Effects of copper vapor laser irradiation (λ = 510.6 nm) on the enamel and dentine of human teeth: An ultra-structural morphologic study

Objective: A morphological and ultra-structural study of copper vapor laser (λ = 510.6 nm) effects on enamel and dentine was performed to show the effects of this radiation. Methods: A total of 15 human molars were cut in half; 15 pieces were separated for irradiation on enamel and 15 for dentine. These two groups were further divided into five experimental groups, including a control group, comprised of three half-sections each, irradiated by a CVL laser with a power of 7 W, a repetition rate of 15,000 pulses/sec and exposed at 500, 600, and 800 msec and 1 sec irradiation times with a 5-sec interval between irradiations. Results: In an ultra-structural SEM exam, we observed that on the enamel surfaces irradiated for 1 sec there was morphological alteration that consisted of catering, flaking, and melting on the surfaces. There was no alteration for the other exposure times. On the dentine teeth irradiated for 1 sec, we observed an evident ultra-structural alteration of melted tissue and loss of morphological characteristics. In the dentine group irradiated by 800 msec, we observed ablation and a partial loss of morphological characteristics. In the dentine groups irradiated by 500 and 600 msec, no alteration was observed. Conclusions: The results showed that irradiation with CVL promoted morphologic changes in the enamel as well as in the dentine and demonstrated a need for future studies in order to establish a safe protocol for further use in the odontological practice.

Influência do espaçamento do feixe de laser Nd: YAG na obtenção de óxidos e nitretos na superfície do titânio em pressão atmosférica

Neste trabalho investigou-se a modificação de superfície do titânio pela irradiação com feixe de Laser Nd:YAG. Os parâmetros do laser como a potência, o comprimento de onda, a frequência, a velocidade de varredura e a área de exposição foram mantidos constantes, exceto o espaçamento da matriz, o qual foi de 0,01 e 0,02 mm. A caracterização da superfície foi realizada por Microscopia Eletrônica de Varredura (MEV) e Difração de Raios X (DRX), sendo que os espectros foram refinados pelo método Rietveld. Pela análise de MEV, observou-se uma mudança na topografia, obtendo uma superfície rugosa produzida pelo fenômeno de ablação. As análises por Rietveld dos espectros de difração de raios X detectaram TiN, Ti2N, TiO2 (anatásio e rutilo), sendo que a amostra com espaçamento 0,01 mm apresentou uma maior quantidade de óxidos e nitretos. Isso pode ser devido à sobreposição do feixe, induzindo à formação de uma superfície com maior estabilidade termodinâmica. Os óxidos e nitretos obtidos são de grande importância, pois são responsáveis por produzir uma maior interação entre o osso-implante.

Caracterização mecânica e microestrutural de juntas soldadas a laser em aços maraging com posterior tratamento térmico e termoquímico de superfície a plasma

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Avaliação in vitro de superfícies de titânio irradiadas com laser de Er,Cr:YSGG

Introduction: As a new alternative in the complementary treatment lasers teem different systems were employed in the decontamination of dental surfaces implants however, some systems have caused significant changes in its surface. Purpose: Analyze by Scanning Electron Microscopy (SEM) the effects of laser irradiation of Er,Cr: YSGG on different surfaces of titanium. Material and method: Study of 20 titanium discs, and 10 Machined Surface (MS) and 10 surfaces treated with acid (AC). The 10 discs with the same treatment were divided into two groups with five units each, the irradiation was performed in powers of 1 W and 2 W. Result: Showed that the irradiation with 1 W of power resulted in no significant morphological changes in the MS-irradiated compared to non-irradiated surfaces. In MS surfaces, minor changes were observed in the increase of 1000× when compared to non-irradiated surface. With 2 W of power, there were no significant morphological changes in the MS, compared to non-irradiated areas. In AC some changes were observed in the increase of X 1000, showing areas of wear suggestive of treatment and some areas with melting point. Conclusion: Considering the results and the parameters used in this study it was concluded that the Er, Cr: YSGG irradiation can be used for the machined surfaces of implants, but in acid-treated surfaces irradiation parameters should be more controlled.

