Effects of surface roughness, texture and polymer degradation on cathodic delamination of epoxy coated steel samples

International Nuclear Information System (INIS)

Khun, N.W.; Frankel, G.S.

2013-01-01

Highlights: ► Cathodic delamination of epoxy coated steel samples was studied using SKP. ► Delamination of the coating decreased with increased substrate surface roughness. ► Delamination of the coating was faster on the substrate with parallel surface scratches. ► Delamination of the coating exposed to weathering conditions increased with prolonged exposure. - Abstract: The Scanning Kelvin Probe (SKP) technique was used to investigate the effects of surface roughness, texture and polymer degradation on cathodic delamination of epoxy coated steel. The cathodic delamination rate of the epoxy coatings dramatically decreased with increased surface roughness of the underlying steel substrate. The surface texture of the steel substrates also had a significant effect in that samples with parallel abrasion lines exhibiting faster cathodic delamination in the direction of the lines compared to the direction perpendicular to the lines. The cathodic delamination kinetics of epoxy coatings previously exposed to weathering conditions increased with prolonged exposure due to pronounced polymer degradation. SEM observation confirmed that the cyclic exposure to UV radiation and water condensation caused severe deterioration in the polymer structures with surface cracking and erosion. The SKP results clearly showed that the cathodic delamination of the epoxy coatings was significantly influenced by the surface features of the underlying steel substrates and the degradation of the coatings.

Thermal degradation of CR-39 polymer in an inert atmosphere

International Nuclear Information System (INIS)

Kalsi, P.C.; Pandey, A.K.; Iyer, R.H.; Singh Mudher, K.D.

1995-01-01

The thermal degradation of CR-39 (allyl diglycol carbonate), a polymer widely used in nuclear science and technology, in an inert atmosphere has been studied using thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques. The results are compared with the thermal degradation data of the polymer in an air atmosphere. The present studies showed that the thermal degradation of the polymer proceeds in two steps in an argon atmosphere as compared to three steps in air atmosphere. The mass losses in air are higher than that in argon due to the oxidative decomposition of the residue. The kinetics of the different stages of degradation were also evaluated from the TG curves. (author). 7 refs., 1 tab

Development of Bioorthogonally Degradable Linkers and Polymers Using alpha-Azidoethers

Science.gov (United States)

Rajagopalan, Chandrasekhar Ramasubramanian

Degradable polymers have gained a lot of attention in recent years for applications in biotechnology and medicine. External control over polymer degradation can be obtained by incorporating functional groups that cleave in the presence of triggers that would normally be absent in biological environments, i.e. are bioorthogonal. This thesis explores the use of chemically cleavable alpha-azidoethers as a new method to obtain external control over the degradation behavior of polymers. My first goal is to illustrate the potential of alpha-azidoethers toward developing cleavable linkers. We have studied the relationship between alpha-azidoether structure and hydrolytic stability, to prepare linkers that withstand background hydrolytic cleavage until they are exposed to the cleaving trigger. The cleavage kinetics of the alpha-azidoether functional group was quantified. In addition to the conventionally used tris(2-carboxyethyl)phosphine (TCEP), dihydrolipoic acid (DHLA), a previously unexplored, biocompatible reducing agent, was also evaluated as a cleaving trigger. Based on these results, we have proposed design rules for utilizing alpha-azidoethers as cleavable linkers in applications that require bioorthogonal control over linker cleavage. Secondly, the alpha-azidoether cleavable linker chemistry was implemented into the development of polymeric materials. Two different types of polymers were developed. Polyamides incorporating alpha-azidoethers along the backbone were synthesized, and their physical properties and chemically triggered degradation behavior were characterized. The degradation timescale of these polymers can be tuned simply by manipulating the concentration of the externally applied chemical trigger. The alpha-azidoether functional group was then utilized to develop a unique triggered-release polymeric adhesive for potential applications in dental adhesive formulations. A methacrylamide-phosphonate adhesive monomer incorporating an alpha

Determination of Polymers Thermal Degradation by Color Change Analysis

Directory of Open Access Journals (Sweden)

Andrés Felipe Rojas González

2016-01-01

Full Text Available Context: It has been observed that thermal degradation of thermoplastic polymers, when they are reprocessed by injection, extrusion and extrusion / injection, undergo color changes in the product, although it not has been established as this change occurs. Method: It analyzed the effect on thermal degradation caused by polymer type, processing type, polymer grade, rotation speed of the extrusion screw and number of reprocessing, which is quantified by the color change using an empirical equation, with experimental data obtained by analysis through a microcolor colorimeter. Results: It was found that the color change analysis provides information about progress of the thermal degradation and stability of thermoplastic polymers, which are undergoing to multiple reprocessing events and processes. Conclusions: It was established that this technique can be implemented as a simple and efficient measure of thermoplastic products quality control, according to their color change.

Application of controlled radiation-induced degradation in polymers: less exploited aspect of radiation processing of polymers

International Nuclear Information System (INIS)

Haji Saeid, M.; Guven, O.

2007-01-01

Industrial use of ionizing radiation treatment has been most successful in applications related to polymeric materials. The polymer, plastics and rubber industries have benefited from the unique advantages of ionizing radiation since its inception as an industrial tool to modify their properties and manufacture novel materials with value addition to the end product. The established and emerging applications of electron beam processing of polymers are based on the well known ultimate effects of ionizing radiation on polymers namely, crosslinking, curing, grafting and chain scissioning. Radiation-induced crosslinking dominates most applications, whereas the chain scissioning effect is much less explored and currently limited to radiation-induced degradation of Teflon, cellulose and polypropylene. The controlling of radiation-induced degradation for achieving a target average molecular weight or distribution has been evaluated for some polysaccharides, biopolymers and waste inner tubes whereas mitigation of the degradative effects of radiation has been analyzed from the point of view of using certain stabilizers, copolymers and annealing at an appropriate temperature. Several new or highly specialized techniques such as positron annihilation lifetime spectroscopy. Rutherford backscattering, elastic recoil detection analysis and solid waste NMR spectroscopy and gas chromatography-mass spectroscopy have been applied to the study or radiation-induced degradation. New information has been collected on the morphological changes associated with radiation-induced degradation processes, including chain scission, oxidation and free volume alteration. The IAEA coordinated research project (CRP) on Controlling of Degradation Effects in Radiation Processing of Polymers dealt with the role and importance of using ionizing radiation in controlling properties of natural and synthetic polymers through its degradative effect. This paper provides a summary of most important results

Mechanisms of polymer degradation using an oxygen plasma generator

Science.gov (United States)

Colony, Joe A.; Sanford, Edward L.

1987-01-01

An RF oxygen plasma generator was used to produce polymer degradation which appears to be similar to that which has been observed in low Earth orbit. Mechanisms of this type of degradation were studied by collecting the reaction products in a cryogenic trap and identifying the molecular species using infrared, mass spectral, and X-ray diffraction techniques. No structurally dependent species were found from Kapton, Teflon, or Saran polymers. However, very reactive free radical entities are produced during the polymer degradation, as well as carbon dioxide and water. Reactions of the free radicals with the glass reaction vessel, with copper metal in the cold trap, and with a triphenyl phosphate scavenger in the cold trap, demonstrated the reactivity of the primary products.

ANTI-BIOFOULING BY DEGRADATION OF POLYMERS

Institute of Scientific and Technical Information of China (English)

Chun-feng Ma; Hong-jun Yang; Guang-zhao Zhang

2012-01-01

Copolymers of methyl methacrylate (MMA) and acrylate terminated poly(ethylene oxide-co-ethylene carbonate)(PEOC) macromonomer (PEOCA) were synthesized,and the degradation of the polymers was investigated by use of quartz crystal microbalance with dissipation (QCM-D).It is shown that the polymeric surface exhibits degradation in seawater depending on the content of the side chains.Field tests in seawater show that the surface constructed by the copolymer can effectively inhibit marine biofouling because it can be self-renewed due to degradation of the copolymer.

The biochemistry and molecular biology of xenobiotic polymer degradation by microorganisms.

Science.gov (United States)

Kawai, Fusako

2010-01-01

Research on microbial degradation of xenobiotic polymers has been underway for more than 40 years. It has exploited a new field not only in applied microbiology but also in environmental microbiology, and has greatly contributed to polymer science by initiating the design of biodegradable polymers. Owing to the development of analytical tools and technology, molecular biological and biochemical advances have made it possible to prospect for degrading microorganisms in the environment and to determine the mechanisms involved in biodegradation when xenobiotic polymers are introduced into the environment and are exposed to microbial attack. In this review, the molecular biological and biochemical aspects of the microbial degradation of xenobiotic polymers are summarized, and possible applications of potent microorganisms, enzymes, and genes in environmental biotechnology are suggested.

Polymer degradation rate control of hybrid rocket combustion

Science.gov (United States)

Stickler, D. B.; Ramohalli, K. N. R.

1970-01-01

Polymer degradation to small fragments is treated as a rate controlling step in hybrid rocket combustion. Both numerical and approximate analytical solutions of the complete energy and polymer chain bond conservation equations for the condensed phase are obtained. Comparison with inert atmosphere data is very good. It is found that the intersect of curves of pyrolysis rate versus interface temperature for hybrid combustors, with the thermal degradation theory, falls at a pyrolysis rate very close to that for which a pressure dependence begins to be observable. Since simple thermal degradation cannot give sufficient depolymerization at higher pyrolysis rates, it is suggested that oxidative catalysis of the process occurs at the surface, giving a first order dependence on reactive species concentration at the wall. Estimates of the ratio of this activation energy and interface temperature are in agreement with best fit procedures for hybrid combustion data. Requisite active species concentrations and flux are shown to be compatible with turbulent transport. Pressure dependence of hybrid rocket fuel regression rate is thus shown to be describable in a consistent manner in terms of reactive species catalysis of polymer degradation.

Thermal Degradation of Lead Monoxide Filled Polymer Composite Radiation Shields

International Nuclear Information System (INIS)

Harish, V.; Nagaiah, N.

2011-01-01

Lead monoxide filled Isophthalate resin particulate polymer composites were prepared with different filler concentrations and investigated for physical, thermal, mechanical and gamma radiation shielding characteristics. This paper discusses about the thermo gravimetric analysis of the composites done to understand their thermal properties especially the effect of filler concentration on the thermal stability and degradation rate of composites. Pristine polymer exhibits single stage degradation whereas filled composites exhibit two stage degradation processes. Further, the IDT values as well as degradation rates decrease with the increased filler content in the composite.

Thermal Degradation and Identification of Heat-Sensitive Polymers

Science.gov (United States)

Clough, Stuart C.; Goldman, Emma W.

2005-01-01

A study demonstrates the thermal degradation of two heat-sensitive polymers, namely, polystyrene and poly (methyl methacrylate). The experiment described in the study introduces undergraduate students to polymer structure as well as the application of spectroscopic techniques to the solution of structural problems.

Controlling of degradation effects in radiation processing of polymers. Second RCM report

International Nuclear Information System (INIS)

2005-08-01

The research and development works carried out by the participants of the CRP (Coordinated Research Project) dealt with natural polymers, synthetic polymers and new techniques for better understanding of radiation degradation of polymers. It includes progress in radiation degradation of polysaccharides from agricultural products (including sodium alginate, carrageenans, chitosan and gum acacia); use of radiation-degradation for doping of conductive polymers; controlling degradation processes in artificial joint implants, surface treatment of materials and food packaging; stabilizer additives for radiation environments; surface treatment of materials; and application of specialized analytical techniques (positron annihilation spectroscopy, ESR, RBS, ERDA, NMR/isotopic-labeling) to gain improved understanding of radiation degradation effects and mechanisms. Projects within the RCM group span the spectrum from fundamental studies through specific technological applications. Participants from Czech Republic, Spain and Turkey benefited from scientific collaboration with Bulgaria on PAS

Kinetics and mechanism of thermal degradation of pentose- and hexose-based carbohydrate polymers.

Science.gov (United States)

Akbar, Jamshed; Iqbal, Mohammad S; Massey, Shazma; Masih, Rashid

2012-10-15

This work aims at study of thermal degradation kinetics and mechanism of pentose- and hexose-based carbohydrate polymers isolated from Plantago ovata (PO), Salvia aegyptiaca (SA) and Ocimum basilicum (OB). The analysis was performed by isoconversional method. The materials exhibited mainly two-stage degradation. The weight loss at ambient-115°C characterized by low activation energy corresponds to loss of moisture. The kinetic triplets consisting of E, A and g(α) model of the materials were determined. The major degradation stage represents a loss of high boiling volatile components. This stage is exothermic in nature. Above 340°C complete degradation takes place leaving a residue of 10-15%. The master plots of g(α) function clearly differentiated the degradation mechanism of hexose-based OB and SA polymers and pentose-based PO polymer. The pentose-based carbohydrate polymer showed D(4) type and the hexose-based polymers showed A(4) type degradation mechanism. Copyright © 2012 Elsevier Ltd. All rights reserved.

Probing cell internalisation mechanics with polymer capsules.

Science.gov (United States)

Chen, Xi; Cui, Jiwei; Ping, Yuan; Suma, Tomoya; Cavalieri, Francesca; Besford, Quinn A; Chen, George; Braunger, Julia A; Caruso, Frank

2016-10-06

We report polymer capsule-based probes for quantifying the pressure exerted by cells during capsule internalisation (P in ). Poly(methacrylic acid) (PMA) capsules with tuneable mechanical properties were fabricated through layer-by-layer assembly. The P in was quantified by correlating the cell-induced deformation with the ex situ osmotically induced deformation of the polymer capsules. Ultimately, we found that human monocyte-derived macrophage THP-1 cells exerted up to approximately 360 kPa on the capsules during internalisation.

Photo-degradation of high efficiency fullerene-free polymer solar cells.

Science.gov (United States)

Upama, Mushfika Baishakhi; Wright, Matthew; Mahmud, Md Arafat; Elumalai, Naveen Kumar; Mahboubi Soufiani, Arman; Wang, Dian; Xu, Cheng; Uddin, Ashraf

2017-12-07

Polymer solar cells are a promising technology for the commercialization of low cost, large scale organic solar cells. With the evolution of high efficiency (>13%) non-fullerene polymer solar cells, the stability of the cells has become a crucial parameter to be considered. Among the several degradation mechanisms of polymer solar cells, burn-in photo-degradation is relatively less studied. Herein, we present the first systematic study of photo-degradation of novel PBDB-T:ITIC fullerene-free polymer solar cells. The thermally treated and as-prepared PBDB-T:ITIC solar cells were exposed to continuous 1 sun illumination for 5 hours. The aged devices exhibited rapid losses in the short-circuit current density and fill factor. The severe short-circuit current and fill factor burn in losses were attributed to trap mediated charge recombination, as evidenced by an increase in Urbach energy for aged devices.

Radiation degradation of α-substituted acrylate polymers and copolymers

International Nuclear Information System (INIS)

Helbert, J.N.; Caplan, P.J.; Poindexter, E.H.

1977-01-01

Radiation degradation is observed in poly(methyl α-chloroacrylate), poly(methyl α-cyanoacrylate), and poly (α-chloroacrylonitrile) homopolymers and their respective MMA copolymers when γ-irradiated in vacuo. Polymer degradation susceptibilities are quantified in terms of G(scission radicals) and G(scission) -- G(crosslinks), measured by EPR and membrane osmometry, respectively; values by these two methods are compared. Higher G(rads) values ranging from 2 to 6 and [G(s) -- G(x)] values ranging from 2 to 11 are obtained for the substituted polymers and copolymers relative to the values for PMMA (1.6; 1.9), a standard e-beam positive resist, which suggests that these modified polymers are more sensitive e-beam resists than PMMA

Main chain acid-degradable polymers for the delivery of bioactive materials

Science.gov (United States)

Frechet, Jean M. J. [Oakland, CA; Standley, Stephany M [Evanston, IL; Jain, Rachna [Milpitas, CA; Lee, Cameron C [Cambridge, MA

2012-03-20

Novel main chain acid degradable polymer backbones and drug delivery systems comprised of materials capable of delivering bioactive materials to cells for use as vaccines or other therapeutic agents are described. The polymers are synthesized using monomers that contain acid-degradable linkages cleavable under mild acidic conditions. The main chain of the resulting polymers readily degrade into many small molecules at low pH, but remain relatively stable and intact at physiological pH. The new materials have the common characteristic of being able to degrade by acid hydrolysis under conditions commonly found within the endosomal or lysosomal compartments of cells thereby releasing their payload within the cell. The materials can also be used for the delivery of therapeutics to the acidic regions of tumors and other sites of inflammation.

A model for hydrolytic degradation and erosion of biodegradable polymers.

Science.gov (United States)

Sevim, Kevser; Pan, Jingzhe

2018-01-15

For aliphatic polyesters such as PLAs and PGAs, there is a strong interplay between the hydrolytic degradation and erosion - degradation leads to a critically low molecular weight at which erosion starts. This paper considers the underlying physical and chemical processes of hydrolytic degradation and erosion. Several kinetic mechanisms are incorporated into a mathematical model in an attempt to explain different behaviours of mass loss observed in experiments. In the combined model, autocatalytic hydrolysis, oligomer production and their diffusion are considered together with surface and interior erosion using a set of differential equations and Monte Carlo technique. Oligomer and drug diffusion are modelled using Fick's law with the diffusion coefficients dependent on porosity. The porosity is due to the formation of cavities which are a result of polymer erosion. The model can follow mass loss and drug release up to 100%, which cannot be explained using a simple reaction-diffusion. The model is applied to two case studies from the literature to demonstrate its validity. The case studies show that a critical molecular weight for the onset of polymer erosion and an incubation period for the polymer dissolution are two critical factors that need to be considered when predicting mass loss and drug release. In order to design bioresorbable implants, it is important to have a mathematical model to predict polymer degradation and corresponding drug release. However, very different behaviours of polymer degradation have been observed and there is no single model that can capture all these behaviours. For the first time, the model presented in this paper is capable of capture all these observed behaviours by switching on and off different underlying mechanisms. Unlike the existing reaction-diffusion models, the model presented here can follow the degradation and drug release all the way to the full disappearance of an implant. Crown Copyright © 2017. Published by

EPR spin probe and spin label studies of some low molecular and polymer micelles

Science.gov (United States)

Wasserman, A. M.; Kasaikin, V. A.; Timofeev, V. P.

1998-12-01

The rotational mobility of spin probes of different shape and size in low molecular and polymer micelles has been studied. Several probes having nitroxide fragment localized either in the vicinity of micelle interface or in the hydrocarbon core have been used. Upon increasing the number of carbon atoms in hydrocarbon chain of detergent from 7 to 13 (sodium alkyl sulfate micelles) or from 12 to 16 (alkyltrimethylammonium bromide micelles) the rotational mobility of spin probes is decreased by the factor 1.5-2.0. The spin probe rotational mobility in polymer micelles (the complexes of alkyltrimethylammonium bromides and polymethacrylic or polyacrylic acids) is less than mobility in free micelles of the same surfactants. The study of EPR-spectra of spin labeled polymethacrylic acid (PMA) indicated that formation of water soluble complexes of polymer and alkyltrimethylammonium bromides in alkaline solutions (pH 9) does not affect the polymer segmental mobility. On the other hand, the polymer complexes formation in slightly acidic water solution (pH 6) breaks down the compact PMA conformation, thus increasing the polymer segmental mobility. Possible structures of polymer micelles are discussed.

Spin Transfer in Polymer Degradation of Abnormal Linkage

Science.gov (United States)

Yu, Tianrong; Tian, Chuanjin; Liu, Xizhe; Wang, Jia; Gao, Yang; Wang, Zhigang

2017-07-01

The degradation of polymer materials plays an important role in production and life. In this work, the degradation mechanism of poly-α-methylstyrene (PAMS) tetramers with abnormal linkage was investigated by using density functional theory (DFT). Calculated results indicate that the head-to-head and the tail-to-tail reactions needed to overcome the energy barriers are about 0.15 eV and about 1.26 eV, respectively. The broken C-C bond at the unsaturated end of the chain leads to the dissociation of alpha-methylstyrene (AMS) monomers one by one. Furthermore, the analyses of bond characteristics are in good agreement with the results of energy barriers. In addition, the spin population analysis presents an interesting net spin transfer process in depolymerization reactions. We hope that the current theoretical results provide useful help to understand the degradation mechanism of polymers.

Localized Enzymatic Degradation of Polymers: Physics and Scaling Laws

Science.gov (United States)

Lalitha Sridhar, Shankar; Vernerey, Franck

2018-03-01

Biodegradable polymers are naturally abundant in living matter and have led to great advances in controlling environmental pollution due to synthetic polymer products, harnessing renewable energy from biofuels, and in the field of biomedicine. One of the most prevalent mechanisms of biodegradation involves enzyme-catalyzed depolymerization by biological agents. Despite numerous studies dedicated to understanding polymer biodegradation in different environments, a simple model that predicts the macroscopic behavior (mass and structural loss) in terms of microphysical processes (enzyme transport and reaction) is lacking. An interesting phenomenon occurs when an enzyme source (released by a biological agent) attacks a tight polymer mesh that restricts free diffusion. A fuzzy interface separating the intact and fully degraded polymer propagates away from the source and into the polymer as the enzymes diffuse and react in time. Understanding the characteristics of this interface will provide crucial insight into the biodegradation process and potential ways to precisely control it. In this work, we present a centrosymmetric model of biodegradation by characterizing the moving fuzzy interface in terms of its speed and width. The model predicts that the characteristics of this interface are governed by two time scales, namely the polymer degradation and enzyme transport times, which in turn depend on four main polymer and enzyme properties. A key finding of this work is simple scaling laws that can be used to guide biodegradation of polymers in different applications.

Evaluating polymer degradation with complex mixtures using a simplified surface area method.

Science.gov (United States)

Steele, Kandace M; Pelham, Todd; Phalen, Robert N

2017-09-01

Chemical-resistant gloves, designed to protect workers from chemical hazards, are made from a variety of polymer materials such as plastic, rubber, and synthetic rubber. One material does not provide protection against all chemicals, thus proper polymer selection is critical. Standardized testing, such as chemical degradation tests, are used to aid in the selection process. The current methods of degradation ratings based on changes in weight or tensile properties can be expensive and data often do not exist for complex chemical mixtures. There are hundreds of thousands of chemical products on the market that do not have chemical resistance data for polymer selection. The method described in this study provides an inexpensive alternative to gravimetric analysis. This method uses surface area change to evaluate degradation of a polymer material. Degradation tests for 5 polymer types against 50 complex mixtures were conducted using both gravimetric and surface area methods. The percent change data were compared between the two methods. The resulting regression line was y = 0.48x + 0.019, in units of percent, and the Pearson correlation coefficient was r = 0.9537 (p ≤ 0.05), which indicated a strong correlation between percent weight change and percent surface area change. On average, the percent change for surface area was about half that of the weight change. Using this information, an equivalent rating system was developed for determining the chemical degradation of polymer gloves using surface area.

Concentrated Light for Accelerated Photo Degradation of Polymer Materials

DEFF Research Database (Denmark)

Madsen, Morten Vesterager; Tromholt, Thomas; Norrman, Kion

2013-01-01

Concentrated light is used to perform photochemical degradation of polymer solar cell materials with acceleration factors up to 1200. At constant temperature the photon efficiency in regards to photo degradation is constant for 1–150 suns and oxygen diffusion rates are not a limiting factor...

Stability and Degradation of Organic and Polymer Solar Cells

DEFF Research Database (Denmark)

Organic photovoltaics (OPV) are a new generation of solar cells with the potential to offer very short energy pay back times, mechanical flexibility and significantly lower production costs compared to traditional crystalline photovoltaic systems. A weakness of OPV is their comparative instability...... during operation and this is a critical area of research towards the successful development and commercialization of these 3rd generation solar cells. Covering both small molecule and polymer solar cells, Stability and Degradation of Organic and Polymer Solar Cells summarizes the state of the art...... understanding of stability and provides a detailed analysis of the mechanisms by which degradation occurs. Following an introductory chapter which compares different photovoltaic technologies, the book focuses on OPV degradation, discussing the origin and characterization of the instability and describing...

Spatial degradation mapping and componentwise degradation tracking in polymer-fullerene blends

DEFF Research Database (Denmark)

Pedersen, Emil Bøje Lind; Tromholt, Thomas; Madsen, Morten Vesterager

2014-01-01

Using X-ray absorption the effects of photodegradation in active layer materials for polymer solar cells are investigated. Through the observation of changes in the X-ray absorption energy spectra the degradation of the individual components is tracked in blends of poly-3-hexyl-thiophene (P3HT) a...

Effects of frequency and a radical scavenger on ultrasonic degradation of water-soluble polymers.

Science.gov (United States)

Koda, Shinobu; Taguchi, Kimihiko; Futamura, Kazunori

2011-01-01

Ultrasonic degradation of methyl cellulose, pullulan, dextran and poly(ethylene oxide) in aqueous solutions was investigated at the frequencies of 20 and 500 kHz, where the ultrasonic power delivered into solutions was kept constant (22 W). The number average molecular mass and the polydispersity were obtained as a function of sonication time. The degradation under sonication at the 500 kHz frequency proceeded faster in comparison with the 20 kHz sonication for four polymers. The addition of a radical scavenger, t-BuOH, resulted in suppression of degradation of water-soluble polymers. The degradation rate constants were estimated from the plot of molecular weight against sonication time. The degradation rate of methyl cellulose was the largest one among the investigated polymers. The difference in the degradation rates was discussed in terms of the flexibility and the hydrodynamic radius of polymer chains in aqueous solutions. Copyright © 2010 Elsevier B.V. All rights reserved.

Stability and Degradation of Polymer Solar cells

DEFF Research Database (Denmark)

Norrman, Kion

The current state-of-the-art allows for roll-to-roll manufacture of polymer solar cells in high volume with stability and efficiency sufficient to grant success in low-energy applications. However, further improvement is needed for the successful application of the devices in real life applications....... This is obtained by detailed knowledge of the degradation mechanisms. Methods to compare and standardize device stability are urgently needed. Methodologies to study failure mechanism that are based on physical processes (e.g. morphological changes) are well-established. However, methodologies to study chemical...... degradation mechanisms are currently scarce. An overview of known degradation mechanisms will be presented and discussed in relation to state-of-the-art methodologies to study failure mechanisms with focus on chemical degradation....

Monitoring of the Enzymatically Catalyzed Degradation of Biodegradable Polymers by Means of Capacitive Field-Effect Sensors.

Science.gov (United States)

Schusser, Sebastian; Krischer, Maximilian; Bäcker, Matthias; Poghossian, Arshak; Wagner, Patrick; Schöning, Michael J

2015-07-07

Designing novel or optimizing existing biodegradable polymers for biomedical applications requires numerous tests on the effect of substances on the degradation process. In the present work, polymer-modified electrolyte-insulator-semiconductor (PMEIS) sensors have been applied for monitoring an enzymatically catalyzed degradation of polymers for the first time. The thin films of biodegradable polymer poly(D,L-lactic acid) and enzyme lipase were used as a model system. During degradation, the sensors were read-out by means of impedance spectroscopy. In order to interpret the data obtained from impedance measurements, an electrical equivalent circuit model was developed. In addition, morphological investigations of the polymer surface have been performed by means of in situ atomic force microscopy. The sensor signal change, which reflects the progress of degradation, indicates an accelerated degradation in the presence of the enzyme compared to hydrolysis in neutral pH buffer media. The degradation rate increases with increasing enzyme concentration. The obtained results demonstrate the potential of PMEIS sensors as a very promising tool for in situ and real-time monitoring of degradation of polymers.

Capillary levelling as a probe of rheology in polymer thin films

Science.gov (United States)

McGraw, Joshua D.; Jago, Nick M.; Dalnoki-Veress, Kari

2011-03-01

While measuring the rheology of bulk polymer systems is routine, when the size of a system becomes comparable to the molecular size, flow properties are poorly understood and hard to measure. Here, we present the results of experiments that are easily performed and can probe the rheological properties of polymer films that are mere tens of nanometres in thickness. We prepare glassy bilayer polymer films with height profiles well approximated by a step function. Upon annealing above the glass transition, broadening of the height profiles due to gradients in the Laplace pressure is observed. By validating the technique as a probe of the rheology with a range of molecular weights, we will show that this robust technique can be used to investigate the effects of confinement and interfaces on the rheology of ultrathin polymer films. Financial support from NSERC of Canada is gratefully acknowledged.

Accelerated Testing Of Photothermal Degradation Of Polymers

Science.gov (United States)

Kim, Soon Sam; Liang, Ranty Hing; Tsay, Fun-Dow

1989-01-01

Electron-spin-resonance (ESR) spectroscopy and Arrhenius plots used to determine maximum safe temperature for accelerated testing of photothermal degradation of polymers. Aging accelerated by increasing illumination, temperature, or both. Results of aging tests at temperatures higher than those encountered in normal use valid as long as mechanism of degradation same throughout range of temperatures. Transition between different mechanisms at some temperature identified via transition between activation energies, manifesting itself as change in slope of Arrhenius plot at that temperature.

Degradation Testing of Fluorotelomer-based polymers (FTPs)

Science.gov (United States)

Over the last decade, concern about sources of per and polyfluorochemicals (PFCs) have led to an increasing need for information on the microbial and/or abiotic degradation of polymer materials that contain PFC structural fragments that may be released. EPA, OECD, ASTM and other...

Experimental degradation of polymer shopping bags (standard and degradable plastic, and biodegradable) in the gastrointestinal fluids of sea turtles.

Science.gov (United States)

Müller, Christin; Townsend, Kathy; Matschullat, Jörg

2012-02-01

The persistence of marine debris such as discarded polymer bags has become globally an increasing hazard to marine life. To date, over 177 marine species have been recorded to ingest man-made polymers that cause life-threatening complications such as gut impaction and perforation. This study set out to test the decay characteristics of three common types of shopping bag polymers in sea turtle gastrointestinal fluids (GIF): standard and degradable plastic, and biodegradable. Fluids were obtained from the stomachs, small intestines and large intestines of a freshly dead Green turtle (Chelonia mydas) and a Loggerhead turtle (Caretta caretta). Controls were carried out with salt and freshwater. The degradation rate was measured over 49 days, based on mass loss. Degradation rates of the standard and the degradable plastic bags after 49 days across all treatments and controls were negligible. The biodegradable bags showed mass losses between 3 and 9%. This was a much slower rate than reported by the manufacturers in an industrial composting situation (100% in 49 days). The GIF of the herbivorous Green turtle showed an increased capacity to break down the biodegradable polymer relative to the carnivorous Loggerhead, but at a much lower rate than digestion of natural vegetative matter. While the breakdown rate of biodegradable polymers in the intestinal fluids of sea turtles is greater than standard and degradable plastics, it is proposed that this is not rapid enough to prevent morbidity. Further study is recommended to investigate the speed at which biodegradable polymers decompose outside of industrial composting situations, and their durability in marine and freshwater systems. Copyright © 2011 Elsevier B.V. All rights reserved.

Insights into the Mechanism and Kinetics of Thermo-Oxidative Degradation of HFPE High Performance Polymer.

Science.gov (United States)

Kunnikuruvan, Sooraj; Parandekar, Priya V; Prakash, Om; Tsotsis, Thomas K; Nair, Nisanth N

2016-06-02

The growing requisite for materials having high thermo-oxidative stability makes the design and development of high performance materials an active area of research. Fluorination of the polymer backbone is a widely applied strategy to improve various properties of the polymer, most importantly the thermo-oxidative stability. Many of these fluorinated polymers are known to have thermo-oxidative stability up to 700 K. However, for space and aerospace applications, it is important to improve its thermo-oxidative stability beyond 700 K. Molecular-level details of the thermo-oxidative degradation of such polymers can provide vital information to improve the polymer. In this spirit, we have applied quantum mechanical and microkinetic analysis to scrutinize the mechanism and kinetics of the thermo-oxidative degradation of a fluorinated polymer with phenylethenyl end-cap, HFPE. This study gives an insight into the thermo-oxidative degradation of HFPE and explains most of the experimental observations on the thermo-oxidative degradation of this polymer. Thermolysis of C-CF3 bond in the dianhydride component (6FDA) of HFPE is found to be the rate-determining step of the degradation. Reaction pathways that are responsible for the experimentally observed weight loss of the polymer is also scrutinized. On the basis of these results, we propose a modification of HFPE polymer to improve its thermo-oxidative stability.

Suite of Activity-Based Probes for Cellulose-Degrading Enzymes

Energy Technology Data Exchange (ETDEWEB)

Chauvigne-Hines, Lacie M.; Anderson, Lindsey N.; Weaver, Holly M.; Brown, Joseph N.; Koech, Phillip K.; Nicora, Carrie D.; Hofstad, Beth A.; Smith, Richard D.; Wilkins, Michael J.; Callister, Stephen J.; Wright, Aaron T.

2012-12-19

Microbial glycoside hydrolases play a dominant role in the biochemical conversion of cellulosic biomass to high-value biofuels. Anaerobic cellulolytic bacteria are capable of producing multicomplex catalytic subunits containing cell-adherent cellulases, hemicellulases, xylanases, and other glycoside hydrolases to facilitate the degradation of highly recalcitrant cellulose and other related plant cell wall polysaccharides. Clostridium thermocellum is a cellulosome producing bacterium that couples rapid reproduction rates to highly efficient degradation of crystalline cellulose. Herein, we have developed and applied a suite of difluoromethylphenyl aglycone, N-halogenated glycosylamine, and 2-deoxy-2-fluoroglycoside activity-based protein profiling (ABPP) probes to the direct labeling of the C. thermocellum cellulosomal secretome. These activity-based probes (ABPs) were synthesized with alkynes to harness the utility and multimodal possibilities of click chemistry, and to increase enzyme active site inclusion for LC-MS analysis. We directly analyzed ABP-labeled and unlabeled global MS data, revealing ABP selectivity for glycoside hydrolase (GH) enzymes in addition to a large collection of integral cellulosome-containing proteins. By identifying reactivity and selectivity profiles for each ABP, we demonstrate our ability to widely profile the functional cellulose degrading machinery of the bacterium. Derivatization of the ABPs, including reactive groups, acetylation of the glycoside binding groups, and mono- and disaccharide binding groups, resulted in considerable variability in protein labeling. Our probe suite is applicable to aerobic and anaerobic cellulose degrading systems, and facilitates a greater understanding of the organismal role associated within biofuel development.

In vitro degradation of biodegradable polymer-coated magnesium under cell culture condition

Energy Technology Data Exchange (ETDEWEB)

Xu Liping [Biometals Group, Biomaterials Unit, International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1, Namiki, Tsukuba, Ibaraki, 305-0044 (Japan); Yamamoto, Akiko, E-mail: yamamoto.akiko@nims.go.jp [Biometals Group, Biomaterials Unit, International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1, Namiki, Tsukuba, Ibaraki, 305-0044 (Japan)

2012-06-15

Magnesium (Mg) coated with four kinds of polymers, poly (L-lactic acid) (PLLA)-high molecular weight (HMW), PLLA-low molecular weight (LMW), poly ({epsilon}-caprolactone) (PCL)-HMW and PCL-LMW, and uncoated Mg were immersed under cell culture condition to study the degradation/corrosion behavior of the polymer-coated Mg. The releases of Mg{sup 2+} are measured during the immersion. Surface morphology and chemical composition are observed and identified by SEM and EDX. The tomography is obtained by X-ray CT observation and degradation rate is calculated by image analysis after 10-day immersion. All kinds of polymer-coated Mg showed significantly low release of Mg{sup 2+} (p < 0.05) in the whole immersion process comparing to that of uncoated Mg. In SEM and EDX results show, a corrosion layer can be observed on both polymer-coated and uncoated Mg after immersion. There is no obvious difference on the morphology and chemical composition of the corrosion layer between polymer-coated and uncoated Mg, indicating the corrosion/degradation process and corrosion product of Mg substrate are not changed by the polymer films under the present condition compared with uncoated Mg. Concerning the tomography and degradation rate of 10-day immersion, it can be found that the polymer-coated Mg shows a significantly low corrosion rate (p < 0.05) compared with that of uncoated Mg. PLLA coated Mg shows relatively uniform corrosion than PCL coated Mg and uncoated Mg. The largest pitting corrosion depth of PCL-LMW is about 3 times as large as the PLLA-LMW, which might be attributed to the difference of polymer microstructure. It is suggested that PLLA coating might be a suitable option for retarding the loss of mechanical properties of Mg substrate.

In vitro degradation of biodegradable polymer-coated magnesium under cell culture condition

International Nuclear Information System (INIS)

Xu Liping; Yamamoto, Akiko

2012-01-01

Magnesium (Mg) coated with four kinds of polymers, poly (L-lactic acid) (PLLA)-high molecular weight (HMW), PLLA-low molecular weight (LMW), poly (ε-caprolactone) (PCL)-HMW and PCL-LMW, and uncoated Mg were immersed under cell culture condition to study the degradation/corrosion behavior of the polymer-coated Mg. The releases of Mg 2+ are measured during the immersion. Surface morphology and chemical composition are observed and identified by SEM and EDX. The tomography is obtained by X-ray CT observation and degradation rate is calculated by image analysis after 10-day immersion. All kinds of polymer-coated Mg showed significantly low release of Mg 2+ (p < 0.05) in the whole immersion process comparing to that of uncoated Mg. In SEM and EDX results show, a corrosion layer can be observed on both polymer-coated and uncoated Mg after immersion. There is no obvious difference on the morphology and chemical composition of the corrosion layer between polymer-coated and uncoated Mg, indicating the corrosion/degradation process and corrosion product of Mg substrate are not changed by the polymer films under the present condition compared with uncoated Mg. Concerning the tomography and degradation rate of 10-day immersion, it can be found that the polymer-coated Mg shows a significantly low corrosion rate (p < 0.05) compared with that of uncoated Mg. PLLA coated Mg shows relatively uniform corrosion than PCL coated Mg and uncoated Mg. The largest pitting corrosion depth of PCL-LMW is about 3 times as large as the PLLA-LMW, which might be attributed to the difference of polymer microstructure. It is suggested that PLLA coating might be a suitable option for retarding the loss of mechanical properties of Mg substrate.

