Nmr imaging of the diffusion of water into poly(tetrahydrofurfuryl methacrylate-co-hydroxyethyl methacrylate)

0Nuclear magnetic resonance (n.m.r.) imaging was used to study the ingress of water into poly(tetrahydrofurfuryl methacrylate-co-hydroxyethyl methacrylate). The study offers strong evidence that the diffusion is Fickian in nature. The diffusion coefficient, D, obtained by fitting the underlying diffusion profile, attainable from the images, according to the equation for Fickian diffusion, is 1.5 x 10(-11) m(2) s(-1), which is in good correlation with the value of 2.1 x 10(-11) m(2) s(-1), obtained from mass uptake measurements. Additionally, from the T-2-weighted images, Superimposed features observed in addition to the underlying Fickian diffusion profiles were shown to have a longer spin-spin relaxation time, T-2. This Suggests the presence of two types of water within the polymer matrix; a less mobile phase of absorbed water that is interacting strongly with the polymer matrix and a more mobile phase of absorbed water residing within the cracks observed in the environmental scanning electron micrograph. (C) 1997 Elsevier Science Ltd.

Physicochemical Properties of Methacrylate Resin-based Root Canal Sealers

Introduction: This study assessed in vitro the physicochemical properties of 2 methacrylate resin-based sealers (Epiphany SE and Hybrid Root SEAL), comparing the results with a well-established epoxy resin-based sealer (AH Plus). Methods: Five samples of each material were used for each test (setting time, flow, radiopacity, dimensional change after setting, and solubility) according to American National Standards Institute/American Dental Association (ANSI/ADA) Specification 57. The samples were assigned to 3 groups: I, AH Plus; II, Epiphany SE; and III, Hybrid Root SEAL. The distilled and deionized water used at the solubility test was submitted to atomic absorption spectrometry to observe the presence of Ca2+, K+, Ni2+, and Zn2+ ions. In addition, the surface morphology of the specimens was analyzed by means of scanning electron microscopy (SEM). Statistical analysis was performed by using one-way analysis of variance and Tukey-Kramer test (P < .05). Results: Flow, radiopacity, and solubility of all sealers were in accordance with ANSI/ADA. The setting time of Hybrid Root SEAL did not agree with ANSUADA requirements. The dimensional change of all sealers was greater than the values considered acceptable by ANSI/ADA. The spectrometry analysis showed significant Ca2+ ions release for AH Plus. In SEM analysis, Hybrid Root SEAL presented spherical monomers with inferior size than AH Plus and Epiphany SE. Conclusions: It might be concluded that physicochemical properties of the tested sealers conformed to ANSI/ADA (2000) standardization, except for the setting time of Hybrid Root SEAL and the dimensional change of all sealers, which did not fulfill the ANSI/ADA requirements. (J Endod 2010;36:1531-1536)

Push-out strength of methacrylate resin-based sealers to root canal walls

P>Aim To assess the push-out strength of Epiphany SE, Epiphany and Hybrid Root SEAL to the dentine walls of root canals. Methodology Sixty roots of canines were prepared and distributed to six groups (n = 10) according to the filling material: GI - Epiphany SE, GII - Epiphany primer and sealer, GIII - Epiphany primer, sealer and resinous solvent, GIV - Clearfil DC Bond and Epiphany sealer, GV - Clearfil, Epiphany sealer and solvent and GVI - Hybrid Root SEAL. Resilon cones were used in all groups. Roots were sectioned transversally to obtain three slices from each third. One slice was subjected to the push-out test (MPa), and results were analysed by anova and Tukey`s test (P < 0.05). The other two slices were prepared for scanning electron microscopy (SEM). Failure mode was also analysed. Results A statistically significant difference (P < 0.05) occurred between Hybrid Root SEAL (5.27 +/- 2.07) and the other materials, GI (0.40 +/- 0.23), GII (0.78 +/- 0.45), GIII (0.57 +/- 0.28), GIV (0.40 +/- 0.24) and GV (0.50 +/- 0.41), which did not differ significantly from each other (P > 0.05). Adhesive failures predominated in groups I, II, IV and V, whilst mixed and cohesive failures were the most frequent in groups III and VI, respectively. There were gaps in the adhesive interface of GI and GII, continuity areas of the filling material with dentine in GIV and GV and good adaptation of the interface of GVI. Conclusion Hybrid Root SEAL had greater push-out strength to root canal dentine than Epiphany SE and Epiphany. The use of primer, solvent and adhesive system did not influence the adhesion of Epiphany.