Influência dos tratamentos térmicos na microestrutura e nos micromecanismos de fratura da liga ti-6al-4v produzida por sinterização direta de metal por laser (DMLS)

Pós-graduação em Engenharia Mecânica - FEIS

Reparo ósseo em scaffolds de TI6AL4V sinterizados pela tecnologia de sinterização direta de metais a laser (DMLS) submetidos a tratamento de superfície associado à aplicação de ultrassom de baixa intensidade (LIPUS)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of pulse repetition rate and number of pulses in the analysis of polypropylene and high density polyethylene by nanosecond infrared laser induced breakdown spectroscopy

Pulse repetition rates and the number of laser pulses are among the most important parameters that do affect the analysis of solid materials by laser induced breakdown spectroscopy, and the knowledge of their effects is of fundamental importance for suggesting analytical strategies when dealing with laser ablation processes of polymers. In this contribution, the influence of these parameters in the ablated mass and in the features of craters was evaluated in polypropylene and high density polyethylene plates containing pigment-based PbCrO4. Surface characterization and craters profile were carried out by perfilometry and scanning electron microscopy. Area, volume and profile of craters were obtained using Taylor Map software. A laser induced breakdown spectroscopy system consisted of a Q-Switched Nd:YAG laser (1064 nm, 5 ns) and an Echelle spectrometer equipped with ICCD detector were used. The evaluated operating conditions consisted of 10, 25 and 50 laser pulses at 1, 5 and 10 Hz, 250 mJ/pulse (85 J cm(-2)), 2 mu s delay time and 6 mu s integration time gate. Differences in the topographical features among craters of both polymers were observed. The decrease in the repetition rate resulted in irregular craters and formation of edges, especially in polypropylene sample. The differences in the topographical features and ablated masses were attributed to the influence of the degree of crystallinity, crystalline melting temperature and glass transition temperature in the ablation process of the high density polyethylene and polypropylene. It was also observed that the intensities of chromium and lead emission signals obtained at 10 Hz were two times higher than at 5 Hz by keeping the number of laser pulses constant. (C) 2011 Elsevier B. V. All rights reserved.

Nd:YAG Laser Irradiation of Etched/Unetched Dentin Through an Uncured Two-step Etch-and-Rinse Adhesive and its Effect on Microtensile Bond Strength

Purpose: To evaluate whether Nd:YAG laser irradiation of etched and unetched dentin through an uncured adhesive affected the microtensile bond strength (pTBS). Materials and Methods: Flat dentin surfaces were created in 19 extracted human third molars. Adper Single Bond (SB) adhesive was applied over etched (groups 1 to 3) or unetched dentin (groups 4 to 6). The dentin was then irradiated with a Nd:YAG laser through the uncured adhesive, using 0.75 or 1 W power settings, except for the control groups (groups 1 and 4). The adhesive was light cured and composite crowns were built up. After 24 h, the teeth were sectioned into beams, with cross-sectional areas of 0.49 mm(2), and were stressed under tension. Data were statistically analyzed using two-way ANOVA and Tukey's test (alpha = 5%). Dentin surfaces of fractured specimens and the interfaces of untested beams were observed under scanning electron microscopy (SEM). Results: Acid etching, laser irradiation, and their interaction significantly affected bonding (p < 0.05). Laser irradiation did not improve bonding of etched dentin to resin (p > 0.05). However, higher pTBS means were found on unetched lased dentin (groups 5 and 6), but only in comparison to group 4, where neither lasing nor etching was performed. Groups 4 to 6 showed the lowest pTBS means among all groups tested (p < 0.05). Laser irradiation did not change the characteristics of the hybrid layers created, while solidification globules were observed on lased dentin surfaces under SEM. Conclusion: Laser irradiation of dentin through the uncured adhesive did not significantly improve the pTBS in comparison to the suggested manufacturer's technique.

Influence of prior 810-nm-diode intracanal laser irradiation on hydrophilic resin-based sealer obturation

Dentin wall structural changes caused by 810-nm-diode laser irradiation can influence the sealing ability of endodontic sealers. The objective of this study was to evaluate the apical leakage of AH Plus and RealSeal resin-based sealers with and without prior diode laser irradiation. Fifty-two single-rooted mandibular premolars were prepared and divided into 4 groups, according to the endodontic sealer used and the use or non-use of laser irradiation. The protocol for laser irradiation was 2.5W, continuous wave in scanning mode, with 4 exposures per tooth. After sample preparation, apical leakage of 50% ammoniacal silver nitrate impregnation was analyzed. When the teeth were not exposed to irradiation, the Real Seal sealer achieved the highest scores, showing the least leakage, with significant differences at the 5% level (Kruskal-Wallis test, p = 0.0004), compared with AH Plus. When the teeth were exposed to the 810-nm-diode laser irradiation, the sealing ability of AH Plus sealer was improved (p = 0282). In the Real Seal groups, the intracanal laser irradiation did not interfere with the leakage index, showing similar results in the GRS and GRSd groups (p = 0.1009).

