Modification of Natural Rubber using Thermoset Resins

This thesis presents the findings of a study on incorporating vanous thermoset resins into natural rubber for property improvement. Natural rubber is an important elastomer with the unique attribute of being a renewable agricultural product. The study was undertaken to investigate the extent to which the drawbacks of natural rubber, especially its poor thermal and oil resistance propel1ies could be nullified by blending with common thermoset resins. A thorough and comparative understanding of the perfonnance of different resins from this viewpoint will be beneficial for both natural IUbber processors and consumers. In this study the thennoset resins used were epoxy resin, phenolics, epoxidised phenolics and unsaturated polyester resin.The resins were incorporated into NR during compounding and their effects on the properties of NR were studied after vulcanization. Properties were studied for both gum and filled N R compounds. The important properties studied are cure characteristics, mechanical properties, ageing propel1ies, thermal propel1ies, crosslink density and extractability. Characterization studies were also conducted using FTIR, TGA and DSC.Improvement in mechanical properties was noticed in many cases. The results show that most resins lead to a reduction in the cure time of NR. The perfonnance of epoxy resin is most noticeable in this respect. Mechanical properties of the modified IUbber show maximum improvement in the case of epoxidised novolacs. Most resins are seen to improve the thermal and oil resistance propel1ies of NR. Epoxy novolacs show maximum effect in this respect also. However the presence of tillers is found to moderate the positive effects of the thermoset resins considerably.

Digital image correlation analysis of the load transfer by implant-supported restorations

This study compared splinted and non-splinted implant-supported prosthesis with and without a distal proximal contact using a digital image correlation method. An epoxy resin model was made with acrylic resin replicas of a mandibular first premolar and second molar and with threaded implants replacing the second premolar and first molar. Splinted and non-splinted metal-ceramic screw-retained crowns were fabricated and loaded with and without the presence of the second molar. A single-camera measuring system was used to record the in-plane deformation on the model surface at a frequency of 1.0 Hz under a load from 0 to 250 N. The images were then analyzed with specialist software to determine the direct (horizontal) and shear strains along the model. Not splinting the crowns resulted in higher stress transfer to the supporting implants when the second molar replica was absent. The presence of a second molar and an effective interproximal contact contributed to lower stress transfer to the supporting structures even for non-splinted restorations. Shear strains were higher in the region between the molars when the second molar was absent, regardless of splinting. The opposite was found for the region between the implants, which had higher shear strain values when the second molar was present. When an effective distal contact is absent, non-splinted implant-supported restorations introduce higher direct strains to the supporting structures under loading. Shear strains appear to be dependent also on the region within the model, with different regions showing different trends in strain changes in the absence of an effective distal contact. (C) 2011 Elsevier Ltd. All rights reserved.

Effects of gamma radiation on the photoluminescence properties of polycarbonate matrices doped with terbium complex

Luminescent films containing terbium complex [Tb(acac)(3)(H(2)O)(3)] (acac = acetylacetonate) doped into a polycarbonate (PC) matrix were prepared and irradiated at low-dose gamma radiation with ratio of 5 and 10 kGy. The PC polymer was doped with 5% (w/w) of the Tb(3+) complex. The thermal behavior was investigated by utilization of differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA). Changes in thermal stability due to the addition of doping agent into the polycarbonate matrix. Based on the emission spectra of PC:5% Tb(acac)(3) film were observed the characteristic bands arising from the (5)D(4) -> (7)F(J) transitions of Tb(3+) ion (J = 0-6), indicating the ability to obtain the luminescent films. Doped samples irradiated at low dose of gamma irradiation showed a decrease in luminescence intensity with increasing of the dose. (C) 2009 Elsevier Ltd. All rights reserved.

