Thermal and radiation curing of phenylethynyl terminated macromers

The thermal and gamma-irradiation induced curing of two phenylethynyl terminated composite resin systems, DFB/BPF and PETI5A, was investigated. Thermal curing of these matrix resin samples was performed at a temperature of 360 degrees C, gamma irradiation of the samples was conducted at 300 degrees C at a dose rate of 2.2 kGy h(-1). The reaction and subsequent loss of ethynyl groups in the resins for both cure methods was demonstrated by observing the decrease of the 2215 cm(-1) peak in the Raman spectra of the resins. Fully cured resin samples were found to have glass transition temperatures of 244-246 degrees C and 278-280 degrees C for DFB/BPF and PETI5A respectively. Similar relationships between T-g and fractional conversion were observed in both resins. The apparent polymerization rate, R-p, for thermal cure at 360 degrees C, was found to be 4.79 x 10(-2)% s(-1) in PETI5A and 3.22 x 10(-2)% s(-1) in DFB/BPF. Catastrophic degradation under nitrogen was observed to commence near 450 degrees C and 530 degrees C, with 5% weight losses occurring at 455 degrees C and 540 degrees C for DFB/BPF and PETI5A respectively. Gamma radiation induced cure at 300 degrees C was shown to be feasible, with full cure being reached with doses of 40 kGy for DFB/BPF and 100 kGy for PETI5A.

C-13-NMR, H-1-NMR, and FT-Raman study of radiation-induced modifications in radiation dosimetry polymer gels

H-1- and C-13-NMR spectroscopy and FT-Raman spectroscopy are used to investigate the properties of a polymer gel dosimeter post-irradiation. The polymer gel (PACT) is composed of acrylamide, N,N'-methylene-bisacrylamide, gelatin, and water. The formation of a polyacrylamide network within the gelatin matrix follows a dose dependence nonlinearly correlated to the disappearance of the double bonds from the dissolved monomers within the absorbed dose range of 0-50 Gy. The signal from the gelatin remains constant with irradiation. We show that the NMR spin-spin relaxation times (T-2) of PAGs irradiated to up to 50 Gy measured in a NMR spectrometer and a clinical magnetic resonance imaging scanner can be modeled using the spectroscopic intensity of the growing polymer network. More specifically, we show that the nonlinear T-2 dependence against dose can be understood in terms of the fraction of protons in three different proton pools. (C) 2000 John Wiley & Sons, Inc.

The relationship between radiation-induced chemical processes and transverse relaxation times in polymer gel dosimeters

The effects of ionizing radiation in different compositions of polymer gel dosimeters are investigated using FT-Raman spectroscopy and NMR T-2 relaxation times. The dosimeters are manufactured from different concentrations of comonomers (acrylamide and N,N'-methylene-bis-acrylamide) dispersed in different concentrations of an aqueous gelatin matrix. Results are analysed using a model of fast exchange of magnetization between three proton pools. The fraction of protons in each pool is determined using the known chemical composition of the dosimeter and FT-Raman spectroscopy. Based on these results, the physical and chemical processes in interplay in the dosimeters are examined in view of their effect on the changes in T-2 The precipitation of growing macroradicals and the scavenging of free radicals by gelatin are used to explain the rate of polymerization. The model describes the changes in T-2 as a function of the absorbed dose up to 50 Gy for the different compositions. This is expected to aid the theoretical design of new, more efficient dosimeters, since it was demonstrated that the optimum dosimeter (i.e, with the lowest dose resolution) must have a range of relaxation times which match the range of T-2 values which can be determined with the lowest uncertainty using an MRI scanner.

Modelling of post-irradiation events in polymer gel dosimeters

The nuclear magnetic resonance (NMR) spin-spin relaxation time (T-2) is related to the radiation-dependent concentration of polymer formed in polymer gel dosimeters manufactured from monomers in an aqueous gelatin matrix. Changes in T-2 with time post-irradiation have been reported in the literature but their nature is not fully understood. We investigated those changes with time after irradiation using FT-Raman spectroscopy and the precise determination of T-2 at high magnetic field in a polymer gel dosimeter, A model of fast exchange of magnetization taking into account ongoing gelation and strengthening of the gelatin matrix as well as the polymerization of the monomers with time is presented. Published data on the changes of T-2 in gelatin gels as a function of post-manufacture time are used and fitted closely by the model presented. The same set of parameters characterizing the variations of T-2 in gelatin gels and the increasing concentration of polymer determined from Fr-Raman spectroscopy are used successfully in the modelling of irradiated polymer gel dosimeters. Minimal variations in T-2 in an irradiated PAG dosimeter are observed after 13 h.