Thermal alteration and morphological changes of sound and demineralized primary dentin after Er:YAG laser ablation

The purpose of this study was to assess the influence of Er:YAG laser pulse repetition rate on the thermal alterations occurring during laser ablation of sound and demineralized primary dentin. The morphological changes at the lased areas were examined by scanning electronic microscopy (SEM). To this end, 60 fragments of 30 sound primary molars were selected and randomly assigned to two groups (n = 30); namely A sound dentin (control) and B demineralized dentin. Each group was divided into three subgroups (n = 10) according to the employed laser frequencies: I4 Hz; II6 Hz, and III10 Hz. Specimens in group B were submitted to a pH-cycling regimen for 21 consecutive days. The irradiation was performed with a 250 mJ pulse energy in the noncontact and focused mode, in the presence of a fine water mist at 1.5 mL/min, for 15 s. The measured temperature was recorded by type K thermocouples adapted to the dentin wall relative to the pulp chamber. Three samples of each group were analyzed by SEM. The data were submitted to the nonparametric Kruskal-Wallis test and to qualitative SEM analysis. The results revealed that the temperature increase did not promote any damage to the dental structure. Data analysis demonstrated that in group A, there was a statistically significant difference among all the subgroups and the temperature rise was directly proportional to the increase in frequency. In group B, there was no difference between subgroup I and II in terms of temperature. The superficial dentin observed by SEM displayed irregularities that augmented with rising frequency, both in sound and demineralized tissues. In conclusion, temperature rise and morphological alterations are directly related to frequency increment in both demineralized and sound dentin. Microsc. Res. Tech., 2011. (c) 2011 Wiley Periodicals, Inc.

Screening of CO2 Laser (10.6 mu m) Parameters for Prevention of Enamel Erosion

Objective: The aim of this study was to screen CO2 laser (10.6 mu m) parameters to increase enamel resistance to a continuous-flow erosive challenge. Background data: A new clinical CO2 laser providing pulses of hundreds of microseconds, a range known to increase tooth acid-resistance, has been introduced in the market. Methods: Different laser parameters were tested in 12 groups (n = 20) with varying fluences from 0.1 to 0.9 J/cm(2), pulse durations from 80 to 400 mu s and repetition rates from 180 to 700 Hz. Non-lased samples (n = 30) served as controls. All samples were eroded by exposure to hydrochloric acid (pH 2.6) under continuous acid flow (60 mu L/min). Calcium and phosphate release into acid was monitored colorimetrically at 30 sec intervals up to 5 min and at 1 min intervals up to a total erosion time of 15 min. Scanning electron microscopic (SEM) analysis was performed in lased samples (n = 3). Data were statistically analysed by one-way ANOVA (p < 0.05) and Dunnett's post-hoc tests. Results: Calcium and phosphate release were significantly reduced by a maximum of 20% over time in samples irradiated with 0.4 J/cm(2) (200 mu s) at 450 Hz. Short-time reduction of calcium loss (<= 1.5 min) could be also achieved by irradiation with 0.7 J/cm(2) (300 mu s) at 200 and 300 Hz. Both parameters revealed surface modification. Conclusions: A set of CO2 laser parameters was found that could significantly reduce enamel mineral loss (20%) under in vitro erosive conditions. However, as all parameters also caused surface cracking, they are not recommended for clinical use.

Thermal effects and morphological aspects of human dentin surface irradiated with different frequencies of Er:YAG laser

This study reports the effects on micromorphology and temperature rise in human dentin using different frequencies of Er:YAG laser. Sixty human dentin fragments were randomly assigned into two groups (n = 30): carious or sound dentin. Both groups were divided into three subgroups (n = 10), according to the Er:YAG laser frequency used: 4, 6, or 10 Hz (energy: 200 mJ; irradiation distance: 12 mm; and irradiation time: 20 s). A thermocouple adapted to the tooth fragment recorded the initial temperature value (degrees C); then, the temperature was measured after the end of the irradiation (20 s). Morphological analysis was performed using images obtained with scanning electron microscope. There was no difference between the temperatures obtained with 4 and 6 Hz; the highest temperatures were achieved with 10 Hz. No difference was observed between carious and sound dentin. Morphological analyses revealed that all frequencies promoted irregular surface in sound dentin, being observed more selectively ablation especially in intertubular dentin with tubule protrusion. The caries dentin presented flat surface for all frequencies used. Both substrates revealed absence of any signs of thermal damage. It may be concluded that the parameters used in this study are capable to remove caries lesion, having acceptable limits of temperature rise and no significant morphological alterations on dentin surface. Microsc. Res. Tech. 2012. (c) 2012 Wiley Periodicals, Inc.

