Effect of LED and Argon Laser on Degree of Conversion and Temperature Rise of Hybrid and Low Shrinkage Composite Resins

PubMed Central

Pahlevan, Ayob; Tabatabaei, Masumeh Hasani; Arami, Sakineh; Valizadeh, Sara

2016-01-01

Objectives: Different light curing units are used for polymerization of composite resins. The aim of this study was to evaluate the degree of conversion (DC) and temperature rise in hybrid and low shrinkage composite resins cured by LED and Argon Laser curing lights. Materials and Methods: DC was measured using FTIR spectroscopy. For measuring temperature rise, composite resin samples were placed in Teflon molds and cured from the top. The thermocouple under samples recorded the temperature rise. After initial radiation and specimens reaching the ambient temperature, reirradiation was done and temperature was recorded again. Both temperature rise and DC data submitted to one-way ANOVA and Tukey-HSD tests (5% significance). Results: The obtained results revealed that DC was not significantly different between the understudy composite resins or curing units. Low shrinkage composite resin showed a significantly higher temperature rise than hybrid composite resin. Argon laser caused the lowest temperature rise among the curing units. Conclusion: Energy density of light curing units was correlated with the DC. Type of composite resin and light curing unit had a significant effect on temperature rise due to polymerization and curing unit, respectively. PMID:27843507

Effect of LED and Argon Laser on Degree of Conversion and Temperature Rise of Hybrid and Low Shrinkage Composite Resins.

PubMed

Pahlevan, Ayob; Tabatabaei, Masumeh Hasani; Arami, Sakineh; Valizadeh, Sara

2016-01-01

Different light curing units are used for polymerization of composite resins. The aim of this study was to evaluate the degree of conversion (DC) and temperature rise in hybrid and low shrinkage composite resins cured by LED and Argon Laser curing lights. DC was measured using FTIR spectroscopy. For measuring temperature rise, composite resin samples were placed in Teflon molds and cured from the top. The thermocouple under samples recorded the temperature rise. After initial radiation and specimens reaching the ambient temperature, reirradiation was done and temperature was recorded again. Both temperature rise and DC data submitted to one-way ANOVA and Tukey-HSD tests (5% significance). The obtained results revealed that DC was not significantly different between the understudy composite resins or curing units. Low shrinkage composite resin showed a significantly higher temperature rise than hybrid composite resin. Argon laser caused the lowest temperature rise among the curing units. Energy density of light curing units was correlated with the DC. Type of composite resin and light curing unit had a significant effect on temperature rise due to polymerization and curing unit, respectively.

Characteristics of low polymerization shrinkage flowable resin composites in newly-developed cavity base materials for bulk filling technique.

PubMed

Nitta, Keiko; Nomoto, Rie; Tsubota, Yuji; Tsuchikawa, Masuji; Hayakawa, Tohru

2017-11-29

The purpose of this study was to evaluate polymerization shrinkage and other physical properties of newly-developed cavity base materials for bulk filling technique, with the brand name BULK BASE (BBS). Polymerization shrinkage was measured according to ISO/FDIS 17304. BBS showed the significantly lowest polymerization shrinkage and significantly higher depth of cure than conventional flowable resin composites (p<0.05). The Knoop hardness, flexural strength and elastic modulus of that were significantly lower than conventional flowable resin composites (p<0.05). BBS had the significantly greatest filler content (p<0.05). SEM images of the surface showed failure of fillers. The lowest polymerization shrinkage was due to the incorporation of a new type of low shrinkage monomer, which has urethane moieties. There were no clear correlations between inorganic filler contents and polymerization shrinkage, flexural strength and elastic modulus. In conclusion, the low polymerization shrinkage of BBS will be useful for cavity treatment in dental clinics.

A new method to measure the polymerization shrinkage kinetics of light cured composites.

PubMed

Lee, I B; Cho, B H; Son, H H; Um, C M

2005-04-01

This study was undertaken to develop a new measurement method to determine the initial dynamic volumetric shrinkage of composite resins during polymerization, and to investigate the effect of curing light intensity on the polymerization shrinkage kinetics. The instrument was basically an electromagnetic balance that was constructed with a force transducer using a position sensitive photo detector (PSPD) and a negative feedback servo amplifier. The volumetric change of composites during polymerization was detected continuously as a buoyancy change in distilled water by means of the Archimedes' principle. Using this new instrument, the dynamic patterns of the polymerization shrinkage of seven commercial composite resins were measured. The polymerization shrinkage of the composites was 1.92 approximately 4.05 volume %. The shrinkage of a packable composite was the lowest, and that of a flowable composite was the highest. The maximum rate of polymerization shrinkage increased with increasing light intensity but the peak shrinkage rate time decreased with increasing light intensity. A strong positive relationship was observed between the square root of the light intensity and the maximum shrinkage rate. The shrinkage rate per unit time, dVol%/dt, showed that the instrument can be a valuable research method for investigating the polymerization reaction kinetics. This new shrinkage-measuring instrument has some advantages that it was insensitive to temperature changes and could measure the dynamic volumetric shrinkage in real time without complicated processes. Therefore, it can be used to characterize the shrinkage kinetics in a wide range of commercial and experimental visible-light-cure materials in relation to their composition and chemistry.

Polymerization shrinkage stress of composite resins and resin cements - What do we need to know?

PubMed

Soares, Carlos José; Faria-E-Silva, André Luis; Rodrigues, Monise de Paula; Vilela, Andomar Bruno Fernandes; Pfeifer, Carmem Silvia; Tantbirojn, Daranee; Versluis, Antheunis

2017-08-28

Polymerization shrinkage stress of resin-based materials have been related to several unwanted clinical consequences, such as enamel crack propagation, cusp deflection, marginal and internal gaps, and decreased bond strength. Despite the absence of strong evidence relating polymerization shrinkage to secondary caries or fracture of posterior teeth, shrinkage stress has been associated with post-operative sensitivity and marginal stain. The latter is often erroneously used as a criterion for replacement of composite restorations. Therefore, an indirect correlation can emerge between shrinkage stress and the longevity of composite restorations or resin-bonded ceramic restorations. The relationship between shrinkage and stress can be best studied in laboratory experiments and a combination of various methodologies. The objective of this review article is to discuss the concept and consequences of polymerization shrinkage and shrinkage stress of composite resins and resin cements. Literature relating to polymerization shrinkage and shrinkage stress generation, research methodologies, and contributing factors are selected and reviewed. Clinical techniques that could reduce shrinkage stress and new developments on low-shrink dental materials are also discussed.

Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition

PubMed Central

Song, Han Byul; Wang, Xiance; Patton, James R.; Stansbury, Jeffrey W.; Bowman, Christopher N.

2017-01-01

Objectives Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Methods Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized silica microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. Results The photo-CuAAC polymerization of composites containing between 0 and 60 wt% microfiller achieved ~99% conversion with a dramatic reduction in the maximum heat of reaction (~20 °C decrease) for the 60 wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60 wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01 MPa, equivalent flexural modulus of 6.1±0.7 GPa, equivalent flexural strength of 107±9 MPa, and more than 10 times higher energy absorption of 10±1 MJ m−3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Significance Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. PMID:28363645

Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition.

PubMed

Song, Han Byul; Wang, Xiance; Patton, James R; Stansbury, Jeffrey W; Bowman, Christopher N

2017-06-01

Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized glass microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. The photo-CuAAC polymerization of composites containing between 0 and 60wt% microfiller achieved ∼99% conversion with a dramatic reduction in the maximum heat of reaction (∼20°C decrease) for the 60wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01MPa, equivalent flexural modulus of 6.1±0.7GPa, equivalent flexural strength of 107±9MPa, and more than 10 times higher energy absorption of 10±1MJm -3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

405 nm diode laser, halogen lamp and LED device comparison in dental composites cure: an "in vitro" experimental trial.

PubMed

Fornaini, C; Lagori, G; Merigo, E; Rocca, J-P; Chiusano, M; Cucinotta, A

2015-12-30

A 405 nm diode laser is indicated for composite materials polymerizing, thanks to the recent evolution in their compositions, absorbing in blue part of the spectrum. The purpose of this research was to evaluate its performance on two different kinds of composite resins. Two different composites were polymerized with a traditional halogen lamp, a LED device and a 405 nm diode laser. The depth of the cure, the volumetric shrinkage, and the degree of the conversion (DC%) of the double bond during the curing process were measured. One-way ANOVA test, Kruskal-Wallis tests, and Dunn comparison tests were used for statistic analysis. Regarding the depth of polymerization, the laser had the worst performance on one composite while on the other, no significant difference with the other devices was observed. The volumetric shrinkage showed that laser produced the lowest change in both of the composites. The DC% measure confirmed these findings. Based on the results of this preliminary study, it is not possible to recommend the 405 nm diode laser for the polymerization of dental composites.

Stress reduction in phase-separated, cross-linked networks: influence of phase structure and kinetics of reaction

PubMed Central

Szczepanski, Caroline R.; Stansbury, Jeffrey W.

2014-01-01

A mechanism for polymerization shrinkage and stress reduction was developed for heterogeneous networks formed via ambient, photo-initiated polymerization-induced phase separation (PIPS). The material system used consists of a bulk homopolymer matrix of triethylene glycol dimethacrylate (TEGDMA) modified with one of three non-reactive, linear prepolymers (poly-methyl, ethyl and butyl methacrylate). At higher prepolymer loading levels (10–20 wt%) an enhanced reduction in both shrinkage and polymerization stress is observed. The onset of gelation in these materials is delayed to a higher degree of methacrylate conversion (~15–25%), providing more time for phase structure evolution by thermodynamically driven monomer diffusion between immiscible phases prior to network macro-gelation. The resulting phase structure was probed by introducing a fluorescently tagged prepolymer into the matrix. The phase structure evolves from a dispersion of prepolymer at low loading levels to a fully co-continuous heterogeneous network at higher loadings. The bulk modulus in phase separated networks is equivalent or greater than that of poly(TEGDMA), despite a reduced polymerization rate and cross-link density in the prepolymer-rich domains. PMID:25418999

Alternative methods for determining shrinkage in restorative resin composites.

PubMed

de Melo Monteiro, Gabriela Queiroz; Montes, Marcos Antonio Japiassú Resende; Rolim, Tiago Vieira; de Oliveira Mota, Cláudia Cristina Brainer; de Barros Correia Kyotoku, Bernardo; Gomes, Anderson Stevens Leônidas; de Freitas, Anderson Zanardi

2011-08-01

The purpose of this study was to evaluate polymerization shrinkage of resin composites using a coordinate measuring machine, optical coherence tomography and a more widely known method, such as Archimedes Principle. Two null hypothesis were tested: (1) there are no differences between the materials tested; (2) there are no differences between the methods used for polymerization shrinkage measurements. Polymerization shrinkage of seven resin-based dental composites (Filtek Z250™, Filtek Z350™, Filtek P90™/3M ESPE, Esthet-X™, TPH Spectrum™/Dentsply 4 Seasons™, Tetric Ceram™/Ivoclar-Vivadent) was measured. For coordinate measuring machine measurements, composites were applied to a cylindrical Teflon mold (7 mm × 2 mm), polymerized and removed from the mold. The difference between the volume of the mold and the volume of the specimen was calculated as a percentage. Optical coherence tomography was also used for linear shrinkage evaluations. The thickness of the specimens was measured before and after photoactivation. Polymerization shrinkage was also measured using Archimedes Principle of buoyancy (n=5). Statistical analysis of the data was performed with ANOVA and the Games-Howell test. The results show that polymerization shrinkage values vary with the method used. Despite numerical differences the ranking of the resins was very similar with Filtek P90 presenting the lowest shrinkage values. Because of the variations in the results, reported values could only be used to compare materials within the same method. However, it is possible rank composites for polymerization shrinkage and to relate these data from different test methods. Independently of the method used, reduced polymerization shrinkage was found for silorane resin-based composite. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

An in situ evaluation of the polymerization shrinkage, degree of conversion, and bond strength of resin cements used for luting fiber posts.

PubMed

Pulido, Camilo Andrés; de Oliveira Franco, Ana Paula Gebert; Gomes, Giovana Mongruel; Bittencourt, Bruna Fortes; Kalinowski, Hypolito José; Gomes, João Carlos; Gomes, Osnara Maria Mongruel

2016-10-01

The behavior and magnitude of the deformations that occur during polymerization and the behavior of the luting agents of glass fiber posts inside the root canal require quantification. The purpose of this in vitro study was to investigate the in situ polymerization shrinkage, degree of conversion, and bond strength inside the root canal of resin cements used to lute fiber posts. Thirty maxillary canines were prepared to lute fiber posts. The teeth were randomly divided into 2 groups (n=15) according to the cementation system used, which included ARC, the conventional dual-polymerized resin cement RelyX ARC, and the U200 system, a self-adhesive resin cement, RelyX U200. Two fiber optic sensors with recorded Bragg gratings (FBG) were attached to each post before inserting the resin cement inside the root canal to measure the polymerization shrinkage (PS) of the cements in the cervical and apical root regions (με). Specimens were sectioned (into cervical and apical regions) to evaluate bond strength (BS) with a push-out test and degree of conversion (DC) with micro-Raman spectroscopy. Data were statistically analyzed with 2-way ANOVA and the Tukey honestly significant difference post hoc test (α=.05). The ARC and U200 system showed similar PS values (-276.4 ±129.2 με and -252.1 ±119.2 με, respectively). DC values from ARC were higher (87.5 ±2.7%) than those of U200 (55.9 ±9.7%). The cervical region showed higher DC values (74.8 ±15.2%) and PS values (-381.6 ±53.0 με) than those of the apical region (68.5 ±20.1% and -146.9 ±43.5 με, respectively) for both of the resin cements. BS was only statistically different between the cervical and apical regions for ARC (P<.05). The ARC system showed the highest PS and DC values compared with U200; and for both of the resin cements, the PS and DC values were higher at the cervical region than at the apical region of the canal root. BS was higher in the cervical region only for ARC. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Effects of Prepolymerized Particle Size and Polymerization Kinetics on Volumetric Shrinkage of Dental Modeling Resins

PubMed Central

Ha, Jung-Yun; Chun, Ju-Na; Son, Jun Sik; Kim, Kyo-Han

2014-01-01

Dental modeling resins have been developed for use in areas where highly precise resin structures are needed. The manufacturers claim that these polymethyl methacrylate/methyl methacrylate (PMMA/MMA) resins show little or no shrinkage after polymerization. This study examined the polymerization shrinkage of five dental modeling resins as well as one temporary PMMA/MMA resin (control). The morphology and the particle size of the prepolymerized PMMA powders were investigated by scanning electron microscopy and laser diffraction particle size analysis, respectively. Linear polymerization shrinkage strains of the resins were monitored for 20 minutes using a custom-made linometer, and the final values (at 20 minutes) were converted into volumetric shrinkages. The final volumetric shrinkage values for the modeling resins were statistically similar (P > 0.05) or significantly larger (P < 0.05) than that of the control resin and were related to the polymerization kinetics (P < 0.05) rather than the PMMA bead size (P = 0.335). Therefore, the optimal control of the polymerization kinetics seems to be more important for producing high-precision resin structures rather than the use of dental modeling resins. PMID:24779020

Industrially relevant epoxy-acrylate hybrid resin photopolymerizations

NASA Astrophysics Data System (ADS)

Ajiboye, Gbenga I.

Photopolymerization of epoxy-acrylate hybrid resins takes advantages of inherent properties present in the free-radical and cationic reactions to reduce oxygen inhibition problems that plague free-radical reactions. Similarly, the combined reaction mechanisms reduce moisture sensitivity of the cationic reactions. Despite the advantages of epoxy-acrylate hybrid resins, problems persist that need to be addressed. For example, low conversion and polymerization rate of the epoxides are a problem, because the fast acrylate conversion prevents the epoxide from reaching high conversion. Controlling phase separation is challenging, since two moieties with different properties are reacting. The physical properties of the polymer will be impacted by the availability of different moieties. High shrinkage stress results from the acrylate moiety, causing buckling and cracking in film and coating applications. The overall goal of this study is to use the fundamental knowledge of epoxy-acrylate hybrid resins to formulate industrially viable polymers. In order to achieve this goal, the study focuses on the following objectives: (I) determine the apparent activation energy of the hybrid monomer METHB, (II) increase epoxide conversion and polymerization rate of hybrid formulations, and (III) control physical properties in epoxy-acrylate hybrid resins. In order to increase the epoxide conversion and rate of polymerization, the sensitivity of epoxides to alcohol is used to facilitate the activated monomer (AM) mechanism and induce a covalent bond between the epoxide and acrylate polymers through the hydroxyl group. It is hypothesized that if the AM mechanism is facilitated, epoxide conversion will increase. As a result, the resins can be tailored to control phase separation and physical properties, and shrinkage stress can be reduced. In pursuit of these objectives, the hybrid monomer METHB was polymerized at temperatures ranging from 30°C to 70°C to obtain apparent activation energy of 23.49 kJ/mol for acrylate and 57 kJ/mol for epoxide moeities. Then, hybrid systems pairing hydroxyl-containing acrylates with epoxides were formulated to promote the faster AM mechanism. Monomer composition was changed in the presence of hydroxyl-containing acrylate, and initiators were carefully selected in order to control phase separation. The conversion of acrylate and epoxide was monitored in real time by Raman spectroscopy. The physical and mechanical properties were monitored using dynamic mechanical analysis. Epoxide conversion and rate of polymerization in epoxide-acrylate hybrid monomer systems were shown to increase through the introduction of a hydroxyl group on the meth/acrylate monomer, taking advantage of the faster AM mechanism. In addition, this covalent bond linking the epoxide network to the meth/acrylate polymer chains resulted in little or no phase separation and a reduction of the Tg for the hybrid polymer compared to the neat epoxide. Fundamental knowledge gained from this research will enable the use of epoxy-acrylate hybrid resins in variety of applications. For instance, shrinkage may be reduced in dental fillings, noise and vibration problems in aircraft and other machinery may be controlled, and photopolymerization cost could be reduced in thin film applications.

New Polymeric Precursors of Silicon Carbide

NASA Technical Reports Server (NTRS)

Litt, M.; Kumar, K.

1987-01-01

Silicon carbide made by pyrolizing polymers. Method conceived for preparation of poly(decamethylcyclohexasilanes) as precursors for preparation of silicon carbide at high yield. Technical potential of polysilanes as precursors of SiC ceramics being explored. Potential limited by intractability of some polysilanes; formation of small, cyclic polycarbosilane fragments during pyrolysis; and overall low char yield and large shrinkage in conversion to ceramics.

Analytical methods for the measurement of polymerization kinetics and stresses of dental resin-based composites: A review

PubMed Central

Ghavami-Lahiji, Mehrsima; Hooshmand, Tabassom

2017-01-01

Resin-based composites are commonly used restorative materials in dentistry. Such tooth-colored restorations can adhere to the dental tissues. One drawback is that the polymerization shrinkage and induced stresses during the curing procedure is an inherent property of resin composite materials that might impair their performance. This review focuses on the significant developments of laboratory tools in the measurement of polymerization shrinkage and stresses of dental resin-based materials during polymerization. An electronic search of publications from January 1977 to July 2016 was made using ScienceDirect, PubMed, Medline, and Google Scholar databases. The search included only English-language articles. Only studies that performed laboratory methods to evaluate the amount of the polymerization shrinkage and/or stresses of dental resin-based materials during polymerization were selected. The results indicated that various techniques have been introduced with different mechanical/physical bases. Besides, there are factors that may contribute the differences between the various methods in measuring the amount of shrinkages and stresses of resin composites. The search for an ideal and standard apparatus for measuring shrinkage stress and volumetric polymerization shrinkage of resin-based materials in dentistry is still required. Researchers and clinicians must be aware of differences between analytical methods to make proper interpretation and indications of each technique relevant to a clinical situation. PMID:28928776

Strategies to overcome polymerization shrinkage--materials and techniques. A review.

PubMed

Malhotra, Neeraj; Kundabala, M; Shashirashmi, Acharya

2010-03-01

Stress generation at tissue/resin composite interfaces is one of the important reasons for failure of resin-based composite (RBC) restorations owing to the inherent property of polymerization shrinkage. Unrelieved stresses can weaken the bond between the tooth structure and the restoration, eventually producing a gap at the restoration margins. This can lead to postoperative sensitivity, secondary caries, fracture of the restorations, marginal deterioration and discoloration. As polymerization shrinkage cannot be eliminated completely, various techniques and protocols have been suggested in the manipulation of, and restorative procedures for, RBCs to minimize the shrinkage and associated stresses. Introduction of various newer monomer systems (siloranes) may also overcome this problem of shrinkage stress. This review emphasizes the various material science advances and techniques advocated that are currently available or under trial/testing phase to deal with polymerization shrinkage in a clinical environment. Minimizing the shrinkage stresses in RBC restorations may lead to improvement in the success rate and survival of restorations. Thus, it is important for dental practitioners to be aware of various techniques and materials available to reduce these shrinkage stresses and be updated with the current knowledge available to deal with this issue.

A model for shrinkage strain in photo polymerization of dental composites.

PubMed

Petrovic, Ljubomir M; Atanackovic, Teodor M

2008-04-01

We formulate a new model for the shrinkage strain developed during photo polymerization in dental composites. The model is based on the diffusion type fractional order equation, since it has been proved that polymerization reaction is diffusion controlled (Atai M, Watts DC. A new kinetic model for the photo polymerization shrinkage-strain of dental composites and resin-monomers. Dent Mater 2006;22:785-91). Our model strongly confirms the observation by Atai and Watts (see reference details above) and their experimental results. The shrinkage strain is modeled by a nonlinear differential equation in (see reference details above) and that equation must be solved numerically. In our approach, we use the linear fractional order differential equation to describe the strain rate due to photo polymerization. This equation is solved exactly. As shrinkage is a consequence of the polymerization reaction and polymerization reaction is diffusion controlled, we postulate that shrinkage strain rate is described by a diffusion type equation. We find explicit form of solution to this equation and determine the strain in the resin monomers. Also by using equations of linear viscoelasticity, we determine stresses in the polymer due to the shrinkage. The time evolution of stresses implies that the maximal stresses are developed at the very beginning of the polymerization process. The stress in a dental composite that is light treated has the largest value short time after the treatment starts. The strain settles at the constant value in the time of about 100s (for the cases treated in Atai and Watts). From the model developed here, the shrinkage strain of dental composites and resin monomers is analytically determined. The maximal value of stresses is important, since this value must be smaller than the adhesive bond strength at cavo-restoration interface. The maximum stress determined here depends on the diffusivity coefficient. Since diffusivity coefficient increases as polymerization proceeds, it follows that the periods of light treatments should be shorter at the beginning of the treatment and longer at the end of the treatment, with dark interval between the initial low intensity and following high intensity curing. This is because at the end of polymerization the stress relaxation cannot take place.

Dimethacrylate network formation and polymer property evolution as determined by the selection of monomers and curing conditions

PubMed Central

Stansbury, Jeffrey W.

2011-01-01

Objectives This overview is intended to highlight connections between monomer structure and the development of highly crosslinked photopolymer networks including the conversion dependent properties of shrinkage, modulus and stress. Methods A review is provided that combines the polymer science and dental materials literature along with examples of relevant experimental results, which include measurements of reaction kinetics, photorheology as well as polymerization shrinkage and stress. Results While new monomers are continually under development for dental materials applications, mixtures of dimethacrylate monomers persist as the most common form of dental resins used on composite restorative materials. Monomer viscosity and reaction potential is derived from molecular structure and by employing real-time near-infrared spectroscopic techniques, the development of macromolecular networks is linked to the evolution of polymerization shrinkage (measured by linometer), modulus (measured by photorheometer), and stress (measured by tensometer). Relationships between the respective polymer properties are examined. Significance Through a better understanding of the polymer network formation and property development processes using conventional dimethacrylate monomer formulations, the rational design of improved materials is facilitated with the ultimate goal of achieving dental polymers that deliver enhanced clinical outcomes. PMID:22192248

3D full field strain analysis of polymerization shrinkage in a dental composite.

PubMed

Martinsen, Michael; El-Hajjar, Rani F; Berzins, David W

2013-08-01

The objective of this research was to study the polymerization shrinkage in a dental composite using 3D digital image correlation (DIC). Using 2 coupled cameras, digital images were taken of bar-shaped composite (Premise Universal Composite; Kerr) specimens before light curing and after for 10 min. Three-dimensional DIC was used to assess in-plane and out-of-plane deformations associated with polymerization shrinkage. The results show the polymerization shrinkage to be highly variable with the peak values occurring 0.6-0.8mm away from the surface. Volumetric shrinkage began to significantly decrease at 3.2mm from the specimen surface and reached a minimum at 4mm within the composite. Approximately 25-30% of the strain registered at 5 min occurred after light-activation. Application of 3D DIC dental applications can be performed without the need for assumptions on the deformation field. Understanding the local deformations and strain fields from the initial polymerization shrinkage can lead to a better understanding of the composite material and interaction with surrounding tooth structure, aiding in their further development and clinical prognosis. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A new approach to network heterogeneity: Polymerization Induced Phase Separation in photo-initiated, free-radical methacrylic systems

PubMed Central

Szczepanski, Caroline R.; Pfeifer, Carmem S.; Stansbury, Jeffrey W.

2012-01-01

Non-reactive, thermoplastic prepolymers (poly- methyl, ethyl and butyl methacrylate) were added to a model homopolymer matrix composed of triethylene glycol dimethacrylate (TEGDMA) to form heterogeneous networks via polymerization induced phase separation (PIPS). PIPS creates networks with distinct phase structure that can partially compensate for volumetric shrinkage during polymerization through localized internal volume expansion. This investigation utilizes purely photo-initiated, free-radical systems, broadening the scope of applications for PIPS since these processing conditions have not been studied previously. The introduction of prepolymer into TEGDMA monomer resulted in stable, homogeneous monomer formulations, most of which underwent PIPS upon photo-irradiation, creating heterogeneous networks. During polymerization the presence of prepolymer enhanced autoacceleration, allowing for a more extensive ambient cure of the material. Phase separation, as characterized by dynamic changes in sample turbidity, was monitored simultaneously with monomer conversion and either preceded or was coincident with network gelation. Dynamic mechanical analysis shows a broadening of the tan delta peak and secondary peak formation, characteristic of phase-separated materials, indicating one phase rich in prepolymer and another depleted form upon phase separation. In certain cases, PIPS leads to an enhanced physical reduction of volumetric shrinkage, which is attractive for many applications including dental composite materials. PMID:23109733

Evaluation of shrinkage polymerization and temperature of different acrylic resins used to splinting transfer copings in indirect impression technique

NASA Astrophysics Data System (ADS)

Franco, Ana Paula G. O.; Karam, Leandro Z.; Galvão, José R.; Kalinowski, Hypolito J.

2015-09-01

The aim of the present study was evaluate the shrinkage polymerization and temperature of different acrylic resins used to splinting transfer copings in indirect impression technique. Two implants were placed in an artificial bone, with the two transfer copings joined with dental floss and acrylic resins; two dental resins are used. Measurements of deformation and temperature were performed with Fiber Braggs grating sensor for 17 minutes. The results revealed that one type of resin shows greater values of polymerization shrinkage than the other. Pattern resins did not present lower values of shrinkage, as usually reported by the manufacturer.

Experimental evaluation and simulation of volumetric shrinkage and warpage on polymeric composite reinforced with short natural fibers

NASA Astrophysics Data System (ADS)

Santos, Jonnathan D.; Fajardo, Jorge I.; Cuji, Alvaro R.; García, Jaime A.; Garzón, Luis E.; López, Luis M.

2015-09-01

A polymeric natural fiber-reinforced composite is developed by extrusion and injection molding process. The shrinkage and warpage of high-density polyethylene reinforced with short natural fibers of Guadua angustifolia Kunth are analyzed by experimental measurements and computer simulations. Autodesk Moldflow® and Solid Works® are employed to simulate both volumetric shrinkage and warpage of injected parts at different configurations: 0 wt.%, 20 wt.%, 30 wt.% and 40 wt.% reinforcing on shrinkage and warpage behavior of polymer composite. Become evident the restrictive effect of reinforcing on the volumetric shrinkage and warpage of injected parts. The results indicate that volumetric shrinkage of natural composite is reduced up to 58% with fiber increasing, whereas the warpage shows a reduction form 79% to 86% with major fiber content. These results suggest that it is a highly beneficial use of natural fibers to improve the assembly properties of polymeric natural fiber-reinforced composites.

Dental Composites with Calcium / Strontium Phosphates and Polylysine.

PubMed

Panpisut, Piyaphong; Liaqat, Saad; Zacharaki, Eleni; Xia, Wendy; Petridis, Haralampos; Young, Anne Margaret

2016-01-01

This study developed light cured dental composites with added monocalcium phosphate monohydrate (MCPM), tristrontium phosphate (TSrP) and antimicrobial polylysine (PLS). The aim was to produce composites that have enhanced water sorption induced expansion, can promote apatite precipitation and release polylysine. Experimental composite formulations consisted of light activated dimethacrylate monomers combined with 80 wt% powder. The powder phase contained a dental glass with and without PLS (2.5 wt%) and/or reactive phosphate fillers (15 wt% TSrP and 10 wt% MCPM). The commercial composite, Z250, was used as a control. Monomer conversion and calculated polymerization shrinkage were assessed using FTIR. Subsequent mass or volume changes in water versus simulated body fluid (SBF) were quantified using gravimetric studies. These were used, along with Raman and SEM, to assess apatite precipitation on the composite surface. PLS release was determined using UV spectroscopy. Furthermore, biaxial flexural strengths after 24 hours of SBF immersion were obtained. Monomer conversion of the composites decreased upon the addition of phosphate fillers (from 76 to 64%) but was always higher than that of Z250 (54%). Phosphate addition increased water sorption induced expansion from 2 to 4% helping to balance the calculated polymerization shrinkage of ~ 3.4%. Phosphate addition promoted apatite precipitation from SBF. Polylysine increased the apatite layer thickness from ~ 10 to 20 μm after 4 weeks. The novel composites showed a burst release of PLS (3.7%) followed by diffusion-controlled release irrespective of phosphate addition. PLS and phosphates decreased strength from 154 MPa on average by 17% and 18%, respectively. All formulations, however, had greater strength than the ISO 4049 requirement of > 80 MPa. The addition of MCPM with TSrP promoted hygroscopic expansion, and apatite formation. These properties are expected to help compensate polymerization shrinkage and help remineralize demineralized dentin. Polylysine can be released from the composites at early time. This may kill residual bacteria.

Low shrinkage light curable nanocomposite for dental restorative material.

PubMed

Chen, Min-Huey; Chen, Ci-Rong; Hsu, Seng-Haw; Sun, Shih-Po; Su, Wei-Fang

2006-02-01

The aim of this study was to develop a low shrinkage visible light curable nanocomposite dental restorative material without sacrificing the other properties of conventional materials. This nanocomposite was developed by using an epoxy resin 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate (ERL4221) matrix with 55% wt of 70-100 nm nanosilica fillers through ring-opening polymerization. GPS (gamma-glycidoxypropyl trimethoxysilane) was used to modify the surfaces of silica nanoparticles. The nanocomposite was shown to exhibit low polymerization shrinkage strain, which is only a quarter of currently used methacrylate-based composites. It also exhibited a low thermal expansion coefficient of 49.8 microm/m degrees C which is comparable to that of the methacrylate based composites (51.2 microm/m degrees C). The strong interfacial interactions between the resin and fillers at nanoscales were demonstrated by an observed high strength and high thermal stability of the nanocomposite. A microhardness of 62 KHN and a tensile strength of 47 MPa were reached. A high degree of conversion ( approximately 70%) can be obtained after less than 60 s of irradiation upon the nanocomposite. A transmission electron microscope (TEM) study of the nanocomposite showed no aggregation of fillers. Comparable results to the methacrylate based composites were obtained from the one day MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide) cytotoxicity test. The developed epoxy resin based nanocomposite demonstrated low shrinkage and high strength and is suitable for dental restorative material applications.

Low-shrink composite resins: a review of their history, strategies for managing shrinkage, and clinical significance.

PubMed

Pitel, Mark L

2013-09-01

Despite numerous advances in composite resin technology over the course of many decades, shrinkage behavior and the resultant stresses inherent to direct placed composite restorations continue to challenge clinicians. This overview of composite resins includes a review of their history and development along with a discussion of strategies for reducing polymerization shrinkage. An assessment of the clinical significance of these materials is also provided, including a discussion of the differences between polymerization shrinkage and stress, incremental layering versus bulk placement, and the emergence of lower shrinkage stress monomer chemistry.

Polymerization stresses in low-shrinkage dental resin composites measured by crack analysis.

PubMed

Yamamoto, Takatsugu; Kubota, Yu; Momoi, Yasuko; Ferracane, Jack L

2012-09-01

The objective of this study was to compare several dental restoratives currently advertised as low-shrinkage composites (Clearfil Majesty Posterior, Kalore, Reflexions XLS Dentin and Venus Diamond) with a microfill composite (Heliomolar) in terms of polymerization stress, polymerization shrinkage and elastic modulus. Cracks were made at several distances from the edge of a precision cavity in a soda-lime glass disk. The composites were placed into the cavity and lengths of the cracks were measured before and after light curing. Polymerization stresses generated in the glass at 2 and 10 min after the irradiation were calculated from the crack lengths and K(c) of the glass. Polymerization shrinkage and elastic modulus of the composites also were measured at 2 and 10 min after irradiation using a video-imaging device and a nanoindenter, respectively. The data were statistically analyzed by ANOVAs and Tukey's test (p<0.05). The stress was significantly affected by composite brand, distance and time. The stress was directly proportional to time and inversely proportional to distance from the edge of the cavity. Clearfil Majesty Posterior demonstrated the highest stress and it resulted in the fracture of the glass at 2 min. Venus Diamond and Heliomolar exhibited the greatest shrinkage at both times. The elastic moduli of Clearfil Majesty Posterior and Reflexions XLS Dentin were greatest at 2 and 10 min, respectively. Among the four low-shrinkage composites, two demonstrated significantly reduced polymerization stress compared to Heliomolar, which has previously been shown in in vitro tests to generate low curing stress. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

DH and ESPI laser interferometry applied to the restoration shrinkage assessment

NASA Astrophysics Data System (ADS)

Campos, L. M. P.; Parra, D. F.; Vasconcelos, M. R.; Vaz, M.; Monteiro, J.

2014-01-01

In dental restoration postoperative marginal leakage is commonly associated to polymerization shrinkage effects. In consequence the longevity and quality of restorative treatment depends on the shrinkage mechanisms of the composite filling during the polymerization. In this work the development of new techniques for evaluation of those effects under light-induced polymerization of dental nano composite fillings is reported. The composite resins activated by visible light, initiate the polymerization process by absorbing light in wavelengths at about 470 nm. The techniques employed in the contraction assessment were digital holography (DH) and Electronic Speckle Pattern Interferometry (ESPI) based on laser interferometry. A satisfactory resolution was achieved in the non-contact displacement field measurements on small objects concerning the experimental dental samples. According to a specific clinical protocol, natural teeth were used (human mandibular premolars). A class I cavity was drilled and restored with nano composite material, according to Black principles. The polymerization was monitored by DH and ESPI in real time during the cure reaction of the restoration. The total displacement reported for the material in relation of the tooth wall was 3.7 μm (natural tooth). The technique showed the entire tooth surface (wall) deforming during polymerization shrinkage.

Polymerization shrinkage kinetics and shrinkage-stress in dental resin-composites.

PubMed

Al Sunbul, Hanan; Silikas, Nick; Watts, David C

2016-08-01

To investigate a set of resin-composites and the effect of their composition on polymerization shrinkage strain and strain kinetics, shrinkage stress and the apparent elastic modulus. Eighteen commercially available resin-composites were investigated. Three specimens (n=3) were made per material and light-cured with an LED unit (1200mW/cm(2)) for 20s. The bonded-disk method was used to measure the shrinkage strain and Bioman shrinkage stress instrument was used to measure shrinkage stress. The shrinkage strain kinetics at 23°C was monitored for 60min. Maximum strain and stress was evaluated at 60min. The shrinkage strain rate was calculated using numerical differentiation. The shrinkage strain values ranged from 1.83 (0.09) % for Tetric Evoceram (TEC) to 4.68 (0.04) % for Beautifil flow plus (BFP). The shrinkage strain rate ranged from 0.11 (0.01%s(-1)) for Gaenial posterior (GA-P) to 0.59 (0.07) %s(-1) for BFP. Shrinkage stress values ranged from 3.94 (0.40)MPa for TET to 10.45 (0.41)MPa for BFP. The apparent elastic modulus ranged from 153.56 (18.7)MPa for Ever X posterior (EVX) to 277.34 (25.5) MPa for Grandio SO heavy flow (GSO). The nature of the monomer system determines the amount of the bulk contraction that occurs during polymerization and the resultant stress. Higher values of shrinkage strain and stress were demonstrated by the investigated flowable materials. The bulk-fill materials showed comparable result when compared to the traditional resin-composites. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Evaluation of the polymerization shrinkage of experimental flowable composite resins through optical coherence tomography

NASA Astrophysics Data System (ADS)

Carneiro, Vanda S. M.; Mota, Cláudia C. B. O.; Souza, Alex F.; Cajazeira, Marlus R. R.; Gerbi, Marleny E. M. M.; Gomes, Anderson S. L.

2018-02-01

This study evaluated the polymerization shrinkage of two experimental flowable composite resins (CR) with different proportions of Urethane dimethacrylate (UDMA)/triethylene glycol dimethacrylate (TEGDMA) monomers in the organic matrix (50:50 and 60:40, respectively). A commercially available flowable CR, Tetric N-Flow (Ivoclair Vivadent, Liechtenstein, Germany), was employed as the control group. The resins were inserted in a cylindrical teflon mold (7 mm diameter, 0.6 mm height) and scanned with OCT before photoactivation, immediately after and 15 minutes after light-curing (Radii-Cal, SDI, Australia, 1,200 mW/cm2 ) exposure. A Callisto SD-OCT system (Thorlabs Inc, USA), operating at 930 nm central wavelength was employed for imaging acquisition. Cross-sectional OCT images were captured with 8 mm transverse scanning (2000x512 matrix), and processed by the ImageJ software, for comparison between the scanning times and between groups. Pearson correlation showed significant shrinkage for all groups in each time analyzed. Kruskal-Wallis test showed greater polymerization shrinkage for the 50:50 UDMA/TEGDMA group (p=0.001), followed by the control group (p=0.018). TEGDMA concentration was proportionally related to the polymerization shrinkage of the flowable composite resins.

Dental composite polymerization: a three different sources comparison

NASA Astrophysics Data System (ADS)

Sozzi, Michele; Fornaini, Carlo; Lagori, Giuseppe; Merigo, Elisabetta; Cucinotta, Annamaria; Vescovi, Paolo; Selleri, Stefano

2015-02-01

The introduction of photo-activators, with absorption spectra in the violet region, in composite resins raised interest in the use of 405 nm diode lasers for polymerization. The purpose of this research is the evaluation of the resins polymerization by means of violet diode laser compared to traditional lamps. Two different resins have been used for the experiments: Filtek Supreme XT flow (3M ESPE, USA) and Tetric Evo flow (Ivoclar, Vivadent). The photo-activator used is Camphoroquinone, alone, or in combination with Lucirin TPO. The resins have been cured with an halogen lamp (Heliolux DXL, Vivadent Ivoclar, Austria), a broadband LED curing light (Valo Ultradent, USA) and a 405 nm laser (Euphoton, Italy). The measure of cure depth, of the volumetric shrinkage, and the conversion degree (DC%) of the double bond during the curing process have been evaluated. A composite layer of 3 mm was cured in Filtek Supreme resin (Camphoroquinone activator), lower if compared to the use of the other two light sources. Tests on Tetric Evo (Camphoroquinone + Lucirin) didn't show any improvement of the use of laser compared to the halogen lamp and the broadband LED. By measuring the volumetric shrinkage the laser induced the lower change with both the composites. In terms of DC% the lower performance was obtained with the laser. Considering that the polymerization process strongly depends on the kind of composite used the effectiveness of 405 nm laser proved to be lower than halogen lamps and broadband LEDs.

Time dependence of composite shrinkage using halogen and LED light curing.

PubMed

Uhl, Alexander; Mills, Robin W; Rzanny, Angelika E; Jandt, Klaus D

2005-03-01

The polymerization shrinkage of light cured dental composites presents the major drawback for these aesthetically adaptable restorative materials. LED based light curing technology has recently become commercially available. Therefore, the aim of the present study was to investigate if there was a statistically significant difference in linear and volumetric composite shrinkage strain if a LED LCU is used for the light curing process rather than a conventional halogen LCU. The volumetric shrinkage strain was determined using the Archimedes buoyancy principle after 5, 10, 20, 40 s of light curing and after 120 s following the 40 s light curing time period. The linear shrinkage strain was determined with a dynamic mechanical analyzer for the composites Z100, Spectrum, Solitaire2 and Definite polymerized with the LCUs Trilight (halogen), Freelight I (LED) and LED63 (LED LCU prototype). The changes in irradiance and spectra of the LCUs were measured after 0, 312 and 360 min of duty time. In general there was no considerable difference in shrinkage of the composites Z100, Spectrum or Solitaire2 when the LED63 was used instead of the Trilight. There was, however, a statistically significant difference in shrinkage strain when the composite Definite was polymerized with the LED63 instead of the Trilight. The spectrum of the Trilight changed during the experiment considerably whereas the LED63 showed an almost constant light output. The Freelight I dropped considerably in irradiance and had to be withdrawn from the study because of technical problems. The composites containing only the photoinitiator camphorquinone showed similar shrinkage strain behaviour when a LED or halogen LCU is used for the polymerization. The irradiance of some LED LCUs can also decrease over time and should therefore be checked on a regular basis.

Polymerization shrinkage and hygroscopic expansion of contemporary posterior resin-based filling materials--a comparative study.

PubMed

Rüttermann, Stefan; Krüger, Sören; Raab, Wolfgang H-M; Janda, Ralf

2007-10-01

To investigate the polymerization shrinkage and hygroscopic expansion of contemporary posterior resin-based filling materials. The densities of SureFil (SU), CeramXMono (CM), Clearfil AP-X (CF), Solitaire 2 (SO), TetricEvoCeram (TE), and Filtek P60 (FT) were measured using the Archimedes' principle prior to and 15min after curing for 20, 40 and 60s and after 1h, 24h, 7 d, and 30 d storage at 37 degrees C in water. Volumetric changes (DeltaV) in percent after polymerization and after each storage period in water were calculated from the changes of densities. Water sorption and solubility were determined after 30 d for all specimens and their curing times. Two-way ANOVA was calculated for shrinkage and repeated measures ANOVA was calculated for hygroscopic expansion (p<0.05). DeltaV depended on filler load but not on curing time (SU approximately -2.0%, CM approximately -2.6%, CF approximately -2.1%, SO approximately -3.3%, TE approximately -1.7%, FT approximately -1.8%). Hygroscopic expansion depended on water sorption and solubility. Except for SU, all materials showed DeltaV approximately +1% after water storage. Polymerization shrinkage depended on the type of resin-based filling material but not on curing time. Shrinkage was not compensated by hygroscopic expansion.

Polymerization shrinkage of different types of composite resins and microleakage with and without liner in class II cavities.

PubMed

Karaman, E; Ozgunaltay, G

2014-01-01

To determine the volumetric polymerization shrinkage of four different types of composite resin and to evaluate microleakage of these materials in class II (MOD) cavities with and without a resin-modified glass ionomer cement (RMGIC) liner, in vitro. One hundred twenty-eight extracted human upper premolar teeth were used. After the teeth were divided into eight groups (n=16), standardized MOD cavities were prepared. Then the teeth were restored with different resin composites (Filtek Supreme XT, Filtek P 60, Filtek Silorane, Filtek Z 250) with and without a RMGIC liner (Vitrebond). The restorations were finished and polished after 24 hours. Following thermocycling, the teeth were immersed in 0.5% basic fuchsin for 24 hours, then midsagitally sectioned in a mesiodistal plane and examined for microleakage using a stereomicroscope. The volumetric polymerization shrinkage of materials was measured using a video imaging device (Acuvol, Bisco, Inc). Data were statistically analyzed with Kruskal-Wallis and Mann-Whitney U-tests. All teeth showed microleakage, but placement of RMGIC liner reduced microleakage. No statistically significant differences were found in microleakage between the teeth restored without RMGIC liner (p>0.05). Filtek Silorane showed significantly less volumetric polymerization shrinkage than the methacrylate-based composite resins (p<0.05). The use of RMGIC liner with both silorane- and methacrylate-based composite resin restorations resulted in reduced microleakage. The volumetric polymerization shrinkage was least with the silorane-based composite.

A study of polymerization shrinkage kinetics using digital image correlation.

PubMed

Lau, Andrew; Li, Jianying; Heo, Young Cheul; Fok, Alex

2015-04-01

To investigate the polymerization shrinkage kinetics of dental resin composites by measuring in real time the full-field shrinkage strain using a novel technique based on digital image correlation (DIC). Polymerization shrinkage in resin composite specimens (Filtek LS and Z100) was measured as a function of time and position. The main experimental setup included a CCD camera and an external shutter inversely synchronized to that of the camera. The specimens (2 mm × 4 mm × 5 mm) were irradiated for 40s at 1200 mW/cm(2), while alternating image acquisition and obstruction of the curing light occurred at 15 fps. The acquired images were processed using proprietary software to obtain the full-field strain maps as a function of time. Z100 showed a higher final shrinkage value and rate of development than LS. The final volumetric shrinkage for Z100 and LS were 1.99% and 1.19%, respectively. The shrinkage behavior followed an established shrinkage strain kinetics model. The corresponding characteristic time and reaction order exponent for LS and Z100 were calculated to be approximately 23s and 0.84, and 14s and 0.7, respectively, at a distance of 1.0mm from the irradiated surface, the position where maximum shrinkage strain occurred. Thermal expansion from the exothermic reaction could have affected the accuracy of these parameters. The new DIC method using an inversely synchronized shutter provided realtime, full-field results that could aid in assessing the shrinkage strain kinetics of dental resin composites as a function of specimen depth. It could also help determine the optimal curing modes for dental resin composites. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Measurement of the full-field polymerization shrinkage and depth of cure of dental composites using digital image correlation.

PubMed

Li, Jianying; Fok, Alex S L; Satterthwaite, Julian; Watts, David C

2009-05-01

The aim of this study was to measure the full-field polymerization shrinkage of dental composites using optical image correlation method. Bar specimens of cross-section 4mm x 2mm and length 10mm approximately were light cured with two irradiances, 450 mW/cm(2) and 180 mW/cm(2), respectively. The curing light was generated with Optilux 501 (Kerr) and the two different irradiances were achieved by adjusting the distance between the light tip and the specimen. A single-camera 2D measuring system was used to record the deformation of the composite specimen for 30 min at a frequency of 0.1 Hz. The specimen surface under observation was sprayed with paint to produce sufficient contrast to allow tracking of individual points on the surface. The curing light was applied to one end of the specimen for 40s during which the painted surface was fully covered. After curing, the cover was removed immediately so that deformation of the painted surface could be recorded by the camera. The images were then analyzed with specialist software and the volumetric shrinkage determined along the beam length. A typical shrinkage strain field obtained on a specimen surface was highly non-uniform, even at positions of constant distance from the irradiation surface, indicating possible heterogeneity in material composition and shrinkage behavior in the composite. The maximum volumetric shrinkage strain of approximately 1.5% occurred at a subsurface distance of about 1mm, instead of at the irradiation surface. After reaching its peak value, the shrinkage strain then gradually decreased with increasing distance along the beam length, before leveling off to a value of approximately 0.2% at a distance of 4-5mm. The maximum volumetric shrinkage obtained agreed well with the value of 1.6% reported by the manufacturer for the composite examined in this work. Using irradiance of 180 mW/cm(2) resulted in only slightly less polymerization shrinkage than using irradiance of 450 mW/cm(2). Compared to the other measurement methods, the image correlation method is capable of producing full-field information about the polymerization shrinkage behavior of dental composites.

Replacement of glass particles by multidirectional short glass fibers in experimental composites: Effects on degree of conversion, mechanical properties and polymerization shrinkage.

PubMed

Bocalon, Anne C E; Mita, Daniela; Narumyia, Isabela; Shouha, Paul; Xavier, Tathy A; Braga, Roberto Ruggiero

2016-09-01

To test the null hypothesis that the replacement of a small fraction of glass particles with random short glass fibers does not affect degree of conversion (DC), flexural strength (FS), fracture toughness (FT) and post-gel polymerization shrinkage (PS) of experimental composites. Four experimental photocurable composites containing 1 BisGMA:1 TEGDMA (by weight) and 60vol% of fillers were prepared. The reinforcing phase was constituted by barium glass particles (2μm) and 0%, 2.5%, 5.0% or 7.5% of silanated glass fibers (1.4mm in length, 7-13μm in diameter). DC (n=4) was obtained using near-FTIR. FS (n=10) was calculated via biaxial flexural test and FT (n=10) used the "single edge notched beam" method. PS at 5min (n=8) was determined using the strain gage method. Data were analyzed by ANOVA/Tukey test (DC, FS, PS) or Kruskal-Wallis/Dunn's test (FT, alpha: 5% for both tests). DC was similar among groups (p>0.05). Only the composite containing 5.0% of fibers presented lower FS than the control (p<0.001). FT increased significantly between the control (1.3±0.17MPam(0.5)) and the composites containing either 5.0% (2.7±0.6MPam(0.5)) or 7.5% of fibers (2.8±0.6MPam(0.5), p<0.001). PS in relation to control was significantly reduced at 2.5% fibers (from 0.81±0.13% to 0.57±0.13%) and further reduced between 5.0% and 7.5% (from 0.42±0.12% to 0.23±0.07%, p<0.001). The replacement of a small fraction of filler particles with glass fibers significantly increased fracture toughness and reduced post-gel shrinkage of experimental composites. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Mechanical properties and polymerization shrinkage of composite resins light-cured using two different lasers.

PubMed

Kim, Tae-Wan; Lee, Jang-Hoon; Jeong, Seung-Hwa; Ko, Ching-Chang; Kim, Hyung-Il; Kwon, Yong Hoon

2015-04-01

The purpose of the present study was to investigate the usefulness of 457 and 473 nm lasers for the curing of composite resins during the restoration of damaged tooth cavity. Monochromaticity and coherence are attractive features of laser compared with most other light sources. Better polymerization of composite resins can be expected. Eight composite resins were light cured using these two lasers and a light-emitting diode (LED) light-curing unit (LCU). To evaluate the degrees of polymerization achieved, polymerization shrinkage and flexural and compressive properties were measured and compared. Polymerization shrinkage values by 457 and 473 nm laser, and LED ranged from 10.9 to 26.8, from 13.2 to 26.1, and from 11.5 to 26.3 μm, respectively. The values by 457 nm laser was significantly different from those by 473 and LED LCU (p<0.05). However, there was no statistical difference between values by 473 and LED LCU. Before immersion in distilled water, flexural strength (FS) and compressive modulus (CM) of the specimens were inconsistently influenced by LCUs. On the other hand, flexural modulus (FM) and compressive strength (CS) were not significantly different for the three LCUs (p>0.05). For the tested LCUs, no specific LCU could consistently achieve highest strength and modulus from the specimens tested. Two lasers (457 and 473 nm) can polymerize composite resins to the level that LED LCU can achieve despite inconsistent trends of polymerization shrinkage and flexural and compressive properties of the tested specimens.

Polymerization Behavior and Mechanical Properties of High-Viscosity Bulk Fill and Low Shrinkage Resin Composites.

PubMed

Shibasaki, S; Takamizawa, T; Nojiri, K; Imai, A; Tsujimoto, A; Endo, H; Suzuki, S; Suda, S; Barkmeier, W W; Latta, M A; Miyazaki, M

The present study determined the mechanical properties and volumetric polymerization shrinkage of different categories of resin composite. Three high viscosity bulk fill resin composites were tested: Tetric EvoCeram Bulk Fill (TB, Ivoclar Vivadent), Filtek Bulk Fill posterior restorative (FB, 3M ESPE), and Sonic Fill (SF, Kerr Corp). Two low-shrinkage resin composites, Kalore (KL, GC Corp) and Filtek LS Posterior (LS, 3M ESPE), were used. Three conventional resin composites, Herculite Ultra (HU, Kerr Corp), Estelite ∑ Quick (EQ, Tokuyama Dental), and Filtek Supreme Ultra (SU, 3M ESPE), were used as comparison materials. Following ISO Specification 4049, six specimens for each resin composite were used to determine flexural strength, elastic modulus, and resilience. Volumetric polymerization shrinkage was determined using a water-filled dilatometer. Data were evaluated using analysis of variance followed by Tukey's honestly significant difference test (α=0.05). The flexural strength of the resin composites ranged from 115.4 to 148.1 MPa, the elastic modulus ranged from 5.6 to 13.4 GPa, and the resilience ranged from 0.70 to 1.0 MJ/m 3 . There were significant differences in flexural properties between the materials but no clear outliers. Volumetric changes as a function of time over a duration of 180 seconds depended on the type of resin composite. However, for all the resin composites, apart from LS, volumetric shrinkage began soon after the start of light irradiation, and a rapid decrease in volume during light irradiation followed by a slower decrease was observed. The low shrinkage resin composites KL and LS showed significantly lower volumetric shrinkage than the other tested materials at the measuring point of 180 seconds. In contrast, the three bulk fill resin composites showed higher volumetric change than the other resin composites. The findings from this study provide clinicians with valuable information regarding the mechanical properties and polymerization kinetics of these categories of current resin composite.

Recent advances and developments in composite dental restorative materials.

PubMed

Cramer, N B; Stansbury, J W; Bowman, C N

2011-04-01

Composite dental restorations represent a unique class of biomaterials with severe restrictions on biocompatibility, curing behavior, esthetics, and ultimate material properties. These materials are presently limited by shrinkage and polymerization-induced shrinkage stress, limited toughness, the presence of unreacted monomer that remains following the polymerization, and several other factors. Fortunately, these materials have been the focus of a great deal of research in recent years with the goal of improving restoration performance by changing the initiation system, monomers, and fillers and their coupling agents, and by developing novel polymerization strategies. Here, we review the general characteristics of the polymerization reaction and recent approaches that have been taken to improve composite restorative performance.

Recent Advances and Developments in Composite Dental Restorative Materials

PubMed Central

Cramer, N.B.; Stansbury, J.W.; Bowman, C.N.

2011-01-01

Composite dental restorations represent a unique class of biomaterials with severe restrictions on biocompatibility, curing behavior, esthetics, and ultimate material properties. These materials are presently limited by shrinkage and polymerization-induced shrinkage stress, limited toughness, the presence of unreacted monomer that remains following the polymerization, and several other factors. Fortunately, these materials have been the focus of a great deal of research in recent years with the goal of improving restoration performance by changing the initiation system, monomers, and fillers and their coupling agents, and by developing novel polymerization strategies. Here, we review the general characteristics of the polymerization reaction and recent approaches that have been taken to improve composite restorative performance. PMID:20924063

Sol-gel chemistry by ring-opening polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

RAHIMIAN,KAMYAR; LOY,DOUGLAS A.

2000-02-07

Sol-gel processing of materials is plagued by shrinkage during polymerization of the alkoxide monomers and processing (aging and drying) of the resulting gels. The authors have developed a new class of hybrid organic-inorganic materials based on the solventless ring-opening polymerization (ROP) of monomers bearing the 2,2,5,5-tetramethyl-2,5-disilaoxacyclopentyl group, which permits them to drastically reduce shrinkage in sol-gel processed materials. Because the monomers are polymerized through a chain growth mechanism catalyzed by base rather than the step growth mechanism normally used in sol-gel systems, hydrolysis and condensation products are entirely eliminated. Furthermore, since water is not required for hydrolysis, an alcohol solventmore » is not necessary. Monomers with two disilaoxacyclopentyl groups, separated by a rigid phenylene group or a more flexible alkylene group, were prepared through disilylation of the corresponding diacetylenes, followed by ring closure and hydrogenation. Anionic polymerization of these materials, either neat or with 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane as a copolymer, affords thermally stable transparent gels with no visible shrinkage. These materials provide an easy route to the introduction of sol-gel type materials in encapsulation of microelectronics, which they have successfully demonstrated.« less

Depth of cure, flexural properties and volumetric shrinkage of low and high viscosity bulk-fill giomers and resin composites.

PubMed

Tsujimoto, Akimasa; Barkmeier, Wayne W; Takamizawa, Toshiki; Latta, Mark A; Miyazaki, Masashi

2017-03-31

The purpose of this study was to investigate the depth of cure, flexural properties and volumetric shrinkage of low and high viscosity bulk-fill giomers and resin composites. Depth of cure and flexural properties were determined according to ISO 4049, and volumetric shrinkage was measured using a dilatometer. The depths of cure of giomers were significantly lower than those of resin composites, regardless of photo polymerization times. No difference in flexural strength and modulus was found among either high or low viscosity bulk fill materials. Volumetric shrinkage of low and high viscosity bulk-fill resin composites was significantly less than low and high viscosity giomers. Depth of cure of both low and high viscosity bulk-fill materials is time dependent. Flexural strength and modulus of high viscosity or low viscosity bulk-fill giomer or resin composite materials are not different for their respective category. Resin composites exhibited less polymerization shrinkage than giomers.

Structure/property relationships in methacrylate/dimethacrylate polymers for dental applications

NASA Astrophysics Data System (ADS)

Mehlem, Jeremy John

Since its invention Bis-GMA or one of its analogs has been the main component of the polymer portion of composites for dental restorations. The need for dilution of Bis-GMA and its analogs to optimize its properties has long been recognized. Bis-GMA is a highly viscous monomer. This high viscosity leads to early vitrification, which limits conversion during cure. This viscosity also limits filler loading. Vitrification at low conversions leads to heterogeneous systems composed of low and high cross-link density phases. The low cross-link density phases behave as defects in the system; therefore, if the amount of low cross-link density phases in the system can be reduced and a more uniform network structure can be achieved, then the mechanical properties of the resin can be improved. Since the increase in viscosity during cure causes vitrification, it is logical that a system with a low initial viscosity will delay the onset of vitrification. Reactive diluents such as triethylene glycol dimethacrylate (TEGDMA) are effective at lower levels. However, large amounts negatively affect matrix properties by increasing polymerization shrinkage and water sorption. Shrinkage has been cited as one of the main deficiencies in dental composites. The goal of this project is to improve upon standard viscosity modifying comonomers such as triethylene glycol dimethacrylate. The comonomers that were explored were phenyloxyethyl methacrylate, cyclohexyl methacrylate, and tert-butylcylcohexyl methacrylate. Multicomponent systems based on analogs of ethylene glycol dimethacrylates with different length ethyl glycol chains were also examined. The substitution of monomethacrylates for TEGDMA as a comonomer resulted in enhanced or negligible affects on the mechanical properties of Bis-MEPP based polymer systems while reducing polymerization shrinkage. 129Xenon NMR and TappingMode(TM) AFM were used to characterize the heterogeneity of dimethacrylates systems during their cure cycle as well as in their final state. Using these methods the size of the high and low cross-link density phase was examined and determined to be on the order of 50--150 nanometers. Model compounds based on phenylethyl methacrylate were formulated to determine how of nadic methyl anhydride and maleic anhydride incorporate into dimethacrylate resin systems.

Modeling dental composite shrinkage by digital image correlation and finite element methods

NASA Astrophysics Data System (ADS)

Chen, Terry Yuan-Fang; Huang, Pin-Sheng; Chuang, Shu-Fen

2014-10-01

Dental composites are light-curable resin-based materials with an inherent defect of polymerization shrinkage which may cause tooth deflection and debonding of restorations. This study aimed to combine digital image correlation (DIC) and finite element analysis (FEA) to model the shrinkage behaviors under different light curing regimens. Extracted human molars were prepared with proximal cavities for composite restorations, and then divided into three groups to receive different light curing protocols: regular intensity, low intensity, and step-curing consisting of low and high intensities. For each tooth, the composite fillings were consecutively placed under both unbonded and bonded conditions. At first, the shrinkage of the unbonded restorations was analyzed by DIC and adopted as the setting of FEA. The simulated shrinkage behaviors obtained from FEA were further validated by the measurements in the bonded cases. The results showed that different light curing regimens affected the shrinkage in unbonded restorations, with regular intensity showing the greatest shrinkage strain on the top surface. The shrinkage centers in the bonded cases were located closer to the cavity floor than those in the unbonded cases, and were less affected by curing regimens. The FEA results showed that the stress was modulated by the accumulated light energy density, while step-curing may alleviate the tensile stress along the cavity walls. In this study, DIC provides a complete description of the polymerization shrinkage behaviors of dental composites, which may facilitate the stress analysis in the numerical investigation.

Quaternary ammonium silane-functionalized, methacrylate resin composition with antimicrobial activities and self-repair potential

PubMed Central

Gong, Shi-qiang; Niu, Li-na; Kemp, Lisa K.; Yiu, Cynthia K.Y.; Ryou, Heonjune; Qi, Yi-pin; Blizzard, John D.; Nikonov, Sergey; Brackett, Martha G.; Messer, Regina L.W.; Wu, Christine D.; Mao, Jing; Brister, L. Bryan; Rueggeberg, Frederick A.; Arola, Dwayne D.; Pashley, David H.; Tay, Franklin R.

2012-01-01

Design of antimicrobial polymers for enhancing healthcare issues and minimizing environmental problems is an important endeavor with both fundamental and practical implications. Quaternary ammonium silane-functionalized methacrylate (QAMS) represents an example of antimicrobial macromonomers synthesized by a sol-gel chemical route; these compounds possess flexible Si-O-Si bonds. In present work, a partially-hydrolyzed QAMS copolymerized with bis-GMA is introduced. This methacrylate resin was shown to possess desirable mechanical properties with both a high degree of conversion and minimal polymerization shrinkage. Kill-on-contact microbiocidal activities of this resin were demonstrated using single-species biofilms of Streptococcus mutans (ATCC 36558), Actinomyces naeslundii (ATCC 12104) and Candida albicans (ATCC 90028). Improved mechanical properties after hydration provided the proof-of-concept that QAMS-incorporated resin exhibits self-repair potential via water-induced condensation of organic modified silicate (ormosil) phases within the polymerized resin matrix. PMID:22659173

A comparison of stresses in molar teeth restored with inlays and direct restorations, including polymerization shrinkage of composite resin and tooth loading during mastication.

PubMed

Dejak, Beata; Młotkowski, Andrzej

2015-03-01

Polymerization shrinkage of composites is one of the main causes of leakage around dental restorations. Despite the large numbers of studies there is no consensus, what kind of teeth reconstruction--direct or indirect composite restorations are the most beneficial and the most durable. The aim was to compare equivalent stresses and contact adhesive stresses in molar teeth with class II MOD cavities, which were restored with inlays and direct restorations (taking into account polymerization shrinkage of composite resin) during simulated mastication. The study was conducted using the finite elements method with the application of contact elements. Three 3D models of first molars were created: model A was an intact tooth; model B--a tooth with a composite inlay, and model C--a tooth with a direct composite restoration. Polymerization linear shrinkage 0.7% of a direct composite restoration and resin luting cement was simulated (load 1). A computer simulation of mastication was performed (load 2). In these 2 situations, equivalent stresses according to the modified von Mises criterion (mvM) in the materials of mandibular first molar models with different restorations were calculated and compared. Contact stresses in the luting cement-tooth tissue adhesive interface around the restorations were also assessed and analyzed. Equivalent stresses in a tooth with a direct composite restoration (the entire volume of which was affected by polymerization shrinkage) were many times higher than in the tooth restored with a composite inlay (where shrinkage was present only in a thin layer of the luting cement). In dentin and enamel the stress values were 8-14 times higher, and were 13 times higher in the direct restoration than in the inlay. Likewise, contact stresses in the adhesive bond around the direct restoration were 6.5-7.7 times higher compared to an extraorally cured restoration. In the masticatory simulation, shear contact stresses in the adhesive bond around the direct composite restoration reached the highest values 32.8 MPa and significantly exceeded the shear strength of the connection between the resin luting cement and the tooth structure. Equivalent stresses in the tooth structures restored with inlays and in the restoration material itself and contact stresses at the tooth-luting cement adhesive interface are many times lower compared to teeth with direct composite restorations. Teeth with indirect restorations are potentially less susceptible to damage compared to those with direct restorations. Composite inlays also ensure a better seal compared to direct restorations. Polymerization shrinkage determines stress levels in teeth with direct restorations, while its impact on adhesion in indirectly restored teeth is insignificant. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Determination of double bond conversion in dental resins by near infrared spectroscopy.

PubMed

Stansbury, J W; Dickens, S H

2001-01-01

This study determined the validity and practicality of near infrared (NIR) spectroscopic techniques for measurement of conversion in dental resins. Conversion measurements by NIR and mid-IR were compared using two techniques: (1) The conversion of 3mm thick photopolymerized Bis-GMA/TEGDMA resin specimens was determined by transmission NIR. Specimens were then ground and reanalyzed in KBr pellet form by mid-IR. (2) As further verification, thin resin films were photocured and analyzed by mid-IR. Multiple thin films were then compressed into a thick pellet for examination by NIR. Conversion values obtained by NIR and mid-IR techniques did not differ significantly. A correction for changing specimen thickness due to polymerization shrinkage was applied to NIR conversion measurements since an internal standard reference peak was not employed. Sensitivity of the NIR technique was superior to those based on the mid-IR. The nondestructive analysis of conversion in dental resins by NIR offers advantages of convenience, practical specimen dimensions and precision compared with standard mid-IR analytical procedures. Because glass is virtually transparent in the NIR spectrum, this technique has excellent potential for use with filled dental resins as well.

Effect of immediate or delayed light activation on curing kinetics and shrinkage stress of dual-cure resin cements.

PubMed

Faria-e-Silva, Andre; Boaro, Leticia; Braga, Roberto; Piva, Evandro; Arias, Vanessa; Martins, Luis

2011-01-01

This study evaluated the effect of light activation (absence, immediate, or delayed) on conversion kinetics and polymerization stress of three commercial dual-cured resin cements (Enforce, RelyX ARC, and Panavia F). Degree of conversion (DC) was monitored for 30 minutes using real-time near–Fourier transform infrared spectroscopy. The cement was mixed, placed on the spectrometer sample holder, and light activated either immediately or after five minutes (delayed light activation). When no light activation was performed, the materials were protected from light exposure (control). DC was evaluated at five and 30 minutes postmixture. Maximum rates of polymerization (Rp(max)) were obtained from the first derivative of the DC vs time curve. Polymerization stress was monitored for 30 minutes in 1-mm-thick specimens inserted between two cylinders attached to a universal testing machine. Data were submitted to analysis of variance/Tukey tests (α=0.05). Immediate light activation promoted the highest DC at five minutes. At 30 minutes, only RelyX ARC did not present a significant difference in DC between activation modes. Enforce and Panavia F presented higher Rp(max) for immediate and delayed light-activation, respectively. RelyX ARC showed similar Rp(max) for all activation modes. The absence of light activation resulted in the lowest stress followed by delayed light activation, while immediate light activation led to the highest values. RelyX ARC showed higher stress than Enforce, while the stress of Panavia F was similar to that of the others. Delayed light activation reduced the polymerization stress of the resin cements tested without jeopardizing DC.

Advanced clay nanocomposites based on in situ photopolymerization utilizing novel polymerizable organoclays

NASA Astrophysics Data System (ADS)

Kim, Soon Ki

Polymer nanocomposite technology has had significant impact on material design. With the environmental advantages of photopolymerization, a research has recently focused on producing nanocomposites utilizing inexpensive clay particles based on in situ photopolymerization. In this research, novel polymerizable organoclays and thiol-ene photopolymerization have been utilized to develop advanced photopolymer clay nanocomposites and to overcome several limitations in conventional free radical photopolymers. To this end, factors important in nanocomposite processes such as monomer composition, clay dispersion, and photopolymerization behavior in combination with the evolution of ultimate nanocomposite properties have been investigated. For monomer-organoclay compositions, higher chemical compatibility of components induces enhanced clay exfoliation, resulting in photopolymerization rate increases due to an amplified clay template effect. Additionally, by affecting the stoichiometric ratio between thiol and acrylate double bond in the clay gallery, thiolated organoclays enhance thiol-ene copolymerization with increased final thiol conversion while acrylated organoclays encourage acrylate homopolymerization. In accordance with the reaction behavior, incorporation of thiolated organoclays makes polymer chains more flexible with decreased glass transition temperature due to higher formation of thio-ether linkages while adding acrylated organoclays significantly increases the modulus. Photopolymer nanocomposites also help overcome two major drawbacks in conventional free radical photopolymerization, namely severe polymerization shrinkage and oxygen inhibition during polymerization. With addition of a low level of thiol monomers, the oxygen inhibition in various acrylate systems can be overcome by addition of only 5wt% thiolated organoclay. The same amount of polymerizable organoclay also induces up to 90% decreases in the shrinkage stress for acrylate or thiol-acrylate systems. However, nonreactive clays do not reduce the stress substantially and even decreases the polymerization rate in air. Additionally, the clay morphology and polymerization behavior are closely related with evolution of ultimate nanocomposite performance. Use of polymerizable organoclay significantly improves overall toughness of nanocomposites by increasing either modulus or elongation at break based on the type of polymerizable organoclay, which demonstrates the promise of this technology as a modulation and/or optimization tool for nanocomposite properties.

A technique for improved maxillary record base adaptation through controlled polymerization of light-activated dental resins.

PubMed

Hopkins, D S; Phoenix, R D; Abrahamsen, T C

1997-09-01

A technique for the fabrication of light-activated maxillary record bases is described. The use of a segmental polymerization process provides improved palatal adaptation by minimizing the effects of polymerization shrinkage. Utilization of this technique results in record bases that are well adapted to the corresponding master casts.

The effect of filler content and processing variables on dimensional accuracy of experimental composite inlay material.

PubMed

Razak, A A; Harrison, A

1997-04-01

Dimensional accuracy of a composite inlay restoration is important to ensure an accurate fit and to minimize cementation stresses. A method was developed to measure dimensional accuracy and stability of a composite inlay. A standard Class II (MOD) inlay cavity stainless steel mold was made with six circular indentations placed on the occlusal floor of the cavity and four indentations on each gingival floor to act as datum points in the measurement of linear polymerization shrinkage. The inlay restorations were prepared from an inlay-onlay composite material of different filler contents (50%, 65%, and 79% by weight). For each filler content group, three curing methods were used: light curing only, light curing and heat curing at 100 degrees C for 5 minutes, and light curing and heat curing at 100 degrees C for 5 minutes and then storage in distilled water for 7 days. The accuracy of the MOD inlays was determined by measuring the shrinkage of the restoration on the occlusal floor areas and the gingival seats. The results demonstrated an inverse linear relationship between filler content and polymerization shrinkage. There was a tendency for the light-curing and heat-curing method to show an increase in polymerization shrinkage. An expansion was recorded between the mesial and distal boxes when the specimens were soaked in water for 7 days. This study suggested that the inlay mold limits the physical shrinkage that can occur between the mesial and distal axial walls of the inlay restoration because the inlay cannot shrink to a smaller dimension than the mold. Water sorption then causes hygroscopic expansion, which enlarges the distance between the mesial and distal walls.

Polymerization shrinkage of a dental resin composite determined by a fiber optic Fizeau interferometer

NASA Astrophysics Data System (ADS)

Arenas, Gustavo; Noriega, Sergio; Vallo, Claudia; Duchowicz, Ricardo

2007-03-01

A fiber optic sensing method based on a Fizeau-type interferometric scheme was employed for monitoring linear polymerization shrinkage in dental restoratives. This technique offers several advantages over the conventional methods of measuring polymerization contraction. This simple, compact, non-invasive and self-calibrating system competes with both conventional and other high-resolution bulk interferometric techniques. In this work, an analysis of the quality of interference signal and fringes visibility was performed in order to characterize their resolution and application range. The measurements of percent linear contraction as a function of the sample thickness were carried out in this study on two dental composites: Filtek P60 (3M ESPE) Posterior Restorer and Filtek Z250 (3M ESPE) Universal Restorer. The results were discussed with respect to others obtained employing alternative techniques.

Thermo/pH dual-stimuli-responsive drug delivery for chemo-/photothermal therapy monitored by cell imaging.

PubMed

Shu, Yang; Song, Rusheng; Zheng, Anqi; Huang, Jingli; Chen, Mingli; Wang, Jianhua

2018-05-01

A thermo/pH dual-stimuli-responsive drug delivery system (DDS) based on polymer coated mesoporous silica nanostructures (MSNs) is developed for facilitating chemotherapy and photothermal therapy. Thermo/pH-responsive polymer, poly((N-isopropylacrylamide, NIPAM)-co-methacrylic acid, MA), is grafted onto MSNs by in situ polymerization, followed by loading a chemotherapeutic drug (doxorubicin hydrochloride, DOX) and a near-infrared-absorbing phototherapeutic agent (indocyanine green, ICG) to construct the intelligent drug delivery system, shortly as DOX-ICG-MSN@p(NIPAM-co-MA). At NIR irradiation, the photothermal conversion capability of ICG raises the temperature of the DDS and opens the gatekeeper by shrinkage of the copolymer p(NIPAM-co-MA), which triggers controlled release of DOX at an elevated temperature. On the other hand, drug release is also realized at pH 5.3, a characteristic pH value in cancer cell microenvironment, at which it not only causes the shrinkage of the pH-sensitive polymeric moiety of methacrylic acid in MSN@p(NIPAM-co-MA) but also deteriorates electrostatic interaction of DOX molecules in the mesoporous channel by protonation of silanols. In addition, ICG further ensures photothermal therapy (PTT) and photodynamic therapy (PDT). The cytotoxicity assay of HeLa cells shows obvious synergistic effect by demonstrating that the combined use of DOX and ICG is more effective in killing HeLa cells than free DOX and ICG. The endocytosis of the drug is monitored by cell imaging. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of 457 nm diode-pumped solid state laser on the polymerization composite resins: microhardness, cross-link density, and polymerization shrinkage.

PubMed

Son, Sung-Ae; Park, Jeong-Kil; Jung, Kyoung-Hwa; Ko, Ching-Chang; Jeong, Chang-Mo; Kwon, Yong Hoon

2015-01-01

The purpose of the present study was to test the usefulness of 457 nm diode-pumped solid state (DPSS) laser as a light source to cure composite resins. Five different composite resins were light cured using three different light-curing units (LCUs): a DPSS 457 nm laser (LAS), a light-emitting diode (LED), and quartz-tungsten-halogen (QTH) units. The light intensity of LAS was 560 mW/cm(2), whereas LED and QTH LCUs was ∼900 mW/cm(2). The degree of polymerization was tested by evaluating microhardness, cross-link density, and polymerization shrinkage. Before water immersion, the microhardness of laser-treated specimens ranged from 40.8 to 84.7 HV and from 31.7 to 79.0 HV on the top and bottom surfaces, respectively, and these values were 3.3-23.2% and 2.9-31.1% lower than the highest microhardness obtained using LED or QTH LCUs. Also, laser-treated specimens had lower top and bottom microhardnesses than the other LCUs treated specimens by 2.4-19.4% and 1.4-27.8%, respectively. After ethanol immersion for 24 h, the microhardness of laser-treated specimens ranged from 20.3 to 63.2 HV on top and bottom surfaces, but from 24.9 to 71.5 HV when specimens were cured using the other LCUs. Polymerization shrinkage was 9.8-14.7 μm for laser-treated specimens, and these were significantly similar or lower (10.2-16.0 μm) than those obtained using the other LCUs. The results may suggest that the 457 nm DPSS laser can be used as a light source for light-curing dental resin composites.

Poly(propylene glycol) and urethane dimethacrylates improve conversion of dental composites and reveal complexity of cytocompatibility testing.

PubMed

Walters, Nick J; Xia, Wendy; Salih, Vehid; Ashley, Paul F; Young, Anne M

2016-02-01

To determine the effects of various monomers on conversion and cytocompatibility of dental composites and to improve these properties without detrimentally affecting mechanical properties, depth of cure and shrinkage. Composites containing urethane dimethacrylate (UDMA) or bisphenol A glycidyl methacrylate (Bis-GMA) with poly(propylene glycol) dimethacrylate (PPGDMA) or triethylene glycol dimethacrylate (TEGDMA) were characterized using the following techniques: conversion (FTIR at 1 and 4mm depths), depth of cure (BS EN ISO 4049:2009 and FTIR), shrinkage (BS EN ISO 17304:2013 and FTIR), strength and modulus (biaxial flexural test) and water sorption. Cytocompatibility of composites and their liquid phase components was assessed using three assays (resazurin, WST-8 and MTS). UDMA significantly improved conversion, BFS and depth of cure compared to Bis-GMA, without increasing shrinkage. UDMA was cytotoxic at lower concentrations than Bis-GMA, but extracts of Bis-GMA-containing composites were less cytocompatible than of those containing UDMA. PPGDMA improved conversion and depth of cure compared to TEGDMA, without detrimentally affecting shrinkage. TEGDMA was shown by all assays to be highly toxic. Resazurin, but not WST-8 and MTS, suggested that PPGDMA exhibited improved cytocompatibility compared to TEGDMA. The use of UDMA and PPGDMA results in composites with excellent conversion, depth of cure and mechanical properties, without increasing shrinkage. Composites containing UDMA appear to be slightly more cytocompatible than those containing Bis-GMA. These monomers may therefore improve the material properties of dental restorations, particularly bulk fill materials. The effect of diluent monomer on cytocompatibility requires further investigation. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Shrinkage Stresses Generated during Resin-Composite Applications: A Review

PubMed Central

Schneider, Luis Felipe J.; Cavalcante, Larissa Maria; Silikas, Nick

2010-01-01

Many developments have been made in the field of resin composites for dental applications. However, the manifestation of shrinkage due to the polymerization process continues to be a major problem. The material's shrinkage, associated with dynamic development of elastic modulus, creates stresses within the material and its interface with the tooth structure. As a consequence, marginal failure and subsequent secondary caries, marginal staining, restoration displacement, tooth fracture, and/or post-operative sensitivity are clinical drawbacks of resin-composite applications. The aim of the current paper is to present an overview about the shrinkage stresses created during resin-composite applications, consequences, and advances. The paper is based on results of many researches that are available in the literature. PMID:20948573

Shrinkage of Dental Composite in Simulated Cavity Measured with Digital Image Correlation

PubMed Central

Li, Jianying; Thakur, Preetanjali; Fok, Alex S. L.

2014-01-01

Polymerization shrinkage of dental resin composites can lead to restoration debonding or cracked tooth tissues in composite-restored teeth. In order to understand where and how shrinkage strain and stress develop in such restored teeth, Digital Image Correlation (DIC) was used to provide a comprehensive view of the displacement and strain distributions within model restorations that had undergone polymerization shrinkage. Specimens with model cavities were made of cylindrical glass rods with both diameter and length being 10 mm. The dimensions of the mesial-occlusal-distal (MOD) cavity prepared in each specimen measured 3 mm and 2 mm in width and depth, respectively. After filling the cavity with resin composite, the surface under observation was sprayed with first a thin layer of white paint and then fine black charcoal powder to create high-contrast speckles. Pictures of that surface were then taken before curing and 5 min after. Finally, the two pictures were correlated using DIC software to calculate the displacement and strain distributions. The resin composite shrunk vertically towards the bottom of the cavity, with the top center portion of the restoration having the largest downward displacement. At the same time, it shrunk horizontally towards its vertical midline. Shrinkage of the composite stretched the material in the vicinity of the “tooth-restoration” interface, resulting in cuspal deflections and high tensile strains around the restoration. Material close to the cavity walls or floor had direct strains mostly in the directions perpendicular to the interfaces. Summation of the two direct strain components showed a relatively uniform distribution around the restoration and its magnitude equaled approximately to the volumetric shrinkage strain of the material. PMID:25079865

Analysis of micro-failure behaviors in artificial muscles based on fishing line and sewing thread

NASA Astrophysics Data System (ADS)

Xu, J. B.; Cheng, K. F.; Tu, S. L.; He, X. M.; Ma, C.; Jin, Y. Z.; Kang, X. N.; Sun, T.; Zhang, Y.