Estimation of apparent kinetic parameters of polymer pyrolysis with complex thermal degradation behavior

International Nuclear Information System (INIS)

Srimachai, Taranee; Anantawaraskul, Siripon

2010-01-01

Full text: Thermal degradation behavior during polymer pyrolysis can typically be described using three apparent kinetic parameters (i.e., pre-exponential factor, activation energy, and reaction order). Several efficient techniques have been developed to estimate these apparent kinetic parameters for simple thermal degradation behavior (i.e., single apparent pyrolysis reaction). Unfortunately, these techniques cannot be directly extended to the case of polymer pyrolysis with complex thermal degradation behavior (i.e., multiple concurrent reactions forming single or multiple DTG peaks). In this work, we proposed a deconvolution method to determine the number of apparent reactions and estimate three apparent kinetic parameters and contribution of each reaction for polymer pyrolysis with complex thermal degradation behavior. The proposed technique was validated with the model and experimental pyrolysis data of several polymer blends with known compositions. The results showed that (1) the number of reaction and (2) three apparent kinetic parameters and contribution of each reaction can be estimated reasonably. The simulated DTG curves with estimated parameters also agree well with experimental DTG curves. (author)

乳酸扩链聚合物的降解性能%DEGRADABLE BEHAVIORS OF LACTIDE CHAIN-EXTENED POLYMERS

Institute of Scientific and Technical Information of China (English)

封瑞江

2001-01-01

In this paper,the effects of change of degradable rate and relative molecular mass on the degradable behaviors of four lactide chain-extened polymers are contrasted with those of lactide polymers.The results indicated that the four lactide chain-extened polymers could degrade in this experiment and their degradable rate were lower than that of P-LA.LA-SDI has the highest degradable rates among the four lactide chain-extened polymers,but there was no significant difference among aromatic and aliphatic lactide chain-extened polymers.The results showed that the degradable rates were dependent on experiment methods and condition and also indicated that the relative molecular mass became smaller and smaller with the progress of degradation time.

α-Amino acid containing degradable polymers as functional biomaterials: rational design, synthetic pathway, and biomedical applications.

Science.gov (United States)

Sun, Huanli; Meng, Fenghua; Dias, Aylvin A; Hendriks, Marc; Feijen, Jan; Zhong, Zhiyuan

2011-06-13

Currently, biomedical engineering is rapidly expanding, especially in the areas of drug delivery, gene transfer, tissue engineering, and regenerative medicine. A prerequisite for further development is the design and synthesis of novel multifunctional biomaterials that are biocompatible and biologically active, are biodegradable with a controlled degradation rate, and have tunable mechanical properties. In the past decades, different types of α-amino acid-containing degradable polymers have been actively developed with the aim to obtain biomimicking functional biomaterials. The use of α-amino acids as building units for degradable polymers may offer several advantages: (i) imparting chemical functionality, such as hydroxyl, amine, carboxyl, and thiol groups, which not only results in improved hydrophilicity and possible interactions with proteins and genes, but also facilitates further modification with bioactive molecules (e.g., drugs or biological cues); (ii) possibly improving materials biological properties, including cell-materials interactions (e.g., cell adhesion, migration) and degradability; (iii) enhancing thermal and mechanical properties; and (iv) providing metabolizable building units/blocks. In this paper, recent developments in the field of α-amino acid-containing degradable polymers are reviewed. First, synthetic approaches to prepare α-amino acid-containing degradable polymers will be discussed. Subsequently, the biomedical applications of these polymers in areas such as drug delivery, gene delivery and tissue engineering will be reviewed. Finally, the future perspectives of α-amino acid-containing degradable polymers will be evaluated.

Characterization and characteristics of degradable polymer sacks

International Nuclear Information System (INIS)

Davis, Georgina

2003-01-01

This paper reviews the categories and characteristics of degradable polymers used to manufacture sacks for the collection and subsequent treatment of organic wastes from householders. The characteristics of polyethylene (PE) and starch-based sacks were examined using a number of different methods, including scanning electron microscopy (SEM), chemical analysis and mechanical strength testing of the sacks during their use. The analyses revealed that the characteristics of the PE and starch-based sacks were very different. Photomicrographs indicated that the surface of the PE sack was much smoother than the surface of the starch-based sacks. Polyethylene sacks exhibited a greater mechanical strength, both in the unused state and over time during householder use. The severe loss of mechanical strength during use of the starch-based sacks indicated that only thicker gauge sacks were suitable for the fortnightly kerbside collection of biodegradable municipal waste (BMW). Chemical analysis of two different PE sacks indicated that transition metals and other elements were commonly incorporated into the PE structure in order to facilitate increased polymer degradation

Development of degradable renewable polymers and stimuli-responsive nanocomposites

Science.gov (United States)

Eyiler, Ersan

The overall goal of this research was to explore new living radical polymerization methods and the blending of renewable polymers. Towards this latter goal, polylactic acid (PLA) was blended with a new renewable polymer, poly(trimethylene-malonate) (PTM), with the aim of improving mechanical properties, imparting faster degradation, and examining the relationship between degradation and mechanical properties. Blend films of PLA and PTM with various ratios (5, 10, and 20 wt %) were cast from chloroform. Partially miscible blends exhibited Young's modulus and elongation-to-break values that significantly extend PLA's usefulness. Atomic force microscopy (AFM) data showed that incorporation of 10 wt% PTM into PLA matrix exhibited a Young's modulus of 4.61 GPa, which is significantly higher than that of neat PLA (1.69 GPa). The second part of the bioplastics study involved a one-week hydrolytic degradation study of PTM and another new bioplastic, poly(trimethylene itaconate) (PTI) using DI water (pH 5.4) at room temperature, and the effects of degradation on crystallinity and mechanical properties of these films were examined by differential scanning calorimetry (DSC) and AFM. PTI showed an increase in crystallinity with degradation, which was attributed to predominately degradation of free amorphous regions. Depending on the crystallinity, the elastic modulus increased at first, and decreased slightly. Both bulk and surface-tethered stimuli-responsive polymers were studied on amine functionalized magnetite (Fe3O4) nanoparticles. Stimuli-responsive polymers studied, including poly(N-isopropylacrylamide) (PNIPAM), poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), and poly(itaconic acid) (PIA), were grafted via surface-initiated aqueous atom transfer radical polymerization (SI-ATRP). Both Fourier transform infrared spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS) spectroscopies showed the progression of the grafting. The change in particle size as a

Polyester-Based (Bio)degradable Polymers as Environmentally Friendly Materials for Sustainable Development

Science.gov (United States)

Rydz, Joanna; Sikorska, Wanda; Kyulavska, Mariya; Christova, Darinka

2014-01-01

This review focuses on the polyesters such as polylactide and polyhydroxyalkonoates, as well as polyamides produced from renewable resources, which are currently among the most promising (bio)degradable polymers. Synthetic pathways, favourable properties and utilisation (most important applications) of these attractive polymer families are outlined. Environmental impact and in particular (bio)degradation of aliphatic polyesters, polyamides and related copolymer structures are described in view of the potential applications in various fields. PMID:25551604

Bio-degradable highly fluorescent conjugated polymer nanoparticles for bio-medical imaging applications.

Science.gov (United States)

Repenko, Tatjana; Rix, Anne; Ludwanowski, Simon; Go, Dennis; Kiessling, Fabian; Lederle, Wiltrud; Kuehne, Alexander J C

2017-09-07

Conjugated polymer nanoparticles exhibit strong fluorescence and have been applied for biological fluorescence imaging in cell culture and in small animals. However, conjugated polymer particles are hydrophobic and often chemically inert materials with diameters ranging from below 50 nm to several microns. As such, conjugated polymer nanoparticles cannot be excreted through the renal system. This drawback has prevented their application for clinical bio-medical imaging. Here, we present fully conjugated polymer nanoparticles based on imidazole units. These nanoparticles can be bio-degraded by activated macrophages. Reactive oxygen species induce scission of the conjugated polymer backbone at the imidazole unit, leading to complete decomposition of the particles into soluble low molecular weight fragments. Furthermore, the nanoparticles can be surface functionalized for directed targeting. The approach opens a wide range of opportunities for conjugated polymer particles in the fields of medical imaging, drug-delivery, and theranostics.Conjugated polymer nanoparticles have been applied for biological fluorescence imaging in cell culture and in small animals, but cannot readily be excreted through the renal system. Here the authors show fully conjugated polymer nanoparticles based on imidazole units that can be bio-degraded by activated macrophages.

Construction and applications of DNA probes for detection of polychlorinated biphenyl-degrading genotypes in toxic organic-contaminated soil environments

International Nuclear Information System (INIS)

Walia, S.; Khan, A.; Rosenthal, N.

1990-01-01

Several DNA probes for polychlorinated biphenyl (PCB)-degrading genotypes were constructed from PCB-degrading bacteria. These laboratory-engineered DNA probes were used for the detection, enumeration, and isolation of specific bacteria degrading PCBs. Dot blot analysis of purified DNA from toxic organic chemical-contaminated soil bacterial communities showed positive DNA-DNA hybridization with a 32P-labeled DNA probe (pAW6194, cbpABCD). Less than 1% of bacterial colonies isolated from garden topsoil and greater than 80% of bacteria isolated from PCB-contaminated soils showed DNA homologies with 32P-labeled DNA probes. Some of the PCB-degrading bacterial isolates detected by the DNA probe method did not show biphenyl clearance. The DNA probe method was found to detect additional organisms with greater genetic potential to degrade PCBs than the biphenyl clearance method did. Results from this study demonstrate the usefulness of DNA probes in detecting specific PCB-degrading bacteria, abundance of PCB-degrading genotypes, and genotypic diversity among PCB-degrading bacteria in toxic chemical-polluted soil environments. We suggest that the DNA probe should be used with caution for accurate assessment of PCB-degradative capacity within soils and further recommend that a combination of DNA probe and biodegradation assay be used to determine the abundance of PCB-degrading bacteria in the soil bacterial community

Synthesis and thermal degradation Kinetics of D - (+ - galactose containing polymers

Directory of Open Access Journals (Sweden)

Fehmi Saltan

2013-01-01

Full Text Available In this study, it is investigated the synthesis and characterizations of polymerizable vinyl sugars. Carbohydrate containing polymers were synthesized via free radical polymerization. Thermal behavior of polymer derivatives was analyzed by using DSC and TG. Molecular weight dispersion of polymer derivatives was also analyzed with GPC. Molecular structures were analyzed by FT-IR and 1H-NMR spectrophotometer. We found that molecular weight of copolymers could effect to the thermal stability. According to TG data related to the copolymers, molecular weight of polymers increased while the thermal stability decreased. Thermogravimetric analysis of polymers also investigated. The apparent activation energies for thermal degradation of carbohydrate containing polymers were obtained by integral methods (Flynn - Wall - Ozawa, Kissinger - Akahira - Sunose, and Tang.

ANALYSIS OF THE ELECTROPHYSICAL AND PHOTOELECTRIC PROPERTIES OF NANOCOMPOSITE POLYMERS BY THE MODIFIED KELVIN PROBE

Directory of Open Access Journals (Sweden)

K. U. Pantsialeyeu

2017-01-01

Full Text Available At present for analysis of the homogeneity of materials properties are becoming widely used various modifications of a scanning Kelvin probe. These methods allow mapping the spatial distribution of the electrostatic potential. Analysis of the electropotential profile is not sufficient to describe any specific physical parameters of the polymer nanocomposites. Therefore, we use an external energy impact, such as light. Purpose of paper is the modification of the Kelvin scanning probe and the conduct of experimental studies of the spatial distribution and response of the electrostatic potential of the actual polymer nanocomposites to the optical probing.Carried out the investigations on experimental Low density polyethylene composites. Carbon nanomaterials and nanoparticles of silicon dioxide or aluminum as fillers are used. As a result, maps of the spatial distribution of the electrostatic potential relative values and the surface photovoltage. Statistical analysis of the electrophysical and photoelectric properties homogeneity, depending on the component composition of the composites carried out. In addition, with reference to matrix polymers, the Kelvin scanning probe, in combination with the optical probing, made it possible to detect a piezoelectric effect. The latter, can used as a basis for the development of new methods for studying the mechanical properties of matrix polymers.

Chemical degradation and morphological instabilities during focused ion beam prototyping of polymers.

Science.gov (United States)

Orthacker, A; Schmied, R; Chernev, B; Fröch, J E; Winkler, R; Hobisch, J; Trimmel, G; Plank, H

2014-01-28

Focused ion beam processing of low melting materials, such as polymers or biological samples, often leads to chemical and morphological instabilities which prevent the straight-forward application of this versatile direct-write structuring method. In this study the behaviour of different polymer classes under ion beam exposure is investigated using different patterning parameters and strategies with the aim of (i) correlating local temperatures with the polymers' chemistry and its morphological consequences; and (ii) finding a way of processing sensitive polymers with lowest chemical degradation while maintaining structuring times. It is found that during processing of polymers three temperature regimes can be observed: (1) at low temperatures all polymers investigated show stable chemical and morphological behaviour; (2) very high temperatures lead to strong chemical degradation which entails unpredictable morphologies; and (3) in the intermediate temperature regime the behaviour is found to be strongly material dependent. A detailed look reveals that polymers which rather cross-link in the proximity of the beam show stable morphologies in this intermediate regime, while polymers that rather undergo chain scission show tendencies to develop a creeping phase, where material follows the ion beam movement leading to instable and unpredictable morphologies. Finally a simple, alternative patterning strategy is suggested, which allows stable processing conditions with lowest chemical damage even for challenging polymers undergoing chain scission.

Applicability of X-ray reflectometry to studies of polymer solar cell degradation

DEFF Research Database (Denmark)

Andreasen, Jens Wenzel; Gevorgyan, Suren; Schleputz, C.M.

2008-01-01

Although degradation of polymer solar cells is widely acknowledged, the cause, physical or chemical, has not been identified. The purpose of this work is to determine the applicability of X-ray reflectometry for in situ observation of physical degradation mechanisms. We find that the rough...... interfaces of the polymer solar cell constituent layers seriously obstruct the sensitivity of the technique, rendering it impossible to elucidate changes in the layer/interface structure at the sub-nanometer level. (c) 2008 Elsevier B.V. All rights reserved....

Electroluminescence and electrical degradation of insulating polymers at electrode interfaces under divergent fields

Science.gov (United States)

Zhang, Shuai; Li, Qi; Hu, Jun; Zhang, Bo; He, Jinliang

2018-04-01

Electrical degradation of insulating polymers at electrode interfaces is an essential factor in determining long-term reliability. A critical challenge is that the exact mechanism of degradation is not fully understood, either experimentally or theoretically, due to the inherent complex processes. Consequently, in this study, we investigate electroluminescence (EL) at the interface of an electrode and insulator, and determine the relationship between EL and electrical degradation. Using a tip-plate electrode structure, the unique features of EL under a highly divergent field are investigated. The voltage type (alternating or direct current), the polymer matrix, and the time of pressing are also investigated separately. A study of EL from insulators under a divergent field is provided, and the relationship between EL spectra and degradation is discussed. It is shown that EL spectra under a divergent field have unique characteristics compared with EL spectra from polymer films under a uniform field and the most obvious one is the UV emission. The results obtained in the current investigation bring us a step closer to understanding the process of electrical degradation and provide a potential way to diagnose insulator defects.

Degradation Action of the Anaerobic Bacteria and Oxygen to the Polymer

Institute of Scientific and Technical Information of China (English)

LU Xiang-Guo; ZHANG Ke

2008-01-01

Oxygen could prohibit anaerobic bacterium in the produced water and degrade the polymer molecular chains.Aiming at problems making up aerobic polymer solution by the produced water in Daqing Oil Field, some evaluations were done on the viscosity characteristics of polymer solution and bactericide in anaerobic and aerobic environments. Reasonable aerobic concentration of the produced water was obtained. The experimental results indicate that the viscosity of polymer solution confected by the produced water in the aerobic environment is higher than that of the polymer solution confected by the produced water in the anaerobic environment, and the reasonable ments, but the sterilization effect is better in the aerobic environment.

Enzyme-catalyzed degradation of biodegradable polymers derived from trimethylene carbonate and glycolide by lipases from Candida antarctica and Hog pancreas.

Science.gov (United States)

Liu, Feng; Yang, Jian; Fan, Zhongyong; Li, Suming; Kasperczyk, Janusz; Dobrzynski, Piotr

2012-01-01

Enzyme-catalyzed degradation of poly(trimethylene carbonate) homo-polymer (PTMC) and poly(trimethylene carbonate-co-glycolide) co-polymer (PTGA) was investigated in the presence of lipases from Candida antarctica and Hog pancreas. Degradation was monitored by gravimetry, size-exclusion chromatography (SEC), nuclear magnetic resonance (NMR), tensiometry and environmental scanning electron microscopy (ESEM). PTMC can be rapidly degraded by Candida antarctica lipase with 98% mass loss after 9 days, while degradation by Hog pancreas lipase leads to 27% mass loss. Introduction of 16% glycolide units in PTMC chains strongly affects the enzymatic degradation. Hog pancreas lipase becomes more effective to PTGA co-polymer with a mass loss of 58% after 9 days, while Candida antarctica lipase seems not able to degrade PTGA. Bimodal molecular weight distributions are observed during enzymatic degradation of both PTMC and PTGA, which can be assigned to the fact that the surface is largely degraded while the internal part remains intact. The composition of the PTGA co-polymer remains constant, and ESEM shows that the polymers are homogeneously eroded during enzymatic degradation. Contact angle measurements confirm the enzymatic degradation mechanism, i.e., enzyme adsorption on the polymer surface followed by enzyme-catalyzed chain cleavage.

Methods for Evaluating the Biodegradability of Environmentally Degradable Polymers

NARCIS (Netherlands)

Zee, van der M.

2014-01-01

This chapter presents an overview of the current knowledge on experimental methods for monitoring the biodegradability of polymeric materials. The focus is, in particular, on the biodegradation of materials under environmental conditions. Examples of in vivo degradation of polymers used in

Occurrence, degradation, and effect of polymer-based materials in the environment.

Science.gov (United States)

Lambert, Scott; Sinclair, Chris; Boxall, Alistair

2014-01-01

There is now a plethora of polymer-based materials (PBMs) on the market, because of the increasing demand for cheaper consumable goods, and light-weight industrial materials. Each PBM constitutes a mixture of their representative polymer/sand their various chemical additives. The major polymer types are polyethylene, polypropylene,and polyvinyl chloride, with natural rubber and biodegradable polymers becoming increasingly more important. The most important additives are those that are biologically active, because to be effective such chemicals often have properties that make them resistant to photo-degradation and biodegradation. During their lifecycle,PBMs can be released into the environment form a variety of sources. The principal introduction routes being general littering, dumping of unwanted waste materials,migration from landfills and emission during refuse collection. Once in the environment,PBMs are primarily broken down by photo-degradation processes, but due to the complex chemical makeup of PBMs, receiving environments are potentially exposed to a mixture of macro-, meso-, and micro-size polymer fragments, leached additives, and subsequent degradation products. In environments where sunlight is absent (i.e., soils and the deep sea) degradation for most PBMs is minimal .The majority of literature to date that has addressed the environmental contamination or disposition of PBMs has focused on the marine environment. This is because the oceans are identified as the major sink for macro PBMs, where they are known to present a hazard to wildlife via entanglement and ingestion. The published literature has established the occurrence of microplastics in marine environment and beach sediments, but is inadequate as regards contamination of soils and freshwater sediments. The uptake of microplastics for a limited range of aquatic organisms has also been established, but there is a lack of information regarding soil organisms, and the long-term effects of

Comparative histological evaluation of new tyrosine-derived polymers and poly (L-lactic acid) as a function of polymer degradation.

Science.gov (United States)

Hooper, K A; Macon, N D; Kohn, J

1998-09-05

Previous studies demonstrated that poly(DTE carbonate) and poly (DTE adipate), two tyrosine-derived polymers, have suitable properties for use in biomedical applications. This study reports the evaluation of the in vivo tissue response to these polymers in comparison to poly(L-lactic acid) (PLLA). Typically, the biocompatibility of a material is determined through histological evaluations as a function of implantation time in a suitable animal model. However, due to changes that can occur in the tissue response at different stages of the degradation process, a fixed set of time points is not ideal for comparative evaluations of materials having different rates of degradation. Therefore the tissue response elicited by poly(DTE carbonate), poly(DTE adipate), and PLLA was evaluated as a function of molecular weight. This allowed the tissue response to be compared at corresponding stages of degradation. Poly(DTE adipate) consistently elicited the mildest tissue response, as judged by the width and lack of cellularity of the fibrous capsule formed around the implant. The tissue response to poly(DTE carbonate) was mild throughout the 570 day study. However, the response to PLLA fluctuated as a function of the degree of degradation, exhibiting an increase in the intensity of inflammation as the implant began to lose mass. At the completion of the study, tissue ingrowth into the degrading and disintegrating poly(DTE adipate) implant was evident while no comparative ingrowth of tissue was seen for PLLA. The similarity of the in vivo and in vitro degradation rates of each polymer confirmed the absence of enzymatic involvement in the degradation process. A comparison of molecular weight retention, water uptake, and mass loss in vivo with two commonly used in vitro systems [phosphate-buffered saline (PBS) and simulated body fluid (SBF)] demonstrated that for the two tyrosine-derived polymers the in vivo results were equally well simulated in vitro with PBS and SBF. However

A new scaling for the rotational diffusion of molecular probes in polymer solutions.

Science.gov (United States)

Qing, Jing; Chen, Anpu; Zhao, Nanrong

2017-12-13

In the present work, we propose a new scaling form for the rotational diffusion coefficient of molecular probes in semi-dilute polymer solutions, based on a theoretical study. The mean-field theory for depletion effect and semi-empirical scaling equation for the macroscopic viscosity of polymer solutions are properly incorporated to specify the space-dependent concentration and viscosity profiles in the vicinity of the probe surface. Following the scheme of classical fluid mechanics, we numerically evaluate the shear torque exerted on the probes, which then allows us to further calculate the rotational diffusion coefficient D r . Particular attention is given to the scaling behavior of the retardation factor R rot ≡ D/D r with D being the diffusion coefficient in pure solvent. We find that R rot has little relevance to the macroscopic viscosity of the polymer solution, while it can be well featured by the characteristic length scale r h /δ, i.e. the ratio between the hydrodynamic radius of the probe r h and the depletion thickness δ. Correspondingly, we obtain a novel scaling form for the rotational retardation factor, following R rot = exp[a(r h /δ) b ] with rather robust parameters of a ≃ 0.51 and b ≃ 0.56. We apply the theory to an extensive calculation for various probes in specific polymer solutions of poly(ethylene glycol) (PEG) and dextran. Our theoretical results show good agreements with the experimental data, and clearly demonstrate the validity of the new scaling form. In addition, the difference of the scaling behavior between translational and rotational diffusions is clarified, from which we conclude that the depletion effect plays a more significant role on the local rotational diffusion rather than the long-range translation diffusion.

Mass spectrometric comparison of swift heavy ion-induced and anaerobic thermal degradation of polymers

Science.gov (United States)

Lima, V.; Hossain, U. H.; Walbert, T.; Seidl, T.; Ensinger, W.

2018-03-01

The study of polymers irradiated by highly energetic ions and the resulting radiation-induced degradation is of major importance for space and particle accelerator applications. The mechanism of ion-induced molecular fragmentation of polyethylene, polyethyleneimine and polyamide was investigated by means of mass spectrometry and infrared spectroscopy. The results show that the introduction of nitrogen and oxygen into the polymer influences the stability rendering aliphatic polymers with heteroatoms less stable. A comparison to thermal decomposition data from literature reveals that ion-induced degradation is different in its bond fracture mechanism. While thermal degradation starts at the weakest bond, which is usually the carbon-heteroatom bond, energetic ion irradiation leads in the first step to scission of all types of bonds creating smaller molecular fragments. This is due to the localized extreme energy input under non-equilibrium conditions when the ions transfer kinetic energy onto electrons. These findings are of relevance for the choice of polymers for long-term application in both space and accelerator facilities.

Degradability of an Acrylate-Linked, Fluorotelomer Polymer in Soil

Science.gov (United States)

Fluorotelomer polymers are used in a broad array of products in modern societies worldwide and, if they degrade at significant rates, potentially are a significant source of perfluorooctanoic acid (PFOA) and related compounds to the environment. To evaluate this possibility, we i...

Degradation of Polymers by Ultra-Violet Light

Energy Technology Data Exchange (ETDEWEB)

Turner, D. T. [Camille Dreyfus Laboratory, Research Triangle Institute, Research Triangle Park, NC (United States)

1968-10-15

To reach an understanding of the complex processes which occur when polymers are degraded by ultra-violet light under service conditions it is first judicious to try to elucidate the photochemistry of relatively simple polymer reactions. For this reason, emphasis is given to studies in which purified polymers, in bulk, were exposed to monochromatic radiations in the absence of oxygen. In respect of product analysis, emphasis is given to methods for estimating quantum yields for fractures and crosslinks. Photochemical mechanisms are illustrated by discussion of polystyrene, polytethylene terephthalate) and cellulose. Special emphasis is given to the role of free radicals. Attention is drawn to reports that the course of photolysis may be changed by application of an external pressure of a chemically inert gas, such as nitrogen. The explanation suggested in the literature is that this depends on the ease of escape of hydrogen atoms which, alternatively, might react with trapped polymer radicals. The course of photolysis may also be affected by polymer radicals acting as strongly absorbing chromophores and consequently undergoing further chemical reaction. This is illustrated by reference to the conversion of allyl radicals to alkyl radicals in polyethylene and also by changes observed in the ESR spectrum of polymer radicals trapped in poly (ethylene terephthalate) as a result of exposure to light. It is suggested that this effect is primarily responsible for the evolution of hydrocarbon gases on photolysis of polyethylene or natural rubber. In contrast, radiolysis of these polymers yields almost pure hydrogen because, in this case, energy is absorbed by relatively non-selective processes, i.e. free radicals do not absorb high energy radiation much more strongly than does their polymeric environment. (author)

Novel salicylazo polymers for colon drug delivery: dissolving polymers by means of bacterial degradation.

Science.gov (United States)

Saphier, Sigal; Karton, Yishai

2010-02-01

Novel azo polymers were prepared for colonic drug delivery with a release mechanism based on structural features of azo derivatives designed for rapid bacterial degradation leading to soluble polymers. Two Salicylazo derivatives were prepared and conjugated as side chains at different ratios to methacrylic acid-methyl methacrylate copolymers (Eudragits). The azo compounds were designed to have a hydrophilic and a hydrophobic part on opposite sides of the azo bond. Upon reduction of the azo bonds, the hydrophobic part is released, resulting in a more water soluble polymer. The solubility of the polymeric films was studied relative to Eudragit S known to dissolve toward the end of the small intestine. One of the two azo derivatives prepared gave rise to polymers, which showed reduced solubility relative to Eudragit S. These polymers were subjected to reduction tests in anaerobic rat cecal suspensions by following the release of the hydrophobic product. Reduction rate was found to be rapid, comparable to that of Sulfasalazine. Studies on the azopolymeric films in anaerobic rat cecal suspensions, showed that these polymers dissolve faster than in sterilized suspensions. Solid dosage forms may be coated with these polymers to provide an efficient delivery system to the colon with a rapid release mechanism. (c) 2009 Wiley-Liss, Inc. and the American Pharmacists Association.

Controlling of degradation effects in radiation processing of polymers

International Nuclear Information System (INIS)

2009-05-01

The interest of Member States of the IAEA in introducing radiation technology into the polymer and plastics industry is growing. This publication summarizes a number of studies conducted in the framework of a coordinated research project (CRP) on controlling of degradation effects on polymers by radiation processing technologies. It reviews a variety of applications and details the most important results and achievements of the participating centres and laboratories during the course of the CRP. The publication is intended to be of use to scientists implementing the technology and managers of radiation processing facilities

Oxidation Responsive Polymers with a Triggered Degradation via Arylboronate Self-Immolative Motifs on a Polyphosphazene Backbone.

Science.gov (United States)

Iturmendi, Aitziber; Monkowius, Uwe; Teasdale, Ian

2017-02-21

Oxidation responsive polymers with triggered degradation pathways have been prepared via attachment of self-immolative moieties onto a hydrolytically unstable polyphosphazene backbone. After controlled main-chain growth, postpolymerization functionalization allows the preparation of hydrolytically stable poly(organo)phosphazenes decorated with a phenylboronic ester caging group. In oxidative environments, triggered cleavage of the caging group is followed by self-immolation, exposing the unstable glycine-substituted polyphosphazene which subsequently undergoes to backbone degradation to low-molecular weight molecules. As well as giving mechanistic insights, detailed GPC and 1 H and 31 P NMR analysis reveal the polymers to be stable in aqueous solutions, but show a selective, fast degradation upon exposure to hydrogen peroxide containing solutions. Since the post-polymerization functionalization route allows simple access to polymer backbones with a broad range of molecular weights, the approach of using the inorganic backbone as a platform significantly expands the toolbox of polymers capable of stimuli-responsive degradation.

Friction as a probe of surface properties of a polymer glass

OpenAIRE

Bureau, Lionel

2007-01-01

We probe the temperature dependence of friction at the interface between a glassy poly(methylmethacrylate) lens and a flat substrate coated with a methyl-terminated self-assembled monolayer. The monolayer exhibits density defects which act as pinning sites for the polymer chains. We show that the shear response of such an interface supports the existence, at the surface of the glassy polymer, of a nanometer-thick layer of mobile chains. Friction can be ascribed to the interplay between viscou...

Degradation of homogeneous polymer solutions in high shear turbulent pipe flow

Science.gov (United States)

Elbing, B. R.; Winkel, E. S.; Solomon, M. J.; Ceccio, S. L.

2009-12-01

This study quantifies degradation of polyethylene oxide (PEO) and polyacrylamide (PAM) polymer solutions in large diameter (2.72 cm) turbulent pipe flow at Reynolds numbers to 3 × 105 and shear rates greater than 105 1/s. The present results support a universal scaling law for polymer chain scission reported by Vanapalli et al. (2006) that predicts the maximum chain drag force to be proportional to Re 3/2, validating this scaling law at higher Reynolds numbers than prior studies. Use of this scaling gives estimated backbone bond strengths from PEO and PAM of 3.2 and 3.8 nN, respectively. Additionally, with the use of synthetic seawater as a solvent the onset of drag reduction occurred at higher shear rates relative to the pure water solvent solutions, but had little influence on the extent of degradation at higher shear rates. These results are significant for large diameter pipe flow applications that use polymers to reduce drag.

Cathepsin B-sensitive polymers for compartment-specific degradation and nucleic acid release.

Science.gov (United States)

Chu, David S H; Johnson, Russell N; Pun, Suzie H

2012-02-10

Degradable cationic polymers are desirable for in vivo nucleic acid delivery because they offer significantly decreased toxicity over non-degradable counterparts. Peptide linkers provide chemical stability and high specificity for particular endopeptidases but have not been extensively studied for nucleic acid delivery applications. In this work, enzymatically degradable peptide-HPMA copolymers were synthesized by RAFT polymerization of HPMA with methacrylamido-terminated peptide macromonomers, resulting in polymers with low polydispersity and near quantitative incorporation of peptides. Three peptide-HPMA copolymers were evaluated: (i) pHCathK(10), containing peptides composed of the linker phe-lys-phe-leu (FKFL), a substrate of the endosomal/lysosomal endopeptidase cathepsin B, connected to oligo-(L)-lysine for nucleic acid binding, (ii) pHCath(D)K(10), containing the FKFL linker with oligo-(D)-lysine, and (iii) pH(D)Cath(D)K(10), containing all (D) amino acids. Cathepsin B degraded copolymers pHCathK(10) and pHCath(D)K(10) within 1 h while no degradation of pH(D)Cath(D)K(10) was observed. Polyplexes formed with pHCathK(10) copolymers show DNA release by 4 h of treatment with cathepsin B; comparatively, polyplexes formed with pHCath(D)K(10) and pH(D)Cath(D)K(10) show no DNA release within 8 h. Transfection efficiency in HeLa and NIH/3T3 cells were comparable between the copolymers but pHCathK(10) was less toxic. This work demonstrates the successful application of peptide linkers for degradable cationic polymers and DNA release. Copyright © 2011 Elsevier B.V. All rights reserved.

Well-defined degradable brush polymer-drug conjugates for sustained delivery of Paclitaxel.

Science.gov (United States)

Yu, Yun; Chen, Chih-Kuang; Law, Wing-Cheung; Mok, Jorge; Zou, Jiong; Prasad, Paras N; Cheng, Chong

2013-03-04

To achieve a conjugated drug delivery system with high drug loading but minimal long-term side effects, a degradable brush polymer-drug conjugate (BPDC) was synthesized through azide-alkyne click reaction of acetylene-functionalized polylactide (PLA) with azide-functionalized paclitaxel (PTXL) and poly(ethylene glycol) (PEG). Well-controlled structures of the resulting BPDC and its precursors were verified by (1)H NMR and gel permeation chromatography (GPC) characterizations. With nearly quantitative click efficiency, drug loading amount of the BPDC reached 23.2 wt %. Both dynamic light scattering (DLS) analysis and transmission electron microscopy (TEM) imaging indicated that the BPDC had a nanoscopic size around 10-30 nm. The significant hydrolytic degradability of the PLA backbone of the BPDC was confirmed by GPC analysis of its incubated solution. Drug release study showed that PTXL moieties can be released through the cleavage of the hydrolyzable conjugation linkage in pH 7.4 at 37 °C, with 50% release in about 22 h. As illustrated by cytotoxicity study, while the polymeric scaffold of the BPDC is nontoxic, the BPDC exhibited higher therapeutic efficacy toward MCF-7 cancer cells than free PTXL at 0.1 and 1 μg/mL. Using Nile red as encapsulated fluorescence probe, cell uptake study showed effective internalization of the BPDC into the cells.

Thermal degradation of biocidal organic N-halamines and N-halamine polymers

Energy Technology Data Exchange (ETDEWEB)

Chylińska, Marta; Kaczmarek, Halina, E-mail: halina@chem.umk.pl

2014-05-01

Highlights: • Novel biocidal N-halamines have been substituted to poly(p-methyl styrene). • Thermal stability of all obtained compounds has been studied by thermogravimetry. • Stabilization of selected polymer has been achieved using octyl tin mercaptide. • The mechanism of thermal degradation of N-halamine polymers has been proposed. - Abstract: Novel biocidal organic N-halamines (based on imidazoline dione rings) were used as a substituents for poly(p-methyl styrene). The biocidal polymers and substituents have been investigated using thermogravimetric analysis. The thermal resistance of investigated compounds was compared to those of non-halogenated precursors. The introduction of chlorine atoms to polymers decreases their thermal resistance comparing to precursors but efficient stabilization is possible by using octyl tin mercaptide. The complex mechanism of thermal decomposition of polymers has been discussed.

Sulfur-Doped Carbon Nitride Polymers for Photocatalytic Degradation of Organic Pollutant and Reduction of Cr(VI).

Science.gov (United States)

Zheng, Yun; Yu, Zihao; Lin, Feng; Guo, Fangsong; Alamry, Khalid A; Taib, Layla A; Asiri, Abdullah M; Wang, Xinchen

2017-04-01

As a promising conjugated polymer, binary carbon nitride has attracted extensive attention as a metal-free and visible-light-responsive photocatalyst in the area of photon-involving purification of water and air. Herein, we report sulfur-doped polymeric carbon nitride microrods that are synthesized through thermal polymerization based on trithiocyanuric acid and melamine (TM) supramolecular aggregates. By tuning the polymerization temperature, a series of sulfur-doped carbon nitride microrods are prepared. The degradation of Rhodamine B (RhB) and the reduction of hexavalent chromium Cr(VI) are selected as probe reactions to evaluate the photocatalytic activities. Results show that increasing pyrolysis temperature leads to a large specific surface area, strong visible-light absorption, and accelerated electron-hole separation. Compared to bulk carbon nitride, the highly porous sulfur-doped carbon nitride microrods fabricated at 650 °C exhibit remarkably higher photocatalytic activity for degradation of RhB and reduction of Cr(VI). This work highlights the importance of self-assembly approach and temperature-control strategy in the synthesis of photoactive materials for environmental remediation.

Degradation analysis of the encapsulation polymer in photovoltaic modules by Raman spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Peike, Cornelia

2015-07-01

Understanding the degradation behavior of photovoltaic modules is of great importance for the production of reliable and durable PV modules. Within this work, the applicability of Raman spectroscopy as a non-destructive method for PV module degradation analysis was investigated. In addition, the influence of polymer stabilizers on the photochemical discoloration of EVA as well as the impact of EVA aging on the cell metallization degradation under damp-heat conditions was studied.

Direct detection of additives and degradation products from polymers by liquid extraction surface analysis employing chip-based nanospray mass spectrometry.

Science.gov (United States)

Paine, Martin R L; Barker, Philip J; Maclauglin, Shane A; Mitchell, Todd W; Blanksby, Stephen J

2012-02-29

Polymer-based surface coatings in outdoor applications experience accelerated degradation due to exposure to solar radiation, oxygen and atmospheric pollutants. These deleterious agents cause undesirable changes to the aesthetic and mechanical properties of the polymer, reducing its lifetime. The use of antioxidants such as hindered amine light stabilisers (HALS) retards these degradative processes; however, mechanisms for HALS action and polymer degradation are poorly understood. Detection of the HALS TINUVIN®123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) and the polymer degradation products directly from a polyester-based coil coating was achieved by liquid extraction surface analysis (LESA) coupled to a triple quadrupole QTRAP® 5500 mass spectrometer. The detection of TINUVIN®123 and melamine was confirmed by the characteristic fragmentation pattern observed in LESA-MS/MS spectra that was identical to that reported for authentic samples. Analysis of an unstabilised coil coating by LESA-MS after exposure to 4 years of outdoor field testing revealed the presence of melamine (1,3,5-triazine-2,4,6-triamine) as a polymer degradation product at elevated levels. Changes to the physical appearance of the coil coating, including powder-like deposits on the coating's surface, were observed to coincide with melamine deposits and are indicative of the phenomenon known as polymer 'blooming'. For the first time, in situ detection of analytes from a thermoset polymer coating was accomplished without any sample preparation, providing advantages over traditional extraction-analysis approaches and some contemporary ambient MS methods. Detection of HALS and polymer degradation products such as melamine provides insight into the mechanisms by which degradation occurs and suggests LESA-MS is a powerful new tool for polymer analysis. Copyright © 2012 John Wiley & Sons, Ltd.

Fabrication and in vitro degradation of porous fumarate-based polymer/alumoxane nanocomposite scaffolds for bone tissue engineering.