Outdoor bronze conservation: assessment of protective treatments by accelerated aging and of treatment removal procedures by laser cleaning

Outdoor bronzes exposed to the environment form naturally a layer called patina, which may be able to protect the metallic substrate. However, since the last century, with the appearance of acid rains, a strong change in the nature and properties of the copper based patinas occurred [1]. Studies and general observations have established that bronze corrosion patinas created by acid rain are not only disfiguring in terms of loss of detail and homogeneity, but are also unstable [2]. The unstable patina is partially leached away by rainwater. This leaching is represented by green streaking on bronze monuments [3]. Because of the instability of the patina, conservation techniques are usually required. On a bronze object exposed to the outdoor environment, there are different actions of the rainfall and other atmospheric agents as a function of the monument shape. In fact, we recognize sheltered and unsheltered areas as regards exposure to rainwater [4]. As a consequence of these different actions, two main patina types are formed on monuments exposed to the outdoor environment. These patinas have different electrochemical, morphological and compositional characteristics [1]. In the case of sheltered areas, the patina contains mainly copper products, stratified above a layer strongly enriched in insoluble Sn oxides, located at the interface with the uncorroded metal. Moreover, different colors of the patina result from the exposure geometry. The surface color may be pale green for unsheltered areas, and green and mat black for sheltered areas [4]. Thus, in real outdoor bronze monuments, the corrosion behavior is strongly influenced by the exposure geometry. This must be taken into account when designing conservation procedures, since the patina is in most cases the support on which corrosion inhibitors are applied. Presently, for protecting outdoor bronzes against atmospheric corrosion, inhibitors and protective treatments are used. BTA and its derivatives, which are the most common inhibitors used for copper and its alloy, were found to be toxic for the environment and human health [5, 6]. Moreover, it has been demonstrated that BTA is efficient when applied on bare copper but not as efficient when applied on bare bronze [7]. Thus it was necessary to find alternative compounds. Silane-based inhibitors (already successfully tested on copper and other metallic substrates [8]), were taken into consideration as a non-toxic, environmentally friendly alternative to BTA derivatives for bronze protection. The purpose of this thesis was based on the assessment of the efficiency of a selected compound, to protect the bronze against corrosion, which is the 3-mercapto-propyl-trimethoxy-silane (PropS-SH). It was selected thanks to the collaboration with the Corrosion Studies Centre “Aldo Daccò” at the Università di Ferrara. Since previous studies [9, 10, 11] demonstrated that the addition of nanoparticles to silane-based inhibitors leads to an increase of the protective efficiency, we also wanted to evaluate the influence of the addition of CeO2, La2O3, TiO2 nanoparticles on the protective efficiency of 3-mercapto-propyl-trimethoxy-silane, applied on pre-patinated bronze surfaces. This study is the first section of the thesis. Since restorers have to work on patinated bronzes and not on bare metal (except for contemporary art), it is important to be able to recreate the patina, under laboratory conditions, either in sheltered or unsheltered conditions to test the coating and to obtain reliable results. Therefore, at the University of Bologna, different devices have been designed to simulate the real outdoor conditions and to create a patina which is representative of real application conditions of inhibitor or protective treatments. In particular, accelerated ageing devices by wet & dry (simulating the action of stagnant rain in sheltered areas [12]) and by dropping (simulating the leaching action of the rain in unsheltered areas [1]) tests were used. In the present work, we used the dropping test as a method to produce pre-patinated bronze surfaces for the application of a candidate inhibitor as well as for evaluating its protective efficiency on aged bronze (unsheltered areas). In this thesis, gilded bronzes were also studied. When they are exposed to the outside environment, a corrosion phenomenon appears which is due to the electrochemical couple gold/copper where copper is the anode. In the presence of an electrolyte, this phenomenon results in the formation of corrosion products than will cause a blistering of the gold (or a break-up and loss of the film in some cases). Moreover, because of the diffusion of the copper salts to the surface, aggregates and a greenish film will be formed on the surface of the sample [13]. By coating gilded samples with PropS-SH and PropS-SH containing nano-particles and carrying out accelerated ageing by the dropping test, a discussion is possible on the effectiveness of this coating, either with nano-particles or not, against the corrosion process. This part is the section 2 of this thesis. Finally, a discussion about laser treatment aiming at the assessment of reversibility/re-applicability of the PropS-SH coating can be found in section 3 of this thesis. Because the protective layer loses its efficiency with time, it is necessary to find a way of removing the silane layer, before applying a new one on the “bare” patina. One request is to minimize the damages that a laser treatment would create on the patina. Therefore, different laser fluences (energy/surface) were applied on the sample surface during the treatment process in order to find the best range of fluence. In particular, we made a characterization of surfaces before and after removal of PropS-SH (applied on a naturally patinated surface, and subsequently aged by natural exposure) with laser methods. The laser removal treatment was done by the CNR Institute of Applied Physics “Nello Carrara” of Sesto Fiorentino in Florence. In all the three sections of the thesis, a range of non-destructive spectroscopic methods (Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), μ-Raman spectroscopy, X-Ray diffractometry (XRD)) were used for characterizing the corroded surfaces. AAS (Atomic Absorption Spectroscopy) was used to analyze the ageing solutions from the dropping test in sections 1 and 2.

