Valorização de resíduos industriais na formulação de produtos e pigmentos cerâmicos: processamento e desenvolvimento de cor

A valorização de diferentes resíduos industriais provenientes dosector de tratamento/revestimento de superfícies metálicas pode ser obtida utilizando-os como matérias-primas na formulação de pigmentos cerâmicos, sintetizados pelo método cerâmico convencional. Neste trabalho avaliou-se a viabilidade de incorporar lamas geradas pelos processos de (i) anodização, ricas em alumínio, (ii) de niquelagem e cromagem de torneiras, usadas como fonte de níquel e crómio, e (iii) da decapagem química de aços de uma trefilaria, ricas em ferro, utilizadas por si só, ou em conjunto com matérias-primas comerciais, para a obtenção depigmentos cerâmicos que coram, de forma estável, diversas matrizes cerâmicas e vítreas. Esta solução assegura ainda a inertização de potenciaisespécies perigosas presentes nos resíduos, resultando produtos inócuospara a saúde pública. Procedeu-se à caracterização de cada resíduo, em termos de composição química e mineralógica, comportamento térmico, grau de toxicidade, distribuição granulométrica, teor de humidade, etc. Verificou-se a constância das características das lamas, recorrendo à análise de lotes recolhidos em momentos distintos. Os resíduos são essencialmente constituídos por hidróxidos metálicos e foram utilizados após secagem e desagregação. No entanto, a lama de anodização de alumínio sofreu um tratamento térmico suplementar a 1400ºC. O método de síntese dos pigmentos englobou as seguintes etapas: (i) doseamento; (ii) homogeneização; (iii) calcinação; (iv) lavagem e moagem.Procedeu-se à caracterização dos pigmentos, avaliando a cor por espectroscopia de reflectância difusae pelo método CIELAB e determinando as características físico-químicas relevantes. Posteriormente, testou-se o seu desempenho em produtos cerâmicos distintos (corpos e vidrados), aferindo o desempenho cromático e a estabilidade. Numa primeira fase, desenvolveram-se e caracterizaram-se tipos distintos de pigmentos: (i) com base na estrutura do corundo (ii) verde Victória deuvarovite (iii) violeta de cassiterite com crómio (iv) pigmento carmim de malaiaíte; (v)pretos e castanhos com base na estrutura da espinela. Aprofundaram-se depois os estudos do pigmento carmim de malaiaítee do pigmento preto com base na estrutura da espinela. O pigmento carmim de malaiaíte, CaSnSiO5:Cr2O3, é formulado coma lama gerada no processo de niquelagem e cromagem. Avaliou-se a influência do teor de lama na temperatura de síntese e na qualidade cromática, em comparação com um pigmento formulado com reagentes puros. O pigmento preto com estrutura de espinela de níquel, crómio e ferro, foii formulado exclusivamente a partir das lamas geradas nos processos de cromagem/niquelagem e de decapagem química do aço. Avaliaram-se as características cromáticas e o grau de inertização dos elementos tóxicospresentes, em função da estequiometria e do tratamento térmico. Estudou-se ainda um novo sistema com base na estrutura da hibonite(CaAl12O19), que permite a obtenção de pigmentos azuis e que utiliza a lama de cromagem e niquelagem. As espécies cromóforas (Ni2+ ou Co2+) assumem coordenação tetraédrica quando substituem os iões Al3+ que ocupam as posições M5 da rede da hibonite. A formação simultânea de anortite permite reduzir a temperatura de síntese.Para além do carácter inovador deste pigmento de dissolução sólida, a qualidade cromática e a sua estabilidade são interessantes. Além disso, os teores de cobalto ou níquel são reduzidosrelativamente aos utilizados em formulações comerciais de pigmentos azuis, o que se traduz em importantes vantagens económicas e ambientais.

Trace metals in size-fractionated particulate matter in a Portuguese hospital: exposure risks assessment and comparisons with other countries