2017-06-01

The aim of the present study was to discuss a new and effective method for testing artificial muscles based on micro-failure behaviors analysis. Thermo-mechanical actuators based on fishing line and sewing thread, also, the capability of responding to ambient temperature variations producing a large amount of shrinkage ratio of a resulting variation in longitudinal length. The minimum micro-failure value is 0.02μm and the maximum value is 1.72μm with nylon twist pattern. The discovery of an innovative effective testing of artificial muscles based on polymeric fibers specimens on micro-failure, rupture, slippage, etc. This research finds out a micro-failure behavior analysis of thermo-mechanical actuators based on fishing line and sewing thread. The specimens show large deformations when heated together with warping performance in terms of shrinkage of energy and densities. With the purpose of providing useful analysis data for the further technology applications, we attempt micrometre-sized artificial muscles which were also tested was readily accessible and also can be applied to other polymeric fibers. Effective use of this technique achievement relies on rotate speed, temperature and tensile direction. The results of the tensile testing experiments were outstanding with respect to some important issues related to the response of micro-structure, twisted polymeric fibers and shrinkage ratio.

Evolution of material properties during free radical photopolymerization

NASA Astrophysics Data System (ADS)

Wu, Jiangtao; Zhao, Zeang; Hamel, Craig M.; Mu, Xiaoming; Kuang, Xiao; Guo, Zaoyang; Qi, H. Jerry

2018-03-01

Photopolymerization is a widely used polymerization method in many engineering applications such as coating, dental restoration, and 3D printing. It is a complex chemical and physical process, through which a liquid monomer solution is rapidly converted to a solid polymer. In the most common free-radical photopolymerization process, the photoinitiator in the solution is exposed to light and decomposes into active radicals, which attach to monomers to start the polymerization reaction. The activated monomers then attack Cdbnd C double bonds of unsaturated monomers, which leads to the growth of polymer chains. With increases in the polymer chain length and the average molecular weight, polymer chains start to connect and form a network structure, and the liquid polymer solution becomes a dense solid. During this process, the material properties of the cured polymer change dramatically. In this paper, experiments and theoretical modeling are used to investigate the free-radical photopolymerization reaction kinetics, material property evolution and mechanics during the photopolymerization process. The model employs the first order chemical reaction rate equations to calculate the variation of the species concentrations. The degree of monomer conversion is used as an internal variable that dictates the mechanical properties of the cured polymer at different curing states, including volume shrinkage, glass transition temperature, and nonlinear viscoelastic properties. To capture the nonlinear behavior of the cured polymer under low temperature and finite deformation, a multibranch nonlinear viscoelastic model is developed. A phase evolution model is used to describe the mechanics of the coupling between the crosslink network evolution and mechanical loading during the curing process. The comparison of the model and the experimental results indicates that the model can capture property changes during curing. The model is further applied to investigate the internal stress of a thick sample caused by volume shrinkage during photopolymerization. Changes in the conversion degree gradient and the internal stress during photopolymerization are determined using FEM simulation. The model can be extended to many photocuring processes, such as photopolymerization 3D printing, surface coating and automotive part curing processes.

Development of novel dental nanocomposites reinforced with polyhedral oligomeric silsesquioxane (POSS).

PubMed

Wu, Xiaorong; Sun, Yi; Xie, Weili; Liu, Yanju; Song, Xueyu

2010-05-01

It has been the focus to develop low shrinkage dental composite resins in recent ten years. A major difficulty in developing low shrinkage dental materials is that their deficiency in mechanical properties cannot satisfy the clinical purpose. The aim of this study is to develop novel dental nanocomposites incorporated with polyhedral oligomeric silsesquioxane (POSS). It is especially interesting to evaluate the volumetric shrinkage and mechanical properties, improve the shrinkage, working performances and service life of dental composite resins. The effect of added POSS on the composites' mechanical properties has been evaluated. The weight percentages of added POSS are 0, 2, 5, 10 and 15wt% respectively. Fourier-transform infra-red spectroscopy and X-ray diffraction were used to characterize their microstructures. Physico-mechanical properties that were investigated included volumetric shrinkage, flexural strength, flexural modulus, compressive strength, compressive modulus, Viker's hardness and fracture energy. Furthermore, the possible reinforced mechanism has been discussed. The shrinkage of novel nanocomposites decreased from 3.53% to 2.18%. The nanocomposites incorporated with POSS showed greatly improved mechanical properties, for example, with only 2wt% POSS added, the nanocompsite's flexural strength increased 15%, compressive strength increased 12%, hardness increased 15% and uncommonly, even the toughness of resins was obviously increased. With 5wt% POSS polymerized, compressive strength increased from 192MPa to 251MPa and compressive modulus increased from 3.93GPa to 6.62GPa, but flexure strength began to decline from 87MPa to 75MPa. This finding indicated that the reinforcing mechanism of flexure state maybe different from that of compressive state. The mechanical properties and volumetric shrinkage of dental composite resins polymerized with POSS can be improved significantly. In current study, the nanocomposite with 2wt% POSS incorporated is observed to achieve the best improved effects. 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Evaluation of polymerization shrinkage of resin cements through in vitro and in situ experiments

NASA Astrophysics Data System (ADS)

Franco, A. P. G. O.; Karam, L. Z.; Pulido, C. A.; Gomes, O. M. M.; Kalinowski, H. J.

2014-08-01

The aim of this study was to evaluate the behavior of two types of resin cements , conventional dual and dual self adhesive, through in vitro and in situ experiments. For the in vitro assay were selected two resin cements that were handled and dispensed over a mylar strip supported by a glass plate. The Bragg grating sensors were positioned and another portion of cement. was placed, covered by another mylar strip. For the in situ experiment 16 single-rooted teeth were selected who were divided into 2 groups: group 1 - conventional dual resin cement Relyx ARC and group 2 - dual self adhesive resin cement Relyx U200 ( 3M/ESPE ). The teeth were treated and prepared to receive the intracanal posts. Two Bragg grating sensors were recorded and introduced into the root canal at different apical and coronal positions. The results showed that the in vitro experiment presented similar values of polymerization shrinkage that the in situ experiment made in cervical position; whereas Relyx ARC resulted lower values compared to Relyx U200; and cervical position showed higher shrinkage than the apical.

Influence of curing mode with a LED unit on polymerization contraction kinetics and degree of conversion of dental resin-based materials.

PubMed

Mortier, Eric; Simon, Yorick; Dahoun, Abdelsellam; Gerdolle, David

2009-01-01

The purpose of this study was to evaluate the influence of photopolymerization mode with a light emitting diode (LED) lamp on the curing contraction kinetics and degree of conversion of 3 resin-based restorative materials. The curing contraction kinetics of Admira (ADM), Filtek P60 (P60), and Filtek Flow (FLO) were measured by the glass slide method. The materials were exposed to light from a 1,000 mW/cm-(2) power LED lamp (Elipar Freelight 2) in 3 modes: 2 continuous modes of 20 and 40 seconds (C20 and C40), and 1 exponential mode (E20; 5 seconds of exponential power increase followed by 15 seconds of maximum intensity). The degree of conversion (DC) was measured for each of the materials, and each of the modes by Fourier transformed infra-red spectrometry. P60 had the significantly lowest final contraction and FLO the highest among all light exposure modes. The C20 and C40 modes did not produce any difference in contraction or degree of conversion. The E20 mode led to a significant slowing of contraction speed combined with greater final contraction. Use of a LED lamp (1,000 mW/cm2) in continuous mode reduces the exposure time by half for identical curing shrinkage and degree of conversion.

Photo-crosslinkable cyanoacrylate bioadhesive: shrinkage kinetics, dynamic mechanical properties, and biocompatibility of adhesives containing TMPTMA and POSS nanostructures as crosslinking agents.

PubMed

Ghasaban, S; Atai, M; Imani, M; Zandi, M; Shokrgozar, M-A

2011-11-01

The study investigates the photo-polymerization shrinkage behavior, dynamic mechanical properties, and biocompatibility of cyanoacrylate bioadhesives containing POSS nanostructures and TMPTMA as crosslinking agents. Adhesives containing 2-octyl cyanoacrylate (2-OCA) and different percentages of POSS nanostructures and TMPTMA as crosslinking agents were prepared. The 1-phenyl-1, 2-propanedione (PPD) was incorporated as photo-initiator into the adhesive in 1.5, 3, and 4 wt %. The shrinkage strain of the specimens was measured using bonded-disk technique. Shrinkage strain, shrinkage strain rate, maximum and time at maximum shrinkage strain rate were measured and compared. Mechanical properties of the adhesives were also studied using dynamic mechanical thermal analysis (DMTA). Biocompatibility of the adhesives was examined by MTT method. The results showed that shrinkage strain increased with increasing the initiator concentration up to 3 wt % in POSS-containing and 1.5 wt % in TMPTMA-containing specimens and plateaued out at higher concentrations. By increasing the crosslinking agent, shrinkage strain, and shrinkage strain rate increased and the time at maximum shrinkage strain rate decreased. The study indicates that the incorporation of crosslinking agents into the cyanoacrylate adhesives resulted in improved mechanical properties. Preliminary MTT studies also revealed better biocompatibility profile for the adhesives containing crosslinking agents comparing to the neat specimens. Copyright © 2011 Wiley Periodicals, Inc.

Biological and nano-indentation properties of polybenzoxazine-based composites reinforced with zirconia particles as a novel biomaterial.

PubMed

Lotfi, L; Javadpour, J; Naimi-Jamal, M R

2018-01-01

The biological and mechanical properties of substances are relevant to their application as biomaterials and there are many efforts to enhance biocompatibility and mechanical properties of bio-medical materials. In this study, to achieve a low rate of shrinkage during polymerization, good mechanical properties, and excellent biocompatibility, benzoxazine based composites were synthesized. Benzoxazine monomer was synthesized using a solventless method. FTIR and DSC analysis were carried out to determine the appropriate polymerization temperature. The low viscosity of the benzoxazine monomer at 70°C attract us to use in situ polymerization after high speed ball milling of the benzoxazine and it mixture with different weight fractions of zirconia particles. Dispersion and adhesion between the ceramic and polymer components were evaluate by SEM. To evaluate the biological properties and toxicity of the polybenzoxazine-based composite samples reinforced with zirconia particles, 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide assay was conducted. The micromechanical properties of each composite were evaluated by more than 20 nanoindentation tests and 3 nanoscratching tests. Surface topography of scratched regions was investigated using Atomic Force Microscopy. Shrinkage was simulated by Materials Studio software. SEM images showed good dispersion and adhesion between the ceramic and polymer components. Biocompatibility assay showed excellent in vitro biocompatibility. Nano-indentation force-displacement curves showed matrix, reinforcement and interphase regions in specimens and excellent homogeneity in mechanical properties. The nanoindentation results showed that the addition of zirconia particles to the polybenzoxazine matrix increased the modulus and hardness of the neat polybenzoxazine; however, by adding more than an optimum level of reinforcement particles, the mechanical properties decreased due to the agglomeration of reinforcement particles and weak interphase that cause inappropriate load transferring between matrix and reinforcement particles. Results of nano-scratching tests showed effects of zirconia particles as reinforcement on the coeffiecient of friction of the synthesized composites. Shrinkage simulation showed a low rate of shrinkage for polybenzoxazine in comparison with other low shrinkage polymers, such as Bis-GMA. Polybenzoxazine based composites that reinforced with an optimum amount of zirconia particles (60% wt micro and 10% wt nano-particles) could be used as a novel biomaterial duo to its excellent biocompatibility, good mechanical properties, appropriate viscosity and low rate of polymeization shrinkage.

Interaction of LED light with coinitiator-containing composite resins: effect of dual peaks.

PubMed

Sim, Jae-Seong; Seol, Hyo-Joung; Park, Jeong-Kil; Garcia-Godoy, Franklin; Kim, Hyung-Il; Kwon, Yong Hoon

2012-10-01

Recently the colour stability of composite resins has been an issue due to the emphasis on the aesthetics of restored teeth. The purpose of the present study was to investigate how dual-peak LED units affect the polymerization of coinitiator-containing composite resins. Five composite resins [coinitiator-containing: Aelite LS Posterior (AL), Tetric EvoCeram (TE), and Vit-l-escence (VI); only CQ-containing: Grandio (GD) and Filtek Z350 (Z3)] were light cured using four different light-curing units (LCUs). Among them, Bluephase G2 (BP) and G-light (GL) were dual-peak LED LCUs. Microhardness, polymerization shrinkage, flexural, and compressive properties were measured. BP and GL had no consistent effect on the microhardness of AL, TE, and VI on the top and bottom surfaces of resin specimens. Among the specimens, AL and VI showed the least (9.86-10.41 μm) and greatest (17.58-19.21 μm) polymerization shrinkage, respectively. However, the effect of BP and GL on the shrinkage of specimens was not consistent. Among the specimens, GD showed the greatest flexural properties [strength (FS) and modulus (FM)] and TE showed the lowest flexural and compressive properties [strength (CS) and modulus (CM)]. In same resin product, maximum FS and CS differences due to the different LCUs were 10.3-21.0% and 3.6-9.2%, respectively. Furthermore, the influences of BP and GL on FS and CS were not consistent. The tested dual-peak LED LCUs had no consistent synergic effect on the polymerization of coinitiator-containing composite resins as compared with QTH and single-peak LED LCUs. The dual-peak LED LCUs achieve a similar degree of polymerization in coinitiator-composite resins as QTH and single-peak LED LCUs did. Choice of LCU does not appear to be a determinant of the light curing of coinitiator-composite resins. Copyright © 2012 Elsevier Ltd. All rights reserved.

Determination of residual stresses in objects at their additive manufacturing by layer-by-layer photopolymerization method

NASA Astrophysics Data System (ADS)

Bychkov, P. S.; Chentsov, A. V.; Kozintsev, V. M.; Popov, A. L.

2018-04-01

A calculation-experimental technique is developed for identification of the shrinkage stresses generated in objects after their additive manufacturing by layer-by-layer photopolymerization. The technique is based on the analysis of shrinkage deformations at bending occurring in a series of samples in the form of plates-stripes with identical sizes, but with different time of polymerization which is predetermined during their production on the 3D printer.

Acoustic emission analysis of tooth-composite interfacial debonding.

PubMed

Cho, N Y; Ferracane, J L; Lee, I B

2013-01-01

This study detected tooth-composite interfacial debonding during composite restoration by means of acoustic emission (AE) analysis and investigated the effects of composite properties and adhesives on AE characteristics. The polymerization shrinkage, peak shrinkage rate, flexural modulus, and shrinkage stress of a methacrylate-based universal hybrid, a flowable, and a silorane-based composite were measured. Class I cavities on 49 extracted premolars were restored with 1 of the 3 composites and 1 of the following adhesives: 2 etch-and-rinse adhesives, 2 self-etch adhesives, and an adhesive for the silorane-based composite. AE analysis was done for 2,000 sec during light-curing. The silorane-based composite exhibited the lowest shrinkage (rate), the longest time to peak shrinkage rate, the lowest shrinkage stress, and the fewest AE events. AE events were detected immediately after the beginning of light-curing in most composite-adhesive combinations, but not until 40 sec after light-curing began for the silorane-based composite. AE events were concentrated at the initial stage of curing in self-etch adhesives compared with etch-and-rinse adhesives. Reducing the shrinkage (rate) of composites resulted in reduced shrinkage stress and less debonding, as evidenced by fewer AE events. AE is an effective technique for monitoring, in real time, the debonding kinetics at the tooth-composite interface.

Microhardness of resin composites polymerized by plasma arc or conventional visible light curing.

PubMed

Park, S Ho; Krejci, I; Lutz, F

2002-01-01

This study evaluated the effectiveness of the plasma arc curing (PAC) unit for composite curing. To compare its effectiveness with conventional quartz tungsten halogen (QTH) light curing units, the microhardness of two composites (Z100 and Tetric Ceram) that had been light cured by the PAC or QTH units, were compared according to the depth from the composite surface. In addition, linear polymerization shrinkage was compared using a custom-made linometer between composites which were light cured by PAC or QTH units. Measuring polymerization shrinkage for two resin composites (Z100 and Tetric Ceram) was performed after polymerization with either QTH or PAC units. In the case of curing with the PAC unit, the composite was light cured with Apollo 95E for two (Group 1), three (Group 2), six (Group 3) or 2 x 6 (Group 4) seconds. For light curing with the QTH unit, the composite was light cured for 60 seconds with Optilux 500 (Group 5). The linear polymerization shrinkage of composites was determined in the linometer. Two resin composites were used to measure microhardness. Two-mm thick samples were light cured for three seconds (Group 1), six seconds (Group 2) or 12 (2 x 6) seconds (Group 3) with Apollo 95E or they were conventionally light cured with Optilux 500 for 30 seconds (Group 4) or 60 seconds (Group 5). For 3 mm thick samples, the composites were light cured for six seconds (Group 1), 12 (2 x 6) seconds (Group 2) or 18 (3 x 6) seconds (Group 3) with Apollo 95E or they were conventionally light cured with Optilux 500 for 30 seconds (Group 4) or 60 seconds (Group 5). Twenty samples were assigned to each group. The microhardness of the upper and lower surfaces was measured with a Vickers hardness-measuring instrument under load. The difference in microhardness between the upper and lower surfaces in each group was analyzed by paired t-test. For the upper or lower surfaces, one-way ANOVA with Tukey was used. For Tetric Ceram, the amount of polymerization shrinkage was lower when cured with the Apollo 95E for two or three seconds than when cured for six and 12 (2 x 6) seconds, or for 60 seconds with Optilux 500 (p<0.05). For Z100, the amount of linear polymerization shrinkage was lower when cured with the Apollo 95E for two, three and six seconds than for 12 (2 x 6) seconds with Apollo 95E or for 60 seconds with the Optilux 500 (p<0.05). The results of the microhardness test indicated that there was no statistically significant difference in microhardness between groups for the upper surface. However, for the lower surface, when the composites were light cured with Apollo 95E for three seconds as recommended by the manufacturer, microhardness of the lower surface was usually lower than that of the upper surface and did not cure sufficiently. Conclusively, when compared with conventional QTH unit, the PAC unit, Apollo 95E did not properly cure the lower composite surface when the layer thickness exceeded 2 mm. In addition, three seconds of curing time, which the manufacturer recommended, was insufficient for optimal curing of composites.

Influence of thermal expansion on shrinkage during photopolymerization of dental resins based on bis-GMA/TEGDMA.

PubMed

Mucci, Veronica; Arenas, Gustavo; Duchowicz, Ricardo; Cook, Wayne D; Vallo, Claudia

2009-01-01

The aim of this study was to assess volume changes that occur during photopolymerization of unfilled dental resins based on bis-GMA-TEGDMA. The resins were activated for visible light polymerization by the addition of camphorquinone (CQ) in combination with dimethylamino ethylmethacrylate (DMAEMA) or ethyl-4-dimethyl aminobenzoate (EDMAB). A fibre-optic sensing method based on a Fizeau-type interferometric scheme was employed for monitoring contraction during photopolymerization. Measurements were carried out on 10mm diameter specimens of different thicknesses (1 and 2mm). The high exothermic nature of the polymerization resulted in volume expansion during the heating, and this effect was more pronounced when the sample thickness increased. Two approaches to assess volume changes due to thermal effects are presented. Due to the difference in thermal expansion coefficients between the rubbery and glassy resins, the increase of volume due to thermal expansion was greater than the decrease in volume due to thermal contraction. As a result, the volume of the vitrified resins was greater than that calculated from polymerization contraction. The observed trends of shrinkage versus sample thickness are explained in terms of light attenuation across the path length during photopolymerization. Results obtained in this research highlight the inherent interlinking of non-isothermal photopolymerization and volumetric changes in bulk polymerizing systems.

COMPARATIVE ANALYSIS OF THE SHRINKAGE STRESS OF COMPOSITE RESINS

PubMed Central

Pereira, Rosana Aparecida; de Araujo, Paulo Amarante; Castañeda-Espinosa, Juan Carlos; Mondelli, Rafael Francisco Lia

2008-01-01

The aim of this study was to compare the shrinkage stress of composite resins by three methods. In the first method, composites were inserted between two stainless steel plates. One of the plates was connected to a 20 kgf load cell of a universal testing machine (EMIC-DL-500). In the second method, disk-shaped cavities were prepared in 2-mm-thick Teflon molds and filled with the different composites. Gaps between the composites and molds formed after polymerization were evaluated microscopically. In the third method, the wall-to-wall shrinkage stress of the resins that were placed in bovine dentin cavities was evaluated. The gaps were measured microscopically. Data were analyzed by one-way ANOVA and Tukey's test (α=0.05). The obtained contraction forces were: Grandio = 12.18 ± 0.428N; Filtek Z 250 = 11.80 ± 0.760N; Filtek Supreme = 11.80 ± 0.707 N; and Admira = 11.89 ± 0.647 N. The gaps obtained between composites and Teflon molds were: Filtek Z 250 = 0.51 ± 0.0357%; Filtek Supreme = 0.36 ± 0.0438%; Admira = 0.25 ± 0.0346% and Grandio = 0.16 ± 0.008%. The gaps obtained in wall-to-wall contraction were: Filtek Z 250 = 11.33 ± 2.160 μm; Filtek Supreme = 10.66 ± 1.211μm; Admira = 11.16 ± 2.041 μm and Grandio = 10.50 ± 1.224 μm. There were no significant differences among the composite resins obtained with the first (shrinkage stress generated during polymerization) and third method (wall-to-wall shrinkage). The composite resins obtained with the second method (Teflon method) differed significantly regarding gap formation. PMID:19089286

Filler/ Polycarbosilane Systems as CMC Matrix Precursors

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.

1998-01-01

Pyrolytic conversion of polymeric precursors to ceramics is accompanied by loss of volatiles and large volume changes. Infiltration of a low viscosity polymer into a fiber preform will fill small spaces within fiber tows by capillary forces, but create large matrix cracks within large, intertow areas. One approach to minimizing shrinkage and reducing the number of required infiltration cycles is to use particulate fillers. In this study, Starfire allylhydridopolycarbosilane (AHPCS) was blended with a silicon carbide powder, with and without dispersant, using shear mixing. The polymer and polymer/particle interactions were characterized using nuclear magnetic resonance, differential scanning calorimetry, thermogravimetric analysis and rheometry. Polymer/particulate slurries and suspensions were used to infiltrate a figidized preform of an eight ply five harness satin CG Nicalon fiber having a dual layer BN/SiC interface coating, and the resulting composites characterized by optical and scanning electron microscopy.

Effects of a low-shrinkage methacrylate monomer and monoacylphosphine oxide photoinitiator on curing efficiency and mechanical properties of experimental resin-based composites.

PubMed

Manojlovic, Dragica; Dramićanin, Miroslav D; Milosevic, Milos; Zeković, Ivana; Cvijović-Alagić, Ivana; Mitrovic, Nenad; Miletic, Vesna

2016-01-01

This study investigated the degree of conversion, depth of cure, Vickers hardness, flexural strength, flexural modulus and volumetric shrinkage of experimental composite containing a low shrinkage monomer FIT-852 (FIT; Esstech Inc.) and photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO; Sigma Aldrich) compared to conventional composite containing Bisphenol A-glycidyl methacrylate (BisGMA) and camphorquinone-amine photoinitiator system. The degree of conversion was generally higher in FIT-based composites (45-64% range) than in BisGMA-based composites (34-58% range). Vickers hardness, flexural strength and modulus were higher in BisGMA-based composites. A polywave light-curing unit was generally more efficient in terms of conversion and hardness of experimental composites than a monowave unit. FIT-based composite containing TPO showed the depth of cure below 2mm irrespective of the curing light. The depth of cure of FIT-based composite containing CQ and BisGMA-based composites with either photoinitiator was in the range of 2.8-3.0mm. Volumetric shrinkage of FIT-based composite (0.9-5.7% range) was lower than that of BisGMA-based composite (2.2-12% range). FIT may be used as a shrinkage reducing monomer compatible with the conventional CQ-amine system as well as the alternative TPO photoinitiator. However, the depth of cure of FIT_TPO composite requires boosting to achieve clinically recommended thickness of 2mm. Copyright © 2015 Elsevier B.V. All rights reserved.

Improved performance of Bis-GMA/TEGDMA dental composites by net-like structures formed from SiO2 nanofiber fillers.

PubMed

Wang, Xiaoyan; Cai, Qing; Zhang, Xuehui; Wei, Yan; Xu, Mingming; Yang, Xiaoping; Ma, Qi; Cheng, Yali; Deng, Xuliang

2016-02-01

The major objective of this study was to explore the effects of silicon dioxide (SiO2) nanofibers on the performance of 2, 2-bis-[4-(methacryloxypropoxy)-phenyl]-propane (Bis-GMA)/tri-(ethyleneglycol) dimethacrylate (TEGDMA) dental composites. At first, the mechanical properties of Bis-GMA/TEGDMA (50/50, w/w) resins containing different contents of SiO2 nanofibers were evaluated to identify the appropriate composition to achieve the significant reinforcing effect. Secondly, optimized contents (5 or 10wt.%) of SiO2 nanofibers were mixed into resins together with SiO2 microparticles, which was 60wt.% of the resin. Controls for comparison were Bis-GMA/TEGDMA resins containing only SiO2 microparticles (60wt.%) or with additional SiO2 nanoparticles (5 or 10wt.%). Properties including abrasion, polymerization shrinkage and mechanical properties were evaluated to determine the contribution of SiO2 nanofibers. In comparison with SiO2 nanoparticles, SiO2 nanofibers improved the overall performance of Bis-GMA/TEGDMA composite resins, especially in improving abrasion resistance and decreasing polymerization shrinkage. The explanations were that one-dimensional SiO2 nanofibers were able to shield particular fillers from being abraded off, and able to form a kind of overlapped fibrous network to resist polymerization shrinkage. With these approaches, SiO2 nanofiber-containing Bis-GMA composite resins were envisioned a promising choice to achieve long-term durable restorations in clinical therapies. Copyright © 2015. Published by Elsevier B.V.

Evaluation of the physical properties of dental resin composites using optical fiber sensing technology.

PubMed

Rajan, Ginu; Shouha, Paul; Ellakwa, Ayman; Bhowmik, Kishore; Xi, Jiangtao; Prusty, Gangadhara

2016-09-01

The characterization of the physical properties of dental resin composites is fraught with difficulties relating to significant intra and inter test parameter variabilities and is relatively time consuming and expensive. The main aim of this study was to evaluate whether optical fiber Bragg grating (FBG) sensing system may become a viable tool to study dental material characteristics. Of particular focus was the potential for the system to demonstrate a multi parameter all-in-one feature. A miniature FBG was embedded in six different dental resin composites and employed as a sensor to evaluate linear polymerization shrinkage, thermal expansion and water sorption. Six commercially available dental composites with different filler types and volume are evaluated. The tests are repeated with three sets of samples. The curing characteristics and residual strain gradient exhibited by the cured dental composites were also observed and commented. Among the studied samples, SDR shows lowest polymerization shrinkage, while Beautifil FO3 shows the highest. The results also show clear distinction between particle filler type and fiber reinforcement based composites in their polymerization shrinkage properties. The agreement of the results with existing literatures show that FBG based system provides accurate results. Polymerization shrinkage rate of the samples are also obtained. Thermal expansion of the composites are measured using the FBG sensing method for the first time and is correlated with resin type, volume, filler type and glass transition temperature. The water sorption characteristics of the dental composite are also successfully measured using the FBG sensing method. The high level of repeatability and the low standard deviations shown in the results indicate good reliability with the use of FBG sensors. This study demonstrates how optical fiber technology can provide simple and reliable methods of measuring the critical physical properties of dental composites. In addition due to the embedding and preservation of the sensor within the samples multiple parameters can be tested for with the same sample. These features are expected to greatly assist material science researchers in dentistry as well as other biomedical fields. Of some interest the phenomenon of stress relaxation of dental composite at higher temperature was observed. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Silane–Acrylate Chemistry for Regulating Network Formation in Radical Photopolymerization

PubMed Central

2017-01-01

Photoinitiated silane–ene chemistry has the potential to pave the way toward spatially resolved organosilicon compounds, which might find application in biomedicine, microelectronics, and other advanced fields. Moreover, this approach could serve as a viable alternative to the popular photoinitiated thiol–ene chemistry, which gives access to defined and functional photopolymer networks. A difunctional bis(trimethylsilyl)silane with abstractable hydrogens (DSiH) was successfully synthesized in a simple one-pot procedure. The radical reactivity of DSiH with various homopolymerizable monomers (i.e., (meth)acrylate, vinyl ester, acrylamide) was assessed via 1H NMR spectroscopic studies. DSiH shows good reactivity with acrylates and vinyl esters. The most promising silane–acrylate system was further investigated in cross-linking formulations toward its reactivity (e.g., heat of polymerization, curing time, occurrence of gelation, double-bond conversion) and compared to state-of-the-art thiol–acrylate resins. The storage stability of prepared resin formulations is greatly improved for silane–acrylate systems vs thiol–ene resins. Double-bond conversion at the gel point (DBCgel) and overall DBC were increased, and polymerization-induced shrinkage stress has been significantly reduced with the introduction of silane–acrylate chemistry. Resulting photopolymer networks exhibit a homogeneous network architecture (indicated by a narrow glass transition) that can be tuned by varying silane concentration, and this confirms the postulated regulation of radical network formation. Similar to thiol–acrylate networks, this leads to more flexible photopolymer networks with increased elongation at break and improved impact resistance. Additionally, swelling tests indicate a high gel fraction for silane–acrylate photopolymers. PMID:29033466

Construction of monomer-free, highly crosslinked, water-compatible polymers.

PubMed

Dailing, E A; Lewis, S H; Barros, M D; Stansbury, J W

2014-12-01

Polymeric dental adhesives require the formation of densely crosslinked network structures to best ensure mechanical strength and durability in clinical service. Monomeric precursors to these materials typically consist of mixtures of hydrophilic and hydrophobic components that potentially undergo phase separation in the presence of low concentrations of water, which is detrimental to material performance and has motivated significant investigation into formulations that reduce this effect. We have investigated an approach to network formation based on nanogels that are dispersed in inert solvent and directly polymerized into crosslinked polymers. Monomers of various hydrophilic or hydrophobic characteristics were copolymerized into particulate nanogels bearing internal and external polymerizable functionality. Nanogel dispersions were stable at high concentrations in acetone or, with some exceptions, in water and produced networks with a wide range of mechanical properties. Networks formed rapidly upon light activation and reached high conversion with extremely low volumetric shrinkage. Prepolymerizing monomers into reactive nanostructures significantly changes how hydrophobic materials respond to water compared with networks obtained from polymerizations involving free monomer. The modulus of fully hydrated networks formed solely from nanogels was shown to equal or exceed the modulus in the dry state for networks based on nanogels containing a hydrophobic dimethacrylate and hydrophilic monomethacrylate, a result that was not observed in a hydroxyethyl methacrylate (HEMA) homopolymer or in networks formed from nanogels copolymerized with HEMA. These results highlight the unique approach to network development from nanoscale precursors and properties that have direct implications in functional dental materials. © International & American Associations for Dental Research.

Evaluation of the filler packing structures in dental resin composites: From theory to practice.

PubMed

Wang, Ruili; Habib, Eric; Zhu, X X

2018-07-01

The aim of this study is to evaluate the packing properties of uniform silica particles and their mixture with secondary particles yielding maximally loaded dental composites. We intend to verify the difference between the idealized models (the close-packed structures and the random-packed structures) and the actual experimental results, in order to provide guidance for the preparation of dental composites. The influence of secondary particle size and the resin composition on the physical-mechanical properties and the rheological properties of the experimental dental composites was also investigated. Silica particles (S-920, S-360, and S-195) with average diameters of 920, 360, and 195nm were synthesized via the Stöber process. Their morphology and size distribution were determined by field-emission scanning electron microscopy and laser particle sizer. A series of silica fillers, S-920, S-920+195, S-920+360, and S-920+360+195, were then formulated with two Bis-GMA/TEGDMA resins (weight ratios of 70:30 and 50:50). For these experimental dental composites, their maximum filler loadings were assessed and compared to the theory. The mechanical properties, degree of conversion, depth of cure, and polymerization shrinkage of these composites were then evaluated. Their rheological behaviors were measured with a rheometer. Unimodal S-920 had the maximally filler loading of 70.80wt% with the 5B5T resin, close to the theoretical estimation of the random loose packing (71.92wt%). The maximum loading of the S-920+360+195 filled composite was 72.92wt% for the same resin, compared to the theoretical estimation of 89.29wt% obtained for the close-packed structures. These findings indicate that random loose packing matches more closely to the real packing state for the filler formulations used. When maximally loaded, the composite with S-920+360+195 produced the best mechanical properties and the lowest polymerization shrinkage. The degree of conversion and depth of cure were higher with secondary particles added, and the viscosity of all unpolymerized pastes exhibited shear thinning behavior. Theoretical estimations of filler packing structures provide a useful guidance in the design of multimodal filler formulations and the preparation of dental composites with higher filler loading, improved physical-mechanical properties. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

Photosensitive filler minimizes internal stresses in epoxy resins

NASA Technical Reports Server (NTRS)

Dillon, J. N.

1967-01-01

Photosensitive filler is added to curable epoxy resins to minimize stress from internal shrinkage during curing or polymerization. Cinnamic acid resins and cinnamal ketones may be added in the amount of 1 to 3 percent by weight of the resin mixture.

Radiation-induced polymerization of glass forming systems. VI. Polymerization rate at higher conversion in binary systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaetsu, I.; Ito, A.; Hayashi, K.

1973-08-01

The effect of temperature and composition on the inflection point in the time-conversion curve and the saturated conversion was investigated in the gamma -radio-induced radical polymerization of binary systems consisting of a glass- forming monomer and a solvent. In the polymerization of completely homogeneous systems such as glycidyl methacrylate (GMA) -triacetin and hydroxyethyl methacrylate (HEMA) --propylene glycol systems, the time-conversion curve has an inflection point at polymerization temperatures between T/sub vm/(T/sub v/ of monomer system) and T/sub vp/ (T/sub v/ of polymer system). Such conversions at the inflection point changed monotonically between 0 and 100% in this temperature range. T/submore » v/ was found to be 30 to 50 deg C higher than T/sub g/ (glass transition temperature) and a monotonic function of composition (monomer -- polymer -- solvent). The acceleration effect continued to 100% conversion above T/sub vp/, and no acceleration effect was observed below T/sub vm/. The saturated conversion in homogeneous systems changed monotonically between 0 and 100% for polymerization temperatures between T/sub gm/ (T/sub g/ of monomer system) and T/sub gp/(T of polymer system). T/sub g/ was also a monotonic function of composition. No saturation in conversion was observed above T/sub gp/ , and no polymerization occurred below T/sub gm/. In the polymerization of completely heterogeneous systems such as HEMA-dioctyl phthalate, no acceleration effect was observed at any temperature and composition. The saturated conversion was 100% sbove T/sub g/ of pure HEMA, and no polymerization occurred below this temperature in this system. (auth)« less

Shrinkage vectors of a flowable composite in artificial cavity models with different boundary conditions: Ceramic and Teflon.

PubMed

Kaisarly, Dalia; El Gezawi, Moataz; Xu, Xiaohui; Rösch, Peter; Kunzelmann, Karl-Heinz

2018-01-01

Polymerization shrinkage of dental resin composites leads to stress build-up at the tooth-restoration interface that predisposes the restoration to debonding. In contrast to the heterogeneity of enamel and dentin, this study investigated the effect of boundary conditions in artificial cavity models such as ceramic and Teflon. Ceramic serves as a homogenous substrate that provides optimal bonding conditions, which we presented in the form of etched and silanized ceramic in addition to an etched, silanized and bonded ceramic cavity. In contrast, the Teflon cavity presented a non-adhesive boundary condition that provided an exaggerated condition of poor bonding as in the case of contamination during the application procedure or a poor bonding substrate such as sclerotic or deep dentin. The greatest 3D shrinkage vectors and movement in the axial direction were observed in the ceramic cavity with the bonding agent followed by the silanized ceramic cavity, and smallest shrinkage vectors and axial movements were observed in the Teflon cavity. The shrinkage vectors in the ceramic cavities exhibited downward movement toward the cavity bottom with great downward shrinkage of the free surface. The shrinkage vectors in the Teflon cavity pointed towards the center of the restoration with lateral movement greater at one side denoting the site of first detachment from the cavity walls. These results proved that the boundary conditions, in terms of bonding substrates, significantly influenced the shrinkage direction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heterogeneous chemical reactions: Preparation of monodisperse latexes

NASA Technical Reports Server (NTRS)

Vanderhoff, J. W.; Micale, F. J.; El-Aasser, M. S.; Sterk, A. A.; Bethke, G. W.

1977-01-01

It is demonstrated that a photoinitiated emulsion polymerization can be carried out to a significant conversion in a SPAR rocket prototype polymerization vessel within the six minutes allowed for the experiment. The percentage of conversion was determined by both dilatometry and gravimetric methods with good agreement. The experimental results lead to the following conclusions: (1) emulsion polymerizations can be carried out to conversions as high as 75%, using a stable micellized styrene-SLS system plus photoinitiator; (2) dilatometry can be used to accurately determine both the rate and conversion of polymerization; (3) thermal expansion due to the light source and heat of reaction is small and can be corrected for if necessary; (4) although seeded emulsion polymerizations are unfavorable in photoinitiation, as opposed to chemical initiation, polymerizations can be carried out to at least 15% conversion using 7940A seed particles, with 0.05% solids; and (5) photoinitiation should be used to initiate polymerization in the SPAR rocket experiments because of the mechanical simplicity of the experiment.

Mechanical behavior of bulk direct composite versus block composite and lithium disilicate indirect Class II restorations by CAD-FEM modeling.

PubMed

Ausiello, Pietro; Ciaramella, Stefano; Fabianelli, Andrea; Gloria, Antonio; Martorelli, Massimo; Lanzotti, Antonio; Watts, David C

2017-06-01

To study the influence of resin based and lithium disilicate materials on the stress and strain distributions in adhesive class II mesio-occlusal-distal (MOD) restorations using numerical finite element analysis (FEA). To investigate the materials combinations in the restored teeth during mastication and their ability to relieve stresses. One 3D model of a sound lower molar and three 3D class II MOD cavity models with 95° cavity-margin-angle shapes were modelled. Different material combinations were simulated: model A, with a 10μm thick resin bonding layer and a resin composite bulk filling material; model B, with a 70μm resin cement with an indirect CAD-CAM resin composite inlay; model C, with a 70μm thick resin cement with an indirect lithium disilicate machinable inlay. To simulate polymerization shrinkage effects in the adhesive layers and bulk fill composite, the thermal expansion approach was used. Shell elements were employed for representing the adhesive layers. 3D solid CTETRA elements with four grid points were employed for modelling the food bolus and tooth. Slide-type contact elements were used between the tooth surface and food. A vertical occlusal load of 600 N was applied, and nodal displacements on the bottom cutting surfaces were constrained in all directions. All the materials were assumed to be isotropic and elastic and a static linear analysis was performed. Displacements were different in models A, B and C. Polymerization shrinkage hardly affected model A and mastication only partially affected mechanical behavior. Shrinkage stress peaks were mainly located marginally along the enamel-restoration interface at occlusal and mesio-distal sites. However, at the internal dentinal walls, stress distributions were critical with the highest maximum stresses concentrated in the proximal boxes. In models B and C, shrinkage stress was only produced by the 70μm thick resin layer, but the magnitudes depended on the Young's modulus (E) of the inlay materials. Model B mastication behavior (with E=20GPa) was similar to the sound tooth stress relief pattern. Model B internally showed differences from the sound tooth model but reduced maximum stresses than model A and partially than model C. Model C (with E=70GPa) behaved similarly to model B with well redistributed stresses at the occlusal margins and the lateral sides with higher stress concentrations in the proximal boxes. Models B and C showed a more favorable performance than model A with elastic biomechanics similar to the sound tooth model. Bulk filling resin composite with 1% linear polymerization shrinkage negatively affected the mechanical behavior of class II MOD restored teeth. Class II MOD direct resin composite showed greater potential for damage because of higher internal and marginal stress evolution during resin polymerization shrinkage. With a large class II MOD cavity an indirect composite or a lithium disilicate inlay restoration may provide a mechanical response close to that of a sound tooth. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Equivalent Young's modulus of composite resin for simulation of stress during dental restoration.

PubMed

Park, Jung-Hoon; Choi, Nak-Sam

2017-02-01

For shrinkage stress simulation in dental restoration, the elastic properties of composite resins should be acquired beforehand. This study proposes a formula to measure the equivalent Young's modulus of a composite resin through a calculation scheme of the shrinkage stress in dental restoration. Two types of composite resins remarkably different in the polymerization shrinkage strain were used for experimental verification: the methacrylate-type (Clearfil AP-X) and the silorane-type (Filtek P90). The linear shrinkage strains of the composite resins were gained through the bonded disk method. A formula to calculate the equivalent Young's moduli of composite resin was derived on the basis of the restored ring substrate. Equivalent Young's moduli were measured for the two types of composite resins through the formula. Those values were applied as input to a finite element analysis (FEA) for validation of the calculated shrinkage stress. Both of the measured moduli through the formula were appropriate for stress simulation of dental restoration in that the shrinkage stresses calculated by the FEA were in good agreement within 3.5% with the experimental values. The concept of equivalent Young's modulus so measured could be applied for stress simulation of 2D and 3D dental restoration. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Solventless sol-gel chemistry through ring-opening polymerization of bridged disilaoxacyclopentanes

DOE Office of Scientific and Technical Information (OSTI.GOV)

RAHIMIAN,KAMYAR; LOY,DOUGLAS A.

2000-05-01

Ring-opening polymerization (ROP) of disilaoxacyclopentanes has proven to be an excellent approach to sol-gel type hybrid organic-inorganic materials. These materials have shown promise as precursors for encapsulation and microelectronics applications. The polymers are highly crosslinked and are structurally similar to traditional sol-gels, but unlike typical sol-gels they are prepared by an organic base or Bronsted acid (formic or triflic acid), without the use of solvents and water, they have low VOC's and show little shrinkage during processing.

Polymerization contraction stress in light-cured compomer restorative materials.

PubMed

Chen, H Y; Manhart, J; Kunzelmann, K-H; Hickel, R

2003-11-01

The magnitude and kinetics of polymerization contraction stress build-up may be potential predictors of bond failure of adhesive restorations. The present study determined these properties of seven commercial compomers (Dyract, Dyract AP, F2000 Rasant, Hytac, Compoglass F, Luxat, Glasiosite). Polymerization shrinkage was generated by 40 s light curing the test materials (800 mW/cm2). The contraction force induced was recorded for 300 s at room temperature (23-24 degrees C) by means of a Stress-Strain-Analyzer (C factor=0.33). Maximum contraction stress (MPa), coefficient of near linear fit of contraction force/time (gradient) and relative force rate (%/s) of each material were compared with that of two hybrid composites (Tetric Ceram, Prodigy). The statistical analysis was conducted by ANOVA (alpha=0.05) and post hoc Tukey's test. No statistically significant differences in the maximum stress between Glasiosite (2.27+/-0.06 MPa), Hytac (2.31+/-0.07 MPa) and Tetric Ceram (2.21+/-0.11 MPa), and between Compoglass F (2.60+/-0.18 MPa) and Prodigy (2.70+/-0.06 MPa) were found. The contraction stress of F2000 Rasant (3.41+/-0.09 MPa) and Luxat (3.33+/-0.08 MPa) were significantly highest, whilst Dyract exhibited the significantly lowest shrinkage stress (1.27+/-0.08 MPa) among the tested materials. High contraction stress, early start of stress build-up and rapid contraction force development may lead to failure of bond to tooth structure. This study suggested that the contraction stress and kinetic behavior of compomers are generally similar to those of hybrid composites in a dry condition. Dyract might be superior in maintaining the bond with cavity walls compared to conventional hybrid composites in view of its low shrinkage stress.

Complexity in modeling of residual stresses and strains during polymerization of bone cement: effects of conversion, constraint, heat transfer, and viscoelastic property changes.

PubMed

Gilbert, Jeremy L

2006-12-15

Aseptic loosening of cemented joint prostheses remains a significant concern in orthopedic biomaterials. One possible contributor to cement loosening is the development of porosity, residual stresses, and local fracture of the cement that may arise from the in-situ polymerization of the cement. In-situ polymerization of acrylic bone cement is a complex set of interacting processes that involve polymerization reactions, heat generation and transfer, full or partial mechanical constraint, evolution of conversion- and temperature-dependent viscoelastic material properties, and thermal and conversion-driven changes in the density of the cement. Interactions between heat transfer and polymerization can lead to polymerization fronts moving through the material. Density changes during polymerization can, in the presence of mechanical constraint, lead to the development of locally high residual strain energy and residual stresses. This study models the interactions during bone cement polymerization and determines how residual stresses develop in cement and incorporates temperature and conversion-dependent viscoelastic behavior. The results show that the presence of polymerization fronts in bone cement result in locally high residual strain energies. A novel heredity integral approach is presented to track residual stresses incorporating conversion and temperature dependent material property changes. Finally, the relative contribution of thermal- and conversion-dependent strains to residual stresses is evaluated and it is found that the conversion-based strains are the major contributor to the overall behavior. This framework provides the basis for understanding the complex development of residual stresses and can be used as the basis for developing more complex models of cement behavior.

Shrinkage strain-rates of dental resin-monomer and composite systems.

PubMed

Atai, Mohammad; Watts, David C; Atai, Zahra

2005-08-01

The purpose of this study was to investigate the shrinkage strain rate of different monomers, which are commonly used in dental composites and the effect of monomer functionality and molecular mass on the rate. Bis-GMA, TEGDMA, UDMA, MMA, HEMA, HPMA and different ratios of Bis-GMA/TEGDMA were mixed with Camphorquinone and Dimethyl aminoethyle methacrylate as initiator system. The shrinkage strain of the samples photopolymerised at Ca. 550 mW/cm2 and 23 degrees C was measured using the bonded-disk technique of Watts and Cash (Meas. Sci. Technol. 2 (1991) 788-794), and initial shrinkage-strain rates were obtained by numerical differentiation. Shrinkage-strain rates rose rapidly to a maximum, and then fell rapidly upon vitrification. Strain and initial strain rate were dependent upon monomer functionality, molecular mass and viscosity. Strain rates were correlated with Bis-GMA in Bis-GMA/TEGDMA mixtures up to 75-80 w/w%, due to the higher molecular mass of Bis-GMA affecting termination reactions, and then decreased due to its higher viscosity affecting propagation reactions. Monofunctional monomers exhibited lower rates. UDMA, a difunctional monomer of medium viscosity, showed the highest shrinkage strain rate (P < 0.05). Shrinkage strain rate, related to polymerization rate, is an important factor affecting the biomechanics and marginal integrity of composites cured in dental cavities. This study shows how this is related to monomer molecular structure and viscosity. The results are significant for the production, optimization and clinical application of dental composite restoratives.

Non-strinking siloxane polymers

DOEpatents

Loy, Douglas A.; Rahimian, Kamyar

2001-01-01

Cross-linked polymers formed by ring-opening polymerization of a precursor monomer of the general formula R[CH.sub.2 CH(Si(CH.sub.3).sub.2).sub.2 O].sub.2, where R is a phenyl group or an alkyl group having at least two carbon atoms. A cross-linked polymer is synthesized by mixing the monomer with a co-monomer of the general formula CH.sub.2 CHR.sup.2 (SiMe.sub.2).sub.2 O in the presence of an anionic base to form a cross-linked polymer of recurring units of the general formula R(Me.sub.2 SiOCH.sub.2 CHSiMe.sub.2).sub.2 [CH.sub.2 CHR.sup.2 (SiMe.sub.2).sub.2 O].sub.n, where R.sup.2 is hydrogen, phenyl, ethyl, propyl or butyl. If the precursor monomer is a liquid, the polymer can be directly synthesized in the presence of an anionic base to a cross-linked polymer containing recurring units of the general formula R(Me.sub.2 SiOCH.sub.2 CHSiMe.sub.2).sub.2. The polymers have approximately less than 1% porosity and are thermally stable at temperatures up to approximately 500.degree. C. The conversion to the cross-linked polymer occurs by ring opening polymerization and results in shrinkage of less than approximately 5% by volume.

Three-dimensional printing and deformation behavior of low-density target structures by two-photon polymerization

NASA Astrophysics Data System (ADS)

Liu, Ying; Stein, Ori; Campbell, John H.; Jiang, Lijia; Petta, Nicole; Lu, Yongfeng

2017-08-01

Two-photon polymerization (2PP), a 3D nano to microscale additive manufacturing process, is being used for the first time to fabricate small custom experimental packages ("targets") to support laser-driven high-energy-density (HED) physics research. Of particular interest is the use of 2PP to deterministically print low-density, low atomic-number (CHO) polymer matrices ("foams") at millimeter scale with sub-micrometer resolution. Deformation during development and drying of the foam structures remains a challenge when using certain commercial photo-resins; here we compare use of acrylic resins IP-S and IP-Dip. The mechanical strength of polymeric beam and foam structures is examined particularly the degree of deformation that occurs during the development and drying processes. The magnitude of the shrinkage in the two resins in quantified by printing sample structures and by use of FEA to simulate the deformation. Capillary drying forces are shown to be small and likely below the elastic limit of the core foam structure. In contrast the substantial shrinkage in IP-Dip ( 5-10%) cause large shear stresses and associated plastic deformation particularly near constrained boundaries such as the substrate and locations with sharp density variation. The inherent weakness of stitching boundaries is also evident and in certain cases can lead to delamination. Use of IP-S shows marked reduction in deformation with a minor loss of print resolution

The paradigm of tumor shrinkage and rapid liver remnant hypertrophy for conversion of initially unresectable colorectal liver metastasis: a case report and literature review.

PubMed

Xiao, Nan; Yu, Kailin; Yu, Shaojun; Wu, Jianjun; Wang, Jian; Shan, Siyang; Zheng, Shuchun; Wang, Liuhong; Wang, Jianwei; Peng, Shuyou

2017-08-03

For colorectal liver metastasis (CRLM) patients, hepatic resection is currently the sole cure offering the chance of long-term survival. Tumor shrinkage and planned liver remnant hypertrophy are the two key strategies for conversion of initially unresectable CRLM. First conducted in 2012, associated liver partition and portal vein ligation for staged hepatectomy (ALPPS) allows rapid liver growth. As a means to induce hypertrophy, portal vein embolization (PVE) has been widely applied before extending hepatectomy. Recently, Peng et al. present a new approach of terminal branches portal vein embolization (TBPVE), offering an efficient way to amplify FLR and making chances for surgery in 2 weeks. We reported a 61-year-old woman with synchronous hepatic metastasized carcinoma of the colon sigmoideum underwent TBPVE after 6 cycles of neoadjuvant therapy in order to perform a planned right trisectionectomy. Rapid liver remnant hypertrophy and remarkable tumor shrinkage were achieved, and laparoscopic sigmoidectomy and right trisectionectomy were successfully performed. The postsurgical course was uneventful and 7 months of recurrence-free survival have been witnessed. The dual tactics of tumor shrinkage and planned rapid liver remnant hypertrophy will make concerted efforts to further increase the clinical candidacy for curative resection, which are valuable for further investigation.

Retention of denture bases fabricated by three different processing techniques – An in vivo study

PubMed Central

Chalapathi Kumar, V. H.; Surapaneni, Hemchand; Ravikiran, V.; Chandra, B. Sarat; Balusu, Srilatha; Reddy, V. Naveen

2016-01-01

Aim: Distortion due to Polymerization shrinkage compromises the retention. To evaluate the amount of retention of denture bases fabricated by conventional, anchorized, and injection molding polymerization techniques. Materials and Methods: Ten completely edentulous patients were selected, impressions were made, and master cast obtained was duplicated to fabricate denture bases by three polymerization techniques. Loop was attached to the finished denture bases to estimate the force required to dislodge them by retention apparatus. Readings were subjected to nonparametric Friedman two-way analysis of variance followed by Bonferroni correction methods and Wilcoxon matched-pairs signed-ranks test. Results: Denture bases fabricated by injection molding (3740 g), anchorized techniques (2913 g) recorded greater retention values than conventional technique (2468 g). Significant difference was seen between these techniques. Conclusions: Denture bases obtained by injection molding polymerization technique exhibited maximum retention, followed by anchorized technique, and least retention was seen in conventional molding technique. PMID:27382542

Synthetic polymeric substrates as potent pro-oxidant versus anti-oxidant regulators of cytoskeletal remodeling and cell apoptosis.

PubMed

Sung, Hak-Joon; Chandra, Prafulla; Treiser, Matthew D; Liu, Er; Iovine, Carmine P; Moghe, Prabhas V; Kohn, Joachim

2009-03-01

The role of reactive oxygen species (ROS)-mediated cell signal transduction pathways emanating from engineered cell substrates remains unclear. To elucidate the role, polymers derived from the amino acid L-tyrosine were used as synthetic matrix substrates. Variations in their chemical properties were created by co-polymerizing hydrophobic L-tyrosine derivatives with uncharged hydrophilic poly(ethylene glycol) (PEG, Mw = 1,000 Da), and negatively charged desaminotyrosyl-tyrosine (DT). These substrates were characterized for their intrinsic ability to generate ROS, as well as their ability to elicit Saos-2 cell responses in terms of intracellular ROS production, actin remodeling, and apoptosis. PEG-containing substrates induced both exogenous and intracellular ROS production, whereas the charged substrates reduced production of both types, indicating a coupling of exogenous ROS generation and intracellular ROS production. Furthermore, PEG-mediated ROS induction caused nuclear translocation of glyceraldehyde-3-phosphate dehydrogenase and an increase in caspase-3 activity, confirming a link with apoptosis. PEG-rich pro-oxidant substrates caused cytoskeletal actin remodeling through beta-actin cleavage by caspase-3 into fractins. The fractins co-localized to the mitochondria and reduced the mitochondrial membrane potential. The remnant cytosolic beta-actin was polymerized and condensed, events consistent with apoptotic cell shrinkage. The cytoskeletal remodeling was integral to the further augmentation of intracellular ROS production. Conversely, the anti-oxidant DT-containing charged substrates suppressed the entire cascade of apoptotic progression. We demonstrate that ROS activity serves an important role in "outside-in" signaling for cells grown on substrates: the ROS activity couples exogenous stress, driven by substrate composition, to changes in intracellular signaling. This signaling causes cell apoptosis, which is mediated by actin remodeling.

Structure-Composition-Property Relationships in Polymeric Amorphous Calcium Phosphate-Based Dental Composites †

PubMed Central

O’Donnell, Justin N.R.; Schumacher, Gary E.; Antonucci, Joseph M.; Skrtic, Drago

2009-01-01

Our studies of amorphous calcium phosphate (ACP)-based materials over the last decade have yielded bioactive polymeric composites capable of protecting teeth from demineralization or even regenerating lost tooth mineral. The anti-cariogenic/re-mineralizing potential of these ACP composites originates from their propensity, when exposed to the oral environment, to release in a sustained manner sufficient levels of mineral-forming calcium and phosphate ions to promote formation of stable apatitic tooth mineral. However, the less than optimal ACP filler/resin matrix cohesion, excessive polymerization shrinkage and water sorption of these experimental materials can adversely affect their physicochemical and mechanical properties, and, ultimately, limit their lifespan. This study demonstrates the effects of chemical structure and composition of the methacrylate monomers used to form the matrix phase of composites on degree of vinyl conversion (DVC) and water sorption of both copolymers and composites and the release of mineral ions from the composites. Modification of ACP surface via introducing cations and/or polymers ab initio during filler synthesis failed to yield mechanically improved composites. However, moderate improvement in composite’s mechanical stability without compromising its remineralization potential was achieved by silanization and/or milling of ACP filler. Using ethoxylated bisphenol A dimethacrylate or urethane dimethacrylate as base monomers and adding moderate amounts of hydrophilic 2-hydroxyethyl methacrylate or its isomer ethyl-α-hydroxymethacrylate appears to be a promising route to maximize the remineralizing ability of the filler while maintaining high DVC. Exploration of the structure/composition/property relationships of ACP fillers and polymer matrices is complex but essential for achieving a better understanding of the fundamental mechanisms that govern dissolution/re-precipitation of bioactive ACP fillers, and, ultimately, the suitability of the composites for clinical evaluation. PMID:21966588

A novel headspace gas chromatographic method for in situ monitoring of monomer conversion during polymerization in an emulsion environment.

PubMed

Chai, Xin-Sheng; Zhong, Jin-Feng; Hu, Hui-Chao

2012-05-18

This paper describes a novel multiple-headspace extraction/gas chromatographic (MHE-GC) technique for monitoring monomer conversion during a polymerization reaction in a water-based emulsion environment. The polymerization reaction of methyl methacrylate (MMA) in an aqueous emulsion is used as an example. The reaction was performed in a closed headspace sample vial (as a mini-reactor), with pentane as a tracer. In situ monitoring of the vapor concentration of the tracer, employing a multiple headspace extraction (sampling) scheme, coupled to a GC, makes it possible to quantitatively follow the conversion of MMA during the early stages of polymerization. Data on the integrated amount of the tracer vapor released from the monomer droplet phase during the polymerization is described by a mathematic equation from which the monomer conversion can be calculated. The present method is simple, automated and economical, and provides an efficient tool in the investigation of the reaction kinetics and effects of the reaction conditions on the early stage of polymerization. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of dental restorations and mastication loadings on dentine fatigue behaviour: Image-based modelling approach.

PubMed

Vukicevic, Arso M; Zelic, Ksenija; Jovicic, Gordana; Djuric, Marija; Filipovic, Nenad

2015-05-01

The aim of this study was to use Finite Element Analysis (FEA) to estimate the influence of various mastication loads and different tooth treatments (composite restoration and endodontic treatment) on dentine fatigue. The analysis of fatigue behaviour of human dentine in intact and composite restored teeth with root-canal-treatment using FEA and fatigue theory was performed. Dentine fatigue behaviour was analysed in three virtual models: intact, composite-restored and endodontically-treated tooth. Volumetric change during the polymerization of composite was modelled by thermal expansion in a heat transfer analysis. Low and high shrinkage stresses were obtained by varying the linear shrinkage of composite. Mastication forces were applied occlusally with the load of 100, 150 and 200N. Assuming one million cycles, Fatigue Failure Index (FFI) was determined using Goodman's criterion while residual fatigue lifetime assessment was performed using Paris-power law. The analysis of the Goodman diagram gave both maximal allowed crack size and maximal number of cycles for the given stress ratio. The size of cracks was measured on virtual models. For the given conditions, fatigue-failure is not likely to happen neither in the intact tooth nor in treated teeth with low shrinkage stress. In the cases of high shrinkage stress, crack length was much larger than the maximal allowed crack and failure occurred with 150 and 200N loads. The maximal allowed crack size was slightly lower in the tooth with root canal treatment which induced somewhat higher FFI than in the case of tooth with only composite restoration. Main factors that lead to dentine fatigue are levels of occlusal load and polymerization stress. However, root canal treatment has small influence on dentine fatigue. The methodology proposed in this study provides a new insight into the fatigue behaviour of teeth after dental treatments. Furthermore, it estimates maximal allowed crack size and maximal number of cycles for a specific case. Copyright © 2015 Elsevier Ltd. All rights reserved.

Radiation-induced polymerization of glass-forming systems. IV. Effect of the homogeneity of polymerization phase and polymer concentration on temperature dependence of initial polymerization rate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaetsu, I.; Ito, A.; Hayashi, K.

1973-06-01

The effect of homogeneity of polymerization phase and monomer concentration on the temperature dependence of initial polymerization rate was studied in the radiation-induced radical polymerization of binary systems consisting of glass-forming monomer and solvent. In the polymerization of a completely homogeneous system such as HEMA-propylene glycol, a maximum and a minimum in polymerization rates as a function of temperature, characteristic of the polymerization in glass-forming systems, were observed for all monomer concentrations. However, in the heterogeneous polymerization systems such as HEMA-triacetin and HEMAisoamyl acetate, maximum and minimum rates were observed in monomer-rich compositions but not at low monomer concentrations. Furthermore,more » in the HEMA-dioctyl phthalate polymerization system, which is extremely heterogeneous, no maximum and minimum rates were observed at any monomer concentration. The effect of conversion on the temperature dependence of polymerization rate in homogeneous bulk polymerization of HEMA and GMA was investigated. Maximum and minimum rates were observed clearly in conversions less than 10% in the case of HEMA and less than 50% in the case of GMA, but the maximum and minimum changed to a mere inflection in the curve at higher conversions. A similar effect of polymer concentration on the temperature dependence of polymerization rate in the GMA-poly(methyl methacrylate) system was also observed. It is deduced that the change in temperature dependence of polymerization rate is attributed to the decrease in contribution of mutual termination reaction of growing chain radicals to the polymerization rate. (auth)« less

Dental Resin Cements-The Influence of Water Sorption on Contraction Stress Changes and Hydroscopic Expansion.

PubMed

Sokolowski, Grzegorz; Szczesio, Agata; Bociong, Kinga; Kaluzinska, Karolina; Lapinska, Barbara; Sokolowski, Jerzy; Domarecka, Monika; Lukomska-Szymanska, Monika

2018-06-08

Resin matrix dental materials undergo contraction and expansion changes due to polymerization and water absorption. Both phenomena deform resin-dentin bonding and influence the stress state in restored tooth structure in two opposite directions. The study tested three composite resin cements (Cement-It, NX3, Variolink Esthetic DC), three adhesive resin cements (Estecem, Multilink Automix, Panavia 2.0), and seven self-adhesive resin cements (Breeze, Calibra Universal, MaxCem Elite Chroma, Panavia SA Cement Plus, RelyX U200, SmartCem 2, and SpeedCEM Plus). The stress generated at the restoration-tooth interface during water immersion was evaluated. The shrinkage stress was measured immediately after curing and after 0.5 h, 24 h, 72 h, 96 h, 168 h, 240 h, 336 h, 504 h, 672 h, and 1344 h by means of photoelastic study. Water sorption and solubility were also studied. All tested materials during polymerization generated shrinkage stress ranging from 4.8 MPa up to 15.1 MPa. The decrease in shrinkage strain (not less than 57%) was observed after water storage (56 days). Self-adhesive cements, i.e., MaxCem Elite Chroma, SpeedCem Plus, Panavia SA Plus, and Breeze exhibited high values of water expansion stress (from 0 up to almost 7 MPa). Among other tested materials only composite resin cement Cement It and adhesive resin cement Panavia 2.0 showed water expansion stress (1.6 and 4.8, respectively). The changes in stress value (decrease in contraction stress or built up of hydroscopic expansion) in time were material-dependent.

Solid-State Nanopore.

PubMed

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-20

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Solid-State Nanopore

NASA Astrophysics Data System (ADS)

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-01

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

The impact of MRI steady-state sequences as an additional assessment modality in vestibular schwannoma patients after LINAC stereotactic radiotherapy or radiosurgery.

PubMed

Sauer, Julian P; Kinfe, Thomas M; Pintea, Bogdan; Schäfer, Andreas; Boström, Jan P

2018-05-23

Data concerning the clinical usefulness of steady-state sequences (SSS) for vestibular schwannomas (VS) after linear accelerator (LINAC) stereotactic radiosurgery (SRS) or stereotactic radiotherapy (SRT) are scarce. The aim of the study was to investigate whether SSS provide an additional useful follow-up (FU) tool to the established thin-layered T1 sequences with contrast enhancement. Pre- and post-treatment SSS were identified in 45 consecutive VS patients (2012-2016) with a standardized FU protocol including SSS at 2-3 months and 6 months/yearly in our prospective database and were retrospectively re-evaluated. The SSS were used throughout for the segmentation of the cochlea and partly of the trigeminal nerve in the treatment planning. Data analysis included signal conversion in SSS and possible correlation with neuro-otological outcome and volumetric assessment after a certain time interval. The series included 42 SRS and 3 SRT patients (31 female/14 male; mean age 59.3 years, range: 25-81 years). An SSS signal conversion was observed in 20 tumors (44.4%) within a mean time of 11 months (range: 7-15 months). Mean FU time was 26 months (median of 4 FU visits) and demonstrated tumor volume shrinkage in 29 cases (64.4%) correlating with FU time (p = 0.07). The incidence rate of combined shrinkage and signal conversion (48.3%) compared to those without signal conversion (51.7%) did not differ significantly (p = 0.49). In case of an early signal conversion at the first FU, a weak statistical significance (p = 0.05) for a higher shrinkage rate of VS with signal conversion was found. Side effects in cases with signal conversion (9/20, 45%) were more frequently than without signal conversion (6/25, 24%) without reaching statistical significance (p = 0.13). Our data confirmed the usefulness of SSS for anatomical segmentation of VS in LINAC-SRS/SRT treatment planning and add data supporting their potential as an adjunctive FU option in VS patients.

Various aspects of ultrasound assisted emulsion polymerization process.

PubMed

Korkut, Ibrahim; Bayramoglu, Mahmut

2014-07-01

In this paper, the effects of ultrasonic (US) power, pulse ratio, probe area and recipe composition were investigated on two process responses namely, monomer (methyl methacrylate, MMA) conversion and electrical energy consumption per mass of product polymer (PMMA). Pulsed mode US is more suitable than continuous mode US for emulsion polymerization. The probe (tip) area has little effect on the yield of polymerization when comparing 19 and 13 mm probes, 13 mm probe performing slightly better for high conversion levels. Meanwhile, large probe area is beneficial for high conversion efficiency of electric energy to US energy as well as for high radical generation yield per energy consumed. The conversion increased slightly and electrical energy consumption decreased substantially by using a recipe with high SDS and monomer concentrations. Conclusions presented in this paper may be useful for scale-up of US assisted emulsion polymerization. Copyright © 2014 Elsevier B.V. All rights reserved.

Solventless sol-gel chemistry through ring-opening polymerization of bridged disilaoxacyclopentanes

DOE Office of Scientific and Technical Information (OSTI.GOV)

RAHIMIAN,KAMYAR; LOY,DOUGLAS A.

2000-04-04

Disilaoxacyclopentanes have proven to be excellent precursors to sol-gel type materials. These materials have shown promise as precursors for encapsulation and microelectronics applications. The polymers are highly crosslinked and are structurally similar to traditional sol-gels, but unlike typical sol-gels they are prepared without the use of solvents and water, they have low VOC's and show little shrinkage during processing.

Dental resins properties studied by Bragg gratings

NASA Astrophysics Data System (ADS)

Kalinowski, Hypolito José; Gebert de Oliveira Franco, Ana Paula; Karam, Leandro Zen

2017-08-01

Fibre Bragg sensors are a key device in biomedical research for simultaneous measurement of deformations and temperature. The present study shows results from the characterization of dental resin materials with different composition and applications. The results show that all investigated polymer materials demonstrate a temperature rise within the first few seconds after starting activation procedure. The mode of activation and the material composition influence the polymerization shrinkage values.

Effect of two lasers on the polymerization of composite resins: single vs combination.

PubMed

Ro, Jung-Hoon; Son, Sung-Ae; Park, Jeong-kil; Jeon, Gye-Rok; Ko, Ching-Chang; Kwon, Yong Hoon

2015-07-01

The selection of a light-curing unit for the curing composite resins is important to achieve best outcomes. The purpose of the present study was to test lasers of 457 and 473 nm alone or in combination under different light conditions with respect to the cure of composite resins. Four different composite resins were light cured using five different laser combinations (530 mW/cm(2) 457 nm only, 530 mW/cm(2) 473 nm only, 177 mW/cm(2) 457 + 177 mW/cm(2) 473 nm, 265 mW/cm(2) 457 + 265 mW/cm(2) 473 nm, and 354 mW/cm(2) 457 + 354 mW/cm(2) 473 nm). Microhardness and polymerization shrinkage were evaluated. A light-emitting diode (LED) unit was used for comparison purposes. On top surfaces, after aging for 24 h, microhardness achieved using the LED unit and the lasers with different conditions ranged 42.4-65.5 and 38.9-67.7 Hv, respectively, and on bottom surfaces, corresponding ranges were 25.2-56.1 and 18.5-55.7 Hv, respectively. Of the conditions used, 354 mW/cm(2) 457 nm + 354 mW/cm(2) 473 nm produced the highest bottom microhardness (33.8-55.6 Hv). On top and bottom surfaces, microhardness by the lowest total light intensity, 354 (177 × 2) mW/cm(2), ranged 39.0-60.5 and 18.5-52.8 Hv, respectively. Generally, 530 mW/cm(2) at 457 nm produced the lowest polymerization shrinkage. However, shrinkage values obtained using all five laser conditions were similar. The study shows the lasers of 457 and 473 nm are useful for curing composite resins alone or in combination at much lower light intensities than the LED unit.

Polymerization shrinkage stresses in different restorative techniques for non-carious cervical lesions.

PubMed

de Oliveira Correia, Ayla Macyelle; Tribst, João Paulo Mendes; de Souza Matos, Felipe; Platt, Jeffrey A; Caneppele, Taciana Marco Ferraz; Borges, Alexandre Luiz Souto

2018-06-20

This study evaluated the effect of different restorative techniques for non-carious cervical lesions (NCCL) on polymerization shrinkage stress of resins using three-dimensional (3D) finite element analysis (FEA). 3D-models of a maxillary premolar with a NCCL restored with different filling techniques (bulk filling and incremental) were generated to be compared by nonlinear FEA. The bulk filling technique was used for groups B (NCCL restored with Filtek™ Bulk Fill) and C (Filtek™ Z350 XT). The incremental technique was subdivided according to mode of application: P (2 parallel increments of the Filtek™ Z350 XT), OI (2 oblique increments of the Filtek™ Z350 XT, with incisal first), OIV (2 oblique increments of the Filtek™ Z350 XT, with incisal first and increments with the same volume), OG (2 oblique increments of the Filtek™ Z350 XT, with gingival first) and OGV (2 oblique increments of the Filtek™ Z350 XT, with gingival first and increments with the same volume), resulting in 7 models. All materials were considered isotropic, elastic and linear. The results were expressed in maximum principal stress (MPS). The tension stress distribution was influenced by the restorative technique. The lowest stress concentration occurred in group B followed by OG, OGV, OI, OIV, P and C; the incisal interface was more affected than the gingival. The restoration of NCCLs with bulk fill composite resulted in lower shrinkage stress in the gingival and incisal areas, followed by incremental techniques with the initial increment placed on the gingival wall. The non-carious cervical lesions (NCCLs) restored with bulk fill composite have a more favorable biomechanical behavior. Copyright © 2018. Published by Elsevier Ltd.

A comparative evaluation of polymerization stress data obtained with four different mechanical testing systems.

PubMed

Gonçalves, Flávia; Boaro, Leticia C; Ferracane, Jack L; Braga, Roberto R

2012-06-01

The null hypothesis was that mechanical testing systems used to determine polymerization stress (σ(pol)) would rank a series of composites similarly. Two series of composites were tested in the following systems: universal testing machine (UTM) using glass rods as bonding substrate, UTM/acrylic rods, "low compliance device", and single cantilever device ("Bioman"). One series had five experimental composites containing BisGMA:TEGDMA in equimolar concentrations and 60, 65, 70, 75 or 80 wt% of filler. The other series had five commercial composites: Filtek Z250 (3M ESPE), Filtek A110 (3M ESPE), Tetric Ceram (Ivoclar), Heliomolar (Ivoclar) and Point 4 (Kerr). Specimen geometry, dimensions and curing conditions were similar in all systems. σ(pol) was monitored for 10 min. Volumetric shrinkage (VS) was measured in a mercury dilatometer and elastic modulus (E) was determined by three-point bending. Shrinkage rate was used as a measure of reaction kinetics. ANOVA/Tukey test was performed for each variable, separately for each series. For the experimental composites, σ(pol) decreased with filler content in all systems, following the variation in VS. For commercial materials, σ(pol) did not vary in the UTM/acrylic system and showed very few similarities in rankings in the others tests system. Also, no clear relationships were observed between σ(pol) and VS or E. The testing systems showed a good agreement for the experimental composites, but very few similarities for the commercial composites. Therefore, comparison of polymerization stress results from different devices must be done carefully. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A Study of Energy Conversion Devices Using Photoactive Organometallic Electrocatalysts.

DTIC Science & Technology

1986-05-23

arylisocyanide complexes confined to polymeric thin films in solar energy conversion systems . The chemical systems of interest were chromium...The goals of the project then became threefold: 1) examine the thermo- dynamics an- ’ kinetics of charge transfer in the systems in which we had shown...complexes confined to polymeric thin films in solar energy conversion systems . The chemical systems of interest were chromium, molybdenum and

Pulsed plasma polymerization for controlling shrinkage and surface composition of nanopores

NASA Astrophysics Data System (ADS)

Asghar, Waseem; Ilyas, Azhar; Deshmukh, Rajendra R.; Sumitsawan, Sulak; Timmons, Richard B.; Iqbal, Samir M.

2011-07-01

Solid-state nanopores have emerged as sensors for single molecules and these have been employed to examine the biophysical properties of an increasingly large variety of biomolecules. Herein we describe a novel and facile approach to precisely adjust the pore size, while simultaneously controlling the surface chemical composition of the solid-state nanopores. Specifically, nanopores fabricated using standard ion beam technology are shrunk to the requisite molecular dimensions via the deposition of highly conformal pulsed plasma generated thin polymeric films. The plasma treatment process provides accurate control of the pore size as the conformal film deposition depends linearly on the deposition time. Simultaneously, the pore and channel chemical compositions are controlled by appropriate selection of the gaseous monomer and plasma conditions employed in the deposition of the polymer films. The controlled pore shrinkage is characterized with high resolution AFM, and the film chemistry of the plasma generated polymers is analyzed with FTIR and XPS. The stability and practical utility of this new approach is demonstrated by successful single molecule sensing of double-stranded DNA. The process offers a viable new advance in the fabrication of tailored nanopores, in terms of both the pore size and surface composition, for usage in a wide range of emerging applications.

High performance dental resin composites with hydrolytically stable monomers.

PubMed

Wang, Xiaohong; Huyang, George; Palagummi, Sri Vikram; Liu, Xiaohui; Skrtic, Drago; Beauchamp, Carlos; Bowen, Rafael; Sun, Jirun

2018-02-01

The objectives of this project were to: 1) develop strong and durable dental resin composites by employing new monomers that are hydrolytically stable, and 2) demonstrate that resin composites based on these monomers perform superiorly to the traditional bisphenol A glycidyl dimethacrylate/triethylene glycol dimethacrylate (Bis-GMA/TEGDMA) composites under testing conditions relevant to clinical applications. New resins comprising hydrolytically stable, ether-based monomer, i.e., triethylene glycol divinylbenzyl ether (TEG-DVBE), and urethane dimethacrylate (UDMA) were produced via composition-controlled photo-polymerization. Their composites contained 67.5wt% of micro and 7.5wt% of nano-sized filler. The performances of both copolymers and composites were evaluated by a battery of clinically-relevant assessments: degree of vinyl conversion (DC: FTIR and NIR spectroscopy); refractive index (n: optical microscopy); elastic modulus (E), flexural strength (F) and fracture toughness (K IC ) (universal mechanical testing); Knoop hardness (HK; indentation); water sorption (W sp ) and solubility (W su ) (gravimetry); polymerization shrinkage (S v ; mercury dilatometry) and polymerization stress (tensometer). The experimental UDMA/TEG-DVBE composites were compared with the Bis-GMA/TEGDMA composites containing the identical filler contents, and with the commercial micro hybrid flowable composite. UDMA/TEG-DBVE composites exhibited n, E, W sp , W su and S v equivalent to the controls. They outperformed the controls with respect to F (up to 26.8% increase), K IC (up to 27.7% increase), modulus recovery upon water sorption (full recovery vs. 91.9% recovery), and stress formation (up to 52.7% reduction). In addition, new composites showed up to 27.7% increase in attainable DC compared to the traditional composites. Bis-GMA/TEGDMA controls exceeded the experimental composites with respect to only one property, the composite hardness. Significantly, up to 18.1% lower HK values in the experimental series (0.458GPa) were still above the clinically required threshold of approx. 0.4GPa. Hydrolytic stability, composition-controlled polymerization and the overall enhancement in clinically-relevant properties of the new resin composites make them viable candidates to replace traditional resin composites as a new generation of strong and durable dental restoratives. Copyright © 2017 The Academy of Dental Materials. All rights reserved.

Preparation and characterization of silane-modified SiO2 particles reinforced resin composites with fluorinated acrylate polymer.

PubMed

Liu, Xue; Wang, Zengyao; Zhao, Chengji; Bu, Wenhuan; Na, Hui

2018-04-01

A series of fluorinated dental resin composites were prepared with two kinds of SiO 2 particles. Bis-GMA (bisphenol A-glycerolate dimethacrylate)/4-TF-PQEA (fluorinated acrylate monomer)/TEGDMA (triethylene glycol dimethacrylate) (40/30/30, wt/wt/wt) was introduced as resin matrix. SiO 2 nanopartices (30nm) and SiO 2 microparticles (0.3µm) were silanized with 3-methacryloxypropyl trimethoxysilane (γ-MPS) and used as fillers. After mixing the resin matrix with 0%, 10%, 20%, 30% SiO 2 nanopartices and 0%, 10%, 20%, 30%, 40%, 50% SiO 2 microparticles, respectively, the fluorinated resin composites were obtained. Properties including double bond conversion (DC), polymerization shrinkage (PS), water sorption (W p ), water solubility (W y ), mechanical properties and cytotoxicity were investigated in comparison with those of neat resin system. The results showed that, filler particles could improve the overall performance of resin composites, particularly in improving mechanical properties and reducing PS of composites along with the addition of filler loading. Compared to resin composites containing SiO 2 microparticles, SiO 2 nanoparticles resin composites had higher DC, higher mechanical properties, lower PS and lower W p under the same filler content. Especially, 50% SiO 2 microparticles reinforced resins exhibited the best flexural strength (104.04 ± 7.40MPa), flexural modulus (5.62 ± 0.16GPa), vickers microhardness (37.34 ± 1.13 HV), compressive strength (301.54 ± 5.66MPa) and the lowest polymerization (3.42 ± 0.22%). Copyright © 2018 Elsevier Ltd. All rights reserved.

Multiscale Analysis of the Residual Stresses Occurring During Curing and Cooling of Thick-Wall Cross-Ply Filament-Wound Cylinders

NASA Astrophysics Data System (ADS)

Memarianfard, H.; Turusov, R. A.

2017-11-01

A nonlinear numerical multiscale analysis to predict the residual shrinkage and thermal stresses arising during curing and cooling of thickwall cross-ply filament-wound cylinders of a reinforced polymer is performed at macro- and microscales using the representative volume element (RVE) of the composite. The mechanical behavior of the polymeric matrix is described by a nonlinear viscoelastic model with account of chemical shrinkage. The fiber material is considered elastic, isotropic, and temperature-independent. The maximum residual macrostresses arising during manufacture of the cylinders were calculated. The fields of residual microstresses in the RVE in three different zones across the thickness of the cylinders were found. Results of the microscale analysis showed that microstresses in some zones of RVE were several times higher than macrostresses in these areas.

Poly(n-hexyl methacrylate) polymerization in three-component microemulsion stabilized by a cationic surfactant.

PubMed

Katime, Issa; Arellano, Jesús; Schulz, Pablo

2006-04-15

The polymerization of n-hexyl methacrylate (n-HMA) in three-component microemulsion stabilized with dodecyltrimethylammonium bromide (DTAB) is reported as a function of monomer and initiator concentrations and temperature. The obtained latices were bluish, transparent, and translucent. Particle sizes and molar masses were on the order of 20 nm and 3 x 10(6) g/mol, respectively. In all cases, high reaction rates and final conversions of 98% were obtained. Polymerization temperature has a strong effect on reaction rate and conversion.

Synthesis, characterization, shrinkage and curing kinetics of a new low-shrinkage urethane dimethacrylate monomer for dental applications.

PubMed

Atai, Mohammad; Ahmadi, Mehdi; Babanzadeh, Samal; Watts, David C

2007-08-01

The aim of the study was to synthesize and characterize an isophorone-based urethane dimethacrylate (IP-UDMA) resin-monomer and to investigate its shrinkage and curing kinetics. The IP-UDMA monomer was synthesized through the reaction of polyethylene glycol 400 and isophorone diisocyanate followed by reacting with HEMA to terminate it with methacrylate end groups. The reaction was followed using a standard back titration method and FTIR spectroscopy. The final product was purified and characterized using FTIR, (1)H NMR, elemental analysis and refractive index measurement. The shrinkage-strain of the specimens photopolymerized at circa 700mW/cm(2) was measured using the bonded-disk technique at 23, 35, and 45 degrees C. Initial shrinkage-strain-rates were obtained by numerical differentiation of shrinkage-strain data with respect to time. Degree-of-conversion of the specimens was measured using FTIR spectroscopy. The thermal curing kinetics of the monomer were also studied by differential scanning calorimetry (DSC). The characterization methods confirmed the suggested reaction route and the synthesized monomer. A low shrinkage-strain of about 4% was obtained for the new monomer. The results showed that the shrinkage-strain-rate of the monomer followed the autocatalytic model of Kamal and Sourour [Kamal MR, Sourour S. Kinetic and thermal characterization of thermoset cure. Polym Eng Sci 1973;13(1):59-64], which is used to describe the reaction kinetics of thermoset resins. The model parameters were calculated by linearization of the equation. The model prediction was in a good agreement with the experimental data. The properties of the new monomer compare favorably with properties of the commercially available resins.