Science.gov (United States)

Mistry, Amit S; Cheng, Stacy H; Yeh, Tiffany; Christenson, Elizabeth; Jansen, John A; Mikos, Antonios G

2009-04-01

In this work, the fabrication and in vitro degradation of porous fumarate-based/alumoxane nanocomposites were evaluated for their potential as bone tissue engineering scaffolds. The biodegradable polymer poly (propylene fumarate)/propylene fumarate-diacrylate (PPF/PF-DA), a macrocomposite composed of PPF/PF-DA and boehmite microparticles, and a nanocomposite composed of PPF/PF-DA and surface-modified alumoxane nanoparticles were used to fabricate porous scaffolds by photo-crosslinking and salt-leaching. Scaffolds then underwent 12 weeks of in vitro degradation in phosphate buffered saline at 37 degrees C. The presence of boehmite microparticles and alumoxane nanoparticles in the polymer inhibited scaffold shrinkage during crosslinking. Furthermore, the incorporation of alumoxane nanoparticles into the polymer limited salt-leaching, perhaps due to tighter crosslinking within the nanocomposite. Analysis of crosslinking revealed that the acrylate and overall double bond conversions in the nanocomposite were higher than in the PPF/PF-DA polymer alone, though these differences were not significant. During 12 weeks of in vitro degradation, the nanocomposite lost 5.3% +/- 2.4% of its mass but maintained its compressive mechanical properties and porous architecture. The addition of alumoxane nanoparticles into the fumarate-based polymer did not significantly affect the degradation of the nanocomposite compared with the other materials in terms of mass loss, compressive properties, and porous structure. These results demonstrate the feasibility of fabricating degradable nanocomposite scaffolds for bone tissue engineering by photo-crosslinking and salt-leaching mixtures of fumarate-based polymers, alumoxane nanoparticles, and salt microparticles. Copyright 2008 Wiley Periodicals, Inc.

Scaling of Polymer Degradation Rate within a High-Reynolds-Number Turbulent Boundary Layer

Science.gov (United States)

Elbing, Brian; Solomon, Michael; Perlin, Marc; Dowling, David; Ceccio, Steven

2009-11-01

An experiment conducted at the U.S. Navy's Large Cavitation Channel on a 12.9 m long flat-plate test model produced the first quantitative measurements of polymer molecular weight within a turbulent boundary layer. Testing was conducted at speeds to 20 m/s and downstream distance based Reynolds numbers to 220 million. These results showed that the rate of polymer degradation by scission of the polymer chains increases with increased speed, downstream distance and surface roughness. With the surface fully rough at 20 m/s there was no measureable level of drag reduction at the first measurement location (0.56 m downstream of injection). These results are scaled with the assumption that the rate of degradation is dependent on the polymer residence time in the flow and the local shear rate. A successful collapse of the data within the measurement uncertainty was achieved over a range of flow speed (6.6 to 20 m/s), surface roughness (smooth and fully rough) and downstream distance from injection (0.56 to 9.28 m).

Probing polymer crystallization at processing-relevant cooling rates with synchrotron radiation

Energy Technology Data Exchange (ETDEWEB)

Cavallo, Dario, E-mail: Dario.cavallo@unige.it [University of Genoa, Dept. of Chemistry and Industrial Chemistry, Via Dodecaneso 31, 16146 Genoa (Italy); Portale, Giuseppe [ESRF, Dubble CRG, Netherlands Organization of Scientific Research (NWO), 38043 Grenoble (France); Androsch, René [Martin-Luther-University Halle-Wittenberg, Center of Engineering Sciences, D-06099 Halle/S. (Germany)

2015-12-17

Processing of polymeric materials to produce any kind of goods, from films to complex objects, involves application of flow fields on the polymer melt, accompanied or followed by its rapid cooling. Typically, polymers solidify at cooling rates which span over a wide range, from a few to hundreds of °C/s. A novel method to probe polymer crystallization at processing-relevant cooling rates is proposed. Using a custom-built quenching device, thin polymer films are ballistically cooled from the melt at rates between approximately 10 and 200 °C/s. Thanks to highly brilliant synchrotron radiation and to state-of-the-art X-ray detectors, the crystallization process is followed in real-time, recording about 20 wide angle X-ray diffraction patterns per second while monitoring the instantaneous sample temperature. The method is applied to a series of industrially relevant polymers, such as isotactic polypropylene, its copolymers and virgin and nucleated polyamide-6. Their crystallization behaviour during rapid cooling is discussed, with particular attention to the occurrence of polymorphism, which deeply impact material’s properties.

Quantitation of buried contamination by use of solvents. [degradation of silicone polymers by amine solvents

Science.gov (United States)

Pappas, S. P.; Hsiao, Y. C.; Hill, L. W.

1973-01-01

Spore recovery form cured silicone potting compounds using amine solvents to degrade the cured polymers was investigated. A complete list of solvents and a description of the effect of each on two different silicone polymers is provided.

Polymer Film-Based Screening and Isolation of Polylactic Acid (PLA)-Degrading Microorganisms.

Science.gov (United States)

Kim, Mi Yeon; Kim, Changman; Moon, Jungheun; Heo, Jinhee; Jung, Sokhee P; Kim, Jung Rae

2017-02-28

Polylactic acid (PLA) has been highlighted as an alternative renewable polymer for the replacement of petroleum-based plastic materials, and is considered to be biodegradable. On the other hand, the biodegradation of PLA by terminal degraders, such as microorganisms, requires a lengthy period in the natural environment, and its mechanism is not completely understood. PLA biodegradation studies have been conducted using mainly undefined mixed cultures, but only a few bacterial strains have been isolated and examined. For further characterization of PLA biodegradation, in this study, the PLA-degrading bacteria from digester sludge were isolated and identified using a polymer film-based screening method. The enrichment of sludge on PLA granules was conducted with the serial transference of a subculture into fresh media for 40 days, and the attached biofilm was inoculated on a PLA film on an agar plate. 3D optical microscopy showed that the isolates physically degraded the PLA film due to bacterial degradation. 16S rRNA gene sequencing identified the microbial colonies to be Pseudomonas sp. MYK1 and Bacillus sp. MYK2. The two isolates exhibited significantly higher specific gas production rates from PLA biodegradation compared with that of the initial sludge inoculum.

Polymer degradation in reactive ion etching and its possible application to all dry processes

International Nuclear Information System (INIS)

Hiraoka, H.; Welsh, L.W. Jr.

1981-01-01

Dry etching processes involving CF 4 -plasma and reactive ion etching become increasingly important for microcircuit fabrication techniques. In these techniques polymer degradation and etch resistance against reactive species like F atoms and CF 3 + ions are the key factors in the processes. It is well-known that classical electron beam resists like poly(methyl methacrylate) and poly(1-butene sulfone) are not suitable for dry etching processes because they degrade rapidly under these etching conditions. In order to find a correlation of etching rate and polymer structures the thickness loss of polymer films have been measured for a variety of polymer films in reactive ion etching conditions, where CF 3 + ions are the major reactive species with an accelerating potential of 500 volts. Because of its high CF 4 -plasma and reactive ion etch resistance, and because of its high electron beam sensitivity, poly(methacrylonitrile) provides a positive working electron beam resist uniquely suited for all dry processes. (author)

Study of in vitro degradation of biodegradable polymer based thin ...

African Journals Online (AJOL)

GREGORY

2011-12-16

Dec 16, 2011 ... treatment of bone fracture costs over Ł 900 million annually in the ... implantation when the cells start to migrate deep into the scaffold (Ma .... DISCUSSION. Figure 8 is ... polymer-based materials proceeds via a surface erosion mechanism. ... materials and the critical thickness above which the degradation ...

Degradable polyphosphazene/poly(alpha-hydroxyester) blends: degradation studies.

Science.gov (United States)

Ambrosio, Archel M A; Allcock, Harry R; Katti, Dhirendra S; Laurencin, Cato T

2002-04-01

Biomaterials based on the polymers of lactic acid and glycolic acid and their copolymers are used or studied extensively as implantable devices for drug delivery, tissue engineering and other biomedical applications. Although these polymers have shown good biocompatibility, concerns have been raised regarding their acidic degradation products, which have important implications for long-term implantable systems. Therefore, we have designed a novel biodegradable polyphosphazene/poly(alpha-hydroxyester) blend whose degradation products are less acidic than those of the poly(alpha-hydroxyester) alone. In this study, the degradation characteristics of a blend of poly(lactide-co-glycolide) (50:50 PLAGA) and poly[(50% ethyl glycinato)(50% p-methylphenoxy) phosphazene] (PPHOS-EG50) were qualitatively and quantitatively determined with comparisons made to the parent polymers. Circular matrices (14mm diameter) of the PLAGA, PPHOS-EG50 and PLAGA-PPHOS-EG50 blend were degraded in non-buffered solutions (pH 7.4). The degraded polymers were characterized for percentage mass loss and molecular weight and the degradation medium was characterized for acid released in non-buffered solutions. The amounts of neutralizing base necessary to bring about neutral pH were measured for each polymer or polymer blend during degradation. The poly(phosphazene)/poly(lactide-co-glycolide) blend required significantly less neutralizing base in order to bring about neutral solution pH during the degradation period studied. The results indicated that the blend degraded at a rate intermediate to that of the parent polymers and that the degradation products of the polyphosphazene neutralized the acidic degradation products of PLAGA. Thus, results from these in vitro degradation studies suggest that the PLAGA-PPHOS-EG50 blend may provide a viable improvement to biomaterials based on acid-releasing organic polymers.

The impact of shape memory test on degradation profile of a bioresorbable polymer.

Science.gov (United States)

Musioł, Marta; Jurczyk, Sebastian; Kwiecień, Michał; Smola-Dmochowska, Anna; Domański, Marian; Janeczek, Henryk; Włodarczyk, Jakub; Klim, Magdalena; Rydz, Joanna; Kawalec, Michał; Sobota, Michał

2018-05-01

The semicrystalline poly(L-lactide) (PLLA) belongs to the materials with shape memory effect (SME) and as a bioresorbable and biocompatible polymer it have found many applications in medical and pharmaceutical field. Assessment of the SME impact on the polymer degradation profile plays crucial role in applications such as drug release systems or in regenerative medicine. Herein, the results of in vitro degradation studies of PLLA samples after SME full test cycle are presented. The samples were loaded and deformed in two manners: progressive and non-progressive. The performed experiments illustrate also influence of the material mechanical damages, caused e.g. during incorrect implantation of PLLA product, on hydrolytic degradation profile. Apparently, degradation profiles are significantly different for the material which was not subjected to the deformation and the deformed ones. The materials after deformation of 50% (in SME cycle) was characterized by non-reversible morphology changes. The effect was observed in deformed samples during the SME test which were carried out ten times. Copyright © 2018 Elsevier Ltd. All rights reserved.

Nanoscale indent formation in shape memory polymers using a heated probe tip

Energy Technology Data Exchange (ETDEWEB)

Yang, F [Department of Mechanical Science and Engineering, University of Illinois Urbana-Champaign, Urbana, IL 61801 (United States); Wornyo, E [School of Electrical and Computer Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Gall, K [Department of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States); King, W P [Department of Mechanical Science and Engineering, University of Illinois Urbana-Champaign, Urbana, IL 61801 (United States)

2007-07-18

This paper presents experimental investigation of nanoscale indentation formation in shape memory polymers. The polymers were synthesized by photopolymerizing a tert-butyl acrylate (tBA) monomer with a poly(ethylene glycol dimethacrylate) (PEGDMA) crosslinker. The concentration and the molecular weight of the crosslinker were varied to produce five polymers with tailored properties. Nanoscale indentations were formed on the polymer surfaces by using a heated atomic force microscope (AFM) cantilever at various temperatures near or above the glass transition (between 84 and 215 deg. C) and a range of heating durations from 100 {mu}s to 8 ms. The images of the indents were obtained with the same probe tip at room temperature. The contact pressure, a measure of transient hardness, was derived from the indentation height data as a function of time and temperature for different polymers. With increasing crosslinker molecular weight and decreasing crosslinker concentration, the contact pressures decreased at a fixed maximum load due to increased crosslink spacing in the polymer system. The results provide insight into the nanoscale response of these novel materials.

Mass spectrometry for the elucidation of the subtle molecular structure of biodegradable polymers and their degradation products.

Science.gov (United States)

Kowalczuk, Marek; Adamus, Grażyna

2016-01-01

Contemporary reports by Polish authors on the application of mass spectrometric methods for the elucidation of the subtle molecular structure of biodegradable polymers and their degradation products will be presented. Special emphasis will be given to natural aliphatic (co)polyesters (PHA) and their synthetic analogues, formed through anionic ring-opening polymerization (ROP) of β-substituted β-lactones. Moreover, the application of MS techniques for the evaluation of the structure of biodegradable polymers obtained in ionic and coordination polymerization of cyclic ethers and esters as well as products of step-growth polymerization, in which bifunctional or multifunctional monomers react to form oligomers and eventually long chain polymers, will be discussed. Furthermore, the application of modern MS techniques for the assessment of polymer degradation products, frequently bearing characteristic end groups that can be revealed and differentiated by MS, will be discussed within the context of specific degradation pathways. Finally, recent Polish accomplishments in the area of mass spectrometry will be outlined. © 2015 Wiley Periodicals, Inc.

Ultrasound degradation of xanthan polymer in aqueous solution: Its scission mechanism and the effect of NaCl incorporation.

Science.gov (United States)

Saleh, H M; Annuar, M S M; Simarani, K

2017-11-01

Degradation of xanthan polymer in aqueous solution by ultrasonic irradiation was investigated. The effects of selected variables i.e. sonication intensity, irradiation time, concentration of xanthan gum and molar concentration of NaCl in solution were studied. Combined approach of full factorial design and conventional one-factor-at-a-time was applied to obtain optimum degradation at sonication power intensity of 11.5Wcm -2 , irradiation time 120min and 0.1gL -1 xanthan in a salt-free solution. Molecular weight reduction of xanthan gum under sonication was described by an exponential decay function with higher rate constant for polymer degradation in the salt free solution. The limiting molecular weight where fragments no longer undergo scission was determined from the function. The incorporation of NaCl in xanthan solution resulted in a lower limiting molecular weight. The ultrasound-mediated degradation of aqueous xanthan polymer chain agreed with a random scission model. Side chain of xanthan polymer is proposed to be the primary site of scission action. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermal degradation process of poly (alpha-methylstyrene) microspheres coated with glow discharge polymer

International Nuclear Information System (INIS)

Zhang Zhanwen; Huang Yong; Tang Yongjian; Li Bo; Chen Sufen; He Zhibing

2009-01-01

Glow discharge polymer (GDP) shell was made by the decomposable mandrel technique using poly(alpha-methylstyrene) (PAMS) mandrel. The PAMS degradation rate and the GDP shell surface morphology at different equilibrium temperatures were investigated. Degradation rate was calculated from weight variation of PAMS before and after pyrolysis process. Experiment results indicate that the degradation rate decreases at the fixed equilibrium temperature and graded temperature can improve the rate. The degradation process has an effect on the GDP shell properties. The PAMS doesn't molten to flow liquid during degradation. But the degradation can reduce surface finish of GDP coatings. The GDP shell deffects are the result of the PAMS degradiation process. (authors)

Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

Energy Technology Data Exchange (ETDEWEB)

Liu, Baoxia [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Huang, Yankai [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhu, Xu; Hao, Yuanqiang [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Ding, Yujie [College of Biochemical Engineering, Anhui Polytechnic University, Wuhu 241000 (China); Wei, Wei; Wang, Qi [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Qu, Peng, E-mail: qupeng0212@163.com [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Xu, Maotian, E-mail: xumaotian@sqnc.edu.cn [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China)

2016-03-17

Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg{sup 2+} detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb{sup 3+} from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg{sup 2+} into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg{sup 2+}. As a kind of Hg{sup 2+} nanosensor, the probe exhibited excellent selectivity for Hg{sup 2+} and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg{sup 2+} in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg{sup 2+} was achieved based on time-resolved spectroscopy.

Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

International Nuclear Information System (INIS)

Liu, Baoxia; Huang, Yankai; Zhu, Xu; Hao, Yuanqiang; Ding, Yujie; Wei, Wei; Wang, Qi; Qu, Peng; Xu, Maotian

2016-01-01

Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg"2"+ detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb"3"+ from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg"2"+ into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg"2"+. As a kind of Hg"2"+ nanosensor, the probe exhibited excellent selectivity for Hg"2"+ and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg"2"+ in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg"2"+ was achieved based on time-resolved spectroscopy.

Degradation and stability of R2R manufactured polymer solar cells

DEFF Research Database (Denmark)

Norrman, Kion; Krebs, Frederik C

2009-01-01

Polymer solar cells have many advantages such as light weight, flexibility, environmental friendliness, low thermal budget, low cost and most notably very fast modes of production by printing techniques. Production experiments have shown that it is highly feasible with existing technology to mass...... produce polymer solar cells at a very low cost. We have employed state-of-the-art analytical techniques to address the challenging issues of degradation and stability of R2R manufactured devices. We have specifically studied the relative effect of oxygen and water on the operational devices in regard...

Remote Determination of Time-Dependent Stiffness of Surface-Degrading-Polymer Scaffolds Via Synchrotron-Based Imaging.

Science.gov (United States)

Bawolin, N K; Chen, X B

2017-04-01

Surface-degrading polymers have been widely used to fabricate scaffolds with the mechanical properties appropriate for tissue regeneration/repair. During their surface degradation, the material properties of polymers remain approximately unchanged, but the scaffold geometry and thus mechanical properties vary with time. This paper presents a novel method to determine the time-dependent mechanical properties, particularly stiffness, of scaffolds from the geometric changes captured by synchrotron-based imaging, with the help of finite element analysis (FEA). Three-dimensional (3D) tissue scaffolds were fabricated from surface-degrading polymers, and during their degradation, the tissue scaffolds were imaged via the synchrotron-based imaging to characterize their changing geometry. On this basis, the stiffness behavior of scaffolds was estimated from the FEA, and the results obtained were compared to the direct measurements of scaffold stiffness from the load-displacement material testing. The comparison illustrates that the Young's moduli estimated from the FEA and characterized geometry are in agreement with the ones of direct measurements. The developed method of estimating the mechanical behavior was also demonstrated effective with a nondegrading scaffold that displays the nonlinear stress-strain behavior. The in vivo monitoring of Young's modulus by morphology characterization also suggests the feasibility of characterizing experimentally the difference between in vivo and in vitro surface degradation of tissue engineering constructs.

Thermal degradation of polymer systems having liquid crystalline oligoester segment

Directory of Open Access Journals (Sweden)

Renato Matroniani

Full Text Available Abstract Block copolymers and blends comprised by liquid crystalline oligoester and polystyrene were prepared and their thermal stability were characterized by thermogravimetric analysis (TGA. The samples have shown three main decomposition temperatures due to (1 lost of flexible chain and decomposition of mesogenic segment, (2 decomposition of polystyrene and (3 final decomposition of oligoester rigid segment. Both copolymers and polymer blends presented lower thermal stability compared to polystyrene and oligoester. The residual mass after heating at 600 °C in copolymers and polymer blends were lower than those found in the oligoesters. A degradative process of aromatic segments of oligoester induced by decomposition of polystyrene is suggested.

U-Shaped and Surface Functionalized Polymer Optical Fiber Probe for Glucose Detection.

Science.gov (United States)

Azkune, Mikel; Ruiz-Rubio, Leire; Aldabaldetreku, Gotzon; Arrospide, Eneko; Pérez-Álvarez, Leyre; Bikandi, Iñaki; Zubia, Joseba; Vilas-Vilela, Jose Luis

2017-12-25

In this work we show an optical fiber evanescent wave absorption probe for glucose detection in different physiological media. High selectivity is achieved by functionalizing the surface of an only-core poly(methyl methacrylate) (PMMA) polymer optical fiber with phenilboronic groups, and enhanced sensitivity by using a U-shaped geometry. Employing a supercontinuum light source and a high-resolution spectrometer, absorption measurements are performed in the broadband visible light spectrum. Experimental results suggest the feasibility of such a fiber probe as a low-cost and selective glucose detector.

Drug-releasing shape-memory polymers - the role of morphology, processing effects, and matrix degradation.

Science.gov (United States)

Wischke, Christian; Behl, Marc; Lendlein, Andreas

2013-09-01

Shape-memory polymers (SMPs) have gained interest for temporary drug-release systems that should be anchored in the body by self-sufficient active movements of the polymeric matrix. Based on the so far published scientific literature, this review highlights three aspects that require particular attention when combining SMPs with drug molecules: i) the defined polymer morphology as required for the shape-memory function, ii) the strong effects that processing conditions such as drug-loading methodologies can have on the drug-release pattern from SMPs, and iii) the independent control of drug release and degradation by their timely separation. The combination of SMPs with a drug-release functionality leads to multifunctional carriers that are an interesting technology for pharmaceutical sciences and can be further expanded by new materials such as thermoplastic SMPs or temperature-memory polymers. Experimental studies should include relevant molecules as (model) drugs and provide a thermomechanical characterization also in an aqueous environment, report on the potential effect of drug type and loading levels on the shape-memory functionality, and explore the potential correlation of polymer degradation and drug release.

Enhanced regeneration of degraded polymer solar cells by thermal annealing

Energy Technology Data Exchange (ETDEWEB)

Kumar, Pankaj, E-mail: pankaj@mail.nplindia.ernet.in [CSIR-National Physical Laboratory, Dr. K. S. Krishnan Marg, New Delhi 110012 (India); Centre for Organic Electronics, Physics, University of Newcastle, Callaghan NSW-2308 (Australia); Bilen, Chhinder; Zhou, Xiaojing; Belcher, Warwick J.; Dastoor, Paul C., E-mail: Paul.Dastoor@newcastle.edu.au [Centre for Organic Electronics, Physics, University of Newcastle, Callaghan NSW-2308 (Australia); Feron, Krishna [Centre for Organic Electronics, Physics, University of Newcastle, Callaghan NSW-2308 (Australia); CSIRO Energy Technology, P. O. Box 330, Newcastle NSW 2300 (Australia)

2014-05-12

The degradation and thermal regeneration of poly(3-hexylethiophene) (P3HT):[6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCBM) and P3HT:indene-C{sub 60} bisadduct (ICBA) polymer solar cells, with Ca/Al and Ca/Ag cathodes and indium tin oxide/poly(ethylene-dioxythiophene):polystyrene sulfonate anode have been investigated. Degradation occurs via a combination of three primary pathways: (1) cathodic oxidation, (2) active layer phase segregation, and (3) anodic diffusion. Fully degraded devices were subjected to thermal annealing under inert atmosphere. Degraded solar cells possessing Ca/Ag electrodes were observed to regenerate their performance, whereas solar cells having Ca/Al electrodes exhibited no significant regeneration of device characteristics after thermal annealing. Moreover, the solar cells with a P3HT:ICBA active layer exhibited enhanced regeneration compared to P3HT:PCBM active layer devices as a result of reduced changes to the active layer morphology. Devices combining a Ca/Ag cathode and P3HT:ICBA active layer demonstrated ∼50% performance restoration over several degradation/regeneration cycles.

Enhanced regeneration of degraded polymer solar cells by thermal annealing

International Nuclear Information System (INIS)

Kumar, Pankaj; Bilen, Chhinder; Zhou, Xiaojing; Belcher, Warwick J.; Dastoor, Paul C.; Feron, Krishna

2014-01-01

The degradation and thermal regeneration of poly(3-hexylethiophene) (P3HT):[6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) and P3HT:indene-C 60 bisadduct (ICBA) polymer solar cells, with Ca/Al and Ca/Ag cathodes and indium tin oxide/poly(ethylene-dioxythiophene):polystyrene sulfonate anode have been investigated. Degradation occurs via a combination of three primary pathways: (1) cathodic oxidation, (2) active layer phase segregation, and (3) anodic diffusion. Fully degraded devices were subjected to thermal annealing under inert atmosphere. Degraded solar cells possessing Ca/Ag electrodes were observed to regenerate their performance, whereas solar cells having Ca/Al electrodes exhibited no significant regeneration of device characteristics after thermal annealing. Moreover, the solar cells with a P3HT:ICBA active layer exhibited enhanced regeneration compared to P3HT:PCBM active layer devices as a result of reduced changes to the active layer morphology. Devices combining a Ca/Ag cathode and P3HT:ICBA active layer demonstrated ∼50% performance restoration over several degradation/regeneration cycles

Local impact of humidification on degradation in polymer electrolyte fuel cells

Science.gov (United States)

Sanchez, Daniel G.; Ruiu, Tiziana; Biswas, Indro; Schulze, Mathias; Helmly, Stefan; Friedrich, K. Andreas

2017-06-01

The water level in a polymer electrolyte membrane fuel cell (PEMFC) affects the durability as is seen from the degradation processes during operation a PEMFC with fully- and nonhumidified gas streams as analyzed using an in-situ segmented cell for local current density measurements during a 300 h test operating under constant conditions and using ex situ SEM/EDX and XPS post-test analysis of specific regions. The impact of the RH on spatial distribution of the degradation process results from different water distribution giving different chemical environments. Under nonhumidified gas streams, the cathode inlet region exhibits increased degradation, whereas with fully humidified gases the bottom of the cell had the higher performance losses. The degradation and the degree of reversibility produced by Pt dissolution, PTFE defluorination, and contaminants such as silicon (Si) and nickel (Ni) were locally evaluated.

Modern mass spectrometry in the characterization and degradation of biodegradable polymers

International Nuclear Information System (INIS)

Rizzarelli, Paola; Carroccio, Sabrina

2014-01-01

Graphical abstract: -- Highlights: •Recent trends in the structural characterization of biodegradable polymers by MALDI and ESI MS are discussed. •MALDI MS as a noteworthy tool to follow the synthetic polymerization route of biodegradable materials is evidenced. •Elucidation of degradation mechanisms by modern MS techniques is examined. •ESI MS and HPLC–ESI MS are highlighted as highly suitable methods for structural and quantitative analysis of water-soluble biodegradation products. •Novel MS methods developed ad hoc and new MALDI matrices for biodegradable polymers are reviewed. -- Abstract: In the last decades, the solid-waste management related to the extensively growing production of plastic materials, in concert with their durability, have stimulated increasing interest in biodegradable polymers. At present, a variety of biodegradable polymers has already been introduced onto the market and can now be competitive with non biodegradable thermoplastics in different fields (packaging, biomedical, textile, etc.). However, a significant economical effort is still directed in tailoring structural properties in order to further broaden the range of applications without impairing biodegradation. Improving the performance of biodegradable materials requires a good characterization of both physico-chemical and mechanical parameters. Polymer analysis can involve many different features including detailed characterization of chemical structures and compositions as well as average molecular mass determination. It is of outstanding importance in troubleshooting of a polymer manufacturing process and for quality control, especially in biomedical applications. This review describes recent trends in the structural characterization of biodegradable materials by modern mass spectrometry (MS). It provides an overview of the analytical tools used to evaluate their degradation. Several successful applications of MALDI-TOF MS (matrix assisted laser desorption ionization

Modern mass spectrometry in the characterization and degradation of biodegradable polymers

Energy Technology Data Exchange (ETDEWEB)

Rizzarelli, Paola, E-mail: paola.rizzarelli@cnr.it; Carroccio, Sabrina

2014-01-15

Graphical abstract: -- Highlights: •Recent trends in the structural characterization of biodegradable polymers by MALDI and ESI MS are discussed. •MALDI MS as a noteworthy tool to follow the synthetic polymerization route of biodegradable materials is evidenced. •Elucidation of degradation mechanisms by modern MS techniques is examined. •ESI MS and HPLC–ESI MS are highlighted as highly suitable methods for structural and quantitative analysis of water-soluble biodegradation products. •Novel MS methods developed ad hoc and new MALDI matrices for biodegradable polymers are reviewed. -- Abstract: In the last decades, the solid-waste management related to the extensively growing production of plastic materials, in concert with their durability, have stimulated increasing interest in biodegradable polymers. At present, a variety of biodegradable polymers has already been introduced onto the market and can now be competitive with non biodegradable thermoplastics in different fields (packaging, biomedical, textile, etc.). However, a significant economical effort is still directed in tailoring structural properties in order to further broaden the range of applications without impairing biodegradation. Improving the performance of biodegradable materials requires a good characterization of both physico-chemical and mechanical parameters. Polymer analysis can involve many different features including detailed characterization of chemical structures and compositions as well as average molecular mass determination. It is of outstanding importance in troubleshooting of a polymer manufacturing process and for quality control, especially in biomedical applications. This review describes recent trends in the structural characterization of biodegradable materials by modern mass spectrometry (MS). It provides an overview of the analytical tools used to evaluate their degradation. Several successful applications of MALDI-TOF MS (matrix assisted laser desorption ionization

Probing the surface properties of a polymer glass with macroscopic friction

International Nuclear Information System (INIS)

Bureau, Lionel

2007-01-01

We show how macroscopic friction can be used as a sensitive probe of chain dynamics at the surface of a glassy polymer. We present experiments in which a smooth poly(methylmethacrylate) (PMMA) solid slides on flat surfaces presenting different densities of pinning sites available for polymer/substrate bond formation. These experiments indicate that: (i) at high pinning level, frictional dissipation occurs through the sudden flips of molecular-sized bistable regions localized in a nm-thick layer of confined chains, which responds to shear as an elasto-plastic solid, and (ii) in situations of weak pinning, dissipation appears to be governed by a process akin to that proposed for rubber friction. This suggests that some 'glass-to-rubber' transition occurs at the polymer surface when its interaction with the substrate goes from strong to weak. The temperature-dependence of friction provides further support for the presence of a nm-thick layer at the polymer surface, which exhibits a rubberlike response in situation of weak interaction with the countersurface. This behavior results from the interplay between viscous flow in this surface layer, and shear induced depinning of adsorbed surface chains. Moreover, a quantitative analysis of the results indicates that the pinning dynamics of polymer chains is controlled by localized β rotational motions at the interface

Operational electrochemical stability of thiophene-thiazole copolymers probed by resonant Raman spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Wade, Jessica; Wood, Sebastian; Kim, Ji-Seon, E-mail: ji-seon.kim@imperial.ac.uk [Department of Physics and Centre for Plastic Electronics, Imperial College London, London SW7 2AZ (United Kingdom); Beatrup, Daniel; Hurhangee, Michael; McCulloch, Iain; Durrant, James R. [Department of Chemistry and Centre for Plastic Electronics, Imperial College London, London SW7 2AY (United Kingdom); Bronstein, Hugo [Department of Chemistry and Centre for Plastic Electronics, Imperial College London, London SW7 2AY (United Kingdom); Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom)

2015-06-28

We report on the electrochemical stability of hole polarons in three conjugated polymers probed by resonant Raman spectroscopy. The materials considered are all isostructural to poly(3-hexyl)thiophene, where thiazole units have been included to systematically deepen the energy level of the highest occupied molecular orbital (HOMO). We demonstrate that increasing the thiazole content planarizes the main conjugated backbone of the polymer and improves the electrochemical stability in the ground state. However, these more planar thiazole containing polymers are increasingly susceptible to electrochemical degradation in the polaronic excited state. We identify the degradation mechanism, which targets the C=N bond in the thiazole units and results in disruption of the main polymer backbone conjugation. The introduction of thiazole units to deepen the HOMO energy level and increase the conjugated backbone planarity can be beneficial for the performance of certain optoelectronic devices, but the reduced electrochemical stability of the hole polaron may compromise their operational stability.

Development of specific oligonucleotide probes for the identification and in situ detection of hydrocarbon-degrading Alcanivorax strains.

Science.gov (United States)

Syutsubo, K; Kishira, H; Harayama, S

2001-06-01

The genus Alcanivorax comprises diverse hydrocarbon-degrading marine bacteria. Novel 16S rRNA-targeted oligonucleotide DNA probes (ALV735 and ALV735-b) were developed to quantify two subgroups of the Alcanivorax/Fundibacter group by fluorescence in situ hybridization (FISH), and the conditions for the single-mismatch discrimination of the probes were optimized. The specificity of the probes was improved further using a singly mismatched oligonucleotide as a competitor. The growth of Alcanivorax cells in crude oil-contaminated sea water under the biostimulation condition was investigated by FISH with the probe ALV735, which targeted the main cluster of the Alcanivorax/Fundibacter group. The size of the Alcanivorax population increased with increasing incubation time and accounted for 91% of the 4',6-diamidino-2-phenylindole (DAPI) count after incubation for 2 weeks. The probes developed in this study are useful for detecting Alcanivorax populations in petroleum hydrocarbon-degrading microbial consortia.

Long-term degradation of organic polymers under conditions found in deep repositories for low and intermediate-level wastes; Langzeit-Degradation von organischen Polymeren unter SMA-Tiefenlagerbedingungen

Energy Technology Data Exchange (ETDEWEB)

Warthmann, R.; Mosberger, L.; Baier, U.

2013-06-15

On behalf of Nagra, the Environmental Biotechnology Section of the Zürich University of Applied Sciences in Wädenswil investigated the potential for microbiological degradation of organic polymers under the conditions found in a deep geological repository for low- and intermediate-level waste (L/ILW). The existing scientific literature on the topic was analysed, some thermodynamic calculations carried out and input was elicited from internationally recognised experts in the field. The study was restricted to a few substances which, in terms of mass, are most significant in the Swiss L/ILW inventory; these are polystyrene (PS), polyvinyl chloride (PVC), other plastics and bitumen. There were no clear indications in the literature that the polymer structure of synthetic polymers is biodegraded under anoxic conditions. However, functional groups of ion exchangers and plasticizers in plastics are considered to be readily available and biodegradable. The greatest obstacle to biological degradation of synthetic polymers is depolymerisation to produce labile monomers. As energy is generally required for such breakdown, the chances of this process taking place outside the cells are very low. In so far as they are present, monomers are, in principle, anaerobically biodegradable. Thermodynamic considerations indicate that degradation of synthetic polymers under repository conditions is theoretically possible. However, the degradation of polystyrene is very close to thermodynamic equilibrium and the usable energy for microorganisms would barely be sufficient. Under high H2 partial pressures, it is predicted that there will be a thermodynamic inhibition of anaerobic degradation, as certain interim steps in degradation are endergonic. The starting conditions for microbial growth in a deep repository are unfavourable in terms of availability of water and prevailing pH values. Practically no known microorganisms can tolerate the combination of these conditions; most known

Development of an oxygen-sensitive degradable peptide probe for the imaging of hypoxia-inducible factor-1-active regions in tumors.

Science.gov (United States)

Ueda, Masashi; Ogawa, Kei; Miyano, Azusa; Ono, Masahiro; Kizaka-Kondoh, Shinae; Saji, Hideo

2013-12-01

We aimed to develop a radiolabeled peptide probe for the imaging of hypoxia-inducible factor-1 (HIF-1)-active tumors. We synthesized the peptide probes that contain or lack an essential sequence of the oxygen-dependent degradation of HIF-1α in proteasomes ((123/125)I-DKOP30 or (125)I-mDKOP, respectively). The degradation of probes was evaluated in vitro using cell lysates containing proteasomes. In vivo biodistribution study, planar imaging, autoradiography, and comparison between probe accumulation and HIF-1 transcriptional activity were also performed. The (125)I-DKOP30 underwent degradation in a proteasome-dependent manner, while (125)I-mDKOP was not degraded. Biodistribution analysis showed (125)I-DKOP30 accumulation in tumors. The tumors were clearly visualized by in vivo imaging, and intratumoral distribution of (125)I-DKOP30 coincided with the HIF-1α-positive hypoxic regions. Tumoral accumulation of (125)I-DKOP30 was significantly correlated with HIF-1-dependent luciferase bioluminescence, while that of (125)I-mDKOP was not. (123)I-DKOP30 is a useful peptide probe for the imaging of HIF-1-active tumors.

Imaging the intracellular degradation of biodegradable polymer nanoparticles

Directory of Open Access Journals (Sweden)

Anne-Kathrin Barthel

2014-10-01

Full Text Available In recent years, the development of smart drug delivery systems based on biodegradable polymeric nanoparticles has become of great interest. Drug-loaded nanoparticles can be introduced into the cell interior via endocytotic processes followed by the slow release of the drug due to degradation of the nanoparticle. In this work, poly(L-lactic acid (PLLA was chosen as the biodegradable polymer. Although common degradation of PLLA has been studied in various biological environments, intracellular degradation processes have been examined only to a very limited extent. PLLA nanoparticles with an average diameter of approximately 120 nm were decorated with magnetite nanocrystals and introduced into mesenchymal stem cells (MSCs. The release of the magnetite particles from the surface of the PLLA nanoparticles during the intracellular residence was monitored by transmission electron microscopy (TEM over a period of 14 days. It was demonstrated by the release of the magnetite nanocrystals from the PLLA surface that the PLLA nanoparticles do in fact undergo degradation within the cell. Furthermore, even after 14 days of residence, the PLLA nanoparticles were found in the MSCs. Additionally, the ultrastructural TEM examinations yield insight into the long term intercellular fate of these nanoparticles. From the statistical analysis of ultrastructural details (e.g., number of detached magnetite crystals, and the number of nanoparticles in one endosome, we demonstrate the importance of TEM studies for such applications in addition to fluorescence studies (flow cytometry and confocal laser scanning microscopy.

A high brightness probe of polymer nanoparticles for biological imaging

Science.gov (United States)

Zhou, Sirong; Zhu, Jiarong; Li, Yaping; Feng, Liheng

2018-03-01

Conjugated polymer nanoparticles (CPNs) with high brightness in long wavelength region were prepared by the nano-precipitation method. Based on fluorescence resonance energy transfer (FRET) mechanism, the high brightness property of the CPNs was realized by four different emission polymers. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) displayed that the CPNs possessed a spherical structure and an average diameter of 75 nm. Analysis assays showed that the CPNs had excellent biocompatibility, good photostability and low cytotoxicity. The CPNs were bio-modified with a cell penetrating peptide (Tat, a targeted element) through covalent link. Based on the entire wave fluorescence emission, the functionalized CPNs1-4 can meet multichannel and high throughput assays in cell and organ imaging. The contribution of the work lies in not only providing a new way to obtain a high brightness imaging probe in long wavelength region, but also using targeted cell and organ imaging.