Hospitals are considered as a special and important type of indoor public place where air quality has significant impacts on potential health outcomes. Information on indoor air quality of these environments, concerning exposures to particulate matter (PM) and related toxicity, is limited though. This work aims to evaluate risks associated with inhalation exposure to ten toxic metals and chlorine (As, Ni, Cr, Cd, Pb, Mn, Se, Ba, Al, Si, and Cl) in coarse (PM2.5–10) and fine (PM2.5) particles in a Portuguese hospital in comparison with studies representative of other countries. Samples were collected during 1 month in one urban hospital; elemental PM characterization was determined by proton-induced X-ray emission. Noncarcinogenic and carcinogenic risks were assessed according to the methodology provided by the United States Environmental Protection Agency (USEPA; Region III Risk-Based Concentration Table) for three different age categories of hospital personnel (adults, >20, and <65 years) and patients (considering nine different age groups, i.e., children of 1–3 years to seniors of >65 years). The estimated noncarcinogenic risks due to occupational inhalation exposure to PM2.5-bound metals ranged from 5.88×10−6 for Se (adults, 55–64 years) to 9.35×10−1 for As (adults, 20–24 years) with total noncarcinogenic risks (sum of all metals) above the safe level for all three age categories. As and Cl (the latter due to its high abundances) were the most important contributors (approximately 90 %) to noncarcinogenic risks. For PM2.5–10, noncarcinogenic risks of all metals were acceptable to all age groups. Concerning carcinogenic risks, for Ni and Pb, they were negligible (<1×10−6) in both PM fractions for all age groups of hospital personnel; potential risks were observed for As and Cr with values in PM2.5 exceeding (up to 62 and 5 times, respectively) USEPA guideline across all age groups; for PM2.5–10, increased excess risks of As and Cr were observed particularly for long-term exposures (adults, 55–64 years). Total carcinogenic risks highly (up to 67 times) exceeded the recommended level for all age groups, thus clearly showing that occupational exposure to metals in fine particles pose significant risks. If the extensive working hours of hospital medical staff were considered, the respective noncarcinogenic and carcinogenic risks were increased, the latter for PM2.5 exceeding the USEPA cumulative guideline of 10−4. For adult patients, the estimated noncarcinogenic and carcinogenic risks were approximately three times higher than for personnel, with particular concerns observed for children and adolescents.

Studies on the Nature and Chemistry of Sediments and Water of Periyar and Chalakudy Rivers, Kerala, India

The present study is an attempt to address issues related to sediment properties like texture, mineralogy and geochemistry as well as water quality of two important rivers of central Kerala-the Periyar and the Chalakudy rivers. The main objectives of the study are to investigate the textural and mineralogical characteristics as well as transportation and depositional mechanisms of the sediments of Periyar and Chalakudy rivers, to find out the geochemical variability of organic carbon, phosphorus and certain major (Na,K,Ca and Mg) and minor/trace(Mn,Pb,Ni,Cr, and Zn) elements in the bulk sediments and mud fraction of these rivers, to evaluate the status of heavy metal pollution registered in the sediments of these rivers, to assess the physico-chemical characteristics and water quality of Periyar and Chalakudy rivers and to estimate the dissolved nutrient flux through the Periyar and Chalakudy rivers into the receiving coastal waters. The granulometric characteristics as well as statistical parameters of the sediments of Periyar and Chalakudy rivers depend on the flow pattern controlled by the gradient of the terrain. Compared to Periyar, fluctuations in the dispersal of particles are more in Chalakudy river. In Periyar river, the P and Fe in bulk sediments show a positive correlation with C-org, while in Chalakudy river, both the elements are related to THM concentration. In general, C-org, Fe and P Shows an increasing trend downstream. In Periyar river, the P and Fe in bulk sediments show a positive correlation with C-org, while in Chalakudy river, both the elements are related to THM concentration. Among these two rivers, the pollution of water is several fold higher in Periyar river due to influx due to influx of considerable quantity of liquid and solid wastes of industrial/domestic/urban origin. Nutrient analysis reveals 2-3 times increase in N and P during monsoon season whereas SiO2-Si shows a decreasing trend.

Effects of Platinum on NiPtSiGe/n-SiGe and NiPtSi/n-Si Schottky Contacts

Solid phase reaction of NiPt/Si and NiPt/SiGe is one of the key issues for silicide (germanosilicide) technology. Especially, the NiPtSiGe, in which four elements are involved, is a very complex system. As a result, a detailed study is necessary for the interfacial reaction between NiPt alloy film and SiGe substrate. Besides using traditional material characterization techniques, characterization of Schottky diode is a good measure to detect the interface imperfections or defects, which are not easy to be found on large area blanket samples. The I-V characteristics of 10nm Ni(Pt=0, 5, 10 at.%) germanosilicides/n-Si₀/₇Ge₀.₃ and silicides/n-Si contact annealed at 400 and 500°C were studied. For Schottky contact on n-Si, with the addition of Pt in the Ni(Pt) alloy, the Schottky barrier height (SBH) increases greatly. With the inclusion of a 10% Pt, SBH increases ~0.13 eV. However, for the Schottky contacts on SiGe, with the addition of 10% Pt, the increase of SBH is only ~0.04eV. This is explained by pinning of the Fermi level. The forward I-V characteristics of 10nm Ni(Pt=0, 5, 10 at.%)SiGe/SiGe contacts annealed at 400°C were investigated in the temperature range from 93 to 300K. At higher temperature (>253K) and larger bias at low temperature (<253K), the I-V curves can be well explained by a thermionic emission model. At lower temperature, excess currents at lower forward bias region occur, which can be explained by recombination/generation or patches due to inhomogenity of SBH with pinch-off model or a combination of the above mechanisms.