Influence of light-curing sources on polymerization reaction kinetics of a restorative system.

PubMed

D'Alpino, Paulo H P; Svizero, Nádia R; Pereira, José C; Rueggeberg, Frederick A; Carvalho, Ricardo M; Pashley, David H

2007-02-01

To determine the effect of using a variety of commercial light-curing units on polymerization of a dentin-bonding agent (Adper Single Bond) and of a resin composite (Filtek Z250). Infrared (IR) spectra were obtained kinetically at one scan/second at 2 cm(-1) resolution for a period of 5 minutes and were analyzed for: maximum conversion rate (%/s), time into exposure when maximum rate occurred (seconds), conversion at maximum rate (%), and total conversion (%) at 300 seconds by comparison of aliphatic-to-aromatic absorption IR peak ratios, before and after polymerization. Light units used were: QTH 540 mW/cm2 (XL3000); LED 750 mW/cm2 (Elipar FreeLight 2); PAC 2,130 mW/cm2 (ARC II). Exposure followed manufacturers' recommendations: dentin bonding agent for 10 seconds, RC for 20 seconds (QTH), and 10 seconds (LED and PAC). Polymerization kinetics was evaluated at the bottom surface (2.5 mm thick) for the resin composite and as a thin film for the dentin bonding agent on the diamond surface of an attenuated total reflectance accessory in the IR spectrometer. Values (n = 5) were compared using ANOVA and Tukey's pairwise post-hoc test: pre-set alpha 0.05. PAC produced the highest total conversion and conversion rate for the resin composite (P < 0.05). Total conversion was lower for dentin bonding adhesive using PAC than with LED or QTH (P < 0.05). LED provided the highest proportion of conversion at the maximum rate with respect to conversion at 300 seconds for both materials. QTH demonstrated the lowest maximum rate value that occurred at a longer time into exposure (P < 0.05). Polymerization kinetic parameters varied greatly between the restorative materials as well as among light-curing unit types when compared to values observed when using a QTH light as control.

Single-anchor support and supercritical CO2 drying enable high-precision microfabrication of three-dimensional structures.

PubMed

Maruo, Shoji; Hasegawa, Takuya; Yoshimura, Naoki

2009-11-09

In high-precision two-photon microfabrication of three-dimensional (3-D) polymeric microstructures, supercritical CO(2) drying was employed to reduce surface tension, which tends to cause the collapse of micro/nano structures. Use of supercritical drying allowed high-aspect ratio microstructures, such as micropillars and cantilevers, to be fabricated. We also propose a single-anchor supporting method to eliminate non-uniform shrinkage of polymeric structures otherwise caused by attachment to the substrate. Use of this method permitted frame models such as lattices to be produced without harmful distortion. The combination of supercritical CO(2) drying and the single-anchor supporting method offers reliable high-precision microfabrication of sophisticated, fragile 3-D micro/nano structures.

Tunable, Quantitative Fenton-RAFT Polymerization via Metered Reagent Addition.

PubMed

Nothling, Mitchell D; McKenzie, Thomas G; Reyhani, Amin; Qiao, Greg G

2018-05-10

A continuous supply of radical species is a key requirement for activating chain growth and accessing quantitative monomer conversions in reversible addition-fragmentation chain transfer (RAFT) polymerization. In Fenton-RAFT, activation is provided by hydroxyl radicals, whose indiscriminate reactivity and short-lived nature poses a challenge to accessing extended polymerization times and quantitative monomer conversions. Here, an alternative Fenton-RAFT procedure is presented, whereby radical generation can be finely controlled via metered dosing of a component of the Fenton redox reaction (H 2 O 2 ) using an external pumping system. By limiting the instantaneous flux of radicals and ensuring sustained radical generation over tunable time periods, metered reagent addition reduces unwanted radical "wasting" reactions and provides access to consistent quantitative monomer conversions with high chain-end fidelity. Fine tuning of radical concentration during polymerization is achieved simply via adjustment of reagent dose rate, offering significant potential for automation. This modular strategy holds promise for extending traditional RAFT initiation toward more tightly regulated radical concentration profiles and affords excellent prospects for the automation of Fenton-RAFT polymerization. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of photopolymerization on the degree of conversion, polymerization kinetic, biaxial flexure strength, and modulus of self-adhesive resin cements.

PubMed

Aguiar, Thaiane R; de Oliveira, Michele; Arrais, César A G; Ambrosano, Glaucia M B; Rueggeberg, Frederick; Giannini, Marcelo

2015-02-01

Understanding the effect of the degree of conversion on the mechanical properties of auto- and dual-polymerizing self-adhesive resin cements leads to a better estimation of their performance in different clinical scenarios. The purpose of this study was to evaluate the effect of photopolymerization on the degree of conversion (DC) and polymerization kinetic of 4 dual-polymerized resin cements, 20 minutes after mixing, and its effects on the mechanical properties (biaxial flexural strength [FS] and modulus [FM]) after short-term aging. Conventional (RelyX ARC and Clearfil Esthetic Cement) and self-adhesive resin cements (RelyX Unicem and Clearfil SA Cement) were applied to a Fourier infrared spectrometer to assess the DC (n=5) under the following 3 polymerization conditions: direct light exposure (dual-polymerizing mode), exposure through the prepolymerized disk, or autopolymerizing. The polymerization kinetic was recorded for 20 minutes. Then, disk-shaped specimens (n=11) were prepared to evaluate the effect of polymerization on the FS and FM in both extreme polymerization conditions (dual-polymerizing or autopolymerizing). Data were statistically analyzed by 2-way repeated measure ANOVA (DC) and by 2-way ANOVA (FS and FM), followed by the Tukey-Kramer post hoc test (α=.05). Autopolymerizing groups exhibited reduced DC means, whereas intermediate values were observed when resin cements were polymerized through the disk. All groups exhibited higher DC at the end of 20 minutes. The polymerization kinetic revealed a rising curve, and materials, when directly photopolymerized, reached a plateau immediately after light exposure. Regarding the flexural biaxial testing, most of the resin cements were affected by polymerization mode and differences among groups were product dependent. The resin cements achieved immediate higher DC and mechanical properties when photopolymerized. The total absence of photoactivation may still impair their mechanical properties even after short-term aging. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Plasma Modified Polypropylene Membranes as the Lithium-Ion Battery Separators

NASA Astrophysics Data System (ADS)

Wang, Zhengduo; Zhu, Huiqin; Yang, Lizhen; Wang, Xinwei; Liu, Zhongwei; Chen, Qiang

2016-04-01

To reduce the thermal shrinkage of the polymeric separators and improve the safety of the Li-ion batteries, plasma treatment and plasma enhanced vapor chemical deposition (PECVD) of SiOx-like are carried out on polypropylene (PP) separators, respectively. Critical parameters for separator properties, such as the thermal shrinkage rate, porosity, wettability, and mechanical strength, are evaluated on the plasma treated PP membranes. O2 plasma treatment is found to remarkably improve the wettability, porosity and electrolyte uptake. PECVD SiOx-like coatings are found to be able to effectively reduce the thermal shrinkage rate of the membranes and increase the ionic conductivity. The electrolyte-philicity of the SiOx-like coating surface can be tuned by the varying O2 content in the gas mixture during the deposition. Though still acceptable, the mechanical strength is reduced after PECVD, which is due to the plasma etching. supported by National Natural Science Foundation of China (Nos. 11175024, 11375031), the Beijing Institute of Graphic and Communication Key Project of China (No. 23190113051), the Shenzhen Science and Technology Innovation Committee of China (No. JCYJ20130329181509637), BJNSFC (No. KZ201510015014), and the State Key Laboratory of Electrical Insulation and Power Equipment of China (No. EIPE15208)

Effect of delayed polymerization time and bracket manipulation on orthodontic bracket bonding

NASA Astrophysics Data System (ADS)

Ponikvar, Michael J.

This study examined the effect of bracket manipulation in combination with delayed polymerization times on orthodontic bracket shear bond strength and degree of resin composite conversion. Orthodontics brackets were bonded to extracted third molars in a simulated oral environment after a set period of delayed polymerization time and bracket manipulation. After curing the bracket adhesive, each bracket underwent shear bond strength testing followed by micro-Raman spectroscopy analysis to measure the degree of conversion of the resin composite. Results demonstrated the shear bond strength and the degree of conversion of ceramic brackets did not vary over time. However, with stainless steel brackets there was a significant effect (p ≤ 0.05) of delay time on shear bond strength between the 0.5 min and 10 min bracket groups. In addition, stainless steel brackets showed significant differences related to degree of conversion over time between the 0.5 min and 5 min groups, in addition to the 0.5 min and 10 min groups. This investigation suggests that delaying bracket adhesive polymerization up to a period of 10 min then adjusting the orthodontic bracket may increase both shear bond strength and degree of conversion of stainless steel brackets while having no effect on ceramic brackets.

Development of a practical photochemical energy storage system. Quarterly report. [Interconversion between norbornadiene and quadricyclene for thermochemical heat storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hautala, R.R.; Kutal, C.R.

1977-06-15

Research on polymeric organic sensitizers and polymeric inorganic sensitizers for the conversion of norbornadine to quadricyclene and catalysts for the conversion of quadricyclene to norbornadine is described. The interconversion of norbornadine and quadricyclene is studied for its possible use for thermochemical solar energy storage. (WHK)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spellman, G.P.

A relatively new advanced composite matrix, polycyanate ester, was evaluated for cure shrinkage. The chemical cure shrinkage of composites is difficult to model but a number of clever experimental techniques are available to the investigator. In this work the method of curing a prepreg layup on top of a previously cured laminate of identical ply composition is utilized. The polymeric matrices used in advanced composites have been primarily epoxies and therefore a common system of this type, Fiberite 3501-6, was used as a base case material. Three polycyanate matrix systems were selected for the study. These are: Fiberite 954-2A, YLAmore » RS-3, and Bryte Technology BTCy-1. The first three of these systems were unidirectional prepreg with carbon fiber reinforcement. The Bryte Technology material was reinforced with E-glass fabric. The technique used to evaluate cure shrinkage results in distortion of the flatness of an otherwise symmetric laminate. The first laminate is cured in a conventional fashion. An identical layup is cured on this first laminate. During the second cure all constituents are exposed to the same thermal cycles. However, only the new portion of the laminate will experience volumetric changes associate with matrix cure. The additional strain of cure shrinkage results in an unsymmetric distribution of residual stresses and an associated warpage of the laminate. The baseline material, Fiberite 3501-6, exhibited cure shrinkage that was in accordance with expectations. Cure strains were {minus}4.5E-04. The YLA RS-3 material had cure strains somewhat lower at {minus}3.2E-04. The Fiberite 954-2A cure strain was {minus}1.5E-04 that is 70% lower than the baseline material. The glass fabric material with the Bryte BTCy-1 matrix did not result in meaningful results because the processing methods were not fully compatible with the material.« less

Dynamics of multiple nuclei in Ashbya gossypii hyphae depend on the control of cytoplasmic microtubules length by Bik1, Kip2, Kip3, and not on a capture/shrinkage mechanism.

PubMed

Grava, Sandrine; Philippsen, Peter

2010-11-01

Ashbya gossypii has a budding yeast-like genome but grows exclusively as multinucleated hyphae. In contrast to budding yeast where positioning of nuclei at the bud neck is a major function of cytoplasmic microtubules (cMTs), A. gossypii nuclei are constantly in motion and positioning is not an issue. To investigate the role of cMTs in nuclear oscillation and bypassing, we constructed mutants potentially affecting cMT lengths. Hyphae lacking the plus (+)end marker Bik1 or the kinesin Kip2 cannot polymerize long cMTs and lose wild-type nuclear movements. Interestingly, hyphae lacking the kinesin Kip3 display longer cMTs concomitant with increased nuclear oscillation and bypassing. Polymerization and depolymerization rates of cMTs are 3 times higher in A. gossypii than in budding yeast and cMT catastrophes are rare. Growing cMTs slide along the hyphal cortex and exert pulling forces on nuclei. Surprisingly, a capture/shrinkage mechanism seems to be absent in A. gossypii. cMTs reaching a hyphal tip do not shrink, and cMT +ends accumulate in hyphal tips. Thus, differences in cMT dynamics and length control between budding yeast and A. gossypii are key elements in the adaptation of the cMT cytoskeleton to much longer cells and much higher degrees of nuclear mobilities.

Effect of various light curing times on the elution of composite components.

PubMed

Högg, Christof; Maier, Moritz; Dettinger-Maier, Katherina; He, Xiuli; Rothmund, Lena; Kehe, Kai; Hickel, Reinhard; Reichl, Franz-Xaver

2016-11-01

Polymerization of resin-based composites (RBCs) is incomplete. The aim of the present study was to determine whether a longer curing time than recommended by the manufacturer influences the amount of released composite components of RBCs. The composites Clearfil AP-X and els extra low shrinkage were polymerized for six different curing times: 4, 10, 20, 40, 100, and 200 s. Light curing time recommended by the manufacturer for both composites is 20 s. Subsequently, samples were eluted in methanol and water for 1, 3, and 7 days and analyzed by gas chromatography/mass spectrometry (GC/MS). For Clearfil AP-X ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA), 2-hydroxy-4-methoxybenzophenone (HMBP), camphorquinone (CQ) and 2,6-di-tert-butyl-4-methylphenol (BHT) were detected in methanol. In the aqueous eluate, only TEGDMA was detected. In els extra low shrinkage, HMBP, BHT, and CQ were detected in methanol. Increasing the curing time compared to recommendation of the manufacturer reduces the release of most composite components. This could result in less exposure to human due to these substances. Methacrylates are classified as potential allergens. An increasing number of dentists and patients show allergic reaction to methacrylates. Therefore, a reduced elution of composite components is an advantage.

Light-Curing Volumetric Shrinkage in Dimethacrylate-Based Dental Composites by Nanoindentation and PAL Study.

PubMed

Shpotyuk, Olha; Adamiak, Stanislaw; Bezvushko, Elvira; Cebulski, Jozef; Iskiv, Maryana; Shpotyuk, Oleh; Balitska, Valentina

2017-12-01

Light-curing volumetric shrinkage in dimethacrylate-based dental resin composites Dipol® is examined through comprehensive kinetics research employing nanoindentation measurements and nanoscale atomic-deficient study with lifetime spectroscopy of annihilating positrons. Photopolymerization kinetics determined through nanoindentation testing is shown to be described via single-exponential relaxation function with character time constants reaching respectively 15.0 and 18.7 s for nanohardness and elastic modulus. Atomic-deficient characteristics of composites are extracted from positron lifetime spectra parameterized employing unconstrained x3-term fitting. The tested photopolymerization kinetics can be adequately reflected in time-dependent changes observed in average positron lifetime (with 17.9 s time constant) and fractional free volume of positronium traps (with 18.6 s time constant). This correlation proves that fragmentation of free-volume positronium-trapping sites accompanied by partial positronium-to-positron traps conversion determines the light-curing volumetric shrinkage in the studied composites.

Polymerization Kinetics: Monitoring Monomer Conversion Using an Internal Standard and the Key Role of Sample "t[subscript 0]"

ERIC Educational Resources Information Center

Colombani, Olivier; Langelier, Ophelie; Martwong, Ekkachai; Castignolles, Patrice

2011-01-01

The use of an internal standard is a conventional and convenient way to monitor the conversion of one or several monomers during a controlled radical polymerization. However, the validity of this technique relies on an accurate determination of the initial monomer-to-internal standard ratio, A[subscript 0], because all subsequent calculations of…

Controlled aqueous polymerization of acrylamides and acrylates and "in situ" depolymerization in the presence of dissolved CO2.

PubMed

Lloyd, Danielle J; Nikolaou, Vasiliki; Collins, Jennifer; Waldron, Christopher; Anastasaki, Athina; Bassett, Simon P; Howdle, Steven M; Blanazs, Adam; Wilson, Paul; Kempe, Kristian; Haddleton, David M

2016-05-05

Aqueous copper-mediated radical polymerization of acrylamides and acrylates in carbonated water resulted in high monomer conversions (t < 10 min) before undergoing depolymerization (60 min > t > 10 min). The regenerated monomer was characterized and repolymerized following deoxygenation of the resulting solutions to reyield polymers in high conversions that exhibit low dispersities.

Evaluation of Microleakage and Marginal Ridge Fracture Resistance of Primary Molars Restored with Three Restorative Materials: A Comparative in vitro Study

PubMed Central

Yeolekar, Tapan Satish; Mukunda, KS; Kiran, NK

2015-01-01

ABSTRACT Composite restorations are popular because of their superior esthetics and acceptable clinical performance. But shrinkage is still a drawback. Polymerization shrinkage results in volumetric contraction, leading to deformation of the cusps, microleakage, decrease of marginal adaptation, enamel micro-cracks and postoperative sensitivity. A new class of ring opening resin composite based on silorane chemistry has been introduced with claims of less than 1% shrinkage during polymerization. The present study was conducted to evaluate and compare the ability of low shrink silorane based material, a packable composite and a compomer to resist microleakage in class II restorations on primary molars and evaluate marginal ridge fracture resistance of these materials. Sixty human primary molars were selected. Class II cavities were prepared and the teeth were divided into three groups of twenty each. Groups were as follows group I: low shrink composite resin (Filtek P90). Group II: packable composite (Filtek P60) and Group III: compomer (Compoglass F). Half of the teeth were used for microleakage and the rest for marginal ridge fracture resistance. For microleakage testing, dye penetration method was used with 1% methylene blue dye. Followed by evaluation and grading under stereomicroscope at 10* magnification. Fracture resistance was tested with universal testing machine. It was concluded that low shrink silorane based composite resin showed the least amount of microleakage, whereas compomer showed the highest microleakage. Packable composite resisted fracture of marginal ridge better than other composite resins. Marginal ridge fracture resistance of packable composite was comparable to the intact side. How to cite this article: Yeolekar TS, Chowdhary NR, Mukunda KS, Kiran NK. Evaluation of Microleakage and Marginal Ridge Fracture Resistance of Primary Molars Restored with Three Restorative Materials: A Comparative in vitro Study. Int J Clin Pediatr Dent 2015;8(2):108-113. PMID:26379377

Synthesis and characterization of hydrolysed starch-g-poly(methacrylic acid) composite.

PubMed

Zahran, Magdy K; Ahmed, Enas M; El-Rafie, Mohamed H

2016-06-01

A novel method for the synthesis of starch-g-poly(methacrylic acid) composite was adopted by graft polymerization of hydrolysed starch (HS) and methacrylic acid (MAA) in aqueous medium using an efficient sodium perborate (SPB)-thiourea (TU) redox initiation system. The parameters influencing the redox system efficiency and thence the polymerization method were considered. These parameters comprehended the concentrations of MAA, SPB, TU and SPB/TU molar ratio as well as the polymerization temperature. The polymerization reaction was scrutinized through calculation of the MAA total conversion percent (TC%). The resultant poly(MAA-HS) composite was assessed by evaluating the polymer criteria (the graft yield, GY%; the grafting efficiency, GE%; the homopolymer, HP%; and the total conversion). The comportment of the apparent viscosity of the cooked poly(MAA)-starch composite paste, obtained under diverse polymerization conditions, was examined. Tentative mechanisms, which depict all occasions that happen amid the entire course of the polymerization reaction, have been proffered. Copyright © 2016 Elsevier B.V. All rights reserved.

Health monitoring method for composite materials

DOEpatents

Watkins, Jr., Kenneth S.; Morris, Shelby J [Hampton, VA

2011-04-12

An in-situ method for monitoring the health of a composite component utilizes a condition sensor made of electrically conductive particles dispersed in a polymeric matrix. The sensor is bonded or otherwise formed on the matrix surface of the composite material. Age-related shrinkage of the sensor matrix results in a decrease in the resistivity of the condition sensor. Correlation of measured sensor resistivity with data from aged specimens allows indirect determination of mechanical damage and remaining age of the composite component.

Direct voxel-based comparisons between grey matter shrinkage and glucose hypometabolism in chronic alcoholism.

PubMed

Ritz, Ludivine; Segobin, Shailendra; Lannuzel, Coralie; Boudehent, Céline; Vabret, François; Eustache, Francis; Beaunieux, Hélène; Pitel, Anne L

2016-09-01

Alcoholism is associated with widespread brain structural abnormalities affecting mainly the frontocerebellar and the Papez's circuits. Brain glucose metabolism has received limited attention, and few studies used regions of interest approach and showed reduced global brain metabolism predominantly in the frontal and parietal lobes. Even though these studies have examined the relationship between grey matter shrinkage and hypometabolism, none has performed a direct voxel-by-voxel comparison between the degrees of structural and metabolic abnormalities. Seventeen alcoholic patients and 16 control subjects underwent both structural magnetic resonance imaging and (18)F-2-fluoro-deoxy-glucose-positron emission tomography examinations. Structural abnormalities and hypometabolism were examined in alcoholic patients compared with control subjects using two-sample t-tests. Then, these two patterns of brain damage were directly compared with a paired t-test. Compared to controls, alcoholic patients had grey matter shrinkage and hypometabolism in the fronto-cerebellar circuit and several nodes of Papez's circuit. The direct comparison revealed greater shrinkage than hypometabolism in the cerebellum, cingulate cortex, thalamus and hippocampus and parahippocampal gyrus. Conversely, hypometabolism was more severe than shrinkage in the dorsolateral, premotor and parietal cortices. The distinct profiles of abnormalities found within the Papez's circuit, the fronto-cerebellar circuit and the parietal gyrus in chronic alcoholism suggest the involvement of different pathological mechanisms. © The Author(s) 2015.

Direct voxel-based comparisons between grey matter shrinkage and glucose hypometabolism in chronic alcoholism

PubMed Central

Ritz, Ludivine; Segobin, Shailendra; Lannuzel, Coralie; Boudehent, Céline; Vabret, François; Eustache, Francis; Beaunieux, Hélène

2015-01-01

Alcoholism is associated with widespread brain structural abnormalities affecting mainly the frontocerebellar and the Papez’s circuits. Brain glucose metabolism has received limited attention, and few studies used regions of interest approach and showed reduced global brain metabolism predominantly in the frontal and parietal lobes. Even though these studies have examined the relationship between grey matter shrinkage and hypometabolism, none has performed a direct voxel-by-voxel comparison between the degrees of structural and metabolic abnormalities. Seventeen alcoholic patients and 16 control subjects underwent both structural magnetic resonance imaging and 18F-2-fluoro-deoxy-glucose-positron emission tomography examinations. Structural abnormalities and hypometabolism were examined in alcoholic patients compared with control subjects using two-sample t-tests. Then, these two patterns of brain damage were directly compared with a paired t-test. Compared to controls, alcoholic patients had grey matter shrinkage and hypometabolism in the fronto-cerebellar circuit and several nodes of Papez’s circuit. The direct comparison revealed greater shrinkage than hypometabolism in the cerebellum, cingulate cortex, thalamus and hippocampus and parahippocampal gyrus. Conversely, hypometabolism was more severe than shrinkage in the dorsolateral, premotor and parietal cortices. The distinct profiles of abnormalities found within the Papez’s circuit, the fronto-cerebellar circuit and the parietal gyrus in chronic alcoholism suggest the involvement of different pathological mechanisms. PMID:26661206

The effect of polymerization mode on monomer conversion, free radical entrapment, and interaction with hydroxyapatite of commercial self-adhesive cements.

PubMed

D'Alpino, Paulo Henrique Perlatti; Silva, Marília Santos; Vismara, Marcus Vinícius Gonçalves; Di Hipólito, Vinicius; Miranda González, Alejandra Hortencia; de Oliveira Graeff, Carlos Frederico

2015-06-01

This study evaluated the degree of conversion, the free radical entrapment, and the chemical interaction of self-adhesive resin cements mixed with pure hydroxyapatite, as a function of the polymerization activation mode among a variety of commercial self-adhesive cements. Four cements (Embrace WetBond, MaxCem Elite, Bifix SE, and RelyX U200) were mixed, combined with hydroxyapatite, dispensed into molds, and distributed into three groups, according to polymerization protocols: IP (photoactivation for 40s); DP (delayed photoactivation, 10 min self-curing plus 40s light-activated); and CA (chemical activation, no light exposure). Infrared (IR) spectra were obtained and monomer conversion (%) was calculated by comparing the aliphatic-to-aromatic IR absorption peak ratio before and after polymerization (n=10). The free radical entrapment values of the resin cements were characterized using Electron Paramagnetic Resonance (EPR) and the concentration of spins (number of spins/mass) calculated (n=3). Values were compared using two-way ANOVA and Tukey's post-hoc test (α=5%). X-ray diffraction (XRD) characterized the crystallinity of hydroxyapatite as a function of the chemical interactions with the resin cements. The tested parameters varied as a function of resin cement and polymerization protocol. Embrace WetBond and RelyX U200 demonstrated dependence on photoactivation (immediate or delayed), whereas MaxCem Elite exhibited dependence on the chemical activation mode. Bifix SE presented the best balance based on the parameters analyzed, irrespective of the activation protocol. Choice of polymerization protocol affects the degree of conversion, free radical entrapment, and the chemical interaction between hydroxyapatite and self-adhesive resin cement mixtures. Copyright © 2015 Elsevier Ltd. All rights reserved.

Free-radical solution-polymerization of trifluoronitrosomethane with tetrafluoroethylene

NASA Technical Reports Server (NTRS)

Gdickman, S. A.

1972-01-01

Heavy-walled glass reactor, equipped with aerosol-compatible couplings and needle valve and charged with solvent and initiator, is utilized for polymerization. Polymer conversions and reactor/vessel operation are discussed.

Can pulpal floor debonding be detected from occlusal surface displacement in composite restorations?

PubMed

Novaes, João Batista; Talma, Elissa; Las Casas, Estevam Barbosa; Aregawi, Wondwosen; Kolstad, Lauren Wickham; Mantell, Sue; Wang, Yan; Fok, Alex

2018-01-01

Polymerization shrinkage of resin composite restorations can cause debonding at the tooth-restoration interface. Theory based on the mechanics of materials predicts that debonding at the pulpal floor would half the shrinkage displacement at the occlusal surface. The aim of this study is to test this theory and to examine the possibility of detecting subsurface resin composite restoration debonding by measuring the superficial shrinkage displacements. A commercial dental resin composite with linear shrinkage strain of 0.8% was used to restore 2 groups of 5 model Class-II cavities (8-mm long, 4-mm wide and 4-mm deep) in aluminum blocks (8-mm thick, 10-mm wide and 14-mm tall). Group I had the restorations bonded to all cavity surfaces, while Group II had the restorations not bonded to the cavity floor to simulate debonding. One of the proximal surfaces of each specimen was sprayed with fine carbon powder to allow surface displacement measurement by Digital Image Correlation. Images of the speckled surface were taken before and after cure for displacement calculation. The experiment was simulated using finite element analysis (FEA) for comparison. Group I showed a maximum occlusal displacement of 34.7±6.7μm and a center of contraction (COC) near the pulpal floor. Group II had a COC coinciding with the geometric center and showed a maximum occlusal displacement of 17.4±3.8μm. The difference between the two groups was statistically significant (p-value=0.0007). Similar results were obtained by FEA. The theoretical shrinkage displacement was 44.6 and 22.3μm for Group I and II, respectively. The lower experimental displacements were probably caused by slumping of the resin composite before cure and deformation of the adhesive layer. The results confirmed that the occlusal shrinkage displacement of a resin composite restoration was reduced significantly by pulpal floor debonding. Recent in vitro studies seem to indicate that this reduction in shrinkage displacement could be detected by using the most accurate intraoral scanners currently available. Thus, subject to clinical validation, the occlusal displacement of a resin composite restoration may be used to assess its interfacial integrity. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Shrinkage-stress kinetics of photopolymerised resin-composites

NASA Astrophysics Data System (ADS)

Satterthwaite, Julian D.

The use of directly-placed substances as restorative materials in teeth remains the technique of choice for preserving function and form in teeth that have cavities. The current aesthetic restorative materials of choice are resin-composite materials, although these undergo molecular densification during polymerisation, which has deleterious effects. Although shrinkage-strain is the cause, it is the shrinkage-stress effects that may be seen as being responsible for the problems with adhesive resin-based restorations that are encountered clinically, the bond may fail with separation of the material from the cavity wall, leading to marginal discolouration, pulpal irritation and subsequent necrosis, post operative sensitivity, recurrent caries and eventual failure of restorations. Other outcomes include cohesive fracture of enamel or cusps, cuspal movement (strain) and persistent pain. The aims of this research were to characterise the effects of variations in resin-composite formulation on shrinkage-strain and shrinkage-stress kinetics. In particular, the influence of the size and morphology of the dispersed phase was investigated through the study of experimental formulations. Polymerisation shrinkage-strain kinetics were assessed with the bonded-disk method. It was found that resin-composites with spherical filler particles had significantly lower shrinkage-strain compared to those with irregular filler particles. Additionally, shrinkage-strain was found to be dependent on the size of filler particle, and this trend was related, in part, to differences in the degree of conversion. The data were also used to calculate the activation energy for each material, and a relationship between this and filler particle size for the irregular fillers was demonstrated. A fixed-compliance cantilever beam instrument (Bioman) was used for characterisation of shrinkage-stress kinetics. Significant differences were identified between materials in relation to filler particle size and morphology. A hypothesis for these interactions, relating to surface area effects, was presented. The complex interactions leading to the development of shrinkage-stress were investigated further. Shrinkage-stress over a 24 hour period was assessed, and modelled through application of the Kohlrausch-Williams-Watts equation. The effect of variation in specimen dimensions were assessed, and it was shown that the relationship of the specimen height and diameter to shrinkage-stress is a function not only of the C-factor (the ratio of bonded to unbonded surfaces), but also how the C-factor is created. These relationships were characterised and descriptive equations fitted to the data to describe the phenomena. Shrinkage-stress measurements against a variety of test surfaces were also assessed, and the use of stainless steel as a test surface was validated. Finally, exploratory research was undertaken to develop a moire interferometer for the measurement of in-plane displacements and strain arising in teeth due to polymerisation of resin-composite restorations.

Highly efficient reversible addition-fragmentation chain-transfer polymerization in ethanol/water via flow chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Piaoran; Cao, Peng -Fei; Su, Zhe

Here, utilization of a flow reactor under high pressure allows highly efficient polymer synthesis via reversible addition–fragmentation chain-transfer (RAFT) polymerization in an aqueous system. Compared with the batch reaction, the flow reactor allows the RAFT polymerization to be performed in a high-efficiency manner at the same temperature. The adjustable pressure of the system allows further elevation of the reaction temperature and hence faster polymerization. Other reaction parameters, such as flow rate and initiator concentration, were also well studied to tune the monomer conversion and the molar mass dispersity (Ð) of the obtained polymers. Gel permeation chromatography, nuclear magnetic resonance (NMR),more » and Fourier transform infrared spectroscopies (FTIR) were utilized to monitor the polymerization process. With the initiator concentration of 0.15 mmol L –1, polymerization of poly(ethylene glycol) methyl ethermethacrylate with monomer conversion of 52% at 100 °C under 73 bar can be achieved within 40 min with narrow molar mass dispersity (D) Ð (<1.25). The strategy developed here provides a method to produce well-defined polymers via RAFT polymerization with high efficiency in a continuous manner.« less

Correlation between polymerization shrinkage stress and C-factor depends upon cavity compliance.

PubMed

Wang, Zhengzhi; Chiang, Martin Y M

2016-03-01

The literature reports inconsistent results regarding using configuration factor (C-factor) as an indicator to reflect the generation of polymerization shrinkage stress (PS) from dental restorative composites due to the constraint of cavity configuration. The current study aimed at unraveling the complex effects of C-factor on PS based on analytical and experimental approaches together, such that the reported inconsistency can be explained and a significance of C-factor in clinic can be comprehensively provided. Analytical models based on linear elasticity were established to predict PS measured in instruments (testing systems) with different compliances, and complex effects of C-factor on PS were derived. The analyses were validated by experiments using a cantilever beam-based instrument and systematic variation of instrumental compliance. For a general trend, PS decreased with increasing C-factor when measured by instruments with high compliance. However, this trend gradually diminished and eventually reversed (PS became increased with increasing C-factor) by decreasing the system compliance. Our study indicates that the correlation between PS and C-factor are highly dependent on the compliance of testing instrument for PS measurement. This suggests that the current concept on the role of C-factor in the stress development and transmission to tooth structures, higher C-factor produces higher PS due to reduced flow capacity of more confined materials, can be misleading. Thus, the compliance of the prepared tooth (cavity) structure should also be considered in the effect of C-factor on PS. Published by Elsevier Ltd.

Photo-responsive polymeric micelles.

PubMed

Huang, Yu; Dong, Ruijiao; Zhu, Xinyuan; Yan, Deyue

2014-09-07

Photo-responsive polymeric micelles have received increasing attention in both academic and industrial fields due to their efficient photo-sensitive nature and unique nanostructure. In view of the photo-reaction mechanism, photo-responsive polymeric micelles can be divided into five major types: (1) photoisomerization polymeric micelles, (2) photo-induced rearrangement polymeric micelles, (3) photocleavage polymeric micelles, (4) photo-induced crosslinkable polymeric micelles, and (5) photo-induced energy conversion polymeric micelles. This review highlights the recent advances of photo-responsive polymeric micelles, including the design, synthesis and applications in various biomedical fields. Especially, the influence of different photo-reaction mechanisms on the morphology, structure and properties of the polymeric micelles is emphasized. Finally, the possible future directions and perspectives in this emerging area are briefly discussed.

Characterization of methyltrimethoxysilane sol-gel polymerization and the resulting aerogels

NASA Astrophysics Data System (ADS)

Dong, Hanjiang

Methyl-functionalized porous silica is of considerable interest as a low dielectric constant film for semiconductor devices. The structural development of these materials appears to affect their gelation behaviors and impact their mechanical properties and shrinkage during processing. 29Si solution NMR was used to follow the structural evolution of MTMS (methyltrimethoxysilane) polymerization to gelation or precipitation, and thus to better understand the species that affect these properties and gelation behaviors. The effects of pH, water concentration, type of solvents, and synthesis procedures (single step acid catalysis and two-step acid/base catalysis) on MTMS polymerization were discussed. The reactivity of silicon species with different connectivity and the extent of cyclization were found to depend appreciably on the pH value of the sol. A kinetic model is presented to treat the reactivity of both silicon species involved in condensations separately based on the inductive and steric effects of these silicon species. Extensive cyclization in the presence of acid, which was attributed to the steric effects among numerous reaction pathways for the first time, prevents MTMS gelation, whereas gels were obtained from the two-step method with nearly random condensations. The experimental degree of condensation (DC) at the gel point using the two-step procedure was determined to be 0.86, which is considerably higher than that predicted by the current accepted theories. Both chemical and physical origins of this high value were suggested. Aerogels dried by supercritical CO2 extraction were characterized by FTIR, 13C and 29Si solid-state NMR and nitrogen sorption. The existence of three residual groups (Si-OH, Si-OCH3, and Si-OC2H5) was confirmed, but their concentrations are very low compared to silica aerogels. The low concentrations of the residual groups, along with the presence of Si-CH3, make MTMS aerogels permanently hydrophobic. To enhance applicability, MTMS aerogels were successfully prepared that demonstrated shrinkage less than 10% after supercritical drying; proving that the rigidity of the gel network is not the sole factor, suggesting in the literature, to cause the huge shrinkage in many hybrid aerogels reported. An important finding of this work is that MTMS aerogels can be prepared without tedious solvent exchange and surface modification if the molar ratio of water/MTMS increases to 8, substantially reducing the cost of aerogel production. This result was attributed to MTMS's fully condensation and low concentrations of ring species.

Photoinitiated polymerization of 1-vinylimidazole

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joshi, M.G.; Rodriguez, F.

1984-04-01

The photoinitiated polymerization of 1-vinylimidazole (VI) does not follow the classical kinetic scheme for free radical polymerization. Kinetic results for VI suggest a degradative addition reaction between the macroradical and the monomer to produce a relatively stable, unreactive radical, which does not reinitiate polymerization, is low, 1.5 kcal/mol. Among the 3 photoinitiators used, the highest quantum efficiency was demonstrated by 2,2'-diethoxyacetophenone followed by bezoin methyl ether and benzoin isopropyl ether. Under the experimental conditions used, the polymerization of VI does not proceed to complete conversion, and the phenomenon of dead-end polymerization is observed.

Effect of Layering Methods, Composite Type, and Flowable Liner on the Polymerization Shrinkage Stress of Light Cured Dental Composites

DTIC Science & Technology

2011-08-01

composite (Z350 flowable: 3M ESPE), and a silorane-based composite (P90: 3M ESPE). Scotchbond multipurpose adhesive ( 3M ESPE) was applied prior to...syringe. Composites used for filling the cavities were a methacrylate-based universal hybrid composite (Z250: 3M ESPE, St. Paul, MN, USA), a flowable... adhesive was light cured for 10 s using a LED light curing unit (S10: 3M ESPE), and the light intensity was 1200 mW/cm 2 . An acrylic case with

Composite resins in 2013: an update on their progress.

PubMed

Radz, Gary M

2013-01-01

Having steadily evolved and improved over the past several decades, composite resins are providing clinicians with an increased array of options for successfully restoring teeth in a minimally invasive manner. Numerous advances compared to early composite resin systems, such as increased shade availability, reduced polymerization shrinkage, and the development of nanoparticles, have enabled composite resins to offer long-term esthetic solutions for patients. This article summarizes the changes that have occurred, discusses popular applications for the use of composite materials, and presents brief case studies demonstrating their capabilities.

Thermal plasma process for recovering monomers and high value carbons from polymeric materials

DOEpatents

Knight, Richard; Grossmann, Elihu D.; Guddeti, Ravikishan R.

2002-01-01

The present invention relates to a method of recycling polymeric waste products into monomers and high value forms of carbon by pyrolytic conversion using an induction coupled RF plasma heated reactor.

Dimensional change in complete dentures fabricated by injection molding and microwave processing.

PubMed

Keenan, Phillip L J; Radford, David R; Clark, Robert K F

2003-01-01

Acrylic resin complete dentures undergo dimensional changes during polymerization. Techniques with injection molding and polymerization and microwave polymerization are reported to reduce these changes and thereby improve clinical fit. These dimensional changes need to be quantified. The purpose of this study was to compare differences in dimensional changes of simulated maxillary complete dentures during polymerization and storage in water after injection molding and conventional polymerization, or microwave polymerization against a control of conventionally packed and polymerized simulated maxillary complete dentures. Forty identical maxillary denture bases were prepared in dental wax with anatomic teeth. They were invested and the wax eliminated from the molds. Ten specimens each were randomly assigned to 1 of 4 groups. Group 1 was compression molded and conventionally polymerized; group 2 was injection molded and conventionally polymerized (Success); group 3 was injection molded and microwave polymerized (Acron MC); and group 4 was injection molded and microwave polymerized (Microbase). Intermolar width and changes in vertical dimension of occlusion, were determined after polymerization and after storage in water for 28 days. Measurements in triplicate were made between points scribed on the second molar teeth with a traveling microscope (accurate to 0.005 mm). Vertical dimension of occlusion was measured between points scribed on the upper and lower members of an articulator by use of an internal micrometer (accurate to 0.05 mm). Data were analyzed by use of a 1-way analysis of variance with Tukey post-hoc contrasts (P <.05). Polymerization contractions (intermolar widths) for each group were: group 1, -0.24%; group 2, -0.27%; group 3, -0.35%; and group 4, -0.37%. The Microbase specimens had greater shrinkage than conventionally polymerized specimens, but there were no significant differences between the groups. All injection methods had less postpolymerization increase in vertical dimension of occlusion (0.63 to 0.41 mm) than the conventional Trevalon control (0.74 mm), but only group 4 was significantly different (P<.004). After storage in water for 28 days, all specimens increased in vertical dimension of occlusion (0.10% to 0.16%) from polymerization techniques, but there were no significant differences between groups. Within the limitations of this study, injection molding resulted in a slightly less increase of vertical dimension of occlusion than conventional polymerization techniques, the difference being significant for Microbase compared with the conventional Trevalon control.

Radiation-induced controlled polymerization of acrylic acid by RAFT and RAFT-MADIX methods in protic solvents

NASA Astrophysics Data System (ADS)

Sütekin, S. Duygu; Güven, Olgun

2018-01-01

The kinetic investigation of one-pot synthesis of poly(acrylic acid) (PAA) prepared via gamma radiation induced controlled polymerization was reported. PAA homopolymers were prepared by Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization in the presence of trithiocarbonate-based chain transfer agent (CTA) 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) and also by Reversible Addition-Fragmentation/Macromolecular Design by Inter-change of Xanthates (RAFT/MADIX) polymerization in the presence of a xanthate based CTA O-ethyl-S-(1-methoxycarbonyl) ethyl dithiocarbonate (RA1). The polymerizations were performed at room temperature by the virtue of ionizing radiation. Protic solvents were used for the RAFT polymerization of AA considering environmental profits. The linear first-order kinetic plot, close control of molecular weight by the monomer/CTA molar ratio supported that the polymerization proceeds in a living fashion. The linear increase in molecular weight with conversion monitored by Size Exclusion Chromatography (SEC) is another proof of controlling of polymerization. [Monomer]/[RAFT] ratio and conversion was controlled to obtain PAA in the molecular weight range of 6900-35,800 with narrow molecular weight distributions. Reaction kinetics and effect of the amount of RAFT agent were investigated in detail. Between two different types of CTA, trithiocarbonate based DDMAT was found to be more efficient in terms of low dispersity (Đ) and linear first-order kinetic behavior for the radiation induced controlled synthesis of PAA homopolymers.

Fatigue resistance and crack propensity of novel "super-closed" sandwich composite resin restorations in large MOD defects.

PubMed

Magne, Pascal; Silva, Silvana; Andrada, Mauro de; Maia, Hamilton

2016-01-01

To assess the influence of conventional glass ionomer cement (GIC) vs resin-modified GIC (RMGIC) as a base material for novel, super-closed sandwich restorations (SCSR) and its effect on shrinkage-induced crack propensity and in vitro accelerated fatigue resistance. A standardized MOD slottype tooth preparation was applied to 30 extracted maxillary molars (5 mm depth/5 mm buccolingual width). A modified sandwich restoration was used, in which the enamel/dentin bonding agent was applied first (Optibond FL, Kerr), followed by a Ketac Molar (3M ESPE)(group KM, n = 15) or Fuji II LC (GC) (group FJ, n = 15) base, leaving 2 mm for composite resin material (Miris 2, Coltène-Whaledent). Shrinkageinduced enamel cracks were tracked with photography and transillumination. Samples were loaded until fracture or to a maximum of 185,000 cycles under isometric chewing (5 H z), starting with a load of 200 N (5,000 X), followed by stages of 400, 600, 800, 1,000, 1,200, and 1,400 N at a maximum of 30,000 X each. Groups were compared using the life table survival analysis (α = .008, Bonferroni method). Group FJ showed the highest survival rate (40% intact specimens) but did not differ from group KM (20%) or traditional direct restorations (13%, previous data). SCSR generated less shrinkage-induced cracks. Most failures were re-restorable (above the cementoenamel junction [CEJ]). Inclusion of GIC/RMGIC bases under large direct SCSRs does not affect their fatigue strength but tends to decrease the shrinkage-induced crack propensity. The use of GIC/ RMGIC bases and the SCSR is an easy way to minimize polymerization shrinkage stress in large MOD defects without weakening the restoration.

Shrinkage stress compensation in composite-restored teeth: relaxation or hygroscopic expansion?

PubMed

Meriwether, Laurel A; Blen, Bernard J; Benson, Jarred H; Hatch, Robert H; Tantbirojn, Daranee; Versluis, Antheunis

2013-05-01

Polymerization of composite restorations causes shrinkage, which deforms and thus stresses restored teeth. This shrinkage deformation, however, has been shown to decrease over time. The objective was to investigate whether this reduction was caused by hygroscopic expansion or stress relaxation of the composite/tooth complex. Extracted molars were mounted in rigid stainless steel rings with four spherical reference areas. Twelve molars were prepared with large mesioocclusodistal slots, etched, bonded, and restored with a composite material (Filtek Supreme, 3M ESPE) in two horizontal layers. Ten intact molars were the controls. The teeth were stored either in deionized water or silicone oil. They were scanned after preparation (baseline), restoration (0-week), and after 1, 2, and 4 weeks storage. Scanned tooth surfaces were aligned with the baseline using the unchanged reference areas. Cuspal flexure was calculated from lingual and buccal surface deformation. To verify that the restorations had remained bonded, dye penetration at the interfaces was assessed using basic fuchsin dye. Statistical assessment was done by ANOVA followed by Student-Newman-Keuls post hoc test (p=0.05). Substantial cuspal contraction was found for restored teeth after the composite was cured (13-14 μm cuspal flexure). After 4 weeks cuspal contraction decreased significantly for restored teeth stored in water (7.3 ± 3.2) but not for those stored in silicone oil (11.4 ± 5.0). Dye penetration of the occlusal interface was minimal in both groups (106 ± 87 and 21 ± 28 μm in water and silicone oil, respectively). The results suggest that hygroscopic expansion was the main mechanism for shrinkage stress compensation. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Tailoring of physical properties in highly filled experimental nanohybrid resin composites.

PubMed

Pick, Bárbara; Pelka, Matthias; Belli, Renan; Braga, Roberto R; Lohbauer, Ulrich

2011-07-01

To assess the elastic modulus (EM), volumetric shrinkage (VS), and polymerization shrinkage stress (PSS) of experimental highly filled nanohybrid composites as a function of matrix composition, filler distribution, and density. One regular viscosity nanohybrid composite (Grandio, VOCO, Germany) and one flowable nanohybrid composite (Grandio Flow, VOCO) were tested as references along with six highly filled experimental nanohybrid composites (four Bis-GMA-based, one UDMA-based, and one Ormocer®-based). The experimental composites varied in filler size and density. EM values were obtained from the "three-point bending" load-displacement curve. VS was calculated with Archimedes' buoyancy principle. PSS was determined in 1-mm thick specimens placed between two (poly)methyl methacrylate rods (Ø=6mm) attached to an universal testing machine. Data were analyzed using oneway ANOVA, Tukey's test (α=0.05), and linear regression analyses. The flowable composite exhibited the highest VS and PSS but lowest EM. The PSS was significantly lower with Ormocer. The EM was significantly higher among experimental composites with highest filler levels. No significant differences were found between all other experimental composites regarding VS and PSS. Filler density and size did not influence EM, VS, or PSS. Neither the filler configuration nor matrix composition in the investigated materials significantly influenced composite shrinkage and mechanical properties. The highest filled experimental composite seemed to increase EM by keeping VS and PSS low; however, matrix composition seemed to be the determinant factor for shrinkage and stress development. The Ormocer, with reduced PSS, deserves further investigation. Filler size and density did not influence the tested parameters. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Evaluation of Polymerization Efficacy in Composite Resins via FT-IR Spectroscopy and Vickers Microhardness Test.

PubMed

Jafarzadeh, Tahereh-Sadat; Erfan, Mohammad; Behroozibakhsh, Marjan; Fatemi, Mostafa; Masaeli, Reza; Rezaei, Yashar; Bagheri, Hossein; Erfan, Yasaman

2015-01-01

Background and aims. Polymerization efficacy affects the properties and performance of composite resin restorations.The purpose of this study was to evaluate the effectiveness of polymerization of two micro-hybrid, two nano-hybrid and one nano-filled ormocer-based composite resins, cured by two different light-curing systems, using Fourier transformation infrared (FT-IR) spectroscopy and Vickers microhardness testing at two different depths (top surface, 2 mm). Materials and methods. For FT-IR spectrometry, five cylindrical specimens (5mm in diameter × 2 mm in length) were prepared from each composite resin using Teflon molds and polymerized for 20 seconds. Then, 70-μm wafers were sectioned at the top surface and at2mm from the top surface. The degree of conversion for each sample was calculated using FT-IR spectroscopy. For Vickers micro-hardness testing, three cylindrical specimens were prepared from each composite resin and polymerized for 20 seconds. The Vickers microhardness test (Shimadzu, Type M, Japan) was performed at the top and bottom (depth=2 mm) surfaces of each specimen. Three-way ANOVA with independent variables and Tukey tests were performed at 95% significance level. Results. No significant differences were detected in degree of conversion and microhardness between LED and QTH light-curing units except for the ormocer-based specimen, CeramX, which exhibited significantly higher DC by LED. All the composite resins showed a significantly higher degree of conversion at the surface. Microhardness was not significantly affected by depth, except for Herculite XRV Ultra and CeramX, which showed higher values at the surface. Conclusion. Composite resins containing nano-particles generally exhibited more variations in degree of conversion and microhardness.

Evaluation of Polymerization Efficacy in Composite Resins via FT-IR Spectroscopy and Vickers Microhardness Test

PubMed Central

Jafarzadeh, Tahereh-Sadat; Erfan, Mohammad; Behroozibakhsh, Marjan; Fatemi, Mostafa; Masaeli, Reza; Rezaei, Yashar; Bagheri, Hossein; Erfan, Yasaman

2015-01-01

Background and aims. Polymerization efficacy affects the properties and performance of composite resin restorations.The purpose of this study was to evaluate the effectiveness of polymerization of two micro-hybrid, two nano-hybrid and one nano-filled ormocer-based composite resins, cured by two different light-curing systems, using Fourier transformation infrared (FT-IR) spectroscopy and Vickers microhardness testing at two different depths (top surface, 2 mm). Materials and methods. For FT-IR spectrometry, five cylindrical specimens (5mm in diameter × 2 mm in length) were prepared from each composite resin using Teflon molds and polymerized for 20 seconds. Then, 70-μm wafers were sectioned at the top surface and at2mm from the top surface. The degree of conversion for each sample was calculated using FT-IR spectroscopy. For Vickers micro-hardness testing, three cylindrical specimens were prepared from each composite resin and polymerized for 20 seconds. The Vickers microhardness test (Shimadzu, Type M, Japan) was performed at the top and bottom (depth=2 mm) surfaces of each specimen. Three-way ANOVA with independent variables and Tukey tests were performed at 95% significance level. Results. No significant differences were detected in degree of conversion and microhardness between LED and QTH light-curing units except for the ormocer-based specimen, CeramX, which exhibited significantly higher DC by LED. All the composite resins showed a significantly higher degree of conversion at the surface. Microhardness was not significantly affected by depth, except for Herculite XRV Ultra and CeramX, which showed higher values at the surface. Conclusion. Composite resins containing nano-particles generally exhibited more variations in degree of conversion and microhardness. PMID:26889359

Effect of phase inversion on microporous structure development of Al 2O 3/poly(vinylidene fluoride-hexafluoropropylene)-based ceramic composite separators for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Jeong, Hyun-Seok; Kim, Dong-Won; Jeong, Yeon Uk; Lee, Sang-Young

To improve the thermal shrinkage of the separators that are essential to securing the electrical isolation between electrodes in lithium-ion batteries, we develop a new separator based on a ceramic composite membrane. Introduction of microporous, ceramic coating layers onto both sides of a polyethylene (PE) separator allows such a progress. The ceramic coating layers consist of nano-sized alumina (Al 2O 3) powders and polymeric binders (PVdF-HFP). The microporous structure of the ceramic coating layers is observed to be crucial to governing the thermal shrinkage as well as the ionic transport of the ceramic composite separators. This microporous structure is determined by controlling the phase inversion, more specifically, nonsolvent (water) contents in the coating solutions. To provide a theoretical basis for this approach, a pre-investigation on the phase diagram for a ternary mixture comprising PVdF-HFP, acetone, and water is conducted. On the basis of this observation, the effect of phase inversion on the morphology and air permeability (i.e. Gurley value) of ceramic coating layers is systematically discussed. In addition, to explore the application of ceramic composite separators to lithium-ion batteries, the influence of the structural change in the coating layers on the thermal shrinkage and electrochemical performance of the separators is quantitatively identified.

Insightful understanding of the role of clay topology on the stability of biomimetic hybrid chitosan-clay thin films and CO2-dried porous aerogel microspheres.

PubMed

Frindy, Sana; Primo, Ana; Qaiss, Abou El Kacem; Bouhfid, Rachid; Lahcini, Mohamed; Garcia, Hermenegildo; Bousmina, Mosto; El Kadib, Abdelkrim

2016-08-01

Three natural clay-based microstructures, namely layered montmorillonite (MMT), nanotubular halloysite (HNT) and micro-fibrillar sepiolite (SP) were used for the synthesis of hybrid chitosan-clay thin films and porous aerogel microspheres. At a first glance, a decrease in the viscosity of the three gel-forming solutions was noticed as a result of breaking the mutual polymeric chains interaction by the clay microstructure. Upon casting, chitosan-clay films displayed enhanced hydrophilicity in the order CS

Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of 4-Vinylbenzaldehyde

PubMed Central

Sun, Guorong; Cheng, Chong; Wooley, Karen L.

2008-01-01

The direct reversible addition fragmentation chain transfer (RAFT) polymerization of 4-vinylbenzaldehyde (VBA) was established as a new synthetic method for the preparation of well-defined poly(vinylbenzaldehyde) (PVBA), a polymer having reactive aldehyde side chain substiuents. RAFT polymerization of VBA was investigated using S-1-dodecyl-S’-(α,α’-dimethyl-α”-acetic acid)trithiocarbonate (DDMAT) as chain transfer agent (CTA) and 2,2′-azobis(isobutyronitrile) (AIBN) as initiator in 1,4-dioxane or 2-butanone at 70-75 °C for 7.5-22.5 h. With 45-76% of monomer conversion, the resulting PVBA had well controlled number-average molecular weight (Mn) and low polydispersity (PDI < 1.17). The living characteristic of the RAFT polymerization process was confirmed by the linearity between the Mn values of PVBA and monomer conversions. Well-defined PVBA was further used as a macromolecular chain transfer agent (macro-CTA) in RAFT polymerization of styrene (St), and a block copolymer PVBA-b-PSt with relatively low polydispersity (PDI = 1.20) was successfully synthesized. PMID:19066633

Effect of various visible light photoinitiators on the polymerization and color of light-activated resins.

PubMed

Arikawa, Hiroyuki; Takahashi, Hideo; Kanie, Takahito; Ban, Seiji

2009-07-01

The purpose of this study was to investigate effects of various visible light photoinitiators on the polymerization efficiency and color of the light-activated resins. Four photoinitiators, including camphorquinone, phenylpropanedione, monoacrylphosphine oxide (TPO), and bisacrylphosphine oxide (Ir819), were used. Each photoinitiator was dissolved in a Bis-GMA and TEGDMA monomer mixture. Materials were polymerized using dental quartz-tungsten halogen lamp (QTH), plasma-ark lamp and blue LED light-curing units, and a custom-made violet LED light unit. The degree of monomer conversion and CIE L*a*b* color values of the resins were measured using a FTIR and spectral transmittance meter. The degree of monomer conversions of TPO- and Ir819-containing resins polymerized with the violet-LED unit were higher than camphorquinone-containing resin polymerized with the QTH light-curing unit. The lowest color values were observed for the TPO-containing resin. Our results indicate that the TPO photoinitiator and the violet-LED light unit may provide a useful and improved photopolymerization system for dental light-activated resins.

Supported organometallic catalysts for hydrogenation and Olefin Polymerization

DOEpatents

Marks, Tobin J.; Ahn, Hongsang

2001-01-01

Novel heterogeneous catalysts for the which hydrogenation of olefins and arenes with high conversion rates under ambient conditions and the polymerization of olefins have been developed. The catalysts are synthesized from Ziegler-type precatalysts by supporting them on sulfate-modified zirconia.

Photocatalytic CO2 conversion by polymeric carbon nitrides.

PubMed

Fang, Yuanxing; Wang, Xinchen

2018-05-10

CO2 is a vital compond for life, and its concentration significantly affects the living environment of the Earth. Extensive effort has been devoted to balance its concentration. Among the developed approaches, photocatalytic CO2 conversion is considered as an ideal option. Previous reports suggest polymeric carbon nitride (PCN) can be effectively used as a metal-free photocatalyst to convert CO2. Herein, the recent developments of PCN and the related photocatalysts for CO2 conversion are summarized from the fundamental of using PCN, and their extended applications through molecular modification and physical/chemical coupling with other substances. The concluding remarks finally indicate the future challenges of using PCN materials for relevant solar-driven applications.

A proposal of microtomography evaluation for restoration interface gaps.

PubMed

Meleo, Deborah; Manzon, Licia; Pecci, Raffaella; Zuppante, Francesca; Bedini, Rossella

2012-01-01

Nowadays, several adhesive systems are used in dental restoration and they are evaluated by clinical research. In vitro evaluations are often made by means of traditional observation techniques (for example scanning electron microscope (SEM), while 3D cone-beam microtomography technique (3D micro-CT), that can be able to generate 3D sample images without any sample treatment during acquisition data, is going to be used a lot in the next few years. In dental cavity restored with composite, it is possible to predict the presence of gaps due to polymerization shrinkage; that is the reason this work purpose is to reveal by 3D images and measure by micro-CT analysis the voids generated applying the most used adhesive systems at the moment. By means of microtomographic analysis is proposed an aid to overcome bidimensional SEM investigation limits like random observation of sample surface, sample sectioning (to see inside it with the relative possible structural alterations induced on the same sample) and the gold sputtering treatment. For this experimental work, human crown teeth have been selected, all restored with the same composite material, using five adhesive systems. After about 48 hours each tooth has been acquired by means of Skyscan 1072 micro-CT instrument and then processed by 3D reconstruction and micro-CT analyser software. Three adhesive systems have showed 3D micro-CT images with not as much voids as expected, with a very little extent. This kind of micro-CT in vitro evaluation proposal suggests a method to observe and quantify the voids generated after polymerization shrinkage during tooth restoration.

Effect of a non-thermal, atmospheric-pressure, plasma brush on conversion of model self-etch adhesive formulations compared to conventional photo-polymerization

PubMed Central

Chen, Mingsheng; Zhang, Ying; Yao, Xiaomei; Li, Hao; Yu, Qingsong; Wang, Yong

2012-01-01

Objective To determine the effectiveness and efficiency of non-thermal, atmospheric plasmas for inducing polymerization of model dental self-etch adhesives. Methods The monomer mixtures used were bis-[2-(methacryloyloxy)ethyl] phosphate (2MP) and 2-hydroxyethyl methacrylate (HEMA), with mass ratios of 70/30, 50/50 and 30/70. Water was added to the above formulations: 10–30 wt%. These monomer/water mixtures were treated steadily for 40 s under a non-thermal atmospheric plasma brush working at temperatures from 32° to 35°C. For comparison, photo-initiators were added to the above formulations for photo-polymerization studies, which were light-cured for 40 s. The degree of conversion (DC) of both the plasma- and light-cured samples was measured using FTIR spectroscopy with an attenuated total reflectance attachment. Results The non-thermal plasma brush was effective in inducing polymerization of the model self-etch adhesives. The presence of water did not negatively affect the DC of plasma-cured samples. Indeed, DC values slightly increased, with increasing water content in adhesives: from 58.3% to 68.7% when the water content increased from 10% to 30% in the adhesives with a 50/50 (2MP/HEMA) mass ratio. Conversion values of the plasma-cured groups were higher than those of light-cured samples with the same mass ratio and water content. Spectral differences between the plasma- and light-cured groups indicate subtle structural distinctions in the resultant polymer networks. Significance This research if the first to demonstrate that the non-thermal plasma brush induces polymerization of model adhesives under clinical settings by direct/indirect energy transfer. This device shows promise for polymerization of dental composite restorations having enhanced properties and performance. PMID:23018084

Gel Point Suppression in RAFT Polymerization of Pure Acrylic Cross-Linker Derived from Soybean Oil.

PubMed

Yan, Mengguo; Huang, Yuerui; Lu, Mingjia; Lin, Fang-Yi; Hernández, Nacú B; Cochran, Eric W

2016-08-08

Here we report the reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylated epoxidized soybean oil (AESO), a cross-linker molecule, to high conversion (>50%) and molecular weight (>100 kDa) without macrogelation. Surprisingly, gelation is suppressed in this system far beyond the expectations predicated both on Flory-Stockmeyer theory and multiple other studies of RAFT polymerization featuring cross-linking moieties. By varying AESO and initiator concentrations, we show how intra- versus intermolecular cross-linking compete, yielding a trade-off between the degree of intramolecular linkages and conversion at gel point. We measured polymer chain characteristics, including molecular weight, chain dimensions, polydispersity, and intrinsic viscosity, using multidetector gel permeation chromatography and NMR to track polymerization kinetics. We show that not only the time and conversion at macrogelation, but also the chain architecture, is largely affected by these reaction conditions. At maximal AESO concentration, the gel point approaches that predicted by the Flory-Stockmeyer theory, and increases in an exponential fashion as the AESO concentration decreases. In the most dilute solutions, macrogelation cannot be detected throughout the entire reaction. Instead, cyclization/intramolecular cross-linking reactions dominate, leading to microgelation. This work is important, especially in that it demonstrates that thermoplastic rubbers could be produced based on multifunctional renewable feedstocks.

GDP-tubulin incorporation into growing microtubules modulates polymer stability.

PubMed

Valiron, Odile; Arnal, Isabelle; Caudron, Nicolas; Job, Didier

2010-06-04

Microtubule growth proceeds through the endwise addition of nucleotide-bound tubulin dimers. The microtubule wall is composed of GDP-tubulin subunits, which are thought to come exclusively from the incorporation of GTP-tubulin complexes at microtubule ends followed by GTP hydrolysis within the polymer. The possibility of a direct GDP-tubulin incorporation into growing polymers is regarded as hardly compatible with recent structural data. Here, we have examined GTP-tubulin and GDP-tubulin incorporation into polymerizing microtubules using a minimal assembly system comprised of nucleotide-bound tubulin dimers, in the absence of free nucleotide. We find that GDP-tubulin complexes can efficiently co-polymerize with GTP-tubulin complexes during microtubule assembly. GDP-tubulin incorporation into microtubules occurs with similar efficiency during bulk microtubule assembly as during microtubule growth from seeds or centrosomes. Microtubules formed from GTP-tubulin/GDP-tubulin mixtures display altered microtubule dynamics, in particular a decreased shrinkage rate, apparently due to intrinsic modifications of the polymer disassembly properties. Thus, although microtubules polymerized from GTP-tubulin/GDP-tubulin mixtures or from homogeneous GTP-tubulin solutions are both composed of GDP-tubulin subunits, they have different dynamic properties, and this may reveal a novel form of microtubule "structural plasticity."

Influence of light polymerization modes on degree of conversion and crosslink density of dental composites.

PubMed

da Silva, Eduardo Moreira; Poskus, Laiza Tatiana; Guimarães, José Guilherme Antunes; de Araújo Lima Barcellos, Alexandre; Fellows, Carlos Eduardo

2008-03-01

This study analyzed the influence of light polymerization modes on crosslink density (CD) and the degree of conversion (DC) of dental composites. A minifilled hybrid and a nanofilled dental composite were photoactivated with two light polymerization modes: Conventional-850 mW/cm2 for 20 s and Gradual-50 up to 1,000 mW/cm2 for 10 s+1,000 mW/cm2 for 10 s. DC was determined by the use of FT-Raman-spectrometer. A softening test, using Knoop diamond indentation, was carried out at the top and bottom of 2 mm thick dental composite disks, before and after storage in 100% ethanol for 24 h, in order to represent the amount of crosslink density. Data were analyzed by ANOVA and Student-Newman-Keuls' multiple range test (alpha=0.05). The DC was influenced by light polymerization modes, with Gradual mode presenting lower DC. On bottom surfaces, the nanofilled dental composite was more susceptible to softening by ethanol than minifilled hybrid, and gradual light polymerization of nanofilled dental composite resulted in more softening than when conventional light polymerization was used. The results suggest that nanofilled composites are capable undergoing more plasticization if applied in thick increments.

Impact of solvent selection on graft polymerization of acrylamide onto starch

USDA-ARS?s Scientific Manuscript database

The impact on polymer properties [molecular weight, monomer conversion, graft content, graft efficiency and anhydroglucose units between grafts (AGU/graft)] that result from changing the solvent for the graft co-polymerization of acrylamide onto starch from water to dimethylsulfoxide (DMSO) was eval...

(4-Methoxyphenyl)(3,4,5-trimethoxyphenyl)methanone inhibits tubulin polymerization, induces G{sub 2}/M arrest, and triggers apoptosis in human leukemia HL-60 cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Magalhães, Hemerson I.F.; Centro de Ciências da Saúde, Departamento de Ciências Farmacêuticas, Universidade Federal da Paraíba, João Pessoa, Paraíba; Wilke, Diego V.

2013-10-01

(4-Methoxyphenyl)(3,4,5-trimethoxyphenyl)methanone (PHT) is a known cytotoxic compound belonging to the phenstatin family. However, the exact mechanism of action of PHT-induced cell death remains to be determined. The aim of this study was to investigate the mechanisms underlying PHT-induced cytotoxicity. We found that PHT displayed potent cytotoxicity in different tumor cell lines, showing IC{sub 50} values in the nanomolar range. Cell cycle arrest in G{sub 2}/M phase along with the augmented metaphase cells was found. Cells treated with PHT also showed typical hallmarks of apoptosis such as cell shrinkage, chromatin condensation, phosphatidylserine exposure, increase of the caspase 3/7 and 8 activation,more » loss of mitochondrial membrane potential, and internucleosomal DNA fragmentation without affecting membrane integrity. Studies conducted with isolated tubulin and docking models confirmed that PHT binds to the colchicine site and interferes in the polymerization of microtubules. These results demonstrated that PHT inhibits tubulin polymerization, arrests cancer cells in G{sub 2}/M phase of the cell cycle, and induces their apoptosis, exhibiting promising anticancer therapeutic potential. - Highlights: • PHT inhibits tubulin polymerization. • PHT arrests cancer cells in G{sub 2}/M phase of the cell cycle. • PHT induces caspase-dependent apoptosis.« less

Magnetic Resonance Imaging of Gel-cast Ceramic Composites

DOE R&D Accomplishments Database

Dieckman, S. L.; Balss, K. M.; Waterfield, L. G.; Jendrzejczyk, J. A.; Raptis, A. C.

1997-01-16

Magnetic resonance imaging (MRI) techniques are being employed to aid in the development of advanced near-net-shape gel-cast ceramic composites. MRI is a unique nondestructive evaluation tool that provides information on both the chemical and physical properties of materials. In this effort, MRI imaging was performed to monitor the drying of porous green-state alumina - methacrylamide-N.N`-methylene bisacrylamide (MAM-MBAM) polymerized composite specimens. Studies were performed on several specimens as a function of humidity and time. The mass and shrinkage of the specimens were also monitored and correlated with the water content.

Effect of blue and violet light on polymerization shrinkage vectors of a CQ/TPO-containing composite.

PubMed

Sampaio, Camila S; Atria, Pablo J; Rueggeberg, Frederick A; Yamaguchi, Satoshi; Giannini, Marcelo; Coelho, Paulo G; Hirata, Ronaldo; Puppin-Rontani, Regina M

2017-07-01

To evaluate the effect of light-curing wavelengths on composite filler particle displacement, and thus to visualize localized polymerization shrinkage in a resin-based composite (RBC) containing camphorquinone (CQ) and Lucirin TPO (TPO). Three light-curing units (LCUs) were used to light-cure a RBC containing CQ and TPO: a violet-only, a blue-only, and a dual-wavelength, conventional (Polywave ® , emitting violet and blue wavelengths simultaneously). Zirconia fillers were added to the RBC to act as filler particle displacement tracers. LCUs were characterized for total emitted power (mW) and spectral irradiant output (mW/cm 2 /nm). 2-mm high, 7-mm diameter silanized glass cylindrical specimens were filled in a single increment with the RBC, and micro-computed tomography (μ-CT) scans were obtained before and after light-curing, according to each LCU (n=6). Filler particle movement identified polymerization shrinkage vectors, traced using software, at five depths (from 0 up to 2mm): top, top-middle, middle, middle-bottom and bottom. Considering different RBC depths within the same LCU, use of violet-only and conventional LCUs showed filler particle movement decreased with increased depth. Blue-only LCU showed homogeneous filler particle movement along the depths. Considering the effect of different LCUs within the same depth, filler particle movement within LCUs was not statistically different until the middle of the samples (P>.05). However, at the middle-bottom and bottom depths (1.5 and 2mm, respectively), blue-only LCU compared to violet-only LCU showed higher magnitude of displacement vector values (P<.05). Use of the conventional LCU showed filler displacement magnitudes that were not significantly different than blue-only and violet-only LCUs at any depth (P>.05). With respect to the direction of particle movement vectors, use of violet-only LCU showed a greater displacement when close to the incident violet LED; blue-only LCU showed equally distributed particle displacement values within entire depth among the samples; and the conventional LCU showed greater filler displacement closer to the blue LED locations. Filler particle displacement in a RBC as a result of light-curing is related to localized application of light wavelength and total emitted power of the light emitted on the top surface of the RBC. When the violet LED is present (violet-only and conventional LCUs), filler particle displacement magnitude decreased with increased depth, while results using the blue-only LED show a more consistent pattern of displacement. Clinically, these results correlate to production of different characteristics of curing within a RBC restoration mass, depending on localized wavelengths applied to the irradiated surface. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Physical Properties of an Ag-Doped Bioactive Flowable Composite Resin

PubMed Central

Kattan, Hiba; Chatzistavrou, Xanthippi; Boynton, James; Dennison, Joseph; Yaman, Peter; Papagerakis, Petros

2015-01-01

The aim of this work was to study the physical and antibacterial properties of a flowable resin composite incorporating a sol-gel derived silver doped bioactive glass (Ag-BGCOMP). The depth of the cure was calculated by measuring the surface micro-hardness for the top and bottom surfaces. The volumetric polymerization shrinkage was measured by recording the linear shrinkage as change in length, while the biaxial flexural strength was studied measuring the load at failure. The antibacterial properties of the samples were tested against Streptococcus mutans (S. mutans) and Lactobacillus casei (L. casei). The measured values were slightly decreased for all tested physical properties compared to those of control group (flowable resin composite without Ag-BG), however enhanced bacteria inhibition was observed for Ag-BGCOMP. Ag-BGCOMP could find an application in low stress-bearing areas as well as in small cavity preparations to decrease secondary caries. This work provides a good foundation for future studies on evaluating the effects of Ag-BG addition into packable composites for applications in larger cavity preparations where enhanced mechanical properties are needed. PMID:28793463

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes

NASA Astrophysics Data System (ADS)

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-01

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes.

PubMed

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-06

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

Improved resolution of 3D printed scaffolds by shrinking.

PubMed

Chia, Helena N; Wu, Benjamin M

2015-10-01

Three-dimensional printing (3DP) uses inkjet printheads to selectively deposit liquid binder to adjoin powder particles in a layer-by-layer fashion to create a computer-modeled 3D object. Two general approaches for 3DP have been described for biomedical applications (direct and indirect 3DP). The two approaches offer competing advantages, and both are limited by print resolution. This study describes a materials processing strategy to enhance 3DP resolution by controlled shrinking net-shape scaffolds. Briefly, porogen preforms are printed and infused with the desired monomer or polymer solution. After solidification or polymerization, the porogen is leached and the polymer is allowed to shrink by controlled drying. Heat treatment is performed to retain the dimensions against swelling forces. The main objective of this study is to determine the effects of polymer content and post-processing on dimension, microstructure, and thermomechanical properties of the scaffold. For polyethylene glycol diacrylate (PEG-DA), reducing polymer content corresponded with greater shrinkage with maximum shrinkage of ∼80 vol% at 20% vol% PEG-DA. The secondary heat treatment retains the microarchitecture and new dimensions of the scaffolds, even when the heat-treated scaffolds are immersed into water. To demonstrate shrinkage predictability, 3D components with interlocking positive and negative features were printed, processed, and fitted. This material processing strategy provides an alternative method to enhance the resolution of 3D scaffolds, for a wide range of polymers, without optimizing the binder-powder interaction physics to print each material combination. © 2014 Wiley Periodicals, Inc.

Temperature Rise during Primer, Adhesive, and Composite Resin Photopolymerization of a Low-Shrinkage Composite Resin under Caries-Like Dentin Lesions

PubMed Central

Mousavinasab, Sayed-Mostafa; Khoroushi, Maryam; Moharreri, Mohammadreza

2012-01-01

Objective. This study evaluated temperature rise of low-shrinkage (LS) self-etch primer (P), LS self-etch adhesive (A), and P90 silorane-based composite resin systems, photopolymerized under normal and artificially demineralized dentin. Methods. Forty 1.5 mm-thick dentin discs were prepared from sound human molars, half of which were demineralized. Temperature rise was measured during photopolymerization using a K-type thermocouple under the discs: 10 s and 40 s irradiation of the discs (controls/groups 1 and 2); 10 s irradiation of primer (P), 10 s irradiation of adhesive (A), 40 s irradiation of P90 without P and A, and 40 s irradiation of P90 with P and A (groups 3 to 6, resp.). The samples were photopolymerized using an LED unit under 550 mW/cm2 light intensity. Data was analyzed using repeated measures ANOVA and paired-sample t-test (α = 0.05). Results. There were no significant differences in temperature rise means between the two dentin samples for each irradiation duration (P > 0.0001), with significant differences between the two irradiation durations (P > 0.0001). Temperature rise measured with 40 s irradiation was significantly higher than that of 10 s duration for undemineralized and demineralized dentin P < 0.0001). Conclusions. Light polymerization of P90 low-shrinkage composite resin resulted in temperature rise approaching threshold value under artificially demineralized and undemineralized dentin. PMID:23320185

Multi-walled carbon nanotube structural instability with/without metal nanoparticles under electron beam irradiation

NASA Astrophysics Data System (ADS)

Khan, Imran; Huang, Shengli; Wu, Chenxu

2017-12-01

The structural transformation of multi-walled carbon nanotubes (MWCNT) under electron beam (e-beam) irradiation at room temperature is studied, with respect to a novel passivation effect due to gold nanoparticles (Au NPs). MWCNT structural evolution induced by energetic e-beam irradiation leads to faster shrinkage, as revealed via in situ transmission electron microscopy, while MWCNT surface modification with Au NPs (Au-MWCNT) slows down the shrinkage by impeding the structural evolution process for a prolonged time under the same irradiation conditions. The new relationship between MWCNT and Au-MWCNT shrinking radii and irradiation time illustrates that the MWCNT shrinkage rate is faster than either theoretical predictions or the same process in Au-MWCNTs. As compared with the outer surface energy (positive curvature), the inner surface energy (negative curvature) of the MWCNT contributes more to the athermal evaporation of tube wall atoms, leading to structural instability and shrinkage under e-beam irradiation. Conversely, Au NPs possess only outer surface energy (positive curvature) compared with the MWCNT. Their presence on MWCNT surfaces retards the dynamics of MWCNT structural evolution by slowing down the evaporation process of carbon atoms, thus restricting Au-MWCNT shrinkage. Au NP interaction and growth evolves athermally on MWCNT surfaces, exhibits increase in their size, and indicates the association of this mechanism with the coalescence induced by e-beam activated electronic excitations. Despite their growth, Au NPs show extreme structural stability, and remain crystalline under prolonged irradiation. It is proposed that the surface energy of MWCNTs and Au NPs, together with e-beam activated soft modes or lattice instability effects, predominantly govern all the above varieties of structural evolution.

Wetlands shrinkage, fragmentation and their links to agriculture in the Muleng-Xingkai Plain, China.

PubMed

Song, Kaishan; Wang, Zongming; Li, Lin; Tedesco, Lenore; Li, Fang; Jin, Cui; Du, Jia

2012-11-30

In the past five decades, the wetlands in the Muleng-Xingkai Plain, Northeast China, have experienced rapid shrinkage and fragmentation. In this study, wetlands cover change and agricultural cultivation were investigated through a time series of thematic maps from 1954, and Landsat satellite images representing the last five decades (1976, 1986, 1995, 2000, and 2005). Wetlands shrinkage and fragmentation were studied based on landscape metrics and the land use changes transition matrix. Furthermore, the driving forces were explored according to socioeconomic development and major natural environmental factors. The results indicate a significant decrease in the wetlands area in the past five decades, with an average annual decrease rate of 9004 ha/yr. Of the 625,268 ha of native wetlands in 1954, approximately 64% has been converted to other land use types by 2005, of which conversion to cropland accounts for the largest share (83%). The number of patches decreased from 1272 (1954) to 197 (1986) and subsequently increased to 326 (2005). The mean patch size changed from 480 ha (1954) to 1521 ha (1976), and then steadily decreased to 574 ha (2005). The largest patch index (total core area index) indicates wetlands shrinkage with decreased values from 31.73 (177,935 ha) to 3.45 (39,421 ha) respectively. Climatic changes occurred over the study period, providing a potentially favorable environment for agricultural development. At the same time population, groundwater harvesting, and fertilizer application increased significantly, resulting in wetlands degradation. According to the results, the shrinkage and fragmentation of wetlands could be explained by socioeconomic development and secondarily aided by changing climatic conditions. Copyright © 2012 Elsevier Ltd. All rights reserved.

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy.

PubMed

Marín-Yaseli, Margarita R; Moreno, Miguel; de la Fuente, José L; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-15

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH 4 CN and NaCN, at middle temperatures between 4 and 38°C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH 4 CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy

NASA Astrophysics Data System (ADS)

Marín-Yaseli, Margarita R.; Moreno, Miguel; de la Fuente, José L.; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-01

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH4CN and NaCN, at middle temperatures between 4 and 38 °C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH4CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study.

Aqueous dispersion polymerization: a new paradigm for in situ block copolymer self-assembly in concentrated solution.

PubMed

Sugihara, Shinji; Blanazs, Adam; Armes, Steven P; Ryan, Anthony J; Lewis, Andrew L

2011-10-05

Reversible addition-fragmentation chain transfer polymerization has been utilized to polymerize 2-hydroxypropyl methacrylate (HPMA) using a water-soluble macromolecular chain transfer agent based on poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC). A detailed phase diagram has been elucidated for this aqueous dispersion polymerization formulation that reliably predicts the precise block compositions associated with well-defined particle morphologies (i.e., pure phases). Unlike the ad hoc approaches described in the literature, this strategy enables the facile, efficient, and reproducible preparation of diblock copolymer spheres, worms, or vesicles directly in concentrated aqueous solution. Chain extension of the highly hydrated zwitterionic PMPC block with HPMA in water at 70 °C produces a hydrophobic poly(2-hydroxypropyl methacrylate) (PHPMA) block, which drives in situ self-assembly to form well-defined diblock copolymer spheres, worms, or vesicles. The final particle morphology obtained at full monomer conversion is dictated by (i) the target degree of polymerization of the PHPMA block and (ii) the total solids concentration at which the HPMA polymerization is conducted. Moreover, if the targeted diblock copolymer composition corresponds to vesicle phase space at full monomer conversion, the in situ particle morphology evolves from spheres to worms to vesicles during the in situ polymerization of HPMA. In the case of PMPC(25)-PHPMA(400) particles, this systematic approach allows the direct, reproducible, and highly efficient preparation of either block copolymer vesicles at up to 25% solids or well-defined worms at 16-25% solids in aqueous solution.

System compliance dictates the effect of composite filler content on polymerization shrinkage stress.