Development and applications of advanced probing tools for cell wall biology

DEFF Research Database (Denmark)

Hansen, Aleksander Riise

. In this study, antigens consisting of crude mixtures of alkali extracted polymers from the grass model Brachypodium distachyon were targets for probe generation using a naïve human single domain antibody library. Epitope characterization of positive clones from phage ELISA was then further elucidated...... the function of pectin methyl esterase inhibitors and their role in plant defense against microbial degradation, and cell wall structural dynamics in relation to cell detachment from roots. The second part describes phage display as a method for developing probes against targets that are poor immunogens...

Dual-Color Fluorescence Imaging of Magnetic Nanoparticles in Live Cancer Cells Using Conjugated Polymer Probes

Science.gov (United States)

Sun, Minjie; Sun, Bin; Liu, Yun; Shen, Qun-Dong; Jiang, Shaojun

2016-01-01

Rapid growth in biological applications of nanomaterials brings about pressing needs for exploring nanomaterial-cell interactions. Cationic blue-emissive and anionic green-emissive conjugated polymers are applied as dual-color fluorescence probes to the surface of negatively charged magnetic nanoparticles through sequentially electrostatic adsorption. These conjugated polymers have large extinction coefficients and high fluorescence quantum yield (82% for PFN and 62% for ThPFS). Thereby, one can visualize trace amount (2.7 μg/mL) of fluorescence-labeled nanoparticles within cancer cells by confocal laser scanning microscopy. Fluorescence labeling by the conjugated polymers is also validated for quantitative determination of the internalized nanoparticles in each individual cell by flow cytometry analysis. Extensive overlap of blue and green fluorescence signals in the cytoplasm indicates that both conjugated polymer probes tightly bind to the surface of the nanoparticles during cellular internalization. The highly charged and fluorescence-labeled nanoparticles non-specifically bind to the cell membranes, followed by cellular uptake through endocytosis. The nanoparticles form aggregates inside endosomes, which yields a punctuated staining pattern. Cellular internalization of the nanoparticles is dependent on the dosage and time. Uptake efficiency can be enhanced three-fold by application of an external magnetic field. The nanoparticles are low cytotoxicity and suitable for simultaneously noninvasive fluorescence and magnetic resonance imaging application. PMID:26931282

Biodegradability of PP/HMSPP and natural and synthetic polymers blends in function of gamma irradiation degradation

Science.gov (United States)

Cardoso, Elisabeth C. L.; Scagliusi, Sandra R.; Lima, Luis F. C. P.; Bueno, Nelson R.; Brant, Antonio J. C.; Parra, Duclerc F.; Lugão, Ademar B.

2014-01-01

Polymers are used for numerous applications in different industrial segments, generating enormous quantities of discarding in the environment. Polymeric materials composites account for an estimated from 20 to 30% total volume of solid waste. Polypropylene (PP) undergoes crosslinking and extensive main chain scissions when submitted to ionizing irradiation; as one of the most widely used linear hydrocarbon polymers, PP, made from cheap petrochemical feed stocks, shows easy processing leading it to a comprehensive list of finished products. Consequently, there is accumulation in the environment, at 25 million tons per year rate, since polymeric products are not easily consumed by microorganisms. PP polymers are very bio-resistant due to involvement of only carbon atoms in main chain with no hydrolysable functional group. Several possibilities have been considered to minimize the environmental impact caused by non-degradable plastics, subjecting them to: physical, chemical and biological degradation or combination of all these due to the presence of moisture, air, temperature, light, high energy radiation or microorganisms. There are three main classes of biodegradable polymers: synthetic polymers, natural polymers and blends of polymers in which one or more components are readily consumed by microorganisms. This work aims to biodegradability investigation of a PP/HMSPP (high melt strength polypropylene) blended with sugarcane bagasse, PHB (poly-hydroxy-butyrate) and PLA (poly-lactic acid), both synthetic polymers, at a 10% level, subjected to gamma radiation at 50, 100, 150 and 200 kGy doses. Characterization will comprise IR, DSC, TGA, OIT and Laboratory Soil Burial Test (LSBT).

Long-term degradation of organic polymers under conditions found in deep repositories for low and intermediate-level wastes

International Nuclear Information System (INIS)

Warthmann, R.; Mosberger, L.; Baier, U.

2013-06-01

On behalf of Nagra, the Environmental Biotechnology Section of the Zürich University of Applied Sciences in Wädenswil investigated the potential for microbiological degradation of organic polymers under the conditions found in a deep geological repository for low- and intermediate-level waste (L/ILW). The existing scientific literature on the topic was analysed, some thermodynamic calculations carried out and input was elicited from internationally recognised experts in the field. The study was restricted to a few substances which, in terms of mass, are most significant in the Swiss L/ILW inventory; these are polystyrene (PS), polyvinyl chloride (PVC), other plastics and bitumen. There were no clear indications in the literature that the polymer structure of synthetic polymers is biodegraded under anoxic conditions. However, functional groups of ion exchangers and plasticizers in plastics are considered to be readily available and biodegradable. The greatest obstacle to biological degradation of synthetic polymers is depolymerisation to produce labile monomers. As energy is generally required for such breakdown, the chances of this process taking place outside the cells are very low. In so far as they are present, monomers are, in principle, anaerobically biodegradable. Thermodynamic considerations indicate that degradation of synthetic polymers under repository conditions is theoretically possible. However, the degradation of polystyrene is very close to thermodynamic equilibrium and the usable energy for microorganisms would barely be sufficient. Under high H2 partial pressures, it is predicted that there will be a thermodynamic inhibition of anaerobic degradation, as certain interim steps in degradation are endergonic. The starting conditions for microbial growth in a deep repository are unfavourable in terms of availability of water and prevailing pH values. Practically no known microorganisms can tolerate the combination of these conditions; most known

Sterol metabolism regulates neuroserpin polymer degradation in the absence of the unfolded protein response in the dementia FENIB.

Science.gov (United States)

Roussel, Benoit D; Newton, Timothy M; Malzer, Elke; Simecek, Nikol; Haq, Imran; Thomas, Sally E; Burr, Marian L; Lehner, Paul J; Crowther, Damian C; Marciniak, Stefan J; Lomas, David A

2013-11-15

Mutants of neuroserpin are retained as polymers within the endoplasmic reticulum (ER) of neurones to cause the autosomal dominant dementia familial encephalopathy with neuroserpin inclusion bodies or FENIB. The cellular consequences are unusual in that the ordered polymers activate the ER overload response (EOR) in the absence of the canonical unfolded protein response. We use both cell lines and Drosophila models to show that the G392E mutant of neuroserpin that forms polymers is degraded by UBE2j1 E2 ligase and Hrd1 E3 ligase while truncated neuroserpin, a protein that lacks 132 amino acids, is degraded by UBE2g2 (E2) and gp78 (E3) ligases. The degradation of G392E neuroserpin results from SREBP-dependent activation of the cholesterol biosynthetic pathway in cells that express polymers of neuroserpin (G392E). Inhibition of HMGCoA reductase, the limiting enzyme of the cholesterol biosynthetic pathway, reduced the ubiquitination of G392E neuroserpin in our cell lines and increased the retention of neuroserpin polymers in both HeLa cells and primary neurones. Our data reveal a reciprocal relationship between cholesterol biosynthesis and the clearance of mutant neuroserpin. This represents the first description of a link between sterol metabolism and modulation of the proteotoxicity mediated by the EOR.

Kinetic measurements of the hydrolytic degradation of cefixime: effect of Captisol complexation and water-soluble polymers.

Science.gov (United States)

Mallick, Subrata; Mondal, Arijit; Sannigrahi, Santanu

2008-07-01

We have taken kinetic measurements of the hydrolytic degradation of cefixime, and have studied the effect of Captisol complexation and water-soluble polymers on that degradation. The phase solubility of cefixime in Captisol was determined. Kinetic measurements were carried out as a function of pH and temperature. High-performance liquid chromatography (HPLC) was performed to assay all the samples of phase-solubility analysis and kinetic measurements. Chromatographic separation of the degradation products was also performed by HPLC. FT-IR spectroscopy was used to investigate the presence of any interaction between cefixime and Captisol and soluble polymer. The phase-solubility study showed A(L)-type behaviour. The pH-rate profile of cefixime exhibited a U-shaped profile whilst the degradation of cefixime alone was markedly accelerated with elevated temperature. A strong stabilizing influence of the cefixime-Captisol complexation and hypromellose was observed against aqueous mediated degradation, as compared with povidone and macrogol. The unfavourable effect of povidone and macrogol may have been due to the steric hindrance, which prevented the guest molecule from entering the cyclodextrin cavity, whereas hypromellose did not produce any steric hindrance.

Modeling the Insertion Mechanics of Flexible Neural Probes Coated with Sacrificial Polymers for Optimizing Probe Design

Directory of Open Access Journals (Sweden)

Sagar Singh

2016-03-01

Full Text Available Single-unit recording neural probes have significant advantages towards improving signal-to-noise ratio and specificity for signal acquisition in brain-to-computer interface devices. Long-term effectiveness is unfortunately limited by the chronic injury response, which has been linked to the mechanical mismatch between rigid probes and compliant brain tissue. Small, flexible microelectrodes may overcome this limitation, but insertion of these probes without buckling requires supporting elements such as a stiff coating with a biodegradable polymer. For these coated probes, there is a design trade-off between the potential for successful insertion into brain tissue and the degree of trauma generated by the insertion. The objective of this study was to develop and validate a finite element model (FEM to simulate insertion of coated neural probes of varying dimensions and material properties into brain tissue. Simulations were performed to predict the buckling and insertion forces during insertion of coated probes into a tissue phantom with material properties of brain. The simulations were validated with parallel experimental studies where probes were inserted into agarose tissue phantom, ex vivo chick embryonic brain tissue, and ex vivo rat brain tissue. Experiments were performed with uncoated copper wire and both uncoated and coated SU-8 photoresist and Parylene C probes. Model predictions were found to strongly agree with experimental results (<10% error. The ratio of the predicted buckling force-to-predicted insertion force, where a value greater than one would ideally be expected to result in successful insertion, was plotted against the actual success rate from experiments. A sigmoidal relationship was observed, with a ratio of 1.35 corresponding to equal probability of insertion and failure, and a ratio of 3.5 corresponding to a 100% success rate. This ratio was dubbed the “safety factor”, as it indicated the degree to which the coating

Mathematical modeling of degradation for bulk-erosive polymers: applications in tissue engineering scaffolds and drug delivery systems.

Science.gov (United States)

Chen, Yuhang; Zhou, Shiwei; Li, Qing

2011-03-01

The degradation of polymeric biomaterials, which are widely exploited in tissue engineering and drug delivery systems, has drawn significant attention in recent years. This paper aims to develop a mathematical model that combines stochastic hydrolysis and mass transport to simulate the polymeric degradation and erosion process. The hydrolysis reaction is modeled in a discrete fashion by a fundamental stochastic process and an additional autocatalytic effect induced by the local carboxylic acid concentration in terms of the continuous diffusion equation. Illustrative examples of microparticles and tissue scaffolds demonstrate the applicability of the model. It is found that diffusive transport plays a critical role in determining the degradation pathway, whilst autocatalysis makes the degradation size dependent. The modeling results show good agreement with experimental data in the literature, in which the hydrolysis rate, polymer architecture and matrix size actually work together to determine the characteristics of the degradation and erosion processes of bulk-erosive polymer devices. The proposed degradation model exhibits great potential for the design optimization of drug carriers and tissue scaffolds. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Enzyme-assisted polymer film degradation-enabled biomolecule sensing with poly (N-isopropylacrylamide)-based optical devices.

Science.gov (United States)

Zhang, Wei; Wei, Menglian; Carvalho, Wildemar S P; Serpe, Michael J

2018-01-25

A biosensor for mouse Immunoglobulin G (IgG) was generated from responsive polymer-based interference filters (etalons). To accomplish this, an excess amount of alkaline phosphatase-modified goat anti-mouse IgG (AP-GAM, F(ab') 2 fragment specific to mouse IgG) was added to mouse IgG, and allowed to react for some time. After a given reaction time, the bound AP-GAM could be isolated from the unbound, excess AP-GAM by addition of goat anti-mouse IgG (Fc fragment specific)-modified magnetic microspheres (GAM-M) that bind the mouse IgG bound to AP-GAM. After application of a magnetic field, the free, unbound AP-GAM was isolated from the mixture and exposed to an etalon that has its upper Au surface modified with phosphate-containing polymer that can be degraded by AP-GAM. By the phosphate-containing polymer being degraded by the excess AP-GAM, the cleaved phosphate groups can diffuse into the interference filter's active polymer layer that yields a change in the optical properties that can be related to the amount of IgG in the sample. This concept is extremely straightforward to implement, and can be modified to detect a variety of other analytes of interest. Copyright © 2017 Elsevier B.V. All rights reserved.

Release of engineered nanomaterials from polymer nanocomposites: the effect of matrix degradation.

Science.gov (United States)

Duncan, Timothy V

2015-01-14

Polymer nanocomposites-polymer-based materials that incorporate filler elements possessing at least one dimension in the nanometer range-are increasingly being developed for commercial applications ranging from building infrastructure to food packaging to biomedical devices and implants. Despite a wide range of intended applications, it is also important to understand the potential for exposure to these nanofillers, which could be released during routine use or abuse of these materials so that it can be determined whether they pose a risk to human health or the environment. This article is the second of a pair that review what is known about the release of engineered nanomaterials (ENMs) from polymer nanocomposites. Two roughly separate ENM release paradigms are considered in this series: the release of ENMs via passive diffusion, desorption, and dissolution into external liquid media and the release of ENMs assisted by matrix degradation. The present article is focused primarily on the second paradigm and includes a thorough, critical review of the associated body of peer-reviewed literature on ENM release by matrix degradation mechanisms, including photodegradation, thermal decomposition, mechanical wear, and hydrolysis. These release mechanisms may be especially relevant to nanocomposites that are likely to be subjected to weathering, including construction and infrastructural materials, sporting equipment, and materials that might potentially end up in landfills. This review pays particular attention to studies that shed light on specific release mechanisms and synergistic mechanistic relationships. The review concludes with a short section on knowledge gaps and future research needs.

INS as a probe of inter-monomer angles in polymers

CERN Document Server

Eijck, L V; Grozema, F C; Schepper, I M D; Kearley, G J

2002-01-01

The angle between monomers in conjugated polymers plays an important role in their conductivity. The vibrational spectrum is sensitive to this angle and can be used to probe the distribution of angles in poorly crystalline systems. We show that the INS spectrum is correctly calculated for bithiophene and shows the molecule to be planar in the solid - in agreement with crystallographic measurements. Poor agreement between observed and calculated spectra in the 700-cm sup - sup 1 region may be due to dynamic coupling, but this does not detract from the angle-sensitivity of the spectra. (orig.)

Decades-Scale Degradation of Commercial, Side-Chain, Fluorotelomer-Based Polymers in Soils and Water

Science.gov (United States)

Fluorotelomer-based polymers (FTPs) are a primary product of the jluorotelomer industry, yet the role of commercial FTPs in degrading to form perjluorocarboxylic acids (P FCAs), including perjluorooctanoic acid, and P FCA precursors, remains ill-defined. Here we report on a 376-d...

Fluorescent probe for turn-on sensing of L-cysteine by ensemble of AuNCs and polymer protected AuNPs.

Science.gov (United States)

Xu, Xiaozhe; Qiao, Juan; Li, Nan; Qi, Li; Zhang, Shufeng

2015-06-16

A new fluorescent probe based on ensemble of gold nanoclusters (AuNCs) and polymer protected gold nanoparticles (AuNPs) for turn-on sensing of L-cysteine was designed and prepared. The AuNCs were protected by bovine serum albumin and had strong fluorescence. The polymer protected AuNPs were synthesized by a facile in situ strategy at room temperature and could quench the fluorescence of AuNCs due to the Förster resonance energy transfer. Interestingly, it has been observed that the quenched fluorescence of AuNCs was recovered by L-cysteine, which could induce the aggregation of polymer protected AuNPs by sulfur group. Then the prepared fluorescent probe was successfully used for determination of L-Cys in human urines, which would have an evolving aspect and promote the subsequent exploration. Copyright © 2015 Elsevier B.V. All rights reserved.

Controlling Radiation Degradation of Natural Polymers for Industrial and Agricultural application

International Nuclear Information System (INIS)

Hegazy, E.A.; AbdEl-Rehim, H

2008-01-01

Radiation induced degradation technology is a new and promising application of ionizing radiation to develop viscose, pulp, paper, food preservation, pharmaceutical production, and natural bioactive agents industries. Controlling the degree of degradation, uniform molecular weight distribution, saving achieved in the chemicals (used in conventional methods) on a cost basis, and environmentally friendly process are the beneficial effects of using radiation technology in these industries. However, for some development countries such technology is not economic. Therefore, a great effort should be done to reduce the cost required for such technologies. One of the principle factors for reducing the cost is achieving the degradation at low irradiation doses. The addition of some additives such as potassium per-sulfate (KPS), ammonium per-sulfate (APS), or H 2O2 to natural polymers such as chitosan and Na-alginate during irradiation process accelerates their degradation. The highest degradation rate of polysaccharides obtained when APS was used. The end product of irradiated chitosan, and Na-alginate may be used as food additive or benefited in agricultural purposes. The prepared crosslinked copolymers possessed high and fast swelling properties in simulated urine media and the swelling ratios of CMC-Na /PAAm gels in urine are acceptable for diaper application. (author)

08-ERD-071 Final Report: New Molecular Probes and Catalysts for Bioenergy Research

Energy Technology Data Exchange (ETDEWEB)

Thelen, M P; Rowe, A A; Siebers, A K; Jiao, Y

2011-03-07

A major thrust in bioenergy research is to develop innovative methods for deconstructing plant cell wall polymers, such as cellulose and lignin, into simple monomers that can be biologically converted to ethanol and other fuels. Current techniques for monitoring a broad array of cell wall materials and specific degradation products are expensive and time consuming. To monitor various polymers and assay their breakdown products, molecular probes for detecting specific carbohydrates and lignins are urgently needed. These new probes would extend the limited biochemical techniques available, and enable realtime imaging of ultrastructural changes in plant cells. Furthermore, degradation of plant biomass could be greatly accelerated by the development of catalysts that can hydrolyze key cell wall polysaccharides and lignin. The objective of this project was to develop cheap and efficient DNA reagents (aptamers) used to detect and quantify polysaccharides, lignin, and relevant products of their breakdown. A practical goal of the research was to develop electrochemical aptamer biosensors, which could be integrated into microfluidic devices and used for high-throughput screening of enzymes or biological systems that degrade biomass. Several important model plant cell wall polymers and compounds were targeted for specific binding and purification of aptamers, which were then tested by microscopic imaging, circular dichroism, surface plasmon resonance, fluorescence anisotropy, and electrochemical biosensors. Using this approach, it was anticiated that we could provide a basis for more efficient and economically viable biofuels, and the technologies established could be used to design molecular tools that recognize targets sought in medicine or chemical and biological defense projects.

Thickness dependent structural ordering, degradation and metastability in polysilane thin films: A photoluminescence study on representative σ-conjugated polymers

International Nuclear Information System (INIS)

Urbánek, Pavel; Kuřitka, Ivo

2015-01-01

We present a fundamental experimental study based on the fluorescence investigation of thin σ-conjugated polymer films, where the dependence of optoelectrical properties and UV degradation on film thickness ranging from nano- to microscale was studied. Such extensive and detailed study was performed for the first time and observed spectral shifts in emission and excitation spectra and UV degradation retardation point towards the conclusions that there exists a threshold thickness where the material degradation behavior, electron delocalization and structure suddenly change. The development of well aligned polymeric chain structure between the nano- and micrometer thickness (on the mesoscale) was shown responsible for the manifested phenomena. The material thicker than critical 500 nm has extremely small Stokes' shift, maximum extended σ-delocalization along the silicon polymer backbone and exhibits remarkable UV degradation slowdown and self-recovery ability. On the contrary, the electronic properties of thin films below 80 nm resemble those of random coils in solutions. The films of moderate thickness show relatively steep transition between these two modes of structural ordering and resulting properties. Altogether, we consider this complex phenomenon as a consequence of the mesoscale effect, which is an only recently introduced concept in polymer thin films. - Highlights: • Photoluminescence was used as a tool for structural investigation of polysilanes. • Primary study of strong dependence of thin polymer film structure on mesoscale. • A mesoscale effect observed for the first time on sigma conjugated polymers. • Conjugation length is dramatically extended in thicker films than in nanoscale. • Self-recovery effect was shown to be dependent on the mesoscale as well.

Biodegradability of PP/HMSPP and natural and synthetic polymers blends in function of gamma irradiation degradation

International Nuclear Information System (INIS)

Cardoso, Elisabeth C.L.; Scagliusi, Sandra R.; Lima, Luis F.C.P.; Bueno, Nelson R.; Brant, Antonio J.C.; Parra, Duclerc F.; Lugão, Ademar B.

2014-01-01

Polymers are used for numerous applications in different industrial segments, generating enormous quantities of discarding in the environment. Polymeric materials composites account for an estimated from 20 to 30% total volume of solid waste. Polypropylene (PP) undergoes crosslinking and extensive main chain scissions when submitted to ionizing irradiation; as one of the most widely used linear hydrocarbon polymers, PP, made from cheap petrochemical feed stocks, shows easy processing leading it to a comprehensive list of finished products. Consequently, there is accumulation in the environment, at 25 million tons per year rate, since polymeric products are not easily consumed by microorganisms. PP polymers are very bio-resistant due to involvement of only carbon atoms in main chain with no hydrolysable functional group. Several possibilities have been considered to minimize the environmental impact caused by non-degradable plastics, subjecting them to: physical, chemical and biological degradation or combination of all these due to the presence of moisture, air, temperature, light, high energy radiation or microorganisms. There are three main classes of biodegradable polymers: synthetic polymers, natural polymers and blends of polymers in which one or more components are readily consumed by microorganisms. This work aims to biodegradability investigation of a PP/HMSPP (high melt strength polypropylene) blended with sugarcane bagasse, PHB (poly-hydroxy-butyrate) and PLA (poly-lactic acid), both synthetic polymers, at a 10% level, subjected to gamma radiation at 50, 100, 150 and 200 kGy doses. Characterization will comprise IR, DSC, TGA, OIT and Laboratory Soil Burial Test (LSBT). - Highlights: • Polymeric materials composites account for an estimated from 20 to 30% total volume of solid waste. • Landfills will not be enough for an estimated accumulation of 25 million tons per year of plastics. • Incorporation of natural/synthetic polymers in PP/HMSPP to reduce

Fundamental characteristics of degradation-recoverable solid-state DFB polymer laser.

Science.gov (United States)

Yoshioka, Hiroaki; Yang, Yu; Watanabe, Hirofumi; Oki, Yuji

2012-02-13

A novel solid-state dye laser with degradation recovery was proposed and demonstrated. Polydimethylsiloxane was used as a nanoporous solid matrix to enable the internal circulation of dye molecules in the solid state. An internal circulation model for the dye molecules was also proposed and verified numerically by assuming molecular mobility and using a proposed diffusion equation. The durability of the laser was increased 20.5-fold compared with that of a conventional polymethylmethacrylate laser. This novel laser solves the low-durability problem of dye-doped polymer lasers.

Polymer electrolyte membrane water electrolysis: Restraining degradation in the presence of fluctuating power

Science.gov (United States)

Rakousky, Christoph; Reimer, Uwe; Wippermann, Klaus; Kuhri, Susanne; Carmo, Marcelo; Lueke, Wiebke; Stolten, Detlef

2017-02-01

Polymer electrolyte membrane (PEM) water electrolysis generates 'green' hydrogen when conducted with electricity from renewable - but fluctuating - sources like wind or solar photovoltaic. Unfortunately, the long-term stability of the electrolyzer performance is still not fully understood under these input power profiles. In this study, we contrast the degradation behavior of our PEM water electrolysis single cells that occurs under operation with constant and intermittent power and derive preferable operating states. For this purpose, five different current density profiles are used, of which two were constant and three dynamic. Cells operated at 1 A cm-2 show no degradation. However, degradation was observed for the remaining four profiles, all of which underwent periods of high current density (2 A cm-2). Hereby, constant operation at 2 A cm-2 led to the highest degradation rate (194 μV h-1). Degradation can be greatly reduced when the cells are operated with an intermittent profile. Current density switching has a positive effect on durability, as it causes reversible parts of degradation to recover and results in a substantially reduced degradation per mole of hydrogen produced. Two general degradation phenomena were identified, a decreased anode exchange current density and an increased contact resistance at the titanium porous transport layer (Ti-PTL).

Physical and Degradable Properties of Mulching Films Prepared from Natural Fibers and Biodegradable Polymers

Directory of Open Access Journals (Sweden)

Zhijian Tan

2016-05-01

Full Text Available The use of plastic film in agriculture has the serious drawback of producing vast quantities of waste. In this work, films were prepared from natural fibers and biodegradable polymers as potential substitutes for the conventional non-biodegradable plastic film used as mulching material in agricultural production. The physical properties (e.g., mechanical properties, heat preservation, water permeability, and photopermeability and degradation characteristics (evaluated by micro-organic culture testing and soil burial testing of the films were studied in both laboratory and field tests. The experimental results indicated that these fiber/polymer films exhibited favorable physical properties that were sufficient for use in mulching film applications. Moreover, the degradation degree of the three tested films decreased in the following order: fiber/starch (ST film > fiber/poly(vinyl alcohol (PVA film > fiber/polyacrylate (PA film. The fiber/starch and fiber/PVA films were made from completely biodegradable materials and demonstrated the potential to substitute non-biodegradable films.

Electron Barrier Formation at the Organic-Back Contact Interface is the First Step in Thermal Degradation of Polymer Solar Cells

KAUST Repository

Sachs-Quintana, I. T.

2014-03-24

Long-term stability of polymer solar cells is determined by many factors, one of which is thermal stability. Although many thermal stability studies occur far beyond the operating temperature of a solar cell which is almost always less than 65 °C, thermal degradation is studied at temperatures that the solar cell would encounter in real-world operating conditions. At these temperatures, movement of the polymer and fullerenes, along with adhesion of the polymer to the back contact, creates a barrier for electron extraction. The polymer barrier can be removed and the performance can be restored by peeling off the electrode and depositing a new one. X-ray photoelectron spectroscopy measurements reveal a larger amount of polymer adhered to electrodes peeled from aged devices than electrodes peeled from fresh devices. The degradation caused by hole-transporting polymer adhering to the electrode can be suppressed by using an inverted device where instead of electrons, holes are extracted at the back metal electrode. The problem can be ultimately eliminated by choosing a polymer with a high glass transition temperature. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanochemical degradation of potato starch paste under ultrasonic irradiation

Institute of Scientific and Technical Information of China (English)

LI Jian-bin; LI Lin; LI Bing; CHEN Ling; GUI Lin

2006-01-01

In the paper, changes in the molecular weight, the intrinsic viscosity and the polydispersity (molecular mass distribution) of treated potato starch paste were studied under different ultrasonic conditions which include irradiation time, ultrasonic intensity, potato starch paste concentration, and distance from probe tip on the degradation of potato starch paste. Intrinsic viscosity of potato starch paste was determined following the ASTM (American Society for Testing and Materials) standard practice for dilute solution viscosity of polymers. Molecular mass and polydispersity of potato starch paste were measured on GPC (Gel Permeation Chromatography). The results showed that the average molecular mass and the intrinsic viscosity of starch strongly depended on irradiation time. Degradation increased with prolonged ultrasonic irradiation time, and the increase of ultrasonic intensity could accelerate the degradation, resulting in a faster degradation rate, a lower limiting value and a higher degradation extent. Starch samples were degraded faster in dilute solutions than in concentrated solutions. The molecular mass and the intrinsic viscosity of starch increased with the increase of distance from probe tip. Our results also showed that the polydispersity decreased with ultrasonic irradiation under all ultrasonic conditions. Ultrasonic degradation of potato starch paste occured based on the mechanism of molecular relaxation of starch paste. In the initial stage, ultrasonic degradation of potato starch paste was a random process, and the molecular mass distribution was broad. After that, ultrasonic degradation of potato starch paste changed to a nonrandom process, and the molecular mass distribution became narrower. Finally, molecular mass distribution tended toward a saturation value.

Application of 13C-stable isotope probing to identify RDX-degrading microorganisms in groundwater

International Nuclear Information System (INIS)

Cho, Kun-Ching; Lee, Do Gyun; Roh, HyungKeun; Fuller, Mark E.; Hatzinger, Paul B.; Chu, Kung-Hui

2013-01-01

We employed stable isotope probing (SIP) with 13 C-labeled hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) to identify active microorganisms responsible for RDX biodegradation in groundwater microcosms. Sixteen different 16S rRNA gene sequences were derived from microcosms receiving 13 C-labeled RDX, suggesting the presence of microorganisms able to incorporate carbon from RDX or its breakdown products. The clones, residing in Bacteroidia, Clostridia, α-, β- and δ-Proteobacteria, and Spirochaetes, were different from previously described RDX degraders. A parallel set of microcosms was amended with cheese whey and RDX to evaluate the influence of this co-substrate on the RDX-degrading microbial community. Cheese whey stimulated RDX biotransformation, altered the types of RDX-degrading bacteria, and decreased microbial community diversity. Results of this study suggest that RDX-degrading microorganisms in groundwater are more phylogenetically diverse than what has been inferred from studies with RDX-degrading isolates. Highlights: •SIP identified sixteen groundwater bacteria capable of using RDX and/or its metabolites as a carbon source. •The RDX degraders in groundwater are phylogenetically diverse and different from known RDX degraders. •Cheese whey induced community shift and altered diversity of the RDX-degrading microorganisms over time. -- RDX-degrading bacteria in contaminated groundwater, identified by SIP with 13 C-labeled RDX, are phylogenetically diverse and different from known RDX degraders

The radiation degradation of polypropylene

International Nuclear Information System (INIS)

De Hollain, G.

1977-04-01

Polypropylene is used extensively in the manufacture of disposable medical devices because of its superior properties. Unfortunately this polymer does not lend itself well to radiation sterilization, undergoing serious degradation which affects the mechanical properties of the polymer. In this paper the effects of radiation on the mechanical and physical properties of polypropylene are discussed. A programme of research to minimize the radiation degradation of this polymer through the addition of crosslinking agents to counteract the radiation degradation is proposed. It is furthermore proposed that a process of annealing of the irradiated polymer be investigated in order to minimize the post-irradiation degradation of the polypropylene [af

Thermal degradation characteristics and products obtained after pyrolysis of specific polymers found in Waste Electrical and Electronic Equipment

Institute of Scientific and Technical Information of China (English)

Evangelia C.Vouvoudi; Aristea T.Rousi; Dimitris S.Achilias

2017-01-01

Modern societies strongly support the recycling practices over simple waste accumulation due to environmental harm caused.In the framework of sustainable recycling of plastics from WEEE,pyrolysis is proposed here as a means of obtaining secondary value-added products.The aim of this study was to investigate the thermal degradation and the products obtained after pyrolysis of specific polymers found in the plastic part of WEEE,using thermogravimetric analysis and a pyrolizer equipped with a GC/MS.Polymers studied include ABS,HIPS,PC and a blend having a composition similar to that appearing in WEEE.It was found that,PC shows greater heat endurance compared to the other polymers,whereas ABS depolymerizes in three-steps.The existence of several polymers in the blend results in synergistic effects which decrease the onset and final temperature of degradation.Moreover,the fragmentation occurred in the pyrolyzer,at certain temperatures,resulted in a great variety of compounds,depending on the polymer type,such as monomers,aromatic products,phenolic compounds and hydrocarbons.The main conclusion from this investigation is that pyrolysis could be an effective method for the sustainable recycling of the plastic part of WEEE resulting in a mixture of chemicals with varying composition but being excellent to be used as fuel retrieved from secondary recycling sources.

Construction of porous covalent organic polymer as photocatalysts for RhB degradation under visible light

Institute of Scientific and Technical Information of China (English)

Pingxiao Liu; Lingbao Xing; Hongtao Lin; Haining Wang; Ziyan Zhou; Zhongmin Su

2017-01-01

In the present work,a novel porous,and chemically stable amine-based covalent organic polymer (POP-1) was designed and synthesized under solvothermal conditions.The porosity,crystallinity,chemical stability,electrochemical properties,and diffuse reflectance of POP-1 were investigated via N2 sorption experiment,power X-ray diffraction,thermogravimetric analysis,cyclic voltammetry,and ultraviolet visible near infrared spectrometry,respectively.POP-1 exhibits good chemical stability in both acidic and alkaline aqueous solutions,as well as in organic solvents.Undoped POP-1 can be directly used as a photocatalyst for rhodamine B irradiation degradation under light-emitting diode and natural light.The Ea of POP-1 for RhB degradation is 82.37 kJ/mol.Furthermore,POP-1 can be reused as a catalyst in RhB degradation without degraded catalytic activity.

Modern mass spectrometry in the characterization and degradation of biodegradable polymers.

Science.gov (United States)

Rizzarelli, Paola; Carroccio, Sabrina

2014-01-15

In the last decades, the solid-waste management related to the extensively growing production of plastic materials, in concert with their durability, have stimulated increasing interest in biodegradable polymers. At present, a variety of biodegradable polymers has already been introduced onto the market and can now be competitive with non biodegradable thermoplastics in different fields (packaging, biomedical, textile, etc.). However, a significant economical effort is still directed in tailoring structural properties in order to further broaden the range of applications without impairing biodegradation. Improving the performance of biodegradable materials requires a good characterization of both physico-chemical and mechanical parameters. Polymer analysis can involve many different features including detailed characterization of chemical structures and compositions as well as average molecular mass determination. It is of outstanding importance in troubleshooting of a polymer manufacturing process and for quality control, especially in biomedical applications. This review describes recent trends in the structural characterization of biodegradable materials by modern mass spectrometry (MS). It provides an overview of the analytical tools used to evaluate their degradation. Several successful applications of MALDI-TOF MS (matrix assisted laser desorption ionization time of flight) and ESI MS (electrospray mass spectrometry) for the determination of the structural architecture of biodegradable macromolecules, including their topology, composition, chemical structure of the end groups have been reported. However, MS methodologies have been recently applied to evaluate the biodegradation of polymeric materials. ESI MS represents the most useful technique for characterizing water-soluble polymers possessing different end group structures, with the advantage of being easily interfaced with solution-based separation techniques such as high-performance liquid

PCL-PLLA Semi-IPN Shape Memory Polymers (SMPs): Degradation and Mechanical Properties.

Science.gov (United States)

Woodard, Lindsay N; Page, Vanessa M; Kmetz, Kevin T; Grunlan, Melissa A

2016-12-01

Thermoresponsive shape memory polymers (SMPs) based on poly(ε-caprolactone) (PCL) whose shape may be actuated by a transition temperature (T trans ) have shown utility for a variety of biomedical applications. Important to their utility is the ability to modulate mechanical and degradation properties. Thus, in this work, SMPs are formed as semi-interpenetrating networks (semi-IPNs) comprised of a cross-linked PCL diacrylate (PCL-DA) network and thermoplastic poly(l-lactic acid) (PLLA). The semi-IPN uniquely allows for requisite crystallization of both PCL and PLLA. The influence of PLLA (PCL:PLLA wt% ratio) and PCL-DA molecular weight (n) on film properties are investigated. PCL-PLLA semi-IPNs are able to achieve enhanced mechanical properties and accelerated rates of degradation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Comparison of Degradable Synthetic Polymer Fibers for Anterior Cruciate Ligament Reconstruction

Science.gov (United States)

Tovar, Nick; Bourke, Sharon; Jaffe, Michael; Murthy, N. Sanjeeva; Kohn, Joachim; Gatt, Charles; Dunn, Michael G.

2009-01-01

We compared mechanical properties, degradation rates, and cellular compatibilities of two synthetic polymer fibers potentially useful as ACL reconstruction scaffolds: poly(desaminotyrosyl-tyrosine dodecyl dodecanedioate)(12,10), p(DTD DD) and poly(L-lactic acid), PLLA. The yield stress of ethylene oxide (ETO) sterilized wet fibers was 150 ± 22 MPa and 87 ± 12 MPa for p(DTD DD) and PLLA, respectively, with moduli of 1.7 ± 0.1 MPa and 4.4 ± 0.43 MPa. Strength and molecular weight retention were determined after incubation under physiological conditions at varying times. After 64 weeks strength decreased to 20 and 37% of the initial sterile fiber values and MW decreased to 41% and 36% of the initial values for p(DTD DD) and PLLA, respectively. ETO sterilization had no significant effect on mechanical properties. Differences in mechanical behavior may be due to the semicrystalline nature of PLLA and the small degree of crystallinity induced by mesogenic ordering in p(DTD DD) suggested by DSC analysis. Fibroblast growth was similar on 50-fiber scaffolds of both polymers through 16 days in vitro. These data suggest that p(DTD DD) fibers, with higher strength, lower stiffness, favorable degradation rate and cellular compatibility, may be a superior alternative to PLLA fibers for development of ACL reconstruction scaffolds. PMID:19623532

A new three-dimensional bis(benzimidazole)-based cadmium(II) coordination polymer

Science.gov (United States)

Hao, Shao Yun; Hou, Suo Xia; Hao, Zeng Chuan; Cui, Guang Hua

2018-01-01

A new coordination polymer (CP), formulated as [Cd(L)(DCTP)]n (1) (L = 1,1‧-(1,4-butanediyl)bis(2-methylbenzimidazole), H2DCTP = 2,5-dichloroterephthalic acid), was synthesized under hydrothermal conditions and the performance as luminescent probe was also investigated. Single-crystal X-ray diffraction reveals CP 1 is a 3D 3-fold interpenetrated dia network with large well-defined pores. It is found that CP 1 revealed highly sensitive luminescence sensing for Fe3 + ions in acetonitrile solution with a high quenching efficiency of KSV = 2541.238 L·mol- 1 and a low detection limit of 3.2 μM (S/N = 3). Moreover, the photocatalytic efficiency of 1 for degradation of methylene blue could reach 82.8% after 135 min. Therefore, this coordination polymer could be viewed as multifunctional material for selectively sensing Fe3 + ions and effectively degrading dyes.

Thermal degradation of organo-soluble polyimides

Institute of Scientific and Technical Information of China (English)

黄俐研; 史燚; 金熹高

1999-01-01

The thermal degradation behavior of two organo-soluble polyimides was investigated by high resolution pyrolysis-gas chromatography/mass spectrometry. The pyrolyzates of the polymers at various temperatures were identified and characterized quantitatively. The relationship between the polymer structure and pyrolyzate distribution was discussed. The kinetic parameters of the thermal degradation were calculated based on thermogravimetric measurements. Finally, the thermal degradation mechanism for the polymers was suggested.