Effect of methyl methacrylate monomer on bond strength of denture base resin to acrylic teeth

Bond failures at the acrylic teeth and denture base resin interface are still a common clinical problem in prosthodontics. The effect of methyl methacrylate (MMA) monomer on the bond strength of three types of denture base resins (Acron MC, Lucitone 550 and QC-20) to two types of acrylic teeth (Biotone and Trilux) was evaluated. Twenty specimens were produced for each denture base resin/acrylic tooth combination and were randomly divided into control (acrylic teeth received no surface treatment) and experimental groups (MMA was applied to the surface of the acrylic teeth for 180 s) and were submitted to shear tests (1 mm/mm). Data (MPa) were analyzed using three-way ANOVA/Student`s test (alpha = 0.05). MMA increased the bond strength of Lucitone denture base resins and decreased the bond strength of QC-20. No difference was detected for the bond strength of Acron MC base resin after treatment with MMA. (C) 2008 Elsevier Ltd. All rights reserved.

NMR imaging of water sorption into poly(hydroxyethyl methacrylate-co-tetrahydrofurfuryl methacrylate)

The diffusion of water into a series of hydroxyethyl methacrylate, HEMA, copolymers with tetrahydrofurfuryl methacrylate, THFMA, has been studied over a range of copolymer compositions using NMR imaging analyses. For polyHEMA the diffusion was found to be consistent with a Fickian model. The mass diffusion coefficient of water in polyHEMA at 37 degreesC was determined from the profiles of the diffusion front to be 1.5 x 10(-11) m(2) s(-1), which is less than the value based upon mass uptake, 2.0 x 10(-11) m(2) s(-1). The profiles of the water diffusion front obtained from the NMR images showed that stress was induced at the interface between the rubbery and glassy regions which led to formation of small cracks in this region of the glassy matrix of polyHEMA and its copolymers with mole fractions of HEMA greater than 0.6. Water was shown to be able to enter these cracks forming water pools. For copolymers of HEMA and THFMA with mole fractions of HEMA less than 0.6 the absence of cracks was attributed to the ability of the THFMA sequences to undergo stress relaxation by creep.

Free radical copolymerization of methyl methacrylate and allyl acetate Part 2 structure and properties

The structure of the product from the free radical bulk copolymerization of methyl methacrylate (MMA) and allyl acetate (AAc) was investigated. The mole fraction of AAc plays an important role in the copolymerization of these two monomers. Molecular weight (MW) and molecular weight distribution (MWD) are completely altered when the feed composition is dominantly AAc. NMR spectroscopy confirmed the incorporation of AAc into the polymer. However, no allyl-allyl linkages were observed at low conversions. T-g was found to be affected by the incorporation of AAc into the polymer. (C) 2001 Society of Chemical Industry.

Copolymerization of methyl methacrylate and allyl acetate Part I. Rate of reaction

Free radical bulk copolymerization of methyl methacrylate (MMA) and allyl acetate (AAc) has been investigated using electron spin resonance (ESR) and FT-near infrared (FTNIR) spectroscopy. Data are used to evaluate the rate constants. The mole fraction of AAc plays an important role in the copolymerization of these two monomers. AAc not only delays the Trommsdorff effect but also increases the onset of percentage total conversion at which the Trommsdorff region begins. With AAc fraction 0.5 and higher, no Trommsdorff effect was observed. Inclusion of AAc into copolymer structure mainly occurs in the Trommsdorf region or when the AAc fraction in the comonomer feed is dominant. This is associated with a drop in the concentration of propagating radicals. However, ESR spectra indicate that the MMA propagating radical is predominant during the reaction. In the comonomer mixtures where a Trommsdorff region can be observed, the addition of AAc does not produce any significant change in k(p) and k(t) in the steady state region. Major changes in k(p) and k(t) are observed after the gel point and glassy state, respectively. (C) 2001 Society of Chemical Industry.