PubMed

Wang, Zhengzhi; Chiang, Martin Y M

2016-04-01

The effect of filler content in dental restorative composites on the polymerization shrinkage stress (PS) is not straightforward and has caused much debate in the literature. Our objective in this study was to clarify the PS/filler content relationship based on analytical and experimental approaches, so that guidelines for materials comparison in terms of PS and clinical selection of dental composites with various filler content can be provided. Analytically, a simplified model based on linear elasticity was utilized to predict PS as a function of filler content under various compliances of the testing system, a cantilever beam-based instrument used in this study. The predictions were validated by measuring PS of composites synthesized using 50/50 mixtures of two common dimethacrylate resins with a variety of filler contents. Both experiments and predictions indicated that the influence of filler content on the PS highly depended on the compliance of the testing system. Within the clinic-relevant range of compliances and for the specific sample configuration tested, the PS increased with increasing filler content at low compliance of instrument, while increasing the compliance caused the effect of filler content on the PS to gradually diminish. Eventually, at high compliance, the PS inverted and decreased with increasing filler content. This compliance-dependent effect of filler content on PS suggests: (1) for materials comparison in terms of PS, the specific compliance at which the comparison being done should always be reported and (2) clinically, composites with relatively lower filler content could be selected for such cavities with relatively lower compliance (e.g. a Class-I cavity with thick tooth walls or the basal part in a cavity) and vice versa in order to reduce the final PS. Published by Elsevier Ltd.

Zn-doped etch-and-rinse model dentin adhesives: Dentin bond integrity, biocompatibility, and properties.

PubMed

Barcellos, Daphne Câmara; Fonseca, Beatriz Maria; Pucci, César Rogério; Cavalcanti, Bruno das Neves; Persici, Erasmo De Souza; Gonçalves, Sérgio Eduardo de Paiva

2016-07-01

This study assessed a 6 month resin/dentin bond's durability and cytotoxic effect of Zn-doped model dentin adhesives. The mechanical and physicochemical properties were also tested. A model etch-and-rinse single-bottle adhesive was formulated (55wt.% Bis-GMA, 45wt.% HEMA, 0.5wt.% CQ, 0.5wt.% DMAEMA) and Zinc methacrylate (Zn-Mt) or ZnO nanoparticles (ZnOn) were added to the model's adhesive, resulting in three groups: Group Control (control model adhesive); Group Zn-Mt (1wt.% Zn-Mt incorporated to adhesive) and Group ZnOn (1wt.% ZnOn incorporated to adhesive). The microtensile bond strength (mTBS) was assessed after 24h or 6 months in water storage. Mechanical properties (diametral tensile strength/DTS, flexural strength/FS, flexural modulus/FM, resilience modulus/RM, and compressive strength/CS) and physicochemical properties (polymerization shrinkage/PS, contact angle/CA, water sorption/WS, and water solubility/WS) were also tested. Cytotoxicity was evaluated with SRB biochemical assay. No significant difference in the DTS, FS, FM, CS, CA, WS, and WS were found when 1% of ZnOn or Zn-Mt was added to the model dentin adhesive. Group Zn-Mt decreased the RM of adhesive. Groups Zn-Mt and ZnOn decreased the PS of adhesives. Group ZnOn reduced the cytotoxicity of adhesive. Group ZnOn preserved mTBS after 6 months storage without degradation areas as seen by SEM analysis. The 1wt.% ZnOn may preserve the integrity of the hybrid layer and may reduce cytotoxicity and polymerization shrinkage of model dentin adhesive. The addition of Zn-Mt to the adhesive had no beneficial effects. Copyright © 2016 The Academy of Dental Materials. All rights reserved.

Accuracy of five implant impression technique: effect of splinting materials and methods

PubMed Central

Cho, Sung-Bum

2011-01-01

PURPOSE The aim of this study was to evaluate the effect of dimensional stability of splinting material on the accuracy of master casts. MATERIALS AND METHODS A stainless steel metal model with 6 implants embedded was used as a master model. Implant level impressions were made after square impression copings were splinted using 5 different techniques as follows. (1) Splinted with autopolymerizing resin and sectioned, reconnected to compensate polymerization shrinkage before the impression procedure. (2) Splinted with autopolymerizing resin just before impression procedure. (3) Primary impression made with impression plaster and secondary impression were made over with polyether impression material. (4) Splinted with impression plaster. (5) Splinted with VPS bite registration material. From master model, 5 impressions and 5 experimental casts, total 25 casts were made for each of 5 splinting methods. The distortion values of each splinting methods were measured using coordinate measuring machine, capable of recordings in the x-, y-, z-axes. A one-way analysis of variance (ANOVA) at a confidence level of 95% was used to evaluate the data and Tukey's studentized range test was used to determine significant differences between the groups. RESULTS Group 1 showed best accuracy followed by Group 3 & 4. Group 2 and 5 showed relatively larger distortion value than other groups. No significant difference was found between group 3, 4, 5 in x-axis, group 2, 3, 4 in y-axis and group 1, 3, 4, 5 in z-axis (P<.0001). CONCLUSION Both Splinting impression copings with autopolymerizing resin following compensation of polymerization shrinkage and splinting method with impression plaster can enhance the accuracy of master cast and impression plaster can be used simple and effective splinting material for implant impression procedure. PMID:22259700

Optical Analysis of Transparent Polymeric Material Exposed to Simulated Space Environment

NASA Technical Reports Server (NTRS)

Edwards, David L.; Finckenor, Miria M.

1999-01-01

Transparent polymeric materials are being designed and utilized as solar concentrating lenses for spacecraft power and propulsion systems. These polymeric lenses concentrate solar energy onto energy conversion devices such as solar cells and thermal energy systems. The conversion efficiency is directly related to the transmissivity of the polymeric lens. The Environmental Effects Group of the Marshall Space Flight Center's Materials, Processes, and Manufacturing Department exposed a variety of materials to a simulated space environment and evaluated them for an, change in optical transmission. These materials include Lexan(TM), polyethylene terephthalate (PET). several formulations of Tefzel(TM). and Teflon(TM), and silicone DC 93-500. Samples were exposed to a minimum of 1000 Equivalent Sun Hours (ESH) of near-UV radiation (250 - 400 nm wavelength). Data will be presented on materials exposed to charged particle radiation equivalent to a five-year dose in geosynchronous orbit. These exposures were performed in MSFC's Combined Environmental Effects Test Chamber, a unique facility with the capability to expose materials simultaneously or sequentially to protons, low-energy electrons, high-energy electrons, near UV radiation and vacuum UV radiation.Prolonged exposure to the space environment will decrease the polymer film's transmission and thus reduce the conversion efficiency. A method was developed to normalize the transmission loss and thus rank the materials according to their tolerance to space environmental exposure. Spectral results and the material ranking according to transmission loss are presented.

Solid polymeric electrolyte based dye-sensitized solar cell with improved stability

NASA Astrophysics Data System (ADS)

Prasad, Narottam; Kumar, Manish; Patel, K. R.; Roy, M. S.

2018-05-01

The impact of polymeric electrolyte was investigated over the performance of dye-sensitized solar cell made with Rose Bengal as sensitizer. Further, the selective influence of TiCl4 treatment and pre-sensitizer deoxycholic acid on nc-TiO2 photoanode was determined in terms of improvement in conversion efficiency of the cell. It is found that the effect of TiCl4 treatment was comparatively more than pre-sensitization with de-oxy cholic acid towards improving the efficiency of the cell. The conversion efficiency on TiCl4 treatment was 0.2% whereas on pre-sensitization with deoxy chollic acid it was 0.1%. The combined effect of both TiCl4 treatment & pre-sensitization with deoxycholic acid leads conversion efficiency to 0.33%.

Preparation and characterization of poly(acrylic acid)-hydroxyethyl cellulose graft copolymer.

PubMed

Abdel-Halim, E S

2012-10-01

Poly(acrylic acid) hydroxyethyl cellulose [poly(AA)-HEC] graft copolymer was prepared by polymerizing acrylic acid (AA) with hydroxyethyl cellulose (HEC) using potassium bromate/thiourea dioxide (KBrO(3)/TUD) as redox initiation system. The polymerization reaction was carried out under a variety of conditions including concentrations of AA, KBrO(3) and TUD, material to liquor ratio and polymerization temperature. The polymerization reaction was monitored by withdrawing samples from the reaction medium and measuring the total conversion. The rheological properties of the poly(AA)-HEC graft copolymer were investigated. The total conversion and rheological properties of the graft copolymer depended on the ratio of KBrO(3) to TUD and on acrylic acid concentration as well as temperature and material to liquor ratio. Optimum conditions of the graft copolymer preparation were 30 mmol KBrO(3) and 30 mmol TUD/100g HEC, 100% AA (based on weight of HEC), duration 2h at temperature 50 °C using a material to liquor ratio of 1:10. Copyright © 2012. Published by Elsevier Ltd.

Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide.

PubMed

Schäfer, Pascal M; Fuchs, Martin; Ohligschläger, Andreas; Rittinghaus, Ruth; McKeown, Paul; Akin, Enver; Schmidt, Maximilian; Hoffmann, Alexander; Liauw, Marcel A; Jones, Matthew D; Herres-Pawlis, Sonja

2017-09-22

New zinc guanidine complexes with N,O donor functionalities were prepared, characterized by X-Ray crystallography, and examined for their catalytic activity in the solvent-free ring-opening polymerization (ROP) of technical-grade rac-lactide at 150 °C. All complexes showed a high activity. The fastest complex [ZnCl 2 (DMEGasme)] (C1) produced colorless poly(lactide) (PLA) after 90 min with a conversion of 52 % and high molar masses (M w =69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant k p . Furthermore, a polymerization with the most active complex C1 was monitored by in situ Raman spectroscopy. Overall, conversion of up to 90 % can be obtained. End-group analysis was performed to clarify the mechanism. All four complexes combine robustness against impurities in the lactide with high polymerization rates, and they represent the fastest robust lactide ROP catalysts to date, opening new avenues to a sustainable ROP catalyst family for industrial use. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molar cusp deformation evaluated by micro-CT and enamel crack formation to compare incremental and bulk-filling techniques.

PubMed

Oliveira, Laís Rani Sales; Braga, Stella Sueli Lourenço; Bicalho, Aline Arêdes; Ribeiro, Maria Tereza Hordones; Price, Richard Bengt; Soares, Carlos José

2018-07-01

To describe a method of measuring the molar cusp deformation using micro-computed tomography (micro-CT), the propagation of enamel cracks using transillumination, and the effects of hygroscopic expansion after incremental and bulk-filling resin composite restorations. Twenty human molars received standardized Class II mesio-occlusal-distal cavity preparations. They were restored with either a bulk-fill resin composite, X-tra fil (XTRA), or a conventional resin composite, Filtek Z100 (Z100). The resin composites were tested for post-gel shrinkage using a strain gauge method. Cusp deformation (CD) was evaluated using the images obtained using a micro-CT protocol and using a strain-gauge method. Enamel cracks were detected using transillumination. The post-gel shrinkage of Z100 was higher than XTRA (P < 0.001). The amount of cusp deformation produced using Z100 was higher compared to XTRA, irrespective of the measurement method used (P < 0.001). The thinner lingual cusp always had a higher CD than the buccal cusp, irrespective of the measurement method (P < 0.001). A positive correlation (r = 0.78) was found between cusp deformation measured by micro-CT or by the strain-gauge method. After hygroscopic expansion of the resin composite, the cusp displacement recovered around 85% (P < 0.001). After restoration, Z100 produced more cracks than XTRA (P = 0.012). Micro-CT was an effective method for evaluating the cusp deformation. Transillumination was effective for detecting enamel cracks. There were fewer negative effects of polymerization shrinkage in bulk-fill resin restorations using XTRA than for the conventional incremental filling technique using conventional composite resin Z100. Shrinkage and cusp deformation are directly related to the formation of enamel cracks. Cusp deformation and crack propagation may increase the risk of tooth fracture. Copyright © 2018 Elsevier Ltd. All rights reserved.

Vertical phase separation in bulk heterojunction solar cells formed by in situ polymerization of fulleride

PubMed Central

Zhang, Lipei; Xing, Xing; Zheng, Lingling; Chen, Zhijian; Xiao, Lixin; Qu, Bo; Gong, Qihuang

2014-01-01

Vertical phase separation of the donor and the acceptor in organic bulk heterojunction solar cells is crucial to improve the exciton dissociation and charge transport efficiencies. This is because whilst the exciton diffusion length is limited, the organic film must be thick enough to absorb sufficient light. However, it is still a challenge to control the phase separation of a binary blend in a bulk heterojunction device architecture. Here we report the realization of vertical phase separation induced by in situ photo-polymerization of the acrylate-based fulleride. The power conversion efficiency of the devices with vertical phase separation increased by 20%. By optimising the device architecture, the power conversion efficiency of the single junction device reached 8.47%. We believe that in situ photo-polymerization of acrylate-based fulleride is a universal and controllable way to realise vertical phase separation in organic blends. PMID:24861168

Effect of polyvinyl siloxane impression material on the polymerization of composite resin.

PubMed

Chen, Liang; Kleverlaan, Cornelis Johannes; Liang, Kunneng; Yang, Deqin

2017-04-01

Polyvinyl siloxane impression material has been widely used as a lingual matrix for rebuilding missing tooth structure with composite resin. The composite resin is light polymerized in contact with the polyvinyl siloxane impression material. However, polyvinyl siloxane impression material has been shown to interact with other dental materials. The purpose of this study was to assess the effect of polyvinyl siloxane impression materials on the polymerization of composite resins by assessing the Vickers microhardness and degree of conversion of polyvinyl siloxane. The composite resins were light polymerized in contact with 3 polyvinyl siloxane impression materials (Flexitime Easy Putty; President Light Body; Xantopren L Blue) (n=8) and in contact with a matrix strip as the control group (n=8). Vickers microhardness and degree of conversion on contact surfaces were measured to evaluate the polymerization of composite resins. The depth of the effect was assessed by Vickers microhardness on section surfaces and observed with scanning electron microscopy. The results were analyzed by 1-way analysis of variance and the post hoc Tukey honest significant differences test (α=.05). The Vickers microhardness and degree of conversion values on the contact surfaces of the experiment groups were significantly lower than those of the control group (P<.05); the Vickers microhardness values on the section surfaces indicated that there was no significant difference at the same depth of different groups (P>.05). The scanning electron microscope observation showed that an approximately 10-μm deep unpolymerized layer was found in the experimental group. Polyvinyl siloxane impression materials have an inhibitory effect on the polymerization of the composite resins, but just limited to within approximately 10 μm from the surface in contact with the impression material. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

High strength air-dried aerogels

DOEpatents

Coronado, Paul R.; Satcher, Jr., Joe H.

2012-11-06

A method for the preparation of high strength air-dried organic aerogels. The method involves the sol-gel polymerization of organic gel precursors, such as resorcinol with formaldehyde (RF) in aqueous solvents with R/C ratios greater than about 1000 and R/F ratios less than about 1:2.1. Using a procedure analogous to the preparation of resorcinol-formaldehyde (RF) aerogels, this approach generates wet gels that can be air dried at ambient temperatures and pressures. The method significantly reduces the time and/or energy required to produce a dried aerogel compared to conventional methods using either supercritical solvent extraction. The air dried gel exhibits typically less than 5% shrinkage.

New ROMP Synthesis of Ferrocenyl Dendronized Polymers.

PubMed

Liu, Xiong; Ling, Qiangjun; Zhao, Li; Qiu, Guirong; Wang, Yinghong; Song, Lianxiang; Zhang, Ying; Ruiz, Jaime; Astruc, Didier; Gu, Haibin

2017-10-01

First- and second-generation Percec-type dendronized ferrocenyl norbornene macromonomers containing, respectively, three and nine ferrocenyl termini are synthesized and polymerized by ring-opening metathesis polymerization using Grubbs' third-generation olefin metathesis catalyst with several monomer/catalyst feed ratios between 10 and 50. The rate of polymerization is highly dependent on the generation of the dendronized macromonomers, but all these ring-opening metathesis polymerization reactions are controlled, and near-quantitative monomer conversions are achieved. The numbers of ferrocenyl groups obtained are in agreement with the theoretical ones according to the cyclic voltammetry studies as determined using the Bard-Anson method. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Well-Defined Macromolecules Using Horseradish Peroxidase as a RAFT Initiase.

PubMed

Danielson, Alex P; Bailey-Van Kuren, Dylan; Lucius, Melissa E; Makaroff, Katherine; Williams, Cameron; Page, Richard C; Berberich, Jason A; Konkolewicz, Dominik

2016-02-01

Enzymatic catalysis and control over macromolecular architectures from reversible addition-fragmentation chain transfer polymerization (RAFT) are combined to give a new method of making polymers. Horseradish peroxidase (HRP) is used to catalytically generate radicals using hydrogen peroxide and acetylacetone as a mediator. RAFT is used to control the polymer structure. HRP catalyzed RAFT polymerization gives acrylate and acrylamide polymers with relatively narrow molecular weight distributions. The polymerization is rapid, typically exceeding 90% monomer conversion in 30 min. Complex macromolecular architectures including a block copolymer and a protein-polymer conjugate are synthesized using HRP to catalytically initiate RAFT polymerization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Initiated Chemical Vapor Deposition (iCVD) of Highly Cross-Linked Polymer Films for Advanced Lithium-Ion Battery Separators.

PubMed

Yoo, Youngmin; Kim, Byung Gon; Pak, Kwanyong; Han, Sung Jae; Song, Heon-Sik; Choi, Jang Wook; Im, Sung Gap

2015-08-26

We report an initiated chemical vapor deposition (iCVD) process to coat polyethylene (PE) separators in Li-ion batteries with a highly cross-linked, mechanically strong polymer, namely, polyhexavinyldisiloxane (pHVDS). The highly cross-linked but ultrathin pHVDS films can only be obtained by a vapor-phase process, because the pHVDS is insoluble in most solvents and thus infeasible with conventional solution-based methods. Moreover, even after the pHVDS coating, the initial porous structure of the separator is well preserved owing to the conformal vapor-phase deposition. The coating thickness is delicately controlled by deposition time to the level that the pore size decreases to below 7% compared to the original dimension. The pHVDS-coated PE shows substantially improved thermal stability and electrolyte wettability. After incubation at 140 °C for 30 min, the pHVDS-coated PE causes only a 12% areal shrinkage (versus 90% of the pristine separator). The superior wettability results in increased electrolyte uptake and ionic conductivity, leading to significantly improved rate performance. The current approach is applicable to a wide range of porous polymeric separators that suffer from thermal shrinkage and poor electrolyte wetting.

Dynamics of Actin Cables in Polarized Growth of the Filamentous Fungus Aspergillus nidulans

PubMed Central

Bergs, Anna; Ishitsuka, Yuji; Evangelinos, Minoas; Nienhaus, G. U.; Takeshita, Norio

2016-01-01

Highly polarized growth of filamentous fungi requires a continuous supply of proteins and lipids to the hyphal tip. This transport is managed by vesicle trafficking via the actin and microtubule cytoskeletons and their associated motor proteins. Particularly, actin cables originating from the hyphal tip are essential for hyphal growth. Although, specific marker proteins have been developed to visualize actin cables in filamentous fungi, the exact organization and dynamics of actin cables has remained elusive. Here, we observed actin cables using tropomyosin (TpmA) and Lifeact fused to fluorescent proteins in living Aspergillus nidulans hyphae and studied the dynamics and regulation. GFP tagged TpmA visualized dynamic actin cables formed from the hyphal tip with cycles of elongation and shrinkage. The elongation and shrinkage rates of actin cables were similar and approximately 0.6 μm/s. Comparison of actin markers revealed that high concentrations of Lifeact reduced actin dynamics. Simultaneous visualization of actin cables and microtubules suggests temporally and spatially coordinated polymerization and depolymerization between the two cytoskeletons. Our results provide new insights into the molecular mechanism of ordered polarized growth regulated by actin cables and microtubules. PMID:27242709

Combinatorial enzyme technology: Conversion of pectin to oligo species and its effect on microbial growth

USDA-ARS?s Scientific Manuscript database

Plant cell wall polysaccharides, which consist of polymeric backbones with various types of substitution, were studied using the concept of combinatorial enzyme technology for conversion of agricultural fibers to functional products. Using citrus pectin as the starting substrate, an active oligo spe...

Electron-beam-initiated polymerization of poly(ethylene glycol)-based wood impregnants.

PubMed

Trey, Stacy M; Netrval, Julia; Berglund, Lars; Johansson, Mats

2010-11-01

The current study demonstrates that methacrylate and acrylate poly(ethylene glycol) (PEG) functional oligomers can be effectively impregnated into wood blocks, and cured efficiently to high conversions without catalyst by e-beam radiation, allowing for less susceptibility to leaching, and favorable properties including higher Brinell hardness values. PEG based monomers were chosen because there is a long history of this water-soluble monomer being able to penetrate the cell wall, thus bulking it and decreasing the uptake of water which further protects the wood from fungal attack. Diacrylate, dimethacrylate, and dihydroxyl functional PEG of M(w) 550-575, of concentrations 0, 30, 60, and 100 wt % in water, were vacuum pressure impregnated into Scots Pine blocks of 15 × 25 × 50 mm in an effort to bulk the cell wall. The samples were then irradiated and compared with nonirradiated samples. It was shown by IR, DSC that the acrylate polymers were fully cured to much higher conversions than can be reached with conventional methods. Leaching studies indicated a much lower amount of oligomer loss from the cured vinyl functional PEG chains in comparison to hydroxyl functional PEG indicating a high degree of fastening of the polymer in the wood. The Brinell hardness indicated a significant increase in hardness to hardwood levels in the modified samples compared to the samples of hydroxyl functional PEG and uncured vinyl PEG samples, which actually became softer than the untreated Scots Pine. By monitoring the dimensions of the sample it was found by weight percent gain calculations (WPG %) that water helps to swell the wood structure and allow better access of the oligomers into the cell wall. Further, the cure shrinkage of the wood samples demonstrated infiltration of the oligomers into the cell wall as this was not observed for methyl methacrylate which is well-documented to remain in the lumen. However, dimensional stability of the vinyl polymer modified blocks when placed in water was not observed to the same extent as PEG.

Biocatalytic Synthesis of Poly(δ-Valerolactone) Using a Thermophilic Esterase from Archaeoglobus fulgidus as Catalyst

PubMed Central

Cao, Hong; Han, Haobo; Li, Guangquan; Yang, Jiebing; Zhang, Lingfei; Yang, Yan; Fang, Xuedong; Li, Quanshun

2012-01-01

The ring-opening polymerization of δ-valerolactone catalyzed by a thermophilic esterase from the archaeon Archaeoglobus fulgidus was successfully conducted in organic solvents. The effects of enzyme concentration, temperature, reaction time and reaction medium on monomer conversion and product molecular weight were systematically evaluated. Through the optimization of reaction conditions, poly(δ-valerolactone) was produced in 97% monomer conversion, with a number-average molecular weight of 2225 g/mol, in toluene at 70 °C for 72 h. This paper has produced a new biocatalyst for the synthesis of poly(δ-valerolactone), and also deeper insight has been gained into the mechanism of thermophilic esterase-catalyzed ring-opening polymerization. PMID:23202895

Stimuli Responsive Morphological Changes of Pnipa Polymer Brushes Synthesized on Silicon Substrate

NASA Astrophysics Data System (ADS)

Huda, Muhammad Nurul; Kabir, A. N. M. Hamidul

2013-08-01

High-density polymer brushes were grown from the silicon surface by atom transfer radical polymerization of Poly(N-isopropylacrylamide) (PNIPA) at different polymerization conditions. PNIPA brushes were prepared using Copper (I) Chloride/tris(2-(dimetylamino)ethyl)amine (Me6TREN) as a catalytic system in DMSO at 20°C. Free polymer formed during the brush formation was characterized by gel permeation chromatography. The grafting densities up to 0.52 chains/nm2 were obtained. The layer thickness of polymer brush increases with the increase of conversion of the monomer conversion as well as polymerization time. Atomic force microscopy and air bubble contact angle under pH solution were employed to study the surface morphology, reversible conformational changes of and stimulus-response behavior. PNIPA brushes exhibited a different nanomorphology after treatment with different pH solution. It also revealed a unique reversible wetting behavior with pH. The reversible properties of the PNIPA brushes can be used to regulate the adsorption of the sulfonated PS nanoparticles.

Thiol-Ene functionalized siloxanes for use as elastomeric dental impression materials

PubMed Central

Cole, Megan A.; Jankousky, Katherine C.; Bowman, Christopher N.

2014-01-01

Objectives Thiol- and allyl-functionalized siloxane oligomers are synthesized and evaluated for use as a radical-mediated, rapid set elastomeric dental impression material. Thiol-ene siloxane formulations are crosslinked using a redox-initiated polymerization scheme, and the mechanical properties of the thiol-ene network are manipulated through the incorporation of varying degrees of plasticizer and kaolin filler. Formulations with medium and light body consistencies are further evaluated for their ability to accurately replicate features on both the gross and microscopic levels. We hypothesize that thiol-ene functionalized siloxane systems will exhibit faster setting times and greater detail reproduction than commercially available polyvinylsiloxane (PVS) materials of comparable consistencies. Methods Thiol-ene functionalized siloxane mixtures formulated with varying levels of redox initiators, plasticizer, and kaolin filler are made and evaluated for their polymerization speed (FTIR), consistency (ISO4823.9.2), and surface energy (goniometer). Feature replication is evaluated quantitatively by SEM. The Tg, storage modulus, and creep behavior are determined by DMA. Results Increasing redox initiation rate increases the polymerization rate but at high levels also limits working time. Combining 0.86 wt% oxidizing agent with up to 5 wt% plasticizer gave a working time of 3 min and a setting time of 2 min. The selected medium and light body thiol-ene formulations also achieved greater qualitative detail reproduction than the commercial material and reproduced micrometer patterns with 98% accuracy. Significance Improving detail reproduction and setting speed is a primary focus of dental impression material design and synthesis. Radical-mediated polymerizations, particularly thiol-ene reactions, are recognized for their speed, reduced shrinkage, and ‘click’ nature. PMID:24553250

POLYMERIZATION OF /cap alpha/-METHYLSTYRENE BY ELECTRON IRRADIATION (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Braun, D.; Heufer, G.; Seufert, W.

1964-01-01

Ampoules of alpha -methylstyrene sealed under vacuum were irradiated with 1-Mev electrons in a type JS Van de Graaff generator; comparative experiments with gamma rays were carried out with a /sup 60/Co source of 3000 deg C. High doses of electrons (ca. 10/sup 8/ rad) are necessary for polymerization. The conversion is graphed as a function of dose at 0 deg C; it reaches a maximum plateau of 65% at 4 x 10/sup 8/ rad; this may point to radiolysis of the polymer at doses above this. Polymerization conversion increases with decreasing dose rate, when dose and temperature are heldmore » constant; and conversion increases with decreasing temperature (22% at --22 deg C; 10% at 15 deg C; <1% at 60 deg C), as has been found with gamma rays. In the solid state between --40 deg C and --80 deg C the maximum yield is only about 5%. The molecular weights of all poly- alpha -methylstyrenes thus formed lie between 3000 and 12,000, independently of dose rate and temperature. All polymethylstyrenes formed in the liquid state have approximately the same tacticity independent of temperature (isotactic about 20%; syndiotactic about 80%). This corresponds to the tacticity of polymers formed cationically with Lewis acids. In the solid state the tacticity is: isotactic 38%, syndiotactic, 62%, comparable with the tacticity of anionic polymerization. In the liquid state the tacticity and the sensitivity towards water indicate a cationic mechanism for the reaction. NMR studies also indicate a cationic mechanism. (BBB)« less

Co-sensitization of ZnO by CdS quantum dots in natural dye-sensitized solar cells with polymeric electrolytes to improve the cell stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Junhom, W.; Magaraphan, R.

2015-05-22

The CdS quantum dots (QDs) were deposited on ZnO layer by chemical bath deposition method to absorb light in the shorter wavelength region and used as photoanode in the dye sensitized solar cell (DSSCs) with natural dye extracted from Noni leaves. Microstructures of CdS-ZnO from various dipping time were characterized by XRD, FE-SEM and EDX. The results showed that the CdS is hexagonal structure and the amount of CdS increases when the dipping time increases. The maximal conversion efficiency of 0.292% was achieved by the DSSCs based on CdS QDs-sensitized ZnO film obtained from 9 min-dipping time. Furthermore, the stability ofmore » DSSCs was improved by using polymeric electrolyte. Poly (acrylic acid) (PAA) and Polyacrylamide (PAM) were introduced to CdS QDs-sensitized ZnO film from 9 min-dipping time. Each polymeric electrolyte was prepared by swelling from 0.1-2.0 %w in H2O. The maximal conversion efficiency of 0.207% was achieved for DSSCs based on CdS QDs-sensitized ZnO film with PAM 1.0% and the conversion efficiency was decreased 25% when it was left for1 hr.« less

Co-sensitization of ZnO by CdS quantum dots in natural dye-sensitized solar cells with polymeric electrolytes to improve the cell stability

NASA Astrophysics Data System (ADS)

Junhom, W.; Magaraphan, R.

2015-05-01

The CdS quantum dots (QDs) were deposited on ZnO layer by chemical bath deposition method to absorb light in the shorter wavelength region and used as photoanode in the dye sensitized solar cell (DSSCs) with natural dye extracted from Noni leaves. Microstructures of CdS-ZnO from various dipping time were characterized by XRD, FE-SEM and EDX. The results showed that the CdS is hexagonal structure and the amount of CdS increases when the dipping time increases. The maximal conversion efficiency of 0.292% was achieved by the DSSCs based on CdS QDs-sensitized ZnO film obtained from 9 min-dipping time. Furthermore, the stability of DSSCs was improved by using polymeric electrolyte. Poly (acrylic acid) (PAA) and Polyacrylamide (PAM) were introduced to CdS QDs-sensitized ZnO film from 9 min-dipping time. Each polymeric electrolyte was prepared by swelling from 0.1-2.0 %w in H2O. The maximal conversion efficiency of 0.207% was achieved for DSSCs based on CdS QDs-sensitized ZnO film with PAM 1.0% and the conversion efficiency was decreased 25% when it was left for1 hr.

Sustained-releasing hollow microparticles with dual-anticancer drugs elicit greater shrinkage of tumor spheroids.

PubMed

Baek, Jong-Suep; Choo, Chee Chong; Tan, Nguan Soon; Loo, Say Chye Joachim

2017-10-06

Polymeric particulate delivery systems are vastly explored for the delivery of chemotherapeutic agents. However, the preparation of polymeric particulate systems with the capability of providing sustained release of two or more drugs is still a challenge. Herein, poly (D, L-lactic-co-glycolic acid, 50:50) hollow microparticles co-loaded with doxorubicin and paclitaxel were developed through double-emulsion solvent evaporation technique. Hollow microparticles were formed through the addition of an osmolyte into the fabrication process. The benefits of hollow over solid microparticles were found to be higher encapsulation efficiency and a more rapid drug release rate. Further modification of the hollow microparticles was accomplished through the introduction of methyl-β-cyclodextrin. With this, a higher encapsulation efficiency of both drugs and an enhanced cumulative release were achieved. Spheroid study further demonstrated that the controlled release of the drugs from the methyl-β-cyclodextrin -loaded hollow microparticles exhibited enhanced tumor regressions of MCF-7 tumor spheroids. Such hollow dual-drug-loaded hollow microparticles with sustained releasing capabilities may have a potential for future applications in cancer therapy.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir; Roghani-Mamaqani, Hossein

Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presencemore » of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric analysis shows that thermal stability of the nanocomposites increases by adding nanoparticles content. Decrease of glass transition temperature is also demonstrated by the addition of 3 wt% of silica nanoparticles according to the differential scanning calorimetry results.« less

The effect of high temperature sol-gel polymerization parameters on the microstructure and properties of hydrophobic phenol-formaldehyde/silica hybrid aerogels.

PubMed

Seraji, Mohamad Mehdi; Sameri, Ghasem; Davarpanah, Jamal; Bahramian, Ahmad Reza

2017-05-01

Phenol-formaldehyde/silica hybrid aerogels with different degree of hydrophobicity were successfully synthesized via high temperature sol-gel polymerization. Tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) were used as precursor and co-precursor of the hydrophobic silica-based phase, respectively. The hydrolysis step of silica based sols were conducted by acid catalyzed reactions and HCl was used as hydrolysis catalyst. The chemical structure of prepared hybrid aerogels was characterized by Fourier Transform Infrared spectroscopy (FT-IR). The effect of MTES/TEOS proportion and catalyst content on the morphology and microstructure of samples were investigated by FE-SEM and C, Si mapping analysis. The acid catalyzed hydrolysis of TEOS and MTES sols leads to formation of a sol with primarily silica particles in the organic-inorganic hybrid sol and varying colloid growth mechanisms were occurred with change in MTES and HCl molar ratio. With the increasing of MTES content, the microstructure of samples changed from uniform colloidal network, core-shell structure to polymeric structure with a huge phase separation. The increasing of HCl mole fraction leads to smaller particle size. Moreover, the shrinkage of samples was decreased and water contact angles of the resulted aerogels were increased from 40 to 156.8° with the increases of MTES content. Copyright © 2017 Elsevier Inc. All rights reserved.

Design considerations for multi component molecular-polymeric nonlinear optical materials

NASA Astrophysics Data System (ADS)

Singer, K. D.; Kuzyk, M. G.; Fang, T.; Holland, W. R.; Cahill, P. A.

1990-08-01

We review our work on multi component polymeric nonlinear optical materials. These materials consist of nonlinear optical molecules incorporated in a polymeric host. A cross-linked triazine polymer incorporating a dicyanovinyl terminated azo dye was found to be relatively stable at 85 deg and possess an electro-optic coefficient of 11pm/V. We have also observed the zero dispersion condition in a new anomalous dispersion dye for phase matched second harmonic generation, and expect efficient conversion to the blue. A squarylium dye, ISQ, has been found to possess a large third order nonlinearity, and may display two-level behavior.

Development of dental restorative materials based on visible light-cured multi-methacrylates

NASA Astrophysics Data System (ADS)

Tiba, Amer

The studies described in this dissertation focus on new visible light-curing (VLC) oligomers exhibiting low shrinkage, low water sorption, and improved mechanical properties. A family of multi-methacrylates, based on poly(isopropylidenediphenol) resin (BPA), was synthesized, characterized, and evaluated. The commercial BPA resin is prepared from enzymatic polymerization (oligomerization) of bisphenol A. The BPA resin, having an average of eight phenolic hydroxyl groups per molecule, was treated with propylene carbonate, and the resultant product, i.e., propoxylated BPA (PEBPA) oligomer, was confirmed by Fourier transform infrared spectroscopy (FT-IR) and sp{13}C nuclear magnetic resonance (NMR). The propoxylated BPA was subsequently treated with methacryloyl chloride to produce the multi-methacrylates, identified by FT-IR and NMR. The PEBPA oligomer multimethacrylate: triethylene glycol dimethacrylate (TEGDMA) (50:50/wt:wt) blends were combined with 0.5 wt. % camphoroquinone (CQ) and 1.0 wt. % N,N-dimethylaminoethyl methacrylate (DMAEMA). The control polymers were 2,2-bis(4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl) propane (BisGMA): TEGDMA(50:50/wt:wt) blends having the same levels of CQ/DMAEMA. Differential photocalorimetry (DPC) and differential scanning calorimetry (DSC) showed these multimethacrylate/TEGDMA (neat resin) blends have polymerization characteristics comparable to the BisGMA/TEGDMA controls. These new multifunctional oligomers have lower polymerization shrinkage and lower uptake of water and other liquids, compared to BisGMA based materials. In addition, two experimental oligomers, PEBPA #2 and #3, have higher compressive strength than the BisGMA control. A biocompatibility test of the polymerized multi-methacrylate resins was performed and compared with the conventional BisGMA/TEGDMA resin and blank controls, using cell culture techniques. Human gingival fibroblasts were used for biocompatibility evaluation of these resins. The results revealed that the BPA oligomer (multi-methacrylate) based resin significantly favored the cell growth of the human gingival fibroblasts, compared to the control. An experimental composite was made from EPBPA oligomers (multi-methacrylates). The compressive strength of the experimental EPBPA containing composite was not significantly different than the commercial composite Herculite HXR. SEM photomicrographs revealed more voids in the experimental composites than the commercial composite on both the external surfaces of the prepared specimens and the subsequent fractured surfaces. This is due to the molding technique for specimen preparation and lack of good mechanical mixing for filler incorporation prior to placement of the resin in the mold for subsequent photopolymerization. However, the water sorption for the experimental EPBPA-based composite was significantly lower than the commercial Herculite (HXR) composite. This is most likely related to the hydrophobic nature of the experimental resin. These results suggest that the new type of polyfunctional methacrylate oligomers (PEBPA) have potential application in formulating dental composites as direct esthetic restorative materials with improved properties.

Sulphation of CaO-Based Sorbent Modified in CO2 Looping Cycles

NASA Astrophysics Data System (ADS)

Manovic, Vasilije; Anthony, Edward J.; Loncarevic, Davor

CaO-based looping cycles for CO2 capture at high temperatures are based on cyclical carbonation of CaO and regeneration of CaCO3. The main limitation of natural sorbents is the loss of carrying capacity with increasing numbers of reaction cycles, resulting in spent sorbent ballast. Use of spent sorbent from CO2 looping cycles for SO2 capture is a possible solution investigated in this study. Three limestones were investigated: Kelly Rock (Canada), La Blanca (Spain) and Katowice (Poland). Carbonation/calcination cycles were performed in a tube furnace with original limestones and samples thermally pretreated for different times (i.e., sintered). The spent sorbent samples were sulphated in a thermogravimetric analyzer. Changes in the resulting pore structure were then investigated using mercury porosimetry. Final conversions of both spent and pretreated sorbents after longer sulphation times were comparable or higher than those observed for the original sorbents. Maximum sulphation levels strongly depend on sorbent porosity and pore surface area. The shrinkage of sorbent particles during calcination/cycling resulted in a loss of sorbent porosity (≤48%), which corresponds to maximum sulphation levels ˜55% for spent Kelly Rock and Katowice. However, this is ˜10% higher than for the original samples. By contrast, La Blanca limestone had more pronounced particle shrinkage during pretreatment and cycling, leading to lower porosity, <35%, resulting in sulphation conversion of spent samples <30%, significantly lower than for the original sample (45%). These results showed that spent sorbent samples from CO2 looping cycles can be used as sorbents for SO2 retention if significant porosity loss does not occur during CO2 reaction cycles. For spent Kelly Rock and Katowice samples final conversions are determined by the total pore volume available for the bulky CaSO4 product.

Evaluation of Microleakage in Class II Cavities using Packable Composite Restorations with and without use of Liners.

PubMed

Arora, Rajesh; Kapur, Ravi; Sibal, Nikhil; Juneja, Sumit

2012-09-01

The advent of the esthetic era and advances in adhesive technology saw the emergence of resin composite materials. But the problem of polymerization shrinkage remained. This was due to the contraction of the resin during curing inducing internal and interfacial stresses at the tooth restoration interface, leading to gap formation and subsequent micro-leakage. A number of techniques and modifications in the material have been proposed to minimize polymerization shrinkage and microleakage. In this study, the hypothesis that the placement of resin-modified glass ionomer cement (RMGIC) or flowable composite, as liner, beneath the packable composite, on the gingival surface of the tooth [coronal or apical to cementoenamel junction (CEJ)], could reduce the microleakage in class II composite restorations, was tested. Sixty recently extracted noncarious human mandibular molars were used. The teeth were randomly divided into three groups (20 specimens each): Group I (Filtek P60 with RMGIC liner), group II (Filtek P60 with Filtek Z350 liner) and Group III (Filtek P60 without liner). The teeth of each group were further subdivided into two subgroups (equal number of cavities). Subgroup A gingival seat 1 mm occlusal to CEJ on mesial side. Subgroup B gingival seat 1 mm apical to CEJ on distal side. It was concluded that in class II composite restorations gingival microleakage is more at the dentinal surface than on enamel. The use of a flowable composite and RMGIC, as liners, beneath the packable composite, in class II composite restorations, significantly reduces the microleakage when margins are in dentin, but the reverse is true, when the margins are in enamel. How to cite this article: Arora R, Kapur R, Sibal N, Juneja S. Evaluation of Microleakage in Class II Cavities using Packable Composite Restorations with and without use of Liners. Int J Clin Pediatr Dent 2012;5(3):178-184.

Polymeric carbon nitride nanomesh as an efficient and durable metal-free catalyst for oxidative desulfurization.

PubMed

Shen, Lijuan; Lei, Ganchang; Fang, Yuanxing; Cao, Yanning; Wang, Xinchen; Jiang, Lilong

2018-03-06

We report the first use of polymeric carbon nitride (CN) for the catalytic selective oxidation of H 2 S. The as-prepared CN with unique ultrathin "nanomeshes" structure exhibits excellent H 2 S conversion and high S selectivity. In particular, the CN nanomesh also displays better durability in the desulfurization reaction than traditional catalysts, such as carbon- and iron-based materials.

Use of near-IR to monitor the influence of external heating on dental composite photopolymerization.

PubMed

Trujillo, Marianela; Newman, Sheldon M; Stansbury, Jeffrey W

2004-10-01

This study was conducted to determine the effect of modest external heating on the photopolymerization kinetics and conversion of commercial dental composite restorative materials. A transmission-mode, real-time near-infrared spectroscopic technique was used to monitor the photopolymerization process in the composite materials at various temperatures between 23 and 70 degrees C. Several light curing units, differing in spectral output and power densities were compared at the different cure temperatures. Several significantly different commercial composites were compared for their response. Regardless of the curing light or composite material used, photopolymerization at a moderate curing temperature of 54.5 degrees C resulted in significantly higher immediate and final conversion values compared with room temperature photocuring. Contrary to the room temperature cured materials, at the elevated cure temperature the extent of post-cure was minor and different curing lights produced very uniform conversion values within a given material. The time required to reach a given level of conversion, established as full conversion with the room temperature cure, was reduced typically by 80-90% using the elevated curing conditions. Complementary kinetic studies confirmed the effect of cure temperature on increasing the polymerization rate in dental composites as significant. Increasing the temperature of composite resin within potentially biologically compatible limits can significantly influences resin polymerization. These increased rates and conversion could lead to improved properties of composite restorative materials.

Kinetics of bulk photo-initiated copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerizations.

PubMed

Song, Han Byul; Baranek, Austin; Bowman, Christopher N

2016-01-21

Photoinitiation of polymerizations based on the copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ . Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1 st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm -2 light exposure at 400-500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)'s catalytic lifetime and the nature of the step-growth polymerization.

A Self-Reporting Photocatalyst for Online Fluorescence Monitoring of High Throughput RAFT Polymerization.

PubMed

Yeow, Jonathan; Joshi, Sanket; Chapman, Robert; Boyer, Cyrille Andre Jean Marie

2018-04-25

Translating controlled/living radical polymerization (CLRP) from batch to the high throughput production of polymer libraries presents several challenges in terms of both polymer synthesis and characterization. Although recently there have been significant advances in the field of low volume, high throughput CLRP, techniques able to simultaneously monitor multiple polymerizations in an "online" manner have not yet been developed. Here, we report our discovery that 5,10,15,20-tetraphenyl-21H,23H-porphine zinc (ZnTPP) is a self-reporting photocatalyst that can mediate PET-RAFT polymerization as well as report on monomer conversion via changes in its fluorescence properties. This enables the use of a microplate reader to conduct high throughput "online" monitoring of PET-RAFT polymerizations performed directly in 384-well, low volume microtiter plates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Time-Dependent Effect of Refrigeration on Viscosity and Conversion Kinetics of Dental Adhesive Resins

PubMed Central

Faria-e-Silva, André L; Piva, Evandro; Moraes, Rafael R

2010-01-01

Objectives: This study evaluated the effect of refrigeration at 4°C and post-refrigeration times (immediate, 5, 10, 15, or 20 min) on the viscosity and conversion kinetics of adhesive bonding resins. Methods: Scotchbond Dual-Cure (3M ESPE) and Clearfil SE Bond (Kuraray) were tested. Control samples were kept at 25°C for 24 h. At each post-refrigeration time, the temperature was checked with a K-type thermocouple. Viscosity measurements as a function of temperature were performed using a cone-plate viscometer. Real-time polymerization was monitored by infrared spectroscopy. Degree of conversion (DC) was calculated for each second during polymerization, and the rate of polymerization analyzed. Data were separately submitted to two-way ANOVA and Tukey’s test (P<.05). Results: Clearfil presented faster increase in temperature after exposure to room temperature than Scotchbond. A continuous decrease in viscosity (Pa.s) was observed for both Scotchbond (0.49, 0.34, 0.30, 0.26, 0.23, 0.23) and Clearfil (0.38, 0.37, 0.34, 0.25, 0.24, 0.22). For Scotchbond, higher final DC was detected for the control (62.7%) compared with the immediate (53.3%) and 5 min (54.7%) groups. For Clearfil, the control sample (81.4%) showed higher DC than all refrigerated groups (68.8–69.5%). Clearfil always showed significantly higher DC than Scotchbond. Conclusions: Refrigeration presented a significant time- and material-dependent effect on the viscosity and polymerization kinetics of the bonding resins. Under clinical conditions, adhesive agents should be removed from the refrigerator at least 20 min before being used. PMID:20396445

Characterization of hydrophilic-rich phase mimic in dentin adhesive and computer-aided molecular design of water compatible visible light initiators

NASA Astrophysics Data System (ADS)

Abedin, Farhana

The clinical lifetime of moderate-to-large dental composite restorations is lower than dental amalgam restorations. With the imminent and significant reduction in the use and availability of dental amalgam, the application of composite for the restoration of teeth will increase. Since composite has a higher failure rate, the increased use of composite will translate to an increase in the frequency of dental restoration replacement, overall cost for dental health and discomfort for patients. The composite is too viscous to bond directly to the tooth and thus, a low viscosity adhesive is used to form the bond between the composite and tooth. The bond at the adhesive/tooth is intended to form an impervious seal that protects the restored tooth from acids, oral fluids and bacteria that will undermine the composite restoration. The integrity of the adhesive/tooth bond (the exposed tooth structure is largely composed of enamel and dentin) plays an important role in preventing secondary caries which undermine the composite restoration. This study focuses on the durability of etch-and-rinse dental adhesives. As the adhesive infiltrates the demineralized dentin matrix, it undergoes phase separation into hydrophobic- and hydrophilic-rich phases. The hydrophilic-rich phase contains the conventional hydrophobic photo-initiator system (camphorquinone/ethyl 4-(dimethylamino)benzoate) and cross-linker both in inadequate concentrations. This may compromise the polymerization reaction and the cross-linking density of this phase, making it vulnerable to failure. The goal of this study is to characterize the hydrophilic-rich phase of the dental adhesive by monitoring its polymerization kinetics and glass transition temperature under the presence of an iodonium salt (reaction accelerator), and varying water concentration, photo-initiator concentration and light intensity. The final goal is to develop a computational framework for designing water compatible visible light photosensitizers specifically for the hydrophilic-rich phase of dental adhesives. It was observed that the degree of conversion of the hydrophilic-rich mimics is dominated by the photo-initiator concentration and not the cross-linker. A secondary rate maxima was observed in the case of hydrophilic-rich phase mimics which was associated with the formation of microgels during polymerization. A polymerization mechanism involving polymerization- and solvent-induced phase separation was proposed for the hydrophilic-rich mimics. The hydrophilic dental resins were sensitive to light intensity, i.e. at low light intensities the degree of conversion of the hydrophilic resin was reduced substantially in the presence of camphorquinone/ethyl 4-(dimethylamino)benzoate as photo-initiators, whereas a substantial degree of conversion was observed for the hydrophobic resin even at these lower light intensities. The addition of iodonium salt in the hydrophilic resin significantly improved the degree of conversion of the hydrophilic resin at low light intensities. These studies also showed that the iodonium salt could lead to enhanced cyclization and shorter polymer chain lengths within the hydrophilic-rich phase. For the physically separated hydrophilic-rich phase specimens, it was observed that in the presence of the conventional photo-initiator system (camphorquinone/ethyl 4-(dimethylamino)benzoate), there was no polymerization, mostly due to the insufficient partition concentrations of the photo-initiator components within this phase. The addition of iodoinum salt in this case significantly improved the degree of conversion but it was still significantly lower. These studies indicated that the overall polymerization efficiency of the hydrophilic-rich phase was lower than the hydrophobic-rich phase. The lower polymerization efficiency of the hydrophilic-rich phase led to a phase that lacks integrity; the hydrophilic-rich phase could be infiltrated by oral fluids and cariogenic bacteria. The infiltration of these noxious agents at the interface between the material and tooth could pave the way for enhanced degradation of the tooth structure (collagen and mineral) as well as the adhesive polymer. Novel photosensitizer molecules were proposed to improve the polymerization efficiency of this phase. Computer-aided molecular design (CAMD) was employed to obtain the new photosensitizers. These photosensitizers were capable of improving the degree of conversion of the hydrophilic-rich phase. An enhanced degree of conversion of the hydrophilic-rich phase would lead to a better seal at the adhesive/dentin interface and higher bond strength. Computer-aided molecular design (CAMD) is a fast and inexpensive technique compared to the conventional trial-and-error method to rationally design products. (Abstract shortened by ProQuest.).

Interconnected Porous Polymers with Tunable Pore Throat Size Prepared via Pickering High Internal Phase Emulsions.

PubMed

Xu, Hongyun; Zheng, Xianhua; Huang, Yifei; Wang, Haitao; Du, Qiangguo

2016-01-12

Interconnected macroporous polymers were prepared by copolymerizing methyl acrylate (MA) via Pickering high internal phase emulsion (HIPE) templates with modified silica particles. The pore structure of the obtained polymer foams was observed by field-emission scanning electron microscopy (FE-SEM). Gas permeability was characterized to evaluate the interconnectivity of macroporous polymers. The polymerization shrinkage of continuous phase tends to form open pores while the solid particles surrounding the droplets act as barriers to produce closed pores. These two conflicting factors are crucial in determining the interconnectivity of macroporous polymers. Thus, poly-Pickering HIPEs with high permeability and well-defined pore structure can be achieved by tuning the MA content, the internal phase fraction, and the content of modified silica particles.

Accessing siloxane functionalized polynorbornenes via vinyl-addition polymerization for CO 2 separation membranes

DOE PAGES

Mahurin, Shannon Mark; Sokolov, Alexei P.; Saito, Tomonori; ...

2016-07-06

Here, the vinyl addition polymerization of norbornylbased monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C 6F 5) 2(SbPh 3) 2]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxanesubstituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (T d ≥ 362 °C) and were cast into membranes that displayed high CO 2 permeability and enhanced COmore » 2/N 2 selectivity as compared to related materials.« less

Ring-opening polymerization of DD-lactide catalyzed by Novozyme 435.

PubMed

Hans, Marc; Keul, Helmut; Moeller, Martin

2009-03-10

In contrast to LLA, DLA is converted in toluene solution under mild reaction conditions (50-70 degrees C) using Novozyme 435 (immobilized CALB) to form the corresponding polymer. The influence of several parameters, such as enzyme concentration, temperature and monomer concentration, on the polymerization rate and the monomer conversion was studied. In contrast to the Novozyme 435 catalyzed polymerization of epsilon-caprolactone, enzyme deactivation occurs. It is attributed to the deprivation of water from the enzyme. This work points out that by careful selection of the reaction conditions, it is possible to obtain poly(D-lactide) in reasonable molecular weights and in high yields using Novozyme 435 catalysis.

Reversible addition-fragmentation chain transfer polymerization of N-isopropylacrylamide: a comparison between a conventional and a fast initiator.

PubMed

Bouchékif, Hassen; Narain, Ravin

2007-09-27

The reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) was studied to determine the reasons for deviation of experimental molecular weights to lower molecular weight at high monomer conversion when S-1-dodecyl-S-(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAm) and S,S-bis(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAd) were used as RAFT agents at 65 degrees C. For this purpose, experiments were performed in N,N'-dimethylformamide (DMF) at the NIPAM/CTA ratio of 200 with initiators capable of yielding fast and slow initiation, respectively by photochemical and thermal process, either at ambient temperature or at 65 degrees C. When the polymerization of NIPAM was conducted under these conditions with Irgacure-2959 (IRGC) as photoinitiator, a continuing supply of primary radicals by incremental initiator addition was required to achieve reasonably high conversion. This effect was also apparent by the loss of linearity of the first-order kinetic plot with a conventional initiator (4,4-azobis(4-cyanovaleric acid) (ACVA) as azo-initiator, 10h (t1/2) decomposition at 65 degrees C) indicating that steady-state concentration of the macroradical decreases significantly with the initiator consumption. Nevertheless, polymers with predictable number-average molecular weight Mn (i.e., based on [monomer]/([CTA] + [initiator]) ratio) and narrow polydispersities were obtained (PDIs < 1.2) with CTAm indicating that the process of chain growth was controlled. When CTAd was used, instead of CTAm, the polymers obtained were characterized by a larger polydispersity (1.2 < PDIs < 1.3). The so-called "living steady-state concentration" in chain equilibration together with the linear dependence of Mn vs conversion was observed only when the 200/1 NIPAM/CTA mixture in DMF was subjected to a permanent photoirradiation at 65 degrees C. With ACVA, the deviation of the experimentally measured molecular weights at high conversion was accounted for by the simultaneous self-initiated polymerization of NIPAM with the controlled process in the presence of CTA at 65 degrees C. Similar drift from the linear dependence Mn vs conversion was also observed at 65 degrees C when a significant number of low molecular weight polymer chains were generated intentionally by photodecomposition of IRGC.

Synthesis and Characterization of a Novel Borazine-Type UV Photo-Induced Polymerization of Ceramic Precursors.

PubMed

Wei, Dan; Chen, Lixin; Xu, Tingting; He, Weiqi; Wang, Yi

2016-06-21

A preceramic polymer of B,B',B''-(dimethyl)ethyl-acrylate-silyloxyethyl-borazine was synthesized by three steps from a molecular single-source precursor and characterized by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectrometry. Six-member borazine rings and acrylate groups were effectively introduced into the preceramic polymer to activate UV photo-induced polymerization. Photo-Differential Scanning Calorimetry (Photo-DSC) and real-time FTIR techniques were adapted to investigate the photo-polymerization process. The results revealed that the borazine derivative exhibited dramatic activity by UV polymerization, the double-bond conversion of which reached a maximum in 40 s. Furthermore, the properties of the pyrogenetic products were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), which proved the ceramic annealed at 1100 °C retained the amorphous phase.

Kinetics of corneal thermal shrinkage

NASA Astrophysics Data System (ADS)

Borja, David; Manns, Fabrice; Lee, William E.; Parel, Jean-Marie

2004-07-01

Purpose: The purpose of this study was to determine the effects of temperature and heating duration on the kinetics of thermal shrinkage in corneal strips using a custom-made shrinkage device. Methods: Thermal shrinkage was induced and measured in corneal strips under a constant load placed while bathed in 25% Dextran irrigation solution. A study was performed on 57 Florida Lions Eye Bank donated human cadaver eyes to determine the effect of temperature on the amount and rate of thermal shrinkage. Further experiments were performed on 20 human cadaver eyes to determine the effects of heating duration on permanent shrinkage. Data analysis was performed to determine the effects of temperature, heating duration, and age on the amount and kinetics of shrinkage. Results: Shrinkage consisted of two phases: a shrinkage phase during heating and a regression phase after heating. Permanent shrinkage increased with temperature and duration. The shrinkage and regression time constants followed Arrhenius type temperature dependence. The shrinkage time constants where calculated to be 67, 84, 121, 560 and 1112 (s) at 80, 75, 70, 65, and 60°C respectively. At 65°C the permanent shrinkage time constant was calculated to be 945s. Conclusion: These results show that shrinkage treatments need to raise the temperature of the tissue above 75°C for several seconds in order to prevent regression of the shrinkage effect immediately after treatment and to induce the maximum amount of permanent irreversible shrinkage.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahurin, Shannon Mark; Sokolov, Alexei P.; Saito, Tomonori

Here, the vinyl addition polymerization of norbornylbased monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C 6F 5) 2(SbPh 3) 2]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxanesubstituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (T d ≥ 362 °C) and were cast into membranes that displayed high CO 2 permeability and enhanced COmore » 2/N 2 selectivity as compared to related materials.« less

Novel (meth)acrylate monomers for ultrarapid polymerization and enhanced polymer properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beckel, E. R.; Berchtold, K. A.; Nie, J.

2002-01-01

Ultraviolet light is known to be one of the most efficient methods to initiatc polymeric reactions in the presence of a photonitiator. Photopolymerizations are advantageous because the chemistry of the materials can be tailored to design liquid monomers for ultrarapid polymerization into a solid polymer material. One way to achieve rapid photopolymerizations is to utilize multifunctional (meth)acrylate monomers. which form highly crosslinked polymers; however, these monomers typically do not achieve complete functional group conversion. Recently, Decker et al. developed novel monovinyl acrylate monomers that display polyriicrization kinetics that rival those of multifunctional acrylate monomers. These novel acrylate monomers incorporate secondarymore » functionalities and end groups such as carbonates, carbamates, cyclic carbonates and oxazolidone which promote the increased polymerization kinetics of these monomers. In addition to thc polynierization kinetics, these novel monovinyl monomers form crosslinked polymers, which are characterized by having high strength and high flexibility. Unfortunately, the exact mechanism or mechanisms responsible for the polymerization kinetics and crosslinking are not well understood.« less

Superwettability-Induced Confined Reaction toward High-Performance Flexible Electrodes.

PubMed

Xiong, Weiwei; Liu, Hongliang; Zhou, Yahong; Ding, Yi; Zhang, Xiqi; Jiang, Lei

2016-05-18

To find a general strategy to realize confinement of the conductive layer for high-performance flexible electrodes, with improved interfacial adhesion and high conductivity, is of important scientific significance. In this work, superwettability-induced confined reaction is used to fabricate high-performance flexible Ag/polymer electrodes, showing significantly improved silver conversion efficiency and interfacial adhesion. The as-prepared flexible electrodes by superhydrophilic polymeric surface under oil are highly conductive with an order of magnitude higher than the Ag/polymer electrodes obtained from original polymeric surface. The high conductivity achieved via superhydrophilic confinement is ascribed to the fact that the superhydrophilic polymeric surface can enhance the reaction rate of silver deposition and reduce the size of silver nanoparticles to achieve the densest packing. This new approach will provide a simple method to fabricate flexible and highly conductive Ag/polymer electrodes with excellent adhesion between the conductive layer and the substrate, and can be extended to other metal/polymeric electrodes or alloy/polymeric electrodes.

A New Route for High-Purity Organic Materials: High-Pressure-Ramp-Induced Ultrafast Polymerization of 2-(Hydroxyethyl)Methacrylate

NASA Astrophysics Data System (ADS)

Evlyukhin, E.; Museur, L.; Traore, M.; Perruchot, C.; Zerr, A.; Kanaev, A.

2015-12-01

The synthesis of highly biocompatible polymers is important for modern biotechnologies and medicine. Here, we report a unique process based on a two-step high-pressure ramp (HPR) for the ultrafast and efficient bulk polymerization of 2-(hydroxyethyl)methacrylate (HEMA) at room temperature without photo- and thermal activation or addition of initiator. The HEMA monomers are first activated during the compression step but their reactivity is hindered by the dense glass-like environment. The rapid polymerization occurs in only the second step upon decompression to the liquid state. The conversion yield was found to exceed 90% in the recovered samples. The gel permeation chromatography evidences the overriding role of HEMA2•• biradicals in the polymerization mechanism. The HPR process extends the application field of HP-induced polymerization, beyond the family of crystallized monomers considered up today. It is also an appealing alternative to typical photo- or thermal activation, allowing the efficient synthesis of highly pure organic materials.

Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals.

PubMed

Zhou, Chun-Hui Clayton; Beltramini, Jorge N; Fan, Yong-Xian; Lu, G Q Max

2008-03-01

New opportunities for the conversion of glycerol into value-added chemicals have emerged in recent years as a result of glycerol's unique structure, properties, bioavailability, and renewability. Glycerol is currently produced in large amounts during the transesterification of fatty acids into biodiesel and as such represents a useful by-product. This paper provides a comprehensive review and critical analysis on the different reaction pathways for catalytic conversion of glycerol into commodity chemicals, including selective oxidation, selective hydrogenolysis, selective dehydration, pyrolysis and gasification, steam reforming, thermal reduction into syngas, selective transesterification, selective etherification, oligomerization and polymerization, and conversion of glycerol into glycerol carbonate.

Ten-Year Follow-Up of Endovascular Aneurysm Treatment with Talent Stent-Grafts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pitton, Michael B., E-mail: pitton@radiologie.klinik.uni-mainz.de; Scheschkowski, Tobias; Ring, Markus

2009-09-15

The purpose of this study was to evaluate the clinical results, complications, and secondary interventions during long-term follow-up after endovascular aneurysm repair (EVAR) and to investigate the impact of endoleak sizes on aneurysm shrinkage. From 1997 to March 2007, 127 patients (12 female, 115 male; age, 73.0 {+-} 7.2 years) with abdominal aortic aneurysms were treated with Talent stent-grafts. Follow-up included clinical visits, contrast-enhanced MDCT, and radiographs at 3, 6, and 12 months and then annually. Results were analyzed with respect to clinical outcome, secondary interventions, endoleak rate and management, and change in aneurysm size. There was no need formore » primary conversion surgery. Thirty-day mortality was 1.6% (two myocardial infarctions). Procedure-related morbidity was 2.4% (paraplegia, partial infarction of one kidney, and inguinal bleeding requiring surgery). Mean follow-up was 47.7 {+-} 34.2 months (range, 0-123 months). Thirty-nine patients died during follow-up; three of the deaths were related to aneurysm (aneurysm rupture due to endoleak, n = 1; secondary surgical reintervention n = 2). During follow-up, a total of 29 secondary procedures were performed in 19 patients, including 14 percutaneous procedures (10 patients) and 15 surgical procedures (12 patients), including 4 cases with late conversion to open aortic repair (stent-graft infection, n = 1; migration, endoleak, or endotension, n = 3). Overall mean survival was 84.5 {+-} 4.7 months. Mean survival and freedom from any event was 66.7 {+-} 4.5 months. MRI depicted significantly more endoleaks compared to MDCT (23.5% vs. 14.3%; P < 0.01). Patients in whom all aneurysm side branches were occluded prior to stent-grafting showed a significantly reduced incidence of large endoleaks. Endoleaks >10% of the aneurysm area were associated with reduced aneurysm shrinkage compared to no endoleaks or <10% endoleaks ({Delta} at 3 years, -1.8% vs. -12.0%; P < 0.05). In conclusion, endovascular aneurysm treatment with Talent stent-grafts demonstrated encouraging long-term results with moderate secondary intervention rates. Primary occlusion of all aortic side branches reduced the incidence of large endoleaks. Large endoleaks significantly impaired aneurysm shrinkage, whereas small endoleaks did not.« less

Study of deformation of resin cements used in fixing of root posts through fiber Bragg grating sensors

NASA Astrophysics Data System (ADS)

Pulido, C. A.; Franco, A. P. G. O.; Karam, L. Z.; Kalinowski, H. J.; Gomes, O. M. M.

2014-05-01

The aim of the study was to evaluate the polymerization shrinkage "in situ" in resin cements inside the root canal during the fixation of glass fiber posts. For cementation teeth were randomly divided into 2 groups according to the resin cement used: Group1 - resin cement dual Relyx ARC (3M/ESPE), and Group 2 - resin cement dual Relyx U200 (3M/ESPE). Before inserting the resin cement into the root canal, two Bragg grating sensors were recorded and pasted in the region without contact with the canal, one at the apical and other at the coronal thirds of the post. The sensors measured the deformation of the resin cements in coronal and apical root thirds to obtain the values in micro-strain (μɛ).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennemur, Justin G.; Bates, Frank S.; Hillmyer, Marc A.

Synthesis of poly(methyl ethacrylate), (PMEA), in tetrahydrofuran at -78 °C using anionic polymerization techniques results in high molar mass (>30 kg mol-1), low dispersity (1.3), and high conversion (>81%). The molar masses of a series of samples are consistent with values anticipated by the monomer-to-initiator ratio and conversion. These results represent a significant improvement to earlier reported attempts to prepare PMEA using anionic methods. Successful diblock polymerization of polystyrene-block-PMEA, (PS-PMEA), and poly(4-tert-butylstyrene)-block-PMEA, (PtBS-PMEA), is achieved through sequential anionic polymerization techniques with dispersities as low as 1.06 and segment molar fractions close to those targeted. Broad principal scattering peaks observed bymore » small-angle X-ray scattering (SAXS) for symmetric PS-PMEA at relatively high molar mass (39 kg mol-1) suggests an effective interaction parameter (χeff) that is smaller than for PS-block-poly(methyl methacrylate). On the other hand, PtBS-PMEA block polymers form a well-ordered morphology based on SAXS measurements and is attributable to the more hydrophobic PtBS segment. These results confirm the viability of PMEA as a new constituent in the expanding suite of polymers suitable for preparing nanostructured block polymers.« less

Photo-triggered solvent-free metamorphosis of polymeric materials.

PubMed

Honda, Satoshi; Toyota, Taro

2017-09-11

Liquefaction and solidification of materials are the most fundamental changes observed during thermal phase transitions, yet the design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion remains challenging. Here, we demonstrate that solvent-free repeatable molecular architectural transformation between liquid-star and nonliquid-network polymers that relies on cleavage and reformation of a covalent bond in hexaarylbiimidazole. Liquid four-armed star-shaped poly(n-butyl acrylate) and poly(dimethyl siloxane) with 2,4,5-triphenylimidazole end groups were first synthesized. Subsequent oxidation of the 2,4,5-triphenylimidazoles into 2,4,5-triphenylimidazoryl radicals and their coupling with these liquid star polymers to form hexaarylbiimidazoles afforded the corresponding nonliquid network polymers. The resulting nonliquid network polymers liquefied upon UV irradiation and produced liquid star-shaped polymers with 2,4,5-triphenylimidazoryl radical end groups that reverted to nonliquid network polymers again by recoupling of the generated 2,4,5-triphenylimidazoryl radicals immediately after terminating UV irradiation.The design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion is challenging. Here, the authors show solvent-free repeatable molecular architectural transformation between liquid-star and non-liquid-network polymers by the cleavage and reformation of covalent bonds in the polymer chain.

Methacrylic Zwitterionic, Thermoresponsive, and Hydrophilic (Co)Polymers via Cu(0)-Polymerization: The Importance of Halide Salt Additives.

PubMed

Simula, Alexandre; Anastasaki, Athina; Haddleton, David M

2016-02-01

The synthesis of hydrophilic, thermoresponsive, and zwitterionic polymethacrylates is reported by Cu(0)-mediated reversible deactivation radical polymerization in water and/or water/alcohol mixtures. The predisproportionation of [Cu(I) (PMDETA)Cl] in water prior to initiator and monomer addition is exploited to yield well-defined polymethacrylates with full monomer conversions in 30 min. The addition of supplementary halide salts (NaCl) enables the synthesis of various molecular weight poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA475) (DPn = 10-80, Mn ≈ 10,000-40 000 g mol(-1)) with full monomer conversion and narrow molecular weight distributions attained in all cases (Đ ≈ 1.20-1.30). A bifunctional PEG initiator (average Mn ≈ 1000 g mol(-1)) is utilized for the polymerization of a wide range of methacrylates including 2-dimethylaminoethyl methacrylate, 2-morpholinoethyl methacrylate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and 2-methacryloyloxyethyl phosphorylcholine. Despite the high water content, high end group fidelity is demonstrated by in situ chain extensions and block copolymerizations with PEGMA475 yielding well-defined functional telechelic pentablock copolymers within 2.5 h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure of Polyelectrolyte Brushes in the Presence of Multivalent Counterions

DOE PAGES

Yu, Jing; Mao, Jun; Yuan, Guangcui; ...

2016-07-20

Polyelectrolyte brushes are of great importance to a wide range of fields, ranging from colloidal stabilization to responsive and tunable materials to lubrication. Here, we synthesized high-density polystyrenesulfonate (PSS) brushes using surface initiated atom transfer radical polymerization and performed neutron reflectivity (NR) and surface force measurements using a surface forces apparatus (SFA) to investigate the effect of monovalent Na +, divalent Ca 2+, Mg 2+, and Ba 2+, and trivalent Y 3+ counterions on the structure of the PSS brushes. NR and SFA results demonstrate that in monovalent salt solution the behavior of the PSS brushes agrees with scaling theorymore » well, exhibiting two distinct regimes: the osmotic and salted brush regimes. Introducing trivalent Y 3+ cations causes an abrupt shrinkage of the PSS brush due to the uptake of Y 3+ counterions. The uptake of Y 3+ counterions and shrinkage of the brush are reversible upon increasing the concentration of monovalent salt. Divalent cations, Mg 2+, Ca 2+, and Ba 2+, while all significantly affecting the structure of PSS brushes, show strong ion specific effects that are related to the specific interactions between the divalent cations and the sulfonate groups. Our results demonstrate that the presence of multivalent counterions, even at relatively low concentrations, can strongly affect the structure of polyelectrolyte brushes. Finally, the results also highlight the importance of ion specificity to the structure of polyelectrolyte brushes in solution.« less

Kinetics of bulk photo-initiated copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) polymerizations†

PubMed Central

Song, Han Byul; Baranek, Austin; Bowman, Christopher N.

2016-01-01

Photoinitiation of polymerizations based on the copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ. Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm−2 light exposure at 400–500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)’s catalytic lifetime and the nature of the step-growth polymerization. PMID:27429650

Effect of post-polymerization heat-treatments on degree of conversion, leaching residual MMA and in vitro cytotoxicity of autopolymerizing acrylic repair resin.

PubMed

Bural, Canan; Aktaş, Esin; Deniz, Günnur; Ünlüçerçi, Yeşim; Kızılcan, Nilgün; Bayraktar, Gülsen

2011-11-01

This study evaluated the effect of post-polymerization heat-treatments on degree of conversion (DC), residual methyl methacrylate concentration (MMA(r)) and in vitro cytotoxicity of autopolymerizing acrylic repair resin. A total of 336 specimens were prepared by bench- and hydroflask-curing and subjected to post-polymerization heat-treatments: a) water immersion at 60°C for 30 min, b) microwaving at 500 W for 3 min, c) combined use of water immersion and microwaving d) no treatment (as control). Specimens were eluted in cell culture medium for 1, 2, 5 and 7 days. DC and MMA(r) in eluates were measured by FTIR spectrometry and HPLC, respectively. In vitro cytotoxicity of eluates on L-929 fibroblasts was determined by XTT assay. Data were statistically analyzed with Dunn's multiple comparison and Pearson correlation tests (p≤0.05). DC was highest (99.9%) in bench- and hydroflask-cured groups which were subjected to water immersion. At all elution periods, MMA(r) was detected in eluates of all treatment groups and were higher in bench-cured groups than hydro-flask cured groups. Cell proliferation values indicated slightly cytotoxic effect throughout 7 days; regardless of the curing method or post-polymerization treatment. The correlation between MMA(r) and cell proliferation was negative after elution of 1, 2, 5 days and was only statistically significant (p<0.05) at 5 days. At elution of 7 days, the correlation was positive with no significance. Post-polymerization heat-treatment of autopolymerizing acrylic repair resin by immersion in water at 60°C for 30 min is clinically recommended to improve the DC while reducing the leaching residual MMA. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Modification of linear prepolymers to tailor heterogeneous network formation through photo-initiated Polymerization-Induced Phase Separation

PubMed Central

Szczepanski, Caroline R.; Stansbury, Jeffrey W.

2015-01-01

Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) modified by poly(methyl methacrylate) (PMMA). The molecular weight of PMMA and the rate of network formation (through incident UV-irradiation) were varied to influence both the promotion of phase separation through increases in overall free energy, as well as the extent to which phase development occurs during polymerization through diffusion prior to network gelation. The overall free energy of the polymerizing system increases with PMMA molecular weight, such that PIPS is promoted thermodynamically at low loading levels (5 wt%) of a higher molecular weight PMMA (120 kDa), while a higher loading level (20 wt%) is needed to induce PIPS with lower PMMA molecular weight (11 kDa), and phase separation was not promoted at any loading level tested of the lowest molecular weight PMMA (1 kDa). Due to these differences in overall free energy, systems modified by PMMA (11 kDa) underwent phase separation via Nucleation and Growth, and systems modified by PMMA (120 kDa), followed the Spinodal Decomposition mechanism. Despite differences in phase structure, all materials form a continuous phase rich in TEGDMA homopolymer. At high irradiation intensity (Io=20mW/cm2), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (Io=300µW/cm2) for the first ~50% of reaction to allow phase separation via diffusion, followed by a high intensity flood-cure to achieve a high degree of conversion, was employed to form phase-separated networks with reduced polymerization stress yet equivalent final conversion and modulus. PMID:26190865

Synthesis biolubricant from rubber seed oil

NASA Astrophysics Data System (ADS)

Hung, Nguyen Tran Dong; Tuyen, Dang Thi Hong; Viet, Tran Tan

2017-09-01

The objective was biolubricant preparation from rubber seed oil (RSO) using polymerization reactor with/without catalyst in batch reactor. Before become reactant in polymerization reaction, a non-edible rubber seed oil was converted into methyl ester by esterification/tranesterification reaction with methanol and acid/base catalyst. The polymerization reaction parameters investigated were reaction time, temperature and weight ratio (catalyst with feed), and their effect on the bio lubricant formation. The result show significant conversion of methyl ester to bio lubricant in the temperature reaction of 160°C, reaction time of 2h min and ratio of super acid catalyst (tetrafluoroboric acid-sHBF4) of 3 %w/w. The resulting products were confirmed by GC-MS, FTIR spectroscopy and also analyzed for the viscosity. The best viscosity value of RSOFAME polymer was 110.6 cSt when the condition polymerization reaction were 160 °C, reaction time 3h, 6 wt% mass ratio of oil:catalyst.

Well-Defined High Molecular Weight Polystyrene with High Rates and High Livingness Synthesized via Two-Stage RAFT Emulsion Polymerization.

PubMed

Yan, Kun; Gao, Xiang; Luo, Yingwu

2015-07-01

A highly living polymer with over 100 kg mol(-1) molecular weight is very difficult to achieve by controlled radical polymerization since the unavoidable side reactions of irreversible radical termination and radical chain transfer to monomer reaction become significant. It is reported that over 500 kg mol(-1) polystyrene with high livingness and low dispersity could be synthesized by a facile two-stage reversible addition-fragmentation transfer emulsion polymerization. The monomer conversion reaches 90% within 10 h. High livingness of the product is ascribed to the extremely low initiator concentration and the chain transfer constant for monomer unexpectedly much lower than the well-accepted values in the conventional radical polymerization. The two-stage monomer feeding policy much decreases the dispersity of the product. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Candida antartica lipase B catalyzed polycaprolactone synthesis: effects of organic media and temperature.

PubMed

Kumar, A; Gross, R A

2000-01-01

Engineering of the reaction medium and study of an expanded range of reaction temperatures were carried out in an effort to positively influence the outcome of Novozyme-435 (immobilized Lipase B from Candida antarctica) catalyzed epsilon-CL polymerizations. A series of solvents including acetonitrile, dioxane, tetrahydrofuran, chloroform, butyl ether, isopropyl ether, isooctane, and toluene (log P from -1.1 to 4.5) were evaluated at 70 degrees C. Statistically (ANOVA), two significant regions were observed. Solvents having log P values from -1.1 to 0.49 showed low propagation rates (< or = 30% epsilon-CL conversion in 4 h) and gave products of short chain length (Mn < or = 5200 g/mol). In contrast, solvents with log P values from 1.9 to 4.5 showed enhanced propagation rates and afforded polymers of higher molecular weight (Mn = 11,500-17,000 g/mol). Toluene, a preferred solvent for this work, was studied at epsilon-CL to toluene (wt/vol) ratios from 1:1 to 10:1. The ratio 1:2 was selected since, for polymerizations at 70 degrees C, 0.3 mL of epsilon-CL and 4 h, gave high monomer conversions and Mn values (approximately 85% and approximately 17,000 g/mol, respectively). Increasing the scale of the reaction from 0.3 to 10 mL of CL resulted in a similar isolated product yield, but the Mn increased from 17,200 to 44,800 g/mol. Toluene appeared to help stabilize Novozyme-435 so that lipase-catalyzed polymerizations could be conducted effectively at 90 degrees C. For example, within only 2 h at 90 degrees C (toluene-d8 to epsilon-CL, 5:1, approximately 1% protein), the % monomer conversion reached approximately 90%. Also, the controlled character of these polymerizations as a function of reaction temperature was evaluated.

Repair of dimethacrylate-based composite restorations by a silorane-based composite: a one-year randomized clinical trial.

PubMed

Popoff, D A V; Santa Rosa, T T A; Ferreira, R C; Magalhães, C S; Moreira, A N; Mjör, I A

2012-01-01

To investigate clinical performance of a low-shrinkage silorane-based composite resin when used for repairing conventional dimethacrylate-based composite restorations. Despite the continued development of resin-based materials, polymerization shrinkage and shrinkage stress still require improvement. A silorane-based monomer system was recently made available for dental restorations. This report refers to the use of this material for making repairs and evaluates the clinical performance of this alternative treatment. One operator repaired the defective dimethacrylate-based composite resin restorations that were randomly assigned to one of two treatment groups: control (n=50) repair with Adper SE Plus (3M/ESPE) and Filtek P60 Posterior Restorative (3M/ESPE), and test (n=50) repair with P90 System Adhesive Self-Etch Primer and Bond (3M/ESPE) and Filtek P90 Low Shrink Posterior Restorative (3M/ESPE). After one week, restorations were finished and polished. Two calibrated examiners (Kw≥0.78) evaluated all repaired restorations, blindly and independently, at baseline and one year. The parameters examined were marginal adaptation, anatomic form, surface roughness, marginal discoloration, postoperative sensitivity, and secondary caries. The restorations were classified as Alpha, Bravo, or Charlie, according to modified US Public Health Service criteria. Mann-Whitney and Wilcoxon tests were used to compare the groups. Of the 100 restorations repaired in this study, 93 were reexamined at baseline. Dropout from baseline to one-year recall was 11%. No statistically significant differences were found between the materials for all clinical criteria, at baseline or at one-year recall (p>0.05). No statistically significant differences were registered (p>0.05) for each material when compared for all clinical criteria at baseline and at one-year recall. The hypothesis tested in this randomized controlled clinical trial was accepted. After the one-year evaluations, the silorane-based composite exhibited a similar performance compared with dimethacrylate-based composite when used to make repairs.

Synthesis, characterization and evaluation of a fluorinated resin monomer with low water sorption.

PubMed

Liu, Xue; Wang, Zengyao; Zhao, Chengji; Bu, Wenhuan; Zhang, Yurong; Na, Hui

2018-01-01

A fluorinated acrylate monomer (4-TF-PQEA) without BPA (bisphenol-A) structure was synthesized and mixed with triethylene glycol dimethacrylate (TEGDMA) to used as dental resin system in order to achieve lower water sorption and reduce human exposure to BPA derivatives. Double bond conversion (DC) was measured using Fourier transform infrared spectroscopy (FTIR). Water sorption (WS), water solution (WL) and depth of cure (DOC) were evaluated according to ISO 4049:2009. Water contact angle (CA) was measured using contact angle analyzer. Polymerization shrinkage (PS) was evaluated according to the Archimedes' principle and ISO 17304:2013. Flexural strength (FS) and flexural modulus (FM) were measured by three-point bending test with a universal testing machine according to ISO 4049:2009. Comprehensive strength (CS) and vickers microhardness (VM) were also investigated. Thermal stability test was measure by Thermogravimetric analyzer. Cytotoxicity of three resin systems was tested through MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromid) cytotoxicity method according to the ISO 10993-5:2009. Bisphenol-A glycidyl dimethacrylate (Bis-GMA)/ TEGDMA resin system was used as a control. The results show that 4-TF-PQEA/TEGDMA resin system had lower PS, lower WS and higher DC values than those of Bis-GMA/TEGDMA resin system except some mechanical properties, such as FS, FM and CS. Moreover, properties of other 4-TF-PQEA-containing resin systems were also comparable with those of Bis-GMA/TEGDMA resin system. In particular, the overall performance of resin system consisted of 4-TF-PQEA/Bis-GMA/TEGDMA is optimized when the mixture ratio is 30/40/30(wt/wt/wt). Therefore, the 4-TF-PQEA has potential to be used as resin monomer for dental resin composites to achieve lower water sorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives.

PubMed

Zhang, Ying; Wu, Ningjing; Bai, Xinyan; Xu, Changqi; Liu, Yi; Wang, Yong

2013-10-01

The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022 mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022-0.088 mmol/g). HAp (2-8 wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding. Copyright © 2013 Elsevier B.V. All rights reserved.

Kinetics of waterborne fluoropolymers prepared by one-step semi-continuous emulsion polymerization of chlorotrifluoroethylene, vinyl acetate, butyl acrylate and Veova 10

NASA Astrophysics Data System (ADS)

Liu, H. Z.; Wang, M. H.; Wang, Z. F.; Bian, J. M.