High Temperature Degradation Mechanisms in Polymer Matrix Composites

Science.gov (United States)

Cunningham, Ronan A.

1996-01-01

Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using a coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects

Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR.

Science.gov (United States)

Abraham, Anuji; Crull, George

2014-10-06

A simple and robust method for obtaining fluorine-carbon proximities was established using a (19)F-(13)C heteronuclear correlation (HETCOR) two-dimensional (2D) solid-state nuclear magnetic resonance (ssNMR) experiment under magic-angle spinning (MAS). The method was applied to study a crystalline active pharmaceutical ingredient (API), avagacestat, containing two types of fluorine atoms and its API-polymer composite drug product. These results provide insight into the molecular structure, aid with assigning the carbon resonances, and probe API-polymer proximities in amorphous spray dried dispersions (SDD). This method has an advantage over the commonly used (1)H-(13)C HETCOR because of the large chemical shift dispersion in the fluorine dimension. In the present study, fluorine-carbon distances up to 8 Å were probed, giving insight into the API structure, crystal packing, and assignments. Most importantly, the study demonstrates a method for probing an intimate molecular level contact between an amorphous API and a polymer in an SDD, giving insights into molecular association and understanding of the role of the polymer in API stability (such as recrystallization, degradation, etc.) in such novel composite drug products.

Probing individal subcells of fully printed and coated polymer tandem solar cells using multichromatic opto-electronic characterization methods

DEFF Research Database (Denmark)

Larsen-Olsen, Thue Trofod; Andersen, Thomas Rieks; Dam, Henrik Friis

2015-01-01

In this study, a method to opto-electronically probe the individual junctions and carrier transport across interfaces in fully printed and coated tandem polymer solar cells is described, enabling the identification of efficiency limiting printing/coating defects. The methods used are light beam...

A paradigm for peptide vaccine delivery using viral epitopes encapsulated in degradable polymer hydrogel capsules.

Science.gov (United States)

Chong, Siow-Feng; Sexton, Amy; De Rose, Robert; Kent, Stephen J; Zelikin, Alexander N; Caruso, Frank

2009-10-01

We report on the use of degradable polymer capsules as carriers for the delivery of oligopeptide antigens to professional antigen presenting cells (APCs). To achieve encapsulation, oligopeptide sequences were covalently linked to a negatively charged carrier polymer via biodegradable linkages and the resulting conjugate was then adsorbed onto amine-functionalized silica particles. These peptide-coated particles were then used as templates for the layer-by-layer (LbL) deposition of thiolated poly(methacrylic acid) (PMA(SH)) and poly(vinylpyrrolidone) (PVPON) multilayers. Removal of the silica core and disruption of the hydrogen bonding between PMA(SH) and PVPON by altering the solution pH yielded disulfide-stabilized PMA capsules that retain the encapsulated cargo in an oxidative environment. In the presence of a natural reducing agent, glutathione, cleavage of the disulfide bonds causes release of the peptide from the capsules. The developed strategy provides control over peptide loading into polymer capsules and yields colloidally stable micron- and submicron-sized carriers with uniform size and peptide loading. The conjugation and encapsulation procedures were proven to be non-degrading to the peptide vaccines. The peptide-loaded capsules were successfully used to deliver their cargo to APCs and activate CD8 T lymphocytes in a non-human primate model of SIV infection ex vivo. The reported approach represents a novel paradigm in the delivery of peptide vaccines and other therapeutic agents.

Degradation Patterns in Water and Oxygen of an Inverted Polymer Solar Cell

DEFF Research Database (Denmark)

Norrman, Kion; Vesterager Madsen, Morten; Gevorgyan, Suren

2010-01-01

The spatial distribution of reaction products in multilayer polymer solar cells induced by water and oxygen atmospheres was mapped and used to elucidate the degradation patterns and failure mechanisms in an inverted polymer solar cell. The active material comprised a bulk heterojunction formed...... by poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) sandwiched between a layer of zinc oxide and a layer of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) that acted as, respectively, electron and hole transporting layers between the active material...... and the two electrodes indium−tin−oxide (ITO) and printed silver. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) in conjunction with isotopic labeling using H218O and 18O2 enabled detailed information on where and to what extent uptake took place...

Application of Microextraction Techniques Including SPME and MESI to the Thermal Degradation of Polymers: A Review.

Science.gov (United States)

Kaykhaii, Massoud; Linford, Matthew R

2017-03-04

Here, we discuss the newly developed micro and solventless sample preparation techniques SPME (Solid Phase Microextraction) and MESI (Membrane Extraction with a Sorbent Interface) as applied to the qualitative and quantitative analysis of thermal oxidative degradation products of polymers and their stabilizers. The coupling of these systems to analytical instruments is also described. Our comprehensive literature search revealed that there is no previously published review article on this topic. It is shown that these extraction techniques are valuable sample preparation tools for identifying complex series of degradation products in polymers. In general, the number of products identified by traditional headspace (HS-GC-MS) is much lower than with SPME-GC-MS. MESI is particularly well suited for the detection of non-polar compounds, therefore number of products identified by this technique is not also to the same degree of SPME. Its main advantage, however, is its ability of (semi-) continuous monitoring, but it is more expensive and not yet commercialized.

Fabrication and in vitro degradation of porous fumarate-based polymer/alumoxane nanocomposite scaffolds for bone tissue engineering.

NARCIS (Netherlands)

Mistry, A.S.; Cheng, S.H.; Yeh, T.; Christenson, E.; Jansen, J.A.; Mikos, A.G.

2009-01-01

In this work, the fabrication and in vitro degradation of porous fumarate-based/alumoxane nanocomposites were evaluated for their potential as bone tissue engineering scaffolds. The biodegradable polymer poly (propylene fumarate)/propylene fumarate-diacrylate (PPF/PF-DA), a macrocomposite composed

A Comparison of Degradable Synthetic Polymer Fibers for Anterior Cruciate Ligament Reconstruction

OpenAIRE

Tovar, Nick; Bourke, Sharon; Jaffe, Michael; Murthy, N. Sanjeeva; Kohn, Joachim; Gatt, Charles; Dunn, Michael G.

2010-01-01

We compared mechanical properties, degradation rates, and cellular compatibilities of two synthetic polymer fibers potentially useful as ACL reconstruction scaffolds: poly(desaminotyrosyl-tyrosine dodecyl dodecanedioate)(12,10), p(DTD DD) and poly(L-lactic acid), PLLA. The yield stress of ethylene oxide (ETO) sterilized wet fibers was 150 ± 22 MPa and 87 ± 12 MPa for p(DTD DD) and PLLA, respectively, with moduli of 1.7 ± 0.1 MPa and 4.4 ± 0.43 MPa. Strength and molecular weight retention were...

Electrical condition monitoring method for polymers

Science.gov (United States)

Watkins, Jr. Kenneth S.; Morris, Shelby J.; Masakowski, Daniel D.; Wong, Ching Ping; Luo, Shijian

2010-02-16

An electrical condition monitoring method utilizes measurement of electrical resistivity of a conductive composite degradation sensor to monitor environmentally induced degradation of a polymeric product such as insulated wire and cable. The degradation sensor comprises a polymeric matrix and conductive filler. The polymeric matrix may be a polymer used in the product, or it may be a polymer with degradation properties similar to that of a polymer used in the product. The method comprises a means for communicating the resistivity to a measuring instrument and a means to correlate resistivity of the degradation sensor with environmentally induced degradation of the product.

Pulsed Laser Deposition of Polymers Doped with Fluorescent Probes. Application to Environmental Sensors

International Nuclear Information System (INIS)

Rebollar, E; Villavieja, Mm; Gaspard, S; Oujja, M; Corrales, T; Georgiou, S; Domingo, C; Bosch, P; Castillejo, M

2007-01-01

Pulsed laser deposition (PLD) has been used to obtain thin films of poly(methyl methacrylate) and polystyrene doped with fluorescent probes, amino aromatic compounds S5 and S6, that could be used to sense the presence of contaminating environmental agents. These dopants both in solution and inserted in polymeric films are sensitive to changes in pH, viscosity and polarity, increasing their fluorescence emission and/or modifying the position of their emission band. Films deposits on quartz substrates, obtained by irradiating targets with a Ti:Sapphire laser (800 nm, 120 fs pulse) were analyzed by optical and Environmental Scanning Electron Microscopy, Fluorescence Microscopy, Laser-Induced Fluorescence, Micro Raman Spectroscopy and Flow Injection Analysis-Mass Spectrometry. The transfer of the polymer and the probe to the substrate is observed to be strongly dependent on the optical absorption coefficient of the polymeric component of the target at the irradiation wavelength

Degradation behavior of polymer blend of isotactic polypropylenes with and without unsaturated chain end group

International Nuclear Information System (INIS)

Nakatani, Hisayuki; Kurniawan, Dodik; Taniike, Toshiaki; Terano, Minoru

2008-01-01

In this work, the relationship between the unsaturated chain end group content and the thermal oxidative degradation rate was systematically studied with binary polymer blends of isotactic polypropylene (iPP) with and without the unsaturated chain end group. The iPPs with and without the unsaturated chain end group were synthesized by a metallocene catalyst in the absence of hydrogen and by a Ziegler catalyst in the presence of one, respectively. The thermal oxidative degradation rate of the binary iPP blends was estimated from the molecular weight and the apparent activation energy (ΔE), which were obtained through size exclusion chromatography (SEC) and thermogravimetric analysis (TGA) measurements, respectively. These values exhibited a negative correlation against the mole content of the unsaturated chain end group. The thermal oxidative degradation rate apparently depends on the content of the unsaturated chain end group. This tendency suggests that the unsaturated chain end acts as a radical initiator of the iPP degradation reaction.

Dark electrical bias effect on moisture-induced degradation in inverted lead halide perovskite solar cells measured by advanced chemical probes

KAUST Repository

Barbe, Jeremy; Kumar, Vikas; Newman, Michael; Lee, Harrison; Jain, Sagar Motilal; Chen, Hu; Charbonneau, Cé cile; Rodenburg, C; Tsoi, Wing

2018-01-01

Emerging lead halide perovskite materials have enormous potential for a range of optoelectronic devices, such as solar cells, light emitting diodes, transistors and lasers. However, the large-scale commercialization of these technologies will depend on the ability of the active material to be stable under environmental and operating conditions. In this work, we measured the first time the electrical bias-induced degradation of inverted perovskite solar cells in the dark in different environments and concluded that humidity coupled with electrical bias results in fast degradation of CH3NH3PbI3 into PbI2. Micro-Raman and photoluminescence show that the degradation starts from the edge of the cell due to moisture ingress. By using novel local Raman-transient photocurrent measurements, we were able to probe local ion migration at the degraded region and non-degraded region and found that the formation of PbI2 can passivate perovskite by reducing ion migration. The degradation is far from uniform across different grains as revealed by secondary electron hyperspectral imaging, an advanced scanning electron microscopy technique which allows probing the composition of individual grain from the cross-section. By using potential step chronoamperometry, we also found that the bias degradation is closely related to the density of mobile ions. The unique combination of established methods with several novel analytical tools provides an insight into the origin of the bias-degradation of inverted perovskite solar cells from nano-scale to cell level, and demonstrates the potential of these novel tools for studying the degradation in other perovskite systems.

Dark electrical bias effect on moisture-induced degradation in inverted lead halide perovskite solar cells measured by advanced chemical probes

KAUST Repository

Barbe, Jeremy

2018-02-12

Emerging lead halide perovskite materials have enormous potential for a range of optoelectronic devices, such as solar cells, light emitting diodes, transistors and lasers. However, the large-scale commercialization of these technologies will depend on the ability of the active material to be stable under environmental and operating conditions. In this work, we measured the first time the electrical bias-induced degradation of inverted perovskite solar cells in the dark in different environments and concluded that humidity coupled with electrical bias results in fast degradation of CH3NH3PbI3 into PbI2. Micro-Raman and photoluminescence show that the degradation starts from the edge of the cell due to moisture ingress. By using novel local Raman-transient photocurrent measurements, we were able to probe local ion migration at the degraded region and non-degraded region and found that the formation of PbI2 can passivate perovskite by reducing ion migration. The degradation is far from uniform across different grains as revealed by secondary electron hyperspectral imaging, an advanced scanning electron microscopy technique which allows probing the composition of individual grain from the cross-section. By using potential step chronoamperometry, we also found that the bias degradation is closely related to the density of mobile ions. The unique combination of established methods with several novel analytical tools provides an insight into the origin of the bias-degradation of inverted perovskite solar cells from nano-scale to cell level, and demonstrates the potential of these novel tools for studying the degradation in other perovskite systems.

17O NMR investigation of oxidative degradation in polymers under γ-irradiation

International Nuclear Information System (INIS)

ALAM, TODD M.; CELINA, MATHIAS C.; ASSINK, ROGER A.; CLOUGH, ROGER LEE; GILLEN, KENNETH T.

2000-01-01

The γ-irradiated-oxidation of pentacontane (C 50 H 102 ) and the polymer polyisoprene was investigated as a function of oxidation level using 17 O nuclear magnetic resonance (NMR) spectroscopy. It is demonstrated that by using 17 O labeled O 2 gas during the γ-irradiation process, details about the oxidative degradation mechanisms can be directly obtained from the analysis of the 17 O NMR spectra. Production of carboxylic acids is the primary oxygen-containing functionality during the oxidation of pentacontane, while ethers and alcohols are the dominant oxidation product observed for polyisoprene. The formation of ester species during the oxidation process is very minor for both materials, with water also being produced in significant amounts during the radiolytic oxidation of polyisoprene. The ability to focus on the oxidative component of the degradation process using 17 O NMR spectroscopy demonstrates the selectivity of this technique over more conventional approaches

Effect of polymer degradation on prolonged release of paclitaxel from filomicelles of polylactide/poly(ethylene glycol) block copolymers.

Science.gov (United States)

Jelonek, Katarzyna; Li, Suming; Kasperczyk, Janusz; Wu, Xiaohan; Orchel, Arkadiusz

2017-06-01

Paclitaxel is one of the most efficient anticancer agents, but the conventional dosage formulations cause many side effects. PLA-PEG filomicelles are promising carriers of paclitaxel because high loading capacity and long term release can be achieved. Slow release of cytostatic drugs is very advantageous due to prolonged exposure of tumor cells to cytostatic over multiple cell cycles. The aim of this study was to evaluate the potential of bioresorbable PLA-PEG filomicelles for prolonged delivery of paclitaxel. Paclitaxel is encapsulated in PLLA-PEG filomicelles and PDLLA-PEG spherical micelles. Drug release was studied in PBS at 37°C at various pH values to elucidate the influence of polymer degradation on drug release. NMR, GPC and HPLC were used to follow polymer degradation and drug release. The release of paclitaxel is strongly dependent on the degradation of micelles. A biphasic drug release profile is observed for both PLLA-PEG and PDLLA-PEG micelles: slow release in the first phase and faster release in the second phase. Degradation is faster at acidic pH than at pH7.4, and PLLA-PEG filomicelles degrade less rapidly than PDLLA-PEG spherical micelles, leading to various rates of drug release. The correlation between degradation and drug release is very helpful for the development of novel drug carriers with tailored properties. Importantly, the cytotoxic activity of PLLA-PEG filomicelles was evidenced, thus showing their potential as carrier of antitumor drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

Enzymatic degradation of polycaprolactone–gelatin blend

International Nuclear Information System (INIS)

Banerjee, Aditi; Chatterjee, Kaushik; Madras, Giridhar

2015-01-01

Blends of polycaprolactone (PCL), a synthetic polymer and gelatin, natural polymer offer a optimal combination of strength, water wettability and cytocompatibility for use as a resorbable biomaterial. The enzymatic degradation of PCL, gelatin and PCL–gelatin blended films was studied in the presence of lipase (Novozym 435, immobilized) and lysozyme. Novozym 435 degraded the PCL films whereas lysozyme degraded the gelatin. Though Novozym 435 and lysozyme individually could degrade PCL–gelatin blended films, the combination of these enzymes showed the highest degradation of these blended films. Moreover, the enzymatic degradation was much faster when fresh enzymes were added at regular intervals. The changes in physico-chemical properties of polymer films due to degradation were studied by scanning electron microscopy, Fourier transform infrared spectroscopy and differential scanning calorimetry. These results have important implications for designing resorbable biomedical implants. (paper)

Degadation of semiconducting polymers by concentrated sunlight

DEFF Research Database (Denmark)

Tromholt, Thomas; Manceau, Matthieu; Petersen, Martin Helgesen

2011-01-01

infra-red spectra of MEH-PPV degraded at 1 sun intensity and at high solar concentration only showed minor deviations in degradation mechanisms. The acceleration factor was found to vary linearly with the solar concentration. Finally, a comparison of the degradation rates at 1 sun and 100 suns...... was carried out in a materials study employing five different conjugated polymers relevant to polymer solar cells for which acceleration factors in the range 19–55 were obtained.......A lens based sunlight concentration setup was used to accelerate the degradation of semiconducting polymers. Sunlight was collected outdoor and focused into an optical fiber bundle allowing for indoor experimental work. Photo-degradation of several polymers was studied by UV–vis absorbance...

A New Property of Conjugated Polymer PFP: Catalytic Degradation of Methylene Blue Aqueous Solution

Institute of Scientific and Technical Information of China (English)

无

2005-01-01

A new property of conjugated polymer poly(furancarbinol-co-phenol)(PFP) was studied.The target copolymer was used as a catalyst after proper heating treatment. And dye methylene blue (MB) could be fully degraded and largely mineralized on PFP, under natural light or even in dark, in a few minutes. Furthermore, the catalytic activity could be preserved after several runs and the catalyst was readily separated. The effect of calcination temperature was also observed.

High-molecular-weight polymers containing biodegradable disulfide bonds: synthesis and in vitro verification of intracellular degradation

Czech Academy of Sciences Publication Activity Database

Etrych, Tomáš; Kovář, Lubomír; Šubr, Vladimír; Braunová, Alena; Pechar, Michal; Chytil, Petr; Říhová, Blanka; Ulbrich, Karel

2010-01-01

Roč. 25, č. 1 (2010), s. 5-26 ISSN 0883-9115 R&D Projects: GA AV ČR IAA400500806; GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z40500505; CEZ:AV0Z50200510 Keywords : water-soluble polymers * reductive degradation * HPMA copolymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.610, year: 2010

Thermosetting Phthalocyanine Polymers

Science.gov (United States)

Fohlen, G.; Parker, J.; Achar, B.

1985-01-01

Group of phthalocyanine polymers resist thermal degradation. Polymers expected semiconducting. Principal applications probably in molded or laminated parts that have to withstand high temperatures. Polymers made from either of two classes of monomer: Bisphthalonitriles with imide linkages or Bisphthalonitriles with ester-imide linkages.

Spatial profiling of degradation processes in hindered-amine-stabilized polymers by electron spin resonance imaging of nitroxides

Czech Academy of Sciences Publication Activity Database

Marek, Antonín; Kaprálková, Ludmila; Pfleger, Jiří; Pospíšil, Jan; Pilař, Jan

2005-01-01

Roč. 99, S (2005), s. 195-198 ISSN 0009-2770. [Meeting on Chemistry and Life /3./. Brno, 20.9.2005-22.9.2005] Institutional research plan: CEZ:AV0Z40500505 Keywords : polymer degradation * nitroxides * electron spin resonance imaging Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.445, year: 2005

The Effect of Platinum Electrocatalyst on Membrane Degradation in Polymer Electrolyte Fuel Cells.

Science.gov (United States)

Bodner, Merit; Cermenek, Bernd; Rami, Mija; Hacker, Viktor

2015-12-08

Membrane degradation is a severe factor limiting the lifetime of polymer electrolyte fuel cells. Therefore, obtaining a deeper knowledge is fundamental in order to establish fuel cells as competitive product. A segmented single cell was operated under open circuit voltage with alternating relative humidity. The influence of the catalyst layer on membrane degradation was evaluated by measuring a membrane without electrodes and a membrane-electrode-assembly under identical conditions. After 100 h of accelerated stress testing the proton conductivity of membrane samples near the anode and cathode was investigated by means of ex situ electrochemical impedance spectroscopy. The membrane sample near the cathode inlet exhibited twofold lower membrane resistance and a resulting twofold higher proton conductivity than the membrane sample near the anode inlet. The results from the fluoride ion analysis have shown that the presence of platinum reduces the fluoride emission rate; which supports conclusions drawn from the literature.

Stress and Damage in Polymer Matrix Composite Materials Due to Material Degradation at High Temperatures

Science.gov (United States)

McManus, Hugh L.; Chamis, Christos C.

1996-01-01

This report describes analytical methods for calculating stresses and damage caused by degradation of the matrix constituent in polymer matrix composite materials. Laminate geometry, material properties, and matrix degradation states are specified as functions of position and time. Matrix shrinkage and property changes are modeled as functions of the degradation states. The model is incorporated into an existing composite mechanics computer code. Stresses, strains, and deformations at the laminate, ply, and micro levels are calculated, and from these calculations it is determined if there is failure of any kind. The rationale for the model (based on published experimental work) is presented, its integration into the laminate analysis code is outlined, and example results are given, with comparisons to existing material and structural data. The mechanisms behind the changes in properties and in surface cracking during long-term aging of polyimide matrix composites are clarified. High-temperature-material test methods are also evaluated.

Degradation of non-vulcanized natural rubber - renewable resource for fine chemicals used in polymer synthesis

Directory of Open Access Journals (Sweden)

Alexander Fainleib

2013-01-01

Full Text Available In the current scenario, there is growing interest in the products of degradation of rubber (natural and synthetic for specific applications in different industry sectors, whose benefits in replacing conventionally used products are mainly related to sustainability. Since the degradation products of rubber can be used in different areas, several research groups may have the interest aroused by these products, but are not familiar with the aspects related to the chemical behavior of rubber. This review aims to bring together the key information in the published literature on the degradation of natural rubber, emphasizing metatheses reactions, oxidative damage and splitting of the double bond, in order to serve as a reference source for researchers from different fields interested in obtaining such kind of products. The structures and properties as well as additional chemical transformations resulting in oligomers of isoprene, functionalised oligomers and polymers based on both are also described.

Investigation of the degradation and stability of acrylamide-based polymers in acid solution: Functional monomer modified polyacrylamide

Directory of Open Access Journals (Sweden)

Yuxin Pei

2016-12-01

Full Text Available Acrylamide copolymers are often used as acidizing diverting and thickening agents for their advantageous thickening, flocculation, adhesion and resistance reduction properties. Experimental results indicate that the acid concentration greatly affects the properties of acrylamide polymers, which varies from results reported by other researchers. Considering the theoretical and field application value of the present study, four comparable acrylamide-based polymers were synthesized, and their macro- and micro-changes as well as the related changes in viscosity and molecular weight were studied in high-concentration hydrochloric acid. A proposed mechanism of acrylamide copolymer stability and degradation is provided, and further suggestions are made for the modification of acrylamide copolymers.

Degradation Studies of b-Cyclodextrin Polyurethane Polymers using ...

African Journals Online (AJOL)

NJD

A biodegradable polymer undergoes significant chemical and .... After filter- ing, the isolated white polymer was washed with copious amounts of acetone (3 × 100 mL) to ... polymers to have contact with air, moisture and microorganisms.

Analytical methods for toxic gases from thermal degradation of polymers

Science.gov (United States)

Hsu, M.-T. S.

1977-01-01

Toxic gases evolved from the thermal oxidative degradation of synthetic or natural polymers in small laboratory chambers or in large scale fire tests are measured by several different analytical methods. Gas detector tubes are used for fast on-site detection of suspect toxic gases. The infrared spectroscopic method is an excellent qualitative and quantitative analysis for some toxic gases. Permanent gases such as carbon monoxide, carbon dioxide, methane and ethylene, can be quantitatively determined by gas chromatography. Highly toxic and corrosive gases such as nitrogen oxides, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and sulfur dioxide should be passed into a scrubbing solution for subsequent analysis by either specific ion electrodes or spectrophotometric methods. Low-concentration toxic organic vapors can be concentrated in a cold trap and then analyzed by gas chromatography and mass spectrometry. The limitations of different methods are discussed.

Bacteria and lignin degradation

Institute of Scientific and Technical Information of China (English)

Jing LI; Hongli YUAN; Jinshui YANG

2009-01-01

Lignin is both the most abundant aromatic (phenolic) polymer and the second most abundant raw material.It is degraded and modified by bacteria in the natural world,and bacteria seem to play a leading role in decomposing lignin in aquatic ecosystems.Lignin-degrading bacteria approach the polymer by mechanisms such as tunneling,erosion,and cavitation.With the advantages of immense environmental adaptability and biochemical versatility,bacteria deserve to be studied for their ligninolytic potential.

Polymeric Materials - introduction and degradation

DEFF Research Database (Denmark)

Kontogeorgis, Georgios

1999-01-01

These notes support the polymer part of the courses 91742 and 91762 (Materials and Corrosion/degradation of materials) taught in IFAKthey contain a short introduction on group contribution methods for estimating properties of polymers, polymer thermodynamics, viscoelasticity models as well...

Evaluation of mechano-chemical degradation induced stresses of polyolefin pipes

Energy Technology Data Exchange (ETDEWEB)

Choi, Byoung Ho [Korea Univ., Seoul (Korea, Republic of); Chudnovsky, Alexander [The University of Illinois, Chicago (United States)

2008-07-01

The fracture phenomena in engineering thermoplastics resulting from chemical degradation is usually observed in the form of a microcrack network within a surface layer of degraded polymer exposed to a combined action of mechanical stresses and chemically aggressive environment. Degradation of polymers is usually manifested in a reduction of molecular weight, increase of crystallinity in semi crystalline polymers, increase of material density, a subtle increase in yield strength, and a dramatic reduction in toughness. The critical level of degradation for fracture initiation depends on the rates of toughness deterioration and build-up of the degradation related stresses as well as on the manufacturing and service stresses. In this paper, the evaluation of mechano-chemical degradation induced stress is attempted, and the application of the evaluated stress to the fracture initiation of polymer pipes is presented.

Evaluation of mechano-chemical degradation induced stresses of polyolefin pipes

International Nuclear Information System (INIS)

Choi, Byoung Ho; Chudnovsky, Alexander

2008-01-01

The fracture phenomena in engineering thermoplastics resulting from chemical degradation is usually observed in the form of a microcrack network within a surface layer of degraded polymer exposed to a combined action of mechanical stresses and chemically aggressive environment. Degradation of polymers is usually manifested in a reduction of molecular weight, increase of crystallinity in semi crystalline polymers, increase of material density, a subtle increase in yield strength, and a dramatic reduction in toughness. The critical level of degradation for fracture initiation depends on the rates of toughness deterioration and build-up of the degradation related stresses as well as on the manufacturing and service stresses. In this paper, the evaluation of mechano-chemical degradation induced stress is attempted, and the application of the evaluated stress to the fracture initiation of polymer pipes is presented

Oxidative degradation property of the proton-exchange membranes based on fluorinated polymer using radiation-induced grafting

International Nuclear Information System (INIS)

Mitani, N.; Muto, F.; Fujii, K.; Sato, Y.; Kakigi, T.; Matsuura, A.; Li Jingye; Miura, T.; Oshima, A.; Washio, M.

2006-01-01

To grow popularity of polymer electrolyte fuel cells (PEFCs), it is important that the life-time of FC will be evaluated. In the PEFCs operation, the oxygenated water would be produced by fuel gases crossover reaction. Moreover, the metal ions such as Fe 2+ would dissolve from piping and humidification bubblers in FC systems. As the results, the dissolved metal ions catalyze with oxygenated water, and then active oxidative radicals such as hydroxy and hydroperoxy radicals are induced by Fenton reaction. The oxidative radicals have considered one of the reasons of deterioration of FC performance. In our previous study, the partial-fluorinated sulfonic acid membranes based on crosslinked PTFE (sulfonated RX-PTFE) have been fabricated by pre EB-grafting method. In this study, in order to evaluate the chemical durability exerted on the PEFC performance of sulfonated RX-PTFE, we carried out the accelerated degradation test by Fenton reaction. The test conditions were 6 vol% H 2 O 2 with 5 ppm Fe 2+ solution at 60 degree C. The properties of sulfonated RX-PTFE before and after degradation tests were measured by means of X-ray photoelectron spectroscopy (XPS) and other methods. According to oxidative degradation test, the sulfonated RX-PTFE with higher crosslinking density of main chain became hard to deteriorate. On the contrary, the higher grafting yields became easy to degrade. It is suggested that the oxidative degradation would be greatly influenced to the grafted chain length and crosslinking density of main chain. From XPS after Fenton treated sulfonated RX-PTFE, the signal of S 2p and S 2s was disappeared. And also, by TGA and TG-MS analysis, it was found that the reduction of grafted chains was taken place. Furthermore, the crosslinked PTFE chains may be degraded through the reduction of grafted chain. The PEFC operation tests of sulfonated RX-PTFE before and after degradation tests were carried out. When the weight loss of sulfonated RX-PTFE was almost the same

COMMUNICATION: Toward a self-deploying shape memory polymer neuronal electrode

Science.gov (United States)

Sharp, Andrew A.; Panchawagh, Hrishikesh V.; Ortega, Alicia; Artale, Ryan; Richardson-Burns, Sarah; Finch, Dudley S.; Gall, Ken; Mahajan, Roop L.; Restrepo, Diego

2006-12-01

The widespread application of neuronal probes for chronic recording of brain activity and functional stimulation has been slow to develop partially due to long-term biocompatibility problems with existing metallic and ceramic probes and the tissue damage caused during probe insertion. Stiff probes are easily inserted into soft brain tissue but cause astrocytic scars that become insulating sheaths between electrodes and neurons. In this communication, we explore the feasibility of a new approach to the composition and implantation of chronic electrode arrays. We demonstrate that softer polymer-based probes can be inserted into the olfactory bulb of a mouse and that slow insertion of the probes reduces astrocytic scarring. We further present the development of a micromachined shape memory polymer probe, which provides a vehicle to self-deploy an electrode at suitably slow rates and which can provide sufficient force to penetrate the brain. The deployment rate and composition of shape memory polymer probes can be tailored by polymer chemistry and actuator design. We conclude that it is feasible to fabricate shape memory polymer-based electrodes that would slowly self-implant compliant conductors into the brain, and both decrease initial trauma resulting from implantation and enhance long-term biocompatibility for long-term neuronal measurement and stimulation.

Mechanism of radiation-induced degradation in mechanical properties of polymer matrix composites

International Nuclear Information System (INIS)

Egusa, Shigenori

1988-01-01

Four kinds of polymer matrix composites (filler, E-glass or carbon fibre cloth; matrix, epoxy or polyimide resin) and pure epoxy and polyimide resins were irradiated with 60 Co γ-rays or 2 MeV electrons at room temperature. Mechanical tests were then carried out at 77K and at room temperature. Following irradiation, the Young's (tensile) modulus of these composites and pure resins remains practically unchanged even at 170 MGy for both test temperatures. The ultimate strength, however, decreases appreciably with increasing dose. The dose dependence of the composite strength depends not only on the combination of fibre and matrix in the composite but also on the test temperature. A relationship is found between the composite ultimate strain and the matrix ultimate strain, thus indicating that the dose dependence of the composite strength is virtually determined by a change in the matrix ultimate strain due to irradiation. Based on this finding, we propose a mechanism of radiation-induced degradation of a polymer matrix composite in order to explain the dose dependence of the composite strength measured at 77 K and at room temperature. (author)

The rheology, degradation, processing, and characterization of renewable resource polymers

Science.gov (United States)

Conrad, Jason David

Renewable resource polymers have become an increasingly popular alternative to conventional fossil fuel based polymers over the past couple decades. The push by the government as well as both industrial and consumer markets to go "green" has provided the drive for companies to research and develop new materials that are more environmentally friendly and which are derived from renewable materials. Two polymers that are currently being produced commercially are poly-lactic acid (PLA) and polyhydroxyalkanoate (PHA) copolymers, both of which can be derived from renewable feedstocks and have shown to exhibit similar properties to conventional materials such as polypropylene, polyethylene, polystyrene, and PET. PLA and PHA are being used in many applications including food packaging, disposable cups, grocery bags, and biomedical applications. In this work, we report on the rheological properties of blends of PLA and PHA copolymers. The specific materials used in the study include Natureworks RTM 7000D grade PLA and PHA copolymers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Blends ranging from 10 to 50 percent PHA by weight are also examined. Shear and extensional experiments are performed to characterize the flow behavior of the materials in different flow fields. Transient experiments are performed to study the shear rheology over time in order to determine how the viscoelastic properties change under typical processing conditions and understand the thermal degradation behavior of the materials. For the blends, it is determined that increasing the PHA concentration in the blend results in a decrease in viscosity and increase in degradation. Models are fit to the viscosity of the blends using the pure material viscosities in order to be able to predict the behavior at a given blend composition. We also investigate the processability of these materials into films and examine the resultant properties of the cast films. The mechanical and thermal properties of the

Polymer light emitting diodes

International Nuclear Information System (INIS)

Gautier-Thianche, Emmmanuelle

1998-01-01

We study sandwich type semiconducting polymer light emitting diodes; anode/polymer/cathode. ITO is selected as anode, this polymer is a blend of a commercially available polymer with a high hole transport ability: polyvinyl-carbazole and a laser dye: coumarin-515. Magnesium covered with silver is chosen for the anode. We study the influence of polymer thickness and coumarin doping ratio on electroluminescence spectrum, electric characteristics and quantum efficiency. An important drawback is that diodes lifetime remains low. In the second part of our study we determine degradations causes with X-Ray reflectivity experiments. It may be due to ITO very high roughness. We realize a new type of planar electroluminescent device: a channel type electroluminescent device in which polymer layer is inserted into an aluminium channel. Such a device is by far more stable than using classical sandwich structures with the same polymer composition: indeed, charges are generated by internal-field ionization and there is no injection from the electrode to the polymer. This avoids electrochemical reactions at electrodes, thus reducing degradations routes. (author) [fr

Coating and Interface Degradation of Coated steel, Part 2: Accelerated Laboratory Tests

International Nuclear Information System (INIS)

Cambier, S.M.; Frankel, G.S.

2014-01-01

In a previous paper, it was demonstrated that the measurement of cathodic delamination by the Scanning Kelvin Probe can assess the interface stability of poly(vinyl butyral) (PVB) coated steel after field exposure. This technique was utilized to characterize the degradation of the polymer/metal interface in several outdoor climates. In this paper, the effects of environmental factors on the interface degradation were investigated in the laboratory. The mechanisms measured in the field were reproduced to provide input in the development of an appropriate accelerated test for PVB coated steel. The ASTM B117 and G154 standardized tests were investigated individually and sequentially. The interface stability improved after 24 h of ASTM G154 exposure. After 144 h of exposure to ASTM G154 exposure, polymer oxidation took place simultaneously with interface degradation. The condensation phase of the ASTM G154 test was responsible for the interface improvement while the ultraviolet radiation triggered the interface degradation. Pre-exposure to ASTM G154 delayed wet de-adhesion during ASTM B117 exposure. After wet de-adhesion caused by 6 h of ASTM B117, exposure to ASTM G154 for 24 h increased the interface stability. The effects of ultraviolet radiation, relative humidity, temperature and environment on interface degradation were investigated in a special chamber. Humidity was the primary factor found to influence the interface improvement during G154 exposure. A wet/dry salt fog cycle with irradiation by an ultraviolet or filtered xenon arc lamp around room temperature was suggested to reproduce the competition between the interface improvement and the interface degradation that takes place in the field

A microstructured Polymer Optical Fiber Biosensor

DEFF Research Database (Denmark)

Emiliyanov, Grigoriy Andreev; Jensen, Jesper Bo; Hoiby, Poul E.

2006-01-01

We demonstrate selective detection of fluorophore labeled antibodies from minute samples probed by a sensor layer of the complementary biomolecules immobilized inside the air holes of microstructured Polymer Optical Fibers.......We demonstrate selective detection of fluorophore labeled antibodies from minute samples probed by a sensor layer of the complementary biomolecules immobilized inside the air holes of microstructured Polymer Optical Fibers....

Substrate Shift Reveals Roles for Members of Bacterial Consortia in Degradation of Plant Cell Wall Polymers

Directory of Open Access Journals (Sweden)

Camila Carlos

2018-03-01

Full Text Available Deconstructing the intricate matrix of cellulose, hemicellulose, and lignin poses a major challenge in biofuel production. In diverse environments in nature, some microbial communities, are able to overcome plant biomass recalcitrance. Identifying key degraders of each component of plant cell wall can help improve biological degradation of plant feedstock. Here, we sequenced the metagenome of lignocellulose-adapted microbial consortia sub-cultured on xylan and alkali lignin media. We observed a drastic shift on community composition after sub-culturing, independently of the original consortia. Proteobacteria relative abundance increased after growth in alkali lignin medium, while Bacteroidetes abundance increased after growth in xylan medium. At the genus level, Pseudomonas was more abundant in the communities growing on alkali lignin, Sphingobacterium in the communities growing on xylan and Cellulomonas abundance was the highest in the original microbial consortia. We also observed functional convergence of microbial communities after incubation in alkali lignin, due to an enrichment of genes involved in benzoate degradation and catechol ortho-cleavage pathways. Our results represent an important step toward the elucidation of key members of microbial communities on lignocellulose degradation and may aide the design of novel lignocellulolytic microbial consortia that are able to efficiently degrade plant cell wall polymers.

Substrate Shift Reveals Roles for Members of Bacterial Consortia in Degradation of Plant Cell Wall Polymers.