Effect of Misfit on Preload Maintenance of Retention Screws of Implant-Supported Prostheses

The aim of this study was to evaluate the effect of unilateral misfit at different levels on a crown-implant-retention screw system of implant-supported crowns. Hexagon castable UCLA abutments were cast in Co-Cr alloy to fabricate 48 metallic crowns divided into four groups (n = 12). Group A: crowns did not present misfit; Groups B, C and D: crowns were fabricated with unilateral misfit of 50, 100, and 200 mu m, respectively. The crowns were attached by titanium retention screw with 30 N/cm to external hexagonal osseointegrated implants embedded in acrylic resin. After 2 min, the retention screw of each replica was submitted to detorque evaluation by an analogic torque gauge. Three retention screws were used to perform detorque evaluation at each replica and the procedure was repeated twice with each screw. Each group was submitted to 72 detorque measurements. Data were evaluated by ANOVA and Tukey test (P < 0.05). All groups exhibited significant decrease (P < 0.05) in preload and the lowest decrease occurred in Group A. Groups B, C, and D were statistically significant different from Group A (P < 0.05), but there was no statistically significant difference between Groups B and D (P > 0.05). Crowns with unilateral misfit presented higher preload decrease than crowns completely fitted to osseointegrated implants.

Effect of axial loads on implanted-supported partial fixed prostheses by strain gauge analysis

Objectives: The present study used strain gauge analysis to perform an in vitro evaluation of the effect of axial loading on 3 elements of implant-supported partial fixed prostheses, varying the type of prosthetic cylinder and the loading points. Material and methods: Three internal hexagon implants were linearly embedded in a polyurethane block. Microunit abutments were connected to the implants applying a torque of 20 Ncm, and prefabricated Co-Cr cylinders and plastic prosthetic cylinders were screwed onto the abutments, which received standard patterns cast in Co-Cr alloy (n=5). Four strain gauges (SG) were bonded onto the surface of the block tangentially to the implants, SG 01 mesially to implant 1, SG 02 and SG 03 mesially and distally to implant 2, respectively, and SG 04 distally to implant 3. Each metallic structure was screwed onto the abutments with a 10 Ncm torque and an axial load of 30 kg was applied at five predetermined points (A, B, C, D, E). The data obtained from the strain gauge analyses were analyzed statistically by RM ANOVA and Tukey's test, with a level of significance of p<0.05. Results: There was a significant difference for the loading point (p=0.0001), with point B generating the smallest microdeformation (239.49 mu epsilon) and point D the highest (442.77 mu epsilon). No significant difference was found for the cylinder type (p=0.748). Conclusions: It was concluded that the type of cylinder did not affect in the magnitude of microdeformation, but the axial loading location influenced this magnitude.

Influence of Surface Treatment on the Shear Bond Strength of Ceramics Fused to Cobalt-Chromium

Purpose: To evaluate the influence of surface treatment on the shear bond strength between a Co-Cr alloy and two ceramics.Materials and Methods: Forty-eight metal cylinders were made (thickness: 4 mm, height: 3.7 mm) according ISO TR 11405. The 48 metallic cylinders were divided into four groups (n = 12), according to the veneering ceramic (StarLight Ceram and Duceram Kiss) and surface treatments: air-particle abrasion with Al(2)O(3) or tungsten drill (W). Gr1: StarLight + Al(2)O(3); Gr2: StarLight + W; Gr3: Duceram + Al(2)O(3); and Gr4: Duceram + W. The specimens were aged using thermal cycling (3000 x, 5 to 55 degrees C, dwell time: 30 seconds, transfer time: 2 seconds). The shear test was performed with a universal testing machine, using a load cell of 100 kg (speed: 0.5 mm/min) and a specific device. The bond strength data were analyzed using ANOVA and Tukey's test (5%), and the failure modes were analyzed using an optical microscope (30x).Results: The means and standard deviations of the shear bond strengths were (MPa): G1 (57.97 +/- 11.34); G2 (40.62 +/- 12.96); G3 (47.09 +/- 13.19); and G4 (36.80 +/- 8.86). Ceramic (p = 0.03252) and surface treatment (p = 0.0002) significantly affected the mean bond strength values.Conclusions: Air-particle abrasion with Al(2)O(3) improved the shear bond strength between metal and ceramics used.