2018-01-01

Due to using gaseous fluorine monomer with toxicity, waterborne fluoropolymers are synthesized by semi-continuous high-pressure emulsion polymerization method which differs from free-pressure emulsion polymerization. To dates, the research on preparing process and kinetics for high-pressure emulsion polymerization is reported relatively less, which hinders researchers from understanding of mechanisms for monomer-fluorinated emulsion polymerization. The paper also provides a new method by element auxiliary analysis to calculate kinetics parameters of high-pressure emulsion polymerization. Based on aforementioned consideration, waterborne fluoropolymers were prepared by copolymerization of chlorotrifluoroethylene (CTFE), vinyl acetate (VAc), butyl acrylate (BA) and vinyl ester of versatic acid (Veova 10) using potassium persulfate as initiator and mixed surfactants. The kinetics of emulsion polymerization of waterborne fluoropolymers was then investigated. Effects of emulsifier concentration, initiator concentration, and polymerization temperature on polymerization rate (Rp) were evaluated, and relationship was described as Rp∝[I]0.10 and Rp∝[E]0.12. The apparent activation energy was determined to be 33.61 kJ·mol-1. Moreover, the relative conversion rate of CTFE with the other monomers was observed, and results indicated that CTFE monomer more uniformly copolymerized with the other monomers. The resulting emulsion properties and pressure change in an autoclave were evaluated at different stirring rates. The initial reaction time, defined as the beginning time of dropwise addition, was determined by the change in solid content and particle size of emulsion.

Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives

PubMed Central

Zhang, Ying; Wu, Ningjing; Bai, Xinyan; Xu, Changqi; Liu, Yi; Wang, Yong

2013-01-01

The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022 mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022–0.088 mmol/g). HAp (2–8 wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding. PMID:23910263

Impedance changes during setting of amorphous calcium phosphate composites.

PubMed

Par, Matej; Šantić, Ana; Gamulin, Ozren; Marovic, Danijela; Moguš-Milanković, Andrea; Tarle, Zrinka

2016-11-01

To investigate the electrical properties of experimental light-curable composite materials based on amorphous calcium phosphate (ACP) with the admixture of silanized barium glass and silica fillers. Short-term setting was investigated by impedance measurements at a frequency of 1kHz, while for the long-term setting the impedance spectra were measured consecutively over a frequency range of 0.05Hz to 1MHz for 24h. The analysis of electrical resistivity changes during curing allowed the extraction of relevant kinetic parameters. The impedance results were correlated to the degree of conversion assessed by Raman spectroscopy, water content determined by gravimetry, light transmittance measured by CCD spectrometer and microstructural features observed by scanning electron microscopy. ACP-based composites have shown higher immediate degree of conversion and less post-cure polymerization than the control composites, but lower polymerization rate. The polymerization rate assessed by impedance measurements correlated well with the light transmittance. The differences in the electrical conductivity values observed among the materials were correlated to the amount of water introduced into composites by the ACP filler. High correlation was found between the degree of conversion and electrical resistivity. Equivalent circuit modeling revealed two electrical contributions for the ACP-based composites and a single contribution for the control composites. The impedance spectroscopy has proven a valuable method for gaining insight into various features of ACP-based composites. Better understanding of the properties of ACP-based composites should further the development of these promising bioactive materials. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Delayed photo-activation and addition of thio-urethane: Impact on polymerization kinetics and stress of dual-cured resin cements.

PubMed

Faria-E-Silva, André L; Pfeifer, Carmem S

2017-10-01

1) to determine the moment during the redox polymerization reaction of dual cure cements at which to photo-activate the material in order to reduce the polymerization stress, and 2) to evaluate possible synergistic effects between adding chain transfer agents and delayed photo-activation. The two pastes of an experimental dual-cure material were mixed, and the polymerization kinetics of the redox phase was followed. The moment when the material reached its maximum rate of redox polymerization (MRRP) of cement was determined. The degree of conversion (DC) and maximum rates of polymerization (Rp max ) were assessed for materials where: the photoactivation immediately followed material mixing, at MRRP, 1min before and 1min after MRRP. Thio-urethane (TU) additives were synthesized and added to the cement (20% wt), which was then cured under the same conditions. The polymerization kinetics was evaluated for both cements photo-activated immediately or at MRRP, followed by measurements of polymerization stress, flexural strength (FS) and elastic modulus (EM). Knoop hardness was measured before and after ethanol storage. Photo-activating the cement at or after MRRP reduced the Rp max and the polymerization stress. Addition of TU promoted additional and more significant reduction, while not affecting the Rp max . Greater hardness loss was observed for cements with TU, but the final hardness was similar for all experimental conditions. Addition of TU slightly reduced the EM and did not affect the FS. Delayed photo-activation and addition of TU significantly reduce the polymerization stress of dual-cured cements. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermally resistant polymers for fuel tank sealants

NASA Technical Reports Server (NTRS)

Webster, J. A.

1972-01-01

Conversion of fluorocarbon dicarboxylic acid to intermediates whose terminal functional groups permit polymerization is discussed. Resulting polymers are used as fuel tank sealers for jet fuels at elevated temperatures. Stability and fuel resistance of the prototype polymers is explained.

Biosynthesis of Plant and Animal Foods.

ERIC Educational Resources Information Center

Dunne, C. Patrick

1984-01-01

Presents a biochemical overview of the synthesis of food biopolymers that constitute macronutrients in the plant or animal cell. Emphasizes involvement of enzymes in steps characterized by accumulation of materials, activation, polymerization, postpolymerization conversion, and formation of structural components. (JN)

In vitro assessment of polymerization procedures in Class II restorations: sealing, FTIR, and microhardness evaluations.

PubMed

Tassery, H; de Donato, P; Barrès, O; Déjou, J

2001-01-01

This study was undertaken to evaluate several polymerization and filling procedures (incremental, bulk, light-tip, soft-cured, plasma devices) in Class II restorations through (1) a sealing evaluation of restorations filled with Tetric Ceram (TC) and Bisfil 2B (B2B, self-cured composite used as a control), (2) a FTIR analysis measuring the variations of the degree of conversion in terms of area unit ratio of the relevant resin composites and (3) a microhardness test to corroborate the FTIR analysis. The length of the tracer penetration was measured from the gingival margin up to the cavity wall with an episcope on sectioned teeth. A ceramic mould, simulating a Class II, was filled according to the different groups and the samples were analyzed with a Bruker IFS 55 spectrometer on ultrathin sections (3 mu). The results were analyzed in terms of area unit ratio and total exposed energy. Under the same conditions, a microhardness test was run with a Frank Weihem machine. The results of the sealing evaluation for light-tip, incremental and self-cured techniques did not differ. The plasma procedure failed in this evaluation as the bottom increment was not polymerized. The smallest area unit ratio (the best degree of conversion) was observed in 2 groups: one, the combination of the light-tip and soft process, and two, the self-cured resin composite (B2B). The distance at which the plasma procedure failed to cure the resin composite was between 3.5 and 4.5 mm. The microhardness test confirmed the FTIR analysis except for the group G2 (TC + light-tip). As also shown by FTIR analysis, no difference between the two relevant levels was observed with the hardness test. The dentin marginal sealing efficiency of Tetric Ceram restorations was increased with the light-tip technique, but was not better than the self-cured resin composite (B2B). For Tetric Ceram, the combination of the light-tip and soft process leads to a higher degree of conversion than the other groups. There is no linear relationship between the degree of conversion, the microhardness and the total exposed energy. The combination of the soft polymerization and the light-tip device might be an alternative restorative technique to the current incremental technique.

Photo-induced living radical polymerization of acrylates utilizing a discrete copper(II)-formate complex.

PubMed

Anastasaki, Athina; Nikolaou, Vasiliki; Brandford-Adams, Francesca; Nurumbetov, Gabit; Zhang, Qiang; Clarkson, Guy J; Fox, David J; Wilson, Paul; Kempe, Kristian; Haddleton, David M

2015-04-04

A photo-polymerization protocol, utilizing a pre-formed and well-characterized Cu(II) formate complex, [Cu(Me6-Tren)(O2CH)](ClO4), mediated by UV light is described. In the absence of additional reducing agents and/or photosensitizers, ppm concentrations of the oxidatively stable [Cu(Me6-Tren)(O2CH)](ClO4), furnish near-quantitative conversions within 2 h, yielding poly(acrylates) with low dispersities (∼1.10) and exceptional end-group fidelity, capable of undergoing in situ chain extension and block copolymerization.

Cu-catalyzed multicomponent polymerization to synthesize a library of poly(N-sulfonylamidines).

PubMed

Lee, In-Hwan; Kim, Hyunseok; Choi, Tae-Lim

2013-03-13

We report a versatile Cu-catalyzed multicomponent polymerization (MCP) technique that enables the synthesis of high-molecular-weight, defect-free poly(N-sulfonylamidines) from monomers of diynes, sulfonyl azides, and diamines. Through a series of optimizations, we discovered that the addition of excess triethylamine and the use of N,N'-dimethylformamide as a solvent are key factors to ensure efficient MCP. Formation of cyclic polyamidines was a side reaction during polymerization, but it was readily controlled by using diynes or diamines with long or rigid moieties. In addition, this polymerization is highly selective for three-component reactions over click reactions. The combination of the above factors enables the synthesis of high-molecular-weight polymers, which was challenging in previous MCPs. All three kinds of monomers (diynes, sulfonyl azides, and diamines) are readily accessible and stable under the reaction conditions, with various monomers undergoing successful polymerization regardless of their steric and electronic properties. Thus, we synthesized various high-molecular-weight, defect-free polyamidines from a broad range of monomers while overcoming the limitations of previous MCPs, such as low conversion and defects in the polymer structures.

The Effect of Surfactant and Compatibilizer on Inorganic Loading and Properties of PPO-based EPMM Membranes

NASA Astrophysics Data System (ADS)

Bissadi, Golnaz

Hybrid membranes represent a promising alternative to the limitations of organic and inorganic materials for high productivity and selectivity gas separation membranes. In this study, the previously developed concept of emulsion-polymerized mixed matrix (EPMM) membranes was further advanced by investigating the effects of surfactant and compatibilizer on inorganic loading in poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based EPMM membranes, in which inorganic part of the membranes originated from tetraethylorthosilicate (TEOS). The polymerization of TEOS, which consists of hydrolysis of TEOS and condensation of the hydrolyzed TEOS, was carried out as (i) one- and (ii) two-step processes. In the one-step process, the hydrolysis and condensation take place in the same environment of a weak acid provided by the aqueous solution of aluminum hydroxonitrate and sodium carbonate. In the two-step process, the hydrolysis takes place in the environment of a strong acid (solution of hydrochloric acid), whereas the condensation takes place in weak base environment obtained by adding excess of the ammonium hydroxide solution to the acidic solution of the hydrolyzed TEOS. For both one- and two-step processes, the emulsion polymerization of TEOS was carried out in two types of emulsions made of (i) pure trichloroethylene (TCE) solvent, and (ii) 10 w/v% solution of PPO in TCE, using different combinations of the compatibilizer (ethanol) and the surfactant (n-octanol). The experiments with pure TCE, which are referred to as a gravimetric powder method (GPM) allowed assessing the effect of different experimental parameters on the conversion of TEOS. The GPM tests also provided a guide for the synthesis of casting emulsions containing PPO, from which the EPMM membranes were prepared using a spin coating technique. The synthesized EPMM membranes were characterized using 29Si nuclear magnetic resonance (29Si NMR), differential scanning calorimetry (DSC), inductively coupled plasma mass spectrometry (ICP-MS), and gas permeation measurements carried out in a constant pressure (CP) system. The 29Si NMR analysis verified polymerization of TEOS in the emulsions made of pure TCE, and the PPO solution in TCE. The conversions of TEOS in the two-step process in the two types of emulsions were very close to each other. In the case of the one-step process, the conversions in the TCE emulsion were significantly greater than those in the emulsion of the PPO solution in TCE. Consequently, the conversions of TEOS in the EPMM membranes made in the two-step process were greater than those in the EPMM membranes made in the one-step process. The latter ranged between 10 - 20%, while the highest conversion in the two-step process was 74% in the presence of pure compatibilizer with no surfactant. Despite greater conversions and hence the greater inorganic loadings, the EPMM membranes prepared in the two-step process had glass transition temperatures (Tg) only slightly greater than the reference PPO membranes. In contrast, despite relatively low inorganic loadings, the EPMM membranes prepared in the one-step process had Tgs markedly greater than PPO, and showed the expected trend of an increase in Tg with the inorganic loading. These results indicate that in the case of the one-step process the polymerized TEOS was well integrated with the PPO chains and the interactions between the two phases lead to high Tgs. On the other hand, this was not the case for the EPMM membranes prepared in the two-step process, suggesting possible phase separation between the polymerized TEOS and the organic phase. The latter was confirmed by detecting no selectivity in the EPMM membranes prepared by the two-step process. In contrast, the EPMM membranes prepared in the one-step process in the presence of the compatibilizer and no surfactant showed 50% greater O2 permeability coefficient and a slightly greater O2/N2 permeability ratio compared to the reference PPO membranes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asamoto, Shingo, E-mail: asamoto@mail.saitama-u.ac.j; Ohtsuka, Ayumu; Kuwahara, Yuta

In this paper, the effects of actual environmental actions on shrinkage, creep and shrinkage cracking of concrete are studied comprehensively. Prismatic specimens of plain concrete were exposed to three sets of artificial outdoor conditions with or without solar radiation and rain to examine the shrinkage. For the purpose of studying shrinkage cracking behavior, prismatic concrete specimens with reinforcing steel were also subjected to the above conditions at the same time. The shrinkage behavior is described focusing on the effects of solar radiation and rain based on the moisture loss. The significant environment actions to induce shrinkage cracks are investigated frommore » viewpoints of the amount of the shrinkage and the tensile strength. Finally, specific compressive creep behavior according to solar radiation and rainfall is discussed. It is found that rain can greatly inhibit the progresses of concrete shrinkage and creep while solar radiation is likely to promote shrinkage cracking and creep.« less

Effect of antioxidants on the dentin interface bond stability of adhesives exposed to hydrolytic degradation.

PubMed

Gotti, Valéria B; Feitosa, Victor P; Sauro, Salvatore; Correr-Sobrinho, Lourenço; Leal, Fernanda B; Stansbury, Jeffrey W; Correr, Américo B

2015-02-01

This study assessed the effect of antioxidants vitamin C (Vit. C), vitamin E (Vit. E) and quercetin (Querc) on the dentin bonding performance, degree of conversion, and rate of polymerization of three commercial adhesive systems (Adper Single Bond 2 [SB], Clearfil SE Bond [CSE], Adper Easy Bond [EB]). Human premolars were restored using antioxidant-doped adhesives. The samples were stored for 24 h in distilled water or 6 months under simulated pulpal pressure. Teeth were cut into sticks and the microtensile bond strength (μTBS) to dentin was tested in a universal testing machine. Qualitative nanoleakage analysis was performed from a central stick of each restored tooth. Degree of conversion and rate of polymerization of adhesive systems were evaluated in triplicate using real-time FT-IR. Although the inclusion of the antioxidants negatively affected the μTBS over 24 h, the antioxidant-doped adhesives maintained (SB-Vit. C, SB-Vit. E, CSE-Vit. C, EB-Querc) or increased (SB-Querc, CSE-Vit. E, CSE-Querc, EB-Vit. E, and EB-Vit. C) their μTBS during 6 months of storage. Only the μTBS of Adper Single Bond 2 dropped significantly after 6 months among the control groups. Slight changes in the nanoleakage pattern after aging were observed in all groups, except for the EB-control group, which showed a noteworthy increase in nanoleakage after 6 months, and for EB-Vit. C, which presented a remarkable decrease. A lower degree of conversion was obtained with all antioxidants in SB and EB, except for the EB-Vit. E group. Similar degrees of conversion were attained in control and experimental groups for CSE. The rate of polymerization was reduced in antioxidant-doped adhesives. The performance of antioxidants changed according to the adhesive system to which they were added, and antioxidant-doped adhesives appear to have a positive effect on the adhesive interface durability, since their bond strength obtained after 24 h was maintained or increased over time.

Synthesis and evaluation on pH- and temperature-responsive chitosan-p(MAA-co-NIPAM) hydrogels.

PubMed

Rasib, S Z M; Ahmad, Z; Khan, A; Akil, H M; Othman, M B H; Hamid, Z A A; Ullah, F

2018-03-01

In this study, chitosan-poly(methacrylic acid-co-N-isopropylacrylamide) [chitosan-p(MAA-co-NIPAM)] hydrogels were synthesized by emulsion polymerization. In order to be used as a carrier for drug delivery systems, the hydrogels had to be biocompatible, biodegradable and multi-responsive. The polymerization was performed by copolymerize MAA and NIPAM with chitosan polymer to produce a chitosan-based hydrogel. Due to instability during synthesis and complexity of components to produce the hydrogel, further study at different times of reaction is important to observe the synthesis process, the effect of end product on swelling behaviour and the most important is to find the best way to control the hydrogel synthesis in order to have an optimal swelling behaviour for drug release application. Studied by using Fourier transform infra-red (FTIR) spectroscopy found that, the synthesized was successfully produced stable chitosan-based hydrogel with PNIPAM continuously covered the outer surface of hydrogel which influenced much on the stability during synthesis. The chitosan and PMAA increased the zeta potential of the hydrogel and the chitosan capable to control shrinkage above human body temperature. The chitosan-p(MAA-co-NIPAM) hydrogels also responses to pH and temperature thus improved the ability to performance as a drug carrier. Copyright © 2017 Elsevier B.V. All rights reserved.

Contributions on the Study of the Compressive Strength of the Light-Cured Composite Resins

PubMed Central

Manolea, H.; Degeratu, Sonia; Deva, V.; Coles, Evantia; Draghici, Emma

2009-01-01

The mechanical properties of the light-cured composite resins are related to the material composition, but also vary according to the light-source characteristics used for polymerization. In this study we followed the compressive strength variation for a light-cured composite resin according to the time of exposure to the curing light. With that end in view,18 test pieces were made from a light-cured hybrid composite material (Filtek Z250). The test pieces where then submitted to a compressive force by a mechanical properties universal testing machine. Our results didn’t show an increase of the compressive strength according to the light-curing time increasing, than only in the light-curing time limit indicated by the manufacturer. A longer light-curing time may induce a shrinkage polymerization growth with the formation of internal tensions inside the material. The composite materials light-curing in short layers as long as there is indicated by the manufacturer seems to be a safer method to make the best from a resin qualities, then an exaggerated increase of the light-curing time. The light-curing is indicated to be done in the direction of the compressive forces. To confirm this supposition other mechanical tests are also necessary PMID:24778814

Production of continuous mullite fiber via sol-gel processing

NASA Technical Reports Server (NTRS)

Tucker, Dennis S.; Sparks, J. Scott; Esker, David C.

1990-01-01

The development of a continuous ceramic fiber which could be used in rocket engine and rocket boosters applications was investigated at the Marshall Space Flight Center. Methods of ceramic fiber production such as melt spinning, chemical vapor deposition, and precursor polymeric fiber decomposition are discussed and compared with sol-gel processing. The production of ceramics via the sol-gel method consists of two steps, hydrolysis and polycondensation, to form the preceramic, followed by consolidation into the glass or ceramic structure. The advantages of the sol-gel method include better homogeneity and purity, lower preparation temperature, and the ability to form unique compositions. The disadvantages are the high cost of raw materials, large shrinkage during drying and firing which can lead to cracks, and long processing times. Preparation procedures for aluminosilicate sol-gel and for continuous mullite fibers are described.

Evaluation of the Effect of Porcelain Laminate Thickness on Degree of Conversion of Light Cure and Dual Cure Resin Cements Using FTIR

PubMed Central

Hoorizad Ganjkar, Maryam; Heshmat, Haleh; Hassan Ahangari, Reza

2017-01-01

Statement of the Problem: Increasing the thickness of the veneering porcelain may affect the polymerization of resin cements. Incomplete polymerization of resin cements can lead to compromised quality of restoration and decrease the longevity of indirect restorations. Purpose: This study sought to assess the effect of IPS Empress porcelain thickness on the degree of conversion of light-cure and dual-cure resin cements using Fourier transform infrared spectroscopy. Materials and Method: In this experimental study, IPS Empress porcelain discs (A2 shade) with 10mm diameter and 0.5, 1 and 1.5 mm thicknesses were fabricated. Choice2 (Bisco, USA) and Nexus3 (Kerr, USA) resin cements were light cured through the three porcelain thicknesses in two groups of 3 samples using a LED light-curing unit (LEDemetron II; Kerr, USA). The control group samples were cured individually with no porcelain disc. The degree of conversion of resin cements was determined using FTIR (Bruker; Equinox55, Germany). The data were analyzed using Dunn’s test. Results: The degree of conversion (in percent) beneath the 0.5, 1.5 and 2 mm thicknesses of IPS Empress was 68.67±0.88, 71.06±0.94 and 72.51±0.41 for Choice2 resin cement and 69.60±2.12, 69.64±1.63 and 69.24±2.12 for Nexus3, respectively. Porcelain thickness and type of resin cement had no significant effect on degree of conversion (p≥ 0.05). Conclusion: It seems that increasing the porcelain thickness by up to 1.5 mm has no adverse effect on degree of conversion of both dual cure and light cure resin cements evaluated in this study. PMID:28280757

Conjugated Polymers Via Direct Arylation Polymerization in Continuous Flow: Minimizing the Cost and Batch-to-Batch Variations for High-Throughput Energy Conversion.

PubMed

Gobalasingham, Nemal S; Carlé, Jon E; Krebs, Frederik C; Thompson, Barry C; Bundgaard, Eva; Helgesen, Martin

2017-11-01

Continuous flow methods are utilized in conjunction with direct arylation polymerization (DArP) for the scaled synthesis of the roll-to-roll compatible polymer, poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(4,7-di(thiophen-2-yl)-benzo[c][1,2,5]thiadiazole)] (PPDTBT). PPDTBT is based on simple, inexpensive, and scalable monomers using thienyl-flanked benzothiadiazole as the acceptor, which is the first β-unprotected substrate to be used in continuous flow via DArP, enabling critical evaluation of the suitability of this emerging synthetic method for minimizing defects and for the scaled synthesis of high-performance materials. To demonstrate the usefulness of the method, DArP-prepared PPDTBT via continuous flow synthesis is employed for the preparation of indium tin oxide (ITO)-free and flexible roll-coated solar cells to achieve a power conversion efficiency of 3.5% for 1 cm 2 devices, which is comparable to the performance of PPDTBT polymerized through Stille cross coupling. These efforts demonstrate the distinct advantages of the continuous flow protocol with DArP avoiding use of toxic tin chemicals, reducing the associated costs of polymer upscaling, and minimizing batch-to-batch variations for high-quality material. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemoselective, Stereospecific, and Living Polymerization of Polar Divinyl Monomers by Chiral Zirconocenium Catalysts.

PubMed

Vidal, Fernando; Gowda, Ravikumar R; Chen, Eugene Y-X

2015-07-29

This contribution reports the first chemoselective, stereospecific, and living polymerization of polar divinyl monomers, enabled by chiral ansa-zirconocenium catalysts through an enantiomorphic-site controlled coordination-addition polymerization mechanism. Silyl-bridged-ansa-zirconocenium ester enolate 2 has been synthesized and structurally characterized, but it exhibits low to negligible activity and stereospecificity in the polymerization of polar divinyl monomers including vinyl methacrylate (VMA), allyl methacrylate (AMA), 4-vinylbenzyl methacrylate (VBMA), and N,N-diallyl acrylamide (DAA). In contrast, ethylene-bridged-ansa-zirconocenium ester enolate 1 is highly active and stereospecific in the polymerization of such monomers including AMA, VBMA, and DAA. The polymerization by 1 is perfectly chemoselective for all four polar divinyl monomers, proceeding exclusively through conjugate addition across the methacrylic C═C bond, while leaving the pendant C═C bonds intact. The polymerization of DAA is most stereospecific and controlled, producing essentially stereoperfect isotactic PDAA with [mmmm] > 99%, M(n) matching the theoretical value (thus a quantitative initiation efficiency), and a narrow molecular weight distribution (Đ = 1.06-1.16). The stereospecificity is slightly lower for the AMA polymerization but still leading to highly isotactic poly(allyl methacrylate) (PAMA) with 95-97% [mm]. The polymerization of VBMA is further less stereospecific, affording PVBMA with 90-94% [mm], while the polymerization VMA is least stereospecific. Several lines of evidence from both homo- and block copolymerization results have demonstrated living characteristics of the AMA polymerization by 1. Mechanistic studies of this polymerization have yielded a monometallic coordination-addition polymerization mechanism involving the eight-membered chelating intermediate. Post-functionalization of isotactic polymers bearing the pendant vinyl group on every repeating unit via the thiol-ene "click" reaction achieves a full conversion of all the pendant double bonds to the corresponding thioether bonds. Photocuring of such isotactic polymers is also successful, producing an elastic material readily characterizable by dynamic mechanical analysis.

One-Pot Enzymatic Production of Lignin-Composites.

PubMed

Ion, Sabina; Opris, Cristina; Cojocaru, Bogdan; Tudorache, Madalina; Zgura, Irina; Galca, Aurelian C; Bodescu, Adina M; Enache, Madalin; Maria, Gabriel-Mihai; Parvulescu, Vasile I

2018-01-01

A novel and efficient one-pot system for green production of artificial lignin bio-composites has been developed. Monolignols such as sinapyl (SA) and coniferyl (CA) alcohols were linked together with caffeic acid (CafAc) affording a polymeric network similar with natural lignin. The interaction of the dissolved SA/CA with CafAc already bound on a solid support (S C2 /S C6 -CafAc) allowed the attachment of the polymeric product direct on the support surface (S C2 /S C6 -CafAc-L 1 and S C2 /S C6 -CafAc-L 2 , from CA and SA, respectively). Accordingly, this procedure offers the advantage of a simultaneous polymer production and deposition. Chemically, oxi-copolymerization of phenolic derivatives (SA/CA and CAfAc) was performed with H 2 O 2 as oxidation reagent using peroxidase enzyme (2-1B mutant of versatile peroxidase from Pleurotus eryngii ) as catalyst. The system performance reached a maximum of conversion for SA and CA of 71.1 and 49.8%, respectively. The conversion is affected by the system polarity as resulted from the addition of a co-solvent (e.g., MeOH, EtOH, or THF). The chemical structure, morphology, and properties of the bio-composites surface were investigated using different techniques, e.g., FTIR, TPD-NH 3 , TGA, contact angle, and SEM. Thus, it was demonstrated that the SA monolignol favored bio-composites with a dense polymeric surface, high acidity, and low hydrophobicity, while CA allowed the production of thinner polymeric layers with high hydrophobicity.

Synthesis and structures of bis-ligated zinc complexes supported by tridentate ketoimines that initiate L-lactide polymerization.

PubMed

Gerling, Kimberly A; Rezayee, Nomaan M; Rheingold, Arnold L; Green, David B; Fritsch, Joseph M

2014-11-21

Eight bis-ligated, homoleptic, zinc complexes were synthesized through the reaction of NNO Schiff base ketoimines bearing varying substituents with diethyl zinc in an inert atmosphere glovebox at room temperature and isolated in 62-95% yield. The complexes were characterized with (1)H, (13)C, and (19)F nuclear magnetic resonance spectroscopy, absorbance spectroscopy, high resolution mass spectrometry, elemental analysis, and single crystal X-ray crystallography. The complexes were shown to adopt distorted octahedral coordination geometry around zinc. The (1)H and (19)F NMR spectra of complexes 1-7 showed stable zinc coordination at 300 K while the effect of steric encumbrance and two trifluoromethyl groups in complex 8 was investigated with variable temperature NMR. The bis-ligated zinc complexes were effective initiators for the ring opening polymerization of L-lactide into poly-L-lactic acid (PLLA). With [L-lac]/[Zn complex] = 50, the bis-ligated zinc complexes yielded percentage conversion of 14-98% with polymerization times varying from 15-1440 min, where the longest reaction times were required when two trifluoromethyl groups were present. The addition of 4-fluorophenol co-catalyst resulted in up to a 5-fold increase in the percentage conversion in toluene solution and up to a 14-fold increase in bulk melt polymerization with reductions in the poly-dispersity index values for the isolated PLLA. Addition of 4-fluorophenol to complex 1 was studied with (1)H and (19)F NMR and appeared to yield an in situ generated zinc alkoxide complex.

Influence of length-to-diameter ratio on shrinkage of basalt fiber concrete

NASA Astrophysics Data System (ADS)

Ruijie, MA; Yang, Jiansen; Liu, Yuan; Zheng, Xiaojun

2017-09-01

In order to study the shrinkage performance of basalt concrete, using the shrinkage rate as index, the work not only studied the influence of different length-to-diameter ratio (LDR) on plastic shrinkage and drying shrinkage of basalt fiber concrete, but also analyzed the action mechanism. The results show that when the fiber content is 0.1%, the LDR of 800 and 1200 take better effects on reducing plastic shrinkage, however the fiber content is 0.3%, that of LDR 600 is better. To improve drying shrinkage, the fiber of LDR 800 takes best effect. In the concrete structure, the adding basalt fibers form a uniform and chaotic supporting system, optimize the pore and the void structure of concrete, make the material further compacted, reduce the water loss, so as to decrease the shrinkage of concrete effectively.

Pretreating wheat straw by phosphoric acid plus hydrogen peroxide for enzymatic saccharification and ethanol production at high solid loading.

PubMed

Qiu, Jingwen; Ma, Lunjie; Shen, Fei; Yang, Gang; Zhang, Yanzong; Deng, Shihuai; Zhang, Jing; Zeng, Yongmei; Hu, Yaodong

2017-08-01

Wheat straw was pretreated by phosphoric acid plus hydrogen peroxide (PHP) for enzymatic hydrolysis and ethanol fermentation at high solid loadings. Results indicated solid loading could reach 20% with 77.4% cellulose-glucose conversion and glucose concentration of 164.9g/L in hydrolysate, it even was promoted to 25% with only 3.4% decrease on cellulose-glucose conversion as the pretreated-wheat straw was dewatered by air-drying. 72.9% cellulose-glucose conversion still was achieved as the minimized enzyme input of 20mg protein/g cellulose was employed for hydrolysis at 20% solid loading. In the corresponding conditions, 100g wheat straw can yield 11.2g ethanol with concentration of 71.2g/L by simultaneous saccharification and fermentation. Thus, PHP-pretreatment benefitted the glucose or ethanol yield at high solid loadings with lower enzyme input. Additionally, decreases on the maximal cellulase adsorption and the direct-orange/direct-blue indicated drying the PHP-pretreated substrates negatively affected the hydrolysis due to the shrinkage of cellulase-size-accommodable pores. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of concrete shrinkage performance specifications.

DOT National Transportation Integrated Search

2003-01-01

During its service life, concrete undergoes volume changes. One of the types of deformation is shrinkage. The four main types of shrinkage associated with concrete are plastic, autogenous, carbonation, and drying shrinkage. The volume changes in conc...

Nucleation of polystyrene latex particles in the presence of gamma-methacryloxypropyltrimethoxysilane: functionalized silica particles.

PubMed

Bourgeat-Lami, Elodie; Insulaire, Mickaelle; Reculusa, Stéphane; Perro, Adeline; Ravaine, Serge; Duguet, Etienne

2006-02-01

Silica/polystyrene nanocomposite particles with different morphologies were synthesized through emulsion polymerization of styrene in the presence of silica particles previously modified by gamma-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant under basic conditions. The MPS grafting density on the silica surface was determined using the depletion method and plotted against the initial MPS concentration. The influence of the MPS grafting density, the silica particles size and concentration and the nature of the surfactant on the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy images showed the formation of polymer spheres around silica for MPS grafting densities lower than typically 1 micromole x m(-2) while the conversion versus time curves indicated a strong acceleration effect under such conditions. In contrast, polymerizations performed in the presence of a larger amount of MPS moieties or in the presence of a non ionic emulsifier resulted in the formation of "excentered" core-shell morphologies and lower polymerization rates. The paper identifies the parameters that allow to control particles morphology and polymerization kinetics and describes the mechanism of formation of the nanocomposite colloids.

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers

PubMed Central

Kim, Moon Suk; Lee, Sang Bong

2014-01-01

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO >> GME >>> GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively. PMID:28788147

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers.

PubMed

Kim, Moon Suk; Lee, Sang Bong

2014-07-31

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF₆). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO > GME > GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively.

Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities

NASA Astrophysics Data System (ADS)

McLeod, David Charles

Macromolecules that contain electrophilic moieties, such as benzyl halides, activated esters, and epoxides, will readily undergo efficient nucleophilic substitution reactions with a wide variety of compounds under mild conditions, and are therefore ideally suited to act as "universal" precursors to functional materials. Epoxide-containing polymers derived from the radical polymerization of commercially-available glycidyl methacrylate are often employed in this role; however, methacrylic polymers suffer from certain limitations as a result of the incorporated ester groups, which are not stabile in the presence of strong nucleophiles, acids, bases, or esterase enzymes. Styrenic polymers that do not contain labile carbonyl moieties are usually the precursors of choice when high chemical stability is desired in the end product, but the production of functional materials from epoxide-containing styrenic polymers is relatively unexplored. In this dissertation, improved methods were developed for synthesizing 4-vinylphenyloxirane (4VPO) and 4-vinylphenyl glycidyl ether (4VPGE), two of the better-known epoxide-containing styrenic monomers, in high-yield and purity. Well-defined, epoxide-containing styrenic polymers with targeted molecular weights, narrow molecular weight distributions, and controlled architectures (specifically, linear and star-shaped homopolymers, as well as linear block copolymers with styrene) were produced from 4VPO and 4VPGE for the first time using reversible-deactivation radical polymerization techniques, such as low-catalyst-concentration atom transfer radical polymerization (LCC ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. The robust nature and utility of poly4VPO and poly4VPGE were then demonstrated by the efficient, ring-opening modification of the pendant epoxide groups with a structurally- and functionally-diverse array of alcohols under acidic conditions at ambient temperature. The macromolecular compositions, architectures, and thermal stabilities of the resulting ?-hydroxy ether-functionalized homopolymers were evaluated using NMR and FTIR spectroscopy, size exclusion chromatography, and thermal gravimetric analysis. Aziridines and thiiranes (saturated, three-membered heterocycles containing either a single nitrogen or sulfur atom, respectively) are also susceptible to nucleophilic ring-opening reactions, and functional materials derived from aziridine- or thiirane-containing polymers could potentially have many interesting properties as a result of their high amine or thiol content, such as the ability to form pH- or redox-responsive structures. The synthesis of polymers containing aziridines that are activated towards nucleophilic ring-opening by C-aryl and/or N-sulfonyl substituents is unprecedented in the literature. Efficient methods for synthesizing styrenic monomers that contain these highly-reactive functionalities, namely 2-(4-vinylphenyl)aziridine (VPA) and its sulfonyl-activated derivative, N-mesyl-2-(4-vinylphenyl)aziridine (NMVPA), were developed utilizing 4VPO as a starting material. VPA was polymerized under LCC ATRP and RAFT conditions, but these methods were ineffective at producing well-defined polymers due to side reactions between the aziridine groups and the polymerization mediating compounds. Nitroxide-mediated radical polymerization (NMRP) produced well-defined polyVPA at low to moderate conversions of monomer, but cross-linking side reactions were evident at higher monomer conversions. Nearly all undesirable side reactions were prevented by attaching a mesyl group to the aziridine nitrogen atom, and well-defined polyNMVPA was realized under RAFT and NMRP conditions. Under ATRP conditions, reactions between the aziridine groups and catalyst still occurred, so the polymerization of NMVPA was not controlled using this technique. The synthesis of thiirane-containing styrenic polymers from either 2-(4-vinylphenyl)thiirane (VPT) or 2-((4-vinylphenoxy)methyl)thiirane (VPOMT), which were produced in a facile manner from 4VPO or 4VPGE, respectively, was attempted under conventional radical polymerization and RAFT polymerization conditions. Rapid desulfurization or ring-opening polymerization of VPT occurred when elevated temperatures or UV radiation was applied to reactions containing this monomer. The more-stable VPOMT monomer was successfully polymerized at elevated temperatures using thermally-labile azo-type initiators, and, under RAFT conditions, polymers of VPOMT increased in molecular weight as higher conversions of monomer were reached; however, the polymers produced under RAFT conditions were ill-defined and eventually underwent macrogelation, due to cross-linking side reactions of the thiirane moieties.

Theoretical prediction and experimental determination of the effect of mold characteristics on temperature and monomer conversion fraction profiles during polymerization of a PMMA-based bone cement.

PubMed

Vallo, Claudia I

2002-01-01

The present work is concerned with applications of a kinetic model for free-radical polymerization of a polymethylmethacrylate-based bone cement. Autocatalytic behavior at the first part of the reaction as well as a diffusion control phenomenon near vitrification are described by the model. Comparison of theoretical computations with experimental measurements for the temperature evolution during batch casting demonstrated the capacity of the proposed model to represent the kinetic behavior of the polymerization reaction. Temperature evolution and monomer conversion were simulated for the cure of the cement in molds made of different materials. The maximum monomer conversion fraction was markedly influenced by the physical properties of the mold material. The unreacted monomer acts as a plasticizer that influences the mechanical behavior of the cement. Hence, the same cement formulation cured in molds of different materials may result in different mechanical response because of the differences in the amounts of residual monomer. Standardization of the mold type to prepare specimens for the mechanical characterization of bone cements is recommended. Theoretical prediction of temperature evolution during hip replacement indicated that for cement thickness lower than 6 mm the peak temperature at the bone-cement interface was below the limit stated for thermal injury (50 degrees C for more than 1 min). The use of thin cement layers is recommended to diminish the risk of thermal injury; however, it is accompanied by an increase in the amount of unreacted monomer present in the cured material. Copyright 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 627-642, 2002

DOE Office of Scientific and Technical Information (OSTI.GOV)

Redline, Erica Marie; Bolintineanu, Dan S.; Lane, J. Matthew

The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. Themore » methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for the UDMA system, with parameters calibrated based on fully atomistic simulations of the UDMA monomer in the liquid state. Detailed metrics based on network graph theoretical approaches were implemented to quantify the bond network topology resulting from simulations. For a broad range of polymerization parameters, no discernible differences were seen between TRP and CRP UDMA simulations at equal conversions, although clear differences exist as a function of conversion. Both findings are consistent with experiments. Despite a number of shortcomings, these models have demonstrated the potential of molecular simulations for studying network topology in these systems.« less

Evaluation of shrinkage and cracking in concrete of ring test by acoustic emission method

NASA Astrophysics Data System (ADS)

Watanabe, Takeshi; Hashimoto, Chikanori

2015-03-01

Drying shrinkage of concrete is one of the typical problems related to reduce durability and defilation of concrete structures. Lime stone, expansive additive and low-heat Portland cement are used to reduce drying shrinkage in Japan. Drying shrinkage is commonly evaluated by methods of measurement for length change of mortar and concrete. In these methods, there is detected strain due to drying shrinkage of free body, although visible cracking does not occur. In this study, the ring test was employed to detect strain and age cracking of concrete. The acoustic emission (AE) method was adopted to detect micro cracking due to shrinkage. It was recognized that in concrete using lime stone, expansive additive and low-heat Portland cement are effective to decrease drying shrinkage and visible cracking. Micro cracking due to shrinkage of this concrete was detected and evaluated by the AE method.

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers

PubMed Central

2016-01-01

RAFT solution polymerization of N-(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA63–PNMEPx diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in Mn with increasing PNMEP DP. A gradual increase in Mw/Mn was also observed when targeting higher DPs. However, this problem could be minimized (Mw/Mn < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA63–PNMEPx particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA85–PNMEPx diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses. PMID:27375300

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

PubMed

Cunningham, Victoria J; Derry, Matthew J; Fielding, Lee A; Musa, Osama M; Armes, Steven P

2016-06-28

RAFT solution polymerization of N -(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA 63 -PNMEP x diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in M n with increasing PNMEP DP. A gradual increase in M w / M n was also observed when targeting higher DPs. However, this problem could be minimized ( M w / M n < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1 H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA 63 -PNMEP x particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA 85 -PNMEP x diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses.

Polymeric capsule-cushioned leukocyte cell membrane vesicles as a biomimetic delivery platform

NASA Astrophysics Data System (ADS)

Gao, Changyong; Wu, Zhiguang; Lin, Zhihua; Lin, Xiankun; He, Qiang

2016-02-01

We report a biomimetic delivery of microsized capsule-cushioned leukocyte membrane vesicles (CLMVs) through the conversion of freshly reassembled leukocyte membrane vesicles (LMVs), including membrane lipids and membrane-bound proteins onto the surface of layer-by-layer assembled polymeric multilayer microcapsules. The leukocyte membrane coating was verified by using electron microscopy, a quartz crystal microbalance, dynamic light scattering, and confocal laser scanning microscopy. The resulting CLMVs have the ability to effectively evade clearance by the immune system and thus prolong the circulation time in mice. Moreover, we also show that the right-side-out leukocyte membrane coating can distinctly improve the accumulation of capsules in tumor sites through the molecular recognition of membrane-bound proteins of CLMVs with those of tumor cells in vitro and in vivo. The natural cell membrane camouflaged polymeric multilayer capsules with the immunosuppressive and tumor-recognition functionalities of natural leukocytes provide a new biomimetic delivery platform for disease therapy.We report a biomimetic delivery of microsized capsule-cushioned leukocyte membrane vesicles (CLMVs) through the conversion of freshly reassembled leukocyte membrane vesicles (LMVs), including membrane lipids and membrane-bound proteins onto the surface of layer-by-layer assembled polymeric multilayer microcapsules. The leukocyte membrane coating was verified by using electron microscopy, a quartz crystal microbalance, dynamic light scattering, and confocal laser scanning microscopy. The resulting CLMVs have the ability to effectively evade clearance by the immune system and thus prolong the circulation time in mice. Moreover, we also show that the right-side-out leukocyte membrane coating can distinctly improve the accumulation of capsules in tumor sites through the molecular recognition of membrane-bound proteins of CLMVs with those of tumor cells in vitro and in vivo. The natural cell membrane camouflaged polymeric multilayer capsules with the immunosuppressive and tumor-recognition functionalities of natural leukocytes provide a new biomimetic delivery platform for disease therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08407e

Photopolymerization of N,N-dimethylaminobenzyl alcohol as amine co-initiator for light-cured dental resins.

PubMed

Schroeder, Walter F; Cook, Wayne D; Vallo, Claudia I

2008-05-01

The present study was carried out in order to assess the suitability of N,N-dimethylaminobenzyl alcohol (DMOH) as co-initiator of camphorquinone (CQ) and 1-phenyl-1,2-propanedione (PPD) in light-cured dental resins. DMOH was synthesized and used as co-initiator for the photopolymerization of a model resin based on {2,2-bis[4-(2-hydroxy-3-methacryloxyprop-1-oxy)phenyl]propane} (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA). Experimental formulations containing CQ or PPD in combination with DMOH at different concentrations were studied. The photopolymerization was carried out by means of a commercial light-emitting diode (LED) curing unit. The evolution of double bonds consumption versus irradiation time was followed by near-infrared spectroscopy (NIR). The photon absorption efficiency (PAE) of the photopolymerization process was calculated from the spectral distribution of the LED unit and the molar absorption coefficient distributions of PPD and CQ. DMOH is an efficient photoreducer of CQ and PPD resulting in higher polymerization rate and higher double bond conversion compared with dimethylaminoethylmethacrylate. The PAE for PPD was higher than that for CQ. However, the polymerization initiated by PPD progressed at a lower rate and exhibited lower values of final conversion compared with the resins containing CQ. This observation indicates that the lower polymerization rate of the PPD/amine system should be explained in terms of the mechanism of generating primary radicals by PPD, which is less efficient compared with CQ. The DMOH/benzoyl peroxide redox system, has recently been proposed as a more biocompatible accelerator for the polymerization of bone cements based on poly(methyl methacrylate), because cytotoxity tests have demonstrated that DMOH possesses better biocompatibility properties compared with traditional tertiary amines. The results obtained in the present study reveal the suitability of the CQ/DMOH initiator system for the polymerization of light-cured dental composites.

Frontal Conversion and Uniformity in 3D Printing by Photopolymerisation

PubMed Central

Vitale, Alessandra; Cabral, João T.

2016-01-01

We investigate the impact of the non-uniform spatio-temporal conversion, intrinsic to photopolymerisation, in the context of light-driven 3D printing of polymers. The polymerisation kinetics of a series of model acrylate and thiol-ene systems, both neat and doped with a light-absorbing dye, is investigated experimentally and analysed according to a descriptive coarse-grained model for photopolymerisation. In particular, we focus on the relative kinetics of polymerisation with those of 3D printing, by comparing the evolution of the position of the conversion profile (zf) to the sequential displacement of the object stage (∆z). After quantifying the characteristic sigmoidal monomer-to-polymer conversion of the various systems, with a combination of patterning experiments, FT-IR mapping, and modelling, we compute representative regimes for which zf is smaller, commensurate with, or larger than ∆z. While non-monotonic conversion can be detrimental to 3D printing, for instance in causing differential shrinkage of inhomogeneity in material properties, we identify opportunities for facile fabrication of modulated materials in the z-direction (i.e., along the illuminated axis). Our simple framework and model, based on directly measured parameters, can thus be employed in photopolymerisation-based 3D printing, both in process optimisation and in the precise design of complex, internally stratified materials by coupling the z-stage displacement and frontal polymerisation kinetics. PMID:28773881

Polymerization of plant oils in carbon dioxide media

USDA-ARS?s Scientific Manuscript database

The conversion of plant oils to polymers has attracted renewed attention in recent years to replace or augment the traditional petrochemical-based polymers and resins. This is because of concern for the environment, waste disposal, and depletion of fossil and non-renewable feedstocks. Usually, polym...

Comparative studies of thin film growth on aluminium by AFM, TEM and GDOES characterization

NASA Astrophysics Data System (ADS)

Qi, Jiantao; Thompson, George E.

2016-07-01

In this present study, comparative studies of trivalent chromium conversion coating formation, associated with aluminium dissolution process, have been investigated using atomic force microscopy (AFM), transmission electron microscopy (TEM) and glow-discharge optical emission spectroscopy (GDOES). High-resolution electron micrographs revealed the evident and uniform coating initiation on the whole surface after conversion treatment for only 30 s, although a network of metal ridges was created by HF etching pre-treatment. In terms of conversion treatment process on electropolished aluminium, constant kinetics of coating growth, ∼0.30 ± 0.2 nm/s, were found after the prolonged conversion treatment for 600 s. The availability of electrolyte anions for coating deposition determined the growth process. Simultaneously, a proceeding process of aluminium dissolution during conversion treatment, of ∼0.11 ± 0.02 nm/s, was found for the first time, indicating constant kinetics of anodic reactions. The distinct process of aluminium consumption was assigned with loss of corrosion protection of the deposited coating material as evidenced in the electrochemical impedance spectroscopy. Based on the present data, a new mechanism of coating growth on aluminium was proposed, and it consisted of an activation period (0-30 s), a linear growth period (0.30 nm/s, up for 600 s) and limited growth period (0.17 nm/s, 600-1200 s). In addition, the air-drying post-treatment and a high-vacuum environment in the microscope revealed a coating shrinkage, especially in the coatings after conversion treatments for longer time.

Competitive light absorbers in photoactive dental resin-based materials.

PubMed

Hadis, Mohammed A; Shortall, Adrian C; Palin, William M

2012-08-01

The absorbance profile of photoinitiators prior to, during and following polymerization of light curable resin-based materials will have a significant effect on the cure and color properties of the final material. So-called "colorless" photoinitiators are used in some light-activated resin-based composite restorative materials to lessen the yellowing effect of camphoroquinone (CQ) in order to improve the esthetic quality of dental restorations. This work characterizes absorption properties of commonly used photoinitiators, an acylphosphine oxide (TPO) and CQ, and assesses their influence on material discoloration. Dimethacrylate resin formulations contained low (0.0134 mol/dm(3)), intermediate (0.0405 mol/dm(3)) or high (0.0678 mol/dm(3)) concentrations of the photoinitiators and the inhibitor, butylated hydroxytoluene (BHT) at 0, 0.1 or 0.2% by mass. Disc shaped specimens (n = 3) of each resin were polymerized for 60s using a halogen light curing unit. Dynamic measurements of photoinitiator absorption, polymer conversion and reaction temperature were performed. A spectrophotometer was used to measure the color change before and after cure. GLM three-way analysis of variance revealed significant differences (p<0.001), where photoinitiator concentration (df = 2; F = 618.83)>photoinitiator type (df = 1; F = 176.12)>% BHT (df = 2, F = 13.17). BHT concentration affected the rate of polymerization and produced lower conversion in some of the CQ-based resins. Significant differences between photoinitiator type and concentrations were seen in color (where TPO resins became yellower and camphoroquinone resins became less yellow upon irradiation). Reaction temperature, kinetics and conversion also differed significantly for both initiators (p<0.001). Despite TPO-based resins producing a visually perceptible color change upon polymerization, the color change was significantly less than that produced with CQ-based resins. Although some photoinitiators such as TPO may be a more esthetic alternative to CQ, they may actually cause significant color contamination when used in high concentrations and therefore manufacturers should limit its concentration in order to improve its esthetic quality. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Mechanisms and significance of eryptosis.

PubMed

Lang, Florian; Lang, Karl S; Lang, Philipp A; Huber, Stephan M; Wieder, Thomas

2006-01-01

Suicidal death of erythrocytes (eryptosis) is characterized by cell shrinkage, membrane blebbing, activation of proteases, and phosphatidylserine exposure at the outer membrane leaflet. Exposed phosphatidylserine is recognized by macrophages that engulf and degrade the affected cells. Eryptosis is triggered by erythrocyte injury after several stressors, including oxidative stress. Besides caspase activation after oxidative stress, two signaling pathways converge to trigger eryptosis: (a) formation of prostaglandin E(2) leads to activation of Ca(2+)-permeable cation channels, and (b) the phospholipase A(2)-mediated release of platelet-activating factor activates a sphingomyelinase, leading to formation of ceramide. Increased cytosolic Ca(2+) activity and enhanced ceramide levels lead to membrane scrambling with subsequent phosphatidylserine exposure. Moreover, Ca(2+) activates Ca(2+)-sensitive K(2+) channels, leading to cellular KCl loss and cell shrinkage. In addition, Ca(2+) stimulates the protease calpain, resulting in degradation of the cytoskeleton. Eryptosis is inhibited by erythropoietin, which thus extends the life span of circulating erythrocytes. Eryptosis may be a mechanism of defective erythrocytes to escape hemolysis. Conversely, excessive eryptosis favors the development of anemia. Conditions with excessive eryptosis include iron deficiency, lead or mercury intoxication, sickle cell anemia, thalassemia, glucose 6- phosphate dehydrogenase deficiency, malaria, and infection with hemolysin-forming pathogens.

Phosphines bearing alkyne substituents: synthesis and hydrophosphination polymerization.

PubMed

Greenberg, Sharonna; Stephan, Douglas W

2009-09-07

A synthetic route is described for a series of phosphines bearing pendant alkyne substituents, from the conversion of BrC(6)H(2)R(2)C[triple bond]CR' (R = Me, i-Pr; R' = Ph, SiMe(3)) to [(mu-Br)Cu(Et(2)N)(2)PC(6)H(2)R(2)C[triple bond]CR'](2) and subsequently to Cl(2)PC(6)H(2)R(2)C[triple bond]CR' and H(2)PC(6)H(2)R(2)C[triple bond]CR'. Lithiation and subsequent alkylation yield the secondary phosphines R(H)PC(6)H(2)(i-Pr)(2)C[triple bond]CPh (R = CH(2)i-Pr, CH(2)Ph). Intermolecular hydrophosphination-polymerization is used to prepare the polymeric species [RPC(6)H(2)(i-Pr)(2)CH=CPh](n), which can then be sulfurized to give [RP(S)C(6)H(2)(i-Pr)(2)CH=CPh](n). The polymeric products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gel permeation chromatography. These data indicate a degree of polymerization (DP(n)) of up to 60. Discussion of the mechanism is augmented with gas-phase density functional theory calculations.

Real-time synchronous measurement of curing characteristics and polymerization stress in bone cements with a cantilever-beam based instrument

NASA Astrophysics Data System (ADS)

Palagummi, Sri Vikram; Landis, Forrest A.; Chiang, Martin Y. M.

2018-03-01

An instrumentation capable of simultaneously determining degree of conversion (DC), polymerization stress (PS), and polymerization exotherm (PE) in real time was introduced to self-curing bone cements. This comprises the combination of an in situ high-speed near-infrared spectrometer, a cantilever-beam instrument with compliance-variable feature, and a microprobe thermocouple. Two polymethylmethacrylate-based commercial bone cements, containing essentially the same raw materials but differ in their viscosity for orthopedic applications, were used to demonstrate the applicability of the instrumentation. The results show that for both the cements studied the final DC was marginally different, the final PS was different at the low compliance, the peak of the PE was similar, and their polymerization rates were significantly different. Systematic variation of instrumental compliance for testing reveals differences in the characteristics of PS profiles of both the cements. This emphasizes the importance of instrumental compliance in obtaining an accurate understanding of PS evaluation. Finally, the key advantage for the simultaneous measurements is that these polymerization properties can be correlated directly, thus providing higher measurement confidence and enables a more in-depth understanding of the network formation process.

Effect of denture cleaning on abrasion resistance and surface topography of polymerized CAD CAM acrylic resin denture base

PubMed Central

Shinawi, Lana Ahmed

2017-01-01

Background The application of computer-aided design computer-aided manufacturing (CAD CAM) technology in the fabrication of complete dentures, offers numerous advantages as it provides optimum fit and eliminates polymerization shrinkage of the acrylic base. Additionally, the porosity and surface roughness of CAD CAM resins is less compared to conventionally processed resins which leads to a decrease in the adhesion of bacteria on the denture base, which is associated with many conditions including halitosis and aspiration pneumonia in elderly denture wearers. Aim To evaluate the influence of tooth brushing with dentifrices on CAD CAM resin blocks in terms of abrasion resistance, surface roughness and scanning electron photomicrography. Methods This experimental study was carried out at the Faculty of Dentistry of King Abdulaziz University during 2016. A total of 40 rectangular shaped polymerized CAD CAM resin samples were subjected to 40.000 and 60.000 brushing strokes under a 200-gram vertical load simulating three years of tooth brushing strokes using commercially available denture cleaning dentifrice. Data were analyzed by SPSS version 20, using descriptive statistics and ANOVA. Results ANOVA test revealed a statistical significant weight loss of CAD CAM acrylic resin denture base specimens following 40.000 and 60.000 brushing strokes as well as a statistical significant change (p=0.0.5) in the surface roughness following brushing. The CAD CAM resin samples SEM baseline imaging revealed a relatively smooth homogenous surface, but following 40,000 and 60,000 brushing strokes, imaging displayed the presence of small scratches on the surface. Conclusion CAD CAM resin displayed a homogenous surface initially with low surface roughness that was significantly affected following simulating three years of manual brushing, but despite the significant weight loss, the findings are within the clinically acceptable limits. PMID:28713496

Effect of denture cleaning on abrasion resistance and surface topography of polymerized CAD CAM acrylic resin denture base.

PubMed

Shinawi, Lana Ahmed

2017-05-01

The application of computer-aided design computer-aided manufacturing (CAD CAM) technology in the fabrication of complete dentures, offers numerous advantages as it provides optimum fit and eliminates polymerization shrinkage of the acrylic base. Additionally, the porosity and surface roughness of CAD CAM resins is less compared to conventionally processed resins which leads to a decrease in the adhesion of bacteria on the denture base, which is associated with many conditions including halitosis and aspiration pneumonia in elderly denture wearers. To evaluate the influence of tooth brushing with dentifrices on CAD CAM resin blocks in terms of abrasion resistance, surface roughness and scanning electron photomicrography. This experimental study was carried out at the Faculty of Dentistry of King Abdulaziz University during 2016. A total of 40 rectangular shaped polymerized CAD CAM resin samples were subjected to 40.000 and 60.000 brushing strokes under a 200-gram vertical load simulating three years of tooth brushing strokes using commercially available denture cleaning dentifrice. Data were analyzed by SPSS version 20, using descriptive statistics and ANOVA. ANOVA test revealed a statistical significant weight loss of CAD CAM acrylic resin denture base specimens following 40.000 and 60.000 brushing strokes as well as a statistical significant change (p=0.0.5) in the surface roughness following brushing. The CAD CAM resin samples SEM baseline imaging revealed a relatively smooth homogenous surface, but following 40,000 and 60,000 brushing strokes, imaging displayed the presence of small scratches on the surface. CAD CAM resin displayed a homogenous surface initially with low surface roughness that was significantly affected following simulating three years of manual brushing, but despite the significant weight loss, the findings are within the clinically acceptable limits.

Elucidation of a side reaction occurring during nitroxide-mediated polymerization of cyclic ketene acetals by tandem mass spectrometric end-group analysis of aliphatic polyesters.

PubMed

Albergaria Pereira, Bruna de Fátima; Tardy, Antoine; Monnier, Valérie; Guillaneuf, Yohann; Gigmes, Didier; Charles, Laurence

2015-12-15

In order to prevent side reactions while developing new polymerization processes, their mechanism has to be understood and one first key insight is the structure of the end-groups in polymeric by-products. The synthetic method scrutinized here is the nitroxide-mediated polymerization (NMP) of a cyclic ketene acetal, a promising alternative process to the production of polyesters. Polymer end-group characterization was performed by mass spectrometry (MS), combining elemental composition information derived from accurate mass data in the MS mode with fragmentation features recorded in the MS/MS mode. Electrospray was used as the ionization method to ensure the integrity of original chain terminations and a quadrupole time-of-flight (QTOF) instrument was employed for high-resolution mass measurements in both MS and tandem mass spectrometry (MS/MS) modes. Occurrence of side reactions in the studied polymerization method, first evidenced by an unusual increase in dispersity with conversion, was confirmed in MS with the detection of two polymeric impurities in addition to the expected species. Fragmentation rules were first established for this new polyester family in order to derive useful structural information from MS/MS data. In addition to a usual NMP by-product, the initiating group of the second polymeric impurities revealed the degradation of the nitroxide moiety. Unambiguous MS/MS identification of end-groups in by-products sampled from the polymerization medium allowed an unusual side reaction to be identified during the NMP preparation of polyesters. On-going optimization of the polymerization method aims at preventing this undesired process. Copyright © 2015 John Wiley & Sons, Ltd.

Long-term outcomes and sac volume shrinkage after endovascular popliteal artery aneurysm repair.

PubMed

Piazza, M; Menegolo, M; Ferrari, A; Bonvini, S; Ricotta, J J; Frigatti, P; Grego, F; Antonello, M

2014-08-01

The aim was to evaluate long-term outcomes and sac volume shrinkage after endovascular popliteal artery aneurysm repair (EVPAR). This study was a retrospective review of all EVPAR cases between 1999 and 2012. Sac volume shrinkage, long-term patency, limb salvage, and survival were evaluated using Kaplan-Meier estimates. The association of anatomical and clinical characteristics with patency was evaluated using multivariate analysis. Forty-six EVPAR were carried out in 42 patients (mean age 78 years, 86% male; mean sac volume 45.5 ± 3.5 mL). In 93% of cases (n = 43) the procedure was elective, while in 7% of cases it was for rupture (n = 2) or acute thrombosis (n = 1). Of the 43 patients who underwent elective repair, 58% were asymptomatic and 42% symptomatic (14 claudication, 3 rest pain, and 1 compression symptoms). Technical success was 98%. Mean duration of follow-up was 56 ± 21 months. Primary patency at 1, 3, and 5 years was 82% (SE 2), 79% (SE 4), and 76% (SE 4), while secondary patency was 90% (SE 5), 85% (SE 4), and 82% (SE 1) respectively; at 5 years there was 98% limb salvage and an 84% survival rate. During follow-up 11 limbs had stent graft failure: six required conversion, one underwent amputation, and four continued with mild claudication. Of those with graft failure, 63% (7/11) occurred within the first year of follow-up. The mean aneurysm sac volume shrinkage between preoperative and 5-year post-procedure measurement was significant (45.5 ± 3.5 mL vs. 23.0 ± 5.0 mL; p < .001). Segment coverage >20 cm was a negative predictor for patency (HR 2.76; 95% CI 0.23; p = .032). EVPAR provides successful aneurysm exclusion with good long-term patency, excellent limb salvage, and survival rates. Close surveillance is nevertheless required, particularly during the first postoperative year. Patients requiring long segment coverage (>20 cm) may be at increased risk for failure. Copyright © 2014 European Society for Vascular Surgery. Published by Elsevier Ltd. All rights reserved.

Hydrolyzable Poly[Poly(Ethylene Glycol) Methyl Ether Acrylate]-Colistin Prodrugs through Copper-Mediated Photoinduced Living Radical Polymerization.

PubMed

Zhu, Chongyu; Schneider, Elena K; Nikolaou, Vasiliki; Klein, Tobias; Li, Jian; Davis, Thomas P; Whittaker, Michael R; Wilson, Paul; Kempe, Kristian; Velkov, Tony; Haddleton, David M

2017-07-19

Through the recently developed copper-mediated photoinduced living radical polymerization (CP-LRP), a novel and well-defined polymeric prodrug of the antimicrobial lipopeptide colistin has been developed. A colistin initiator (Boc 5 -col-Br 2 ) was synthesized through the modification of colistin on both of its threonine residues using a cleavable initiator linker, 2-(2-bromo-2-methylpropanoyloxy) acetic acid (BMPAA), and used for the polymerization of acrylates via CP-LRP. Polymerization proceeds from both sites of the colistin initiator, and through the polymerization of poly(ethylene glycol) methyl ether acrylate (PEGA 480 ), three water-soluble polymer-colistin conjugates (col-PPEGA, having degrees of polymerization of 5, 10, and 20) were achieved with high yield (conversion of ≥93%) and narrow dispersities (Đ < 1.3) in 2-4 h. Little or no effect on the structure and activity of the colistin was observed during the synthesis, and most of the active colistin can be recovered from the conjugates in vitro within 2 days. Furthermore, in vitro biological analyses including disk diffusion, broth microdilution, and time-kill studies suggested that all of the conjugates have the ability to inhibit the growth of multidrug-resistant (MDR) Gram-negative bacteria, of which col-PPEGA DP5 and DP10 showed similar or better antibacterial performance compared to the clinically relevant colistin prodrug CMS, indicating their potential as an alternative antimicrobial therapy. Moreover, considering the control over the polymerization, the CP-LRP technique has the potential to provide an alternative platform for the development of polymer bioconjugates.

Evaluation of supercritical CO2 dried cellulose aerogels as nano-biomaterials

NASA Astrophysics Data System (ADS)

Lee, Sinah; Kang, Kyu-Young; Jeong, Myung-Joon; Potthast, Antje; Liebner, Falk

2017-10-01

Cellulose is the renewable, biodegradable and abundant resource and is suggested as an alternative material to silica due to the high price and environmental load of silica. The first step for cellulose aerogel production is to dissolve cellulose, and hydrated calcium thiocyanate molten salt is one of the most effective solvents for preparing porous material. Cellulose aerogels were prepared from dissolved cellulose samples of different degree of polymerization (DP) and drying methods, and tested with shrinkage, density and mechanical strength. Supercritical CO2 dried cellulose aerogels shrank less compared to freeze-dried cellulose aerogels, whereas the densities were increased according to the DP increases in both cellulose aerogels. Furthermore, scanning electron microscope (SEM) images showed that the higher DP cellulose aerogels were more uniform with micro-porous structure. Regarding the mechanical strength of cellulose aerogels, supercritical CO2 dried cellulose aerogels with higher molecular weight were much more solid.

Synthesis and characterization of nanoporous silica aerogel beads using cheap industrial grade sodium silacte precursor

NASA Astrophysics Data System (ADS)

Khan, Tasneem M. A.; Khan, Asiya; Sarawade, Pradip B.

2018-05-01

We report a method to synthesize low-density transparent mesoporous silica aerogel beads by ambient pressure drying (APD). The beads were prepared by acid-base sol-gel polymerization of sodium silicate in via the ball dropping method (BDM). To minimize shrinkage during drying, wet silica beads were initially prepared; their surfaces were then modified using trimethylchlorosilane (TMCS) via simultaneous solvent exchange and surface modification. The specific surface area and cumulative pore volume of the silica aerogel beads increased with an increase in the %V of TMCS. Silica aerogel beads with low packing bed density, high surface area, and large cumulative pore volume was obtained when TMCS was used. Properties of the final product were examined by BET, and TG-DT analyses. The hydrophobic silica aerogel beads were thermally stable up to 350°C. We discuss our results and compare our findings for modified versus unmodified silica beads.

Health, Height, Height Shrinkage, and SES at Older Ages: Evidence from China†

PubMed Central

Huang, Wei; Lei, Xiaoyan; Ridder, Geert; Strauss, John

2015-01-01

In this paper, we build on the literature that examines associations between height and health outcomes of the elderly. We investigate the associations of height shrinkage at older ages with socioeconomic status, finding that height shrinkage for both men and women is negatively associated with better schooling, current urban residence, and household per capita expenditures. We then investigate the relationships between pre-shrinkage height, height shrinkage, and a rich set of health outcomes of older respondents, finding that height shrinkage is positively associated with poor health outcomes across a variety of outcomes, being especially strong for cognition outcomes. PMID:26594311

PLASTIC SHRINKAGE CONTROLLING EFFECT BY POLYPROPYLENE SHORT FIBER WITH HYDROPHILY

NASA Astrophysics Data System (ADS)

Hosoda, Akira; Sadatsuki, Yoshitomo; Oshima, Akihiro; Ishii, Akina; Tsubaki, Tatsuya

The aim of this research is to clarify the mechanism of controlling plastic shrinkage crack by adding small amout of synthetic short fiber, and to propose optimum polypropylene short fiber to control plastic shrinkage crack. In this research, the effect of the hydrophily of polypropylene fiber was investigated in the amount of plastic shrinkage of mortar, total area of plastic shrinkage crack, and bond properties between fiber and mortar. The plastic shrinkage test of morar was conducted under high temperature, low relative humidity, and constant wind velocity. When polypropylene fiber had hydrophily, the amount of plastic shrinkage of mortar was restrained, which was because cement paste in morar was captured by hydrophilic fiber and then bleeding of mortar was restrained. With hydrophily, plastic shrinkage of mortar was restrained and bridging effect was improved due to better bond, which led to remarkable reduction of plastic shrinkage crack. Based on experimental results, the way of developing optimum polypropylene short fiber for actual construction was proposed. The fiber should have large hydrophily and small diameter, and should be used in as small amount as possible in order not to disturb workability of concrete.

Cure shrinkage in casting resins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spencer, J. Brock

2015-02-01

A method is described whereby the shrinkage of a casting resin can be determined. Values for the shrinkage of several resin systems in frequent use by Sandia have been measured. A discussion of possible methods for determining the stresses generated by cure shrinkage and thermal contraction is also included.

An Experimental Study on Shrinkage Strains of Normal-and High-Strength Concrete-Filled Frp Tubes

NASA Astrophysics Data System (ADS)

Vincent, Thomas; Ozbakkaloglu, Togay

2017-09-01

It is now well established that concrete-filled fiber reinforced polymer (FRP) tubes (CFFTs) are an attractive construction technique for new columns, however studies examining concrete shrinkage in CFFTs remain limited. Concrete shrinkage may pose a concern for CFFTs, as in these members the curing of concrete takes place inside the FRP tube. This paper reports the findings from an experimental study on concrete shrinkage strain measurements for CFFTs manufactured with normal- and high-strength concrete (NSC and HSC). A total of 6 aramid FRP (AFRP)-confined concrete specimens with circular cross-sections were manufactured, with 3 specimens each manufactured using NSC and HSC. The specimens were instrumented with surface and embedded strain gauges to monitor shrinkage development of exposed concrete and concrete sealed inside the CFFTs, respectively. All specimens were cylinders with a 152 mm diameter and 305 mm height, and their unconfined concrete strengths were 44.8 or 83.2 MPa. Analysis of the shrinkage measurements from concrete sealed inside the CFFTs revealed that embedment depth and concrete compressive strength only had minor influences on recorded shrinkage strains. However, an analysis of shrinkage measurements from the exposed concrete surface revealed that higher amounts of shrinkage can occur in HSC. Finally, it was observed that shrinkage strains are significantly higher for concrete exposed at the surface compared to concrete sealed inside the CFFTs.

Effect of Shade and Light Curing Mode on the Degree of Conversion of Silorane-Based and Methacrylate-Based Resin Composites.

PubMed

Sm, Mousavinasab; M, Atai; N, Salehi; A, Salehi

2016-12-01

The degree of conversion depends on the material composition, light source properties, distance from light source, light intensity, curing time, and other factors such as shade and translucency. In the present study, we evaluated the effects of different light-curing modes and shades of methacrylate and silorane-based resin composites on the degree of conversion of resin composites (DC). The methacrylate-based (Filtek Z250, 3M, ESPE) and low-shrinkage silorane-based (Filtek P90, 3M, ESPE) resin composites were used in three groups as follows: group 1-Filtek Z250 (shade A3), group 2-Filtek Z250 (shade B2), and group 3-Filtek P90 (shade A3). We used a light-emitting diode (LED) curing unit for photopolymerization. 10 samples were prepared in each group to evaluate the degree of conversion; 5 samples were cured using soft-start curing mode, and the other 5 were cured using standard curing mode. The DC of the resin composites was measured using Fourier Transform Infrared Spectroscopy (FTIR). The data were analyzed using Kruskal Wallis and one-way ANOVA statistical tests. The degree of conversion of silorane-based resin composite was 70 - 75.8% and that of methacrylate-based resin composites was 60.2 - 68.2% (p = 0.009). The degree of conversion of the composite with brighter colour (B2) was statistically more than the darker composite (A3). Higher degree of conversion was achieved applying the standard curing mode. The results of the study showed that the colour and type of the resin composite and also the curing mode influence the degree of conversion of resin composites.

Tailor-made polyfluoroacrylate and its block copolymer by RAFT polymerization in miniemulsion; improved hydrophobicity in the core-shell block copolymer.

PubMed

Chakrabarty, Arindam; Singha, Nikhil K

2013-10-15

Controlled/living radical polymerization (CRP) of a fluoroacrylate was successfully carried out in miniemulsion by Reversible Addition Fragmentation chain Transfer (RAFT) process. In this case, 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) was polymerized using 2-cyanopropyl dodecyl trithiocarbonate (CPDTC) as RAFT agent, Triton X-405 and sodium dodecyl sulfonate (SDS) as surfactant, and potassium persulphate (KPS) or 2,2'-azobis isobutyronitrile (AIBN) as initiator. Being compatible with hydrophobic fluoroacrylate, this RAFT agent offered very high conversion and good control over the molecular weight of the polymer. The miniemulsion was stable without any costabilizer. The long chain dodecyl group (-C12H25) (Z-group in the RAFT agent) had beneficial effect in stabilizing the miniemulsion. When 2-cyano 2-propyl benzodithioate (CPBD) (Z=-C6H5) was used as RAFT agent, the conversion was less and particle size distribution was very broad. Block copolymerization with butyl acrylate (BA) using PHFBA as macro-RAFT agent showed core-shell morphology with the aggregation of PHFBA segment in the shell. GPC as well as DSC analysis confirmed the formation of block copolymer. The core-shell morphology was confirmed by TEM analysis. The block copolymers (PHFBA-b-PBA) showed significantly higher water contact angle (WCA) showing much better hydrophobicity compared to PHFBA alone. Copyright © 2013 Elsevier Inc. All rights reserved.

Net-Immobilization of β-glucosidase on Nonwoven Fabrics to Lower the Cost of “Cellulosic Ethanol” and Increase Cellulose Conversions

PubMed Central

Zhu, Xing; He, Bin; Zhao, Changwen; Fan, Rong; Zhang, Lihua; Wang, Guan; Ma, Yuhong; Yang, Wantai

2016-01-01

The main limitation preventing the use of enzymatic cellulosic ethanol in industrial production is its higher cost which is mainly due to the elevated price of β-glucosidase (BG). Herein, we report on a simple strategy for the in-situ encapsulation of BG for repeated cellulosic ethanol production. In this strategy, BG was net-immobilized into a poly(ethylene glycol) (PEG) net-cloth layer on a PP nonwoven fabric by way of the visible light-induced surface controlled/living graft cross-linking polymerization. The visible light and mild reaction conditions could ensure the activity retention of BG during immobilization, while the non-swelling uniform net-mesh formed by living cross-linking polymerization could prevent the leakage of BG effectively (at the immobilization rate of more than 98.6% and the leakage rate of only 0.4%). When the BG-loaded fabric was used in combination with free cellulase (CEL), the results of the catalytic reaction demonstrated that these BG-loaded fabrics could not only give a 40% increase in cellulose conversions but also be reused for more than fifteen batches without losing the activity. These BG-loaded fabrics with characteristics including easy separation, excellent operation stability, a low cost of the polymeric matrix and a simple fabrication process are particularly interesting for a future bio-fuel production strategy. PMID:27009788

Net-Immobilization of β-glucosidase on Nonwoven Fabrics to Lower the Cost of “Cellulosic Ethanol” and Increase Cellulose Conversions

NASA Astrophysics Data System (ADS)

Zhu, Xing; He, Bin; Zhao, Changwen; Fan, Rong; Zhang, Lihua; Wang, Guan; Ma, Yuhong; Yang, Wantai

2016-03-01

The main limitation preventing the use of enzymatic cellulosic ethanol in industrial production is its higher cost which is mainly due to the elevated price of β-glucosidase (BG). Herein, we report on a simple strategy for the in-situ encapsulation of BG for repeated cellulosic ethanol production. In this strategy, BG was net-immobilized into a poly(ethylene glycol) (PEG) net-cloth layer on a PP nonwoven fabric by way of the visible light-induced surface controlled/living graft cross-linking polymerization. The visible light and mild reaction conditions could ensure the activity retention of BG during immobilization, while the non-swelling uniform net-mesh formed by living cross-linking polymerization could prevent the leakage of BG effectively (at the immobilization rate of more than 98.6% and the leakage rate of only 0.4%). When the BG-loaded fabric was used in combination with free cellulase (CEL), the results of the catalytic reaction demonstrated that these BG-loaded fabrics could not only give a 40% increase in cellulose conversions but also be reused for more than fifteen batches without losing the activity. These BG-loaded fabrics with characteristics including easy separation, excellent operation stability, a low cost of the polymeric matrix and a simple fabrication process are particularly interesting for a future bio-fuel production strategy.

Photochemical removal of aniline in aqueous solutions: switching from photocatalytic degradation to photo-enhanced polymerization recovery.

PubMed

Tang, Heqing; Li, Jing; Bie, Yeqiang; Zhu, Lihua; Zou, Jing

2010-03-15

Organic pollutants may be treated by either a degradation process or a recovery process in the view point of sustainable chemistry. Photocatalytic removal of aniline was investigated in aqueous solutions. It was found that the photocatalytic oxidation of aniline resulted in its degradation or polymerization, depending on its concentration. Hence a new treatment strategy was proposed in combination of photocatalytic degradation and polymerization, where the polymerization was in fact a recovery process. When aniline concentration was as low as 0.1 mmol L(-1), it was possible to photocatalytically degrade aniline, which could be further enhanced by increasing solution pH, modifying TiO(2) surface with the addition of anions, or coupling with the photoreduction of added oxidants. When aniline concentration was increased to about 1 mmol L(-1), the photocatalytic oxidation was observed to yield the polymerization of aniline, leading to nanocomposites of polyaniline (PAN) and TiO(2). Alternatively, the photo-enhanced chemical polymerization of aniline at higher concentrations (>or=50 mmol L(-1)) in the presence of chemical oxidants produced PAN nanostructures. The conversion of pollutant aniline to valuable PAN nanostructures or nano-PAN/TiO(2) composites is suggestive for possible applications in the treatment of aniline wastewaters as a sustainable environmental protection measure. (c) 2009 Elsevier B.V. All rights reserved.

Synthesis and structure of a ferric complex of 2,6-di(1H-pyrazol-3-yl)pyridine and its excellent performance in the redox-controlled living ring-opening polymerization of ε-caprolactone.

PubMed

Fang, Yang-Yang; Gong, Wei-Jie; Shang, Xiu-Juan; Li, Hong-Xi; Gao, Jun; Lang, Jian-Ping

2014-06-14

The reaction of FeCl3 with a pincer ligand, 2,6-di(1H-pyrazol-3-yl)pyridine (bppyH2), produced a mononuclear Fe(III) complex [Fe(bppyH2)Cl3] (1), which could be reduced to the corresponding Fe(II) dichloride complex [Fe(bppyH2)Cl2] (2) by suitable reducing agents such as Cp2Co or Fe powder. 1 and 2 exhibited a reversible transformation from each other with appropriate redox reagents. 1 could be utilized as a pre-catalyst to initiate the ring-opening polymerization of ε-caprolactone in the presence of alcohol but did not work. The 1/alcohol system displayed characteristics of a well-controlled polymerization with the resulting poly(ε-caprolactone) having low molecular weight distributions, a linear tendency of molecular weight evolution with conversion, and polymer growth observed for the sequential additions of ε-caprolactone monomer to the polymerization reaction. The polymerization was completely turned off by the in situ reduction of the catalytic Fe center via Cp2Co and then turned back upon the addition of [Cp2Fe]PF6. The rate of polymerization was modified by switching in situ between the Fe(III) and Fe(II) species.

Simultaneous measurement of polymerization stress and curing kinetics for photo-polymerized composites with high filler contents.

PubMed

Wang, Zhengzhi; Landis, Forrest A; Giuseppetti, Anthony A M; Lin-Gibson, Sheng; Chiang, Martin Y M

2014-12-01

Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈80% (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites. Published by Elsevier Ltd.

Simultaneous Measurement of Polymerization Stress and Curing Kinetics for Photo-polymerized Composites with High Filler Contents

PubMed Central

Wang, Zhengzhi; Landis, Forrest A.; Giuseppetti, Anthony A.M.; Lin-Gibson, Sheng; Chiang, Martin Y.M.

2015-01-01

Objectives Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Methods Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. Results Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈ 80 % (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. Significance The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites. PMID:25443160

Development of shrinkage resistant microfibre-reinforced cement-based composites

NASA Astrophysics Data System (ADS)

Hamedanimojarrad, P.; Adam, G.; Ray, A. S.; Thomas, P. S.; Vessalas, K.

2012-06-01

Different shrinkage types may cause serious durability dilemma on restrained concrete parts due to crack formation and propagation. Several classes of fibres are used by concrete industry in order to reduce crack size and crack number. In previous studies, most of these fibre types were found to be effective in reducing the number and sizes of the cracks, but not in shrinkage strain reduction. This study deals with the influence of a newly introduced type of polyethylene fibre on drying shrinkage reduction. The novel fibre is a polyethylene microfibre in a new geometry, which is proved to reduce the amount of total shrinkage in mortars. This special hydrophobic polyethylene microfibre also reduces moisture loss of mortar samples. The experimental results on short and long-term drying shrinkage as well as on several other properties are reported. The hydrophobic polyethylene microfibre showed promising improvement in shrinkage reduction even at very low concentrations (0.1% of cement weight).

A Monte Carlo Evaluation of Estimated Parameters of Five Shrinkage Estimate Formuli.

ERIC Educational Resources Information Center

Newman, Isadore; And Others

1979-01-01

A Monte Carlo simulation was employed to determine the accuracy with which the shrinkage in R squared can be estimated by five different shrinkage formulas. The study dealt with the use of shrinkage formulas for various sample sizes, different R squared values, and different degrees of multicollinearity. (Author/JKS)

Immobilized enzyme studies in a microscale bioreactor.

PubMed

Jones, Francis; Forrest, Scott; Palmer, Jim; Lu, Zonghuan; Elmore, John; Elmore, Bill B

2004-01-01

Novel microreactors with immobilized enzymes were fabricated using both silicon and polymer-based microfabrication techniques. The effectiveness of these reactors was examined along with their behavior over time. Urease enzyme was successfully incorporated into microchannels of a polymeric matrix of polydimethylsiloxane and through layer-bylayer self-assembly techniques onto silicon. The fabricated microchannels had cross-sectional dimensions ranging from tens to hundreds of micrometers in width and height. The experimental results for continuous-flow microreactors are reported for the conversion of urea to ammonia by urease enzyme. Urea conversions of >90% were observed.