Science.gov (United States)

Carlos, Camila; Fan, Huan; Currie, Cameron R

2018-01-01

Deconstructing the intricate matrix of cellulose, hemicellulose, and lignin poses a major challenge in biofuel production. In diverse environments in nature, some microbial communities, are able to overcome plant biomass recalcitrance. Identifying key degraders of each component of plant cell wall can help improve biological degradation of plant feedstock. Here, we sequenced the metagenome of lignocellulose-adapted microbial consortia sub-cultured on xylan and alkali lignin media. We observed a drastic shift on community composition after sub-culturing, independently of the original consortia. Proteobacteria relative abundance increased after growth in alkali lignin medium, while Bacteroidetes abundance increased after growth in xylan medium. At the genus level, Pseudomonas was more abundant in the communities growing on alkali lignin, Sphingobacterium in the communities growing on xylan and Cellulomonas abundance was the highest in the original microbial consortia. We also observed functional convergence of microbial communities after incubation in alkali lignin, due to an enrichment of genes involved in benzoate degradation and catechol ortho-cleavage pathways. Our results represent an important step toward the elucidation of key members of microbial communities on lignocellulose degradation and may aide the design of novel lignocellulolytic microbial consortia that are able to efficiently degrade plant cell wall polymers.

Retarded Local Dynamics of Single Fluorescent Probes in Polymeric Glass due to Interaction Strengthening

Science.gov (United States)

Zhang, Hao; Yang, Jingfa; Zhao, Jiang

The effect of strengthening of interaction between single fluorescent probes and polymer matrix to the probes dynamics is investigated using single molecule fluorescence defocus microscopy. By introducing multiple hydroxyl groups to the fluorescent probes, which builds up hydrogen bonds between the probe and polymer matrix, the dynamics is discovered to be retarded. This is evidenced by the lowering of the frequency of the vibrational modes in the power spectra of the rotation trajectories of individual fluorescent probes, and also by the lowering of population of rotating probes. The results show that by strengthening the probe-matrix interaction, the local dynamics detected by the probes is equivalent to that detected by a bigger probe, due to the enhanced friction between the probe and the polymer matrix. the National Basic Research Program of China (2012CB821500).

Characterization of para-Nitrophenol-Degrading Bacterial Communities in River Water by Using Functional Markers and Stable Isotope Probing.

Science.gov (United States)

Kowalczyk, Agnieszka; Eyice, Özge; Schäfer, Hendrik; Price, Oliver R; Finnegan, Christopher J; van Egmond, Roger A; Shaw, Liz J; Barrett, Glyn; Bending, Gary D

2015-10-01

Microbial degradation is a major determinant of the fate of pollutants in the environment. para-Nitrophenol (PNP) is an EPA-listed priority pollutant with a wide environmental distribution, but little is known about the microorganisms that degrade it in the environment. We studied the diversity of active PNP-degrading bacterial populations in river water using a novel functional marker approach coupled with [(13)C6]PNP stable isotope probing (SIP). Culturing together with culture-independent terminal restriction fragment length polymorphism analysis of 16S rRNA gene amplicons identified Pseudomonas syringae to be the major driver of PNP degradation in river water microcosms. This was confirmed by SIP-pyrosequencing of amplified 16S rRNA. Similarly, functional gene analysis showed that degradation followed the Gram-negative bacterial pathway and involved pnpA from Pseudomonas spp. However, analysis of maleylacetate reductase (encoded by mar), an enzyme common to late stages of both Gram-negative and Gram-positive bacterial PNP degradation pathways, identified a diverse assemblage of bacteria associated with PNP degradation, suggesting that mar has limited use as a specific marker of PNP biodegradation. Both the pnpA and mar genes were detected in a PNP-degrading isolate, P. syringae AKHD2, which was isolated from river water. Our results suggest that PNP-degrading cultures of Pseudomonas spp. are representative of environmental PNP-degrading populations. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Study on the Degradation of Polylactide Microsphere In Vitro

Institute of Scientific and Technical Information of China (English)

HeYing; WeiShuli

2001-01-01

This report concentrated on the rules and mechanism of the degradation of polylactide and the microspheres. The rate of degradation was assessed with five methods: observation of microsphere surface morphology by SEM, determination of the weight loss of the microspheres, determination of the molecular mass of the polymers by GPC, determination of pH and determination of the contents of lactic acid by UV spectrophotometry. The degradation of polylactide microspheres showed two-phase characteristics. At the early stage of the degradation, the high molecular mass polymers were cleaved into lower molecular mass fractions and at the late stage, there was a period of erosion and weight loss of the microspheres. The degradation was much slower for polymers with a higher molecular mass. The polylactide degradation showed good regularity.

Rapid, Efficient and Versatile Strategies for Functionally Sophisticated Polymers and Nanoparticles: Degradable Polyphosphoesters and Anisotropic Distribution of Chemical Functionalities

Science.gov (United States)

Zhang, Shiyi

The overall emphasis of this dissertation research included two kinds of asymmetrically-functionalized nanoparticles with anisotropic distributions of chemical functionalities, three degradable polymers synthesized by organocatalyzed ring-opening polymerizations, and two polyphosphoester-based nanoparticle systems for various biomedical applications. Inspired by the many hierarchical assembly processes that afford complex materials in Nature, the construction of asymmetrically-functionalized nanoparticles with efficient surface chemistries and the directional organization of those building blocks into complex structures have attracted much attention. The first method generated a Janus-faced polymer nanoparticle that presented two orthogonally click-reactive surface chemistries, thiol and azido. This robust method involved reactive functional group transfer by templating against gold nanoparticle substrates. The second method produced nanoparticles with sandwich-like distribution of crown ether functionalities through a stepwise self-assembly process that utilized crown ether-ammonium supramolecular interactions to mediate inter-particle association and the local intra-particle phase separation of unlike hydrophobic polymers. With the goal to improve the efficiency of the production of degradable polymers with tunable chemical and physical properties, a new type of reactive polyphosphoester was synthesized bearing alkynyl groups by an organocatalyzed ring-opening polymerization, the chemical availability of the alkyne groups was investigated by employing "click" type azide-alkyne Huisgen cycloaddition and thiol-yne radical-mediated reactions. Based on this alkyne-functionalized polyphosphoester polymer and its two available "click" type reactions, two degradable nanoparticle systems were developed. To develop the first system, the well defined poly(ethylene oxide)-block-polyphosphester diblock copolymer was transformed into a multifunctional Paclitaxel drug

The radiation induced degradation of polymers

International Nuclear Information System (INIS)

Wilski, H.

1987-01-01

A compilation was made of all data about the radiation stability of thermoplastic polymeric materials, published in the literature up to the end of 1985. From those experiments in which the irradiation was carried out in air half value doses (elongation) (= hvd) as a measure of radiation stability were extracted and compared on the basis of the chemical structure of the polymers, the chemical composition of the materials under test and the dose rate, respectively. The first result is that our knowledge of the radiation stability of polymers, if irradiated in air, is still very incomplete. On the other hand enough data were found for some polymers, to see that there is a region at low dose rates where the half value dose Dsub(e) increases with the dose rate (dD/dt) according to the equation Dsub(e)=Dsub(el).(dD/dt)sup(n). This seems to be the normal behavior. Values for the hvd at 1 Gy/h (in air) were found to lie between 1 and 500 kGy (with PTFE and PS at the respective ends of the scale), whereas n varied only between 0.1 and 0.4. The range of validity of the equation and the magnitude of the coefficients strongly depend on the chemical nature of the polymer and also on the kind and amount of the additives used. At dose rates in the neighborhood of 10 5 Gy/h the influence of the dose rate (and the atmosphere) disappears. (author)

Application of Nanoparticle Technology to Reduce the Anti-Microbial Resistance through β-Lactam Antibiotic-Polymer Inclusion Nano-Complex.

Science.gov (United States)

Salamanca, Constain H; Yarce, Cristhian J; Roman, Yony; Davalos, Andrés F; Rivera, Gustavo R

2018-02-10

Biocompatible polymeric materials with potential to form functional structures in association with different therapeutic molecules have a high potential for biological, medical and pharmaceutical applications. Therefore, the capability of the inclusion of nano-Complex formed between the sodium salt of poly(maleic acid- alt -octadecene) and a β-lactam drug (ampicillin trihydrate) to avoid the chemical and enzymatic degradation and enhance the biological activity were evaluated. PAM-18Na was produced and characterized, as reported previously. The formation of polymeric hydrophobic aggregates in aqueous solution was determined, using pyrene as a fluorescent probe. Furthermore, the formation of polymer-drug nano-complexes was characterized by Differential Scanning Calorimetry-DSC, viscometric, ultrafiltration/centrifugation assays, zeta potential and size measurements were determined by dynamic light scattering-DLS. The PAM-18Na capacity to avoid the chemical degradation was studied through stress stability tests. The enzymatic degradation was evaluated from a pure β-lactamase, while the biological degradation was determined by different β-lactamase producing Staphylococcus aureus strains. When ampicillin was associated with PAM-18Na, the half-life time in acidic conditions increased, whereas both the enzymatic degradation and the minimum inhibitory concentration decreased to a 90 and 75%, respectively. These results suggest a promissory capability of this polymer to protect the β-lactam drugs against chemical, enzymatic and biological degradation.

Effect of solvents on the enzyme mediated degradation of copolymers

International Nuclear Information System (INIS)

Banerjee, Aditi; Chatterjee, Kaushik; Madras, Giridhar

2015-01-01

The biodegradation of polycaprolactone (PCL), polylactic acid (PLA), polyglycolide (PGA) and their copolymers, poly (lactide-co-glycolide) and poly (D, L-lactide-co-caprolactone) (PLCL) was investigated. The influence of different solvents on the degradation of these polymers at 37 °C in the presence of two different lipases namely Novozym 435 and the free lipase of porcine pancreas was investigated. The rate coefficients for the polymer degradation and enzyme deactivation were determined using continuous distribution kinetics. Among the homopolymers, the degradation of PGA was nearly an order of magnitude lower than that for PCL and PLA. The overall rate coefficients of the copolymers were higher than their respective homopolymers. Thus, PLCL degraded faster than either PCL or PLA. The degradation was highly dependent on the viscosity of the solvent used with the highest degradation observed in acetone. The degradation of the polymers in acetone was nearly twice that observed in dimethyl sulfoxide indicating that the degradation decreases with increase in the solvent viscosity. The degradation of the polymers in water-solvent mixtures indicated an optimal water content of 2.5 wt% of water. (paper)

Semi-Degradable Poly(β-amino ester) Networks with Temporally-Controlled Enhancement of Mechanical Properties

Science.gov (United States)

Safranski, David L.; Weiss, Daiana; Clark, J. Brian; Taylor, W.R.; Gall, Ken

2014-01-01

Biodegradable polymers are clinically used in numerous biomedical applications, and classically show a loss in mechanical properties within weeks of implantation. This work demonstrates a new class of semi-degradable polymers that show an increase in mechanical properties through degradation via a controlled shift in a thermal transition. Semi-degradable polymer networks, poly(β-amino ester)-co-methyl methacrylate, were formed from a low glass transition temperature crosslinker, poly(β-amino ester), and high glass transition temperature monomer, methyl methacrylate, which degraded in a manner dependent upon the crosslinker chemical structure. In vitro and in vivo degradation revealed changes in mechanical behavior due to the degradation of the crosslinker from the polymer network. This novel polymer system demonstrates a strategy to temporally control the mechanical behavior of polymers and to enhance the initial performance of smart biomedical devices. PMID:24769113

Microbial Enzymatic Degradation of Biodegradable Plastics.

Science.gov (United States)

Roohi; Bano, Kulsoom; Kuddus, Mohammed; Zaheer, Mohammed R; Zia, Qamar; Khan, Mohammed F; Ashraf, Ghulam Md; Gupta, Anamika; Aliev, Gjumrakch

2017-01-01

The renewable feedstock derived biodegradable plastics are important in various industries such as packaging, agricultural, paper coating, garbage bags and biomedical implants. The increasing water and waste pollution due to the available decomposition methods of plastic degradation have led to the emergence of biodegradable plastics and biological degradation with microbial (bacteria and fungi) extracellular enzymes. The microbes utilize biodegradable polymers as the substrate under starvation and in unavailability of microbial nutrients. Microbial enzymatic degradation is suitable from bioremediation point of view as no waste accumulation occurs. It is important to understand the microbial interaction and mechanism involved in the enzymatic degradation of biodegradable plastics under the influence of several environmental factors such as applied pH, thermo-stability, substrate molecular weight and/or complexity. To study the surface erosion of polymer film is another approach for hydrolytic degradation characteristion. The degradation of biopolymer is associated with the production of low molecular weight monomer and generation of carbon dioxide, methane and water molecule. This review reported the degradation study of various existing biodegradable plastics along with the potent degrading microbes (bacteria and fungi). Patents available on plastic biodegradation with biotechnological significance is also summarized in this paper. This paper assesses that new disposal technique should be adopted for the degradation of polymers and further research is required for the economical production of biodegradable plastics along with their enzymatic degradation. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Long Range Polymer Chain Dynamics of Highly Flexible Polysiloxane in Solution Probed by Pyrene Excimer Fluorescence

Directory of Open Access Journals (Sweden)

Janine L. Thoma

2018-03-01

Full Text Available A poly(dimethylsiloxane-co-(3-aminopropylmethylsiloxane polymer (PDMS with 20.3 mol % of (3-aminopropylmethyl siloxane monomer has been labeled randomly with 1-pyreneacetyl groups to generate a series of polysiloxanes (Py-PDMS with pyrenyl contents ranging from 0.7 mol % to 5.2 mol % of the total number of structural units. The remainder of the amino groups were acetylated to avoid intra-chain quenching of the excited singlet states of pyrene via exciplex formation with free amino groups while allowing the formation of excimers to proceed. The fluorescence spectra and temporal decays of the Py-PDMS samples were acquired in tetrahydrofuran (THF, N,N-dimethylformamide (DMF, and dioxane. blob, the average rate constant for intra-chain pyrene excimer formation, was determined from the analysis of the fluorescence decays. blob was found to equal 1.16 (±0.13 × 109, 1.14 (±0.12 × 109, and 0.99 (±0.10 × 109 s−1 in THF, DMF, and dioxane, respectively, at room temperature. They are the largest values found to date for any polymeric backbone in these solvents. The qualitative relationship found here between blob and the chemical structures of the polymers indicates that the luminescence characteristics of randomly labeled polymers is a very useful method to probe the long range dynamics of chains of almost any polymer that is amenable to substitution by a lumophore.

Advanced Functional Polymers for Increasing the Stability of Organic Photovoltaics

DEFF Research Database (Denmark)

Bundgaard, Eva; Helgesen, Martin; Carlé, Jon Eggert

2013-01-01

The development of new advanced polymers for improving the stability of OPV is reviewed. Two main degradation pathways for the OPV active layer are identified: photochemically initiated reactions primarily starting in the side chains and morphological changes that degrade the important nanostruct......The development of new advanced polymers for improving the stability of OPV is reviewed. Two main degradation pathways for the OPV active layer are identified: photochemically initiated reactions primarily starting in the side chains and morphological changes that degrade the important...... nanostructure. Chemical units can be introduced that impart an increased stability. Similarly, the morphological degradation of the optimal nanostructure can be reduced. Active polymers and blends with acceptor material are used to create nanoparticle links with controlled size. Most of these advanced polymers...

Semi-degradable poly(β-amino ester) networks with temporally controlled enhancement of mechanical properties.

Science.gov (United States)

Safranski, David L; Weiss, Daiana; Clark, J Brian; Taylor, W Robert; Gall, Ken

2014-08-01

Biodegradable polymers are clinically used in numerous biomedical applications, and classically show a loss of mechanical properties within weeks of implantation. This work demonstrates a new class of semi-degradable polymers that show an increase in mechanical properties through degradation via a controlled shift in a thermal transition. Semi-degradable polymer networks, poly(β-amino ester)-co-methyl methacrylate, were formed from a low glass transition temperature crosslinker, poly(β-amino ester), and high glass transition temperature monomer, methyl methacrylate, which degraded in a manner dependent upon the crosslinker chemical structure. In vitro and in vivo degradation revealed changes in mechanical behavior due to the degradation of the crosslinker from the polymer network. This novel polymer system demonstrates a strategy to temporally control the mechanical behavior of polymers and to enhance the initial performance of smart biomedical devices. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

An approach for degradation of grape seed and skin proanthocyanidin polymers into oligomers by sulphurous acid.

Science.gov (United States)

Luo, Lanxin; Cui, Yan; Cheng, Jinhui; Fang, Bairui; Wei, Zongmin; Sun, Baoshan

2018-08-01

To develop an efficient method for degradation of grape seed and skin proanthocyanidins polymers into oligomers, an optimized sulphurous acid degradation conditions for grape seed with the temperature of 60 °C, reaction time of 60 min and sample-sulphurous acid ratio of 1:0.2, and for grape skin with the temperature of 40 °C, reaction time of 60 min and sample-sulphurous acid ratio of 1:0.2, were established. Afterwards, HSCCC and prep-HPLC were used to fractionate and isolate individual proanthocyanidin oligomers from the degradation products. Total of ten dimeric or trimeric procyanidins were obtained, and most of them presented high yield (from 0.7 mg to 13.6 mg per run in grape seed and from 0.5 mg to 4.1 mg per run in grape skin) and high purity (over 90%). The proposed method provides a new way for large preparation of oligomeric proanthocyanidins from naturally abundant and wasted polymeric ones. Copyright © 2018 Elsevier Ltd. All rights reserved.

A Mechanistic Model for Drug Release in PLGA Biodegradable Stent Coatings Coupled with Polymer Degradation and Erosion

Science.gov (United States)

Zhu, Xiaoxiang; Braatz, Richard D.

2015-01-01

Biodegradable poly(D,L-lactic-co-glycolic acid) (PLGA) coating for applications in drug-eluting stents has been receiving increasing interest as a result of its unique properties compared with biodurable polymers in delivering drug for reducing stents-related side effects. In this work, a mathematical model for describing the PLGA degradation and erosion and coupled drug release from PLGA stent coating is developed and validated. An analytical expression is derived for PLGA mass loss that predicts multiple experimental studies in the literature. An analytical model for the change of the number-average degree of polymerization (or molecular weight) is also derived. The drug transport model incorporates simultaneous drug diffusion through both the polymer solid and the liquid-filled pores in the coating, where an effective drug diffusivity model is derived taking into account factors including polymer molecular weight change, stent coating porosity change, and drug partitioning between solid and aqueous phases. The model is used to describe in vitro sirolimus release from PLGA stent coating, and demonstrates the significance of simultaneous sirolimus release via diffusion through both polymer solid and pore space. The proposed model is compared to existing drug transport models, and the impact of model parameters, limitations and possible extensions of the model are also discussed. PMID:25345656

Durability of radiation-sterilized polymers, 2

International Nuclear Information System (INIS)

Yoshii, Fumio; Sasaki, Takashi; Makuuchi, Keizo; Tamura, Naoyuki

1985-01-01

The degradation during storage after electron beam and γ-ray irradiation on to polymers for disposables syringes was investigated in connection with the decay curves of chemiluminescence amounts. The degradation during storage of homopolypropylene was relatively small, large part of polymers having been degraded during irradiation. The degradation during storage of copolypropylene occurred at earlier stage up to three months, while in later stage, it hardly proceeded. The degradation during storage of electron beam irradiated samples were far smaller than that γ-ray irradiated ones. Irradiation of 2.5 Mrad with electron beam caused degradation only a little during storage. It was suggested that the degradation during storage depend on degree of oxidation during irradiation. The degradation during storage was not observed for radiation resistant polypropylene and polymethylpentene. The degradation during storage of coprolypropylene was affected by atmosphere, being smaller in vacuo than in air. (author)

Degradation and protein release properties of microspheres prepared from biodegradable poly(lactide-co-glycolide) and ABA triblock copolymers: influence of buffer media on polymer erosion and bovine serum albumin release.

Science.gov (United States)

Bittner, B; Witt, C; Mäder, K; Kissel, T

1999-08-05

The aim of the present study was to investigate the influence of the chemical insertion of poly(ethylene oxide), PEO, into a poly(lactide-co-glycolide), PLG, backbone on the mechanisms of in vitro degradation and erosion of the polymer. For this purpose microspheres prepared by a modified W/O/W double emulsion technique using ABA triblock copolymers, consisting of PLG A-blocks attached to central PEO B-blocks were compared with microspheres prepared from PLG. Due to their molecular architecture the ABA triblock copolymers differed in their erosion and degradation behavior from PLG. Degradation occurred faster in the ABA polymers by cleavage of ester bonds inside the polymer backbone. Even erosion was shown to start immediately after incubation in different buffer media. By varying pH and ionic strength of the buffer it was found that both mass loss and molecular weight decay were accelerated in alkaline and acidic pH in the case of the ABA triblock copolymers. Although the pH of the medium had a moderate influence on the degradation of PLG, the molecular weight decay was not accompanied by a mass loss during the observation time. In a second set of experiments we prepared bovine serum albumin, BSA, loaded microspheres from both polymers. The release of BSA from ABA microspheres under in vitro conditions parallels the faster swelling and erosion rates. This could be confirmed by electron paramagnetic resonance, EPR, measurements with spin labeled albumin where an influx of buffer medium into the ABA microspheres was already observed within a few minutes. In contrast, PLG microspheres revealed a burst release without any erosion. The current study shows that the environmental conditions affected the degradation and erosion of the pure polymer microspheres in the same way as the release of the model protein. This leads to the conclusion that the more favorable degradation profile of the ABA triblock copolymers was responsible for the improvement of the release profile.

Radiation degradation of polymethacrylamide

International Nuclear Information System (INIS)

O'Connor, D.J.

1984-01-01

The effects of radiation on polymers have been studied for many years. When polymers are subjected to ultraviolet light or ionizing radiation, chain scission and crosslinking are possible. The radiation degradations of several methacrylate type polymers were investigated. The primary polymer studied was polymethacrylamide (PMAAm). Ultraviolet irradiated PMAAm yielded a five line ESR spectrum with 22 gauss splitting which is believed to arise from a polymeric radical ending with a methacrylamide unit. The results obtained indicate that polymethacrylamide is a polymer which undergoes main chain cleavage upon irradiation. As such this polymer may have potential applicability as a positive resist for fabrication of microelectronic devices

Degradation Studies of β-Cyclodextrin Polyurethane Polymers using

African Journals Online (AJOL)

diisocyanate (TDI) and hexamethylene diisocyanate (HMDI) were carried out by exposing the polymers to different soil types for up to 120 days. The aim of the study was to determine the fate of these novel polymers in the environment.

Autonomous valve for detection of biopolymer degradation

DEFF Research Database (Denmark)

Keller, Stephan Urs; Noeth, Nadine-Nicole; Fetz, Stefanie

2009-01-01

We present a polymer microvalve that allows the detection of biopolymer degradation without the need of external energy. The valve is based on a polymer container filled with a colored marker solution and closed by a thin lid. This structure is covered by a film of poly(L-lactide) and degradation...... of the biopolymer triggers the release of the color which is detected visually. The autonomous valve has potential for the fast testing of biopolymer degradation under various environmental conditions or by specific enzymes....

The guanidinium group as a key part of water-soluble polymer carriers for siRNA complexation and protection against degradation.

Science.gov (United States)

Tabujew, Ilja; Freidel, Christoph; Krieg, Bettina; Helm, Mark; Koynov, Kaloian; Müllen, Klaus; Peneva, Kalina

2014-07-01

Here, the preparation of a novel block copolymer consisting of a statistical copolymer N-(2-hydroxypropyl) methacrylamide-s-N-(3-aminopropyl) methacrylamide and a short terminal 3-guanidinopropyl methacrylamide block is reported. This polymer structure forms neutral but water-soluble nanosized complexes with siRNA. The siRNA block copolymer complexes are first analyzed using agarose gel electrophoresis and their size is determined with fluorescence correlation spectroscopy. The protective properties of the polymer against RNA degradation are investigated by treating the siRNA block copolymer complexes with RNase V1. Heparin competition assays confirm the efficient release of the cargo in vitro. In addition, the utilization of microscale thermophoresis is demonstrated for the determination of the binding strength between a fluorescently labeled polyanion and a polymer molecule. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of electron beam irradiation on the enzymatic degradation of composites based on biodegradable polymers and coconut fiber

Energy Technology Data Exchange (ETDEWEB)

Kodama, Yasko; Bardi, Marcelo Augusto Goncalves; Machado, Luci Diva Brocardo, E-mail: ykodama@ipen.b, E-mail: marcelo.bardi@usp.b, E-mail: lmachado@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Rosa, Derval dos Santos, E-mail: derval.rosa@ufabc.edu.b [Universidade Federal do ABC (UFABC), Santo Andre, SP (Brazil)

2011-07-01

The development of polymeric materials that are susceptible to microbiological degradation and that have properties similar to the conventional polymers would reduce waste deposit. Degradable plastics suffer significant change on chemical structure when submitted to specific environmental condition. PCL and PLLA have been extensively investigated due to their bio-assimilation and because they are considered as eco-friendly. So the degradation of PCL and PLLA homopolymers, PCL:PLLA 20:80 (w:w) blend and coconut fiber-modified composites were studied by means of their degradation under lipase enzyme from Pseudomonas cepacia. Non-irradiated and EB-irradiated samples at 50 kGy and 100 kGy were exposed during 24, 72, 120 and 168 hours to the enzyme-buffer solution and the retained mass of dried samples was accompanied over time. The results were compared to the not submitted to the enzyme solution samples. Degradation rate of PCL was higher than PLLA in the presence of Pseudomonas lipase. PLLA presence reduced PCL's enzymatic degradation in the PCL:PLLA 20:80 w:w blend. After 120 h exposure, blend mass loss variation approached pure PLLA behavior. Composites degradation behavior through time was similar to the blend. Values of retained mass for composites were superior to the blends suggesting that coconut fiber did not significantly degrade in the period of test. Degradation rate of 50 kGy-irradiated PCL slightly reduced, and it was observed increase of degradation rate of samples irradiated with 100 kGy, probably attributed to its crystallinity decrease. Degradation rate of irradiated composite was similar to the blend, suggesting that fiber presence did not affect significantly this parameter. Samples tested during 168 h were affected by the water absorption by PLLA or coconut fibers through time testing. Studied samples degraded accentuatedly in the enzyme presence and were not negatively affected by the radiation processing. (author)

Effect of electron beam irradiation on the enzymatic degradation of composites based on biodegradable polymers and coconut fiber

International Nuclear Information System (INIS)

Kodama, Yasko; Bardi, Marcelo Augusto Goncalves; Machado, Luci Diva Brocardo; Rosa, Derval dos Santos

2011-01-01

The development of polymeric materials that are susceptible to microbiological degradation and that have properties similar to the conventional polymers would reduce waste deposit. Degradable plastics suffer significant change on chemical structure when submitted to specific environmental condition. PCL and PLLA have been extensively investigated due to their bio-assimilation and because they are considered as eco-friendly. So the degradation of PCL and PLLA homopolymers, PCL:PLLA 20:80 (w:w) blend and coconut fiber-modified composites were studied by means of their degradation under lipase enzyme from Pseudomonas cepacia. Non-irradiated and EB-irradiated samples at 50 kGy and 100 kGy were exposed during 24, 72, 120 and 168 hours to the enzyme-buffer solution and the retained mass of dried samples was accompanied over time. The results were compared to the not submitted to the enzyme solution samples. Degradation rate of PCL was higher than PLLA in the presence of Pseudomonas lipase. PLLA presence reduced PCL's enzymatic degradation in the PCL:PLLA 20:80 w:w blend. After 120 h exposure, blend mass loss variation approached pure PLLA behavior. Composites degradation behavior through time was similar to the blend. Values of retained mass for composites were superior to the blends suggesting that coconut fiber did not significantly degrade in the period of test. Degradation rate of 50 kGy-irradiated PCL slightly reduced, and it was observed increase of degradation rate of samples irradiated with 100 kGy, probably attributed to its crystallinity decrease. Degradation rate of irradiated composite was similar to the blend, suggesting that fiber presence did not affect significantly this parameter. Samples tested during 168 h were affected by the water absorption by PLLA or coconut fibers through time testing. Studied samples degraded accentuatedly in the enzyme presence and were not negatively affected by the radiation processing. (author)

Green polymer chemistry: biocatalysis and biomaterials

Science.gov (United States)

This overview briefly surveys the practice of green chemistry in polymer science. Eight related themes can be discerned from the current research activities: 1) biocatalysis, 2) bio-based building blocks and agricultural products, 3) degradable polymers, 4) recycling of polymer products and catalys...

Water-Induced Degradation of Polymer Solar Cells Studied by (H2O)-O-18 Labeling

DEFF Research Database (Denmark)

Norrman, Kion; Gevorgyan, Suren; Krebs, Frederik C

2009-01-01

Water-induced degradation of polymer photovoltaics based on the active materials poly(3-hexylthiophene) (P3HT) or poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEHPPV) was studied. The solar cell devices comprised a bulk heterojunction formed by the active material and [6,6]-phenyl......-C61-butyric acid methyl ester (PCBM) in a standard device geometry. The use of H218O in conjunction with time-of-flight secondary ion mass spectrometry enabled mapping of the parts of the device that were induced by water. A comparison was made between the two active materials and between devices...

Influence of solvents on UV degradation of polysilanes films

International Nuclear Information System (INIS)

Tkacova, M.; Schauer, F.

2014-01-01

In the paper we deal with the UV degradation process in polymers in general and silicon based polymers in particular, using the well-known prototypical polymer poly[methylphenylsilylene] (PMPSi). Attention is focused on the influence of solvents used for films preparation an don the UV degradation process in these films examined by Photoluminescence (PL) spectroscopy and Electrochemical Impedance Spectroscopy (EIS). The goal of the study is oriented on the writing of information into thin polymer films and production of nano masks for semiconductor industry. PMPSi is a prototypical silicon-based polymer from the polysilanes (PS) group that attracted attention because of their nonlinear optical and photoelectrical properties (authors)

Biostable glucose permeable polymer

DEFF Research Database (Denmark)

2017-01-01

A new biostable glucose permeable polymer has been developed which is useful, for example, in implantable glucose sensors. This biostable glucose permeable polymer has a number of advantageous characteristics and, for example, does not undergo hydrolytic cleavage and degradation, thereby providing...... a composition that facilitates long term sensor stability in vivo. The versatile characteristics of this polymer allow it to be used in a variety of contexts, for example to form the body of an implantable glucose sensor. The invention includes the polymer composition, sensor systems formed from this polymer...

Modelling pH-Optimized Degradation of Microgel-Functionalized Polyesters

Directory of Open Access Journals (Sweden)

Lisa Bürgermeister

2016-01-01

Full Text Available We establish a novel mathematical model to describe and analyze pH levels in the vicinity of poly(N-vinylcaprolactam-co-acetoacetoxyethyl methacrylate-co-N-vinylimidazole (VCL/AAEM/VIm microgel-functionalized polymers during biodegradation. Biodegradable polymers, especially aliphatic polyesters (polylactide/polyglycolide/polycaprolactone homo- and copolymers, have a large range of medical applications including delivery systems, scaffolds, or stents for the treatment of cardiovascular diseases. Most of those applications are limited by the inherent drop of pH level during the degradation process. The combination of polymers with VCL/AAEM/VIm-microgels, which aims at stabilizing pH levels, is innovative and requires new mathematical models for the prediction of pH level evaluation. The mathematical model consists of a diffusion-reaction PDE system for the degradation including reaction rate equations and diffusion of acidic degradation products into the vicinity. A system of algebraic equations is coupled to the degradation model in order to describe the buffering action of the microgel. The model is validated against the experimental pH-monitored biodegradation of microgel-functionalized polymer foils and is available for the design of microgel-functionalized polymer components.

Bacteria capable of degrading anthracene, phenanthrene, and fluoranthene as revealed by DNA based stable-isotope probing in a forest soil

Energy Technology Data Exchange (ETDEWEB)

Song, Mengke [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Jiang, Longfei [College of Life Sciences, Nanjing Agricultural University, Nanjing 210095 (China); Zhang, Dayi [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Luo, Chunling, E-mail: clluo@gig.ac.cn [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Wang, Yan [Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Yu, Zhiqiang [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Yin, Hua [College of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); Zhang, Gan [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

2016-05-05

Highlights: • Investigate PAHs degraders in forest carbon-rich soils via DNA-SIP. • Rhodanobacter is identified to metabolite anthracene for the first time. • The first fluoranthene degrader belongs to Acidobacteria. • Different functions of PAHs degraders in forest soils from contaminated soils. - Abstract: Information on microorganisms possessing the ability to metabolize different polycyclic aromatic hydrocarbons (PAHs) in complex environments helps in understanding PAHs behavior in natural environment and developing bioremediation strategies. In the present study, stable-isotope probing (SIP) was applied to investigate degraders of PAHs in a forest soil with the addition of individually {sup 13}C-labeled phenanthrene, anthracene, and fluoranthene. Three distinct phylotypes were identified as the active phenanthrene-, anthracene- and fluoranthene-degrading bacteria. The putative phenanthrene degraders were classified as belonging to the genus Sphingomona. For anthracene, bacteria of the genus Rhodanobacter were the putative degraders, and in the microcosm amended with fluoranthene, the putative degraders were identified as belonging to the phylum Acidobacteria. Our results from DNA-SIP are the first to directly link Rhodanobacter- and Acidobacteria-related bacteria with anthracene and fluoranthene degradation, respectively. The results also illustrate the specificity and diversity of three- and four-ring PAHs degraders in forest soil, contributes to our understanding on natural PAHs biodegradation processes, and also proves the feasibility and practicality of DNA-based SIP for linking functions with identity especially uncultured microorganisms in complex microbial biota.

Control of enzymatic degradation of biodegradable polymers by treatment with biosurfactants, mannosylerythritol lipids, derived from Pseudozyma spp. yeast strains.

Science.gov (United States)

Fukuoka, Tokuma; Shinozaki, Yukiko; Tsuchiya, Wataru; Suzuki, Ken; Watanabe, Takashi; Yamazaki, Toshimasa; Kitamoto, Dai; Kitamoto, Hiroko

2016-02-01

Cutinase-like esterase from the yeasts Pseudozyma antarctica (PaE) shows strong degradation activity in an agricultural biodegradable plastic (BP) model of mulch films composed of poly(butylene succinate-co-adipate) (PBSA). P. antarctica is known to abundantly produce a glycolipid biosurfactant, mannosylerythritol lipid (MEL). Here, the effects of MEL on PaE-catalyzed degradation of BPs were investigated. Based on PBSA dispersion solution, the degradation of PBSA particles by PaE was inhibited in the presence of MEL. MEL behavior on BP substrates was monitored by surface plasmon resonance (SPR) using a sensor chip coated with polymer films. The positive SPR signal shift indicated that MEL readily adsorbed and spread onto the surface of a BP film. The amount of BP degradation by PaE was monitored based on the negative SPR signal shift and was decreased 1.7-fold by MEL pretreatment. Furthermore, the shape of PBSA mulch films in PaE-containing solution was maintained with MEL pretreatment, whereas untreated films were almost completely degraded and dissolved. These results suggest that MEL covering the surface of BP film inhibits adsorption of PaE and PaE-catalyzed degradation of BPs. We applied the above results to control the microbial degradation of BP mulch films. MEL pretreatment significantly inhibited BP mulch film degradation by both PaE solution and BP-degradable microorganism. Moreover, the degradation of these films was recovered after removal of the coated MEL by ethanol treatment. These results demonstrate that the biodegradation of BP films can be readily and reversibly controlled by a physical approach using MEL.

Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

International Nuclear Information System (INIS)

Cui, Zhongping; Qi, Ji; Xu, Xinxin; Liu, Lu; Wang, Yi

2013-01-01

To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer composite material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future

Using DNA-Stable Isotope Probing to Identify MTBE- and TBA-Degrading Microorganisms in Contaminated Groundwater.

Science.gov (United States)

Key, Katherine C; Sublette, Kerry L; Duncan, Kathleen; Mackay, Douglas M; Scow, Kate M; Ogles, Dora

2013-01-01

Although the anaerobic biodegradation of methyl tert -butyl ether (MTBE) and tert -butyl alcohol (TBA) has been documented in the laboratory and the field, knowledge of the microorganisms and mechanisms involved is still lacking. In this study, DNA-stable isotope probing (SIP) was used to identify microorganisms involved in anaerobic fuel oxygenate biodegradation in a sulfate-reducing MTBE and TBA plume. Microorganisms were collected in the field using Bio-Sep® beads amended with 13 C 5 -MTBE, 13 C 1 -MTBE (only methoxy carbon labeled), or 13 C 4 -TBA. 13 C-DNA and 12 C-DNA extracted from the Bio-Sep beads were cloned and 16S rRNA gene sequences were used to identify the indigenous microorganisms involved in degrading the methoxy group of MTBE and the tert -butyl group of MTBE and TBA. Results indicated that microorganisms were actively degrading 13 C-labeled MTBE and TBA in situ and the 13 C was incorporated into their DNA. Several sequences related to known MTBE- and TBA-degraders in the Burkholderiales and the Sphingomonadales orders were detected in all three 13 C clone libraries and were likely to be primary degraders at the site. Sequences related to sulfate-reducing bacteria and iron-reducers, such as Geobacter and Geothrix , were only detected in the clone libraries where MTBE and TBA were fully labeled with 13 C, suggesting that they were involved in processing carbon from the tert -butyl group. Sequences similar to the Pseudomonas genus predominated in the clone library where only the methoxy carbon of MTBE was labeled with 13 C. It is likely that members of this genus were secondary degraders cross-feeding on 13 C-labeled metabolites such as acetate.

BET, thermal degradation, and FTIR spectras of triazine polyamine polymers.

Science.gov (United States)

Can, Mustafa

2017-04-01

Here we show effect of the polyamine polymer chain length to BET isotherms. According to IUPAC classification [1], all three polymers are fitting type 1 physical adsorption isotherm with H3 hysteresis (except for EDA having H2 hysteresis). Moreover, TG and TGA analysis of polymers triazine-ethylenediamine (EDA) and triazine-triethylenetetramine (TETA) are provided. Due to the similarities of the structure, main decomposition temperatures are close to each other (between 593 K and 873 K). In order to understand change of FTIR spectra with adsorption and stripping Au(III), fresh, Au(III) adsorbed and recycled spectras of polymers measured. For further discussions about the effect of chain length to adsorption of Au(III) onto triazine polyamine polymer particles "Au (III) Uptake by Triazine Polyamine Polymers: Mechanism, Kinetic and Equilibrium Studies" Can et al. [2] (article in press).

Leucoagaricus gongylophorus produces diverse enzymes for the degradation of recalcitrant plant polymers in leaf-cutter ant fungus gardens.