The copolymerization of N-vinyl-2-pyrrolidone with 2-hydroxyethyl methacrylate

The bulk free radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with N-vinyl-2-pyrrolidone (VP) was carried out to low conversions at 50 degreesC, using benzoyl peroxide (BPO) as initiator. The compositions of the copolymers; were determined using C-13 NMR spectroscopy. The conversion of monomers to polymers was studied using FT-NIR spectroscopy in order to predict the extent of conversion of monomer to polymer. From model fits to the composition data, a statistical F-test revealed that die penultimate model describes die copolymerization better than die terminal model. Reactivity ratios were calculated by using a non-linear least squares analysis (NLLS) and r(H) = 8.18 and r(V) = 0.097 were found to be the best fit values of the reactivity ratios for the terminal model and r(HH) = 12.0, r(VH) = 2.20, r(VV) = 0.12 and r(HV) = 0.03 for the penultimate model. Predictions were made for changes in compositions as a function of conversion based upon the terminal and penultimate models.

Water sorption into poly[(2-hydroxyethyl methacrylate)-co-(1-vinyl-2-pyrrolidone]at 310 K

Poly(2-hydroxyethyl methacrylate) and copolymers of 2-hydroxyethyl methacrylate (HEMA) and 1-vinyl-2-pyrrolidone (VP) in the form of cylindrical samples (approximate to8mm x 20mm) have been prepared and the sorption of water into these cylinders has been studied by the mass-uptake methods and by magnetic-resonance imaging. The equilibrium water contents for the cylinders were found to vary systematically with the copolymer composition. Diffusion of water into the cylinders was found to follow Fickian behaviour for cylinders with high HEMA contents, with the diffusion coefficients obtained from mass-uptake studies dependent on the copolymer composition, varying from 1.7 x 10(-11) m(2) s(-1) for poly(HEMA) to 2.0 x 10(-11) m(2) s(-1) for poly(HEMA-co-VP) with a composition of 1:1. However, NMR-imaging studies showed that, while the profiles of the water diffusion fronts for cylinders with high HEMA contents were Fickian, that for the 1:1 copolymer was not and indicated that the mechanism was Case III. The polymers which were rich in VP were characterized by a water-sorption process which follows Case-III behaviour. (C) 2003 Society of Chemical Industry.

Simultaneous FT-NIR and ESR analyses to yield propagation rate coefficients for polymerization of methyl methacrylate based monomers

A hyphenated instrumental approach has been used to obtain reliable values for the propagation rate coefficients as a function of conversion for polymerizations of methyl methacrylate (MMA) and a mixture of MMA and ethyleneglycol dimethacrylate (EGDMA) with a 1:1 concentration of double bonds, from near the onset of the Trommsdorf region into the glass region. ESR spectroscopy was used to measure the radical concentration while FT-NIR fibre-optic spectroscopy was employed to measure instantaneously the double-bond concentration within the temperature-controlled cavity of the ESR instrument during polymerization. The advantage of this approach to the measurement of the rate coefficient is that it is equally applicable to branching and linear polymerizations. For the polymerization of methyl methacrylate, the values of the rate coefficient at the lowest conversions at which reliable values could be obtained were in agreement with recently reported values obtained by the PLP-SEC method. For the lowest conversions, the values obtained were 403 1 mol(-1) s(-1) at 306 K for MMA and 5201 mol(-1) s(-1) at 310 K for a 1:1 mixture of MMA and EGDMA. (C) 2003 Society of Chemical Industry.

Poly(2-hydroxyethyl methacrylate): A new star polymer

Multiarm star polymers are attractive materials due to their unusual bulk and solution properties. They are considered analogues of dendrimers with a wide range of applications, such as drug delivery, membranes, coatings and lithography.1 The advent of controlled polymerization made possible the existence of this unique class of organic nanoparticles (ONPs).2 Two major synthetic strategies are usually employed in the preparation of star polymers, the core-first and arm-first approaches. The core-first approach involves a controlled living polymerization using a multiarm initiator core while the arm-first methodology is based in the quenching of living polymers with multifunctional coupling agent or bifunctional vinyl compounds. Herein, we present the synthesis and characterization of a new star polymer, the multiarm star poly(2-hydroxyethyl methacrylate). The tetra-armed star polymer was prepared by reversible addition fragmentation chain-transfer (RAFT) polymerization using the core-first approach. The RAFT chain-transfer agent (RAFT CTA) pentaerythritol tetrakis[2-(dodecylthiocarbonothioylthio)-2-methylpropionate] was used as multiarm initiator core were 2-hydroxyethyl methacrylate (HEMA) was polymerized using AIBN as radical initiator. Structural characterization was performed by 1H NMR and FTIR. The new polymer is able to uptake large quantities of organic solvents, forming gels. The rheological behavior of these gels was also investigated.