Machined and plastic copings in three-element prostheses with different types of implant-abutment joints: a strain gauge comparative analysis

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

Straight and Offset Implant Placement under Axial and Nonaxial Loads in Implant-Supported Prostheses: Strain Gauge Analysis

Purpose: The aim of this in vitro study was to quantify strain development during axial and nonaxial loading using strain gauge analysis for three-element implant-supported FPDs, varying the arrangement of implants: straight line (L) and offset (O). Materials and Methods: Three Morse taper implants arranged in a straight line and three implants arranged in an offset configuration were inserted into two polyurethane blocks. Microunit abutments were screwed onto the implants, applying a 20 Ncm torque. Plastic copings were screwed onto the abutments, which received standard wax patterns cast in Co-Cr alloy (n = 10). Four strain gauges were bonded onto the surface of each block tangential to the implants. The occlusal screws of the superstructure were tightened onto microunit abutments using 10 Ncm and then axial and nonaxial loading of 30 Kg was applied for 10 seconds on the center of each implant and at 1 and 2 mm from the implants, totaling nine load application points. The microdeformations determined at the nine points were recorded by four strain gauges, and the same procedure was performed for all of the frameworks. Three loadings were made per load application point. The magnitude of microstrain on each strain gauge was recorded in units of microstrain (mu). The data were analyzed statistically by two-way ANOVA and Tukey's test (p < 0.05). Results: The configuration factor was statistically significant (p= 0.0004), but the load factor (p= 0.2420) and the interaction between the two factors were not significant (p= 0.5494). Tukey's test revealed differences between axial offset (mu) (183.2 +/- 93.64) and axial straight line (285.3 +/- 61.04) and differences between nonaxial 1 mm offset (201.0 +/- 50.24) and nonaxial 1 mm straight line (315.8 +/- 59.28). Conclusion: There was evidence that offset placement is capable of reducing the strain around an implant. In addition, the type of loading, axial force or nonaxial, did not have an influence until 2 mm.

Electrochemical and structural characterization of heat-treated Cr3C2-NiCr coatings

The influence of heat-treatments on the electrochemical behavior of thermal spray Cr3C2-NiCr coatings prepared by high velocity oxygen fuel (HVOF) was studied in NaCl solution, at 25 degrees C, using open-circuit potential (E-OC) and electrochemical impedance spectroscopy (EIS) measurements. Coating characterization were performed before and after the heat-treatments and electrochemical tests by scanning electron microscopy, X-ray diffraction, and Auger electron spectroscopy. In addition to the changes in the original powder composition occurring during HVOF process, heat-treatment performed at 450 degrees C caused no significant changes in electrochemical response compared with untreated sample, and at 760 degrees C the main difference was the formation of a thin and defective layer of Cr2O3 at the coating surface, which increased the total impedance at the first day of immersion. Higher influence on the electrochemical was noted for samples treated at 880 degrees C, which also showed higher E-OC and total impedance, and lower corrosion current. This behavior was interpreted considering the formation of a chromium oxide layer on the coating surface, dissolution and decomposition of smaller carbide particles and their surface enrichment with Cr due to C diffusion and dissolution into the matrix, and possible Ni, Cr, and Fe diffusion to coating/substrate interface. (c) 2006 the Electrochemical Society.

Comparison of metallic and ceramic tubes as atomization cells for tin determination by TS-FF-AAS

This work describes the development of an analytical procedure for on-line tin determination using thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS). Two tubes were evaluated as atomization cells: a metallic tube (Ni-Cr, principal components composition: 73.95% Ni and 16.05% Cr) and a ceramic tube (99.8% Al2O3). The use of air as the carrier was made by employing a Rheodyne valve to inject the samples, allowing an analytical frequency of 90 h(-1) and avoiding sample dispersion. The carrier flow rate (air), sample volume injected, and acid concentration (HCl) were evaluated for the optimization of the TS-FF-AAS system. The sensitivity for 50 mL of analytical solution with TS-FF-AAS was 2 and 5 times higher (to metallic and ceramic tube, respectively) than using an acetylene-nitrous oxide flame with pneumatic aspiration (requiring a sample volume of approximately 20 times higher.