Calorimetric investigations of luminescent films polycarbonate (PC) doped with europium complex [Eu(TTA)(3)(H(2)O)(2)]

Polymers doped with rare earth complexes are advantaged in film production for many applications in the luminescent field. In this luminescent polycarbonate (PC) films doped with diaquatris(thenoyltrifluoroacetonate)europium(III) complex [Eu(TTA)(3)(H(2)O)(2)] were prepared and their calorimetric and luminescent properties in the solid state are reported. The thermal behavior was investigated by utilization of differential scanning calorimetry (DSC) and thermogravimetry (TG). Due of the addition of rare earth [Eu(TTA)(3)(H(2)O)(2)] into PC matrix, changes were observed in the thermal behavior concerning the glass transition and thermal stability. Characteristic broadened narrow bands arising from the (5)D(0) -> (7)F(J) transitions (J = 4-0) of Eu(3+) ion indicate the incorporation of the Eu(3+) ions in the polymer. The luminescent films show enhancement emission intensity with an increase of rare earth concentration in polymeric matrix accompanied by decrease in thermal stability.

Desenvolvimento de tubulação em compósito polimérico revestida externamente com poliuretano de alta densidade

Pipelines for the transport of crude oil from the production wells to the collecting stations are named production lines . These pipes are subjected to chemical and electrochemical corrosion according to the environment and the type of petroleum transported. Some of these lines, depending upon the composition of the fluid produced, may leak within less than one year of operation due to internal corrosion. This work aims at the development of composite pipes with an external protecting layer of high density polyurethane for use in production lines of onshore oil wells, meeting operational requirements. The pipes were manufactured using glass fibers, epoxy resin, polyester resin, quartz sand and high density polyurethane. The pipes were produced by filament winding with the deposition of high density polyurethane on the external surface and threaded ends (API 15 HR/PM-VII). Three types of pipes were manufactured: glass/epoxy, glass/epoxy with an external polyurethane layer and glass/epoxy with an intermediate layer of glass fiber, polyester, sand and with an external polyurethane layer. The three samples were characterized by Scanning Electronic Microscopy (SEM) and for the determination of constituent content. In addition, the following tests were conducted: hydrostatic test, instant rupture, shorttime failure pressure, Gardner impact, transverse stiffness and axial tension. Field tests were conducted in Mossoró RN (BRAZIL), where 1,677 meters of piping were used. The tests results of the three types of pipes were compared in two events: after two months from manufacturing of the samples and after nine months of field application. The results indicate that the glass/epoxy pipes with an intermediate layer of fiber glass composite, polyester e sand and with an external layer of high density polyurethane showed superior properties as compared to the other two and met the requirements of pressure class, axial tensile strength, transverse stiffness, impact and environmental conditions, for onshore applications as production lines

Desenvolvimento e caracterização de nanocompósito de resina epóxi com nanopartículas de sílica para revestimento de dutos para transporte de petróleo

The use of polymer based coatings is a promising approach to reduce the corrosion problem in carbon steel pipes used for the transport of oil and gas in the oil industry. However, conventional polymer coatings offer limited properties, which often cannot meet design requirements for this type of application, particularly in regard to use temperature and wear resistance. Polymer nanocomposites are known to exhibit superior properties and, therefore, offer great potential for this type of application. Nevertheless, the degree of enhancement of a particular property is greatly dependent upon the matrix/nanoparticle material system used, the matrix/nanoparticle interfacial bonding and also the state of dispersion of the nanoparticle in the polymer matrix. The objective of the present research is to develop and characterize polymer based nanocomposites to be used as coatings in metallic pipelines for the transportation of oil and natural gas. Epoxy/SiO2 nanocomposites with nanoparticle contents of 2, 4, and 8 wt % were processed using a high-energy mill. Modifications of the SiO2 nanoparticles‟ surfaces with two different silane agents were carried out and their effect on the material properties were investigated. The state of dispersion of the materials processed was studied using Scanning and Transmission Electron Microscopy (SEM and TEM) micrographs. Thermogravimetric analysis (TG) were also conducted to determine the thermal stability of the nanocomposites. In addition, the processed nanocomposites were characterized by dynamic mechanical analysis (DMA) to investigate the effect of nanoparticles content and silane treatment on the viscoelastic properties and on the glass transition temperature. Finally, wear tests of the pin-on-disc type were carried out to determine the effects of the nanoparticles and the silane treatments studied. According to the results, the addition of SiO2 nanoparticles treated with silane increased the thermal stability, the storage modulus and Tg of the epoxy resin and decreased wear rate. This confirms that the interaction between the nanoparticles and the polymer chains plays a critical role on the properties of the nanocomposites