High Molecular Weight Methacrylate Sealing of a Bridge Deck, HR-2031, 1988

The Iowa Department of Transportation used a high molecular weight methacrylate (HMWM) resin to seal a 3,340 ft. x 64 ft. bridge deck in October 1986. The sealing was necessary to prevent deicing salt brine from entering a substantial number of transverse cracks that coincided with the epoxy coated top steel and unprotected bottom steel. HMWM resin is a three component product composed of a monomer, a cumene hydroperoxide initiator and a cobalt naphthenate promoter. The HMWM was applied with a dual spray bar system and flat-fan nozzles. Initiated monomer delivered through one spray bar was mixed in the air with promoted monomer from the other spray bar. The application rate averaged 0.956 gallons per 100 square feet for the tined textured driving lanes. Dry sand was broadcast on the surface at an average coverage of 0.58 lbs. per square yard to maintain friction. Coring showed that the HMWM resin penetrated the cracks more than two inches deep. Testing of the treated deck yielded Friction Numbers averaging 33 with a treaded tire compared to 36 prior to treatment. An inspection soon after treatment found five leaky cracks in one of the 15 spans. One inspection during a steady rain showed no leakage, but leakage from numerous cracks occurred during a subsequent rain. A second HMWM application was made on two spans. Leakage through the double application occurred during a rain. Neither the single or double application were successful in preventing leakage through the cracks.

High Molecular Weight Methacrylate Sealing of a Bridge Deck, HR-2031, Construction Report, 1988

The Iowa Department of Transportation used a high molecular weight methacrylate (HMWM) resin to seal a 3,340 ft. x 64 ft. bridge deck in October 1986. The sealing was necessary to prevent deicing salt brine from entering a substantial number of transverse cracks that coincided with the epoxy coated top steel and unprotected bottom steel. HMWM resin is a three component product composed of a monomer, a curnene hydroperoxide initiator and a cobalt naphthenate promoter. The HMWM was applied with a dual spray bar system and flat-fan nozzles. Initiated monomer delivered through one spray bar was mixed in the air with promoted monomer from the other spray bar. The application rate averaged 0.956 gallons per 100 square feet for the tined textured driving lanes. Dry sand was broadcast on the surface at an average coverage of 0.58 lbs. per square yard to maintain friction. Coring showed that the H.MWM resin penetrated the cracks more than two inches deep. Testing of the treated deck yielded Friction Numbers averaging 33 with a treaded tire compared to 36 prior to treatment. An inspection soon after treatment found five leaky cracks in one of the 15 spans. One inspection during a steady rain showed no leakage, but leakage from numerous cracks occurred during a subsequent rain. A second HMWM application was made on two spans to determine if a double application would prevent leakage. This evaluation has not been completed.

Linear block copolymers of L–lactide and 2–dimethylaminoethyl methacrylate : synthesis and properties

Part of the research described in this thesis is conducted in collaboration with Centre d' étude et de Recherche sur les Macromolécules (CERM), Université de Liège, Sart-Tilman, Belgium

Photoacoustic study on photobleaching of Rhodamine 6G doped in poly(methyl methacrylate)

The photobleaching of the lasing dye Rhodamine 6G embedded in the solid matrix poly(methyl methacrylate) was investigated using a photoacoustic technique. Chopped laser radiation from an argon ion laser at four different wavelengths was used for the study. Experimental results indicate that the photobleaching rate is directly proportional to the incident laser power while it decreases with increase in concentration of the dye molecules. In the present case we have not observed any dependence of photobleaching on the chopping frequency. One-photon absorption is found to be responsible for the photobleaching of the dye within the selected range of laser power