Characterization of passive polymer optical waveguides

NASA Astrophysics Data System (ADS)

Joehnck, Matthias; Kalveram, Stefan; Lehmacher, Stefan; Pompe, Guido; Rudolph, Stefan; Neyer, Andreas; Hofstraat, Johannes W.

1999-05-01

The characterization of monomode passive polymer optical devices fabricated according to the POPCORN technology by methods originated from electron, ion and optical spectroscopy is summarized. Impacts of observed waveguide perturbations on the optical characteristics of the waveguide are evaluated. In the POPCORN approach optical components for telecommunication applications are fabricated by photo-curing of liquid halogenated (meth)acrylates which have been applied on moulded thermoplastic substrates. For tuning of waveguide material refractive indices with respect to the substrate refractive index frequently comonomer mixtures are used. The polymerization characteristics, especially the polymerization kinetics of individual monomers, determine the formation of copolymers. Therefore the unsaturation as function of UV-illumination time in the formation of halogenated homo- and copolymers has been examined. From different suitable copolymer system, after characterization of their glass transition temperatures, their curing behavior and their refractive indices as function of the monomer ratios, monomode waveguides applying PMMA substrates have been fabricated. To examine the materials composition also in the 6 X 6 micrometers 2 waveguides they have been visualized by transmission electron microscopy. With this method e.g. segregation phenomena could be observed in the waveguide cross section characterization as well. The optical losses in monomode waveguides caused by segregation and other materials induce defects like micro bubbles formed as a result of shrinkage have been quantized by return loss measurements. Defects causing scattering could be observed by convocal laser scanning microscopy and by conventional light microscopy.

Activation of Actuating Hydrogels with WS2 Nanosheets for Biomimetic Cellular Structures and Steerable Prompt Deformation.

PubMed

Zong, Lu; Li, Xiankai; Han, Xiangsheng; Lv, Lili; Li, Mingjie; You, Jun; Wu, Xiaochen; Li, Chaoxu

2017-09-20

Macroscopic soft actuation is intrinsic to living organisms in nature, including slow deformation (e.g., contraction, bending, twisting, and curling) of plants motivated by microscopic swelling and shrinking of cells, and rapid motion of animals (e.g., deformation of jellyfish) motivated by cooperative nanoscale movement of motor proteins. These actuation behaviors, with an exceptional combination of tunable speed and programmable deformation direction, inspire us to design artificial soft actuators for broad applications in artificial muscles, nanofabrication, chemical valves, microlenses, soft robotics, etc. However, so far artificial soft actuators have been typically produced on the basis of poly(N-isopropylacrylamide) (PNiPAM), whose deformation is motived by volumetric shrinkage and swelling in analogue to plant cells, and exhibits sluggish actuation kinetics. In this study, alginate-exfoliated WS 2 nanosheets were incorporated into ice-template-polymerized PNiPAM hydrogels with the cellular microstructures which mimic plant cells, yet the prompt steerable actuation of animals. Because of the nanosheet-reinforced pore walls formed in situ in freezing polymerization and reasonable hierarchical water channels, this cellular hybrid hydrogel achieves super deformation speed (on the order of magnitude of 10° s), controllable deformation direction, and high near-infrared light responsiveness, offering an unprecedented platform of artificial muscles for various soft robotics and devices (e.g., rotator, microvalve, aquatic swimmer, and water-lifting filter).

Post-veraison irreversible stem shrinkage in grapevine (Vitis vinifera) is caused by periderm formation.

PubMed

Van de Wal, Bart A E; Leroux, Olivier; Steppe, Kathy

2018-05-01

Grapevines are characterized by a period of irreversible stem shrinkage around the onset of ripening of the grape berries. Since this shrinkage is unrelated to meteorological conditions or drought, it is often suggested that it is caused by the increased sink strength of the grape berries during this period. However, no studies so far have experimentally investigated the mechanisms underlying this irreversible stem shrinkage. We therefore combined continuous measurements of stem diameter variations and histology of potted 2-year-old grapevines (Vitis vinifera L. 'Boskoop Glory'). Sink strength was altered by pruning all grape clusters (treatment P), while non-pruned grapevines served as control (treatment C). Unexpectedly, our results showed irreversible post-veraison stem shrinkage in both treatments, suggesting that the shrinkage is not linked to grape berry sink strength. Anatomical analysis indicated that the shrinkage is the result of the formation of successive concentric periderm layers, and the subsequent dehydration and compression of the older bark tissues, an anatomical feature that is characteristic of Vitis stems. Stem shrinkage is hence unrelated to grape berry development, in contrast to what has been previously suggested.

Post-resection mucosal margin shrinkage in oral cancer: quantification and significance.

PubMed

Mistry, Rajesh C; Qureshi, Sajid S; Kumaran, C

2005-08-01

The importance of tumor free margins in outcome of cancer surgery is well known. Often the pathological margins are reported to be significantly smaller than the in situ margins. This discrepancy is due to margin shrinkage the quantum of which has not been studied in patients with oral cancers. To quantify the shrinkage of mucosal margin following excision for carcinoma of the oral tongue and buccal mucosa. Mucosal margins were measured prior to resection and half an hour after excision in 27 patients with carcinoma of the tongue and buccal mucosa. The mean margin shrinkage was assessed and the variables affecting the quantum of shrinkage analyzed. The mean shrinkage from the in situ to the post resection margin status was 22.7% (P < 0.0001). The mean shrinkage of the tongue margins was 23.5%, compared to 21.2% for buccal mucosa margins. The mean shrinkage in T1/T2 tumors (25.6%) was significantly more than in T3/T4 (9.2%, P < 0.011). There is significant shrinkage of mucosal margins after surgery. Hence this should be considered and appropriate margins should be taken at initial resection to prevent the agony of post-operative positive surgical margins. Copyright 2005 Wiley-Liss, Inc.

Study of SEM preparation artefacts with correlative microscopy: Cell shrinkage of adherent cells by HMDS-drying.

PubMed

Katsen-Globa, Alisa; Puetz, Norbert; Gepp, Michael M; Neubauer, Julia C; Zimmermann, Heiko

2016-11-01

One of the often reported artefacts during cell preparation to scanning electron microscopy (SEM) is the shrinkage of cellular objects, that mostly occurs at a certain time-dependent stage of cell drying. Various methods of drying for SEM, such as critical point drying, freeze-drying, as well as hexamethyldisilazane (HMDS)-drying, were usually used. The latter becomes popular since it is a low cost and fast method. However, the correlation of drying duration and real shrinkage of objects was not investigated yet. In this paper, cell shrinkage at each stage of preparation for SEM was studied. We introduce a shrinkage coefficient using correlative light microscopy (LM) and SEM of the same human mesenchymal stem cells (hMSCs). The influence of HMDS-drying duration on the cell shrinkage is shown: the longer drying duration, the more shrinkage is observed. Furthermore, it was demonstrated that cell shrinkage is inversely proportional to cultivation time: the longer cultivation time, the more cell spreading area and the less cell shrinkage. Our results can be applicable for an exact SEM quantification of cell size and determination of cell spreading area in engineering of artificial cellular environments using biomaterials. SCANNING 38:625-633, 2016. © 2016 Wiley Periodicals, Inc. © Wiley Periodicals, Inc.

Thermo-Oxidative Induced Damage in Polymer Composites: Microstructure Image-Based Multi-Scale Modeling and Experimental Validation

NASA Astrophysics Data System (ADS)

Hussein, Rafid M.; Chandrashekhara, K.

2017-11-01

A multi-scale modeling approach is presented to simulate and validate thermo-oxidation shrinkage and cracking damage of a high temperature polymer composite. The multi-scale approach investigates coupled transient diffusion-reaction and static structural at macro- to micro-scale. The micro-scale shrinkage deformation and cracking damage are simulated and validated using 2D and 3D simulations. Localized shrinkage displacement boundary conditions for the micro-scale simulations are determined from the respective meso- and macro-scale simulations, conducted for a cross-ply laminate. The meso-scale geometrical domain and the micro-scale geometry and mesh are developed using the object oriented finite element (OOF). The macro-scale shrinkage and weight loss are measured using unidirectional coupons and used to build the macro-shrinkage model. The cross-ply coupons are used to validate the macro-shrinkage model by the shrinkage profiles acquired using scanning electron images at the cracked surface. The macro-shrinkage model deformation shows a discrepancy when the micro-scale image-based cracking is computed. The local maximum shrinkage strain is assumed to be 13 times the maximum macro-shrinkage strain of 2.5 × 10-5, upon which the discrepancy is minimized. The microcrack damage of the composite is modeled using a static elastic analysis with extended finite element and cohesive surfaces by considering the modulus spatial evolution. The 3D shrinkage displacements are fed to the model using node-wise boundary/domain conditions of the respective oxidized region. Microcrack simulation results: length, meander, and opening are closely matched to the crack in the area of interest for the scanning electron images.

Accelerated Combinatorial High Throughput Star Polymer Synthesis via a Rapid One-Pot Sequential Aqueous RAFT (rosa-RAFT) Polymerization Scheme.

PubMed

Cosson, Steffen; Danial, Maarten; Saint-Amans, Julien Rosselgong; Cooper-White, Justin J

2017-04-01

Advanced polymerization methodologies, such as reversible addition-fragmentation transfer (RAFT), allow unprecedented control over star polymer composition, topology, and functionality. However, using RAFT to produce high throughput (HTP) combinatorial star polymer libraries remains, to date, impracticable due to several technical limitations. Herein, the methodology "rapid one-pot sequential aqueous RAFT" or "rosa-RAFT," in which well-defined homo-, copolymer, and mikto-arm star polymers can be prepared in very low to medium reaction volumes (50 µL to 2 mL) via an "arm-first" approach in air within minutes, is reported. Due to the high conversion of a variety of acrylamide/acrylate monomers achieved during each successive short reaction step (each taking 3 min), the requirement for intermediary purification is avoided, drastically facilitating and accelerating the star synthesis process. The presented methodology enables RAFT to be applied to HTP polymeric bio/nanomaterials discovery pipelines, in which hundreds of complex polymeric formulations can be rapidly produced, screened, and scaled up for assessment in a wide range of applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of imine bond containing insoluble polymeric ligand and its transition metal complexes, structural characterization and catalytic activity on esterification reaction.

PubMed

Gönül, İlyas; Ay, Burak; Karaca, Serkan; Saribiyik, Oguz Yunus; Yildiz, Emel; Serin, Selahattin

2017-01-01

In this study, synthesis of insoluble polymeric ligand (L) and its transition metal complexes [Cu(L)Cl 2 ]·2H 2 O (1) , [Co(L)Cl 2 (H 2 O) 2 ] (2) and [Ni(L)Cl 2 (H 2 O) 2 ] (3) , having the azomethine groups, were synthesized by the condensation reactions of the diamines and dialdehydes. The structural properties were characterized by the analytical and spectroscopic methods using by elemental analysis, Fourier Transform Infrared, Thermo Gravimetric Analysis, Powder X-ray Diffraction, magnetic susceptibility and Inductively Coupled Plasma. The solubilities of the synthesized polymeric materials were also investigated and found as insoluble some organic and inorganic solvents. Additionally, their catalytic performance was carried out for the esterification reaction of acetic acid and butyl acetate. The highest conversion rate is 75.75% by using catalyst 1 . The esterification of butanol gave butyl acetate with 100% selectivity.

Copper mediated polymerization without external deoxygenation or oxygen scavengers.

PubMed

Liarou, Evelina; Whitfield, Richard; Anastasaki, Athina; Engelis, Nikolaos G; Jones, Glen R; Velonia, Kelly; Haddleton, David

2018-05-14

Overcoming the challenge of rigorous deoxygenation in copper mediated controlled radical polymerization processes (e.g. ATRP), we report a simple Cu(0)-RDRP system in the absence of external additives (e.g. reducing agents, enzymes etc.). By simply adjusting the headspace of the reaction vessel, a wide range of monomers, namely acrylates, methacrylates, acrylamides and styrene, can be polymerized in a controlled manner yielding polymers with low dispersities, near-quantitative conversions and high end group fidelity. Significantly, this approach is scalable (~ 125 g), tolerant to elevated temperatures, compatible with both organic and aqueous media and does not rely on external stimuli which may limit the monomer pool. The robustness and versatility of this methodology is further demonstrated by the applicability to a number of other copper mediated techniques including conventional ATRP and light-mediated approaches. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Final Report

NASA Technical Reports Server (NTRS)

1995-01-01

This cooperative agreement explored the novel polymerization of vinylsilane, alone and in combination with other alkenylsilanes, alkylsilanes, and/or crosslinking agents, using dimethyltitanocene as homogeneous catalyst. The reactions were found to be initiated photochemically under mild conditions, and no hydrogen gas was evolved when alkenylsilanes were polymerized. The polymers were found to have predominately a carbosilane-type backbone containing -SiH2-CH2-CH2-Si and -SiH2-CH(CH3)-Si type linkages. The mechanism of polymerization was found to be step-growth. Despite the relatively low molecular weight of the polymer (M(sub n) - 500 and M(sub W) - 1500), pyrolysis resulted in conversion to C-rich SiC ceramic in high char yields (-60%). Copolymerization with methylsilane resulted in higher chars and more crystalline polymer. Addition of crosslinking agents such as polybutadiene or methyltrivinylsilane increased the viscosity of the polymer produced and enabled application as coatings to fiber toes.

Effect of cellulose nanowhiskers functionalization with polyaniline for epoxy coatings

NASA Astrophysics Data System (ADS)

Borsoi, C.; Zattera, A. J.; Ferreira, C. A.

2016-02-01

Functionalization of cellulose nanowhiskers (CNW) was performed by means of chemical synthesis involving polymerization of polyaniline in emeraldine salt form (PAni SE) in the presence of CNW. Thermal, chemical and morphological samples properties were evaluated. Polymeric coatings were obtained with epoxy, aminopropyltriethoxysilane (APS), CNW and CNW/PAni SE applied on carbon steel with a conversion coating of zirconia (Zr) and the mechanical properties were evaluated. With regard to CNW functionalization the sample was encapsulated with PAni SE as observed by FTIR and morphologic analysis, with decreased thermal stability. Regarding the mechanical properties of CNW and CNW/PAni SE polymeric coatings, improvements in flexibility and hardness properties using the APS and Zr layer were observed. The adherence of polymer coatings improved by the incorporation of CNW and CNW/PAni SE. Through morphological analysis it was observed that CNW shows good dispersion in the polymer matrix without agglomerates formation.

Terrestrial evolution of polymerization of amino acids - Heat to ATP

NASA Technical Reports Server (NTRS)

Fox, S. W.; Nakashima, T.

1981-01-01

Sets of amino acids containing sufficient trifunctional monomer are thermally polymerized at temperatures such as 65 deg; the amino acids order themselves. Various polymers have diverse catalytic activities. The polymers aggregate, in aqueous solution, to cell-like structures having those activities plus emergent properties, e.g. proliferatability. Polyamino acids containing sufficient lysine catalyze conversion of free amino acids, by ATP, to small peptides and a high molecular weight fraction. The lysine-rich proteinoid is active in solution, within suspensions of cell-like particles, or in other particles composed of lysine-rich proteinoid and homopolyribonucleotide. Selectivities are observed. An archaic polyamino acid prelude to coded protein synthesis is indicated.

Bifunctional Organic Polymeric Catalysts with a Tunable Acid-Base Distance and Framework Flexibility

PubMed Central

Chen, Huanhui; Wang, Yanan; Wang, Qunlong; Li, Junhui; Yang, Shiqi; Zhu, Zhirong

2014-01-01

Acid-base bifunctional organic polymeric catalysts were synthesized with tunable structures. we demonstrated two synthesis approaches for structural fine-tune. In the first case, the framework flexibility was tuned by changing the ratio of rigid blocks to flexible blocks within the polymer framework. In the second case, we precisely adjusted the acid-base distance by distributing basic monomers to be adjacent to acidic monomers, and by changing the chain length of acidic monomers. In a standard test reaction for the aldol condensation of 4-nitrobenzaldehyde with acetone, the catalysts showed good reusability upon recycling and maintained relatively high conversion percentage. PMID:25267260

Immobilization of Escherichia coli cells with penicillin-amidohydrolase activity on solid polymeric carriers.

PubMed

Zurková, E; Drobník, J; Kálal, J; Svec, F; Tyrácková, V; Vojtísek, V; Zeman, R

1983-09-01

Whole cells of Escherichia coli containing the enzyme penicillinamidohydrolase EC 3.5.1.11 were immobilized on the surface of modified macroporous copolymers of glycidylmethacrylate with ethylenedimethacrylate and of copolymers of methacrylaldehyde (MA) with divinylbenzene (DVB) by means of glutaraldehyde. These polymeric carriers were modified before cell binding by using ammonia or polyamines, especially ethylenediamine and hexamethylenediamine (HMDA). The highest specific activity and the largest yield in cell immobilization were achieved with the macroporous copolymer of MA and DVB modified with HMDA. The material thus obtained was used in repeated conversions of benzylpenicillin to 6-aminopenicillanic acid in a stirred batch reactor.

A Monte Carlo Evaluation of Estimated Parameters of Five Shrinkage Estimate Formuli.

ERIC Educational Resources Information Center

Newman, Isadore; And Others

A Monte Carlo study was conducted to estimate the efficiency of and the relationship between five equations and the use of cross validation as methods for estimating shrinkage in multiple correlations. Two of the methods were intended to estimate shrinkage to population values and the other methods were intended to estimate shrinkage from sample…

Physical properties and depth of cure of a new short fiber reinforced composite.

PubMed

Garoushi, Sufyan; Säilynoja, Eija; Vallittu, Pekka K; Lassila, Lippo

2013-08-01

To determine the physical properties and curing depth of a new short fiber composite intended for posterior large restorations (everX Posterior) in comparison to different commercial posterior composites (Alert, TetricEvoCeram Bulk Fill, Voco X-tra base, SDR, Venus Bulk Fill, SonicFill, Filtek Bulk Fill, Filtek Superme, and Filtek Z250). In addition, length of fiber fillers of composite XENIUS base compared to the previously introduced composite Alert has been measured. The following properties were examined according to ISO standard 4049: flexural strength, flexural modulus, fracture toughness, polymerization shrinkage and depth of cure. The mean and standard deviation were determined and all results were statistically analyzed with analysis of variance ANOVA (a=0.05). XENIUS base composite exhibited the highest fracture toughness (4.6MPam(1/2)) and flexural strength (124.3MPa) values and the lower shrinkage strain (0.17%) among the materials tested. Alert composite revealed the highest flexural modulus value (9.9GPa), which was not significantly different from XENIUS base composite (9.5GPa). Depth of cure of XENIUS base (4.6mm) was similar than those of bulk fill composites and higher than other hybrid composites. The length of fiber fillers in XENIUS base was longer (1.3-2mm) than in Alert (20-60μm). The new short fiber composite differed significantly in its physical properties compared to other materials tested. This suggests that the latter could be used in high-stress bearing areas. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Two year clinical evaluation of a low-shrink resin composite material in UK general dental practices.

PubMed

Burke, F J Trevor; Crisp, Russell J; James, A; Mackenzie, L; Pal, A; Sands, P; Thompson, O; Palin, W M

2011-07-01

A novel resin composite system, Filtek Silorane (3M ESPE) with reduced polymerization shrinkage has recently been introduced. The resin contains an oxygen-containing ring molecule ('oxirane') and cures via a cationic ring-opening reaction rather than a linear chain reaction associated with conventional methacrylates and results in a volumetric shrinkage of ∼1%. The purpose of this study was to review the literature on a recently introduced resin composite material, Filtek Silorane, and evaluate the clinical outcome of restorations formed in this material. Filtek Silorane restorations were placed where indicated in loadbearing situations in the posterior teeth of patients attending five UK dental practices. These were evaluated, after two years, using modified USPHS criteria. A total of 100 restorations, of mean age 25.7 months, in 64 patients, were examined, comprised of 30 Class I and 70 Class II. All restorations were found to be present and intact, there was no secondary caries. Ninety-seven per cent of the restorations were rated optimal for anatomic form, 84% were rated optimal for marginal integrity, 77% were rated optimal for marginal discoloration, 99% were rated optimal for color match, and 93%% of the restorations were rated optimal for surface quality. No restoration was awarded a "fail" grade. No staining of the restoration surfaces was recorded and no patients complained of post-operative sensitivity. It is concluded that, within the limitations of the study, the two year assessment of 100 restorations placed in Filtek Silorane has indicated satisfactory clinical performance. Copyright © 2011. Published by Elsevier Ltd.

Effects of vacuum and ageing on Zr4/Cr3 based conversion coatings on aluminium alloys

NASA Astrophysics Data System (ADS)

Thirupathi, Kalaivanan; Bárczy, Pál; Vad, Kálmán; Csik, Attila; Somosvári, Béla Márton

2018-05-01

In this study, we investigate the impact of ageing and high vacuum on existing environmentally friendly Zr4/Cr3-based conversion coatings. The freshly formed coating undergoes several changes during ageing and exposure to high vacuum. Based on the present data, we propose that the coating formed over AA6082 and AA7075 alloys is sol-gel in nature, confirmed by secondary neutral mass spectroscopy (SNMS) using the depth profiling technique. Our findings reveal that there are elemental level changes that result in shrinkage of the coating. Most Zr ions in the coating are in the solute form, with lesser number of Cr and Al ions that disappear under high vacuum over a certain period of time. The remaining Cr, Zr and O atoms exist in a gelatinous state. During ageing, there is a continuous transition of ions from solute to gelatinous state. In addition, the deposition of coating ions is directly influenced by the substrates and their constituents. The extent of dissolution of aluminium in the conversion bath determines both Zr and Cr ion deposition. For a highly alloyed metal like AA7075, the dissolution rate is disturbed by copper and zinc.

Synthesis of High Molecular Weight Poly(glycerol monomethacrylate) via RAFT Emulsion Polymerization of Isopropylideneglycerol Methacrylate

PubMed Central

2018-01-01

High molecular weight water-soluble polymers are widely used as flocculants or thickeners. However, synthesis of such polymers via solution polymerization invariably results in highly viscous fluids, which makes subsequent processing somewhat problematic. Alternatively, such polymers can be prepared as colloidal dispersions; in principle, this is advantageous because the particulate nature of the polymer chains ensures a much lower fluid viscosity. Herein we exemplify the latter approach by reporting the convenient one-pot synthesis of high molecular weight poly(glycerol monomethacrylate) (PGMA) via the reversible addition–fragmentation chain transfer (RAFT) aqueous emulsion polymerization of a water-immiscible protected monomer precursor, isopropylideneglycerol methacrylate (IPGMA) at 70 °C, using a water-soluble poly(glycerol monomethacrylate) (PGMA) chain transfer agent as a steric stabilizer. This formulation produces a low-viscosity aqueous dispersion of PGMA–PIPGMA diblock copolymer nanoparticles at 20% solids. Subsequent acid deprotection of the hydrophobic core-forming PIPGMA block leads to particle dissolution and affords a viscous aqueous solution comprising high molecular weight PGMA homopolymer chains with a relatively narrow molecular weight distribution. Moreover, it is shown that this latex precursor route offers an important advantage compared to the RAFT aqueous solution polymerization of glycerol monomethacrylate since it provides a significantly faster rate of polymerization (and hence higher monomer conversion) under comparable conditions. PMID:29805184

Shrinkage Degree in $L_{2}$ -Rescale Boosting for Regression.

PubMed

Xu, Lin; Lin, Shaobo; Wang, Yao; Xu, Zongben

2017-08-01

L 2 -rescale boosting ( L 2 -RBoosting) is a variant of L 2 -Boosting, which can essentially improve the generalization performance of L 2 -Boosting. The key feature of L 2 -RBoosting lies in introducing a shrinkage degree to rescale the ensemble estimate in each iteration. Thus, the shrinkage degree determines the performance of L 2 -RBoosting. The aim of this paper is to develop a concrete analysis concerning how to determine the shrinkage degree in L 2 -RBoosting. We propose two feasible ways to select the shrinkage degree. The first one is to parameterize the shrinkage degree and the other one is to develop a data-driven approach. After rigorously analyzing the importance of the shrinkage degree in L 2 -RBoosting, we compare the pros and cons of the proposed methods. We find that although these approaches can reach the same learning rates, the structure of the final estimator of the parameterized approach is better, which sometimes yields a better generalization capability when the number of sample is finite. With this, we recommend to parameterize the shrinkage degree of L 2 -RBoosting. We also present an adaptive parameter-selection strategy for shrinkage degree and verify its feasibility through both theoretical analysis and numerical verification. The obtained results enhance the understanding of L 2 -RBoosting and give guidance on how to use it for regression tasks.

Shrinkage and footage loss from drying 4/4-inch hard maple lumber.

Treesearch

Daniel E. Dunmire

1968-01-01

Equations are presented for estimating shrinkage and resulting footage losses due to drying hard maple lumber. The equations, based on board shrinkage data taken from a representative lumber sample, are chiefly intended for use with lots of hard maple lumber, such as carloads, truckloads, or kiln loads, but also can be used for estimating the average shrinkage of...

Synthesis and structural studies of heterobimetallic alkoxide complexes supported by bis(phenolate) ligands: efficient catalysts for ring-opening polymerization of L-lactide.

PubMed

Chen, Hsuan-Ying; Liu, Mei-Yu; Sutar, Alekha Kumar; Lin, Chu-Chieh

2010-01-18

A series of heterobimetallic titanium(IV) complexes [LTi(O(i)Pr)(mu-O(i)Pr)(2)Li(THF)(2)], [LTi(O(i)Pr)(mu-O(i)Pr)(2)Na(THF)(2)], [LTi(mu-O(i)Pr)(2)Zn(O(i)Pr)(2)], and [LTi(mu-O(i)Pr)(2)Mg(O(i)Pr)(2)] (where L = bidentate bisphenol ligands) have been synthesized and characterized including a structural determination of [L(1)Ti(mu(2)-O(i)Pr)(2)(O(i)Pr)Li(THF)(2)] (1a). These complexes were investigated for their utility in the ring-opening polymerization (ROP) of l-lactide (LA). Polymerization activities have been shown to correlate with the electronic properties of the substituent within the bisphenol ligand. In contrast to monometallic titanium initiator 1e, all the heterobimetallic titanium initiators (Ti-Li, Ti-Na, Ti-Zn, and Ti-Mg) show enhanced catalytic activity toward ring-opening polymerization (ROP) of l-LA. In addition, the use of electron-donating methoxy or methylphenylsulfonyl functional ligands reveals the highest activity. The bisphenol bimetallic complexes give rise to controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number-average molecular weight. The polymerization kinetics using 2c as an initiator were also studied, and the experimental results indicate that the reaction rate is first-order with respect to both monomer and catalyst concentration with a polymerization rate constant, k = 81.64 M(-1) min(-1).

Effect of the Key Mixture Parameters on Shrinkage of Reactive Powder Concrete

PubMed Central

Zubair, Ahmed

2014-01-01

Reactive powder concrete (RPC) mixtures are reported to have excellent mechanical and durability characteristics. However, such concrete mixtures having high amount of cementitious materials may have high early shrinkage causing cracking of concrete. In the present work, an attempt has been made to study the simultaneous effects of three key mixture parameters on shrinkage of the RPC mixtures. Considering three different levels of the three key mixture factors, a total of 27 mixtures of RPC were prepared according to 33 factorial experiment design. The specimens belonging to all 27 mixtures were monitored for shrinkage at different ages over a total period of 90 days. The test results were plotted to observe the variation of shrinkage with time and to see the effects of the key mixture factors. The experimental data pertaining to 90-day shrinkage were used to conduct analysis of variance to identify significance of each factor and to obtain an empirical equation correlating the shrinkage of RPC with the three key mixture factors. The rate of development of shrinkage at early ages was higher. The water to binder ratio was found to be the most prominent factor followed by cement content with the least effect of silica fume content. PMID:25050395

Effect of the key mixture parameters on shrinkage of reactive powder concrete.

PubMed

Ahmad, Shamsad; Zubair, Ahmed; Maslehuddin, Mohammed

2014-01-01

Reactive powder concrete (RPC) mixtures are reported to have excellent mechanical and durability characteristics. However, such concrete mixtures having high amount of cementitious materials may have high early shrinkage causing cracking of concrete. In the present work, an attempt has been made to study the simultaneous effects of three key mixture parameters on shrinkage of the RPC mixtures. Considering three different levels of the three key mixture factors, a total of 27 mixtures of RPC were prepared according to 3(3) factorial experiment design. The specimens belonging to all 27 mixtures were monitored for shrinkage at different ages over a total period of 90 days. The test results were plotted to observe the variation of shrinkage with time and to see the effects of the key mixture factors. The experimental data pertaining to 90-day shrinkage were used to conduct analysis of variance to identify significance of each factor and to obtain an empirical equation correlating the shrinkage of RPC with the three key mixture factors. The rate of development of shrinkage at early ages was higher. The water to binder ratio was found to be the most prominent factor followed by cement content with the least effect of silica fume content.

Four-Phase Dendritic Model for the Prediction of Macrosegregation, Shrinkage Cavity, and Porosity in a 55-Ton Ingot

NASA Astrophysics Data System (ADS)

Ge, Honghao; Ren, Fengli; Li, Jun; Han, Xiujun; Xia, Mingxu; Li, Jianguo

2017-03-01

A four-phase dendritic model was developed to predict the macrosegregation, shrinkage cavity, and porosity during solidification. In this four-phase dendritic model, some important factors, including dendritic structure for equiaxed crystals, melt convection, crystals sedimentation, nucleation, growth, and shrinkage of solidified phases, were taken into consideration. Furthermore, in this four-phase dendritic model, a modified shrinkage criterion was established to predict shrinkage porosity (microporosity) of a 55-ton industrial Fe-3.3 wt pct C ingot. The predicted macrosegregation pattern and shrinkage cavity shape are in a good agreement with experimental results. The shrinkage cavity has a significant effect on the formation of positive segregation in hot top region, which generally forms during the last stage of ingot casting. The dendritic equiaxed grains also play an important role on the formation of A-segregation. A three-dimensional laminar structure of A-segregation in industrial ingot was, for the first time, predicted by using a 3D case simulation.

Variation of Shrinkage Strain within the Depth of Concrete Beams.

PubMed

Jeong, Jong-Hyun; Park, Yeong-Seong; Lee, Yong-Hak

2015-11-16

The variation of shrinkage strain within beam depth was examined through four series of time-dependent laboratory experiments on unreinforced concrete beam specimens. Two types of beam specimens, horizontally cast and vertically cast, were tested; shrinkage variation was observed in the horizontally cast specimens. This indicated that the shrinkage variation within the beam depth was due to water bleeding and tamping during the placement of the fresh concrete. Shrinkage strains were measured within the beam depth by two types of strain gages, surface-attached and embedded. The shrinkage strain distribution within the beam depth showed a consistent tendency for the two types of gages. The test beams were cut into four sections after completion of the test, and the cutting planes were divided into four equal sub-areas to measure the aggregate concentration for each sub-area of the cutting plane. The aggregate concentration increased towards the bottom of the beam. The shrinkage strain distribution was estimated by Hobbs' equation, which accounts for the change of aggregate volume concentration.

Variation of Shrinkage Strain within the Depth of Concrete Beams

PubMed Central

Jeong, Jong-Hyun; Park, Yeong-Seong; Lee, Yong-Hak

2015-01-01

The variation of shrinkage strain within beam depth was examined through four series of time-dependent laboratory experiments on unreinforced concrete beam specimens. Two types of beam specimens, horizontally cast and vertically cast, were tested; shrinkage variation was observed in the horizontally cast specimens. This indicated that the shrinkage variation within the beam depth was due to water bleeding and tamping during the placement of the fresh concrete. Shrinkage strains were measured within the beam depth by two types of strain gages, surface-attached and embedded. The shrinkage strain distribution within the beam depth showed a consistent tendency for the two types of gages. The test beams were cut into four sections after completion of the test, and the cutting planes were divided into four equal sub-areas to measure the aggregate concentration for each sub-area of the cutting plane. The aggregate concentration increased towards the bottom of the beam. The shrinkage strain distribution was estimated by Hobbs’ equation, which accounts for the change of aggregate volume concentration. PMID:28793677

An oxygen-insensitive degradable resist for fabricating metallic patterns on highly curved surfaces by UV-nanoimprint lithography.

PubMed

Hu, Xin; Huang, Shisong; Gu, Ronghua; Yuan, Changsheng; Ge, Haixiong; Chen, Yanfeng

2014-10-01

In this paper, an oxygen-insensitive degradable resist for UV-nanoimprint is designed, com-prising a polycyclic degradable acrylate monomer, 2,10-diacryloyloxymethyl-1,4,9,12-tetraoxa-spiro [4.2.4.2] tetradecane (DAMTT), and a multifunctional thiol monomer pentaerythritol tetra(3-mercaptopropionate) (PETMP). The resist can be quickly UV-cured in the air atmosphere and achieve a high monomer conversion of over 98%, which greatly reduce the adhesion force between the resist and the soft mold. High conversion, in company with an adequate Young's modulus (about 1 GPa) and an extremely low shrinkage (1.34%), promises high nanoimprint resolution of sub-50 nm. The cross-linked resist is able to break into linear molecules in a hot acid solvent. As a result, metallic patterns are fabricated on highly curved surfaces via the lift off process without the assistance of a thermoplastic polymer layer. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Devitrification and shrinkage behavior of silica fibers

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1972-01-01

Devitrification and shrinkage of three batches of silica fibers were investigated in the temperature range of 1200 to 1350 C. Fibers with high water and impurity content devitrified rapidly to cristobalite and quartz and exhibited rapid, but the least amount of, shrinkage. A batch with low water and impurity content devitrified more slowly to cristobalite only and underwent severe shrinkage by the mechanism of viscous flow. A third batch of intermediate purity level and low water content devitrified at a moderate rate mainly to cristobalite but shrunk very rapidly. Completely devitrified silica fibers did not exhibit any further shrinkage.

21 CFR 178.3740 - Plasticizers in polymeric substances.

Code of Federal Regulations, 2014 CFR

2014-04-01

..., hydrogenated (minimum viscosity at 99 °F, 39 Saybolt Universal seconds, as determined by ASTM methods D445-82 (“Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)”) and D2161-82 (“Standard Method for Conversion of Kinematic Viscosity to Saybolt...

Photovoltaic performance of TiO2 electrode adsorbed with gardenia yellow purified by nonionic polymeric sorbent in dye-sensitized solar cells.

PubMed

Kwon, Oh Oun; Kim, Eui Jin; Lee, Jae Hyeok; Kim, Tae Young; Park, Kyung Hee; Kim, Sang Yook; Suh, Hwa Jin; Lee, Hyo Jung; Lee, Jae Wook

2015-02-05

To improve the photovoltaic conversion efficiency in dye-sensitized solar cells (DSSCs), TiO2 electrode adsorbed with gardenia yellow purified by nonionic polymeric sorbent was successfully formulated on nanoporous TiO2 surface. Adsorption and desorption properties of crude gardenia yellow solution on a macroporous resin, XAD-1600, were investigated to purify gardenia yellow because of its strong adsorption and desorption abilities as well as high selectivity. To this end, adsorption equilibrium and kinetic data were measured and fitted using adsorption isotherms and kinetic models. Adsorption and desorption breakthrough curves in a column packed with XAD-1600 resin was obtained to optimize the separation process of gardenia yellow. The photovoltaic performance of the photo-electrode adsorbed with the crude and purified gardenia yellow in DSSCs was compared from current-voltage measurements. The results showed that the photovoltaic conversion efficiency was highly dependent on how to separate and purify gardenia yellow as a photosensitizer. Copyright © 2014 Elsevier B.V. All rights reserved.

Aerosol particle shrinkage event phenomenology in a South European suburban area during 2009-2015

NASA Astrophysics Data System (ADS)

Alonso-Blanco, E.; Gómez-Moreno, F. J.; Núñez, L.; Pujadas, M.; Cusack, M.; Artíñano, B.

2017-07-01

A high number of aerosol particle shrinkage cases (70) have been identified and analyzed from an extensive and representative database of aerosol size distributions obtained between 2009 and 2015 at an urban background site in Madrid (Spain). A descriptive classification based on the process from which the shrinkage began is proposed according which shrinkage events were divided into three groups: (1) NPF + shrinkage (NPF + S) events, (2) aerosol particle growth process + shrinkage (G + S) events, and (3) pure shrinkage (S) events. The largest number of shrinkages corresponded to the S-type followed by NPF + S, while the G + S events were the least frequent group recorded. Duration of shrinkages varied widely from 0.75 to 8.5 h and SR from -1.0 to -11.1 nm h-1. These processes typically occurred in the afternoon, around 18:00 UTC, caused by two situations: i) a wind speed increase usually associated with a change in the wind direction (over 60% of the observations) and ii) the reduction of photochemical activity at the end of the day. All shrinkages were detected during the warm period, mainly between May and August, when local meteorological conditions (high solar irradiance and temperature and low relative humidity), atmospheric processes (high photochemical activity) and availability of aerosol-forming precursors were favorable for their development. As a consequence of these processes, the particles concentration corresponding to the Aitken mode decreased into the nucleation mode. The accumulation mode did not undergo significant changes during these processes. In some cases, a dilution of the particulate content in the ambient air was observed. This work, goes further than others works dealing with aerosol particles shrinkages, as it incorporates as a main novelty a classification methodology for studying these processes. Moreover, compared to other studies, it is supported by a high and representative number of observations. Thus, this study contributes to get a better understanding of this type of atmospheric aerosol transformations and its features.

ROMP-based thermosetting polymers from modified castor oil with various cross-linking agents

NASA Astrophysics Data System (ADS)

Ding, Rui

Polymers derived from bio-renewable resources are finding an increase in global demand. In addition, polymers with distinctive functionalities are required in certain advanced fields, such as aerospace and civil engineering. In an attempt to meet both these needs, the goal of this work aims to develop a range of bio-based thermosetting matrix polymers for potential applications in multifunctional composites. Ring-opening metathesis polymerization (ROMP), which recently has been explored as a powerful method in polymer chemistry, was employed as a unique pathway to polymerize agricultural oil-based reactants. Specifically, a novel norbornyl-functionalized castor oil alcohol (NCA) was investigated to polymerize different cross-linking agents using ROMP. The effects of incorporating dicyclopentadiene (DCPD) and a norbornene-based crosslinker (CL) were systematically evaluated with respect to curing behavior and thermal mechanical properties of the polymers. Isothermal differential scanning calorimetry (DSC) was used to investigate the conversion during cure. Dynamic DSC scans at multiple heating rates revealed conversion-dependent activation energy by Ozawa-Flynn-Wall analysis. The glass transition temperature, storage modulus, and loss modulus for NCA/DCPD and NCA/CL copolymers with different cross-linking agent loading were compared using dynamic mechanical analysis. Cross-link density was examined to explain the very different dynamic mechanical behavior. Mechanical stress-strain curves were developed through tensile test, and thermal stability of the cross-linked polymers was evaluated by thermogravimetric analysis to further investigate the structure-property relationships in these systems.

Induction Curing of Thiol-acrylate and Thiolene Composite Systems

PubMed Central

Ye, Sheng; Cramer, Neil B.; Stevens, Blake E.; Sani, Robert L.; Bowman, Christopher N.

2011-01-01

Induction curing is demonstrated as a novel type of in situ radiation curing that maintains most of the advantages of photocuring while eliminating the restriction of light accessibility. Induction curing is utilized to polymerize opaque composites comprised of thiol-acrylate and thiol-ene resins, nanoscale magnetic particles, and carbon nanotubes. Nanoscale magnetic particles are dispersed in the resin and upon exposure to the magnetic field, these particles lead to induction heating that rapidly initiates the polymerization. Heat transfer profiles and reaction kinetics of the samples are modeled during the reactions with varying induction heater power, species concentration, species type and sample thickness, and the model is compared with the experimental results. Thiol-ene polymerizations achieved full conversion between 1.5 minutes and 1 hour, depending on the field intensity and the composition, with the maximum reaction temperature decreasing from 146 – 87 °C when the induction heater power was decreased from 8 – 3 kW. The polymerization reactions of the thiol-acrylate system were demonstrated to achieve full conversion between 0.6 and 30 minutes with maximum temperatures from 139 to 86 °C. The experimental behavior was characterized and the temperature profile modeled for the thiol-acrylate composite comprised of sub100nm nickel particles and induction heater power in the range of 32 to 20 kW. A 9°C average deviation was observed between the modeling and experimental results for the maximum temperature rise. The model also was utilized to predict reaction temperatures and kinetics for systems with varying thermal initiator concentration, initiator half-life, monomer molecular weight and temperature gradients in samples with varying thickness, thereby demonstrating that induction curing represents a designable and tunable polymerization method. Finally, induction curing was utilized to cure thiol-acrylate systems containing carbon nanotubes where 1 wt% carbon nanotubes resulted in systems where the storage modulus increased from 17.6 ± 0.2 to 21.6 ± 0.1 MPa and an electrical conductivity that increased from <10−7 to 0.33 ± 0.5 S/m. PMID:21765552

Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization

PubMed Central

2016-01-01

The need for polymers for high-end applications, coupled with the desire to mimic nature’s macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design. PMID:26795940

Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization.

PubMed

Olsén, Peter; Odelius, Karin; Albertsson, Ann-Christine

2016-03-14

The need for polymers for high-end applications, coupled with the desire to mimic nature's macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design.

Thermoelectrically controlled device for studies of temperature-induced corneal shrinkage

NASA Astrophysics Data System (ADS)

Borja, David; Manns, Fabrice; Fernandez, Viviana; Lamar, Peggy; Soederberg, Per G.; Parel, Jean-Marie A.

2002-06-01

The purpose of this study was to design and calibrate a device to measure the dynamics of thermal shrinkage in corneal and scleral strips. The apparatus consists of a thermoelectric cell controlled by a temperature controller designed to generate temperatures up to 90 degree(s)C in rectangular corneal strips; a copper cuvette filled with Dextran solution that holds the corneal strip and a displacement sensor that measures the change in length of the tissue during heat-induced shrinkage. The device was tested on corneal tissue from Florida Eye-Bank eyes that were cut into 2x4mm rectangular strips. Preliminary results indicate that our system can reproducibly create and accurately measure thermally induced corneal shrinkage. Shrinkage experiments will be used to optimize laser parameters for corneal shrinkage during laser thermokeratoplasty and laser scleral buckling.

Effects of molecular structure of the resins on the volumetric shrinkage and the mechanical strength of dental restorative composites.

PubMed

Kim, L U; Kim, J W; Kim, C K

2006-09-01

To prepare a dental composite that has a low amount of curing shrinkage and excellent mechanical strength, various 2,2-bis[4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane (Bis-GMA) derivatives were synthesized via molecular structure design, and afterward, properties of their mixtures were explored. Bis-GMA derivatives, which were obtained by substituting methyl groups for hydrogen on the phenyl ring in the Bis-GMA, exhibited lower curing shrinkage than Bis-GMA, whereas their viscosities were higher than that of Bis-GMA. Other Bis-GMA derivatives, which contained a glycidyl methacrylate as a molecular end group exhibited reduced curing shrinkage and viscosity. Methoxy substitution for hydroxyl groups on the Bis-GMA derivatives was performed for the further reduction of the viscosity and curing shrinkage. Various resin mixtures, which had the same viscosity as the commercial one, were prepared, and their curing shrinkage was examined. A resin mixture containing 2,2-bis[3,5-dimethyl, 4-(2-methoxy-3-methacryloyloxy propoxy) phenyl] propane] (TMBis-M-GMA) as a base resin and 4-tert-butylphenoxy-2-methyoxypropyl methacrylate (t-BP-M-GMA) as a diluent exhibited the lowest curing shrinkage among them. The composite prepared from this resin mixture also exhibited the lowest curing shrinkage along with enhanced mechanical properties.

Feasibility of the Simultaneous Determination of Monomer Concentrations and Particle Size in Emulsion Polymerization Using in Situ Raman Spectroscopy

PubMed Central

2015-01-01

An immersion Raman probe was used in emulsion copolymerization reactions to measure monomer concentrations and particle sizes. Quantitative determination of monomer concentrations is feasible in two-monomer copolymerizations, but only the overall conversion could be measured by Raman spectroscopy in a four-monomer copolymerization. The feasibility of measuring monomer conversion and particle size was established using partial least-squares (PLS) calibration models. A simplified theoretical framework for the measurement of particle sizes based on photon scattering is presented, based on the elastic-sphere-vibration and surface-tension models. PMID:26900256

Direct conversion of bio-ethanol to isobutene on nanosized Zn(x)Zr(y)O(z) mixed oxides with balanced acid-base sites.

PubMed

Sun, Junming; Zhu, Kake; Gao, Feng; Wang, Chongmin; Liu, Jun; Peden, Charles H F; Wang, Yong

2011-07-27

We report the design and synthesis of nanosized Zn(x)Zr(y)O(z) mixed oxides for direct and high-yield conversion of bio-ethanol to isobutene (~83%). ZnO is addded to ZrO(2) to selectively passivate zirconia's strong Lewis acidic sites and weaken Brönsted acidic sites, while simultaneously introducing basicity. As a result, the undesired reactions of bio-ethanol dehydration and acetone polymerization/coking are suppressed. Instead, a surface basic site-catalyzed ethanol dehydrogenation to acetaldehyde, acetaldehyde to acetone conversion via a complex pathway including aldol-condensation/dehydrogenation, and a Brönsted acidic site-catalyzed acetone-to-isobutene reaction pathway dominates on the nanosized Zn(x)Zr(y)O(z) mixed oxide catalyst, leading to a highly selective process for direct conversion of bio-ethanol to isobutene.

Comparison of Different Encapsulating Adhesives to Enhance the Efficiencies and Lifetimes of Polymeric Solar Cells

NASA Astrophysics Data System (ADS)

Chung, Ming-Hua; Chen, Chen-Ming; Hsieh, Tsung-Eong; Tang, Rong-Ming; Tsai, Yu Sheng; Chu, Wei-Ping; Liu, Mark O.; Juang, Fuh-Shyang

2009-04-01

Polymeric solar cells (PSCs) with a derivative of C60 [[6,6]-phenyl C61-butyric acid methyl ester (PCBM)], and 3-hexylthiophene (P3HT) as active layers have been fabricated. The PSC devices were also packaged with glass and novel UV glues to improve their lifetimes and power conversion efficiencies (PCEs). After encapsulation with UV glue I, II, and III, the PCEs of PSCs reached 4, 4.82, and 6%, respectively, and their half-lifetimes increased to 16-18, 26-28, and 90 h, respectively, while the PCEs and half-lifetimes of PSCs without encapsulation were 3.76% and 2.5 h, respectively.

Comparative Study of Shrinkage and Non-Shrinkage Model of Food Drying

NASA Astrophysics Data System (ADS)

Shahari, N.; Jamil, N.; Rasmani, KA.

2016-08-01

A single phase heat and mass model has always been used to represent the moisture and temperature distribution during the drying of food. Several effects of the drying process, such as physical and structural changes, have been considered in order to increase understanding of the movement of water and temperature. However, the comparison between the heat and mass equation with and without structural change (in terms of shrinkage), which can affect the accuracy of the prediction model, has been little investigated. In this paper, two mathematical models to describe the heat and mass transfer in food, with and without the assumption of structural change, were analysed. The equations were solved using the finite difference method. The converted coordinate system was introduced within the numerical computations for the shrinkage model. The result shows that the temperature with shrinkage predicts a higher temperature at a specific time compared to that of the non-shrinkage model. Furthermore, the predicted moisture content decreased faster at a specific time when the shrinkage effect was included in the model.

Shrinkage stress in concrete under dry-wet cycles: an example with concrete column

NASA Astrophysics Data System (ADS)

Gao, Yuan; Zhang, Jun; Luosun, Yiming

2014-02-01

This paper focuses on the simulation of shrinkage stress in concrete structures under dry-wet environments. In the modeling, an integrative model for autogenous and drying shrinkage predictions of concrete under dry-wet cycles is introduced first. Second, a model taking both cement hydration and moisture diffusion into account synchronously is used to calculate the distribution of interior humidity in concrete. Using the above two models, the distributions of shrinkage strain and stress in concrete columns made by normal and high strength concrete respectively under dry-wet cycles are calculated. The model results show that shrinkage gradient along the radial direction of the column from the center to outer surface increases with age as the outer circumference suffers to dry. The maximum and minimum shrinkage occur at the outer surface and the center of the column, respectively, under drying condition. As wetting starts, the shrinkage strain decreases with increase of interior humidity. The closer to the wetting face, the higher the humidity and the lower the shrinkage strain, as well as the lower the shrinkage stress. As results of the dry-wet cycles acting on the outer circumference of the column, cyclic stress status is developed within the area close to the outer surface of the column. The depth of the influencing zone of dry-wet cyclic action is influenced by concrete strength and dry-wet regime. For low strength concrete, relatively deeper influencing zone is expected compared with that of high strength concrete. The models are verified by concrete-steel composite ring tests and a good agreement between model and test results is found.

Evaluation of mechanism of cold atmospheric pressure plasma assisted polymerization of acrylic acid on low density polyethylene (LDPE) film surfaces: Influence of various gaseous plasma pretreatment

NASA Astrophysics Data System (ADS)

Ramkumar, M. C.; Pandiyaraj, K. Navaneetha; Arun Kumar, A.; Padmanabhan, P. V. A.; Uday Kumar, S.; Gopinath, P.; Bendavid, A.; Cools, P.; De Geyter, N.; Morent, R.; Deshmukh, R. R.

2018-05-01

Owing to its exceptional physiochemical properties, low density poly ethylene (LDPE) has wide range of tissue engineering applications. Conversely, its inadequate surface properties make LDPE an ineffectual candidate for cell compatible applications. Consequently, plasma-assisted polymerization with a selected precursor is a good choice for enhancing its biocompatibility. The present investigation studies the efficiency of plasma polymerization of acrylic acid (AAC) on various gaseous plasma pretreated LDPE films by cold atmospheric pressure plasma, to enhance its cytocompatibility. The change in chemical composition and surface topography of various gaseous plasma pretreated and acrylic deposited LDPE films has been assessed by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The changes in hydrophilic nature of surface modified LDPE films were studied by contact angle (CA) analysis. Cytocompatibility of the AAC/LDPE films was also studied in vitro, using RIN-5F cells. The results acquired by the XPS and AFM analysis clearly proved that cold atmospheric pressure (CAP) plasma assisted polymerization of AAC enhances various surface properties including carboxylic acid functional group density and increased surface roughness on various gaseous plasma treated AAC/LDPE film surfaces. Moreover, contact angle analysis clearly showed that the plasma polymerized samples were hydrophilic in nature. In vitro cytocompatibility analysis undoubtedly validates that the AAC polymerized various plasma pretreated LDPE films surfaces stimulate cell distribution and proliferation compared to pristine LDPE films. Similarly, cytotoxicity analysis indicates that the AAC deposited various gaseous plasma pretreated LDPE film can be considered as non-toxic as well as stimulating cell viability significantly. The cytocompatible properties of AAC polymerized Ar + O2 plasma pretreated LDPE films were found to be more pronounced compared to the other plasma pretreated AAC/LDPE films.

Drying shrinkage problems in high PI subgrade soils.

DOT National Transportation Integrated Search

2014-01-01

The main objective of this study was to investigate the longitudinal cracking in pavements due to drying : shrinkage of high PI subgrade soils. The study involved laboartory soil testing and modeling. The : shrinkage cracks usually occur within the v...

The double nucleation model for sickle cell haemoglobin polymerization: full integration and comparison with experimental data.

PubMed

Medkour, Terkia; Ferrone, Frank; Galactéros, Frédéric; Hannaert, Patrick

2008-06-01

Sickle cell haemoglobin (HbS) polymerization reduces erythrocyte deformability, causing deleterous vaso-occlusions. The double-nucleation model states that polymers grow from HbS aggregates, the nuclei, (i) in solution (homogeneous nucleation), (ii) onto existing polymers (heterogeneous nucleation). When linearized at initial HbS concentration, this model predicts early polymerization and its characteristic delay-time (Ferrone et al. J Mol Biol 183(4):591-610, 611-631, 1985). Addressing its relevance for describing complete polymerization, we constructed the full, non-linearized model (Simulink), The MathWorks). Here, we compare the simulated outputs to experimental progress curves (n = 6-8 different [HbS], 3-6 mM range, from Ferrone's group). Within 10% from start, average root mean square (rms) deviation between simulated and experimental curves is 0.04 +/- 0.01 (25 degrees C, n = 8; mean +/- standard error). Conversely, for complete progress curves, averaged rms is 0.48 +/- 0.04. This figure is improved to 0.13 +/- 0.01 by adjusting heterogeneous pathway parameters (p < 0.01): the nucleus stability (sigma(2) micro( cc ): + 40%), and the fraction of polymer surface available for nucleation (phi), from 5e(-7), (3 mM) to 13 (6 mM). Similar results are obtained at 37 degrees C. We conclude that the physico-chemical description of heterogeneous nucleation warrants refinements in order to capture the whole HbS polymerization process.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Mi; Pu, Yunqiao; Yoo, Chang Geun

The native recalcitrance of plants hinders the biomass conversion process using current biorefinery techniques. Down-regulation of the caffeic acid O-methyltransferase (COMT) gene in the lignin biosynthesis pathway of switchgrass reduced the thermochemical and biochemical conversion recalcitrance of biomass. Due to potential environmental influences on lignin biosynthesis and deposition, studying the consequences of physicochemical changes in field-grown plants without pretreatment is essential to evaluate the performance of lignin-altered plants. In this study, we determined the chemical composition, cellulose crystallinity and the degree of its polymerization, molecular weight of hemicellulose, and cellulose accessibility of cell walls in order to better understand themore » fundamental features of why biomass is recalcitrant to conversion without pretreatment. The most important is to investigate whether traits and features are stable in the dynamics of field environmental effects over multiple years.« less

Conversion of polymers of methyl- and vinylsilane to Si-C ceramics

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.; Kacik, Terrance A.; Bu, Xin-Ya; Masnovi, John; Heimann, Paula J.; Beyene, Kassahun

1994-01-01

Poly(methylsilane) and poly(vinylsilane) were synthesized using a titanocene catalyst, and their pyrolytic conversion to ceramics was followed using a combination of thermal analysis and infrared spectroscopy. The two polymers have distinctly different backbone structures, as determined by Si NMR; methylsilane polymerizes to a polysilane, while vinylsilane polymers have predominately polycarbosilane backbone, with some polysilane structure as well. The pyrolysis path and char yield were dependent primarily on backbone structure, with little influence of polymer molecular weight. The majority of the weight loss on conversion occurs below 650 degrees C, although bond rearrangement continues to 1400 degrees C. Poly(vinylsilane) produced a C-rich Si-C ceramic in which the carbon was dispersed on a sufficiently fine level to show resistance to oxidation on heating in air to 1400 degrees C.

Use of hydrophobically modified inulin for the preparation of polymethyl methacrylate/polybutyl acrylate latex particles using a semicontinuous reactor.

PubMed

Obiols-Rabasa, M; Ramos, J; Forcada, J; Esquena, J; Solans, C; Levecke, B; Booten, K; Tadros, Tharwat F

2010-06-01

The seeded semicontinuous emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BuA) stabilized with a graft polymeric surfactant based on inulin, INUTEC SP1, as well as its mixture with sodium lauryl sulfate (SLS) is described. The mixture of SLS and Brij58 (alcohol ethoxylated) and the mixture of SLS and Pluronic P85 (block copolymer PEO-PPO-PEO) are also used as surfactant systems. The addition of methacrylic acid (MAA) or acrylic acid (AA) as comonomers is also studied. Previous results proved this inulin-derivative surfactant, INUTEC SP1, to be very effective on synthesizing latexes using a very low surfactant concentration. The kinetic features of the emulsion polymerization (instantaneous conversion and total conversion) were gravimetrically determined along the reactions. Latex dispersions were characterized by photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM) to obtain the average particle size, the particle size distributions (PSDs) as well as the polydispersity index (PdI). The stability was determined by turbidimetry measurements and expressed in terms of critical coagulation concentration. The results showed that the use of the graft polymeric surfactant allowed obtaining highly stable nanoparticles, at low surfactant concentrations and high solid contents (up to 37 wt %). This is an improvement with respect to previous works, in which a mixture of the graft polymeric surfactant with another surfactant was required to obtain stable nanoparticles with low polydispersity, at high solid content. In the present work, low polydispersity was achieved using INUTEC as the only emulsifier, which was related to the absence of secondary nucleations. When a mixture of INUTEC SP1 and SLS is used, a wider PSD is obtained due to secondary nucleations. Replacing INUTEC SP1 by other nonionic surfactants such as Brij58 or Pluronic P85 leads to an increase of average particle size and wider PSD.

The role of living/controlled radical polymerization in the formation of improved imprinted polymers.

PubMed

Salian, Vishal D; Vaughan, Asa D; Byrne, Mark E

2012-06-01

In this work, living/controlled radical polymerization (LRP) is compared with conventional free radical polymerization in the creation of highly and weakly cross-linked imprinted poly(methacrylic acid-co-ethylene glycol dimethacrylate) networks. It elucidates, for the first time, the effect of LRP on the chain level and begins to explain why the efficiency of the imprinting process is improved using LRP. Imprinted polymers produced via LRP exhibited significantly higher template affinity and capacity compared with polymers prepared using conventional methods. The use of LRP in the creation of highly cross-linked imprinted polymers resulted in a fourfold increase in binding capacity without a decrease in affinity; whereas weakly cross-linked gels demonstrated a nearly threefold increase in binding capacity at equivalent affinity when LRP was used. In addition, by adjusting the double bond conversion, we can choose to increase either the capacity or the affinity in highly cross-linked imprinted polymers, thus allowing the creation of imprinted polymers with tailorable binding parameters. Using free radical polymerization in the creation of polymer chains, as the template-monomer ratio increased, the average molecular weight of the polymer chains decreased despite a slight increase in the double bond conversion. Thus, the polymer chains formed were shorter but greater in number. Using LRP neutralized the effect of the template. The addition of chain transfer agent resulted in slow, uniform, simultaneous chain growth, resulting in the formation of longer more monodisperse chains. Reaction analysis revealed that propagation time was extended threefold in the formation of highly cross-linked polymers when LRP techniques were used. This delayed the transition to the diffusion-controlled stage of the reaction, which in turn led to the observed enhanced binding properties, decreased polydispersity in the chains, and a more homogeneous macromolecular architecture. Copyright © 2012 John Wiley & Sons, Ltd.

Acrylonitrile-Butadiene Rubber (NBR) Prepared via Living/Controlled Radical Polymerization (RAFT).

PubMed

Kaiser, Andreas; Brandau, Sven; Klimpel, Michael; Barner-Kowollik, Christopher

2010-09-15

In the current work we present results on the controlled/living radical copolymerization of acrylonitrile (AN) and 1,3-butadiene (BD) via reversible addition fragmentation chain transfer (RAFT) polymerization techniques. For the first time, a solution polymerization process for the synthesis of nitrile butadiene rubber (NBR) via the use of dithioacetate and trithiocarbonate RAFT agents is described. It is demonstrated that the number average molar mass, $\\overline M _{\\rm n} $, of the NBR can be varied between a few thousand and 60 000 g · mol(-1) with polydispersities between 1.2 and 2.0 (depending on the monomer to polymer conversion). Excellent agreement between the experimentally observed and the theoretically expected molar masses is found. Detailed information on the structure of the synthesized polymers is obtained by variable analytical techniques such as infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and electrospray ionization-mass spectrometry (ESI-MS). Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of imine bond containing insoluble polymeric ligand and its transition metal complexes, structural characterization and catalytic activity on esterification reaction

PubMed Central

Gönül, İlyas; Ay, Burak; Karaca, Serkan; Saribiyik, Oguz Yunus; Yildiz, Emel; Serin, Selahattin

2017-01-01

Abstract In this study, synthesis of insoluble polymeric ligand (L) and its transition metal complexes [Cu(L)Cl2]·2H2O (1), [Co(L)Cl2(H2O)2] (2) and [Ni(L)Cl2(H2O)2] (3), having the azomethine groups, were synthesized by the condensation reactions of the diamines and dialdehydes. The structural properties were characterized by the analytical and spectroscopic methods using by elemental analysis, Fourier Transform Infrared, Thermo Gravimetric Analysis, Powder X-ray Diffraction, magnetic susceptibility and Inductively Coupled Plasma. The solubilities of the synthesized polymeric materials were also investigated and found as insoluble some organic and inorganic solvents. Additionally, their catalytic performance was carried out for the esterification reaction of acetic acid and butyl acetate. The highest conversion rate is 75.75% by using catalyst 1. The esterification of butanol gave butyl acetate with 100% selectivity. PMID:29491815

Structure modification and extracellular polymeric substances conversion during sewage sludge biodrying process.

PubMed

Cai, Lu; Krafft, Thomas; Chen, Tong-Bin; Gao, Ding; Wang, Li

2016-09-01

Biodrying, an economical and energy-saving biomass waste treatment, removes water from waste using the biological heat generated by organic matter degradation. Technical limitations associated with dewatering complicate the biodrying of sewage sludge. This study investigated the sludge alteration associated with its water removal, focusing on sludge form, extracellular polymeric substances, and free water release. An auto-feedback control technology was used for the biodrying; a scanning electron microscope was used to record the morphological change; three-dimensional excitation-emission matrix fluorescence spectroscopy was used to analyze extracellular polymeric substances (EPS) variation, and time domain reflectometry was used to assess the free water release. Over the 20-day biodrying, there was a 62% water removal rate during the first thermophilic phase. Biodrying created a hollow and stratified sludge structure. Aromatic proteins and soluble microbial byproducts in the EPS were significantly degraded. The thermophilic phase was the phase resulting in the greatest free water release. Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of the volumes of bis-acryl and poly(methyl methacrylate) resins on their exothermic behavior during polymerization.

PubMed

Ha, Jung-Yun; Kim, Sung-Hun; Kim, Kyo-Han; Kwon, Tae-Yub

2011-01-01

This study aimed to evaluate the influence of the volumes of a bis-acryl resin (Luxatemp) and a poly(methyl methacrylate) resin (Jet) on their exothermic behaviors during polymerization based on vinyl group conversion. The number of vinyl groups reacted and exotherm were determined based on weight percent of methacrylate groups using FTIR spectroscopy. Temperature changes during polymerization at 23°C were recorded for 20 minutes using a multiple cavity mold overlying a thermocouple. The number of vinyl groups reacted and exotherm of Luxatemp were consistently lower than those of Jet at each resin volume. Mean peak temperature rises of Luxatemp and Jet were in the range of 2.0-6.6°C and 4.2-11.6°C respectively, with Luxatemp and Jet taking 2 and 10 minutes respectively to reach their peak temperatures. As their resin volumes increased, their peak temperatures and total peak areas were also observed to increase significantly (p<0.01).

Pausing kinetics dominates strand-displacement polymerization by reverse transcriptase

PubMed Central

Malik, Omri; Khamis, Hadeel; Rudnizky, Sergei; Marx, Ailie

2017-01-01

Abstract Reverse transcriptase (RT) catalyzes the conversion of the viral RNA into an integration-competent double-stranded DNA, with a variety of enzymatic activities that include the ability to displace a non-template strand concomitantly with polymerization. Here, using high-resolution optical tweezers to follow the activity of the murine leukemia Virus RT, we show that strand-displacement polymerization is frequently interrupted. Abundant pauses are modulated by the strength of the DNA duplex ∼8 bp ahead, indicating the existence of uncharacterized RT/DNA interactions, and correspond to backtracking of the enzyme, whose recovery is also modulated by the duplex strength. Dissociation and reinitiation events, which induce long periods of inactivity and are likely the rate-limiting step in the synthesis of the genome in vivo, are modulated by the template structure and the viral nucleocapsid protein. Our results emphasize the potential regulatory role of conserved structural motifs, and may provide useful information for the development of potent and specific inhibitors. PMID:28973474

A Study on the compensation margin on butt welding joint of Large Steel plates during Shipbuilding construction.

NASA Astrophysics Data System (ADS)

Kim, J.; Jeong, H.; Ji, M.; Jeong, K.; Yun, C.; Lee, J.; Chung, H.

2015-09-01

This paper examines the characteristics of butt welding joint shrinkage for shipbuilding and marine structures main plate. The shrinkage strain of butt welding joint which is caused by the process of heat input and cooling, results in the difference between dimensions of the actual parent metal and the dimensions of design. This, in turn, leads to poor quality in the production of ship blocks and reworking through period of correction brings about impediment on improvement of productivity. Through experiments on butt welding joint's shrinkage strain on large structures main plate, the deformation of welding residual stress in the form of I, Y, V was obtained. In addition, the results of experiments indicate that there is limited range of shrinkage in the range of 1 ∼ 2 mm in 11t ∼ 21.5t thickness and the effect of heat transfer of weld appears to be limited within 1000 mm based on one side of seam line so there was limited impact of weight of parent metal on the shrinkage. Finally, it has been learned that Shrinkage margin needs to be applied differently based on groove phenomenon in the design phase in order to minimize shrinkage.

Review and specification for shrinkage cracks of bridge decks : final report.

DOT National Transportation Integrated Search

2016-12-01

An existing standard method ASTM C157 is used to determine the length change or free shrinkage of an unrestrained concrete specimen. However, in bridge decks, the concrete is actually under restrained conditions, and thus free shrinkage test methods ...

The two sides of the C-factor.

PubMed

Fok, Alex S L; Aregawi, Wondwosen A

2018-04-01

The aim of this paper is to investigate the effects on shrinkage strain/stress development of the lateral constraints at the bonded surfaces of resin composite specimens used in laboratory measurement. Using three-dimensional (3D) Hooke's law, a recently developed shrinkage stress theory is extended to 3D to include the additional out-of-plane strain/stress induced by the lateral constraints at the bonded surfaces through the Poisson's ratio effect. The model contains a parameter that defines the relative thickness of the boundary layers, adjacent to the bonded surfaces, that are under such multiaxial stresses. The resulting differential equation is solved for the shrinkage stress under different boundary conditions. The accuracy of the model is assessed by comparing the numerical solutions with a wide range of experimental data, which include those from both shrinkage strain and shrinkage stress measurements. There is good agreement between theory and experiments. The model correctly predicts the different instrument-dependent effects that a specimen's configuration factor (C-factor) has on shrinkage stress. That is, for noncompliant stress-measuring instruments, shrinkage stress increases with the C-factor of the cylindrical specimen; while the opposite is true for compliant instruments. The model also provides a correction factor, which is a function of the C-factor, Poisson's ratio and boundary layer thickness of the specimen, for shrinkage strain measured using the bonded-disc method. For the resin composite examined, the boundary layers have a combined thickness that is ∼11.5% of the specimen's diameter. The theory provides a physical and mechanical basis for the C-factor using principles of engineering mechanics. The correction factor it provides allows the linear shrinkage strain of a resin composite to be obtained more accurately from the bonded-disc method. Published by Elsevier Ltd.

Strain and temperature measurement in pultrusion processes by fiber Bragg grating sensors

NASA Astrophysics Data System (ADS)

Tucci, Fausto; Rubino, Felice; Carlone, Pierpaolo

2018-05-01

Injection Pultrusion (IP) is one of the most effective processes, in terms of productivity and costs, to manufacture fiber reinforced polymers. In IP roving of fiber are driven through an injection chamber in which they are impregnated by the resin and then formed in a shaped die. The die is heated in order to cure the resin. Pultruded products are in most cases characterized by constant cross-section profile, whereas unidirectional long fibers are mainly used as reinforcing material. Two relevant phenomena occur within the injection chamber and the heated die, namely the impregnation of the fibers and the polymerization of the resin. Furthermore, thermal expansion, resin chemical shrinkage and the interaction between the die and the impregnated fibers strongly influence the process [1]. Clearly, thermal and mechanical fields significantly impact on these strictly chained behaviours. The use of thermocouples to evaluate temperature within pultrusion die is already widespread, but they are not capable to acquire any information concerning stress-strain levels. In the present work Fibers Bragg Gratings (FBG) sensors were used to measure thermal and strain profiles in selected material location within the injection chamber and the curing die. Being the differences among the spectres transmitted and received are related to the variations in both temperature and strain, commercial FBG sensors were opportunely modified and calibrated. The optical fibers were hooked to the fibers entering into the injection pultrusion die. Taking the pulling speed into account, each waveform acquired was correlated to a position within the die. Obtained data highlight the effect of the heat generation due to resin reaction as well as longitudinal strains related to the pulling force, the thermal expansion and the chemical shrinkage of the resin system.

Tris(trimethylsilyl)silane as a co-initiator for dental adhesive: Photo-polymerization kinetics and dynamic mechanical property

PubMed Central

Song, Linyong; Ye, Qiang; Ge, Xueping; Misra, Anil; Spencer, Paulette

2017-01-01

Objectives The purpose of this study was to evaluate the polymerization behavior of a model dentin adhesive with tris(trimethylsilyl)silane (TTMSS) as a co-initiator, and to investigate the polymerization kinetics and mechanical properties of copolymers in dry and wet conditions. Methods A co-monomer mixture based on HEMA/BisGMA (45/55, w/w) was used as a model dentin adhesive. The photoinitiator system included camphorquinone (CQ) as the photosensitizer and the co-initiator was ethyl-4-(dimethylamino) benzoate (EDMAB) or TTMSS. Iodonium salt, diphenyliodonium hexafluorophosphate (DPIHP) serving as a catalyst, was selectively added into the adhesive formulations. The control and the experimental formulations were characterized with regard to the degree of conversion (DC) and dynamic mechanical properties under dry and wet conditions. Results In two-component photoinitiator system (CQ/TTMSS), with an increase of TTMSS concentration, the polymerization rate and DC of C═C double bond increased, and showed a dependence on the irradiation time and curing light intensity. The copolymers that contained the three-component photoinitiator system (CQ/TTMSS/DPIHP) showed similar dynamic mechanical properties, under both dry and wet conditions, to the EDMAB-containing system. Significance The DC of formulations using TTMSS as co-initiator showed a strong dependence on irradiation time. With the addition of TTMSS, the maximum polymerization rate can be adjusted and the network structure became more homogenous. The results indicated that the TTMSS could be used as a substitute for amine-type co-initiator in visible-light induced free radical polymerization of methacrylate-based dentin adhesives. PMID:26616688

Origin of the anomalous decrease in the apparent density of polymer gels observed by multi-echo reflection ultrasound spectroscopy.

PubMed

Takeda, Kohsuke; Norisuye, Tomohisa; Tran-Cong-Miyata, Qui

2013-07-01

Multi-echo reflection ultrasound spectroscopy (MERUS), which enables one to simultaneously evaluate the attenuation coefficient α, the sound velocity v and the density ρ, has been developed for measurements of elastic moduli. In the present study, the technique was further developed to analyze systems undergoing gelation where an unphysical decrease in the apparent density was previously observed after polymerization. The main reason for this problem was that the shrinkage accompanying the gelation led to a small gap between the cell wall and the sample, resulting in the superposition of the reflected signals which were not separable into individual components. By taking into account the multiply reflecting echoes at the interface of the gap, the corrected densities were systematically obtained and compared with the results for the floating test. The present technique opens a new route to simultaneously evaluate the three parameters α, v and ρ and also the sample thickness for solid thin films. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of Resin Composition on the Defect Formation in Alumina Manufactured by Stereolithography

PubMed Central

Johansson, Emil; Lidström, Oscar; Johansson, Jan; Lyckfeldt, Ola; Adolfsson, Erik

2017-01-01

Stereolithography (SL) is a technique allowing additive manufacturing of complex ceramic parts by selective photopolymerization of a photocurable suspension containing photocurable monomer, photoinitiator, and a ceramic powder. The manufactured three-dimensional object is cleaned and converted into a dense ceramic part by thermal debinding of the polymer network and subsequent sintering. The debinding is the most critical and time-consuming step, and often the source of cracks. In this study, photocurable alumina suspensions have been developed, and the influence of resin composition on defect formation has been investigated. The suspensions were characterized in terms of rheology and curing behaviour, and cross-sections of sintered specimens manufactured by SL were evaluated by SEM. It was found that the addition of a non-reactive component to the photocurable resin reduced polymerization shrinkage and altered the thermal decomposition of the polymer matrix, which led to a reduction in both delamination and intra-laminar cracks. Using a non-reactive component that decomposed rather than evaporated led to less residual porosity. PMID:28772496

Mesoporous and biocompatible surface active silica aerogel synthesis using choline formate ionic liquid.

PubMed

Meera, Kamal Mohamed Seeni; Sankar, Rajavelu Murali; Jaisankar, Sellamuthu N; Mandal, Asit Baran

2011-09-01

In this paper, we report the preparation and characterization of mesoporous and biocompatible transparent silica aerogel by the sol-gel polymerization of tetraethyl orthosilicate using ionic liquid. Choline cation based ionic liquid allows the silica framework to form in a non collapsing environment and controls the pore size of the gel. FT-IR spectra reveal the interaction of ionic liquid with surface -OH of the gel. DSC thermogram giving the evidence of confinement of ionic liquid within the silica matrix, which helps to avoid the shrinkage of the gel during the aging process. Nitrogen sorption measurements of gel prepared with ionic liquid exhibit a low surface area of 100.53 m2/g and high average pore size of 3.74 nm. MTT assay proves the biocompatibility and cell viability of the prepared gels. This new nanoporous silica material can be applied to immobilize biological molecules, which may retain their stability over a longer period. Copyright © 2011 Elsevier B.V. All rights reserved.

Comparison of shrinkage related properties of various patch repair materials

NASA Astrophysics Data System (ADS)

Kristiawan, S. A.; Fitrianto, R. S.

2017-02-01

A patch repair material has been developed in the form of unsaturated polyester resin (UPR)-mortar. The performance and durability of this material are governed by its compatibility with the concrete being repaired. One of the compatibility issue that should be tackled is the dimensional compatibility as a result of differential shrinkage between the repair material and the concrete substrate. This research aims to evaluate such shrinkage related properties of UPR-mortar and to compare with those of other patch repair materials. The investigation includes the following aspects: free shrinkage, resistance to delamination and cracking. The results indicate that UPR-mortar poses a lower free shrinkage, lower risk of both delamination and cracking tendency in comparison to other repair materials.

Reducing composite restoration polymerization shrinkage stress through resin modified glass-ionomer based adhesives.

PubMed

Naoum, S J; Mutzelburg, P R; Shumack, T G; Thode, Djg; Martin, F E; Ellakwa, A E

2015-12-01

The aim of this study was to determine whether employing resin modified glass-ionomer based adhesives can reduce polymerization contraction stress generated at the interface of restorative composite adhesive systems. Five resin based adhesives (G Bond, Optibond-All-in-One, Optibond-Solo, Optibond-XTR and Scotchbond-Universal) and two resin modified glass-ionomer based adhesives (Riva Bond-LC, Fuji Bond-LC) were analysed. Each adhesive was applied to bond restorative composite Filtek-Z250 to opposing acrylic rods secured within a universal testing machine. Stress developed at the interface of each adhesive-restorative composite system (n = 5) was calculated at 5-minute intervals over 6 hours. The resin based adhesive-restorative composite systems (RBA-RCS) demonstrated similar interface stress profiles over 6 hours; initial rapid contraction stress development (0-300 seconds) followed by continued contraction stress development ≤0.02MPa/s (300 seconds - 6 hours). The interface stress profile of the resin modified glass-ionomer based adhesive-restorative composite systems (RMGIBA-RCS) differed substantially to the RBA-RCS in several ways. Firstly, during 0-300 seconds the rate of contraction stress development at the interface of the RMGIBA-RCS was significantly (p < 0.05) lower than at the interface of the RBA-RCS. Secondly, at 300 seconds and 6 hours the interface contraction stress magnitude of the RMGIBA-RCS was significantly (p < 0.05) lower than the stress of all assessed RBA-RCS. Thirdly, from 300 seconds to 6 hours both the magnitude and rate of interface stress of the RMGIBA-RCS continued to decline over the 6 hours from the 300 seconds peak. The use of resin modified glass-ionomer based adhesives can significantly reduce the magnitude and rate of polymerization contraction stress developed at the interface of adhesive-restorative composite systems. © 2015 Australian Dental Association.

Evaluation of polymerization-dependent changes in color and translucency of resin composites using two formulae.

PubMed

Paravina, Rade D; Kimura, Mikio; Powers, John M

2005-09-01

The aim of this study was to evaluate polymerization-dependent changes in the color and translucency parameter (TP) of resin composites and to compare results obtained using two color-difference metric formulae, CIELAB and CIEDE 2000. Twenty-eight shades of commercial resin composites were analyzed. Specimens (n = 5) were made as discs, 11 mm in diameter and 2-mm thick, using cylindrical molds. Data were collected before and after composite polymerization, using a spectrophotometer. In regard to in vitro color changes of composites (DeltaE*) a DeltaE76 of 3.7 or greater was considered to be an unacceptable color change. Data were analyzed by analysis of variance, and Fisher's protected least significant difference (PLSD) intervals for comparison of means were calculated at the 0.05 level of significance. Mean polymerization-dependent differences in color were DeltaE00 = 4.48 (2.11) and DeltaE76 = 5.51 (2.68). The DeltaTP00 range was 2.57, while the DeltaTP76 range was 2.89. Mean polymerization-dependent differences in translucency were DeltaTP00 = 0.84 (0.77) and DeltaTP76 = 0.87 (0.76). Analysis of variance showed significant differences among composites, shades, and their interactions (P < 0.0001; power = 1.0). Regression equations and r values for the two color-difference formulae and all evaluated TP values showed very strong correlation. In conclusion, within the limitations of this study, polymerization-dependent changes in color and translucency were highly varied. The majority of shades showed polymerization-dependent differences in color higher than the DeltaE76 = 3.7. The TP generally increased after light polymerization by light activation. The very strong correlation (r > 0.97) between the two color-difference formulae indicates that the limitations of the CIELAB system do not appear to be a problem when evaluating composites; however, recorded differences between DeltaE76 and DeltaE00 values stress the importance of data conversion.

Modified creep and shrinkage prediction model B3 for serviceability limit state analysis of composite slabs

NASA Astrophysics Data System (ADS)

Gholamhoseini, Alireza

2016-03-01

Relatively little research has been reported on the time-dependent in-service behavior of composite concrete slabs with profiled steel decking as permanent formwork and little guidance is available for calculating long-term deflections. The drying shrinkage profile through the thickness of a composite slab is greatly affected by the impermeable steel deck at the slab soffit, and this has only recently been quantified. This paper presents the results of long-term laboratory tests on composite slabs subjected to both drying shrinkage and sustained loads. Based on laboratory measurements, a design model for the shrinkage strain profile through the thickness of a slab is proposed. The design model is based on some modifications to an existing creep and shrinkage prediction model B3. In addition, an analytical model is developed to calculate the time-dependent deflection of composite slabs taking into account the time-dependent effects of creep and shrinkage. The calculated deflections are shown to be in good agreement with the experimental measurements.

Silks produced by insect labial glands

PubMed Central

Sutherland, Tara

2008-01-01

Insect silks are secreted from diverse gland types; this chapter deals with the silks produced by labial glands of Holometabola (insects with pupa in their life cycle). Labial silk glands are composed of a few tens or hundreds of large polyploid cells that secrete polymerizing proteins which are stored in the gland lumen as a semi-liquid gel. Polymerization is based on weak molecular interactions between repetitive amino acid motifs present in one or more silk proteins; cross-linking by disulfide bonds may be important in the silks spun under water. The mechanism of long-term storage of the silk dope inside the glands and its conversion into the silk fiber during spinning is not fully understood. The conversion occurs within seconds at ambient temperature and pressure, under minimal drawing force and in some cases under water. The silk filament is largely built of proteins called fibroins and in Lepidoptera and Trichoptera coated by glue-type proteins known as sericins. Silks often contain small amounts of additional proteins of poorly known function. The silk components controlling dope storage and filament formation seem to be conserved at the level of orders, while the nature of polymerizing motifs in the fibroins, which determine the physical properties of silk, differ at the level of family and even genus. Most silks are based on fibroin β-sheets interrupted with other structures such as α-helices but the silk proteins of certain sawflies have predominantly a collagen-like or polyglycine II arrangement and the silks of social Hymenoptera are formed from proteins in a coiled coil arrangement. PMID:19221523

Thermocapillary migration of a drop: an exact solution with Newtonian interfacial rheology and stretching/shrinkage of interfacial area elements for small Marangoni numbers

NASA Technical Reports Server (NTRS)

Balasubramaniam, R.; Subramanian, R. Shankar

2004-01-01

In this paper we analyze the effects of the following phenomena associated with the thermocapillary migration of a drop. The first is the influence of Newtonian surface rheology of the interface and the second is that of the energy changes associated with stretching and shrinkage of the interfacial area elements, when the drop is in motion. The former occurs because of dissipative processes in the interfacial region, such as when surfactant molecules are adsorbed at the interface in sufficient concentration. The interface is typically modeled in this instance by ascribing to it a surface viscosity. This is a different effect from that of interfacial tension gradients arising from surfactant concentration gradients. The stretching and shrinkage of interfacial area elements leads to changes in the internal energy of these elements that affects the transport of energy in the fluids adjoining the interface. When an element on the interface is stretched, its internal energy increases because of the increase in its area. This energy is supplied by the neighboring fluids that are cooled as a consequence. Conversely, when an element on the interface shrinks, the adjoining fluids are warmed. In the case of a moving drop, elements of interfacial area are stretched in the forward half of the drop, and are shrunk in the rear half. Consequently, the temperature variation on the surface of the drop and its migration speed are modified. The analysis of the motion of a drop including these effects was first performed by LeVan in 1981, in the limit when convective transport of momentum and energy are negligible. We extend the analysis of LeVan to include the convective transport of momentum by demonstrating that an exact solution of the momentum equation is obtained for an arbitrary value of the Reynolds number. This solution is then used to calculate the slightly deformed shape of the drop from a sphere.