Electrical scanning probe microscopy on organic optoelectronic structures

In the field of organic optoelectronics, the nanoscale structure of the materials has huge im-pact on the device performance. Here, scanning force microscopy (SFM) techniques become increasingly important. In addition to topographic information, various surface properties can be recorded on a nanometer length scale, such as electrical conductivity (conductive scanning force microscopy, C-SFM) and surface potential (Kelvin probe force microscopy, KPFM).rnrnIn the context of this work, the electrical SFM modes were applied to study the interplay be-tween morphology and electrical properties in hybrid optoelectronic structures, developed in the group of Prof. J. Gutmann (MPI-P Mainz). In particular, I investigated the working prin-ciple of a novel integrated electron blocking layer system. A structure of electrically conduct-ing pathways along crystalline TiO2 particles in an insulating matrix of a polymer derived ceramic was found and insulating defect structures could be identified. In order to get insights into the internal structure of a device I investigated a working hybrid solar cell by preparing a cross cut with focused ion beam polishing. With C-SFM, the functional layers could be identified and the charge transport properties of the novel active layer composite material could be studied. rnrnIn C-SFM, soft surfaces can be permanently damaged by (i) tip induced forces, (ii) high elec-tric fields and (iii) high current densities close to the SFM-tip. Thus, an alternative operation based on torsion mode topography imaging in combination with current mapping was intro-duced. In torsion mode, the SFM-tip vibrates laterally and in close proximity to the sample surface. Thus, an electrical contact between tip and sample can be established. In a series of reference experiments on standard surfaces, the working mechanism of scanning conductive torsion mode microscopy (SCTMM) was investigated. Moreover, I studied samples covered with free standing semiconducting polymer nano-pillars that were developed in the group of Dr. P. Theato (University Mainz). The application of SCTMM allowed non-destructive imag-ing of the flexible surface at high resolution while measuring the conductance on individual pillarsrnrnIn order to study light induced electrical effects on the level of single nanostructures, a new SFM setup was built. It is equipped with a laser sample illumination and placed in inert at-mosphere. With this photoelectric SFM, I investigated the light induced response in function-alized nanorods that were developed in the group of Prof. R. Zentel (University Mainz). A block-copolymer containing an anchor block and dye moiety and a semiconducting conju-gated polymer moiety was synthesized and covalently bound to ZnO nanorods. This system forms an electron donor/acceptor interface and can thus be seen as a model system of a solar cell on the nanoscale. With a KPFM study on the illuminated samples, the light induced charge separation between the nanorod and the polymeric corona could not only be visualized, but also quantified.rnrnThe results demonstrate that electrical scanning force microscopy can study fundamental processes in nanostructures and give invaluable feedback to the synthetic chemists for the optimization of functional nanomaterials.rn

Real-Time Multimodal Retinal Image Registration for a Computer Assisted Laser Photocoagulation System

An algorithm for the real-time registration of a retinal video sequence captured with a scanning digital ophthalmoscope (SDO) to a retinal composite image is presented. This method is designed for a computer-assisted retinal laser photocoagulation system to compensate for retinal motion and hence enhance the accuracy, speed, and patient safety of retinal laser treatments. The procedure combines intensity and feature-based registration techniques. For the registration of an individual frame, the translational frame-to-frame motion between preceding and current frame is detected by normalized cross correlation. Next, vessel points on the current video frame are identified and an initial transformation estimate is constructed from the calculated translation vector and the quadratic registration matrix of the previous frame. The vessel points are then iteratively matched to the segmented vessel centerline of the composite image to refine the initial transformation and register the video frame to the composite image. Criteria for image quality and algorithm convergence are introduced, which assess the exclusion of single frames from the registration process and enable a loss of tracking signal if necessary. The algorithm was successfully applied to ten different video sequences recorded from patients. It revealed an average accuracy of 2.47 ± 2.0 pixels (∼23.2 ± 18.8 μm) for 2764 evaluated video frames and demonstrated that it meets the clinical requirements.