Science.gov (United States)

Aylward, Frank O; Burnum-Johnson, Kristin E; Tringe, Susannah G; Teiling, Clotilde; Tremmel, Daniel M; Moeller, Joseph A; Scott, Jarrod J; Barry, Kerrie W; Piehowski, Paul D; Nicora, Carrie D; Malfatti, Stephanie A; Monroe, Matthew E; Purvine, Samuel O; Goodwin, Lynne A; Smith, Richard D; Weinstock, George M; Gerardo, Nicole M; Suen, Garret; Lipton, Mary S; Currie, Cameron R

2013-06-01

Plants represent a large reservoir of organic carbon comprised primarily of recalcitrant polymers that most metazoans are unable to deconstruct. Many herbivores gain access to nutrients in this material indirectly by associating with microbial symbionts, and leaf-cutter ants are a paradigmatic example. These ants use fresh foliar biomass as manure to cultivate gardens composed primarily of Leucoagaricus gongylophorus, a basidiomycetous fungus that produces specialized hyphal swellings that serve as a food source for the host ant colony. Although leaf-cutter ants are conspicuous herbivores that contribute substantially to carbon turnover in Neotropical ecosystems, the process through which plant biomass is degraded in their fungus gardens is not well understood. Here we present the first draft genome of L. gongylophorus, and, using genomic and metaproteomic tools, we investigate its role in lignocellulose degradation in the gardens of both Atta cephalotes and Acromyrmex echinatior leaf-cutter ants. We show that L. gongylophorus produces a diversity of lignocellulases in ant gardens and is likely the primary driver of plant biomass degradation in these ecosystems. We also show that this fungus produces distinct sets of lignocellulases throughout the different stages of biomass degradation, including numerous cellulases and laccases that likely play an important role in lignocellulose degradation. Our study provides a detailed analysis of plant biomass degradation in leaf-cutter ant fungus gardens and insight into the enzymes underlying the symbiosis between these dominant herbivores and their obligate fungal cultivar.

Leucoagaricus gongylophorus Produces Diverse Enzymes for the Degradation of Recalcitrant Plant Polymers in Leaf-Cutter Ant Fungus Gardens

Energy Technology Data Exchange (ETDEWEB)

Aylward, Frank O. [Univ. of Wisconsin, Madison, WI (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Burnum-Johnson, Kristin E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Tringe, Susannah G. [Dept. of Energy Joint Genome Inst., Walnut Creek, CA (United States); Teiling, Clotilde [Roche Diagnostics, Indianapolis, IN (United States); Tremmel, Daniel [Univ. of Wisconsin, Madison, WI (United States); Moeller, Joseph [Univ. of Wisconsin, Madison, WI (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Scott, Jarrod J. [Univ. of Wisconsin, Madison, WI (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Barry, Kerrie W. [Dept. of Energy Joint Genome Inst., Walnut Creek, CA (United States); Piehowski, Paul D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Nicora, Carrie D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Malfatti, Stephanie [Dept. of Energy Joint Genome Inst., Walnut Creek, CA (United States); Monroe, Matthew E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Purvine, Samuel O. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Goodwin, Lynne A. [Dept. of Energy Joint Genome Inst., Walnut Creek, CA (United States); Smith, Richard D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Weinstock, George [Washington Univ. School of Medicine, St. Louis, MS (United States); Gerardo, Nicole [Emory Univ., Atlanta, GA (United States); Suen, Garret [Dept. of Energy Joint Genome Inst., Walnut Creek, CA (United States); Lipton, Mary S. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Currie, Cameron R. [Univ. of Wisconsin, Madison, WI (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Smothsonian Tropical Research Inst., Balboa (Panama)

2013-06-12

Plants represent a large reservoir of organic carbon comprised largely of recalcitrant polymers that most metazoans are unable to deconstruct. Many herbivores gain access to nutrients in this material indirectly by associating with microbial symbionts, and leaf-cutter ants are a paradigmatic example. These ants use fresh foliar biomass as manure to cultivate fungus gardens composed primarily of Leucoagaricus gongylophorus, a basidiomycetous symbiont that produces specialized hyphal swellings that serve as a food source for the host ant colony. Although leaf-cutter ants are conspicuous herbivores that contribute substantially to carbon turnover in Neotropical ecosystems, the process through which plant biomass is degraded in their fungus gardens is not well understood. Here we present the first draft genome of L. gongylophorus, and using genomic, metaproteomic, and phylogenetic tools we investigate its role in lignocellulose degradation in the fungus gardens of both Atta cephalotes and Acromyrmex echinatior leaf-cutter ants. We show that L. gongylophorus produces a diversity of lignocellulases in fungus gardens, and is likely the primary driver of plant biomass degradation in these ecosystems. We also show that this fungus produces distinct sets of lignocellulases throughout the different stages of biomass degradation, including numerous cellulases and laccases that may be playing an important but previously uncharacterized role in lignocellulose degradation. Our study provides a comprehensive analysis of plant biomass degradation in leaf-cutter ant fungus gardens and provides insight into the molecular dynamics underlying the symbiosis between these dominant herbivores and their obligate fungal cultivar.

Bacterial enzymes involved in lignin degradation

NARCIS (Netherlands)

de Gonzalo, Gonzalo; Colpa, Dana I; Habib, Mohamed H M; Fraaije, Marco W

2016-01-01

Lignin forms a large part of plant biomass. It is a highly heterogeneous polymer of 4-hydroxyphenylpropanoid units and is embedded within polysaccharide polymers forming lignocellulose. Lignin provides strength and rigidity to plants and is rather resilient towards degradation. To improve the

Hydrolytic And Enzymatic Degradation Characteristics Of Biodegradable Aliphatic Polysters

Institute of Scientific and Technical Information of China (English)

LI Suming

2004-01-01

Aliphatic polyesters, especially those derived from lactide (PLA), glycolide (PGA) and ε-caprolactone (PCL), are being investigated worldwide for applications in the field of surgery (suture material, devices for internal bone fracture fixation), pharmacology (sustained drug delivery systems), and tissue engineering (scaffold for tissue regeneration) [1,2]. This is mainly due to their good biocompatibility and variable degradability. These polymers present also a growing interest for environmental applications in agriculture (mulch films) and in our everyday life (packaging material)as the development of biodegradable materials is now considered as one of the potential solutions to the problem of plastic waste management.For both biomedical and environmental applications, it is of major importance to understand the degradation characteristics of the polymers. The hydrolytic degradation of aliphatic polyesters has been investigated by many research groups. Our group has shown that degradation of PLAGA large size devices is faster inside than at the surface. This heterogeneous degradation is due to the autocatalytic effect of carboxylic endgroups formed by ester bond cleavage. Moreover,degradation-induced morphological and compositional changes were also elucidated. In the case of PCL, the hydrolytic degradation is very slow due to its hydrophobicity and crystallinity.The enzymatic degradation of these polymers has been investigated by a number of authors. A specific enzyme, proteinase K, has been shown to have significant effects on PLA degradation. This enzyme preferentially degrade L-lactate units as opposed to D-lactate ones, amorphous zones as opposed to crystalline ones [3]. The enzymatic degradation of PCL polymers has also been investigated. A number of lipase-type enzymes were found to significantly accelerate the degradation of PCL despite its high crystallinity. In the case of PLA/PCL blends, the two components exhibited well separated crystalline domains

Metallic microwires obtained as replicas of etched ion tracks in polymer matrixes: Microscopy and emission properties

International Nuclear Information System (INIS)

Zagorski, D.L.; Bedin, S.A.; Oleinikov, V.A.; Polyakov, N.B.; Rybalko, O.G.; Mchedlishvili, B.V.

2009-01-01

Specially prepared porous matrixes (with through and dead-end pores of cylindrical or conical forms) were used as the templates for making ensembles of microwires. The process of electrodeposition of metal (Cu) into these pores was investigated. AFM technique was used for studying the 'composite material' (metal microwires embedded into the polymer matrix). It was shown that the combination of different modes of AFM (tapping with phase-contrast mode, contact with lateral force mode) makes it possible to detect metal in the polymer matrix. Additional spread resistance mode in the contact regime allowed to measure the electrical conductivity of a single wire. The ensembles of free-standing microwires (metallic replicas of the pores obtained after removing of the polymer matrix) were used as the substrates (for deposition of the probe) for ion emission in the mass-spectrometer. It was shown that the intensity of formed ion beam increases with increasing of power of the laser pulse and with increasing of the mass of the probe. The intensity of mass-spectra signal on the power of laser pulse has a threshold character with saturation accompanied with the appearance of dimer ions. At the same time this intensity decreases with the increasing of the surface density of wires. The effect of degradation of wires during the laser pulse irradiation was found.

Flexible poly(methyl methacrylate)-based neural probe: An affordable implementation

Science.gov (United States)

Gasemi, Pejman; Veladi, Hadi; Shahabi, Parviz; Khalilzadeh, Emad

2018-03-01

This research presents a novel technique used to fabricate a deep brain stimulation probe based on a commercial poly(methyl methacrylate) (PMMA) polymer. This technique is developed to overcome the high cost of available probes crucial for chronic stimulation and recording in neural disorders such as Parkinson’s disease and epilepsy. The probe is made of PMMA and its mechanical properties have been customized by controlling the reaction conditions. The polymer is adjusted to be stiff enough to be easily inserted and, on the other hand, soft enough to perform required movements. As cost is one of the issues in the use of neural probes, a simple process is proposed for the production of PMMA neural probes without using expensive equipment and operations, and without compromising performance and quality. An in vivo animal test was conducted to observe the recording capability of a PMMA probe.

Degradation of Polymer-Coated Materials

Science.gov (United States)

2013-10-01

W. Kammlott, Science, 1984. 224(4649): p. 599-601. 18. B. Millet , C. Fiaud, and C. Hinnen, Corrosion Science, 1995. 37(12): p. 1903-1918. 19. Z. Y...M. M. Sutter, B. Millet , C. Fiaud, and D. Lincot, Journal of Electroanalytical Chemistry, 1995. 386(1-2): p. 101-109. 50. W. Siripala and K. P...between 800-900 cm-1 and above 1200 cm-1 which are attributed to polymer finger -print 267 modes.37,38 This confirms that the assembled KP-Raman

Review of radiation processing of natural polymer

International Nuclear Information System (INIS)

Khairul Zaman

2007-01-01

In recent years, natural polymers are being investigated with renewed interest because of their abundant quantity and unique characteristics such as inherent biocompatibility, biodegradability and renewable. It is also known as green polymer. Natural polymers such as carrageen, alginate, chitin/chitosan and starch are traditionally used in food-based industry. But now, the applications of natural polymers are being sought in knowledge-driven areas such as healthcare, agro-technology and industry. Radiation degraded alginates, carrangeenan and chitosan as plant growth promoter and protector have been developed. Radiation degraded chitosan, carraneenan and starch have also been used together with synthetic polymers for hydrogel production to be used for wound dressing, skin moisturization and for biodegradable packaging films and foams. Radiation crosslinking of natural polymer derivatives such as carboxymethyl chitosan, carboxymethyl starch have been successfully developed in Japan and used for various applications such as removal of pollutants, removal of waters from liverstock excrete as well as for bedsores protection mat. (author)

Photochemical stability of π-conjugated polymers for polymer solar cells: a rule of thumb

DEFF Research Database (Denmark)

Manceau, Matthieu; Bundgaard, Eva; Carlé, Jon Eggert

2011-01-01

A comparative photochemical stability study of a wide range of π-conjugated polymers relevant to polymer solar cells is presented. The behavior of each material has been investigated under simulated sunlight (1 sun, 1000 W m−2, AM 1.5G) and ambient atmosphere. Degradation was monitored during age...... ageing combining UV-visible and infrared spectroscopies. From the comparison of the collected data, the influence of the polymer chemical structure on its stability has been discussed. General rules relative to the polymer structure–stability relationship are proposed....

Hydrothermal synthesis of Bismuth(III) coordination polymer and its transformation to nano α-Bi{sub 2}O{sub 3} for photocatalytic degradation

Energy Technology Data Exchange (ETDEWEB)

Huang, Ya-Jing; Zheng, Yue-Qing, E-mail: zhengnbu@163.com; Zhu, Hong-Lin; Wang, Jin-Jian

2016-07-15

A new Bi(III) coordination polymer Bi{sub 2}(Hpdc){sub 2}(pdc){sub 2}·2H{sub 2}O (H{sub 2}pdc=pyridine-2,6-dicarboxylic acid) was synthesized by hydrothermal method. Solid state thermal decomposition of this complex under 500 °C for 1 h led to the foliated Bi{sub 2}O{sub 3} nanoparticles, which were then characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Comparative study on their photocatalytic activity toward the degradation of rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) in polluted water was explored, and the mechanism of these photocatalytic degradation was discussed. These results provided some interesting insights into their photocatalytic applications. - Graphical abstract: We regard Bi{sub 2}(Hpdc){sub 2}(pdc){sub 2}·2H{sub 2}O with 1D chain structures as the precursor, then calcinate the complex to prepare nano-powder α-Bi{sub 2}O{sub 3}. The photochemical experiment indicates that Bi{sub 2}(Hpdc){sub 2}(pdc){sub 2}·2H{sub 2}O can be used as an efficient photocatalyst for the degradation of RhB and MB. Interestingly, nano α-Bi{sub 2}O{sub 3} shows higher activity than the commercial Bi{sub 2}O{sub 3} for the degradation of RhB, MB or MO. Display Omitted - Highlights: • A novel dinuclear Bi(III) coordination polymer is hydrothermally synthesized. • Calcinating the precursor Bi-CP will result in the nano Bi{sub 2}O{sub 3} with foliated morphology. • Nano Bi{sub 2}O{sub 3} shows higher activity than the commercial Bi{sub 2}O{sub 3} for the degradation of dyes.

Ultrasonic degradation of butadiene, styrene and their copolymers.

Science.gov (United States)

Sathiskumar, P S; Madras, Giridhar

2012-05-01

Ultrasonic degradation of commercially important polymers, styrene-butadiene (SBR) rubber, acrylonitrile-butadiene (NBR) rubber, styrene-acrylonitrile (SAN), polybutadiene rubber and polystyrene were investigated. The molecular weight distributions were measured using gel permeation chromatography (GPC). A model based on continuous distribution kinetics approach was used to study the time evolution of molecular weight distribution for these polymers during degradation. The effect of solvent properties and ultrasound intensity on the degradation of SBR rubber was investigated using different pure solvents and mixed solvents of varying volatility and different ultrasonic intensities. Copyright © 2011 Elsevier B.V. All rights reserved.

IMPORTANT DEGRADATIONS IN POLYETHYLENE TERAPHTALATE EXTRUSION PROCESS

Directory of Open Access Journals (Sweden)

Şule ALTUN

2003-01-01

Full Text Available Polyethylene terephthalate (PET is one of the most used thermo-plastic polymers. The total consumption of PET has been about 30 million tons in the year 2000. Polyester fibers constitute about 60 % of total synthetic fibers consumption. During extrusion, PET polymer is faced to thermal, thermo-oxidative and hydrolytic degradation, which result in severe reduction in its molecular weight, thereby adversely affecting its subsequent melt processability. Therefore, it is essential to understand degradation processes of PET during melt extrusion.

The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells.

Science.gov (United States)

Heckler, Ilona M; Kesters, Jurgen; Defour, Maxime; Madsen, Morten V; Penxten, Huguette; D'Haen, Jan; Van Mele, Bruno; Maes, Wouter; Bundgaard, Eva

2016-03-09

The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[ c ][1,2,5]thiadiazole (BT) or thiazolo[5,4- d ]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs' lifetime.

The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells

Directory of Open Access Journals (Sweden)

Ilona M. Heckler

2016-03-01

Full Text Available The stability of polymer solar cells (PSCs can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyldialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT or thiazolo[5,4-d]thiazole (TzTz acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10% of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs’ lifetime.

Hyperbranched Polymers - Engineering Materials and Degradation Behavior

National Research Council Canada - National Science Library

Wooley, Karen

2000-01-01

.... In the studies supported under this grant, hyperbranched polycarbonates were designed as analogs to common engineering polymers to investigate the effects of branching upon the chain-chain packing...

Polymer and Polymer Gel of Liquid Crystalline Semiconductors

Institute of Scientific and Technical Information of China (English)

Teppei Shimakawa; Naoki Yoshimoto; Jun-ichi Hanna

2004-01-01

It prepared a polymer and polymer gel of a liquid crystalline (LC) semiconductor having a 2-phenylnaphthalene moiety and studied their charge carrier transport properties by the time-of-flight technique. It is found that polyacrylate having the mesogenic core moiety of 2-phenylnaphtalene (PNP-acrylate) exhibited a comparable mobility of 10-4cm2/Vs in smectic A phase to those in smectic A (SmA) phase of small molecular liquid crystals with the same core moiety, e.g., 6-(4'-octylphenyl)- 2-dodecyloxynaphthalene (8-PNP-O12), and an enhanced mobility up to 10-3cm2/Vs in the LC-glassy phase at room temperature, when mixed with a small amount of 8-PNP-O12. On the other hand, the polymer gel consisting of 20 wt %-hexamethylenediacrylate (HDA)-based cross-linked polymer and 8-PNP-O12 exhibited no degraded mobility when cross-linked at the mesophase. These results indicate that the polymer and polymer composite of liquid crystalline semiconductors provide us with an easy way to realize a quality organic semiconductor thin film for the immediate device applications.

Polymers in the gut compress the colonic mucus hydrogel.

Science.gov (United States)

Datta, Sujit S; Preska Steinberg, Asher; Ismagilov, Rustem F

2016-06-28

Colonic mucus is a key biological hydrogel that protects the gut from infection and physical damage and mediates host-microbe interactions and drug delivery. However, little is known about how its structure is influenced by materials it comes into contact with regularly. For example, the gut abounds in polymers such as dietary fibers or administered therapeutics, yet whether such polymers interact with the mucus hydrogel, and if so, how, remains unclear. Although several biological processes have been identified as potential regulators of mucus structure, the polymeric composition of the gut environment has been ignored. Here, we demonstrate that gut polymers do in fact regulate mucus hydrogel structure, and that polymer-mucus interactions can be described using a thermodynamic model based on Flory-Huggins solution theory. We found that both dietary and therapeutic polymers dramatically compressed murine colonic mucus ex vivo and in vivo. This behavior depended strongly on both polymer concentration and molecular weight, in agreement with the predictions of our thermodynamic model. Moreover, exposure to polymer-rich luminal fluid from germ-free mice strongly compressed the mucus hydrogel, whereas exposure to luminal fluid from specific-pathogen-free mice-whose microbiota degrade gut polymers-did not; this suggests that gut microbes modulate mucus structure by degrading polymers. These findings highlight the role of mucus as a responsive biomaterial, and reveal a mechanism of mucus restructuring that must be integrated into the design and interpretation of studies involving therapeutic polymers, dietary fibers, and fiber-degrading gut microbes.

Synthesis, characterisation and non-isothermal degradation kinetics ...

Indian Academy of Sciences (India)

Thus, obtained co-polymer was charac- terized by Fourier transform ... used, the Kissinger method yielded the lowest degradation kinetics. The degradation ... addition of amines with alkenes in methanol water medium, report is available in the ...

Interplay of Interfacial Layers and Blend Composition To Reduce Thermal Degradation of Polymer Solar Cells at High Temperature.

Science.gov (United States)

Ben Dkhil, Sadok; Pfannmöller, Martin; Schröder, Rasmus R; Alkarsifi, Riva; Gaceur, Meriem; Köntges, Wolfgang; Heidari, Hamed; Bals, Sara; Margeat, Olivier; Ackermann, Jörg; Videlot-Ackermann, Christine

2018-01-31

The thermal stability of printed polymer solar cells at elevated temperatures needs to be improved to achieve high-throughput fabrication including annealing steps as well as long-term stability. During device processing, thermal annealing impacts both the organic photoactive layer, and the two interfacial layers make detailed studies of degradation mechanism delicate. A recently identified thermally stable poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl

Degradation of polycarbonate induced by gamma radiation

International Nuclear Information System (INIS)

Araujo, E.S. de; Guedes, S.M.L.

1992-01-01

Polycarbonate (PC) DUROLON amorphous, of molecular weight 22000 g/mol is used in medical supplies and may be sterilized by gamma radiation. The main chain scission and polymer degradation occur when this polymer is irradiated. The value G = 1.54 to DUROLON was obtained by equation: 10 6 /M v = 10 6 /M v' + 0.054 G R. The degradation without crosslinking it is not general rule to all types of polycarbonates; an comparison was realized. The infrared (FT-IR) spectra of irradiated PC by gamma rays with different doses showed the main chain scissions in carbonyl groups. The mechanism of polymeric degradation to DUROLON, observed by NMR spectra, is a recombination of phenoxy and phenyl radicals. (author)

Rapidly Degradable Pyrotechnic System

Science.gov (United States)

2009-02-01

material system (structural polymer and degradation agent ) for producing a high strength, non-corroding, highly inert, environmentally safe, extended...polymer sites in the active enzyme center differs dramatically between alkyl and aromatic polyesters. More specifically, as the degree of backbone...capped and centrifuged at 3,000 g. This procedure was repeated twice. To the remaining biomass pellet 15 mL of 1 mg/mL solution of N-ethyl-N- nitrosourea

Degradable conjugated polymers for the selective sorting of semiconducting carbon nanotubes

Science.gov (United States)

Gopalan, Padma; Arnold, Michael Scott; Kansiusarulsamy, Catherine Kanimozhi; Brady, Gerald Joseph; Shea, Matthew John

2018-04-10

Conjugated polymers composed of bi-pyridine units linked to 9,9-dialkyl fluorenyl-2,7-diyl units via imine linkages along the polymer backbone are provided. Also provided are semiconducting single-walled carbon nanotubes coated with the conjugated polymers and methods of sorting and separating s-SWCNTs from a sample comprising a mixture of s-SWCNTs and metallic single-walled carbon nanotubes using the conjugated polymers.

Simultaneous Thermal and Gamma Radiation Aging of Electrical Cable Polymers

Energy Technology Data Exchange (ETDEWEB)

Fifield, Leonard S.

2018-04-11

The polymers used for insulation in nuclear power plant electrical cables are susceptible to aging during long term operation. Elevated temperature is the primary contributor to changes in polymer structure that result loss of mechanical and electrical properties, but gamma radiation is also a significant source of degradation for polymers used within relevant plant locations. Despite many years of polymer degradation research, the combined effects of simultaneous exposure to thermal and radiation stress are not well understood. As nuclear operators contemplate and prepare for extended operations beyond initial license periods, a predictive understanding of exposure-based cable material degradation is becoming an increasingly important input to safety, licensing, operations and economic decisions. We are focusing on carefully-controlled simultaneous thermal and gamma radiation accelerating aging and characterization of the most common nuclear cable polymers to understand the relative contributions of temperature, time, dose and dose rate to changes in cable polymer material structure and properties. Improved understanding of cable performance in long term operation will help support continued sustainable nuclear power generation.

Sandwich-format 3D printed microfluidic mixers: a flexible platform for multi-probe analysis

International Nuclear Information System (INIS)

Kise, Drew P; Reddish, Michael J; Brian Dyer, R

2015-01-01

We report on a microfluidic mixer fabrication platform that increases the versatility and flexibility of mixers for biomolecular applications. A sandwich-format design allows the application of multiple spectroscopic probes to the same mixer. A polymer spacer is ‘sandwiched’ between two transparent windows, creating a closed microfluidic system. The channels of the mixer are defined by regions in the polymer spacer that lack material and therefore the polymer need not be transparent in the spectral region of interest. Suitable window materials such as CaF 2 make the device accessible to a wide range of optical probe wavelengths, from the deep UV to the mid-IR. In this study, we use a commercially available 3D printer to print the polymer spacers to apply three different channel designs into the passive, continuous-flow mixer, and integrated them with three different spectroscopic probes. All three spectroscopic probes are applicable to each mixer without further changes. The sandwich-format mixer coupled with cost-effective 3D printed fabrication techniques could increase the applicability and accessibility of microfluidic mixing to intricate kinetic schemes and monitoring chemical synthesis in cases where only one probe technique proves insufficient. (paper)

Contribution to the study of particle resuspension kinetics during thermal degradation of polymers.

Science.gov (United States)

Ouf, F-X; Delcour, S; Azema, N; Coppalle, A; Ferry, L; Gensdarmes, F; Lopez-Cuesta, J-M; Niang, A; Pontreau, S; Yon, J

2013-04-15

Experimental results are reported on the resuspension of particles deposited on polymer samples representative of glove boxes used in the nuclear industry, under thermal degradation. A parametric study was carried out on the effects of heat flux, air flow rate, fuel type and particle size distribution. Small-scale experiments were conducted on 10 cm × 10 cm PolyMethyl MethAcrylate (PMMA) and PolyCarbonate (PC) samples covered with aluminium oxide particles with physical geometric diameters of 0.7 and 3.6 μm. It was observed for both polymer (fuel) samples that heat flux has no effect on the airborne release fraction (ARF), whereas particle size is a significant parameter. In the case of the PMMA sample, ARF values for 0.7 and 3.6 μm diameter particles range from 12.2% (± 6.2%) to 2.1% (± 0.6%), respectively, whereas the respective values for the PC sample range from 3.2% (± 0.8%) to 6.9% (± 3.9%). As the particle diameter increases, a significant decrease in particle release is observed for the PMMA sample, whereas an increase is observed for the PC sample. Furthermore, a peak airborne release rate is observed during the first instants of PMMA exposure to thermal stress. An empirical relationship has been proposed between the duration of this peak release and the external heat flux. Copyright © 2013 Elsevier B.V. All rights reserved.

Microscopic investigation of InGaN/GaN heterostructure laser diode degradation using Kelvin probe force microscopy

International Nuclear Information System (INIS)

Lochthofen, A; Mertin, W; Bacher, G; Furitsch, M; Bruederl, G; Strauss, U; Haerle, V

2008-01-01

We report on Kelvin probe force microscopy (KPFM) measurements on fresh and artificially aged InGaN/GaN laser test structures. In the case of an unbiased laser diode, a comparison of the surface potential between a fresh and a stressed laser diode shows a pronounced modification of the laser facet due to the aging process. Performing KPFM measurements under forward bias, a correlation between the macroscopic I-V characteristics and the microscopic voltage drop across the heterostructure layer sequence is found. This clearly demonstrates the potential of KPFM for investigating InGaN/GaN laser diode degradation

Substrate-Wrapped, Single-Walled Carbon Nanotube Probes for Hydrolytic Enzyme Characterization.

Science.gov (United States)

Kallmyer, Nathaniel E; Musielewicz, Joseph; Sutter, Joel; Reuel, Nigel F

2018-04-17

Hydrolytic enzymes are a topic of continual study and improvement due to their industrial impact and biological implications; however, the ability to measure the activity of these enzymes, especially in high-throughput assays, is limited to an established, few enzymes and often involves the measurement of secondary byproducts or the design of a complex degradation probe. Herein, a versatile single-walled carbon nanotube (SWNT)-based biosensor that is straightforward to produce and measure is described. The hydrolytic enzyme substrate is rendered as an amphiphilic polymer, which is then used to solubilize the hydrophobic nanotubes. When the target enzyme degrades the wrapping, the SWNT fluorescent signal is quenched due to increased solvent accessibility and aggregation, allowing quantitative measurement of hydrolytic enzyme activity. Using (6,5) chiral SWNT suspended with polypeptides and polysaccharides, turnover frequencies are estimated for cellulase, pectinase, and bacterial protease. Responses are recorded for concentrations as low as 5 fM using a well-characterized protease, Proteinase K. An established trypsin-based plate reader assay is used to compare this nanotube probe assay with standard techniques. Furthermore, the effect of freeze-thaw cycles and elevated temperature on enzyme activity is measured, suggesting freezing to have minimal impact even after 10 cycles and heating to be detrimental above 60 °C. Finally, rapid optimization of enzyme operating conditions is demonstrated by generating a response surface of cellulase activity with respect to temperature and pH to determine optimal conditions within 2 h of serial scans.

Unraveling micro- and nanoscale degradation processes during operation of high-temperature polymer-electrolyte-membrane fuel cells

Science.gov (United States)

Hengge, K.; Heinzl, C.; Perchthaler, M.; Varley, D.; Lochner, T.; Scheu, C.

2017-10-01

The work in hand presents an electron microscopy based in-depth study of micro- and nanoscale degradation processes that take place during the operation of high-temperature polymer-electrolyte-membrane fuel cells (HT-PEMFCs). Carbon supported Pt particles were used as cathodic catalyst material and the bimetallic, carbon supported Pt/Ru system was applied as anode. As membrane, cross-linked polybenzimidazole was used. Scanning electron microscopy analysis of cross-sections of as-prepared and long-term operated membrane-electrode-assemblies revealed insight into micrometer scale degradation processes: operation-caused catalyst redistribution and thinning of the membrane and electrodes. Transmission electron microscopy investigations were performed to unravel the nanometer scale phenomena: a band of Pt and Pt/Ru nanoparticles was detected in the membrane adjacent to the cathode catalyst layer. Quantification of the elemental composition of several individual nanoparticles and the overall band area revealed that they stem from both anode and cathode catalyst layers. The results presented do not demonstrate any catastrophic failure but rather intermediate states during fuel cell operation and indications to proceed with targeted HT-PEMFC optimization.

Degradation mechanisms of poly (lactic-co-glycolic acid) films in vitro under static and dynamic environment

Institute of Scientific and Technical Information of China (English)

HUANG Ying-ying; QI Min; ZHANG Meng; LIU Hong-ze; YANG Da-zhi

2006-01-01

To understand their degradation mechanisms,PLGA (50:50) polymer films were prepared and eroded in the static and dynamic medium system. The degradation behavior was characterized through weight-average molecular weight change,mass loss,water uptake,etc. The results show that in dynamic system,significant mass loss begins until 10 d while mass loss does not begin until 30 d later,while weight-average molecular weight decreases observably at the beginning,and the appeasable mass loss happens in 20 d in static system,which suggests that the dynamic degradation rate is slower even than degradation in static medium. A mechanism was proposed that specimens in static medium take up water homogeneously and cause the polymer chains to degrade all over the specimen cross sections,which creates free carboxylic acid groups which lead to a decrease of pH value inside the swollen polymer and accelerate degradation of the polymer. While pH value inside polymer keeps constant in dynamic medium because of flowing of simulated medium,which make the hydrolytic cleavage of ester bonds inside specimen delayed.

Polycarbonate radiolytic degradation and stabilization

International Nuclear Information System (INIS)

Araujo, E.S. de

1994-01-01

Polycarbonate Durolon, useful for medical supplies fabrication, is submitted to gamma radiation for sterilization purposes. Scissions in main chain occur, in carbonyl groups, producing molecular degradations and yellowness. The radiolytic stabilization is obtained through additive to the polymer. In this work some degradation and stabilization aspects are presented. (L.C.J.A.). 7 refs, 7 figs, 2 tabs

Mapping intermediate degradation products of poly(lactic-co-glycolic acid) in vitro.

Science.gov (United States)

Li, Jian; Nemes, Peter; Guo, Ji

2018-04-01

There is widespread interest in using absorbable polymers, such as poly(lactic-co-glycolic acid) (PLGA), as components in the design and manufacture of new-generation drug eluting stents (DES). PLGA undergoes hydrolysis to progressively degrade through intermediate chemical entities to simple organic acids that are ultimately absorbed by the human body. Understanding the composition and structure of these intermediate degradation products is critical not only to elucidate polymer degradation pathways accurately, but also to assess the safety and performance of absorbable cardiovascular implants. However, analytical approaches to determining the intermediate degradation products have yet to be established and evaluated in a standard or regulatory setting. Hence, we developed a methodology using electrospray ionization mass spectrometry to qualitatively and quantitatively describe intermediate degradation products generated in vitro from two PLGA formulations commonly used in DES. Furthermore, we assessed the temporal evolution of these degradation products using time-lapse experiments. Our data demonstrated that PLGA degradation products via heterogeneous cleavage of ester bonds are modulated by multiple intrinsic and environmental factors, including polymer chemical composition, degradants solubility in water, and polymer synthesis process. We anticipate the methodologies and outcomes presented in this work will elevate the mechanistic understanding of comprehensive degradation profiles of absorbable polymeric devices, and facilitate the design and regulation of cardiovascular implants by supporting the assessments of the associated biological response to degradation products. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1129-1137, 2018. © 2017 Wiley Periodicals, Inc.

Development of a novel fluorescent imaging probe for tumor hypoxia by use of a fusion protein with oxygen-dependent degradation domain of HIF-1α

Science.gov (United States)

Tanaka, Shotaro; Kizaka-Kondoh, Shinae; Harada, Hiroshi; Hiraoka, Masahiro

2007-02-01

More malignant tumors contain more hypoxic regions. In hypoxic tumor cells, expression of a series of hypoxiaresponsive genes related to malignant phenotype such as angiogenesis and metastasis are induced. Hypoxia-inducible factor-1 (HIF-1) is a master transcriptional activator of such genes, and thus imaging of hypoxic tumor cells where HIF-1 is active, is important in cancer therapy. We have been developing PTD-ODD fusion proteins, which contain protein transduction domain (PTD) and the VHL-mediated protein destruction motif in oxygen-dependent degradation (ODD) domain of HIF-1 alpha subunit (HIF-1α). Thus PTD-ODD fusion proteins can be delivered to any tissue in vivo through PTD function and specifically stabilized in hypoxic cells through ODD function. To investigate if PTD-ODD fusion protein can be applied to construct hypoxia-specific imaging probes, we first constructed a fluorescent probe because optical imaging enable us to evaluate a probe easily, quickly and economically in a small animal. We first construct a model fusion porein PTD-ODD-EGFP-Cy5.5 named POEC, which is PTD-ODD protein fused with EGFP for in vitro imaging and stabilization of fusion protein, and conjugated with a near-infrared dye Cy5.5. This probe is designed to be degraded in normoxic cells through the function of ODD domain and followed by quick clearance of free fluorescent dye. On the other hand, this prove is stabilized in hypoxic tumor cells and thus the dye is stayed in the cells. Between normoxic and hypoxic conditions, the difference in the clearance rate of the dye will reveals suited contrast for tumor-hypoxia imaging. The optical imaging probe has not been optimized yet but the results presented here exhibit a potential of PTD-ODD fusion protein as a hypoxia-specific imaging probe.

Application to the radiation processing of polymer

Energy Technology Data Exchange (ETDEWEB)

Yoshii, Fumio [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment

2003-02-01

Polypropylene (PP) and biodegradable polymer (blend of poly ({epsilon}-caploracton) 30/polybutylenesuccynate 70), PHB02 were irradiated with an electron beam to improve processability for production of thin film and foam. The processability of the polymer was improved due to enhancement of melt strength with irradiation at the dose range between 10 and 100 kGy. Increase of melt strength is due to entanglement of branch structure formed by irradiation. Possibility of high-speed production of thin film and production of foam have been achieved by this process. The soil degradation test showed that biodegradable polymer film buried in the soil was almost entirely degraded (97%) after two months and completely degraded after two and a half months. In the case of foam samples, 65% degradation was achieved after four months. Radiation crosslinked water-soluble polymer form hydrogel, which absorb much water. The hydrogel prepared by irradiation of polymer in aqueous solution was applied as dressing for healing of wound. In order to evaluate the healing effect of the polyethylene oxide (PEO) hydrogel dressing, wounds formed on the back of marmots were covered by the hydrogel. The healing under the wet environment of the hydrogel dressing had three advantages, compared with that of gauze dressing, which gives a dry environment: (1) enhancement of healing rate, (2) facilitation for changing the dressing, i.e. the hydrogel can be peeled off without any damage to the regenerated skin surface, and (3) hydrogel dressing material does not remain stuck on the wound. (author)

Application to the radiation processing of polymer

International Nuclear Information System (INIS)

Yoshii, Fumio

2003-01-01

Polypropylene (PP) and biodegradable polymer (blend of poly (ε-caploracton) 30/polybutylenesuccynate 70), PHB02 were irradiated with an electron beam to improve processability for production of thin film and foam. The processability of the polymer was improved due to enhancement of melt strength with irradiation at the dose range between 10 and 100 kGy. Increase of melt strength is due to entanglement of branch structure formed by irradiation. Possibility of high-speed production of thin film and production of foam have been achieved by this process. The soil degradation test showed that biodegradable polymer film buried in the soil was almost entirely degraded (97%) after two months and completely degraded after two and a half months. In the case of foam samples, 65% degradation was achieved after four months. Radiation crosslinked water-soluble polymer form hydrogel, which absorb much water. The hydrogel prepared by irradiation of polymer in aqueous solution was applied as dressing for healing of wound. In order to evaluate the healing effect of the polyethylene oxide (PEO) hydrogel dressing, wounds formed on the back of marmots were covered by the hydrogel. The healing under the wet environment of the hydrogel dressing had three advantages, compared with that of gauze dressing, which gives a dry environment: (1) enhancement of healing rate, (2) facilitation for changing the dressing, i.e. the hydrogel can be peeled off without any damage to the regenerated skin surface, and (3) hydrogel dressing material does not remain stuck on the wound. (author)

In vitro Degradation of Butanediamine-Grafted Poly(DL-Lactic acids)

Institute of Scientific and Technical Information of China (English)

无

2007-01-01

The degradation of butanediamine-grafted poly(DL-lactic acid) polymers (BDPLAs) in vitro together with PDLLA and maleic anhydride-grafted poly(DL-lactic acid) polymers (MPLAs) was investigated by observation of the changes of the pH value of incubation media, and weight loss ratio during degradation duration of 12 weeks. The results reveal that the acidity of PDLLA degradation products was weakened or neutralized by grafting butanediamine onto PDLLA. A uniform degradation of BDPLAs was observed in comparison with an acidity-induced auto-accelerating degradation featured by PDLLA and MPLAs. The biodegradation behaviors of BDPLAs can be adjusted by controlling the content of BDA. BDPLAs might be a new derivative of PDLLA-based biodegradable materials for medical applications without acidity-caused irritations and acidity-induced auto-accelerating degradation behavior as that of PDLLA.

Stable isotope probing reveals the importance of Comamonas and Pseudomonadaceae in RDX degradation in samples from a Navy detonation site.