Polymer:fullerene solar cells: materials, processing issues, and cell layouts to reach power conversion efficiency over 10%, a review

NASA Astrophysics Data System (ADS)

Etxebarria, Ikerne; Ajuria, Jon; Pacios, Roberto

2015-01-01

In spite of the impressive development achieved by organic photovoltaics throughout the last decades, especially in terms of reported power conversion efficiencies, there are still important technological and fundamental obstacles to circumvent before they can be implemented into reliable and long-lasting applications. Regarding device processing, the synthesis of highly soluble polymeric semiconductors first, and then fullerene derivatives, was initially considered as an important breakthrough that would definitely change the fabrication of photovoltaics once and for all. The potential and the expectation raised by this technology is such that it is very difficult to keep track of the most significant progresses being now published in different and even monographic journals. In this paper, we review the development of polymeric solar cells from its origin to the most efficient devices published to date. We separate these achievements into three different categories traditionally followed by the scientific community to push devices over 10% power conversion efficiency: active materials, strategies-fabrication/processing procedures-that can mainly modify the active film morphology, and all the different cell layout/architectures that have been used in order to extract as high a photocurrent as possible from the Sun. The synthesis of new donors, the use of additives and postprocessing techniques, buffer interlayers, inverted and tandem designs are some of the most important aspects that are reviewed in detail in this paper. All have equally contributed to develop this technology and bring it at the doors of commercialization.

Photo-polymerization shrinkage-stress kinetics in resin-composites: methods development.

PubMed

Watts, D C; Marouf, A S; Al-Hindi, A M

2003-01-01

Studies of free shrinkage-strain kinetics on restoratives have begun to multiply. However, there have been fewer investigations of the more difficult problem of concurrent stress-kinetic measurements. The aim was to outline design parameters for a new methodology for this problem, amenable especially to light-cured materials, and to present illustrative results for a range of restorative composites. Absolute values of stress measurable for a given material and geometry are dependent upon the stiffness of the measurement system. In an infinitely stiff system, the measured stress would also tend towards infinity. Real teeth and their cavities are not infinitely stiff; they have elastic and visco-elastic compliance. Consequently, it is important that some minimal, but essentially constant compliance be allowed, whatever the final or time-dependent modulus of the material may be. This goal has been realised by measurement of the time-development, for a disk-geometry specimen (phi=10, h approximately 1.0 mm) of stress (S(r)), with a calibrated cantilever beam-geometry load cell. A novel specimen-holder design was used for this purpose, held in a rigid base assembly. Specimen thicknesses (or gap-widths) of 0.8 and 1.2 mm were specifically investigated on four representative resin-composites. Concurrent measurements were made of the end-displacement of the cantilever load cell, relative to a lower glass plate retaining the specimen. Load-calibration of the cantilever load cell gave an end-displacement per unit stress of circa 6 microm/MPa. This compares with literature values for cuspal compliance or displacement of circa 20 microm. Re-normalisation of the stress-data was implemented. This was accomplished assuming Hooke's law behavior at each instant and equivalent to a stiffer system, with a correction (multiplier) factor of 4 on the raw-stress values. For the materials examined, resultant maximum-stress levels determined were circa 5-8 MPa Stress-levels obtained at 1.2mm thickness were slightly higher (11-15%) than the level of stress obtained at 0.8 mm thickness. This is attributable to the greater mass of material undergoing shrinkage at 1.2 mm, offset slightly by the different C-factors. The new device is a practical and self-contained system for rapid and accurate measurement of stress-kinetics in photo-polymerising and also self-cure materials.

Fastest Formation Routes of Nanocarbons in Solution Plasma Processes.

PubMed

Morishita, Tetsunori; Ueno, Tomonaga; Panomsuwan, Gasidit; Hieda, Junko; Yoshida, Akihito; Bratescu, Maria Antoaneta; Saito, Nagahiro

2016-11-14

Although solution-plasma processing enables room-temperature synthesis of nanocarbons, the underlying mechanisms are not well understood. We investigated the routes of solution-plasma-induced nanocarbon formation from hexane, hexadecane, cyclohexane, and benzene. The synthesis rate from benzene was the highest. However, the nanocarbons from linear molecules were more crystalline than those from ring molecules. Linear molecules decomposed into shorter olefins, whereas ring molecules were reconstructed in the plasma. In the saturated ring molecules, C-H dissociation proceeded, followed by conversion into unsaturated ring molecules. However, unsaturated ring molecules were directly polymerized through cation radicals, such as benzene radical cation, and were converted into two- and three-ring molecules at the plasma-solution interface. The nanocarbons from linear molecules were synthesized in plasma from small molecules such as C 2 under heat; the obtained products were the same as those obtained via pyrolysis synthesis. Conversely, the nanocarbons obtained from ring molecules were directly synthesized through an intermediate, such as benzene radical cation, at the interface between plasma and solution, resulting in the same products as those obtained via polymerization. These two different reaction fields provide a reasonable explanation for the fastest synthesis rate observed in the case of benzene.

Fastest Formation Routes of Nanocarbons in Solution Plasma Processes

PubMed Central

Morishita, Tetsunori; Ueno, Tomonaga; Panomsuwan, Gasidit; Hieda, Junko; Yoshida, Akihito; Bratescu, Maria Antoaneta; Saito, Nagahiro

2016-01-01

Although solution-plasma processing enables room-temperature synthesis of nanocarbons, the underlying mechanisms are not well understood. We investigated the routes of solution-plasma-induced nanocarbon formation from hexane, hexadecane, cyclohexane, and benzene. The synthesis rate from benzene was the highest. However, the nanocarbons from linear molecules were more crystalline than those from ring molecules. Linear molecules decomposed into shorter olefins, whereas ring molecules were reconstructed in the plasma. In the saturated ring molecules, C–H dissociation proceeded, followed by conversion into unsaturated ring molecules. However, unsaturated ring molecules were directly polymerized through cation radicals, such as benzene radical cation, and were converted into two- and three-ring molecules at the plasma–solution interface. The nanocarbons from linear molecules were synthesized in plasma from small molecules such as C2 under heat; the obtained products were the same as those obtained via pyrolysis synthesis. Conversely, the nanocarbons obtained from ring molecules were directly synthesized through an intermediate, such as benzene radical cation, at the interface between plasma and solution, resulting in the same products as those obtained via polymerization. These two different reaction fields provide a reasonable explanation for the fastest synthesis rate observed in the case of benzene. PMID:27841288

Design and Application of Nanogel-Based Polymer Networks

NASA Astrophysics Data System (ADS)

Dailing, Eric Alan

Crosslinked polymer networks have wide application in biomaterials, from soft hydrogel scaffolds for cell culture and tissue engineering to glassy, high modulus dental restoratives. Composite materials formed with nanogels as a means for tuning network structure on the nanoscale have been reported, but no investigation into nanogels as the primary network component has been explored to this point. This thesis was dedicated to studying network formation from the direct polymerization of nanogels and investigating applications for these unique materials. Covalently crosslinked polymer networks were synthesized from polymerizable nanogels without the use of reactive small monomers or oligomers. Network properties were controlled by the chemical and physical properties of the nanogel, allowing for materials to be designed from nanostructured macromolecular precursors. Nanogels were synthesized from a thermally initiated solution free radical polymerization of a monomethacrylate, a dimethacrylate, and a thiol-based chain transfer agent. Monomers with a range of hydrophilic and hydrophobic character were copolymerized, and polymerizable groups were introduced through an alcohol-isocyanate click reaction. Nanogels were dispersible in water up to 75 wt%, including nanogels that contained a relatively high fraction of a conventionally water-insoluble component. Nanogels with molecular weights that ranged from 10's to 100's of kDa and hydrodynamic radii between 4 and 10 nm were obtained. Macroscopic crosslinked polymer networks were synthesized from the photopolymerization of methacrylate-functionalized nanogels in inert solvent, which was typically water. The nanogel composition and internal branching density affected both covalent and non-covalent interparticle interactions, which dictated the final mechanical properties of the networks. Nanogels with progressively disparate hydrophilic and hydrophobic character were synthesized to explore the potential for creating densely crosslinked, small monomer free dental materials. Nanogel-based networks showed no decrease in flexural modulus between the dry and water-equilibrated states in contrast to nanogel-monomer composites that exhibited a decrease in modulus upon water infiltration. The nanogel networks also exhibited higher conversion and lower volumetric shrinkage compared to the composite networks. Adhesive nanogels were designed with amphiphilic character and specific hydrogen-bonding groups. These nanogels gelled within 10 s of low intensity UV light exposure and demonstrated the ability to bond strongly to both hydrophilic and hydrophobic substrates that were dry or under water. Nanogel-based coatings were explored as a means to create multistructured, multifunctional polymer networks. Shape memory polymers were coated with nanogels through a dip-coating and subsequent photocrosslinking method. The presence of the coating did not affect the shape recovery of the polymer, and coatings formed with dexamethasone-loaded nanogels were demonstrated to release a physiologically relevant amount of the anti-inflammatory drug. These materials have potential application as minimally invasive implantable devices. Coatings were also formed from interfacial redox polymerizations. Nanogels with varying crosslinking density were coated onto dexamethasone-loaded networks, which had the effect of changing the diffusion coefficient of dexamethasone as it was released from the core network. A fluorescein-loaded nanogel was coated onto a rhodamine-loaded network, which provided multidrug release from both the coating and the core material through two distinct release profiles.

Design and evaluation of high-volume fly ash (HVFA) concrete mixes, report D : creep, shrinkage, and abrasion resistance of HVFA concrete.

DOT National Transportation Integrated Search

2012-10-01

The main objective of this study was to determine the effect on shrinkage, creep, : and abrasion resistance of high-volume fly ash (HVFA) concrete. The HVFA concrete : test program consisted of comparing the shrinkage, creep, and abrasion performance...

Temperature dependence of autogenous shrinkage of silica fume cement pastes with a very low water–binder ratio

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maruyama, I., E-mail: ippei@dali.nuac.nagoya-u.ac.jp; Teramoto, A.

Ultra-high-strength concrete with a large unit cement content undergoes considerable temperature increase inside members due to hydration heat, leading to a higher risk of internal cracking. Hence, the temperature dependence of autogenous shrinkage of cement pastes made with silica fume premixed cement with a water–binder ratio of 0.15 was studied extensively. Development of autogenous shrinkage showed different behaviors before and after the inflection point, and dependence on the temperature after mixing and subsequent temperature histories. The difference in autogenous shrinkage behavior poses problems for winter construction because autogenous shrinkage may increase with decrease in temperature after mixing before the inflectionmore » point and with increase in temperature inside concrete members with large cross sections.« less

Effects of long-term preservation on amphibian body conditions: implications for historical morphological research

PubMed Central

Shu, Guocheng; Gong, Yuzhou; Xie, Feng; Wu, Nicholas C.

2017-01-01

Measurements of historical specimens are widely applied in studies of taxonomy, systematics, and ecology, but biologists often assume that the effects of preservative chemicals on the morphology of amphibian specimens are minimal in their analyses. We compared the body length and body mass of 182 samples of 13 live and preserved (up to 10 years) anuran species and found that the body length and body mass of preserved specimens significantly decreased by 6.1% and 24.8%, respectively, compared to those measurements of their live counterparts. The changes in body length and mass also exhibited highly significant variations between species. Similarly, there were significant differences in shrinkage of body length and body mass between sexes, where males showed greater shrinkage in body length and body mass compared to females. Preservation distorted the magnitude of the interspecific differences in body length observed in the fresh specimens. Overall, the reduction in body length or mass was greater in longer or heavier individuals. Due to the effects of preservation on amphibian morphology, we propose two parsimonious conversion equations to back-calculate the original body length and body mass of studied anurans for researchers working with historical data, since morphological data from preserved specimens may lead to incorrect biological interpretations when comparing to fresh specimens. Therefore, researchers should correct for errors due to preservation effects that may lead to the misinterpretation of results. PMID:28929024

Leaf Shrinkage with Dehydration: Coordination with Hydraulic Vulnerability and Drought Tolerance1[C][W][OPEN

PubMed Central

Scoffoni, Christine; Vuong, Christine; Diep, Steven; Cochard, Hervé; Sack, Lawren

2014-01-01

Leaf shrinkage with dehydration has attracted attention for over 100 years, especially as it becomes visibly extreme during drought. However, little has been known of its correlation with physiology. Computer simulations of the leaf hydraulic system showed that a reduction of hydraulic conductance of the mesophyll pathways outside the xylem would cause a strong decline of leaf hydraulic conductance (Kleaf). For 14 diverse species, we tested the hypothesis that shrinkage during dehydration (i.e. in whole leaf, cell and airspace thickness, and leaf area) is associated with reduction in Kleaf at declining leaf water potential (Ψleaf). We tested hypotheses for the linkage of leaf shrinkage with structural and physiological water relations parameters, including modulus of elasticity, osmotic pressure at full turgor, turgor loss point (TLP), and cuticular conductance. Species originating from moist habitats showed substantial shrinkage during dehydration before reaching TLP, in contrast with species originating from dry habitats. Across species, the decline of Kleaf with mild dehydration (i.e. the initial slope of the Kleaf versus Ψleaf curve) correlated with the decline of leaf thickness (the slope of the leaf thickness versus Ψleaf curve), as expected based on predictions from computer simulations. Leaf thickness shrinkage before TLP correlated across species with lower modulus of elasticity and with less negative osmotic pressure at full turgor, as did leaf area shrinkage between full turgor and oven desiccation. These findings point to a role for leaf shrinkage in hydraulic decline during mild dehydration, with potential impacts on drought adaptation for cells and leaves, influencing plant ecological distributions. PMID:24306532

Mechanism of Macrosegregation Formation in Continuous Casting Slab: A Numerical Simulation Study

NASA Astrophysics Data System (ADS)

Jiang, Dongbin; Wang, Weiling; Luo, Sen; Ji, Cheng; Zhu, Miaoyong

2017-12-01

Solidified shell bulging is supposed to be the main reason for slab center segregation, while the influence of thermal shrinkage rarely has been considered. In this article, a thermal shrinkage model coupled with the multiphase solidification model is developed to investigate the effect of the thermal shrinkage, solidification shrinkage, grain sedimentation, and thermal flow on solute transport in the continuous casting slab. In this model, the initial equiaxed grains contract freely with the temperature decrease, while the coherent equiaxed grains and columnar phase move directionally toward the slab surface. The results demonstrate that the center positive segregation accompanied by negative segregation in the periphery zone is mainly caused by thermal shrinkage. During the solidification process, liquid phase first transports toward the slab surface to compensate for thermal shrinkage, which is similar to the case considering solidification shrinkage, and then it moves opposite to the slab center near the solidification end. It is attributed to the sharp decrease of center temperature and the intensive contract of solid phase, which cause the enriched liquid to be squeezed out. With the effect of grain sedimentation and thermal flow, the negative segregation at the external arc side (zone A1) and the positive segregation near the columnar-to-equiaxed transition at the inner arc side (position B1) come into being. Besides, it is found that the grain sedimentation and thermal flow only influence solute transport before equiaxed grains impinge with each other, while the solidification and thermal shrinkage still affect solute redistribution in the later stage.

Leaf shrinkage with dehydration: coordination with hydraulic vulnerability and drought tolerance.

PubMed

Scoffoni, Christine; Vuong, Christine; Diep, Steven; Cochard, Hervé; Sack, Lawren

2014-04-01

Leaf shrinkage with dehydration has attracted attention for over 100 years, especially as it becomes visibly extreme during drought. However, little has been known of its correlation with physiology. Computer simulations of the leaf hydraulic system showed that a reduction of hydraulic conductance of the mesophyll pathways outside the xylem would cause a strong decline of leaf hydraulic conductance (K(leaf)). For 14 diverse species, we tested the hypothesis that shrinkage during dehydration (i.e. in whole leaf, cell and airspace thickness, and leaf area) is associated with reduction in K(leaf) at declining leaf water potential (Ψ(leaf)). We tested hypotheses for the linkage of leaf shrinkage with structural and physiological water relations parameters, including modulus of elasticity, osmotic pressure at full turgor, turgor loss point (TLP), and cuticular conductance. Species originating from moist habitats showed substantial shrinkage during dehydration before reaching TLP, in contrast with species originating from dry habitats. Across species, the decline of K(leaf) with mild dehydration (i.e. the initial slope of the K(leaf) versus Ψ(leaf) curve) correlated with the decline of leaf thickness (the slope of the leaf thickness versus Ψ(leaf) curve), as expected based on predictions from computer simulations. Leaf thickness shrinkage before TLP correlated across species with lower modulus of elasticity and with less negative osmotic pressure at full turgor, as did leaf area shrinkage between full turgor and oven desiccation. These findings point to a role for leaf shrinkage in hydraulic decline during mild dehydration, with potential impacts on drought adaptation for cells and leaves, influencing plant ecological distributions.

Drying Shrinkage of Mortar Incorporating High Volume Oil Palm Biomass Waste

NASA Astrophysics Data System (ADS)

Shukor Lim, Nor Hasanah Abdul; Samadi, Mostafa; Rahman Mohd. Sam, Abdul; Khalid, Nur Hafizah Abd; Nabilah Sarbini, Noor; Farhayu Ariffin, Nur; Warid Hussin, Mohd; Ismail, Mohammed A.

2018-03-01

This paper studies the drying shrinkage of mortar incorporating oil palm biomass waste including Palm Oil Fuel Ash, Oil Palm Kernel Shell and Oil Palm Fibre. Nano size of palm oil fuel ash was used up to 80 % as cement replacement by weight. The ash has been treated to improve the physical and chemical properties of mortar. The mass ratio of sand to blended ashes was 3:1. The test was carried out using 25 × 25 × 160 mm prism for drying shrinkage tests and 70 × 70 ×70 mm for compressive strength test. The results show that the shrinkage value of biomass mortar is reduced by 31% compared with OPC mortar thus, showing better performance in restraining deformation of the mortar while the compressive strength increased by 24% compared with OPC mortar at later age. The study gives a better understanding of how the biomass waste affect on mortar compressive strength and drying shrinkage behaviour. Overall, the oil palm biomass waste can be used to produce a better performance mortar at later age in terms of compressive strength and drying shrinkage.

Switching from Controlled Ring-Opening Polymerization (cROP) to Controlled Ring-Closing Depolymerization (cRCDP) by Adjusting the Reaction Parameters That Determine the Ceiling Temperature

PubMed Central

2016-01-01

Full control over the ceiling temperature (Tc) enables a selective transition between the monomeric and polymeric state. This is exemplified by the conversion of the monomer 2-allyloxymethyl-2-ethyl-trimethylene carbonate (AOMEC) to poly(AOMEC) and back to AOMEC within 10 h by controlling the reaction from conditions that favor ring-opening polymerization (Tc > T0) (where T0 is the reaction temperature) to conditions that favor ring-closing depolymerization (Tc < T0). The ring-closing depolymerization (RCDP) mirrors the polymerization behavior with a clear relation between the monomer concentration and the molecular weight of the polymer, indicating that RCDP occurs at the chain end. The Tc of the polymerization system is highly dependent on the nature of the solvent, for example, in toluene, the Tc of AOMEC is 234 °C and in acetonitrile Tc = 142 °C at the same initial monomer concentration of 2 M. The control over the monomer to polymer equilibrium sets new standards for the selective degradation of polymers, the controlled release of active components, monomer synthesis and material recycling. In particular, the knowledge of the monomer to polymer equilibrium of polymers in solution under selected environmental conditions is of paramount importance for in vivo applications, where the polymer chain is subjected to both high dilution and a high polarity medium in the presence of catalysts, that is, very different conditions from which the polymer was formed. PMID:27783494

Synthesis of isotactic-heterotactic stereoblock (hard-soft) poly(lactide) with tacticity control through immortal coordination polymerization.

PubMed

Zhao, Wei; Wang, Yang; Liu, Xinli; Chen, Xuesi; Cui, Dongmei

2012-10-01

A one-pot method for the preparation of a new family of PLA materials is reported that combines heterotactic (soft) and isotactic stereoblocks (hard). The ring-opening polymerization of rac-lactide with a salan-rare-earth-metal-alkyl complex in the presence of excess triethanolamine was performed in an immortal mode to give three-armed heterotactic poly(lactide) (soft) with excellent end-hydroxy fidelity. The in situ addition of a salen-aluminum-alkyl precursor to the above polymerization system under any monomer-conversion conditions activated the "dormant" hydroxy-ended PLA chains to propagate through the incorporation of the remaining rac-lactide monomer, but with isospecific selectivity (hard). The resultant PLA had a three-armed architecture with controlled molecular weight and extremely narrow molecular-weight distribution (PDI<1.08). More strikingly, each side-arm simultaneously possessed highly heterotactic (soft) and highly isotactic (hard) segments and the ratio of these two stereoregular sequences could be swiftly adjusted by tuning the addition time of the salen-aluminum-alkyl precursor to the polymerization system. Therefore, star-shaped hard-soft stereoblock poly(lactide)s with various P(m) values and crystallinity were achieved in a single reactor for the first time. This strategy should be applicable to the synthesis of a series of new types of stereoblock polyesters by using an immortal-polymerization process and a proper choice of specific, selective metal-based catalysts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Disintegration of nano-embedded microparticles after deposition on mucus: A mechanistic study.

PubMed

Ruge, Christian A; Bohr, Adam; Beck-Broichsitter, Moritz; Nicolas, Valérie; Tsapis, Nicolas; Fattal, Elias

2016-03-01

The conversion of colloidal drug carriers/polymeric nanoparticles into dry microparticulate powders (e.g., by spray-drying) is a prominent approach to overcome the aerodynamic limitations of these formulations for delivery via inhalation. However, to what extent such nano-embedded microparticles disintegrate into individual/intact nanoparticles after contacting relevant physiological media has so far not been addressed. Polymeric nanoparticles were spray-dried into nano-embedded microparticles (NEMs) using different amounts of trehalose as embedding matrix excipient. Formulations were characterized and then evaluated for their disintegration behavior after aerosolization onto model mucus. Although a rapid and complete aqueous redispersion was observed for specific excipient/nanoparticle weight ratios (i.e., greater than 1/1), the same formulations revealed no disintegration after deposition onto a static mucus layer. Double-labeled NEMs powders (i.e., dual color staining of polymeric nanoparticles and trehalose) demonstrated rapid matrix dissolution, while the nanoparticle aggregates persisted. When deposited onto agitated mucus, however, sufficient disintegration of NEMs into individual polymeric nanoparticles was observed. These findings indicate that mechanical forces are necessary to overcome the attraction between individual nanoparticles found within the NEMs. Thus, it remains questionable whether the lung mechanics (e.g., breathing, mucociliary clearance) acting on these formulations will contribute to the overall disintegration process. Copyright © 2015 Elsevier B.V. All rights reserved.

Functionalized polycarbonate derived from tartaric acid: enzymatic ring-opening polymerization of a seven-membered cyclic carbonate.

PubMed

Wu, Ruizhi; Al-Azemi, Talal F; Bisht, Kirpal S

2008-10-01

Enantiomerically pure functional polycarbonate was synthesized from a novel seven-membered cyclic carbonate monomer derived from naturally occurring L-tartaric acid. The monomer was synthesized in three steps and screened for polymerization with four commercially available lipases from different sources at 80 degrees C, in bulk. The ring-opening polymerization (ROP) was affected by the source of the enzyme; the highest number-average molecular weight, M(n) = 15500 g/mol (PDI = 1.7; [alpha]D(20) = +77.8, T(m) = 58.8 degrees C) optically active polycarbonate was obtained with lipase Novozyme-435. The relationship between monomer conversion, reaction time, molecular weight, and molecular weight distribution were investigated for Novozyme-435 catalyzed ROP. Deprotection of the ketal groups was achieved with minimal polymer chain cleavage (M(n) = 10000 g/mol, PDI = 2.0) and resulted in optically pure polycarbonate ([alpha]D(20) = +56) bearing hydroxy functional groups. Deprotected poly(ITC) shows T(m) of 60.2 degrees C and DeltaH(f) = 69.56 J/g and similar to that of the poly(ITC), a glass transition temperature was not found. The availability of the pendant hydroxyl group is expected to enhance the biodegradability of the polymer and serves in a variety of potential biomedical applications such as polymeric drug delivery systems.

Efficiency of polymerization of bulk-fill composite resins: a systematic review.

PubMed

Reis, André Figueiredo; Vestphal, Mariana; Amaral, Roberto Cesar do; Rodrigues, José Augusto; Roulet, Jean-François; Roscoe, Marina Guimarães

2017-08-28

This systematic review assessed the literature to evaluate the efficiency of polymerization of bulk-fill composite resins at 4 mm restoration depth. PubMed, Cochrane, Scopus and Web of Science databases were searched with no restrictions on year, publication status, or article's language. Selection criteria included studies that evaluated bulk-fill composite resin when inserted in a minimum thickness of 4 mm, followed by curing according to the manufacturers' instructions; presented sound statistical data; and comparison with a control group and/or a reference measurement of quality of polymerization. The evidence level was evaluated by qualitative scoring system and classified as high-, moderate- and low- evidence level. A total of 534 articles were retrieved in the initial search. After the review process, only 10 full-text articles met the inclusion criteria. Most articles included (80%) were classified as high evidence level. Among several techniques, microhardness was the most frequently method performed by the studies included in this systematic review. Irrespective to the "in vitro" method performed, bulk fill RBCs were partially likely to fulfill the important requirement regarding properly curing in 4 mm of cavity depth measured by depth of cure and / or degree of conversion. In general, low viscosities BFCs performed better regarding polymerization efficiency compared to the high viscosities BFCs.

Biodegradable polymer adhesives, hybrids and nanomaterials

NASA Astrophysics Data System (ADS)

Mylonakis, Andreas

Biodegradable polymeric products and organic-inorganic hybrid materials for a diversity of applications are the two main fields on which this research has been focused. A novel biodegradable adhesive, which mimics marine adhesive proteins, has been synthesized by the covalent incorporation of 3,4-dihydroxybenzoic acid onto the chitosan backbone. The adhesive strength of these materials varies with the molecular weight of the polysaccharide, the amount of diphenolics present and the curing time. Infrared spectroscopy (IR), nuclear magnetic resonance spectroscopy (NMR) and ultraviolet-visible spectroscopy (UV) have been used to qualitatively and quantitatively establish the amount of the diphenolic moiety present on the backbone of the biodegradable polymers. The as synthesized polymers combine both the adhesive capability of the diphenolic function and the healing effect of chitosan. The biocompatibility and biodegradability of these modified chitosans offer the promise of utility of these novel materials in dental and medical applications. Organic-inorganic hybrid materials with low volume shrinkage and excellent mechanical properties were synthesized by the covalent incorporation of 2-hydroxyethyl methacrylate and glycidyl methacrylate on pre-hydrolyzed sol-gel silica. These hybrid materials exhibited low volume shrinkage during polymerization and were crack-free during storage for about twelve months. The mechanical properties of these materials are composition dependent. Incorporation of silica effectively increased the compressive yield stress and modulus of the obtained poly(HEMAGMA-silica) hybrid materials. A series of new electroactive hybrid materials have been synthesized by covalent incorporation of polyaniline into polyacrylate-silica hybrids. The formulation involves the radical co-polymerization of glycidyl methacrylate-polyaniline (GMA-PANi) and glycidyl methacrylate2-hydroxyethyl methacrylate-silica (GMA-HEMA-silica) to yield poly(HEMA-GMA-silica)-polyaniline (PHGS-PANi) hybrids. The chromoelectrochemical study suggests that these materials can have tunable colors upon change of potential and/or pH, and thus may find applications as chemical or biological sensors and electro-optical devices. Moreover, conductivity measurements and mechanical testing of these materials show that these materials can be prepared to have both a reasonably high conductivity and excellent mechanical properties. A novel technology for maintaining the enzymatic activity, during storage in harsh media, such as organic solvents and high pH aqueous solutions, has been explored. The non-surfactant templated sol-gel method has been utilized to incorporate horseradish peroxidase (HRP) enzyme into the pores of mesoporous organosilicas followed by the application of a second acrylic protective layer. Results indicate that such doubly encapsulated HRP showed many orders of magnitude higher residual activity after storage in harsh media, as compared to the native enzyme under the same conditions. This method is expected to be useful for stabilizing other enzymes as well, in hostile environments. The electrochemical study of a novel electroactive aniline trimer-silane compound and other well defined aniline oligomers with end group substitution has been investigated. Results demonstrate that substitution with electron-donating or electron-withdrawing groups has a profound effect on the electrochemistry of such compounds. Additionally, the formation of interesting oxygen adducts by both wet and dry prolonged oxygenation of iron phthalocyanines (alpha- and beta-form) has been achieved. Finally, the fabrication of a novel fluorescent nanoelectrode with applications in neuroscience has been explored.

Advanced shrink material for NTD process with lower Y/X shrinkage bias of elongated patterns

NASA Astrophysics Data System (ADS)

Miyamoto, Yoshihiro; Sekito, Takashi; Sagan, John; Horiba, Yuko; Kinuta, Takafumi; Nagahara, Tatsuro; Tarutani, Shinji

2015-03-01

Negative tone shrink materials (NSM) suitable for resolution enhancement of negative tone development (NTD) 193nm immersion resists have been developed. While this technology is being expanded to integrated circuits (IC) manufacturing, there still have two major problems to apply various processes. One of them is shrink ID bias which means shrink differences between isolated (I) and dense (D) CDs, and the other one is Y/X shrinkage bias which means shrinkage differences between major axis (Y) and minor axis (X) of the elongated or oval shape pattern. While we have presented the improvement of shrink ID bias at SPIE2014 [1], the reduction of Y/X shrinkage bias was the examination theme for quite some time. In this paper, we present Y/X shrinkage bias of current NTD shrink material, new concept material for Y/X bias reduction and the result of new shrink material. Current NTD shrink model has Y/X bias of 1.6 (Y shrink=16nm) at a mixing bake (MB) of 150°C on AZ AX2110P NTD elongated pattern of X=70nm and Y=210nm ADI. This means shrinkage of Y has larger shrinkage than X and that makes difficult to apply shrink material. We expected that the characteristic shape of elongated pattern was one of the root-cause for Y/X bias, and then simulated how to achieve equivalent shrinkage at Y and X. We concluded that available resist volume per each Y and X unit was not equivalent and need new shrink concept to solve Y/X bias. Based on our new concept, we prepared new shrink material which has lower Y/X bias and larger shrink amount compared with current NTD shrink material. Finally we have achieved lower Y/X bias from 1.6 to 1.1 at MB150°C and moreover got higher shrinkage than current NTD shrink material from 10.1nm to 16.7nm.

Mechanism for Angular Deformation of L-shaped Specimens —Influence of Filling Material and Shrinkage Factor—

NASA Astrophysics Data System (ADS)

Furuhashi, Hiroshi; Aoki, Takerou; Okabe, Sayaka; Arai, Tsuyoshi; Seto, Masahiro; Yamabe, Masashi

L-shape is the important and fundamental shape for injection molded parts. Therefore to reveal the corner angular deformation mechanism of this shape is also valuable for understanding the warpage mechanism of injection molded parts. In this study, we investigated the influence of the filling materials (fiber, talc and not filled) and two kinds of anisotropic shrinkage factors, solidification shrinkage and shrinkage caused by thermal expansion coefficient during cooling, to the angular deformation of L-shaped specimens and the following conclusions were obtained 1) The anisotropic solidification shrinkage of MD/TD and the anisotropic thermal expansion coefficient of MD/TD are considered to cause the angular deformation of L-shaped specimens. But the contribution ratios of these two anisotropies depend on the filling material for plastics. 2) The angular deformation of PP and PBT filled with glass fiber is mainly caused by the anisotropic thermal expansion coefficient and on the other hand, that of PP and PBT without filling material is caused by anisotropic solidification shrinkage. However both anisotropies cause the angular deformation of PP filled with talc. 3) The plate thickness dependence of the angular deformation of PP filled with talc is the singular peculiar phenomenon. The plate thickness dependence of anisotropic solidification shrinkage of this material (it is also singular) is considered to have an important influence on this phenomenon.

Novel Precursor Approached for CMC Derived by Polymer Pyrolysis

DTIC Science & Technology

1994-02-15

to remove signals from probe polymer materials. C. Pyrolysis Methods The conversion of polymeric PMVS to SiC -containing ceramic was studied by... Composite Fabrication Methods Ceramic matrix composites with different matrix compositions were fabricated using the Polymer Impregnation- Pyrolysis (PIP...Pyrolyzed composites were re- infiltrated with the appropriate polymer matrix source under vacuum, and cured in an autoclave under 100 psi overpressure of N2

Optimizing Glassy Polymer Network Morphology for Nano-particle Dispersion, Stabilization and Performance

DTIC Science & Technology

2016-10-03

dissolution, toughener dissolution and controlled chain-extension reactions in the continuous reactor high temperature “hot-zone” to advance conversion...rheology and tack. 2. Simultaneous MWCNT dispersion and stabilization in the continuous reactor low temperature “cold-zone” leading to an increased...Weight and Low Dispersity Polyacrylonitrile by Low Temperature RAFT Polymerization, Moskowitz, Jeremy, Abel, Brooks, McCormick, Charles, Wiggins

Hardness, density, and shrinkage characteristics of silk-oak from Hawaii

Treesearch

R. L. Youngs

1964-01-01

Shrinkage, specific gravity, and hardness of two shipments of silk-oak (Grevillea robusta) from Hawaii were evaluated to provide basic information pertinent to the use of the wood for cabinet and furniture purposes. The wood resembles Hawaii-grown shamel ash (Fraxinus uhdei ) in the properties evaluated. Shrinkage compares well with that of black cherry, silver maple,...

Creep and drying shrinkage of high performance concrete for the skyway structures of the new San Francisco-Oakland Bay Bridge and cement paste.

DOT National Transportation Integrated Search

2011-04-01

The objective of this study was to determine the influence of admixtures on long term drying shrinkage and creep of high : strength concrete (HSC). Creep and shrinkage of the mix utilized in segments of the Skyway Structure of the San : Francisco-Oak...

Creep and drying shrinkage of high performance concrete for the skyway structures of the new San Francisco-Oakland Bay Bridge and cement paste

DOT National Transportation Integrated Search

2011-03-01

The objective of this study was to determine the influence of admixtures on long term drying shrinkage and creep of high : strength concrete (HSC). Creep and shrinkage of the mix utilized in segments of the Skyway Structure of the San : Francisco-Oak...

Characterization and prediction of monomer-based dose rate effects in electron-beam polymerization

NASA Astrophysics Data System (ADS)

Schissel, Sage M.; Lapin, Stephen C.; Jessop, Julie L. P.

2017-12-01

Properties of some materials produced by electron-beam (EB) induced polymerization appear dependent upon the rate at which the initiating dose was delivered. However, the magnitude of these dose rate effects (DREs) can vary greatly with different monomer formulations, suggesting DREs are dependent on chemical structure. The relationship among dose, dose rate, conversion, and the glass transition temperature (Tg) of the cured material was explored for an acrylate monomer series. A strong correlation was determined between the DRE magnitude and monomer size, and this correlation may be attributed to chain transfer. Using the Tg shift caused by changes in dose, a preliminary predictive relationship was developed to estimate the magnitude of the Tg DRE, enabling scale-up of process variables for polymers prone to dose rate effects.

Development of high shrinkage polyethylene terephthalate (PET) shape memory polymer tendons for concrete crack closure

NASA Astrophysics Data System (ADS)

Teall, Oliver; Pilegis, Martins; Sweeney, John; Gough, Tim; Thompson, Glen; Jefferson, Anthony; Lark, Robert; Gardner, Diane

2017-04-01

The shrinkage force exerted by restrained shape memory polymers (SMPs) can potentially be used to close cracks in structural concrete. This paper describes the physical processing and experimental work undertaken to develop high shrinkage die-drawn polyethylene terephthalate (PET) SMP tendons for use within a crack closure system. The extrusion and die-drawing procedure used to manufacture a series of PET tendon samples is described. The results from a set of restrained shrinkage tests, undertaken at differing activation temperatures, are also presented along with the mechanical properties of the most promising samples. The stress developed within the tendons is found to be related to the activation temperature, the cross-sectional area and to the draw rate used during manufacture. Comparisons with commercially-available PET strip samples used in previous research are made, demonstrating an increase in restrained shrinkage stress by a factor of two for manufactured PET filament samples.

Effect of proanthocyanidins and photo-initiators on photo-polymerization of a dental adhesive

PubMed Central

Liu, Yi; Wang, Yong

2012-01-01

Objectives To evaluate the effects of proanthocyanidins (PA) and photoinitiator type on the degree of conversion (DC) and polymerization rate (PR) of a model dental adhesive. Methods Three types of photo-initiation systems were introduced into the Bis-GMA/HEMA co-monomer mixture, resulting in four resin formulations including CQ/A (0.5 wt% CQ and EDMAB), CQ/A/I-1 (0.5 wt% CQ, EDMAB and DPIHP), CQ/A/I-2 (1.0 wt% CQ, EDMAB and DPIHP), and TPO (2.1 wt% TPO). For each resin formulation, adhesives containing 0, 2.5%, 5% and 10% of PA with respect to the weight of resin were produced after mixing the resin with various amount of PA/ethanol solution. When light-cured, the RP and DC of each adhesive was determined using ATR- FTIR spectroscopy. Results Across and within the initiator groups, the DC followed the general trend of CQ/A < CQ/A/I-1 < CQ/A/I-2 < TPO and 0-PA > 2.5-PA > 5-PA > 10-PA, respectively. The change of PR with respect to photo-initiation systems and PA content was in a similar but less pronounced pattern. Conclusion PA hampered the polymerization of all adhesives regardless of photoinitiators used. The initiator formulations CQ/A/I-2 and TPO are better fit for PA-containing adhesives, both leading to > 65% DC in the presence of 5% PA. Clinical significance The inclusion of PA in dental adhesives has been limited by its interference with the light-curing of adhesive resins. This study found photo-initiation formulations that could maintain a satisfactory degree of monomer conversion while a significant amount of PA is incorporated. PMID:23079281

Highly Efficient and Facile Photocatalytic Recycling System Suitable for ICAR ATRP of Hydrophilic Monomers.

PubMed

Jiang, Xiaowu; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2016-08-01

Photoinduced initiators for continuous activator regeneration atom transfer radical polymerization (ATRP) of hydrophilic monomers in heptane/ethanol latent-biphasic system for copper catalyst separation and recycling have been realized for the first time at room temperature with different wavelengths of visible light LED (green, blue, purple, and white LED) as external stimulus, using 2-bromophenylacetate as the ATRP initiator and camphorquinone/triethylamine as the photoinitiator. In this system, hybrid catalyst complex (HCc) is synthesized as a novel nonpolar catalyst, which is preferentially dissolved in heptane. The hydrophilic polymers obtained catalyzed by HCc in heptane/ethanol mixture solvent show typical "living" features, for example, the values of Mn,GPC increase linearly with monomer conversion up to quantitative level (>96%) and the molecular weight distributions were kept narrow (Mw /Mn < 1.20) throughout the polymerization process. It should be noted that the excellent controllability of this novel polymerization system can be achieved even after 5 catalyst recycling experiments under LED irradiation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Boosting the power conversion efficiency of perovskite solar cells using self-organized polymeric hole extraction layers with high work function.

PubMed

Lim, Kyung-Geun; Kim, Hak-Beom; Jeong, Jaeki; Kim, Hobeom; Kim, Jin Young; Lee, Tae-Woo

2014-10-08

A self-organized hole extraction layer (SOHEL) with high work function (WF) is designed for energy level alignment with the ionization potential level of CH3 NH3 PbI3 . The SOHEL increases the built-in potential, photocurrent, and power conversion efficiency (PCE) of CH3 NH3 PbI3 perovskite solar cells. Thus, interface engineering of the positive electrode of solution-processed planar heterojunction solar cells using a high-WF SOHEL is a very effective way to achieve high device efficiency (PCE = 11.7% on glass). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shear bond strengths of composite to dentin using six dental adhesive systems.

PubMed

Triolo, P T; Swift, E J; Barkmeier, W W

1995-01-01

The development of adhesive agents for bonding composite to dentin has rapidly evolved in recent years. It is postulated that dentin bond strengths in the range of 17 MPa are sufficient to resist the polymerization shrinkage of composite resins. The purpose of this study was to evaluate the shear bond strengths of the following dentin adhesive systems: All-Bond 2 (Bisco), Imperva Bond (Shofu), Optibond (Kerr), Permagen (Ultradent), ProBond (Caulk/Dentsply), and Scotchbond Multi-Purpose (3M). Sixty human molars (10 per group) were mounted in phenolic rings, and the occlusal surfaces were flat ground in dentin to 600 grit. The prepared dentin bonding sites were treated according to the directions for each of the systems evaluated. A gelatin capsule technique was used to bond Bis-Fil composite cylinders to the teeth. The specimens were stored in water at 37 degrees C for 24 hours. Mean shear bond strengths were as follows: Scotchbond Multi-Purpose: 23.1 +/- 2.6 MPa, All-Bond 2: 21.4 +/- 7.8 MPa, Imperva Bond: 19.8 +/- 6.1 MPa, Optibond: 19.7 +/- 3.6 MPa, ProBond: 16.3 +/- 4.5 MPa, and Permagen: 16.2 +/- 3.0 MPa. There was not a significant difference (P<0.05) in the bond strengths of Scotchbond Multi-Purpose, All-Bond 2, Imperva Bond, and Optibond. The bond strengths of Scotchbond Multi-Purpose and All-Bond 2 were significantly greater (P<0.05) than ProBond and Permagen. Current-generation dentin adhesive systems have approached or exceeded the theoretical threshold value to resist contraction stresses during polymerization of resin materials.

Development of high-viscosity, two-paste bioactive bone cements.

PubMed

Deb, S; Aiyathurai, L; Roether, J A; Luklinska, Z B

2005-06-01

Self-curing two-paste bone cements have been developed using methacrylate monomers with a view to formulate cements with low polymerization exotherm, low shrinkage, better mechanical properties, and improved adhesion to bone and implant surfaces. The monomers include bis-phenol A glycidyl dimethacrylate (bis-GMA), urethane dimethacrylate (UDMA) and triethylene glycol dimethacrylate (TEGDMA) as a viscosity modifier. Two-paste systems were formulated containing 60% by weight of a bioactive ceramic, hydroxyapatite. A methacroyloxy silane (A174) was used as a coupling agent due to its higher water stability in comparison to other aminosilanes to silanate the hydroxyapatite particles prior to composite formulation. A comparison of the FT-infrared spectrum of hydroxyapatite and silanated hydroxyapatite showed the presence of the carbonyl groups ( approximately 1720 cm(-1)), -C=C-( approximately 1630 cm(-1)) and Si-O- (1300-1250 cm(-1)) which indicated the availability of silane groups on the filler surface. Two methods of mixing were effected to form the bone cement: firstly by mixing in an open bowl and secondly by extruding the two pastes by an auto-mixing tip using a gun to dispense the pastes. Both types of cements yielded low polymerization exotherms with good mechanical properties; however, the lower viscosity of UDMA allowed better extrusion and handling properties. A biologically active apatite layer formed on the bone cement surface within a short period after its immersion in simulated body fluid, demonstrating in vitro bioactivity of the composite. This preliminary data thus suggests that UDMA is a viable alternative to bis-GMA as a polymerizable matrix in the formation of bone cements.

Microfluidic conceived Trojan microcarriers for oral delivery of nanoparticles.

PubMed

Khan, Ikram Ullah; Serra, Christophe A; Anton, Nicolas; Er-Rafik, Mériem; Blanck, C; Schmutz, Marc; Kraus, Isabelle; Messaddeq, Nadia; Sutter, Christophe; Anton, Halina; Klymchenko, Andrey S; Vandamme, Thierry F

2015-09-30

In this study, we report on a novel method for the synthesis of poly(acrylamide) Trojan microparticles containing ketoprofen loaded poly(ethyl acrylate) or poly(methyl acrylate) nanoparticles. To develop these composite particles, a polymerizable nanoemulsion was used as a template. This nanoemulsion was obtained in an elongational-flow micromixer (μRMX) which was linked to a capillary-based microfluidic device for its emulsification into micron range droplets. Downstream, the microdroplets were hardened into Trojan particles in the size range of 213-308 μm by UV initiated free radical polymerization. The nanoemulsion size varied from 98 -132 nm upon changes in surfactant concentration and number of operating cycles in μRMX. SEM and confocal microscopy confirmed the Trojan morphology. Under SEM it was observed that the polymerization reduced the size of the nanoemulsion down to 20-32 nm for poly(ethyl acrylate) and 10-15 nm for poly(methyl acrylate) nanoparticles. This shrinkage was confirmed by cryo-TEM studies. We further showed that Trojan microparticles released embedded nanoparticles on contact with suitable media as confirmed by transmission electron microscopy. In a USP phosphate buffer solution of pH 6.8, Trojan microparticles containing poly(ethyl acrylate) nanoparticles released 35% of encapsulated ketoprofen over 24h. The low release of the drug was attributed to the overall low concentration of nanoparticles and attachment of some of nanoparticles to the poly(acrylamide) matrix. Thus, this novel method has shown possibility to develop Trojan particles convieniently with potential to deliver nanoparticles in the gastrointestinal tract. Copyright © 2015 Elsevier B.V. All rights reserved.

Surface charge-conversion polymeric nanoparticles for photodynamic treatment of urinary tract bacterial infections

NASA Astrophysics Data System (ADS)

Liu, Shijie; Qiao, Shenglin; Li, Lili; Qi, Guobin; Lin, Yaoxin; Qiao, Zengying; Wang, Hao; Shao, Chen

2015-12-01

Urinary tract infections are typical bacterial infections which result in a number of economic burdens. With increasing antibiotic resistance, it is urgent that new approaches are explored that can eliminate pathogenic bacteria without inducing drug resistance. Antimicrobial photodynamic therapy (PDT) is a new promising tactic. It is a gentle in situ photochemical reaction in which a photosensitizer (PS) generates reactive oxygen species (ROS) under laser irradiation. In this work, we have demonstrated Chlorin e6 (Ce6) encapsulated charge-conversion polymeric nanoparticles (NPs) for efficiently targeting and killing pathogenic bacteria in a weakly acidic urinary tract infection environment. Owing to the surface charge conversion of NPs in an acidic environment, the NPs exhibited enhanced recognition for Gram-positive (ex. S. aureus) and Gram-negative (ex. E. coli) bacteria due to the charge interaction. Also, those NPs showed significant antibacterial efficacy in vitro with low cytotoxicity. The MIC value of NPs to E. coli is 17.91 μg ml-1, compared with the free Ce6 value of 29.85 μg ml-1. Finally, a mouse acute cystitis model was used to assess the photodynamic therapy effects in urinary tract infections. A significant decline (P < 0.05) in bacterial cells between NPs and free Ce6 occurred in urine after photodynamic therapy treatment. And the plated counting results revealed a remarkable bacterial cells drop (P < 0.05) in the sacrificed bladder tissue. Above all, this nanotechnology strategy opens a new door for the treatment of urinary tract infections with minimal side effects.

Surface charge-conversion polymeric nanoparticles for photodynamic treatment of urinary tract bacterial infections.

PubMed

Liu, Shijie; Qiao, Shenglin; Li, Lili; Qi, Guobin; Lin, Yaoxin; Qiao, Zengying; Wang, Hao; Shao, Chen

2015-12-11

Urinary tract infections are typical bacterial infections which result in a number of economic burdens. With increasing antibiotic resistance, it is urgent that new approaches are explored that can eliminate pathogenic bacteria without inducing drug resistance. Antimicrobial photodynamic therapy (PDT) is a new promising tactic. It is a gentle in situ photochemical reaction in which a photosensitizer (PS) generates reactive oxygen species (ROS) under laser irradiation. In this work, we have demonstrated Chlorin e6 (Ce6) encapsulated charge-conversion polymeric nanoparticles (NPs) for efficiently targeting and killing pathogenic bacteria in a weakly acidic urinary tract infection environment. Owing to the surface charge conversion of NPs in an acidic environment, the NPs exhibited enhanced recognition for Gram-positive (ex. S. aureus) and Gram-negative (ex. E. coli) bacteria due to the charge interaction. Also, those NPs showed significant antibacterial efficacy in vitro with low cytotoxicity. The MIC value of NPs to E. coli is 17.91 μg ml(-1), compared with the free Ce6 value of 29.85 μg ml(-1). Finally, a mouse acute cystitis model was used to assess the photodynamic therapy effects in urinary tract infections. A significant decline (P < 0.05) in bacterial cells between NPs and free Ce6 occurred in urine after photodynamic therapy treatment. And the plated counting results revealed a remarkable bacterial cells drop (P < 0.05) in the sacrificed bladder tissue. Above all, this nanotechnology strategy opens a new door for the treatment of urinary tract infections with minimal side effects.

Non-Ionotropic NMDA Receptor Signaling Drives Activity-Induced Dendritic Spine Shrinkage.

PubMed

Stein, Ivar S; Gray, John A; Zito, Karen

2015-09-02

The elimination of dendritic spine synapses is a critical step in the refinement of neuronal circuits during development of the cerebral cortex. Several studies have shown that activity-induced shrinkage and retraction of dendritic spines depend on activation of the NMDA-type glutamate receptor (NMDAR), which leads to influx of extracellular calcium ions and activation of calcium-dependent phosphatases that modify regulators of the spine cytoskeleton, suggesting that influx of extracellular calcium ions drives spine shrinkage. Intriguingly, a recent report revealed a novel non-ionotropic function of the NMDAR in the regulation of synaptic strength, which relies on glutamate binding but is independent of ion flux through the receptor (Nabavi et al., 2013). Here, we tested whether non-ionotropic NMDAR signaling could also play a role in driving structural plasticity of dendritic spines. Using two-photon glutamate uncaging and time-lapse imaging of rat hippocampal CA1 neurons, we show that low-frequency glutamatergic stimulation results in shrinkage of dendritic spines even in the presence of the NMDAR d-serine/glycine binding site antagonist 7-chlorokynurenic acid (7CK), which fully blocks NMDAR-mediated currents and Ca(2+) transients. Notably, application of 7CK or MK-801 also converts spine enlargement resulting from a high-frequency uncaging stimulus into spine shrinkage, demonstrating that strong Ca(2+) influx through the NMDAR normally overcomes a non-ionotropic shrinkage signal to drive spine growth. Our results support a model in which NMDAR signaling, independent of ion flux, drives structural shrinkage at spiny synapses. Dendritic spine elimination is vital for the refinement of neural circuits during development and has been linked to improvements in behavioral performance in the adult. Spine shrinkage and elimination have been widely accepted to depend on Ca(2+) influx through NMDA-type glutamate receptors (NMDARs) in conjunction with long-term depression (LTD) of synaptic strength. Here, we use two-photon glutamate uncaging and time-lapse imaging to show that non-ionotropic NMDAR signaling can drive shrinkage of dendritic spines, independent of NMDAR-mediated Ca(2+) influx. Signaling through p38 MAPK was required for this activity-dependent spine shrinkage. Our results provide fundamental new insights into the signaling mechanisms that support experience-dependent changes in brain structure. Copyright © 2015 the authors 0270-6474/15/3512303-06$15.00/0.

Study of traits and recalcitrance reduction of field-grown COMT down-regulated switchgrass

DOE PAGES

Li, Mi; Pu, Yunqiao; Yoo, Chang Geun; ...

2017-01-03

The native recalcitrance of plants hinders the biomass conversion process using current biorefinery techniques. Down-regulation of the caffeic acid O-methyltransferase (COMT) gene in the lignin biosynthesis pathway of switchgrass reduced the thermochemical and biochemical conversion recalcitrance of biomass. Due to potential environmental influences on lignin biosynthesis and deposition, studying the consequences of physicochemical changes in field-grown plants without pretreatment is essential to evaluate the performance of lignin-altered plants. In this study, we determined the chemical composition, cellulose crystallinity and the degree of its polymerization, molecular weight of hemicellulose, and cellulose accessibility of cell walls in order to better understand themore » fundamental features of why biomass is recalcitrant to conversion without pretreatment. The most important is to investigate whether traits and features are stable in the dynamics of field environmental effects over multiple years.« less

Self-repairing vanadium-zirconium composite conversion coating for aluminum alloys

NASA Astrophysics Data System (ADS)

Zhong, Xin; Wu, Xiaosong; Jia, Yuyu; Liu, Yali

2013-09-01

In this paper, new self-repairing vanadium-zirconium composite conversion coating was prepared and investigated by Electrochemical impedance spectra (EIS), Scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. EIS results showed that V-Zr conversion coating with hydrogen peroxide modified (VZO) revealed an increasing corrosion resistance in corrosive media which meant a certain self-repairing effect. SEM comparison photos also disclosed that VZO treated with scratches was gradually ameliorated from the initial cracked configuration to fewer cracks and more fillers through an immersion of 3.5% NaCl solution. XPS results demonstrated that the content of vanadium on VZO increased and zirconium declined when immersed in the corrosive solution. This explained further that the self-repairing ability could be related to vanadium. From the above results, we inferred possible structures of VZO and proposed that self-repairing effect was achieved through a hydrolysis condensation polymerization process of vanadate in the localized corrosion area.

Sintering behavior and mechanical properties of zirconia compacts fabricated by uniaxial press forming.

PubMed

Oh, Gye-Jeong; Yun, Kwi-Dug; Lee, Kwang-Min; Lim, Hyun-Pil; Park, Sang-Won

2010-09-01

The purpose of this study was to compare the linear sintering behavior of presintered zirconia blocks of various densities. The mechanical properties of the resulting sintered zirconia blocks were then analyzed. Three experimental groups of dental zirconia blocks, with a different presintering density each, were designed in the present study. Kavo Everest® ZS blanks (Kavo, Biberach, Germany) were used as a control group. The experimental group blocks were fabricated from commercial yttria-stabilized tetragonal zirconia powder (KZ-3YF (SD) Type A, KCM. Corporation, Nagoya, Japan). The biaxial flexural strengths, microhardnesses, and microstructures of the sintered blocks were then investigated. The linear sintering shrinkages of blocks were calculated and compared. Despite their different presintered densities, the sintered blocks of the control and experimental groups showed similar mechanical properties. However, the sintered block had different linear sintering shrinkage rate depending on the density of the presintered block. As the density of the presintered block increased, the linear sintering shrinkage decreased. In the experimental blocks, the three sectioned pieces of each block showed the different linear shrinkage depending on the area. The tops of the experimental blocks showed the lowest linear sintering shrinkage, whereas the bottoms of the experimental blocks showed the highest linear sintering shrinkage. Within the limitations of this study, the density difference of the presintered zirconia block did not affect the mechanical properties of the sintered zirconia block, but affected the linear sintering shrinkage of the zirconia block.

Sintering behavior and mechanical properties of zirconia compacts fabricated by uniaxial press forming

PubMed Central

Oh, Gye-Jeong; Yun, Kwi-Dug; Lee, Kwang-Min; Lim, Hyun-Pil

2010-01-01

PURPOSE The purpose of this study was to compare the linear sintering behavior of presintered zirconia blocks of various densities. The mechanical properties of the resulting sintered zirconia blocks were then analyzed. MATERIALS AND METHODS Three experimental groups of dental zirconia blocks, with a different presintering density each, were designed in the present study. Kavo Everest® ZS blanks (Kavo, Biberach, Germany) were used as a control group. The experimental group blocks were fabricated from commercial yttria-stabilized tetragonal zirconia powder (KZ-3YF (SD) Type A, KCM. Corporation, Nagoya, Japan). The biaxial flexural strengths, microhardnesses, and microstructures of the sintered blocks were then investigated. The linear sintering shrinkages of blocks were calculated and compared. RESULTS Despite their different presintered densities, the sintered blocks of the control and experimental groups showed similar mechanical properties. However, the sintered block had different linear sintering shrinkage rate depending on the density of the presintered block. As the density of the presintered block increased, the linear sintering shrinkage decreased. In the experimental blocks, the three sectioned pieces of each block showed the different linear shrinkage depending on the area. The tops of the experimental blocks showed the lowest linear sintering shrinkage, whereas the bottoms of the experimental blocks showed the highest linear sintering shrinkage. CONCLUSION Within the limitations of this study, the density difference of the presintered zirconia block did not affect the mechanical properties of the sintered zirconia block, but affected the linear sintering shrinkage of the zirconia block. PMID:21165274

The effect of mucosal cuff shrinkage around dental implants during healing abutment replacement.

PubMed

Nissan, J; Zenziper, E; Rosner, O; Kolerman, R; Chaushu, L; Chaushu, G

2015-10-01

Soft tissue shrinkage during the course of restoring dental implants may result in biological and prosthodontic difficulties. This study was conducted to measure the continuous shrinkage of the mucosal cuff around dental implants following the removal of the healing abutment up to 60 s. Individuals treated with implant-supported fixed partial dentures were included. Implant data--location, type, length, diameter and healing abutments' dimensions--were recorded. Mucosal cuff shrinkage, following removal of the healing abutments, was measured in bucco-lingual direction at four time points--immediately after 20, 40 and 60 s. anova was used to for statistical analysis. Eighty-seven patients (49 women and 38 men) with a total of 311 implants were evaluated (120 maxilla; 191 mandible; 291 posterior segments; 20 anterior segments). Two-hundred and five (66%) implants displayed thick and 106 (34%) thin gingival biotype. Time was the sole statistically significant parameter affecting mucosal cuff shrinkage around dental implants (P < 0.001). From time 0 to 20, 40 and 60 s, the mean diameter changed from 4.1 to 4.07, 3.4 and 2.81 mm, respectively. The shrinkage was 1%, 17% and 31%, respectively. The gingival biotype had no statistically significant influence on mucosal cuff shrinkage (P = 0.672). Time required replacing a healing abutment with a prosthetic element should be minimised (up to 20/40 s), to avoid pain, discomfort and misfit. © 2015 John Wiley & Sons Ltd.

Investigation on Failures of Composite Beam and Substrate Concrete due to Drying Shrinkage Property of Repair Materials

NASA Astrophysics Data System (ADS)

Pattnaik, Rashmi Ranjan

2017-06-01

A Finite Element Analysis (FEA) and an experimental study was conducted on composite beam of repair material and substrate concrete to investigate the failures of the composite beam due to drying shrinkage property of the repair materials. In FEA, the stress distribution in the composite beam due to two concentrate load and shrinkage of repair materials were investigated in addition to the deflected shape of the composite beam. The stress distributions and load deflection shapes of the finite element model were investigated to aid in analysis of the experimental findings. In the experimental findings, the mechanical properties such as compressive strength, split tensile strength, flexural strength, and load-deflection curves were studied in addition to slant shear bond strength, drying shrinkage and failure patterns of the composite beam specimens. Flexure test was conducted to simulate tensile stress at the interface between the repair material and substrate concrete. The results of FEA were used to analyze the experimental results. It was observed that the repair materials with low drying shrinkage are showing compatible failure in the flexure test of the composite beam and deform adequately in the load deflection curves. Also, the flexural strength of the composite beam with low drying shrinkage repair materials showed higher flexural strength as compared to the composite beams with higher drying shrinkage value of the repair materials even though the strength of those materials were more.

Analysis of the temporal effects on grating evolution in photopolymer

NASA Astrophysics Data System (ADS)

Kelly, John V.; Gleeson, Michael R.; Close, Ciara E.; O'Neill, Feidhlim T.; Sheridan, John T.; Gallego, Sergi; Neipp, Cristian

2006-04-01

The nonlocal polymerization driven diffusion model is used to describe holographic grating formation in acrylamidebased photopolymer. The free radical chain polymerization process results in polymer being generated nonlocal both in space and time to the point of chain initiation. A Gaussian spatial material response function and an exponential temporal material response function are used to account for these effects. In this paper we firstly examine the nature of the temporal evolution of grating formation for short recording periods. It is shown that in this case, temporal effects become most notable and the inclusion of the nonlocal temporal response function is shown to be necessary to accurately describe the process. In particular, brief post exposure selfamplification of the refractive index modulation is noted. This is attributed to continued chain growth for a brief period after exposure. Following this a slight decay in the grating amplitude also occurs. This we believe is due to the continued diffusion of monomer after exposure. Since the sinusoidal recording pattern generates a monomer concentration gradient during the recording process monomer diffusion occurs both during and after exposure. The evolution of the refractive index modulation is determined by the respective refractive index values of the recording material components. From independent measurements it is noted that the refractive index value of the monomer is slightly less than that of the background material. Therefore as monomer diffuses back into the dark regions, a reduction in overall refractive index modulation occurs. Volume changes occurring within the material also affect the nature of grating evolution. To model these effects we employ a free volume concept. Due to the fact that the covalent single carbon bond in the polymer is up to 50% shorter than the van der Waals bond in the liquid monomer state, free volume is created when monomer is converted to polymer. For each bond conversion we assume a hole is generated which then collapses at some characteristic rate constant. Incorporating each of these effects into our model, the model is then solved using a Finite-Difference Time- Domain method (FDTD). The Lorentz-Lorenz relation is used to determine the overall evolution refractive index modulation and the corresponding diffraction efficiency of the resulting grating is calculated using Rigorous Coupled Wave Analysis (RCWA). Fits are then carried out to experimental data for 1 second exposures. Good quality fits are achieved and material parameters extracted. Monomer diffusion rates are determined to be of the order of D ~ 10 -10 cm 2/s and the time constant of the nonlocal material temporal response function being of the order of τ n ~ 10 -2s. Material shrinkage occurring over these recording periods is also determined.

Polymerization Behavior of Hydrophilic-Rich Phase of Dentin Adhesive

PubMed Central

Abedin, F.; Parthasarathy, R.; Misra, A.; Spencer, P.

2015-01-01

The 2-fold objectives of this study were 1) to understand whether model hydrophobic- and hydrophilic-rich phase mimics of dentin adhesive polymerize similarly and 2) to determine which factor, the dimethacrylate component, bisphenol A glycerolate dimethacrylate (BisGMA) or photoinitiator concentration, has greater influence on the polymerization of the hydrophilic-rich phase mimic. Current dentin adhesives are sensitive to moisture, as evidenced by nanoleakage in the hybrid layer and phase separation into hydrophobic- and hydrophilic-rich phases. Phase separation leads to limited availability of the cross-linkable dimethacrylate monomer and hydrophobic photoinitiators within the hydrophilic-rich phase. Model hydrophobic-rich phase was prepared as a single-phase solution by adding maximum wt% deuterium oxide (D2O) to HEMA/BisGMA neat resins containing 45 wt% 2-hydroxyethyl methacrylate (HEMA). Mimics of the hydrophilic-rich phase were prepared similarly but using HEMA/BisGMA neat resins containing 95, 99, 99.5, and 100 wt% HEMA. The hydrophilic-rich mimics were prepared with standard or reduced photoinitiator content. The photoinitiator systems were camphorquinone (CQ)/ethyl 4-(dimethylamino)benzoate (EDMAB) with or without [3-(3, 4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-2-hydroxypropyl]trimethylammonium chloride (QTX). The polymerization kinetics was monitored using a Fourier transform infrared spectrophotometer with a time-resolved collection mode. The hydrophobic-rich phase exhibited a significantly higher polymerization rate compared with the hydrophilic-rich phase. Postpolymerization resulting in the secondary rate maxima was observed for the hydrophilic-rich mimic. The hydrophilic-rich mimics with standard photoinitiator concentration but varying cross-linker (BisGMA) content showed postpolymerization and a substantial degree of conversion. In contrast, the corresponding formulations with reduced photoinitiator concentrations exhibited lower polymerization and inhibition/delay of postpolymerization within 2 h. Under conditions relevant to the wet, oral environment, photoinitiator content plays an important role in the polymerization of the hydrophilic-rich phase mimic. Since the hydrophilic-rich phase is primarily water and monomethacrylate monomer (e.g., HEMA as determined previously), substantial polymerization is important to limit the potential toxic response from HEMA leaching into the surrounding tissues. PMID:25576471

Microhardness of light- and dual-polymerizable luting resins polymerized through 7.5-mm-thick endocrowns.

PubMed

Gregor, Ladislav; Bouillaguet, Serge; Onisor, Ioana; Ardu, Stefano; Krejci, Ivo; Rocca, Giovanni Tommaso

2014-10-01

The complete polymerization of luting resins through thick indirect restorations is still questioned. The purpose of this study was to evaluate the degree of polymerization of light- and dual-polymerizable luting resins under thick indirect composite resin and ceramic endocrowns by means of Vickers microhardness measurements. The Vickers microhardness measurements of a light-polymerizable microhybrid composite resin and a dual-polymerizable luting cement directly polymerized in a natural tooth mold for 40 seconds with a high-power light-emitting diode lamp (control) were compared with measurements after indirect irradiation through 7.5-mm-thick composite resin and ceramic endocrowns for 3 × 90 seconds. A test-to-control microhardness values ratio of 0.80 at a depth of 0.5 mm below the surface was assumed as the criterion for adequate conversion. For the Vickers microhardness measurements of a dual-polymerizable luting cement, no differences (P>.05) were found between Vickers microhardness control values and values reported after polymerization through composite resin and ceramic endocrowns. For The Vickers microhardness measurements (±SD) of a light-polymerizable microhybrid composite resin, control values were significantly (P<.05) higher (111 ±3.3) than those reported after polymerization through composite resin (100.5 ±3.8) and ceramic (99.7 ±2.3) endocrowns. However, the hardness values of The Vickers microhardness measurements of a light-polymerizable microhybrid composite resin polymerized through the endocrowns were approximately 10% to 12% lower than those of the control values. Two-way ANOVA showed the influence of the luting material on the Vickers microhardness values (P<.05). The effect of endocrown material was not significant (P>.05). Under the conditions of this in vitro study, Vickers microhardness values of the dual-polymerizable resin cement and the light-polymerizable restorative composite resin irradiated for 3 × 90 seconds with a high irradiance light-emitting diode lamp through 7.5-mm-thick endocrowns reached at least 80% of the control Vickers microhardness values, which means that both materials can be adequately polymerized when they are used for luting thick indirect restorations. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Stabilization of miniemulsion droplets by cerium oxide nanoparticles: a step toward the elaboration of armored composite latexes.

PubMed

Zgheib, Nancy; Putaux, Jean-Luc; Thill, Antoine; D'Agosto, Franck; Lansalot, Muriel; Bourgeat-Lami, Elodie

2012-04-10

Stable methyl methacrylate (MMA) miniemulsions were successfully prepared using for the first time cerium oxide (CeO(2)) nanoparticles as solid stabilizers in the absence of any molecular surfactant. The interaction between MMA droplets and CeO(2) nanoparticles was induced by the use of methacrylic acid (MAA) as a comonomer. Both MAA and CeO(2) contents played a key role on the diameter and the stability of the droplets formed during the emulsification step. Cryo-transmission electron microscopy (TEM) images of the suspensions formed with 35 wt % of CeO(2) showed the presence of polydisperse 50-150 nm spherical droplets. More surprisingly, some nonspherical (likely discoidal) objects that could be the result of the sonication step were also observed. The subsequent polymerization of these Pickering miniemulsion droplets led to the formation of composite PMMA latex particles armored with CeO(2). In all cases, the conversion was limited to ca. 85%, concomitant with a loss of stability of the latex for CeO(2) contents lower than 35 wt %. This stability issues were likely related to the screening of the cationic charges present on CeO(2) nanoparticles upon polymerization. TEM images showed mostly spherical particles with a diameter ranging from 100 to 400 nm and homogeneously covered with CeO(2). Besides, for particles typically larger than 200 nm, a buckled morphology was observed supporting the presence of residual monomer at the end of the polymerization and consistent with the limited conversion. The versatility of these systems was further demonstrated using 35 wt % of CeO(2) and replacing MMA by n-butyl acrylate (BA) either alone or in combination with MMA. Stable monomer emulsions were always obtained, with the droplet size increasing with the hydrophobicity of the oil phase, pointing out the key influence of the wettability of the solid stabilizer. The polymerization of Pickering miniemulsion stabilized by CeO(2) nanoparticles proved to be an efficient strategy to form armored composite latex particles which may find applications in coating technology. © 2012 American Chemical Society

The effect of hydroxyapatite presence on the degree of conversion and polymerization rate in a model self-etching adhesive

PubMed Central

Zhang, Ying; Wang, Yong

2011-01-01

Objective The effect of hydroxyapatite (HAp) content on photopolymerization of a model self-etching adhesive was studied by using attenuated total reflectance Fourier transform infrared (ATR/FT-IR) spectroscopy. Materials and methods The model adhesive contained two monomers: bis[2-(methacryloyloxy)ethyl] phosphate (2MP) and 2-hydroxyethyl methacrylate (HEMA) using a 1:1 mass ratio, representing an acidic formulation. Camphorquinone and ethyl 4-dimethylaminobenzoate were added to enable visible light photopolymerization in a constant concentration of 0.022 mmol per gram monomer. HAp [Ca10(OH)2(PO4)6] powder were added to the test solutions to obtain mass fraction of 0, 1, 2, 3, 4 wt%. The degree of conversion (DC) and the polymerization rate (PR) with/without HAp were determined using ATR/FT-IR with a time-based spectrum analysis. Results Monomer DC and PR were significantly enhanced by addition of HAp. Incorporation of 4 wt% of HAp increased DC from 20.8 (±0.3) % to 93.4 (±1.1) %, and PR from 0.42 (±0.01) %/s to 3.21 (±0.07) %/s. The pH of adhesive solutions was measured and correlated with DC and PR. The pH of test solutions was also controlled using a base (sodium hydroxide, NaOH) to similar values as when using HAp. Results indicated that both the DC and PR increased with increasing pH, regardless of additive, confirming the role of pH on polymerization. From the IR spectral comparison, changes in molecular structures of the self-etching adhesive after the addition of HAp were observed, which were correlated with the specific interaction between 2MP and HAp. The effect of viscosity was also proposed to be another possible reason for the improved polymerization. Significance The photopolymerization of a self-etching adhesive was enhanced / accelerated in the presence of HAp. The results provide the critical information for understanding the interactions/bonding between self-etching adhesives and tooth substrates. PMID:22032933

[Correlation between degree of conversion, microhardness and inorganic content in composites].

PubMed

Neves, Alisson Discacciati; Discacciati, José Augusto César; Orêfice, Rodrigo Lambert; Jansen, Wellington Corrêa

2002-01-01

The purpose of this study was to evaluate the correlation between degree of conversion and microhardness in dental composites, as well as the effect of the inorganic content and type of photo-curing unit on these parameters. Three indirect composites (Artglass, Solidex and Zeta LC) were polymerized by means of three different laboratorial units (UniXS, Solidilite and an experimental device). For each material, fifteen samples were prepared using a metal matrix. The degree of conversion was analyzed by means of infrared spectroscopy, and microhardness was also assessed. The inorganic content was measured by means of thermogravimetric analysis (TGA). The Pearson s test was carried out in order to determine correlations. The degree of conversion of Artglass ranged from 37.5% to 79.2%, and its microhardness, from 32.4 to 50.3 (r = 0.904). The degree of conversion of Solidex ranged from 41.2% to 60.4%, and its microhardness, from 33.3 to 44.1 (r = 0.707). The degree of conversion and the microhardness of Zeta LC ranged from 62.0% to 78.0% and from 22.6 to 33.6, respectively (r = 0.710). It was concluded that the utilization of different photo-curing units caused variations on the degree of conversion, as a result of specific characteristics of each unit. For each material, there was strong correlation between the degree of conversion and microhardness. In addition, when different materials were compared, microhardness was more affected by filler content than by the degree of conversion.

Radical Polymerization of Vinyl Acetate and Methyl Methacrylate Using Organochromium Initiators Complexed with Macrocyclic Polyamines

DTIC Science & Technology

1994-06-30

conversion, the increase was faster than at later stages. and therefore the steric strain enfosced by the 5gn backone dpdson Th efficiency of initation...BPOJ),- 0.25M. Cr(OAc)2jDPO, THF. 200CC IVAclo - SMK [Cr2io - [DPOJ~i 0.25M. (UI - (Cr2+’Jo (LIgl - (Cr2൒ 0 _ In the absence of any liganda, a

Novel, Solvent Free, Single Ion Conductive Polymer Electrolytes (Warsaw-2001)

DTIC Science & Technology

2004-10-18

application in lithium and lithium - ion batteries , characterized by limited participation of anions in the transport of electrical charge. Studies...with studies on novel chemical energy conversion and storage devices mainly lithium or lithium ion batteries and fuel cells [1]. Our work within...this part of the project dealt with these novel ideas in the field of lithium or lithium - ion batteries based on polymeric solid electrolytes. The solid

Visualizing chemical functionality in plant cell walls

DOE PAGES

Zeng, Yining; Himmel, Michael E.; Ding, Shi-You

2017-11-30

Understanding plant cell wall cross-linking chemistry and polymeric architecture is key to the efficient utilization of biomass in all prospects from rational genetic modification to downstream chemical and biological conversion to produce fuels and value chemicals. In fact, the bulk properties of cell wall recalcitrance are collectively determined by its chemical features over a wide range of length scales from tissue, cellular to polymeric architectures. Microscopic visualization of cell walls from the nanometer to the micrometer scale offers an in situ approach to study their chemical functionality considering its spatial and chemical complexity, particularly the capabilities of characterizing biomass non-destructivelymore » and in real-time during conversion processes. Microscopic characterization has revealed heterogeneity in the distribution of chemical features, which would otherwise be hidden in bulk analysis. Key microscopic features include cell wall type, wall layering, and wall composition - especially cellulose and lignin distributions. Microscopic tools, such as atomic force microscopy, stimulated Raman scattering microscopy, and fluorescence microscopy, have been applied to investigations of cell wall structure and chemistry from the native wall to wall treated by thermal chemical pretreatment and enzymatic hydrolysis. While advancing our current understanding of plant cell wall recalcitrance and deconstruction, microscopic tools with improved spatial resolution will steadily enhance our fundamental understanding of cell wall function.« less

Effect of initiator concentration to low-density polyethylene production in a tubular reactor

NASA Astrophysics Data System (ADS)

Azmi, A.; Aziz, N.

2016-11-01

Low-density polyethylene (LDPE) is one of the most widely used polymers in the world, which is produced in high-capacity tubular and autoclave reactors. As the LDPE industry turn into more competitive and its market profit margins become tighter, manufacturers have to develop solutions to debottleneck the reactor output while abiding to the stringent product specification. A single polyolefin plant producing ten to forty grades of LDPE with various melt flow index (MFI), therefore understanding the reaction mechanism, the operating conditions as well as the dynamic behavior of tubular reactor is essential before any improvement can take place. In the present work, a steady state mathematical model representing a tubular reactor for the production of LDPE is simulated using MATLAB R2015a®. The model developed is a function of feed inlet, reactor jacket, single initiator injector and outlet stream. Analysis on the effect of initiator concentration (CI) shows sudden declining trend of initiator's concentration which indicates that all of the initiators are exhausted after polymerization reaction and no further reaction occur from this point onwards. Furthermore, the results demonstrate that the concentration of initiator gives significant impact on reactor temperature's profile and monomer conversion rate, since higher initiator concentration promotes greater polymerization rate, and therefore leads to higher monomer conversion throughput.

Visualizing chemical functionality in plant cell walls

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, Yining; Himmel, Michael E.; Ding, Shi-You

Understanding plant cell wall cross-linking chemistry and polymeric architecture is key to the efficient utilization of biomass in all prospects from rational genetic modification to downstream chemical and biological conversion to produce fuels and value chemicals. In fact, the bulk properties of cell wall recalcitrance are collectively determined by its chemical features over a wide range of length scales from tissue, cellular to polymeric architectures. Microscopic visualization of cell walls from the nanometer to the micrometer scale offers an in situ approach to study their chemical functionality considering its spatial and chemical complexity, particularly the capabilities of characterizing biomass non-destructivelymore » and in real-time during conversion processes. Microscopic characterization has revealed heterogeneity in the distribution of chemical features, which would otherwise be hidden in bulk analysis. Key microscopic features include cell wall type, wall layering, and wall composition - especially cellulose and lignin distributions. Microscopic tools, such as atomic force microscopy, stimulated Raman scattering microscopy, and fluorescence microscopy, have been applied to investigations of cell wall structure and chemistry from the native wall to wall treated by thermal chemical pretreatment and enzymatic hydrolysis. While advancing our current understanding of plant cell wall recalcitrance and deconstruction, microscopic tools with improved spatial resolution will steadily enhance our fundamental understanding of cell wall function.« less

Visualizing chemical functionality in plant cell walls.

PubMed

Zeng, Yining; Himmel, Michael E; Ding, Shi-You

2017-01-01

Understanding plant cell wall cross-linking chemistry and polymeric architecture is key to the efficient utilization of biomass in all prospects from rational genetic modification to downstream chemical and biological conversion to produce fuels and value chemicals. In fact, the bulk properties of cell wall recalcitrance are collectively determined by its chemical features over a wide range of length scales from tissue, cellular to polymeric architectures. Microscopic visualization of cell walls from the nanometer to the micrometer scale offers an in situ approach to study their chemical functionality considering its spatial and chemical complexity, particularly the capabilities of characterizing biomass non-destructively and in real-time during conversion processes. Microscopic characterization has revealed heterogeneity in the distribution of chemical features, which would otherwise be hidden in bulk analysis. Key microscopic features include cell wall type, wall layering, and wall composition-especially cellulose and lignin distributions. Microscopic tools, such as atomic force microscopy, stimulated Raman scattering microscopy, and fluorescence microscopy, have been applied to investigations of cell wall structure and chemistry from the native wall to wall treated by thermal chemical pretreatment and enzymatic hydrolysis. While advancing our current understanding of plant cell wall recalcitrance and deconstruction, microscopic tools with improved spatial resolution will steadily enhance our fundamental understanding of cell wall function.

Novel Self-Assembling Amino Acid-Derived Block Copolymer with Changeable Polymer Backbone Structure.

PubMed

Koga, Tomoyuki; Aso, Eri; Higashi, Nobuyuki

2016-11-29

Block copolymers have attracted much attention as potentially interesting building blocks for the development of novel nanostructured materials in recent years. Herein, we report a new type of self-assembling block copolymer with changeable polymer backbone structure, poly(Fmoc-Ser) ester -b-PSt, which was synthesized by combining the polycondensation of 9-fluorenylmethoxycarbonyl-serine (Fmoc-Ser) with the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St). This block copolymer showed the direct conversion of the backbone structure from polyester to polypeptide through a multi O,N-acyl migration triggered by base-induced deprotection of Fmoc groups in organic solvent. Such polymer-to-polymer conversion was found to occur quantitatively without decrease in degree of polymerization and to cause a drastic change in self-assembling property of the block copolymer. On the basis of several morphological analyses using FTIR spectroscopy, atomic force, and transmission and scanning electron microscopies, the resulting peptide block copolymer was found to self-assemble into a vesicle-like hollow nanosphere with relatively uniform diameter of ca. 300 nm in toluene. In this case, the peptide block generated from polyester formed β-sheet structure, indicating the self-assembly via peptide-guided route. We believe the findings presented in this study offer a new concept for the development of self-assembling block copolymer system.

