are limited owing to its inherent brittleness. Due to its excellent mechanical properties and bending strength, carbon nanotubes (CNT) is an ideal reinforcement for A1203 matrix to improve its fracture toughness. The role of CNT dispersion in the fracture toughening of the plasma sprayed A1203-CNT nanocomposite coating is discussed in the current work. Pretreatment of powder feedstock is required for dispersing CNTs in the matrix. Four coatings namely spray dried A1203 (A-SD), A1203 blended with 4wt.% CNT (A4C-B), composite spray dried A1203-4wt.% CNT (A4C-SD) and composite spray dried A1203-8wt.% CNT (A8CSD), are synthesized by plasma spraying. Owing to extreme temperatures and velocities involved in the plasma spraying of ceramics, retention of CNTs in the resulting coatings necessitates optimizing plasma processing parameters using an inflight particle diagnostic sensor. A bimodal microstructure was obtained in the matrix that consists of fully melted and resolidified structure and solid state sintered structure. CNTs are retained both in the fully melted region and solid-state sintered regions of processed coatings. Fracture toughness of A-SD, A4C-B, A4C-SD and A8C-SD coatings was 3.22, 3.86, 4.60 and 5.04 MPa m1/2 respectively. This affirms the improvement of fracture toughness from 20 % (in A4C-B coating) to 43% (in A4C-SD coating) when compared to the A-SD coating because of the CNT dispersion. Fracture toughness improvement from 43 % (in A4C-SD) to 57% (in A8C-SD) coating is evinced because of the CNT content. Reinforcement by CNTs is described by its bridging, anchoring, hook formation, impact alignment, fusion with splat, and mesh formation. The A1203/CNT interface is critical in assisting the stress transfer and utilizing excellent mechanical properties of CNTs. Mathematical and computational modeling using ab-initio principle is applied to understand the wetting behavior at the A1203/CNTinterface. Contrasting storage modulus was obtained by nanoindentation (~ 210, 250, 250-350 and 325-420 GPa in A-SD, A4C-B, A4C-SD, and A8C-SD coatings respectively) depicting the toughening associated with CNT content and dispersion.
Resumo:
Ferroelectric ceramics with perovskite structure (ABO3) are widely used in solid state memories (FeRAM’s and DRAM's) as well as multilayered capacitors, especially as a thin films. When doped with zirconium ions, BaTiO3-based materials form a solid solution known as barium zirconate titanate (BaTi1-xZrxO3). Also called BZT, this material can undergo significant changes in their electrical properties for a small variation of zirconium content in the crystal lattice. The present work is the study of the effects of deposition parameters of BaTi0,75Zr0,25O3 thin films by spin-coating method on their morphology and physical properties, through an experimental design of the Box-Behnken type. The resin used in the process has been synthesized by the polymeric precursor method (Pechini) and subsequently split into three portions each of which has its viscosity adjusted to 10, 20 and 30 mPa∙s by means of a rotary viscometer. The resins were then deposited on Pt/Ti/SiO2/Si substrates by spin-coating method on 15 different combinations of viscosity, spin speed (3000, 5500 and 8000 rpm) and the number of deposited layers (5, 8 and 11 layers) and then calcined at 800 ° C for 1 h. The phase composition of the films was analyzed by X-ray diffraction (XRD) and indexed with the JCPDS 36-0019. Surface morphology and grain size were observed by atomic force microscopy (AFM) indicating uniform films and average grain size around 40 nm. Images of the cross section of the films were obtained by scanning electron microscopy field emission (SEM-FEG), indicating very uniform thicknesses ranging from 140-700 nm between samples. Capacitance measurements were performed at room temperature using an impedance analyzer. The films presented dielectric constant values of 55-305 at 100kHz and low dielectric loss. The design indicated no significant interaction effects between the deposition parameters on the thickness of the films. The response surface methodology enabled better observes the simultaneous effect of variables.