Desempenho mecânico de compósitos híbridos de fibras naturais e poliéster não saturado

With the objective to promote sustainable development, the fibres found in nature in abundance, which are biodegradable, of low cost in comparison to synthetic fibres are being used in the manufacture of composites. The mechanical behavior of the curauá and pineapple leaf fibre (PALF) composites in different proportions, 25% x 75% (P1), 50% x 50% (P2) e 75% x 25% (P3) were respectively studied, being initially treated with a 2% aqueous solution of sodium hydroxide. Mechanical analyses indicated that with respect to studies of traction, for the combination of P1 and P3, better results of 22.17 MPa and 16.98 MPa, were obtained respectively, which are higher than that of the combination P2. The results of the same pattern were obtained for analysis of bending resistance where P1 is 1.21% and P3 represents 0.96%. In the case of resistance to bending, best results were obtained for the combination P1 at 49.07 MPa. However, when Young's modulus values were calculated, the values were different to the pattern of the results of other tests, where the combination P2 with the value of 4.06 GPa is greater than the other combinations. This shows that the PALF had a greater influence in relation to curauá fibre. The analysis of the results generally shows that in combinations of two vegetable fibers of cellulosic origin, the fiber which shows higher percentage (75%) is the best option than to the composition of 50%/50%. In the meantime, according to the results obtained in this study, in the case where the application should withstand bending loads, the better composition would be 50%/50%

Avaliação mecânica e microestrutural de compósitos de poliéster com adição de cargas minerais e resíduos industriais

With the current growth in consumption of industrialized products and the resulting increase in garbage production, their adequate disposal has become one of the greatest challenges of modern society. The use of industrial solid residues as fillers in composite materials is an idea that emerges aiming at investigating alternatives for reusing these residues, and, at the same time, developing materials with superior properties. In this work, the influence of the addition of sand, diatomite, and industrial residues of polyester and EVA (ethylene vinyl acetate), on the mechanical properties of polymer matrix composites, was studied. The main objective was to evaluate the mechanical properties of the materials with the addition of recycled residue fillers, and compare to those of the pure polyester resin. Composite specimens were fabricated and tested for the evaluation of the flexural properties and Charpy impact resistance. After the mechanical tests, the fracture surface of the specimens was analyzed by scanning electron microscopy (SEM). The results indicate that some of the composites with fillers presented greater Young s modulus than the pure resin; in particular composites made with sand and diatomite, where the increase in modulus was about 168 %. The composites with polyester and EVA presented Young s modulus lower than the resin. Both strength and maximum strain were reduced when fillers were added. The impact resistance was reduced in all composites with fillers when compared to the pure resin, with the exception of the composites with EVA, where an increase of about 6 % was observed. Based on the mechanical tests, microscopy analyses and the compatibility of fillers with the polyester resin, the use of industrial solid residues in composites may be viable, considering that for each type of filler there will be a specific application

Evaluation of the physical and chemical properties of two commercial and three experimental root-end filling materials

Objective. The aim of this study was to evaluate the pH, calcium release, setting time, and solubility of two commercially available mineral trioxide aggregate (MTA) cements (white MTA Angelus and MTA Bio), and of three experimental cements (light-cured MTA, Portland cement with 20% bismuth oxide and 5% calcium sulfate, and an epoxy resin-based cement).Study design. For evaluation of pH and calcium ion release, polyethylene tubes with 1.0 mm internal diameter and 10.0 mm length were filled with the cements and immediately immersed in flasks containing 10 mL deionized water. After 3, 24, 72, and 168 hours, the tubes were removed and the water from the previous container was measured for its pH and calcium content with a pH meter and an atomic absorption spectrophotometer. For analysis of the setting time, Gilmore needles weighing 100 g and 456.5 g were used, in accordance with the American Society for Testing and Materials specification no. C266-03. Solubility of each cement was also tested.Results. All the cements were alkaline and released calcium ions, with a declining trend over time. After 3 hours, Portland cement + bismuth oxide and MTA Bio had the highest pH and light-cured MTA the lowest. After 1 week, MTA Bio had the highest pH and light-cured MTA and epoxy resin-based cement the lowest. Regarding calcium ion release, after 3 hours, Portland cement + bismuth oxide showed the highest release. After 1 week, MTA Bio had the highest. Epoxy resin-based cement and light-cured MTA had the lowest calcium release in all evaluation periods. Regarding setting times, white MTA Angelus and MTA Bio had the shortest, Portland cement + bismuth oxide had an intermediate setting time, and the epoxy resin-based cement had the longest. The materials that showed the lowest solubility values were the epoxy resin-based cement, Portland cement + bismuth oxide, and light-cured MTA. The highest solubility values were presented in white MTA Angelus and MTA Bio.Conclusions. The white MTA Angelus and MTA Bio had the shortest setting times, higher pH and calcium ion release, and the highest solubility. In contrast, the epoxy resin-based cement and light-cured MTA showed lower values of solubility, pH, and calcium ion release. (Oral Surg Oral Med Oral Pathol Oral Radiol Endod 2010; 110: 250-256)