Fiber-optic epoxy composite cure sensor. I. Dependence of refractive index of an autocatalytic reaction epoxy system at 850 nm on temperature and extent of cure

NASA Astrophysics Data System (ADS)

Lam, Kai-Yuen; Afromowitz, Martin A.

1995-09-01

We discuss the behavior of the refractive index of a typical epoxy-aromatic diamine system. Near 850 nm the index of refraction is found to be largely controlled by the density of the epoxy. Models are derived to describe its dependence on temperature and extent of cure. Within the range of temperatures studied, the refractive index decreases linearly with increasing temperature. In addition, as the epoxy is cured, the refractive index increases linearly with conversion to the gel point. >From then on, shrinkage in the volume of the epoxy is restricted by local viscosity. Therefore the linear relationship between the refractive index and the extent of cure does not hold beyond the gel point.

Inorganic-ligand exchanging time effect in PbS quantum dot solar cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Byung-Sung; Hong, John; Hou, Bo

2016-08-08

We investigate time-dependent inorganic ligand exchanging effect and photovoltaic performance of lead sulfide (PbS) nanocrystal films. With optimal processing time, volume shrinkage induced by residual oleic acid of the PbS colloidal quantum dot (CQD) was minimized and a crack-free film was obtained with improved flatness. Furthermore, sufficient surface passivation significantly increased the packing density by replacing from long oleic acid to a short iodide molecule. It thus facilities exciton dissociation via enhanced charge carrier transport in PbS CQD films, resulting in the improved power conversion efficiency from 3.39% to 6.62%. We also found that excess iodine ions on the PbSmore » surface rather hinder high photovoltaic performance of the CQD solar cell.« less

Assessment of novel maleic anhydride copolymers prepared via nitroxide-mediated radical polymerization as CaSO4 crystal growth inhibitors.

PubMed

Al-Roomi, Yousef Mohammad; Hussain, Kaneez Fatema

2017-04-01

Calcium sulfate is one of the dominant scales which, unlike carbonate scale, are not easily removable by acid. To inhibit CaSO 4 scale formation in artificial cooling water systems, well-defined low molecular weight maleic anhydride and n-alkylacrylamide copolymers (YMR-S series) were synthesized via nitroxide-mediated radical polymerization initiated by benzoyl peroxide in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy at varying concentrations. These polymerizations exhibit living polymerization characteristics; that is, they show linear growth in chain length as a function of monomer conversion, and have narrow molecular weight distributions. Resultant polymers were characterized by means of 1 H-NMR and 13 C-NMR. The inhibition behavior of these YMR-S series polymers against CaSO 4 was evaluated using the static scale inhibition method and a dynamic tube block test. The inhibition ability on the CaSO 4 scale is 99.5% with 9 ppm dosage level at pH 10.45 and temperature 70°C. Scanning electronic microscope analysis proved the morphological changes of the CaSO 4 scales due to the strong inhibition action of YMR-S polymers. It is also observed that the antiscaling effect of the copolymers greatly depends on the molecular weight, and the optimum range is below 20,000 and approximately in the range 500-2000.

Effect of shape on bone cement polymerization time in knee joint replacement surgery

PubMed Central

Yoon, Jung-Ro; Ko, Young-Rok; Shin, Young-Soo

2018-01-01

Abstract Background: Although many factors are known to influence the polymerization time of bone cement, it remains unclear which bone cement shape predicts the precise polymerization time. The purpose of this study was to investigate whether different cement shapes influenced polymerization time and to identify the relationship between cement shape and ambient operating theater temperature, relative humidity, and equilibration time. Methods: Samples were gathered prospectively from 237 patients undergoing primary total knee arthroplasty. The cement components were made into 2 different shapes: lump and pan. The time at which no macroscopic indentation of both cement models was possible was recorded as the polymerization time. Results: There was no significant difference between hand mixing (lump shape: 789.3 ± 128.4 seconds, P = .591; pan shape: 899.3 ± 152.2 seconds, P = .584) and vacuum mixing (lump shape: 780.2 ± 131.1 seconds, P = .591; pan shape: 909.9 ± 143.3 seconds, P = .584) in terms of polymerization time. Conversely, the polymerization time was significantly shorter for Antibiotic Simplex (lump shape: 757.4 ± 114.9 seconds, P = .001; pan shape: 879.5 ± 125.0 seconds, P < .001) when compared with Palacos R+G (lump shape: 829.0 ± 139.3 seconds, P = .001; pan shape: 942.9 ± 172.0 seconds, P < .001). Polymerization time was also significantly longer (P < .001) for the pan shape model (904 ± 148.0 seconds) when compared with the lump shape model (785.2 ± 129.4 seconds). In addition, the polymerization time decreased with increasing temperature (lump shape: R2 = 0.334, P < .001; pan shape: R2 = 0.375, P < .001), humidity (lump shape: R2 = 0.091, P < .001; pan shape: R2 = 0.106, P < .001), and equilibration time (lump shape: R2 = 0.073, P < .001; pan shape: R2 = 0.044, P < .001). Conclusions: The polymerization time was equally affected by temperature, relative humidity, and equilibration time regardless of bone cement shape. Furthermore, the pan shape model better reflected the cement polymerization time between implant and bone compared with the lump shape model. The current findings suggest that, clinically, constant pressure with the knee in <45° of flexion needs to be applied until remaining pan shaped cement is completely polymerized. PMID:29703041

Modeling and Analysis of Process Parameters for Evaluating Shrinkage Problems During Plastic Injection Molding of a DVD-ROM Cover

NASA Astrophysics Data System (ADS)

Öktem, H.

2012-01-01

Plastic injection molding plays a key role in the production of high-quality plastic parts. Shrinkage is one of the most significant problems of a plastic part in terms of quality in the plastic injection molding. This article focuses on the study of the modeling and analysis of the effects of process parameters on the shrinkage by evaluating the quality of the plastic part of a DVD-ROM cover made with Acrylonitrile Butadiene Styrene (ABS) polymer material. An effective regression model was developed to determine the mathematical relationship between the process parameters (mold temperature, melt temperature, injection pressure, injection time, and cooling time) and the volumetric shrinkage by utilizing the analysis data. Finite element (FE) analyses designed by Taguchi (L27) orthogonal arrays were run in the Moldflow simulation program. Analysis of variance (ANOVA) was then performed to check the adequacy of the regression model and to determine the effect of the process parameters on the shrinkage. Experiments were conducted to control the accuracy of the regression model with the FE analyses obtained from Moldflow. The results show that the regression model agrees very well with the FE analyses and the experiments. From this, it can be concluded that this study succeeded in modeling the shrinkage problem in our application.

Statistical Study to Evaluate the Effect of Processing Variables on Shrinkage Incidence During Solidification of Nodular Cast Irons

NASA Astrophysics Data System (ADS)

Gutiérrez, J. M.; Natxiondo, A.; Nieves, J.; Zabala, A.; Sertucha, J.

2017-04-01

The study of shrinkage incidence variations in nodular cast irons is an important aspect of manufacturing processes. These variations change the feeding requirements on castings and the optimization of risers' size is consequently affected when avoiding the formation of shrinkage defects. The effect of a number of processing variables on the shrinkage size has been studied using a layout specifically designed for this purpose. The β parameter has been defined as the relative volume reduction from the pouring temperature up to the room temperature. It is observed that shrinkage size and β decrease as effective carbon content increases and when inoculant is added in the pouring stream. A similar effect is found when the parameters selected from cooling curves show high graphite nucleation during solidification of cast irons for a given inoculation level. Pearson statistical analysis has been used to analyze the correlations among all involved variables and a group of Bayesian networks have been subsequently built so as to get the best accurate model for predicting β as a function of the input processing variables. The developed models can be used in foundry plants to study the shrinkage incidence variations in the manufacturing process and to optimize the related costs.

Geosynthetic clay liners shrinkage under simulated daily thermal cycles.

PubMed

Sarabadani, Hamid; Rayhani, Mohammad T

2014-06-01

Geosynthetic clay liners are used as part of composite liner systems in municipal solid waste landfills and other applications to restrict the escape of contaminants into the surrounding environment. This is attainable provided that the geosynthetic clay liner panels continuously cover the subsoil. Previous case histories, however, have shown that some geosynthetic clay liner panels are prone to significant shrinkage and separation when an overlying geomembrane is exposed to solar radiation. Experimental models were initiated to evaluate the potential shrinkage of different geosynthetic clay liner products placed over sand and clay subsoils, subjected to simulated daily thermal cycles (60°C for 8 hours and 22°C for 16 hours) modelling field conditions in which the liner is exposed to solar radiation. The variation of geosynthetic clay liner shrinkage was evaluated at specified times by a photogrammetry technique. The manufacturing techniques, the initial moisture content, and the aspect ratio (ratio of length to width) of the geosynthetic clay liner were found to considerably affect the shrinkage of geosynthetic clay liners. The particle size distribution of the subsoil and the associated suction at the geosynthetic clay liner-subsoil interface was also found to have significant effects on the shrinkage of the geosynthetic clay liner. © The Author(s) 2014.

Shrinkage modeling of concrete reinforced by palm fibres in hot dry environments

NASA Astrophysics Data System (ADS)

Akchiche, Hamida; Kriker, Abdelouahed

2017-02-01

The cement materials, such as concrete and conventional mortar present very little resistance to traction and cracking, these hydraulic materials which induces large withdrawals on materials and cracks in structures. The hot dry environments such as: the Saharan regions of Algeria, Indeed, concrete structures in these regions are very fragile, and present high shrinkage. Strengthening of these materials by fibers can provide technical solutions for improving the mechanical performance. The aim of this study is firstly, to reduce the shrinkage of conventional concrete with its reinforcement with date palm fibers. In fact, Algeria has an extraordinary resources in natural fibers (from Palm, Abaca, Hemp) but without valorization in practical areas, especially in building materials. Secondly, to model the shrinkage behavior of concrete was reinforced by date palm fibers. In the literature, several models for still fiber concrete were founded but few are offers for natural fiber concretes. To do so, a still fiber concretes model of YOUNG - CHERN was used. According to the results, a reduction of shrinkage with reinforcement by date palm fibers was showed. A good ability of molding of shrinkage of date palm reinforced concrete with YOUNG - CHERN Modified model was obtained. In fact, a good correlation between experimental data and the model data was recorded.

Some Issues of Shrinkage-Reducing Admixtures Application in Alkali-Activated Slag Systems

PubMed Central

Bílek, Vlastimil; Kalina, Lukáš; Novotný, Radoslav; Tkacz, Jakub; Pařízek, Ladislav

2016-01-01

Significant drying shrinkage is one of the main limitations for the wider utilization of alkali-activated slag (AAS). Few previous works revealed that it is possible to reduce AAS drying shrinkage by the use of shrinkage-reducing admixtures (SRAs). However, these studies were mainly focused on SRA based on polypropylene glycol, while as it is shown in this paper, the behavior of SRA based on 2-methyl-2,4-pentanediol can be significantly different. While 0.25% and 0.50% had only a minor effect on the AAS properties, 1.0% of this SRA reduced the drying shrinkage of waterglass-activated slag mortar by more than 80%, but it greatly reduced early strengths simultaneously. This feature was further studied by isothermal calorimetry, mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). Calorimetric experiments showed that 1% of SRA modified the second peak of the pre-induction period and delayed the maximum of the main hydration peak by several days, which corresponds well with observed strength development as well as with the MIP and SEM results. These observations proved the certain incompatibility of SRA with the studied AAS system, because the drying shrinkage reduction was induced by the strong retardation of hydration, resulting in a coarsening of the pore structure rather than the proper function of the SRA. PMID:28773584

Robust adhesive precision bonding in automated assembly cells

NASA Astrophysics Data System (ADS)

Müller, Tobias; Haag, Sebastian; Bastuck, Thomas; Gisler, Thomas; Moser, Hansruedi; Uusimaa, Petteri; Axt, Christoph; Brecher, Christian

2014-03-01

Diode lasers are gaining importance, making their way to higher output powers along with improved BPP. The assembly of micro-optics for diode laser systems goes along with the highest requirements regarding assembly precision. Assembly costs for micro-optics are driven by the requirements regarding alignment in a submicron and the corresponding challenges induced by adhesive bonding. For micro-optic assembly tasks a major challenge in adhesive bonding at highest precision level is the fact, that the bonding process is irreversible. Accordingly, the first bonding attempt needs to be successful. Today's UV-curing adhesives inherit shrinkage effects crucial for submicron tolerances of e.g. FACs. The impact of the shrinkage effects can be tackled by a suitable bonding area design, such as minimal adhesive gaps and an adapted shrinkage offset value for the specific assembly parameters. Compensating shrinkage effects is difficult, as the shrinkage of UV-curing adhesives is not constant between two different lots and varies even over the storage period even under ideal circumstances as first test results indicate. An up-to-date characterization of the adhesive appears necessary for maximum precision in optics assembly to reach highest output yields, minimal tolerances and ideal beamshaping results. Therefore, a measurement setup to precisely determine the up-to-date level of shrinkage has been setup. The goal is to provide necessary information on current shrinkage to the operator or assembly cell to adjust the compensation offset on a daily basis. Impacts of this information are expected to be an improved beam shaping result and a first-time-right production.

The potential of computer vision, optical backscattering parameters and artificial neural network modelling in monitoring the shrinkage of sweet potato (Ipomoea batatas L.) during drying.

PubMed

Onwude, Daniel I; Hashim, Norhashila; Abdan, Khalina; Janius, Rimfiel; Chen, Guangnan

2018-03-01

Drying is a method used to preserve agricultural crops. During the drying of products with high moisture content, structural changes in shape, volume, area, density and porosity occur. These changes could affect the final quality of dried product and also the effective design of drying equipment. Therefore, this study investigated a novel approach in monitoring and predicting the shrinkage of sweet potato during drying. Drying experiments were conducted at temperatures of 50-70 °C and samples thicknesses of 2-6 mm. The volume and surface area obtained from camera vision, and the perimeter and illuminated area from backscattered optical images were analysed and used to evaluate the shrinkage of sweet potato during drying. The relationship between dimensionless moisture content and shrinkage of sweet potato in terms of volume, surface area, perimeter and illuminated area was found to be linearly correlated. The results also demonstrated that the shrinkage of sweet potato based on computer vision and backscattered optical parameters is affected by the product thickness, drying temperature and drying time. A multilayer perceptron (MLP) artificial neural network with input layer containing three cells, two hidden layers (18 neurons), and five cells for output layer, was used to develop a model that can monitor, control and predict the shrinkage parameters and moisture content of sweet potato slices under different drying conditions. The developed ANN model satisfactorily predicted the shrinkage and dimensionless moisture content of sweet potato with correlation coefficient greater than 0.95. Combined computer vision, laser light backscattering imaging and artificial neural network can be used as a non-destructive, rapid and easily adaptable technique for in-line monitoring, predicting and controlling the shrinkage and moisture changes of food and agricultural crops during drying. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Two-Color Single-Photon Photoinitiation and Photoinhibition for Subdiffraction Photolithography

NASA Astrophysics Data System (ADS)

Scott, Timothy F.; Kowalski, Benjamin A.; Sullivan, Amy C.; Bowman, Christopher N.; McLeod, Robert R.

2009-05-01

Controlling and reducing the developed region initiated by photoexposure is one of the fundamental goals of optical lithography. Here, we demonstrate a two-color irradiation scheme whereby initiating species are generated by single-photon absorption at one wavelength while inhibiting species are generated by single-photon absorption at a second, independent wavelength. Co-irradiation at the second wavelength thus reduces the polymerization rate, delaying gelation of the material and facilitating enhanced spatial control over the polymerization. Appropriate overlapping of the two beams produces structures with both feature sizes and monomer conversions otherwise unobtainable with use of single- or two-photon absorption photopolymerization. Additionally, the generated inhibiting species rapidly recombine when irradiation with the second wavelength ceases, allowing for fast sequential exposures not limited by memory effects in the material and thus enabling fabrication of complex two- or three-dimensional structures.

Influence of nanometer scale particulate fillers on some properties of microfilled composite resin.

PubMed

Garoushi, Sufyan; Lassila, Lippo V J; Vallittu, Pekka K

2011-07-01

The aim of this study was to evaluate the effect of different weight fractions of nanometer sized particulate filler on properties of microfilled composite resin. Composite resin was prepared by mixing 33 wt% of resin matrix to the 67 wt% of silane treated microfine silica particulate fillers with various fractions of nanometer sized fillers (0, 10, 15, 20, 30 wt%) using a high speed mixing machine. Test specimens made of the composites were tested with a three-point bending test with a speed of 1.0 mm/min until fracture. Surface microhardess (Vicker's microhardness) was also determined. The volumetric shrinkage in percent was calculated as a buoyancy change in distilled water by means of the Archimedes principle. The degree of monomer conversion (DC%) of the experimental composites containing different nanofiller fractions was measured using FTIR spectroscopy. Surface roughness (Ra) was determined using a surface profilometer. Nanowear measurements were carried out using a nanoindentation device. The water uptake of specimens was also measured. Parameters were statistically analysed by ANOVA (P < 0.05). The group without nanofillers showed the highest flexural strength and modulus, DC% and Ra value. The group with 30% nanofillers had the highest water uptake and volumetric shrinkage. No significant difference was found in Vicker's microhardness and the nanowear of the composites. The plain microfilled composite demonstrated superior properties compared to the composites loaded with nanofillers with the exception of surface roughness.

Effect of Surface Treatment on the Properties of Wool Fabric

NASA Astrophysics Data System (ADS)

Kan, C. W.; Yuen, C. W. M.; Chan, C. K.; Lau, M. P.

Wool fiber is commonly used in textile industry, however, it has some technical problems which affect the quality and performance of the finished products such as felting shrinkage, handle, lustre, pilling, and dyeability. These problems may be attributed mainly in the presence of wool scales on the fiber surface. Recently, chemical treatments such as oxidation and reduction are the commonly used descaling methods in the industry. However, as a result of the pollution caused by various chemical treatments, physical treatment such as low temperature plasma (LTP) treatment has been introduced recently because it is similarly capable of achieving a comparable descaling effect. Most of the discussions on the applications of LTP treatment on wool fiber were focused on applying this technique for improving the surface wettability and shrink resistance. Meanwhile, little discussion has been made on the mechanical properties, thermal properties, and the air permeability. In this paper, wool fabric was treated with LTP treatment with the use of a non-polymerizing gas, namely oxygen. After the LTP treatment, the fabrics low-stress mechanical properties, air permeability, and thermal properties were evaluated and discussed.

Update on dental nanocomposites.

PubMed

Chen, M-H

2010-06-01

Dental resin-composites are comprised of a photo-polymerizable organic resin matrix and mixed with silane-treated reinforcing inorganic fillers. In the development of the composites, the three main components can be modified: the inorganic fillers, the organic resin matrix, and the silane coupling agents. The aim of this article is to review recent studies of the development of dental nanocomposites and their clinical applications. In nanocomposites, nanofillers are added and distributed in a dispersed form or as clusters. For increasing the mineral content of the tooth, calcium and phosphate ion-releasing composites and fluoride-releasing nanocomposites were developed by the addition of DCPA-whiskers or TTCP-whiskers or by the use of calcium fluoride or kaolinite. For enhancing mechanical properties, nanocomposites reinforced with nanofibers or nanoparticles were investigated. For reducing polymerization shrinkage, investigators modified the resin matrix by using methacrylate and epoxy functionalized nanocomposites based on silsesquioxane cores or epoxy-resin-based nanocomposites. The effects of silanization were also studied. Clinical consideration of light-curing modes and mechanical properties of nanocomposites, especially strength durability after immersion, was also addressed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffman, D.M.; Jessop, E.S.; Swansiger, R.W.

Cast cure, extrusion cast, and paste extrudable explosives have not been designed for transferring through long tortuous paths or into fine three dimensional shapes. To allow the crystalline explosive to flow a lubricating fluid is required. The energetic liquid ethane trinitrate (TMETN) was used as the lubricant to maximize the explosive energy. TMETN is a liquid nitrate ester which requires stabilization with conventional free radical stabilizers such as 2- nitrodiphenylamine, methyl-nitroanaline, or ethyl centrylite. Since these injection moldable explosives are expected to cure in place, a polyesterurethane binder based on polymeric isocyanate of hexamethylene diisocyanate and polycaprolactone polyols is dissolvedmore » in TMETN. The solubility of the polymer precursors in TMETN also reduces the energetic liquids sensitivity. The latent cure catalyst Dabco T-131 was used to minimize shrinkage associated with thermal expansion, reduce cost associated with oven cures, to give 4-6 hour potlife and overnight cure to handling strength. The product RX-08-HD is a new, low-viscosity, injection moldable explosive that can be extruded into complex, void-free shapes. Combined with appropriate design and other aspects of weaponization, RX-08-HD has produced outstanding results.« less

Holographic recording properties in thick films of ULSH-500 photopolymer

NASA Astrophysics Data System (ADS)

Waldman, David A.; Li, H.-Y. S.; Cetin, Erdem A.

1998-06-01

The photopolymer holographic recording materials, ULSH-500, based upon cationic ring-opening polymerization, has been further optimized for recording in an increased film thickness of 200 micrometers . The dynamic range attained, at least M/# equals 16, is substantially greater than previously reported, while concurrently the inherent low transverse shrinkage and high sensitivity characteristics of the material have been retained. Dynamic range or cumulative grating strength, (Sigma) (eta) i0.5, has been determined from co-locationally recorded peristrophic and angle multiplexed plane-wave gratings which exhibit low diffraction efficiencies between about 0.1 and 0.2%. Good Bragg selectivity consistent with the imaged thickness and sinc2 function behavior is observed for the multiplexed holograms, and both the angular response and the diffraction efficiency are stable without the need for post-imaging fixing procedures. Sensitivity is in the range of 1 to 10 cm/mJ, and the refractive index modulation achievable during consumption of the accessible dynamic range is n1 equals 1.3 X 10-2 at the read wavelength of 514.5 nm.

Chiral Amine Synthesis Using ω-Transaminases: An Amine Donor that Displaces Equilibria and Enables High-Throughput Screening**

PubMed Central

Green, Anthony P; Turner, Nicholas J; O'Reilly, Elaine

2014-01-01

The widespread application of ω-transaminases as biocatalysts for chiral amine synthesis has been hampered by fundamental challenges, including unfavorable equilibrium positions and product inhibition. Herein, an efficient process that allows reactions to proceed in high conversion in the absence of by-product removal using only one equivalent of a diamine donor (ortho-xylylenediamine) is reported. This operationally simple method is compatible with the most widely used (R)- and (S)-selective ω-TAs and is particularly suitable for the conversion of substrates with unfavorable equilibrium positions (e.g., 1-indanone). Significantly, spontaneous polymerization of the isoindole by-product generates colored derivatives, providing a high-throughput screening platform to identify desired ω-TA activity. PMID:25138082

Cross-Linking Reactions for the Conversion of Polyphosphazenes into Useful Materials

DTIC Science & Technology

1994-05-18

Characteristics of Polymeric Materials Polymers form one of the largest classes of materials.I Together with ceramics, metals, and a number of inorganic ...the (mainly inorganic ) ceramics, semiconductors, metals, and electro-optical materials. As such, they provide access to combinations of properties that...are not found in any of the classical materials areas. Because the field of inorganic /organic materials is one of the most promising areas for the

Characterization of cure kinetics and physical properties of a high performance, glass fiber-reinforced epoxy prepreg and a novel fluorine-modified, amine-cured commercial epoxy

NASA Astrophysics Data System (ADS)

Bilyeu, Bryan

Kinetic equation parameters for the curing reaction of a commercial glass fiber reinforced high performance epoxy prepreg composed of the tetrafunctional epoxy tetraglycidyl 4,4-diaminodiphenyl methane (TGDDM), the tetrafunctional amine curing agent 4,4'-diaminodiphenylsulfone (DDS) and an ionic initiator/accelerator, are determined by various thermal analysis techniques and the results compared. The reaction is monitored by heat generated determined by differential scanning calorimetry (DSC) and by high speed DSC when the reaction rate is high. The changes in physical properties indicating increasing conversion are followed by shifts in glass transition temperature determined by DSC, temperature-modulated DSC (TMDSC), step scan DSC and high speed DSC, thermomechanical (TMA) and dynamic mechanical (DMA) analysis and thermally stimulated depolarization (TSD). Changes in viscosity, also indicative of degree of conversion, are monitored by DMA. Thermal stability as a function of degree of cure is monitored by thermogravimetric analysis (TGA). The parameters of the general kinetic equations, including activation energy and rate constant, are explained and used to compare results of various techniques. The utilities of the kinetic descriptions are demonstrated in the construction of a useful time-temperature-transformation (TTT) diagram and a continuous heating transformation (CHT) diagram for rapid determination of processing parameters in the processing of prepregs. Shrinkage due to both resin consolidation and fiber rearrangement is measured as the linear expansion of the piston on a quartz dilatometry cell using TMA. The shrinkage of prepregs was determined to depend on the curing temperature, pressure applied and the fiber orientation. Chemical modification of an epoxy was done by mixing a fluorinated aromatic amine (aniline) with a standard aliphatic amine as a curing agent for a commercial Diglycidylether of Bisphenol-A (DGEBA) epoxy. The resulting cured network was tested for wear resistance using tribological techniques. Of the six anilines, 3-fluoroaniline and 4-fluoroaniline were determined to have lower wear than the unmodified epoxy, while the others showed much higher wear rates.

Non-destructive examination of interfacial debonding using acoustic emission.

PubMed

Li, Haiyan; Li, Jianying; Yun, Xiaofei; Liu, Xiaozhou; Fok, Alex Siu-Lun

2011-10-01

This study aims to assess the viability of using the acoustic emission (AE) measurement technique to detect and monitor in situ the interfacial debonding in resin composite restorations due to build-up of shrinkage stresses during polymerization of the composite. The non-destructive testing technique that measures acoustic emission (AE) was used to detect and monitor the interfacial debonding in resin composite during curing of the composite. Four groups of specimens, n=4 each, were tested: (1) intact human molars with Class-I cavities restored with the composite Z100 (3M ESPE, USA); (2) intact human molars with Class-I cavities restored with the composite Filtek™ P90 (3M ESPE, USA); (3) ring samples prepared from the root of a single bovine tooth and 'restored' with Z100; (4) freestanding pea-size specimens of Z100 directly placed on the AE sensor. The restorations in Groups (1)-(3) were bonded to the tooth tissues with the adhesive Adper™ Scotchbond™ SE Self-Etch (3M ESPE, USA). The composites in all the specimens were cured with a blue light (3M ESPE, USA) for 40s. The AE signals were recorded continuously for 10 min from the start of curing. Non-destructive 3D imaging was performed using X-ray micro-computed tomography (micro-CT) to examine the bonding condition at the tooth-restoration interface. The development of AE events followed roughly that of the shrinkage stress, which was determined separately by the cantilever beam method. The number of AE events in the real human tooth samples was more than that in the ring samples, and no AE events were detected in the pea-size specimens placed directly on the AE sensor. The number of AE events recorded in the specimens restored using Z100 was more than that found in specimens restored with Filtek P90. The micro-CT imaging results showed clear interfacial debondings in the tooth specimens restored with Z100 after curing, but no clear debonding was found in the P90 specimens. The AE technique is an effective tool for detecting and monitoring in situ the interfacial debonding of composite restorations during curing. It can potentially be employed to evaluate the development of shrinkage stress and the quality of interfacial bonds in teeth restored with different composite materials, cavity geometries, and restorative techniques. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Photopolymerization of highly filled dimethacrylate-based composites using Type I or Type II photoinitiators and varying co-monomer ratios.

PubMed

Randolph, Luc D; Steinhaus, Johannes; Möginger, Bernhard; Gallez, Bernard; Stansbury, Jeffrey; Palin, William M; Leloup, Gaëtane; Leprince, Julian G

2016-02-01

The use of a Type I photoinitiator (monoacylphosphine oxide, MAPO) was described as advantageous in a model formulation, as compared to the conventional Type II photoinitiator (Camphorquinone, CQ). The aim of the present work was to study the kinetics of polymerization of various composite mixtures (20-40-60-80 mol%) of bisphenol A glycidyl dimethacrylate/triethylene glycol dimethacrylate (BisGMA/TegDMA) containing either CQ or MAPO, based on real-time measurements and on the characterization of various post-cure characteristics. Polymerization kinetics were monitored by Fourier-transform near-infrared spectroscopy (FT-NIRS) and dielectric analysis (DEA). A range of postcure properties was also investigated. FT-NIRS and DEA proved complementary to follow the fast kinetics observed with both systems. Autodecceleration occurred after ≈1 s irradiation for MAPO-composites and ≈5-10 s for CQ-composites. Conversion decreased with increasing initial viscosity for both photoinitiating systems. However despite shorter light exposure (3s for MAPO vs 20s for CQ-composites), MAPO-composites yielded higher conversions for all co-monomer mixtures, except at 20 mol% BisGMA, the less viscous material. MAPO systems were associated with increased amounts of trapped free radicals, improved flexural strength and modulus, and reduced free monomer release for all co-monomer ratios, except at 20 mol% BisGMA. This work confirms the major influence of the initiation system both on the conversion and network cross-linking of highly-filled composites, and further highlights the advantages of using MAPO photoinitiating systems in highly-filled dimethacrylate-based composites provided that sufficient BisGMA content (>40 mol%) and adapted light spectrum are used. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Development of photopolymerizable clay nanocomposites utilizing reactive dispersants

NASA Astrophysics Data System (ADS)

Owusu-Adom, Kwame

Nanocomposites hold tremendous promise for expanding the utility of polymeric materials. However, accessing particulate sizes in the nanoscale domain continues to be a scientific challenge, especially in highly cross-linked photopolymerizable systems. In this study, photopolymerizable nanocomposites utilizing clay nanoparticles and reactive dispersants have been developed. The influence of particle size, dispersant-clay interactions, and surfactant concentration on photopolymerization behavior and nanoparticle dispersion has been elucidated. Clay particles serve as templates upon which surfactants aggregate during photopolymerization. This results in higher photopolymerization rates with addition of increasing concentrations of polymerizable surfactants. Furthermore, polymerizable surfactants induce faster photopolymerization rates compared to non-polymerizable analogues in systems that have ionically-bound dispersants on the particle surface. Utilizing reactive organoclays induces significant changes to the photopolymerization behavior depending on the choice of reactive functionality employed. Faster acrylate photopolymerization rates occur in photopolymer systems containing thiol-modified clays, while much slower rates occur for nonpolymerizable organoclay systems. In addition, chemical compatibility between monomer and clay dispersant (based on chemical similarity or polarity) allows enhancement of exfoliation in photopolymerizable formulations. With polymerizable dispersants, exfoliation is readily achieved in various multifunctional acrylate systems. The degree of exfoliation depends on the position of the reactive group relative to the surfactant's cationic site and the type of functionality. Thiolated organoclays exfoliate during polymerization, while methacrylated clays show substantially less dependence on polymerization behavior. Interestingly, changes in the physical properties of the resulting nanocomposite are independent of the degree of exfoliation in polymerizable organoclay systems. The polymer cross-link density dictates the magnitude of change in both modulus and glass transition temperature of the nanocomposite. Substantial increases in modulus and Tg occur in elastomeric and low cross-link density polymers, while decreases occur in the modulus and Tg of highly cross-linked polymer networks. Finally, these parameters have formed a basis for developing nanocomposites with higher moduli and lower volumetric shrinkage. The photopolymerization rates of these systems are controllable and increase substantially with addition of polymerizable organoclays. Such properties occur in traditional multifunctional acrylate photopolymer systems as well as new binary thiol-(meth)acrylate and ternary thiol-ene-(meth)acrylate photopolymers.

Muscle activity patterns and spinal shrinkage in office workers using a sit-stand workstation versus a sit workstation.

PubMed

Gao, Ying; Cronin, Neil J; Pesola, Arto J; Finni, Taija

2016-10-01

Reducing sitting time by means of sit-stand workstations is an emerging trend, but further evidence is needed regarding their health benefits. This cross-sectional study compared work time muscle activity patterns and spinal shrinkage between office workers (aged 24-62, 58.3% female) who used either a sit-stand workstation (Sit-Stand group, n = 10) or a traditional sit workstation (Sit group, n = 14) for at least the past three months. During one typical workday, muscle inactivity and activity from quadriceps and hamstrings were monitored using electromyography shorts, and spinal shrinkage was measured using stadiometry before and after the workday. Compared with the Sit group, the Sit-Stand group had less muscle inactivity time (66.2 ± 17.1% vs. 80.9 ± 6.4%, p = 0.014) and more light muscle activity time (26.1 ± 12.3% vs. 14.9 ± 6.3%, p = 0.019) with no significant difference in spinal shrinkage (5.62 ± 2.75 mm vs. 6.11 ± 2.44 mm). This study provides evidence that working with sit-stand workstations can promote more light muscle activity time and less inactivity without negative effects on spinal shrinkage. Practitioner Summary: This cross-sectional study compared the effects of using a sit-stand workstation to a sit workstation on muscle activity patterns and spinal shrinkage in office workers. It provides evidence that working with a sit-stand workstation can promote more light muscle activity time and less inactivity without negative effects on spinal shrinkage.

Impact of dose escalation and adaptive radiotherapy for cervical cancers on tumour shrinkage—a modelling study

NASA Astrophysics Data System (ADS)

Røthe Arnesen, Marius; Paulsen Hellebust, Taran; Malinen, Eirik

2017-03-01

Tumour shrinkage occurs during fractionated radiotherapy and is regulated by radiation induced cellular damage, repopulation of viable cells and clearance of dead cells. In some cases additional tumour shrinkage during external beam therapy may be beneficial, particularly for locally advanced cervical cancer where a small tumour volume may simplify and improve brachytherapy. In the current work, a mathematical tumour model is utilized to investigate how local dose escalation affects tumour shrinkage, focusing on implications for brachytherapy. The iterative two-compartment model is based upon linear-quadratic radiation response, a doubling time for viable cells and a half-time for clearance of dead cells. The model was individually fitted to clinical tumour volume data from fractionated radiotherapy of 25 cervical cancer patients. Three different fractionation patterns for dose escalation, all with an additional dose of 12.2 Gy, were simulated and compared to standard fractionation in terms of tumour shrinkage. An adaptive strategy where dose escalation was initiated after one week of treatment was also considered. For 22 out of 25 patients, a good model fit was achieved to the observed tumour shrinkage. A large degree of inter-patient variation was seen in predicted volume reduction following dose escalation. For the 10 best responding patients, a mean tumour volume reduction of 34  ±  3% (relative to standard treatment) was estimated at the time of brachytherapy. Timing of initiating dose escalation had a larger impact than the number of fractions applied. In conclusion, the model was found useful in evaluating the impact from dose escalation on tumour shrinkage. The results indicate that dose escalation could be conducted from the start of external beam radiotherapy in order to obtain additional tumour shrinkage before brachytherapy.

Development and Validation of a Constitutive Model for Dental Composites during the Curing Process

NASA Astrophysics Data System (ADS)

Wickham Kolstad, Lauren

Debonding is a critical failure of a dental composites used for dental restorations. Debonding of dental composites can be determined by comparing the shrinkage stress of to the debonding strength of the adhesive that bonds it to the tooth surface. It is difficult to measure shrinkage stress experimentally. In this study, finite element analysis is used to predict the stress in the composite during cure. A new constitutive law is presented that will allow composite developers to evaluate composite shrinkage stress at early stages in the material development. Shrinkage stress and shrinkage strain experimental data were gathered for three dental resins, Z250, Z350, and P90. Experimental data were used to develop a constitutive model for the Young's modulus as a function of time of the dental composite during cure. A Maxwell model, spring and dashpot in series, was used to simulate the composite. The compliance of the shrinkage stress device was also taken into account by including a spring in series with the Maxwell model. A coefficient of thermal expansion was also determined for internal loading of the composite by dividing shrinkage strain by time. Three FEA models are presented. A spring-disk model validates that the constitutive law is self-consistent. A quarter cuspal deflection model uses separate experimental data to verify that the constitutive law is valid. Finally, an axisymmetric tooth model is used to predict interfacial stresses in the composite. These stresses are compared to the debonding strength to check if the composite debonds. The new constitutive model accurately predicted cuspal deflection data. Predictions for interfacial bond stress in the tooth model compare favorably with debonding characteristics observed in practice for dental resins.

Regional Brain Shrinkage over Two Years: Individual Differences and Effects of Pro-Inflammatory Genetic Polymorphisms

PubMed Central

Persson, N.; Ghisletta, P.; Dahle, C.L.; Bender, A.R.; Yang, Y.; Yuan, P.; Daugherty, A.M.; Raz, N.

2014-01-01

We examined regional changes in brain volume in healthy adults (N = 167, age 19-79 years at baseline; N = 90 at follow-up) over approximately two years. With latent change score models, we evaluated mean change and individual differences in rates of change in 10 anatomically-defined and manually-traced regions of interest (ROIs): lateral prefrontal cortex (LPFC), orbital frontal cortex (OF), prefrontal white matter (PFw), hippocampus (HC), parahippocampal gyrus (PhG), caudate nucleus (Cd), putamen (Pt), insula (In), cerebellar hemispheres (CbH), and primary visual cortex (VC). Significant mean shrinkage was observed in the HC, CbH, In, OF, and the PhG, and individual differences in change were noted in all regions, except the OF. Pro-inflammatory genetic variants mediated shrinkage in PhG and CbH. Carriers of two T alleles of interleukin-1β (IL-1βC-511T, rs16944) and a T allele of methylenetetrahydrofolate reductase (MTHFRC677T, rs1801133) polymorphisms showed increased PhG shrinkage. No effects of a pro-inflammatory polymorphism for C-reactive protein (CRP-286C>A>T, rs3091244) or apolipoprotein (APOE) ε4 allele were noted. These results replicate the pattern of brain shrinkage observed in previous studies, with a notable exception of the LPFC thus casting doubt on the unique importance of prefrontal cortex in aging. Larger baseline volumes of CbH and In were associated with increased shrinkage, in conflict with the brain reserve hypothesis. Contrary to previous reports, we observed no significant linear effects of age and hypertension on regional brain shrinkage. Our findings warrant further investigation of the effects of neuroinflammation on structural brain change throughout the lifespan. PMID:25264227

Does expanded polytetrafluoroethylene mesh really shrink after laparoscopic ventral hernia repair?

PubMed

Carter, P R; LeBlanc, K A; Hausmann, M G; Whitaker, J M; Rhynes, V K; Kleinpeter, K P; Allain, B W

2012-06-01

The shrinkage of mesh has been cited as a possible explanation for hernia recurrence. Expanded polytetrafluoroethylene (ePTFE) is unique in that it can be visualized on computed tomography (CT). Some animal studies have shown a greater than 40% rate of contraction of ePTFE; however, very few human studies have been performed. A total of 815 laparoscopic incisional/ventral hernia (LIVH) repairs were performed by a single surgical group. DualMesh Plus (ePTFE) (WL Gore & Associates, Newark, DE) was placed in the majority of these patients using both transfascial sutures and tack fixation. Fifty-eight patients had postoperative CTs of the abdomen and pelvis with ePTFE and known transverse diameter of the implanted mesh. The prosthesis was measured on the CT using the AquariusNet software program (TeraRecon, San Mateo, CA), which outlines the mesh and calculates the total length. Data were collected regarding the original mesh size, known linear dimension of mesh, seroma formation, and time interval since mesh implantation in months. The mean shrinkage rate was 6.7%. The duration of implantation ranged from 6 weeks to 78 months, with a median of 15 months. Seroma was seen in 8.6% (5) of patients. No relationship was identified between the percentage of shrinkage and the original mesh size (P = 0.78), duration of time implanted (P = 0.57), or seroma formation (P = 0.074). In 27.5% (16) of patients, no shrinkage of mesh was identified. Of the patients who did experience mesh shrinkage, the range of shrinkage was 2.6-25%. Our results are markedly different from animal studies and show that ePTFE has minimal shrinkage after LIVH repair. The use of transfascial sutures in addition to tack fixation may have an implication on the mesh contraction rates.

The effect of a nanofilled resin-based coating on water absorption by teeth restored with glass ionomer.

PubMed

Hankins, Amanda D; Hatch, Robert H; Benson, Jarred H; Blen, Bernard J; Tantbirojn, Daranee; Versluis, Antheunis

2014-04-01

A nanofilled, resin-based light-cured coating (G-Coat Plus, GC America, Alsip, Ill.) may reduce water absorption by glass ionomers. The authors investigated this possibility by measuring cuspal flexure caused by swelling of glass ionomer-restored teeth. The authors cut large mesio-occlusodistal slots (4-millimeter wide, 4-mm deep) in 12 extracted premolars and restored them with a glass ionomer cement (Fuji IX GP Extra, GC America). Six teeth were coated, and the other six were uncoated controls. The authors digitized the teeth in three dimensions by using an optical scanner after preparation and restoration and during an eight-week storage in water. They calculated cuspal flexure and analyzed the results by using an analysis of variance and Student-Newman-Keuls post hoc tests (significance level .05). They used dye penetration along the interface to verify bonding. Inward cuspal flexure indicated restoration shrinkage. Coated restorations had significantly higher flexure (mean [standard deviation], -11.9 [3.5] micrometers) than did restorations without coating (-7.3 [1.5] μm). Flexure in both groups decreased significantly (P < .05) during water storage and, after eight weeks, it changed to expansion for uncoated control restorations. Dye penetration along the interfaces was not significant, which ruled out debonding as the cause of cuspal relaxation. Teeth restored with glass ionomer cement exhibited shrinkage, as seen by inward cuspal flexure. The effect of the protective coating on water absorption was evident in the slower shrinkage compensation. The study results show that teeth restored with glass ionomers exhibited setting shrinkage that deformed tooth cusps. Water absorption compensated for the shrinkage. Although the coating may be beneficial for reducing water absorption, it also slows the shrinkage compensation rate (that is, the rate that hygroscopic expansion compensates for cuspal flexure from shrinkage).

Comparison of stereotactic radiosurgery and fractionated stereotactic radiotherapy of acoustic neurinomas according to 3-D tumor volume shrinkage and quality of life.

PubMed

Henzel, Martin; Hamm, Klaus; Sitter, Helmut; Gross, Markus W; Surber, Gunnar; Kleinert, Gabriele; Engenhart-Cabillic, Rita

2009-09-01

Stereotactic radiosurgery (SRS) and also fractionated stereotactic radiotherapy (SRT) offer high local control (LC) rates (> 90%). This study aimed to evaluate three-dimensional (3-D) tumor volume (TV) shrinkage and to assess quality of life (QoL) after SRS/SRT. From 1999 to 2005, 35/74 patients were treated with SRS, and 39/74 with SRT. Median age was 60 years. Treatment was delivered by a linear accelerator. Median single dose was 13 Gy (SRS) or 54 Gy (SRT). Patients were followed up > or = 12 months after SRS/SRT. LC and toxicity were evaluated by clinical examinations and magnetic resonance imaging. 3-D TV shrinkage was evaluated with the planning system. QoL was assessed using the questionnaire Short Form-36. Median follow-up was 50/36 months (SRS/SRT). Actuarial 5-year freedom from progression/overall survival was 88.1%/100% (SRS), and 87.5%/87.2% (SRT). TV shrinkage was 15.1%/40.7% (SRS/SRT; p = 0.01). Single dose (< 13 Gy) was the only determinant factor for TV shrinkage after SRS (p = 0.001). Age, gender, initial TV, and previous operations did not affect TV shrinkage. Acute or late toxicity (> or = grade 3) was never seen. Concerning QoL, no significant differences were observed after SRS/SRT. Previous operations and gender did not affect QoL (p > 0.05). Compared with the German normal population, patients had worse values for all domains except for mental health. TV shrinkage was significantly higher after SRT than after SRS. Main symptoms were not affected by SRS/SRT. Retrospectively, QoL was neither affected by SRS nor by SRT.

Shrinkage and growth compensation in common sunflowers: refining estimates of damage

USGS Publications Warehouse

Sedgwick, James A.; Oldemeye, John L.; Swenson, Elizabeth L.

1986-01-01

Shrinkage and growth compensation of artificially damaged common sunflowers (Helianthus annuus) were studied in central North Dakota during 1981-1982 in an effort to increase accuracy of estimates of blackbird damage to sunflowers. In both years, as plants matured damaged areas on seedheads shrank at a greater rate than the sunflower heads themselves. This differential shrinkage resulted in an underestimation of the area damaged. Sunflower head and damaged-area shrinkage varied widely by time and degree of damage and by size of the seedhead damaged. Because variation in shrinkage by time of damage was so large, predicting when blackbird damage occurs may be the most important factor in estimating seed loss. Yield'occupied seed area was greater (P < 0.05) for damaged than undamaged heads and tended to increase as degree of damage inflicted increased, indicating growth compensation was occurring in response to lost seeds. Yields of undamaged seeds in seedheads damaged during early seed development were higher than those of heads damaged later. This suggested that there was a period of maximal response to damage when plants were best able to redirect growth to seeds remaining in the head. Sunflowers appear to be able to compensate for damage of ≤ 15% of the total hear area. Estimates of damage can be improved by applying empirical results of differential shrinkage and growth compensations.

Effect of the irradiance distribution from light curing units on the local micro-hardness of the surface of dental resins.

PubMed

Haenel, Thomas; Hausnerová, Berenika; Steinhaus, Johannes; Price, Richard B T; Sullivan, Braden; Moeginger, Bernhard

2015-02-01

An inhomogeneous irradiance distribution from a light-curing unit (LCU) can locally cause inhomogeneous curing with locally inadequately cured and/or over-cured areas causing e.g. monomer elution or internal shrinkage stresses, and thus reduce the lifetime of dental resin based composite (RBC) restorations. The aim of the study is to determine both the irradiance distribution of two light curing units (LCUs) and its influence on the local mechanical properties of a RBC. Specimens of Arabesk TOP OA2 were irradiated for 5, 20, and 80s using a Bluephase® 20i LCU in the Low mode (666mW/cm(2)), in the Turbo mode (2222mW/cm(2)) and a Celalux® 2 (1264mW/cm(2)). The degree of conversion (DC) was determined with an ATR-FTIR. The Knoop micro-hardness (average of five specimens) was measured on the specimen surface after 24h of dark and dry storage at room temperature. The irradiance distribution affected the hardness distribution across the surface of the specimens. The hardness distribution corresponded well to the inhomogeneous irradiance distributions of the LCU. The highest reaction rates occurred after approximately 2s light exposure. A DC of 40% was reached after 3.6 or 5.7s, depending on the LCU. The inhomogeneous hardness distribution was still evident after 80s of light exposure. The irradiance distribution from a LCU is reflected in the hardness distribution across the surface. Irradiance level of the LCU and light exposure time do not affect the pattern of the hardness distribution--only the hardness level. In areas of low irradiation this may result in inadequate resin polymerization, poor physical properties, and hence premature failure of the restorations as they are usually much smaller than the investigated specimens. It has to be stressed that inhomogeneous does not necessarily mean poor if in all areas of the restoration enough light intensity is introduced to achieve a high degree of cure. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

An investigation of CO2 laser scleral buckling using moiré interferometry.

PubMed

Maswadi, Saher M; Dyer, Peter E; Verma, Dinesh; Jalabi, Wadah; Dave, Dinesh

2002-01-01

To demonstrate suitability of moiré interferometry to assess and quantify laser-induced shrinkage of scleral collagen for buckling procedures. Scleral buckling of human cadaver eyes was investigated using a Coherent Ultrapulse CO2 laser. Projection moiré interferometry was employed to determine the out-of plane displacement produced by laser exposure, and in-situ optical microscopy of reference markers on the eye was used to measure in-plane shrinkage. Measurements based on moiré interferometry allow a three dimensional view of shape changes in the eye surface as laser treatment proceeds. Out-of-plane displacement reaches up to 1.5 mm with a single laser spot exposure. In-plane shrinkage reached a maximum of around 30%, which is similar to that reported by Sasoh et al (Ophthalmic Surg Lasers. 1998;29:410) for a Tm:YAG laser. The moiré technique is found to be suitable for quantifying the effects of CO2 laser scleral shrinkage and buckling. This can be further developed to provide a standardized method for experimental investigations of other laser sources for scleral shrinkage.

Fabrication and characterization of self-folding thermoplastic sheets using unbalanced thermal shrinkage.

PubMed

Danielson, Christian; Mehrnezhad, Ali; YekrangSafakar, Ashkan; Park, Kidong

2017-06-14

Self-folding or micro-origami technologies are actively investigated as a novel manufacturing process to fabricate three-dimensional macro/micro-structures. In this paper, we present a simple process to produce a self-folding structure with a biaxially oriented polystyrene sheet (BOPS) or Shrinky Dinks. A BOPS sheet is known to shrink to one-third of its original size in plane, when it is heated above 160 °C. A grid pattern is engraved on one side of the BOPS film with a laser engraver to decrease the thermal shrinkage of the engraved side. The thermal shrinkage of the non-engraved side remains the same and this unbalanced thermal shrinkage causes folding of the structure as the structure shrinks at high temperature. We investigated the self-folding mechanism and characterized how the grid geometry, the grid size, and the power of the laser engraver affect the bending curvature. The developed fabrication process to locally modulate thermomechanical properties of the material by engraving the grid pattern and the demonstrated design methodology to harness the unbalanced thermal shrinkage can be applied to develop complicated self-folding macro/micro structures.

An easily regenerable enzyme reactor prepared from polymerized high internal phase emulsions.

PubMed

Ruan, Guihua; Wu, Zhenwei; Huang, Yipeng; Wei, Meiping; Su, Rihui; Du, Fuyou

2016-04-22

A large-scale high-efficient enzyme reactor based on polymerized high internal phase emulsion monolith (polyHIPE) was prepared. First, a porous cross-linked polyHIPE monolith was prepared by in-situ thermal polymerization of a high internal phase emulsion containing styrene, divinylbenzene and polyglutaraldehyde. The enzyme of TPCK-Trypsin was then immobilized on the monolithic polyHIPE. The performance of the resultant enzyme reactor was assessed according to the conversion ability of Nα-benzoyl-l-arginine ethyl ester to Nα-benzoyl-l-arginine, and the protein digestibility of bovine serum albumin (BSA) and cytochrome (Cyt-C). The results showed that the prepared enzyme reactor exhibited high enzyme immobilization efficiency and fast and easy-control protein digestibility. BSA and Cyt-C could be digested in 10 min with sequence coverage of 59% and 78%, respectively. The peptides and residual protein could be easily rinsed out from reactor and the reactor could be regenerated easily with 4 M HCl without any structure destruction. Properties of multiple interconnected chambers with good permeability, fast digestion facility and easily reproducibility indicated that the polyHIPE enzyme reactor was a good selector potentially applied in proteomics and catalysis areas. Copyright © 2016 Elsevier Inc. All rights reserved.

Alkaline Hydrolysis/Polymerization of 2,4,6-Trinitrotoluene: Characterization of Products by 13C and 15N NMR

USGS Publications Warehouse

Thorn, K.A.; Thorne, P.G.; Cox, L.G.

2004-01-01

Alkaline hydrolysis has been investigated as a nonbiological procedure for the destruction of 2,4,6-trinitrotoluene (TNT) in explosives contaminated soils and munitions scrap. Nucleophilic substitutions of the nitro and methyl groups of TNT by hydroxide ion are the initial steps in the alkaline degradation of TNT. Potential applications of the technique include both in situ surface liming and ex situ alkaline treatment of contaminated soils. A number of laboratory studies have reported the formation of an uncharacterized polymeric material upon prolonged treatment of TNT in base. As part of an overall assessment of alkaline hydrolysis as a remediation technique, and to gain a better understanding of the chemical reactions underlying the hydrolysis/polymerization process, the soluble and precipitate fractions of polymeric material produced from the calcium hydroxide hydrolysis of unlabeled and 15N-labeled TNT were analyzed by elemental analysis and 13C and 15N nuclear magnetic resonance spectroscopy. Spectra indicated that reactions leading to polymerization included nucleophilic displacement of nitro groups by hydroxide ion, formation of ketone, carboxyl, alcohol, ether, and other aliphatic carbons, conversion of methyl groups to diphenyl methylene carbons, and recondensation of aromatic amines and reduced forms of nitrite, including ammonia and possibly hydroxylamine, into the polymer. Compared to the distribution of carbons in TNT as 14% sp 3- and 86% sp2-hybridized, the precipitate fraction from hydrolysis of unlabeled TNT contained 33% sp3- and 67% sp 2-hybridized carbons. The concentration of nitrogen in the precipitate was 64% of that in TNT. The 15N NMR spectra showed that, in addition to residual nitro groups, forms of nitrogen present in the filtrate and precipitate fractions include aminohydroquinone, primary amide, indole, imine, and azoxy, among others. Unreacted nitrite was recovered in the filtrate fraction. The toxicities and susceptibilities to microbial or chemical degradation of the polymeric materials remain unknown.

Alkaline hydrolysis/polymerization of 2,4,6-Trinitrotoluene:  Characterization of products by 13C and 15N NMR

USGS Publications Warehouse

Thorn, Kevin A.; Thorne, Philip G.; Cox, Larry G.

2004-01-01

Alkaline hydrolysis has been investigated as a nonbiological procedure for the destruction of 2,4,6-trinitrotoluene (TNT) in explosives contaminated soils and munitions scrap. Nucleophilic substitutions of the nitro and methyl groups of TNT by hydroxide ion are the initial steps in the alkaline degradation of TNT. Potential applications of the technique include both in situ surface liming and ex situ alkaline treatment of contaminated soils. A number of laboratory studies have reported the formation of an uncharacterized polymeric material upon prolonged treatment of TNT in base. As part of an overall assessment of alkaline hydrolysis as a remediation technique, and to gain a better understanding of the chemical reactions underlying the hydrolysis/polymerization process, the soluble and precipitate fractions of polymeric material produced from the calcium hydroxide hydrolysis of unlabeled and 15N-labeled TNT were analyzed by elemental analysis and 13C and 15N nuclear magnetic resonance spectroscopy. Spectra indicated that reactions leading to polymerization included nucleophilic displacement of nitro groups by hydroxide ion, formation of ketone, carboxyl, alcohol, ether, and other aliphatic carbons, conversion of methyl groups to diphenyl methylene carbons, and recondensation of aromatic amines and reduced forms of nitrite, including ammonia and possibly hydroxylamine, into the polymer. Compared to the distribution of carbons in TNT as 14% sp3- and 86% sp2-hybridized, the precipitate fraction from hydrolysis of unlabeled TNT contained 33% sp3- and 67% sp2-hybridized carbons. The concentration of nitrogen in the precipitate was 64% of that in TNT. The 15N NMR spectra showed that, in addition to residual nitro groups, forms of nitrogen present in the filtrate and precipitate fractions include aminohydroquinone, primary amide, indole, imine, and azoxy, among others. Unreacted nitrite was recovered in the filtrate fraction. The toxicities and susceptibilities to microbial or chemical degradation of the polymeric materials remain unknown.

Large Scale Laser Two-Photon Polymerization Structuring for Fabrication of Artificial Polymeric Scaffolds for Regenerative Medicine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malinauskas, M.; Purlys, V.; Zukauskas, A.

2010-11-10

We present a femtosecond Laser Two-Photon Polymerization (LTPP) system of large scale three-dimensional structuring for applications in tissue engineering. The direct laser writing system enables fabrication of artificial polymeric scaffolds over a large area (up to cm in lateral size) with sub-micrometer resolution which could find practical applications in biomedicine and surgery. Yb:KGW femtosecond laser oscillator (Pharos, Light Conversion. Co. Ltd.) is used as an irradiation source (75 fs, 515 nm (frequency doubled), 80 MHz). The sample is mounted on wide range linear motor driven stages having 10 nm sample positioning resolution (XY--ALS130-100, Z--ALS130-50, Aerotech, Inc.). These stages guarantee anmore » overall travelling range of 100 mm into X and Y directions and 50 mm in Z direction and support the linear scanning speed up to 300 mm/s. By moving the sample three-dimensionally the position of laser focus in the photopolymer is changed and one is able to write complex 3D (three-dimensional) structures. An illumination system and CMOS camera enables online process monitoring. Control of all equipment is automated via custom made computer software ''3D-Poli'' specially designed for LTPP applications. Structures can be imported from computer aided design STereoLihography (stl) files or programmed directly. It can be used for rapid LTPP structuring in various photopolymers (SZ2080, AKRE19, PEG-DA-258) which are known to be suitable for bio-applications. Microstructured scaffolds can be produced on different substrates like glass, plastic and metal. In this paper, we present microfabricated polymeric scaffolds over a large area and growing of adult rabbit myogenic stem cells on them. Obtained results show the polymeric scaffolds to be applicable for cell growth practice. It exhibit potential to use it for artificial pericardium in the experimental model in the future.« less

Large Scale Laser Two-Photon Polymerization Structuring for Fabrication of Artificial Polymeric Scaffolds for Regenerative Medicine

NASA Astrophysics Data System (ADS)

Malinauskas, M.; Purlys, V.; Žukauskas, A.; Rutkauskas, M.; Danilevičius, P.; Paipulas, D.; Bičkauskaitė, G.; Bukelskis, L.; Baltriukienė, D.; Širmenis, R.; Gaidukevičiutė, A.; Bukelskienė, V.; Gadonas, R.; Sirvydis, V.; Piskarskas, A.

2010-11-01

We present a femtosecond Laser Two-Photon Polymerization (LTPP) system of large scale three-dimensional structuring for applications in tissue engineering. The direct laser writing system enables fabrication of artificial polymeric scaffolds over a large area (up to cm in lateral size) with sub-micrometer resolution which could find practical applications in biomedicine and surgery. Yb:KGW femtosecond laser oscillator (Pharos, Light Conversion. Co. Ltd.) is used as an irradiation source (75 fs, 515 nm (frequency doubled), 80 MHz). The sample is mounted on wide range linear motor driven stages having 10 nm sample positioning resolution (XY—ALS130-100, Z—ALS130-50, Aerotech, Inc.). These stages guarantee an overall travelling range of 100 mm into X and Y directions and 50 mm in Z direction and support the linear scanning speed up to 300 mm/s. By moving the sample three-dimensionally the position of laser focus in the photopolymer is changed and one is able to write complex 3D (three-dimensional) structures. An illumination system and CMOS camera enables online process monitoring. Control of all equipment is automated via custom made computer software "3D-Poli" specially designed for LTPP applications. Structures can be imported from computer aided design STereoLihography (stl) files or programmed directly. It can be used for rapid LTPP structuring in various photopolymers (SZ2080, AKRE19, PEG-DA-258) which are known to be suitable for bio-applications. Microstructured scaffolds can be produced on different substrates like glass, plastic and metal. In this paper, we present microfabricated polymeric scaffolds over a large area and growing of adult rabbit myogenic stem cells on them. Obtained results show the polymeric scaffolds to be applicable for cell growth practice. It exhibit potential to use it for artificial pericardium in the experimental model in the future.

Advantages and drawbacks of Thiol-ene based resins for 3D-printing

NASA Astrophysics Data System (ADS)

Leonards, Holger; Engelhardt, Sascha; Hoffmann, Andreas; Pongratz, Ludwig; Schriever, Sascha; Bläsius, Jana; Wehner, Martin; Gillner, Arnold

2015-03-01

The technology of 3D printing is conquering the world and awakens the interest of many users in the most varying of applications. New formulation approaches for photo-sensitive thiol-ene resins in combination with various printing technologies, like stereolithography (SLA), projection based printing/digital light processing (DLP) or two-photon polymerization (TPP) are presented. Thiol-ene polymerizations are known for its fast and quantitative reaction and to form highly homogeneous polymer networks. As the resins are locally and temporally photo-curable the polymerization type is very promising for 3D-printing. By using suitable wavelengths, photoinitiator-free fabrication is feasible for single- and two photon induced polymerization. In this paper divinyl ethers of polyethylene glycols in combination with star-shaped tetrathiols were used to design a simple test-system for photo-curable thiol-ene resins. In order to control and improve curing depth and lateral resolution in 3D-polymerization processes, either additives in chemical formulation or process parameters can be changed. The achieved curing depth and resolution limits depend on the applied fabrication method. While two-/multiphoton induced lithography offers the possibility of micron- to sub-micron resolution it lacks in built-up speed. Hence single-photon polymerization is a fast alternative with optimization potential in sub-10-micron resolution. Absorber- and initiator free compositions were developed in order to avoid aging, yellowing and toxicity of resulting products. They can be cured with UV-laser radiation below 300 nm. The development at Fraunhofer ILT is focusing on new applications in the field of medical products and implants, technical products with respect to mechanical properties or optical properties of 3D-printed objects. Recent process results with model system (polyethylene glycol divinylether/ Pentaerithrytol tetrakis (3-mercaptopropionat), Raman measurements of polymer conversion and surface modifications using bifunctional crosslinkers are presented with advantages, drawbacks and a general outlook.

Polymerization kinetics of experimental bioactive composites containing bioactive glass.

PubMed

Par, Matej; Tarle, Zrinka; Hickel, Reinhard; Ilie, Nicoleta

2018-06-21

To investigate the polymerization kinetics and the degree of conversion (DC) of experimental resin composites with varying amount of bioactive glass 45S5 (BG). Experimental resin composites based on a photo-curable Bis-GMA/TEGDMA resin system were prepared. The composite series contained 0, 5, 10, 20, and 40 wt% of BG and reinforcing fillers up to the total filler amount of 70 wt%. Composite specimens were light cured with 1,219 mW/cm 2 for 20 or 40 s and their DC was monitored during 5 min at the data collection rate of 2 s -1 using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The 5-min DC values for experimental composites were in the range of 42.4-55.9% and 47.3-57.9% for curing times of 20 and 40 s, respectively. The differences in the 5-min DC between curing times of 20 s or 40 s became more pronounced in materials with higher BG amount. Within both curing times, a decreasing trend of the 5-min DC values was observed with the increasing percentage of BG fillers. The maximum polymerization rate also decreased consistently with the increasing BG amount. Unsilanized BG fillers showed a dose-dependent inhibitory effect on polymerization rate and the DC. Extending the curing time from 20 to 40 s showed a limited potential to improve the DC of composites with higher BG amount. The observed inhibitory effect of BG fillers on the polymerization of resin composites may have a negative influence on mechanical properties and biocompatibility. Copyright © 2018. Published by Elsevier Ltd.

Experimental and FE displacement and polymerization stress of bonded restorations as a function of the C-Factor, volume and substrate stiffness.

PubMed

Boaro, Letícia Cristina Cidreira; Brandt, William Cunha; Meira, Josete Barbosa Cruz; Rodrigues, Flávia Pires; Palin, William M; Braga, Roberto Ruggiero

2014-02-01

To determine the free surface displacement of resin-composite restorations as a function of the C-Factor, volume and substrate stiffness, and to compare the results with interfacial stress values evaluated by finite element analysis (FEA). Surface displacement was determined by an extensometer using restorations with 4 or 6mm diameter and 1 or 2mm depth, prepared in either bovine teeth or glass. The maximum displacement of the free surface was monitored for 5 min from the start of photoactivation, at an acquisition rate of 1s(-1). Axisymmetric cavity models were performed by FEA. Structural stiffness and maximum stresses were investigated. For glass, displacement showed a stronger correlation with volume (r=0.771) than with C-Factor (r=0.395, p<0.001 for both). For teeth, a stronger correlation was found with C-Factor (r=0.709; p<0.001) than with volume (r=0.546, p<0.001). For similar dimensions, stress and displacement were defined by stiffness. Simultaneous increases in volume and C-Factor led to increases in stress and surface displacement. Maximum stresses were located at the cavosurface angle, internal angle (glass) and at the dentine-enamel junction (teeth). The displacement of the restoration's free surface was related to interfacial stress development. Structural stiffness seems to affect the shrinkage stress at the tooth/resin-composite interface in bonded restorations. Deep restorations are always problematic because they showed high shear stress, regardless of their width. FEA is the only tool capable of detecting shear stress due to polymerization as there is still no reliable experimental alternative. Copyright © 2013 Elsevier Ltd. All rights reserved.

Manufacture of mold of polymeric composite water pipe reinforced charcoal

NASA Astrophysics Data System (ADS)

Zulfikar; Misdawati; Idris, M.; Nasution, F. K.; Harahap, U. N.; Simanjuntak, R. K.; Jufrizal; Pranoto, S.

2018-03-01

In general, household wastewater pipelines currently use thermoplastic pipes of Polyvinyl Chloride (PVC). This material is known to be not high heat resistant, contains hazardous chemicals (toxins), relatively inhospitable, and relatively more expensive. Therefore, researchers make innovations utilizing natural materials in the form of wood charcoal as the basic material of making the water pipe. Making this pipe requires a simple mold design that can be worked in the scale of household and intermediate industries. This research aims to produce water pipe mold with simple design, easy to do, and making time relatively short. Some considerations for molding materials are weight of mold, ease of raw material, strong, sturdy, and able to cast. Pipe molds are grouped into 4 (four) main parts, including: outer diameter pipe molding, pipe inside diameter, pipe holder, and pipe alignment control. Some materials have been tested as raw materials for outer diameter of pipes, such as wood, iron / steel, cement, and thermoset. The best results are obtained on thermoset material, where the process of disassembling is easier and the resulting mold weight is relatively lighter. For the inside diameter of the pipe is used stainless steel, because in addition to be resistant to chemical processes that occur, in this part of the mold must hold the press load due to shrinkage of raw materials of the pipe during the process of hardening (polymerization). Therefore, it needs high pressure resistant material and does not blend with the raw material of the pipe. The base of the mold is made of stainless steel material because it must be resistant to corrosion due to chemical processes. As for the adjustment of the pipe is made of ST 37 carbon steel, because its function is only as a regulator of the alignment of the pipe structure.

Dimensional accuracy of pickup implant impression: an in vitro comparison of novel modular versus standard custom trays.

PubMed

Simeone, Piero; Valentini, Pier Paolo; Pizzoferrato, Roberto; Scudieri, Folco

2011-01-01

The purpose of this in vitro study was to compare the dimensional accuracy of the pickup impression technique using a modular individual tray (MIT) and using a standard individual tray (ST) for multiple internal-connection implants. The roles of both materials and geometric misfits were considered. First, because the MIT relies on the stiffness and elasticity of acrylic resin material, a preliminary investigation of the resin volume contraction during curing and polymerization was done. Then, two sets of specimens were tested to compare the accuracy of the MIT (test group) to that of the ST (control group). The linear and angular displacements of the transfer copings were measured and compared during three different stages of the impression procedure. Experimental measurements were performed with a computerized coordinate measuring machine. The curing dynamic of the acrylic resin was strongly dependent on the physical properties of the acrylic material and the powder/liquid ratio. Specifically, an increase in the powder/liquid ratio accelerated resin polymerization (curing time decreases by 70%) and reduced the final volume contraction by 45%. However, the total shrinkage never exceeded the elastic limits of the material; hence, it did not affect the coping's stability. In the test group, linear errors were reduced by 55% and angular errors were reduced by 65%. Linear and angular displacements of the transfer copings were significantly reduced with the MIT technique, which led to higher dimensional accuracy versus the ST group. The MIT approach, in combination with a thin and uniform amount of acrylic resin in the pickup impression technique, showed no significant permanent distortions in multiple misalignment internal-connection implants compared to the ST technique.

Polymerization shrinkage and spherical glass mega fillers: effects on cuspal deflection

PubMed Central

BASSI, M. ANDREASI; SERRA, S.; ANDRISANI, C.; LICO, S.; BAGGI, L.; LAURITANO, D.

2016-01-01

SUMMARY Purpose The Authors analyzed the effect of spherical glass mega fillers (SGMF) on reducing contraction stress in dental composite resins, by means of a cavity model simulating the cuspal deflection which occurs on filled tooth cavity walls in clinical condition. Materials and methods 20 stylized MOD cavities (C-factor = 0.83) were performed in acrylic resin. The inner surface of each cavity was sand blasted and adhesively treated in order to ensure a valid bond with the composite resin. Three different diameter of SGMF were used (i.e. 1, 1,5, 2 mm). The samples were divided in 4 groups of 5 each: Group 1 samples filled with the composite only; Group 2 samples filled with composite added with SGMFs, Ø1mm (16 spheres for each sample); Group 3 samples filled with composite added with SGMFs, Ø1,5 mm (5 spheres for each sample); Group 4 samples filled with composite added with SGMFs, Ø2 mm (2 spheres for each sample). Digital pictures were taken, in standardized settings, before and immediately after the polymerization of the composite material, placed into the cavities. With a digital image analysis software the distances from the coronal reference points of the cavity walls were measured. Then the difference between the first and second measurement was calculated. The data were analyzed by means of the ANOVA test. Results A significative reduction on cavity walls deflection, when the composite resin is used in addiction with the SGMFs was observed. The SGMFs of smallest diameter (1mm) showed the better outcome. Conclusion The SGMFs are reliable in reducing contraction stress in dental composite resins. PMID:28280535

Minimum risk wavelet shrinkage operator for Poisson image denoising.

PubMed

Cheng, Wu; Hirakawa, Keigo

2015-05-01

The pixel values of images taken by an image sensor are said to be corrupted by Poisson noise. To date, multiscale Poisson image denoising techniques have processed Haar frame and wavelet coefficients--the modeling of coefficients is enabled by the Skellam distribution analysis. We extend these results by solving for shrinkage operators for Skellam that minimizes the risk functional in the multiscale Poisson image denoising setting. The minimum risk shrinkage operator of this kind effectively produces denoised wavelet coefficients with minimum attainable L2 error.

Thiophene dendrimer-based low donor content solar cells

NASA Astrophysics Data System (ADS)

Stoltzfus, Dani M.; Ma, Chang-Qi; Nagiri, Ravi C. R.; Clulow, Andrew J.; Bäuerle, Peter; Burn, Paul L.; Gentle, Ian R.; Meredith, Paul

2016-09-01

Low donor content solar cells containing polymeric and non-polymeric donors blended with fullerenes have been reported to give rise to efficient devices. In this letter, we report that a dendrimeric donor can also be used in solution-processed low donor content devices when blended with a fullerene. A third generation dendrimer containing 42 thiophene units (42T) was found to give power conversion efficiencies of up to 3.5% when blended with PC70BM in optimized devices. The best efficiency was measured with 10 mole percent (mol. %) of 42T in PC70BM and X-ray reflectometry showed that the blends were uniform. Importantly, while 42T comprised 10 mol. % of the film, it made up 31% of the film by volume. Finally, it was found that solvent annealing was required to achieve the largest open circuit voltage and highest device efficiencies.

Bismesitoylphosphinic Acid (BAPO-OH): A Ligand for Copper Complexes and Four-Electron Photoreductant for the Preparation of Copper Nanomaterials.

PubMed

Beil, Andreas; Müller, Georgina; Käser, Debora; Hattendorf, Bodo; Li, Zhongshu; Krumeich, Frank; Rosenthal, Amos; Rana, Vijay Kumar; Schönberg, Hartmut; Benkő, Zoltán; Grützmacher, Hansjörg

2018-05-16

Bismesitoylphosphinic acid, (HO)PO(COMes) 2 (BAPO-OH), is an efficient photoinitiator for free-radical polymerizations of olefins in aqueous phase. Described here are the structures of various copper(II) and copper(I) complexes with BAPO-OH as the ligand. The complex Cu II (BAPO-O) 2 (H 2 O) 2 is photoactive, and under irradiation with UV light in aqueous phase, it serves as a source of metallic copper in high purity and yield (>80 %). Simultaneously, the radical polymerization of acrylates can be initiated and allows the preparation of nanoparticle/polymer nanocomposites in which the metallic Cu nanoparticles are protected against oxidation. The determination of the stoichiometry of the photoreductions suggests an almost quantitative conversion from Cu II into Cu 0 with half an equivalent of BAPO-OH, which serves as a four-electron photoreductant. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arya, Anil; Sharma, Sweety; Sharma, A. L., E-mail: alsharmaiitkgp@gmail.com

Blend polymer electrolytes are prepared for salt concentration (Ö/Li = 4) with the constant ratio (0.5 gm) of PEO and PAN using solution casting technique. The prepared free standing solid polymeric film is characterized by Field Emission Scanning Electron Microscopy (FESEM) which confirms the homogeneous distribution of dissociated salt in blend polymer matrix. After addition of salt the ionic conductivity value is found to be of the order of 7.13 × 10{sup −5} Scm{sup −1} which is three orders higher when compared with pure blend polymer films. The microscopic interaction among the polymer-ion, ion-ion has been confirmed by the Fouriermore » Transform Infrared (FTIR) Spectroscopy. A very fine correlation has been built in the electrical conductivity and FTIR result. On the basis of above finding, a prepared free standing solid polymeric film appears to be appropriate for the energy storage/conversion device applications.« less

A facile molten-salt route to graphene synthesis.

PubMed

Liu, Xiaofeng; Giordano, Cristina; Antonietti, Markus

2014-01-15

Efficient synthetic routes are continuously pursued for graphene in order to implement its applications in different areas. However, direct conversion of simple monomers to graphene through polymerization in a scalable manner remains a major challenge for chemists. Herein, a molten-salt (MS) route for the synthesis of carbon nanostructures and graphene by controlled carbonization of glucose in molten metal chloride is reported. In this process, carbohydrate undergoes polymerization in the presence of strongly interacting ionic species, which leads to nanoporous carbon with amorphous nature and adjustable pore size. At a low precursor concentration, the process converts the sugar molecules (glucose) to rather pure few-layer graphenes. The MS-derived graphenes are strongly hydrophobic and exhibit remarkable selectivity and capacity for absorption of organics. The methodology described may open up a new avenue towards the synthesis and manipulation of carbon materials in liquid media. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequentially Programmable and Cellularly Selective Assembly of Fluorescent Polymerized Vesicles for Monitoring Cell Apoptosis

PubMed Central

Peng, Shu; Pan, Yu‐Chen; Wang, Yaling; Xu, Zhe; Chen, Chao

2017-01-01

Abstract The introduction of controlled self‐assembly into living organisms opens up desired biomedical applications in wide areas including bioimaging/assays, drug delivery, and tissue engineering. Besides the enzyme‐activated examples reported before, controlled self‐assembly under integrated stimuli, especially in the form of sequential input, is unprecedented and ultimately challenging. This study reports a programmable self‐assembling strategy in living cells under sequentially integrated control of both endogenous and exogenous stimuli. Fluorescent polymerized vesicles are constructed by using cholinesterase conversion followed by photopolymerization and thermochromism. Furthermore, as a proof‐of‐principle application, the cell apoptosis involved in the overexpression of cholinesterase in virtue of the generated fluorescence is monitored, showing potential in screening apoptosis‐inducing drugs. The approach exhibits multiple advantages for bioimaging in living cells, including specificity to cholinesterase, red emission, wash free, high signal‐to‐noise ratio. PMID:29201625

Sequentially Programmable and Cellularly Selective Assembly of Fluorescent Polymerized Vesicles for Monitoring Cell Apoptosis.

PubMed

Peng, Shu; Pan, Yu-Chen; Wang, Yaling; Xu, Zhe; Chen, Chao; Ding, Dan; Wang, Yongjian; Guo, Dong-Sheng

2017-11-01

The introduction of controlled self-assembly into living organisms opens up desired biomedical applications in wide areas including bioimaging/assays, drug delivery, and tissue engineering. Besides the enzyme-activated examples reported before, controlled self-assembly under integrated stimuli, especially in the form of sequential input, is unprecedented and ultimately challenging. This study reports a programmable self-assembling strategy in living cells under sequentially integrated control of both endogenous and exogenous stimuli. Fluorescent polymerized vesicles are constructed by using cholinesterase conversion followed by photopolymerization and thermochromism. Furthermore, as a proof-of-principle application, the cell apoptosis involved in the overexpression of cholinesterase in virtue of the generated fluorescence is monitored, showing potential in screening apoptosis-inducing drugs. The approach exhibits multiple advantages for bioimaging in living cells, including specificity to cholinesterase, red emission, wash free, high signal-to-noise ratio.

New core-pyrene π structure organophotocatalysts usable as highly efficient photoinitiators

PubMed Central

Telitel, Sofia; Dumur, Frédéric; Faury, Thomas; Graff, Bernadette; Tehfe, Mohamad-Ali; Fouassier, Jean-Pierre

2013-01-01

Summary Eleven di- and trifunctional compounds based on a core-pyrene π structure (Co_Py) were synthesized and investigated for the formation of free radicals. The application of two- and three-component photoinitiating systems (different Co_Pys with the addition of iodonium or sulfonium salts, alkyl halide or amine) was investigated in detail for cationic and radical photopolymerization reactions under near-UV–vis light. The proposed compounds can behave as new photocatalysts. Successful results in terms of rates of polymerization and final conversions were obtained. The strong MO coupling between the six different cores and the pyrene moiety was studied by DFT calculations. The different chemical intermediates are characterized by ESR and laser flash photolysis experiments. The mechanisms involved in the initiation step are discussed, and relationships between the core structure, the Co_Py absorption property, and the polymerization ability are tentatively proposed. PMID:23766803

Ab-Initio-Based Kinetic Modeling to Understand RAFT Exchange: The Case of 2-Cyano-2-Propyl Dodecyl Trithiocarbonate and Styrene.

PubMed

Desmet, Gilles B; De Rybel, Nils; Van Steenberge, Paul H M; D'hooge, Dagmar R; Reyniers, Marie-Françoise; Marin, Guy B

2018-01-01

Ab-initio-calculated rate coefficients for addition and fragmentation in reversible-addition fragmentation chain transfer (RAFT) polymerization of styrene with 2-cyano-2-propyl dodecyl trithiocarbonate initiated by azobisisobutyronitrile allow the reliable simulation of the experimentally observed conversion, number average chain length, and dispersity. The rate coefficient for addition of a macroradical R i to the macroRAFT agent R i X at 333 K (6.8 10 4 L mol -1 s -1 ) is significantly lower than to the initial RAFT agent R 0 X (3.2 10 6 L mol -1 s -1 ), mainly due to a difference in activation energy (15.4 vs 3.0 kJ mol -1 ), which causes the dispersity to spike in the beginning of the polymerization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polyethylenimine-immobilized core-shell nanoparticles: synthesis, characterization, and biocompatibility test.

PubMed

Ratanajanchai, Montri; Soodvilai, Sunhapas; Pimpha, Nuttaporn; Sunintaboon, Panya

2014-01-01

Herein, we prepared PEI-immobilized core-shell particles possessing various types of polymer cores via a visible light-induced surfactant-free emulsion polymerization (SFEP) of three vinyl monomers: styrene (St), methyl methacrylate (MMA), and 2-hydroxyethyl methacrylate (HEMA). An effect of monomers on the polymerization and characteristics of resulting products was investigated. Monomers with high polarity can provide high monomer conversion, high percentage of grafted PEI, stable particles with uniform size distribution but less amino groups per particles. All prepared nanoparticles exhibited a core-shell nanostructure, containing PEI on the shell with hydrodynamic size around 140-230nm. For in-vitro study in Caco-2 cells, we found that the incorporation of PEI into these core-shell nanoparticles can significantly reduce its cytotoxic effect and also be able to internalized within the cells. Accordingly, these biocompatible particles would be useful for various biomedical applications, including gene transfection and intracellular drug delivery. © 2013.

Improved electron transfer and plasmonic effect in dye-sensitized solar cells with bi-functional Nb-doped TiO2/Ag ternary nanostructures.

PubMed

Park, Jung Tae; Chi, Won Seok; Jeon, Harim; Kim, Jong Hak

2014-03-07

TiO2 nanoparticles are surface-modified via atom transfer radical polymerization (ATRP) with a hydrophilic poly(oxyethylene)methacrylate (POEM), which can coordinate to the Ag precursor, i.e. silver trifluoromethanesulfonate (AgCF3SO3). Following the reduction of Ag ions, a Nb2O5 doping process and calcination at 450 °C, bi-functional Nb-doped TiO2/Ag ternary nanostructures are generated. The resulting nanostructures are characterized by energy-filtering transmission electron microscopy (EF-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. The dye-sensitized solar cell (DSSC) based on the Nb-doped TiO2/Ag nanostructure photoanode with a polymerized ionic liquid (PIL) as the solid polymer electrolyte shows an overall energy conversion efficiency (η) of 6.9%, which is much higher than those of neat TiO2 (4.7%) and Nb-doped TiO2 (5.4%). The enhancement of η is mostly due to the increase of current density, attributed to the improved electron transfer properties including electron injection, collection, and plasmonic effects without the negative effects of charge recombination or problems with corrosion. These properties are supported by intensity modulated photocurrent/voltage spectroscopy (IMPS/IMVS) and incident photon-to-electron conversion efficiency (IPCE) measurements.