Ultrasound evaluation of polymer gel dosimeters

A new method for the evaluation of radiotherapy 3D polymer gel dosimeters has been developed using ultrasound to assess the significant structural changes that occur following irradiation of the dosimeters. The ultrasonic parameters of acoustic speed of propagation, attenuation and transmitted signal intensity were measured as a function of absorbed radiation dose. The dose sensitivities for each parameter were determined as 1.8 x 10(-4) s m(-1) Gy(-1), 3.9 dB m(-1) Gy(-1) and 3.2 V-1 Gy(-1) respectively. All parameters displayed a strong variation with absorbed dose that continued beyond absorbed doses of 15 Gy. The ultrasonic measurements demonstrated a significantly larger dynamic range in dose response curves than that achieved with previously published magnetic resonance imaging (MRI) dose response data. It is concluded that ultrasound shows great potential as a technique for the evaluation of polymer gel dosimeters.

Magnetization transfer imaging for polymer gel dosimetry

Off-resonance RF pre-saturation was used to obtain contrast in MRI images of polymer gel dosimeters irradiated to doses up to 50 Gy. Two different polymer gel dosimeters composed of 2-hydroxyethyl-acryl ate or methacrylic acid monomers mixed with N, N'-methylene-bisacrylamide (BIS), dispersed in an aqueous gelatin matrix were evaluated. Radiation-induced polymerization of the co-monomers generates a fast-relaxing insoluble polymer. Saturation of the polymer using off-resonance Gaussian RF pulses prior to a spin-echo read-out with a short echo time leads to contrast that is dependent on the absorbed dose. This contrast is attributed to magnetization transfer (MT) between free water and the polymer, and direct saturation of water was found to be negligible under the prevailing experimental conditions. The usefulness of MT imaging was assessed by computing the dose resolution obtained with this technique. We found a low value of dose resolution over a wide range of doses could be obtained with a single experiment. This is an advantage over multiple spin echo (MSE) experiments using a single echo spacing where an optimal dose resolution is achieved over only very limited ranges of doses. The results suggest MT imaging protocols may be developed into a useful tool for polymer gel dosimetry.

A new approach to the synthesis of conjugated polymer-nanocrystal composites for heterojunction optoelectronics

We report a simple one pot process for the preparation of lead sulfide (PbS) nanocrystals in the conjugated polymer poly (2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV), and we demonstrate electronic coupling between the two components.

Randomized Evaluation of Two Drug-Eluting Stents With Identical Metallic Platform and Biodegradable Polymer But Different Agents (Paclitaxel or Sirolimus) Compared Against Bare Stents: 1-Year Results of the PAINT Trial

Objectives: We tested two novel drug-eluting stents (DES), covered with a biodegradable-polymer carrier and releasing paclitaxel or sirolimus, which were compared against a bare metal stent (primary objective). The DES differed by the drug, but were identical otherwise, allowing to compare the anti-restenosis effects of sirolimus versus paclitaxel (secondary objective). Background: The efficacy of novel DES with biodegradable polymers should be tested in the context of randomized trials, even when using drugs known to be effective, such as sirolimus and paclitaxel. Methods: Overall, 274 patients with de novo coronary lesions in native vessels scheduled for stent implantation were randomly assigned (2:21 ratio) for the paclitaxel (n = 111), sirolimus (n = 106), or bare metal stent (n = 57) groups. Angiographic follow-up was obtained at 9 months and major cardiac adverse events up to 12 months. Results: Both paclitaxel and sirolimus stents reduced the 9-month in-stent late loss (0.54-0.44 mm, 0.32-0.43 mm, vs. 0.90-0.45 mm respectively), and 1-year risk of target vessel revascularization and combined major adverse cardiac events (P < 0.05 for both, in all comparisons), compared with controls. Sirolimus stents had lower late loss than paclitaxel stents (P < 0.01), but similar 1-year clinical outcomes. There were no differences in the risk of death, infarction, or stent thrombosis among the study groups. Conclusion: Both novel DES were effective in reducing neointimal hyperplasia and 1-year re-intervention, compared to bare metal stents. Our findings also suggest that sirolimus is more effective than paclitaxel in reducing angiographic neointima, although this effect was not associated with better clinical outcomes. (C) 2009 Wiley-Liss, Inc.

Dynamic strain measurement using piezoelectric polymer film

Piezoelectric polymers have been used to form the basis of dynamic strain gauges for the detection of stress waves. The linearity of response was tested using a split Hopkinson pressure bar arrangement. The results obtained illustrate the effectiveness of piezoelectric film strain gauges in the measurement of axial stress waves.