Evaluation of Ultrasonic and ErCr:YSGG Laser Retrograde Cavity Preparation

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

Effects of mechanical cycling on the bonding of zirconia and fiber posts to human root dentin

Purpose: To evaluate the effect of cyclical mechanical loading on the bond strength of a fiber and a zirconia post bonded to root dentin.Materials and Methods: Forty single-rooted human teeth (maxillary incisors and canines) were sectioned, and the root canals were prepared at 12 mm. Twenty randomly seleced specimens received a quartz fiber post (FRC) (D.T. Light-Post) and 20 others received a zirconia post (ZR) (Cosmopost). The posts were resin luted (All Bond 2 + resin cement Duo-link) and each specimen was embedded in epoxy resin inside a PVC cylinder. Ten specimens with FRC post and 10 specimens with ZR post were submitted to fatigue testing (2,000,000 cycles; load: 50 N; angle of 45 degrees; frequency: 8 Hz), while the other 20 specimens were not fatigued. Thus, 4 groups were formed: G1: FRC+O cycles; G2: FRC+2,000,000 cycles; G3: ZR+O cycles; G4: ZR+2,000,000 cycles. Later, the specimens were cut perpendicular to their long axis to form 2-mm-thick disk-shaped samples (4 sections/specimen), which were submitted to the push-out test (1 mm/min). The mean bond strength values (MPa) were calculated for each tooth (n = 10) and data were submitted to statistical analysis (alpha = 0.05).Results: Two-way ANOVA revealed that the bond strength was significantly affected by mechanical cycling (p = 0.0014) and root post (p = 0.0325). The interaction was also statistically significant (p = 0.0010). Tukey's test showed that the mechanical cycling did not affect the bonding of FRC to root dentin, while fatigue impaired the bonding of zirconium to root dentin.Conclusion: (1) the bond strength of the FRC post to root dentin was not reduced after fatigue testing, whereas the bonding of the zirconia post was significantly affected by the fatigue. (2) Cyclical mechanical loading appears to damage the bond strength of the rigid post only.

In vitro evaluation of the effectiveness of irrigants and intracanal medicaments on microorganisms within root canals

Aim To evaluate in vitro the effectiveness of sodium hypochlorite (NaOCl). chlorhexidine (CHX) and live intracanal medicaments on microorganisms within root canals.Methodology Ninety-six human single-rooted extracted teeth were used. After removing the crowns, canal preparation was completed and the external root Surfaces were coated with epoxy resin. Following sterilization. The teeth were contaminated with Candida albicans and enterococcus faecalis. and were incubated at 37 +/- 1 degreesC for 7 days. The teeth were divided according to the irrigant solution or intracanal medicament: group 1. sterile physiologic solution (SPS) and calcium hydroxide (Ca(OH)(2)) paste: group 2. SPS and camphorated paramonochlorophenol (CPMC): group 3.SPS and tricresol formalin: group 4, SPS and CaOH2 + CPMC paste: group 5, SPS and PMC furacin; group 6.2.5%, NaOCl without intracanal medication: group 7, 2.0% CHX without intracanal medication and group 8, SPS Without intracanal medication (control group). Microbiological samples were collected with sterile paper points, and bacterial growth was determined. The data were submitted to the analysis of variance (ANOVA. P = 0.05).Results For C. albicans, groups 3 and S were statistically less effective than groups 1, 2. 4 and 5 (Kruskal-Wallis (K-W) = 65.241; gl = 7; P = 0.001). For E. faecalis, groups 6 and 8 were statistically less effective than groups 1-4 and 7 (K-W = 61.048; gl = 7; P = 0.001).Conclusions Ca(OH)(2) + CPMC paste was the most effective intracanal medicament for the elimination of the two microorganisms; 2.0% CHX solution was more effective than 2.5% NaOCl against E. faecalis.