Shear bond strengths of a ceramic system to alternative metal alloys

Statement of problem. The success of metal-ceramic restorations is influenced by the compatibility between base metal alloys and porcelains. Although porcelain manufacturers recommend their own metal systems as the most compatible for fabricating metal-ceramic prostheses, a number of alloys have been used.Purpose. This study evaluated the shear bond strength between a porcelain system and 4 alternative alloys.Material and methods. Two Ni-Cr alloys: 4 ALL and Wiron 99, and 2 Co-Cr alloys: IPS d.SIGN 20 and Argeloy NP were selected for this study. The porcelain (IPS d.Sign porcelain system) portion of the cylindrical inetal-ceramic specimens was 4 mm thick and 4 mm high; the metal portion was machined to 4 x 4 mm, with a base that was 5 nun thick and 1 mm high. Forty-four specimens were prepared (n=11). Ten specimens from each group were subjected to a shear load oil a universal testing machine using a 1 min/min crosshead speed. One specimen from each group was observed with a scanning electron microscope. Stress at failure (MPa) was determined. The data were analyzed with a 1-way analysis of variance (alpha=.05).Results. The groups, all including IPS d.Sign porcelain, presented the following mean bond strengths (+/-SD) in MPa: 4 ALL, 54.0 +/- 20.0; Wiron, 63.0 +/- 13.5; IPS d.SIGN 20, 71.7 +/- 19.2; Argeloy NP, 55.2 +/- 13.5. No significant differences were found among the shear bond strength values for the metal-ceramic specimens tested.Conclusion. None of the base metal alloys studied demonstrated superior bond strength to the porcelain tested.

Estudo comaprativo da resistência da união esmalt/resina/metal. Efeito de resinas de fixação, artifícios retentivos e ligas metálicas.

The purpose of this study was to compare the enamel/resin/metal bond tensile strength by using human canines, in which castings were bonded. These castings were obtained by Co-Cr or Ni-Cr alloys and showed four types of mechanisms of retention: 50 micrograms aluminum oxide abrasive, electrochemical etch, acrylic beads metal mesh. The castings were bonded utilizing Comspan Opaque and Panavia Ex. The specimens were subjected to tensile forces after 24 hours in an Instron machine. The castings subjected to 50 micrograms aluminum oxide abrasive and bonded utilizing Panavia EX showed the biggest bond tensile strength.

Effect of axial loads on implant-supported partial fixed prostheses by strain gauge analysis

Objectives: The present study used strain gauge analysis to perform an in vitro evaluation of the effect of axial loading on 3 elements of implant-supported partial fixed prostheses, varying the type of prosthetic cylinder and the loading points. Material and methods: Three internal hexagon implants were linearly embedded in a polyurethane block. Microunit abutments were connected to the implants applying a torque of 20 Ncm, and prefabricated Co-Cr cylinders and plastic prosthetic cylinders were screwed onto the abutments, which received standard patterns cast in Co-Cr alloy (n = 5). Four strain gauges (SG) were bonded onto the surface of the block tangentially to the implants, SG 01 mesially to implant 1, SG 02 and SG 03 mesially and distally to implant 2, respectively, and SG 04 distally to implant 3. Each metallic structure was screwed onto the abutments with a 10 Ncm torque and an axial load of 30 kg was applied at five predetermined points (A, B, C, D, E). The data obtained from the strain gauge analyses were analyzed statistically by RM ANOVA and Tukey's test, with a level of significance of p<0.05. Results: There was a significant difference for the loading point (p=0.0001), with point B generating the smallest microdeformation (239.49 με) and point D the highest (442.77 με). No significant difference was found for the cylinder type (p=0.748). Conclusions: It was concluded that the type of cylinder did not affect in the magnitude of microdeformation, but the axial loading location influenced this magnitude.

Automatic microstructural characterization and classification using artificial intelligence techniques on ultrasound signals

Secondary phases such as Laves and carbides are formed during the final solidification stages of nickel based superalloy coatings deposited during the gas tungsten arc welding cold wire process. However, when aged at high temperatures, other phases can precipitate in the microstructure, like the γ″ and δ phases. This work presents a new application and evaluation of artificial intelligent techniques to classify (the background echo and backscattered) ultrasound signals in order to characterize the microstructure of a Ni-based alloy thermally aged at 650 and 950 °C for 10, 100 and 200 h. The background echo and backscattered ultrasound signals were acquired using transducers with frequencies of 4 and 5 MHz. Thus with the use of features extraction techniques, i.e.; detrended fluctuation analysis and the Hurst method, the accuracy and speed in the classification of the secondary phases from ultrasound signals could be studied. The classifiers under study were the recent optimum-path forest (OPF) and the more traditional support vector machines and Bayesian. The experimental results revealed that the OPF classifier was the fastest and most reliable. In addition, the OPF classifier revealed to be a valid and adequate tool for microstructure characterization through ultrasound signals classification due to its speed, sensitivity, accuracy and reliability. © 2013 Elsevier B.V. All rights reserved.