Molecular motion in miscible polymer blends .1. Motion in blends of PEO and PVPh studied by solid-state C-13 T-1 rho measurements

Changes in molecular motion in blends of PEO-PVPh have been studied using measurements of C-13 T-1 rho relaxation times. C-13 T-1 rho relaxation has been confirmed as arising from spin-lattice interactions by observation of the variation in T-1 rho with rf field strength and temperature. In the pure homopolymers a minimum in T-1 rho is observed at ca. 50 K above the glass transition temperatures detected by DSC. After blending, the temperature of the minimum in T-1 rho for PEO increased, while that for PVPh decreased, however, the minima, which correspond to the temperatures where the average correlation times for reorientation are close to 3.1 mu s, are separated by 45 K (in a 45% PEO-PVPh blend). These phenomena are explained in terms of the local nature of T-1 rho measurements. The motions of the individual homopolymer chains are only partially coupled in the blend. A short T-1 rho has been observed for protonated aromatic carbons, and assigned to phenyl rings undergoing large-angle oscillatory motion, The effects of blending, and temperature, on the proportion of rings undergoing oscillatory motion are analyzed.

Histological analysis of cobalt-chromium stents with and without Camouflage (R) polymer coating: experimental porcine carotid artery model

This study evaluated the arterial response to cobalt-chromium stents with and without polymer coating (Camouflage (R), Hemoteq AG, Wuerselen, Germany) implanted in pigs. Cobalt-chromium balloon-expandable stents (4 x 16 mm) were implanted in the common carotid arteries of nine pigs. Histological analysis of endothelialization, inflammation and injury was performed one month later. All stents were successfully deployed, and all but one animal survived the 30 study days. All arteries were patent. Endothelialization was nearly complete in most sections of all carotid stents in both groups. There were mild inflammatory infiltrate and mild-to-moderate injury, which were associated with the stent shafts and not significantly different between groups. Our findings suggest that, in porcine carotid arteries, the histological response to balloon-expandable cobalt-chromium stents coated with polymer (Camouflage (R), Hemoteq AG) is similar to the response to non-coated cobalt-chromium stents.

Evaluation of the Possibility of Removing Staining by Repolishing Composite Resins Submitted to Artificial Aging

This in vitro research verified the possibility of eliminating staining caused by coffee and red wine in five composite resins, after being submitted to thermal cycling. Thirty-six specimens were prepared and immersed in water at 37 degrees C for 24 hours. After polishing, specimen color was measured in a spectrophotometer Cintra 10 UV (Visible Spectrometer, GBC, Braeside, VIC, Australia). All specimens were submitted to thermal cycling at temperatures of 5 and 55 degrees C with a dwell time of 1 minute, for 1,000 cycles in a 75% ethanol/water solution. After thermal cycling, the specimens were immersed in water at 37 degrees C until 7 days had elapsed from the time the specimens were prepared. All specimens were then taken to the spectrophotometer for color measurement. The specimens were divided into three groups (N = 12): distilled water (control), coffee, and red wine. For the staining process to occur on only one surface, all the sides, except one, of the surfaces were isolated with white wax. The specimens were immersed in one of the solutions at 37 degrees C for 14 days. The specimens were dried and taken to the spectrophotometer for color measurement. After this, the specimens were submitted to 20 mu m wear three times, and the color was measured after each one of the wear procedures. Calculation of the color difference was made using CIEDE2000 formula. According to the methodology used in this research, it was concluded that the staining caused by coffee and red wine was superficial and one wear of 20 mu m was sufficient to remove the discoloration.

Do Low-shrink Composites Reduce Polymerization Shrinkage Effects?

Progress in polymer science has led to continuous reduction of polymerization shrinkage, exemplified by a new generation of ""low-shrink composites"". The common inference that shrinkage stress effects will be reduced in teeth restored with such restoratives with lower shrinkage was tested in extracted human premolars. Mesio-occluso-distal slot-shaped cavities were cut and restored with a conventional (SupremePlus) or low-shrink (RefleXions, Premise, Kalore, and LS) composite (N = 5). We digitized the coronal surfaces before and 10 min after restoration to determine cuspal deflection from the buccal and lingual volume change/area. We also determined the main properties involved (total shrinkage, post-gel shrinkage, degree of conversion, and elastic modulus), as well as microleakage, to verify adequate bonding. It was shown that, due to shrinkage stresses, buccal and lingual surfaces pulled inward after restoration (9-14 microns). Only Kalore and LS resulted in significantly lower tooth deformation (ANOVA/Student-Newman-Keuls post hoc, p = 0.05). The other two low-shrink composites, despite having the lowest and highest total shrinkage values, did not cause significant differences in cuspal deflection. Deflection seemed most related to the combination of post-gel shrinkage and elastic modulus. Therefore, even for significantly lower total shrinkage values, shrinkage stress is not necessarily reduced.

Characterization of dimethacrylate polymeric networks: A study of the crosslinked structure formed by monomers used in dental composites

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by (1)H NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/(1)H NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60-40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials. (C) 2010 Elsevier Ltd. All rights reserved.