Effect of mechanical cycling on the push-out bond strength of fiber posts adhesively bonded to human root dentin

This study evaluated the effect of mechanical cycling on the bond strength of fiber posts bonded to root dentin. The hypotheses examined were that bond strength is not changed after fatigue testing and bond strength does not present vast variations according to the type of fiber post. Sixty crownless, single-rooted human teeth were endodontically treated, with the space prepared at 12 mm. Thirty specimens received a quartz fiber post (Q-FRC (DT Light-Post), and the remaining 30 specimens received a glass fiber post (G-FRC) (FRC Postec Plus). All the posts were resin luted (All Bond+Duolink), and each specimen was embedded in a cylinder with epoxy resin. The specimens were divided into six groups: G1-Q-FRC+no cycling, G2- Q-FRC+20,000 cycles (load: 50N, angle of 45 degrees; frequency: 8Hz); G3- Q-FRC+2,000,000 cycles; G4- G-FRC+no cycling; G5- G-FRC+20,000 cycles; G6- GFRC+2,000,000 cycles. The specimens were cut perpendicular to their long axis, forming 2-mm thick disc-samples, which were submitted to the push-out test. ANOVA (alpha=.05) revealed that: (a) QFRC (7.1 +/- 2.2MPa) and G-FRC (6.9 +/- 2.1MPa) were statistically similar (p=0.665); (b) the no cycling groups (7.0 +/- 2.4MPa), 20,000 cycles groups (7.0 +/- 2.1MPa) and 2,000,000 cycles groups (7.0 +/- 2.0MPa) were statistically similar (p=0.996). It concluded that mechanical cycling did not affect the bond strength of two fiber posts bonded to dentin.

BIOSENSORS FOR GLUCOSE NEEDLE-SHAPED FOR IN-VIVO MONITORING

Different procedures for obtaining a needle biosensor for the determination of glucose to be inserted subcutaneously in vivo, have been compared. Platinum wires with a diameter of 75 mum, teflon-coated were inserted in hypodermic needles and fixed with a two-component epoxy resin. Using a dip-coating procedure, several layers were deposited on electrodes. The first coating was cellulose acetate, the second was immobilized glucose oxidase (GOD) mixed with bovine serum albumin (BSA) and glutaraldheyde, the third coating was a polyurethane coating obtained with commercially available products. A large number of electrodes have been tried and statistically evaluated but they seem to be affected by poor reproducibility evidenced by a large spreading in successive calibration curves. Then, the polyurethane coating has been replaced by a thin polycarbonate membrane salinized and fixed on the tip of the needle. Reproducible results were achieved and first results of in vivo measurements on rabbits are reported.

Release of formaldehyde by 4 endodontic sealers

Objective. The purpose of this study was to evaluate the release of formaldehyde by some root canal filling materials. Study design. Two older endodontic sealers, AH 26 and Endomethasone, and 2 recently available sealers, AH Plus and Top Seal, were analyzed. Infrared and electronic spectroscopy were used to determine formaldehyde content after set of the materials. Results. Analysis showed that the AH 26 and Endomethasone sealers released formaldehyde. Although the AH Plus and Top Seal sealers have similar chemical composition, they released formaldehyde in a minimal concentration. Conclusions. The AH 26 and Endomethasone sealers released formaldehyde after setting; however, a minimum release was observed for the AH Plus and Top Seal sealers. Copyright © 1999 by Mosby, Inc.