Science.gov (United States)

Jayamani, Indumathy; Cupples, Alison M

2015-07-01

This study investigated the microorganisms involved in hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) degradation from a detonation area at a Navy base. Using Illumina sequencing, microbial communities were compared between the initial sample, samples following RDX degradation, and controls not amended with RDX to determine which phylotypes increased in abundance following RDX degradation. The effect of glucose on these communities was also examined. In addition, stable isotope probing (SIP) using labeled ((13)C3, (15)N3-ring) RDX was performed. Illumina sequencing revealed that several phylotypes were more abundant following RDX degradation compared to the initial soil and the no-RDX controls. For the glucose-amended samples, this trend was strong for an unclassified Pseudomonadaceae phylotype and for Comamonas. Without glucose, Acinetobacter exhibited the greatest increase following RDX degradation compared to the initial soil and no-RDX controls. Rhodococcus, a known RDX degrader, also increased in abundance following RDX degradation. For the SIP study, unclassified Pseudomonadaceae was the most abundant phylotype in the heavy fractions in both the presence and absence of glucose. In the glucose-amended heavy fractions, the 16S ribosomal RNA (rRNA) genes of Comamonas and Anaeromxyobacter were also present. Without glucose, the heavy fractions also contained the 16S rRNA genes of Azohydromonas and Rhodococcus. However, all four phylotypes were present at a much lower level compared to unclassified Pseudomonadaceae. Overall, these data indicate that unclassified Pseudomonadaceae was primarily responsible for label uptake in both treatments. This study indicates, for the first time, the importance of Comamonas for RDX removal.

SYNTHESES AND PROPERTIES OF SOME ORGANOSILANE POLYMERS

Institute of Scientific and Technical Information of China (English)

ZHANG Xinghua; Robert West

1984-01-01

Some organosilane polymers with high molecular weights have been synthesized by cocondensation of organosilicon dihalide monomers with sodium metal in toluene. These polymers are both soluble in common solvents and meltable at lower temperatures, and can be molded, cast into films or drawn into fibers. Exposure of the solid polymers to ultraviolet light leads to degradation or crosslinking.

Degradation of polyvinyl chloride (PVC) / hydrolyzed collagen (HC) blends active sludge test.

Science.gov (United States)

Agafiţei, Gabriela-Elena; Pascu, Mihaela; Cazacu, Georgeta; Vasile, Cornelia

2008-01-01

Biodegradable polymers represent a solution for the environment protection: they decrease the landfill space, by declining the petrochemical sources, and offer also an alternative solution for the recycling. The behavior during degradation in the presence of active sludge of some polyvinyl chloride (PVC) based blends with variable content of hydrolyzed collagen (HC) has been followed. Some samples were subjected to UV irradiation, for 30 hours. The modifications induced in the environment by the polymer systems (pH variation, bacterial composition), as well as the changes of the properties of the blends (weight losses, aspect etc.) were studied. During the first moments of degradation in active sludge, all the samples absorbed water, behavior which favored the biodegradation. The bacteriological analysis of the sludge indicates the presence of some microbiological species. Generally, the populations of microorganisms decrease, excepting the sulphito-reducing anaerobic bacteria, the actinomycetes and other anaerobic bacteria. PVC/HC blends are degraded with a significant rate in active sewage sludge. More susceptible for the degradation are the UV irradiated blends. After the migration of the components with a small molecular mass in the environment, the natural polymer is degraded. The degradation effect increases with the content in the natural polymer.

Determination of membrane degradation products in the product water of polymer electrolyte membrane fuel cells using liquid chromatography mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Zedda, Marco

2011-05-12

The predominant long term failure of polymer electrolyte membranes (PEM) is caused by hydroxyl radicals generated during fuel cell operation. These radicals attack the polymer, leading to chain scission, unzipping and consequently to membrane decomposition products. The present work has investigated decomposition products of novel sulfonated aromatic hydrocarbon membranes on the basis of a product water analysis. Degradation products from the investigated membrane type and the possibility to detect these compounds in the product water for diagnostic purposes have not been discovered yet. This thesis demonstrates the potential of solid phase extraction and liquid chromatography tandem mass spectrometry (SPE-LC-MS/MS) for the extraction, separation, characterization, identification and quantification of membrane degradation products in the product water of fuel cells. For this purpose, several polar aromatic hydrocarbons with different functional groups were selected as model compounds for the development of reliable extraction, separation and detection methods. The results of this thesis have shown that mixed mode sorbent materials with both weak anion exchange and reversed phase retention properties are well suited for reproducible extraction of both molecules and ions from the product water. The chromatographic separation of various polar aromatic hydrocarbons was achieved by means of phase optimized liquid chromatography using a solvent gradient and on a C18 stationary phase. Sensitive and selective detection of model compounds could be successfully demonstrated by the analysis of the product water using tandem mass spectrometry. The application of a hybrid mass spectrometer (Q Trap) for the characterization of unknown polar aromatic hydrocarbons has led to the identification and confirmation of 4-hydroxybenzoic acid in the product water. In addition, 4-HBA could be verified as a degradation product resulting from PEM decomposition by hydroxyl radicals using an

Irradiation of bioresorbable biomaterials for controlled surface degradation

DEFF Research Database (Denmark)

Simpson, M.; Gilmore, B.F.; Miller, Arne

2014-01-01

Bioresorbable polymers increasingly are the materials of choice for implantable orthopaedic fixation devices. Controlled degradation of these polymers is vital for preservation of mechanical properties during tissue repair and controlled release of incorporated agents such as osteoconductive or a...

A New FRET-Based Sensitive DNA Sensor for Medical Diagnostics using PNA Probe and Water-Soluble Blue Light Emitting Polymer

Directory of Open Access Journals (Sweden)

Nidhi Mathur

2008-01-01

Full Text Available A reliable, fast, and low-cost biosensor for medical diagnostics using DNA sequence detection has been developed and tested for the detection of the bacterium “Bacillus anthracis.” In this sensor, Poly [9,9-di (6,6′- N, N′ trimethylammonium hexylfluorenyl-2, 7-diyl-alt-co- (1,4-phenylene] dibromide salt (PFP has been taken as cationic conjugated polymer (CCP and PNA attached with fluorescein dye (PNAC∗ as a probe. The basic principle of this sensor is that when a PNAC∗ probe is hybridized with a single strand DNA (ssDNA having complementary sequence, Forster resonance energy transfer (FRET may take place from PFP to the PNAC∗/DNA complex. If the FRET is efficient, the photoluminescence from the PFP will be highly quenched and that from PNAC∗ will be enhanced. On the other hand, if the DNA sequence is noncomplementary to PNA, FRET will not occur.

Pyrolysis gas chromatographic study of homo polymers and copolymers of chlorotrifluoroethylene and styrene

International Nuclear Information System (INIS)

Rizvi, M.; Munir, A.

1993-01-01

Polymer degradation reactions have always been important for the development of thermally stable polymers. Among different available techniques, pyrolysis gas chromatography (PGC) has been used frequently to establish thermal stability and the plausible mechanism of degradation reactions. In the present work, homo polymers of chlorotrifluoroethylene (CTFE) and styrene and their copolymers were studied by PGC/IR for separation and identification of degraded products and to understand the degradation mechanism. Besides monomers, C/sub 2/H/sub 4/, C/sub 2/H/sub 2/, SiF/sub 4/, C/sub 6/H/sub 6/ C/sub 3/F/sub 5/Cl, C/sub 7/H sub 8/, C/sub 8/H/sub 10/ are the observed pyrolysis products. Mechanism for different degradation reactions have also been studied. (author)

Abiotic and biotic degradation of oxo-biodegradable plastic bags by Pleurotus ostreatus.

Directory of Open Access Journals (Sweden)

José Maria Rodrigues da Luz

Full Text Available In this study, we evaluated the growth of Pleurotus ostreatus PLO6 using oxo-biodegradable plastics as a carbon and energy source. Oxo-biodegradable polymers contain pro-oxidants that accelerate their physical and biological degradation. These polymers were developed to decrease the accumulation of plastic waste in landfills. To study the degradation of the plastic polymers, oxo-biodegradable plastic bags were exposed to sunlight for up to 120 days, and fragments of these bags were used as substrates for P. ostreatus. We observed that physical treatment alone was not sufficient to initiate degradation. Instead, mechanical modifications and reduced titanium oxide (TiO2 concentrations caused by sunlight exposure triggered microbial degradation. The low specificity of lignocellulolytic enzymes and presence of endomycotic nitrogen-fixing microorganisms were also contributing factors in this process.

Abiotic and biotic degradation of oxo-biodegradable plastic bags by Pleurotus ostreatus.

Science.gov (United States)

da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Bazzolli, Denise Mara Soares; Tótola, Marcos Rogério; Demuner, Antônio Jacinto; Kasuya, Maria Catarina Megumi

2014-01-01

In this study, we evaluated the growth of Pleurotus ostreatus PLO6 using oxo-biodegradable plastics as a carbon and energy source. Oxo-biodegradable polymers contain pro-oxidants that accelerate their physical and biological degradation. These polymers were developed to decrease the accumulation of plastic waste in landfills. To study the degradation of the plastic polymers, oxo-biodegradable plastic bags were exposed to sunlight for up to 120 days, and fragments of these bags were used as substrates for P. ostreatus. We observed that physical treatment alone was not sufficient to initiate degradation. Instead, mechanical modifications and reduced titanium oxide (TiO2) concentrations caused by sunlight exposure triggered microbial degradation. The low specificity of lignocellulolytic enzymes and presence of endomycotic nitrogen-fixing microorganisms were also contributing factors in this process.

Abiotic and Biotic Degradation of Oxo-Biodegradable Plastic Bags by Pleurotus ostreatus

Science.gov (United States)

da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Bazzolli, Denise Mara Soares; Tótola, Marcos Rogério; Demuner, Antônio Jacinto; Kasuya, Maria Catarina Megumi

2014-01-01

In this study, we evaluated the growth of Pleurotus ostreatus PLO6 using oxo-biodegradable plastics as a carbon and energy source. Oxo-biodegradable polymers contain pro-oxidants that accelerate their physical and biological degradation. These polymers were developed to decrease the accumulation of plastic waste in landfills. To study the degradation of the plastic polymers, oxo-biodegradable plastic bags were exposed to sunlight for up to 120 days, and fragments of these bags were used as substrates for P. ostreatus. We observed that physical treatment alone was not sufficient to initiate degradation. Instead, mechanical modifications and reduced titanium oxide (TiO2) concentrations caused by sunlight exposure triggered microbial degradation. The low specificity of lignocellulolytic enzymes and presence of endomycotic nitrogen-fixing microorganisms were also contributing factors in this process. PMID:25419675

Radiation processing of biodegradable polymer hydrogel from cellulose derivatives

International Nuclear Information System (INIS)

Wach, Radoslaw A.; Mitomo, Hiroshi; Yoshii, Fumio; Kume, Tamikazu

2001-01-01

The effects of high-energy radiation on ethers of cellulose: carboxymethyl-, hydroxypropyl- and hydroxyethylcellulose have been investigated. Polymers were irradiated in solid state and aqueous solution at various concentrations. Degree of substitution (DS), the concentration in the solution and irradiation conditions had a significant impact on the obtained products. Irradiation of polymers in solid and in diluted solution resulted in their degradation. A novel hydrogels of such natural polymers were synthesized, without using any additives, by irradiation at high concentration. It was found that high DS of CMC promoted crosslinking and, for all of the ethers, the gel formation occurred easier for more concentrated solutions. Paste-like form of the initial material, when water plasticised the bulk of polymer mass, along with the high dose rate and preventing oxygen accessibility to the sample during irradiation were favorable for hydrogel preparation. Up to 95% of gel fraction was obtained from 50 and 60% CMC solutions irradiated by gamma rays or by a beam of accelerated electrons (EB). The other polymers were more sensitive to the dose rate and formed gels with higher gel fraction while processed by EB. Moreover, polymers (except CMC) treated by gamma rays were susceptible to degradation after application of a dose over 50-100 kGy. The presence of oxygen in the system during irradiation limited a gel content and was prone to easier degradation of already formed gel. Produced hydrogels swelled markedly by absorption when paced in the solvent. Crosslinked polymers showed susceptibility to degradation by cellulase enzyme and by the action of microorganisms in compost or under natural conditions in soil thus could be included into the group of biodegradable materials. (author)

Radiation processing of biodegradable polymer hydrogel from cellulose derivatives

Energy Technology Data Exchange (ETDEWEB)

Wach, Radoslaw A.; Mitomo, Hiroshi [Gunma Univ., Faculty of Engineering, Department of Biological and Chemical Engineering, Kiryu, Gunma (Japan); Yoshii, Fumio; Kume, Tamikazu [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment

2001-03-01

The effects of high-energy radiation on ethers of cellulose: carboxymethyl-, hydroxypropyl- and hydroxyethylcellulose have been investigated. Polymers were irradiated in solid state and aqueous solution at various concentrations. Degree of substitution (DS), the concentration in the solution and irradiation conditions had a significant impact on the obtained products. Irradiation of polymers in solid and in diluted solution resulted in their degradation. A novel hydrogels of such natural polymers were synthesized, without using any additives, by irradiation at high concentration. It was found that high DS of CMC promoted crosslinking and, for all of the ethers, the gel formation occurred easier for more concentrated solutions. Paste-like form of the initial material, when water plasticised the bulk of polymer mass, along with the high dose rate and preventing oxygen accessibility to the sample during irradiation were favorable for hydrogel preparation. Up to 95% of gel fraction was obtained from 50 and 60% CMC solutions irradiated by gamma rays or by a beam of accelerated electrons (EB). The other polymers were more sensitive to the dose rate and formed gels with higher gel fraction while processed by EB. Moreover, polymers (except CMC) treated by gamma rays were susceptible to degradation after application of a dose over 50-100 kGy. The presence of oxygen in the system during irradiation limited a gel content and was prone to easier degradation of already formed gel. Produced hydrogels swelled markedly by absorption when paced in the solvent. Crosslinked polymers showed susceptibility to degradation by cellulase enzyme and by the action of microorganisms in compost or under natural conditions in soil thus could be included into the group of biodegradable materials. (author)

Abiotic and Biotic Degradation of Oxo-Biodegradable Plastic Bags by Pleurotus ostreatus

OpenAIRE

da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Bazzolli, Denise Mara Soares; Tótola, Marcos Rogério; Demuner, Antônio Jacinto; Kasuya, Maria Catarina Megumi

2014-01-01

In this study, we evaluated the growth of Pleurotus ostreatus PLO6 using oxo-biodegradable plastics as a carbon and energy source. Oxo-biodegradable polymers contain pro-oxidants that accelerate their physical and biological degradation. These polymers were developed to decrease the accumulation of plastic waste in landfills. To study the degradation of the plastic polymers, oxo-biodegradable plastic bags were exposed to sunlight for up to 120 days, and fragments of these bags were used as su...

Fracture initiation associated with chemical degradation: observation and modeling

Energy Technology Data Exchange (ETDEWEB)

Byoungho Choi; Zhenwen Zhou; Chudnovsky, Alexander [Illinois Univ., Dept. of Civil and Materials Engineering (M/C 246), Chicago, IL (United States); Stivala, Salvatore S. [Stevens Inst. of Technology, Dept. of Chemistry and Chemical Biology, Hoboken, NJ (United States); Sehanobish, Kalyan; Bosnyak, Clive P. [Dow Chemical Co., Freeport, TX (United States)

2005-01-01

The fracture initiation in engineering thermoplastics resulting from chemical degradation is usually observed in the form of a microcrack network within a surface layer of degraded polymer exposed to a combined action of mechanical stresses and chemically aggressive environment. Degradation of polymers is usually manifested in a reduction of molecular weight, increase of crystallinity in semi crystalline polymers, increase of material density, a subtle increase in yield strength, and a dramatic reduction in toughness. An increase in material density, i.e., shrinkage of the degraded layer is constrained by adjacent unchanged material results in a buildup of tensile stress within the degraded layer and compressive stress in the adjacent unchanged material due to increasing incompatibility between the two. These stresses are an addition to preexisting manufacturing and service stresses. At a certain level of degradation, a combination of toughness reduction and increase of tensile stress result in fracture initiation. A quantitative model of the described above processes is presented in these work. For specificity, the internally pressurized plastic pipes that transport a fluid containing a chemically aggressive (oxidizing) agent is used as the model of fracture initiation. Experimental observations of material density and toughness dependence on degradation reported elsewhere are employed in the model. An equation for determination of a critical level of degradation corresponding to the offset of fracture is constructed. The critical level of degradation for fracture initiation depends on the rates of toughness deterioration and build-up of the degradation related stresses as well as on the manufacturing and service stresses. A method for evaluation of the time interval prior to fracture initiation is also formulated. (Author)

Thermal studies on unirradiated and γ-irradiated polymer of allyl diglycol carbonate

International Nuclear Information System (INIS)

Kalsi, P.C.; Pandey, A.K.; Iyer, R.H.; Singh Mudher, K.D.

1995-01-01

The thermal decomposition of unirradiated and γ-irradiated (5.93-15.5 MRad dose range) allyl diglycol carbonate polymer (trade name, CR-39) was studied by thermogravimetry (TG) and differential thermal analysis (DTA). These studies indicate four main decomposition steps in CR-39 polymer in air. Assessment of the influence of radiation dose on the above range shows that while the 5.93 MRad γ-irradiated polymer CR-39 degrades in three steps, the 15.5 MRad γ-irradiated polymer degrades in only two steps. The kinetics of the different stages of degradation were also evaluated from the TG curves. Irradiation enhances the decomposition rate and the effect increases further with increasing radiation dose. The activation energy values calculated for all the decomposition stages decrease on irradiation

Photochemical stability of conjugated polymers, electron acceptors and blends for polymer solar cells resolved in terms of film thickness and absorbance

DEFF Research Database (Denmark)

Tromholt, Thomas; Vesterager Madsen, Morten; Carlé, Jon Eggert

2012-01-01

Photochemical degradation at 1 sun under AM1.5G illumination was performed on six conjugated polymers and five different electron acceptors. Additionally, the respective polymer:PC60BM and P3HT:electron acceptor blends were studied, and all degradations were resolved in terms of film thickness...... within each material group were found to vary for both the pure polymers and the blends. The stability ranking between the materials of the pure polymers was found to be similar to the ranking for their respective blends, implying that the photochemical stability of a pure polymer is a good measure...... of its associated blend stability. Different electron acceptors were found to stabilize P3HT decreasingly with decreasing donor–acceptor LUMO–LUMO gap. Destabilization of P3HT was observed in the case of the electron acceptor ICBA. Additionally, the decreased stabilization of P3HT by high LUMO electron...

Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

Science.gov (United States)

Ren, Ya-Nan; Xu, Wei; Zhou, Lin-Xia; Zheng, Yue-Qing

2017-07-01

Two mixed uranyl-cadmium malonate coordination polymers [(UO2)2Cd(H-bipy)2(mal)4(H2O)2]·4H2O 1 and [(UO2)Cd(bipy)(mal)2]·H2O 2 (H2mal = malonic acid, bipy =4,4‧-bipyridine) have been synthesized in room temperature. Compound 1 represents a one-dimensional (1D) chain assembly of Cd(II) ions, uranyl centers and malonate ligands. Compound 2 exhibits a two-dimensional (2D) 2D +2D → 3D polycatenated framework based on inclined interlocked 2D 44 sql grids. The two compounds have been characterized by elemental analysis, IR and UV-vis spectroscopy, thermal analysis, powder X-ray diffraction and photoluminescence spectroscopy. And the ferroelectric property of 2 also has been studied. Moreover, compound 2 exhibits good photocatalytic activity for dye degradation under UV light and is excellent adsorbent for removing tetracycline antibiotics in the aqueous solution.

REGULATION OF COAL POLYMER DEGRADATION BY FUNGI

Energy Technology Data Exchange (ETDEWEB)

John A. Bumpus

1998-11-30

A variety of lignin degrading fungi mediate solubilization and subsequent biodegradation of coal macromolecules (a.k.a. coal polymer) from highly oxidized low rank coals such as leonardites. It appears that oxalate or possibly other metal chelators (i.e., certain Krebs Cycle intermediates) mediate solubilization of low rank coals while extracellular oxidases have a role in subsequent oxidation of solubilized coal macromolecule. These processes are under nutritional control. For example, in the case of P. chrysosporium, solubilization of leonardite occurred when the fungi were cultured on most but not all nutrient agars tested and subsequent biodegradation occurred only in nutrient nitrogen limited cultures. Lignin peroxidases mediate oxidation of coal macromolecule in a reaction that is dependent on the presence of veratryl alcohol and hydrogen peroxide. Kinetic evidence suggests that veratryl alcohol is oxidized to the veratryl alcohol cation radical which then mediates oxidation of the coal macromolecule. Results by others suggest that Mn peroxidases mediate formation of reactive Mn{sup 3+} complexes which also mediate oxidation of coal macromolecule. A biomimetic approach was used to study solubilization of a North Dakota leonardite. It was found that a concentration {approximately}75 mM sodium oxalate was optimal for solubilization of this low rank coal. This is important because this is well above the concentration of oxalate produced by fungi in liquid culture. Higher local concentrations probably occur in solid agar cultures and thus may account for the observation that greater solubilization occurs in agar media relative to liquid media. The characteristics of biomimetically solubilized leonardite were similar to those of biologically solubilized leonardite. Perhaps our most interesting observation was that in addition to oxalate, other common Lewis bases (phosphate/hydrogen phosphate/dihydrogen phosphate and bicarbonate/carbonate ions) are able to mediate

Biodegradable polymer for sealing porous PEO layer on pure magnesium: An in vitro degradation study

International Nuclear Information System (INIS)

Alabbasi, Alyaa; Mehjabeen, Afrin; Kannan, M. Bobby; Ye, Qingsong; Blawert, Carsten

2014-01-01

Graphical abstract: - Highlights: • Poly(L-lactide) was used to seal the porous PEO layer on Mg. • The dual-layer coating improved the in vitro degradation resistance of Mg. • Localized degradation was inhibited in the dual-layer coated Mg. - Abstract: An attempt was made to seal the porous silicate-based plasma electrolytic oxidation (PEO) layer on pure magnesium (Mg) with a biodegradable polymer, poly(L-lactide) (PLLA), to delay the localized degradation of magnesium-based implants in body fluid for better in-service mechanical integrity. Firstly, a silicate-based PEO coating on pure magnesium was performed using a pulsed constant current method. In order to seal the pores in the PEO layer, PLLA was coated using a two-step spin coating method. The performance of the PEO–PLLA Mg was evaluated using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The EIS results showed that the polarization resistance (R p ) of the PEO–PLLA Mg was close to two orders of magnitude higher than that of the PEO Mg. While the corrosion current density (i corr ) of the pure Mg was reduced by 65% with the PEO coating, the PEO–PLLA coating reduced the i corr by almost 100%. As expected, the R p of the PEO–PLLA Mg decreased with increase in exposure time. However, it was noted that the R p of the PEO–PLLA Mg even after 100 h was six times higher than that of the PEO Mg after 48 h exposure, and did not show any visible localized attack

Biodegradable polymer for sealing porous PEO layer on pure magnesium: An in vitro degradation study

Energy Technology Data Exchange (ETDEWEB)

Alabbasi, Alyaa; Mehjabeen, Afrin [Biomaterials and Engineering Materials (BEM) Laboratory, James Cook University, Townsville 4811, Queensland (Australia); Kannan, M. Bobby, E-mail: bobby.mathan@jcu.edu.au [Biomaterials and Engineering Materials (BEM) Laboratory, James Cook University, Townsville 4811, Queensland (Australia); Ye, Qingsong [Discipline of Dentistry, James Cook University, Townsville 4811, Queensland (Australia); Blawert, Carsten [Magnesium Innovation Centre, Institute of Materials Research, Helmholtz-Zentrum Geesthacht, Geesthacht 21502 (Germany)

2014-05-01

Graphical abstract: - Highlights: • Poly(L-lactide) was used to seal the porous PEO layer on Mg. • The dual-layer coating improved the in vitro degradation resistance of Mg. • Localized degradation was inhibited in the dual-layer coated Mg. - Abstract: An attempt was made to seal the porous silicate-based plasma electrolytic oxidation (PEO) layer on pure magnesium (Mg) with a biodegradable polymer, poly(L-lactide) (PLLA), to delay the localized degradation of magnesium-based implants in body fluid for better in-service mechanical integrity. Firstly, a silicate-based PEO coating on pure magnesium was performed using a pulsed constant current method. In order to seal the pores in the PEO layer, PLLA was coated using a two-step spin coating method. The performance of the PEO–PLLA Mg was evaluated using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The EIS results showed that the polarization resistance (R{sub p}) of the PEO–PLLA Mg was close to two orders of magnitude higher than that of the PEO Mg. While the corrosion current density (i{sub corr}) of the pure Mg was reduced by 65% with the PEO coating, the PEO–PLLA coating reduced the i{sub corr} by almost 100%. As expected, the R{sub p} of the PEO–PLLA Mg decreased with increase in exposure time. However, it was noted that the R{sub p} of the PEO–PLLA Mg even after 100 h was six times higher than that of the PEO Mg after 48 h exposure, and did not show any visible localized attack.

"Click" synthesis of fatty acid derivatives as fast-degrading polyanhydride precursors.

Science.gov (United States)

Lluch, Cristina; Lligadas, Gerard; Ronda, Joan C; Galià, Marina; Cadiz, Virginia

2011-09-01

Fast-degrading linear and branched polyanhydrides are obtained by melt-condensation of novel di- and tri-carboxylic acid monomers based on oleic and undecylenic acid synthesized using photoinitiated thiol-ene click chemistry. (1)H NMR spectroscopy, size exclusion chromatography, differential scanning calorimetry, thermogravimetric analysis, and FT-IR spectroscopy have been used to fully characterize these polymers. The hydrolytic degradation of these polymers was studied by means of weight loss, anhydride bond loss, and changes in molecular weight, showing fast degrading properties. Drug release studies from the synthesized polyanhydrides have also been conducted, using rhodamine B as a hydrophobic model drug, to evaluate the potential of these polymers in biomedical applications. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interaction of energetic particles with polymer surfaces: surface morphology development and sputtered polymer-fragment ion analysis

International Nuclear Information System (INIS)

Michael, R.S.

1987-01-01

The core of this thesis is based on a series of papers that have been published or will soon be published in which the various processes taking place in the energetic particle-polymer surface interaction scene is investigated. Results presented show different developments on polymer surfaces when compared to the vast experimental data on energetic particle-metal surface interactions. The surface morphology development depends on the physical characteristics of the polymer. Sputtering yields of fluoropolymers were several orders higher than the sputtering yields of aliphatic and aromatic polymers. Depending on the chemical nature of the polymer, the surface morphology development was dependent upon the extent of radiation-damage accumulation. Fast Atom Bombardment Mass Spectrometry at low and high resolution was applied to the characterization of sputtered polymer fragment ions. Fragment ions and their intensities were used to identify polymer samples, observe radiation damage accumulation and probe polymer-polymer interface of a polymer-polymer sandwich structure. A model was proposed which attempts to explain the nature of processes involved in the energetic particle-polymer surface interaction region

Mechanism of radiation-induced degradation of poly(methyl methacrylate)

International Nuclear Information System (INIS)

Ichikawa, Tsuneki; Oyama, Ken-ichi; Yoshida, Hiroshi

1995-01-01

ESR and gel permeation chromatographic measurements of poly(methyl methacrylate) γ-irradiated between 77 K and 300 K have been carried out to elucidate the mechanism of radiation-induced degradation of the polymer. It is revealed that the scission of the main chain is not taken place immediately after the absorption of radiation energy but is induced by the intramolecular radical conversion of the side-chain -COOCH 2 radical to the tertiary -CH 2 -C(CH 3 )- radical followed by the main-chain β-scission of the latter radical. The degradation is not taken place below 190 K, because the side-chain radical starts to convert only above 190 K. The residual monomer in the polymer reacts with the side-chain radical below 190 K to generate the stable propagating-type radical, so that the degradation is suppressed even after warming the polymer to the ambient temperature. (author)

Stabilization of nanosized titanium dioxide by cyclodextrin polymers and its photocatalytic effect on the degradation of wastewater pollutants.

Science.gov (United States)

Agócs, Tamás Zoltán; Puskás, István; Varga, Erzsébet; Molnár, Mónika; Fenyvesi, Éva

2016-01-01

Advanced oxidation processes (AOPs) are considered highly competitive water treatment technologies for the removal of organic pollutants. Among AOP techniques, photocatalysis has recently been the most widely studied. Our aims were to investigate how the dispersion of nanosized titanium dioxide (nanoTiO 2 ) applied in photodegradation-based procedures can be stabilized with cyclodextrins in order to obtain a new, more efficient photocatalyst for the purification of waters polluted by xenobiotics applying UV irradiation. During our work, on the one hand, we studied the behavior and stability of nanoTiO 2 in cyclodextrin solutions. On the other hand, we used various monomer and polymer cyclodextrin derivatives, and assessed the options for nanoTiO 2 stabilization in the presence of various salts and tap water on the basis of turbidity tests. The physical stability of nanoTiO 2 dispersions is diminished in the presence of the salts found in tap water (and occurring also in surface waters and ground water) and they are precipitated immediately. This colloidal instability can be improved by cyclodextrin derivatives. Based on the results of our studies we have selected carboxymethyl β-cyclodextrin polymer (CMBCD-P) for stabilization of nanoTiO 2 dispersions. The photocatalytic degradation of methylene blue and ibuprofen as model organic pollutants in various media (distilled water, NaCl solution and tap water) has been studied using nanoTiO 2 as catalyst stabilized by CMBCD-P. CMBCD-P itself showed a catalytic effect on the UV degradation of methylene blue. In addition to enhancing the colloid stability of nanoTiO 2 CMBCD-P showed also synergistic effects in catalyzing the photodecomposition process of the dye. On the other hand, ibuprofen as a model pharmaceutical, a pollutant of emerging concern (EP), was protected by CMBCD-P against the photocatalytic degradation showing that inclusion complex formation can result in opposite effects depending on the structure of the

Stabilization of nanosized titanium dioxide by cyclodextrin polymers and its photocatalytic effect on the degradation of wastewater pollutants

Directory of Open Access Journals (Sweden)

Tamás Zoltán Agócs

2016-12-01

Full Text Available Advanced oxidation processes (AOPs are considered highly competitive water treatment technologies for the removal of organic pollutants. Among AOP techniques, photocatalysis has recently been the most widely studied. Our aims were to investigate how the dispersion of nanosized titanium dioxide (nanoTiO2 applied in photodegradation-based procedures can be stabilized with cyclodextrins in order to obtain a new, more efficient photocatalyst for the purification of waters polluted by xenobiotics applying UV irradiation. During our work, on the one hand, we studied the behavior and stability of nanoTiO2 in cyclodextrin solutions. On the other hand, we used various monomer and polymer cyclodextrin derivatives, and assessed the options for nanoTiO2 stabilization in the presence of various salts and tap water on the basis of turbidity tests. The physical stability of nanoTiO2 dispersions is diminished in the presence of the salts found in tap water (and occurring also in surface waters and ground water and they are precipitated immediately. This colloidal instability can be improved by cyclodextrin derivatives. Based on the results of our studies we have selected carboxymethyl β-cyclodextrin polymer (CMBCD-P for stabilization of nanoTiO2 dispersions. The photocatalytic degradation of methylene blue and ibuprofen as model organic pollutants in various media (distilled water, NaCl solution and tap water has been studied using nanoTiO2 as catalyst stabilized by CMBCD-P. CMBCD-P itself showed a catalytic effect on the UV degradation of methylene blue. In addition to enhancing the colloid stability of nanoTiO2 CMBCD-P showed also synergistic effects in catalyzing the photodecomposition process of the dye. On the other hand, ibuprofen as a model pharmaceutical, a pollutant of emerging concern (EP, was protected by CMBCD-P against the photocatalytic degradation showing that inclusion complex formation can result in opposite effects depending on the structure

Protease-activated quantum dot probes

International Nuclear Information System (INIS)

Chang, Emmanuel; Miller, Jordan S.; Sun, Jiantang; Yu, William W.; Colvin, Vicki L.; Drezek, Rebekah; West, Jennifer L.

2005-01-01

We have developed a novel nanoparticulate luminescent probe with inherent signal amplification upon interaction with a targeted proteolytic enzyme. This construct may be useful for imaging in cancer detection and diagnosis. In this system, quantum dots (QDs) are bound to gold nanoparticles (AuNPs) via a proteolytically degradable peptide sequence to non-radiatively suppress luminescence. A 71% reduction in luminescence was achieved with conjugation of AuNPs to QDs. Release of AuNPs by peptide cleavage restores radiative QD photoluminescence. Initial studies observed a 52% rise in luminescence over 47 h of exposure to 0.2 mg/mL collagenase. These probes can be customized for targeted degradation simply by changing the sequence of the peptide linker

Photodegradation of polymers physical characteristics and applications

CERN Document Server

Rabek, Jan F

1996-01-01

In this book on physical characteristics and practical aspects of polymer photodegradation Rabek emphasizes the experimental work on the subject. The most important feature of the book is the physical interpretation of polymer degradation, e.g. mechanism of UV/light absorption, formation of excited states, energy transfer mechanism, kinetics, dependence on physical properties of macromolecules and polymer matrices, formation of mechanical defects, practics during environmental ageing. He includes also some aspects of polymer photodegradation in environmental and space condition.

Degradation of thin poly(lactic acid) films: Characterization by capacitance–voltage, atomic force microscopy, scanning electron microscopy and contact-angle measurements

International Nuclear Information System (INIS)

Schusser, S.; Menzel, S.; Bäcker, M.; Leinhos, M.; Poghossian, A.; Wagner, P.; Schöning, M.J.

2013-01-01

For the development of new biopolymers and implantable biomedical devices with predicted biodegradability, simple, non-destructive, fast and inexpensive techniques capable for real-time in situ testing of the degradation kinetics of polymers are highly appreciated. In this work, a capacitive field-effect electrolyte–insulator–semiconductor (EIS) sensor has been applied for real-time in situ monitoring of degradation of thin poly(D,L-lactic acid) (PDLLA) films over a long-time period of one month. Generally, the polymer-modified EIS (PMEIS) sensor is capable of detecting any changes in the bulk, surface and interface properties of the polymer (e.g., thickness, coverage, dielectric constant, surface potential) induced by degradation processes. The time-dependent capacitance–voltage (C–V) characteristics of PMEIS structures were used as an indicator of the polymer degradation. To accelerate the PDLLA degradation, experiments were performed in alkaline buffer solution of pH 10.6. The results of these degradation measurements with the EIS sensor were verified by the detection of lactic acid (product of the PDLLA degradation) in the degradation medium. In addition, the micro-structural and morphological changes of the polymer surface induced by the polymer degradation have been systematically studied by means of scanning-electron microscopy, atomic-force microscopy, optical microscopy, and contact-angle measurements

Electrical four-point probing of spherical metallic thin films coated onto micron sized polymer particles

Energy Technology Data Exchange (ETDEWEB)

Pettersen, Sigurd R., E-mail: sigurd.r.pettersen@ntnu.no, E-mail: jianying.he@ntnu.no; Stokkeland, August Emil; Zhang, Zhiliang; He, Jianying, E-mail: sigurd.r.pettersen@ntnu.no, E-mail: jianying.he@ntnu.no [NTNU Nanomechanical Lab, Department of Structural Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim (Norway); Kristiansen, Helge [NTNU Nanomechanical Lab, Department of Structural Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim (Norway); Conpart AS, Dragonveien 54, NO-2013 Skjetten (Norway); Njagi, John; Goia, Dan V. [Center for Advanced Materials Processing, Clarkson University, Potsdam, New York 13699-5814 (United States); Redford, Keith [Conpart AS, Dragonveien 54, NO-2013 Skjetten (Norway)

2016-07-25

Micron-sized metal-coated polymer spheres are frequently used as filler particles in conductive composites for electronic interconnects. However, the intrinsic electrical resistivity of the spherical thin films has not been attainable due to deficiency in methods that eliminate the effect of contact resistance. In this work, a four-point probing method using vacuum compatible piezo-actuated micro robots was developed to directly investigate the electric properties of individual silver-coated spheres under real-time observation in a scanning electron microscope. Poly(methyl methacrylate) spheres with a diameter of 30 μm and four different film thicknesses (270 nm, 150 nm, 100 nm, and 60 nm) were investigated. By multiplying the experimental results with geometrical correction factors obtained using finite element models, the resistivities of the thin films were estimated for the four thicknesses. These were higher than the resistivity of bulk silver.

Durability Improvements Through Degradation Mechanism Studies

Energy Technology Data Exchange (ETDEWEB)

Borup, Rodney L. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Mukundan, Rangachary [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Spernjak, Dusan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Baker, Andrew M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lujan, Roger W. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Langlois, David Alan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Ahluwalia, Rajesh [Argonne National Lab. (ANL), Argonne, IL (United States); Papadia, D. D. [Argonne National Lab. (ANL), Argonne, IL (United States); Weber, Adam Z. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kusoglu, Ahmet [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Shi, Shouwnen [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); More, K. L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Grot, Steve [Ion Power, New Castle, DE (United States)

2015-08-03

The durability of polymer electrolyte membrane (PEM) fuel cells is a major barrier to the commercialization of these systems for stationary and transportation power applications. By investigating cell component degradation modes and defining the fundamental degradation mechanisms of components and component interactions, new materials can be designed to improve durability. To achieve a deeper understanding of PEM fuel cell durability and component degradation mechanisms, we utilize a multi-institutional and multi-disciplinary team with significant experience investigating these phenomena.

FY1995 synthesis of new erodable polymers response to environmental stimuli; 1995 nendo atarashii kankyo chowagata bunkaisei plastic no kaihatsu

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

Recently, environmental pollution by a large amount of undecomposable waste has became a serious problem. Therefore, biodegradable polymers, which can be degraded by environmental species such as bacteria and enzymes, have been studied extensively. Most of the biodegradable polymers prepared so far were polyester derivatives such as poly(hydroxybutyrate/valerate), poly(lactide) and poly(glycolide). The degradation mechanism is the hydrolysis of the ester groups in the main chain of the polymer which is facilitated by enzyme degradation. Most of the mass-produced polymers, however, are vinyl-polymerized plastics such as poly(ethylene), poly(propylene) and poly(styrene). There is no technology on the degradation of such vinyl polymers except in the lithography field, in which it is known that some vinyl polymers can be used for posi-type resists by decomposition with UV or electron-beam (EB). For creation of degradable polymers, the following three factors must be considered Purpose of the project seriously; 1) What degrades the polymers? 2) Row long does the polymer maintain the initial properties? (Time course of the mechanical strength, etc.) and 3) Bioactivity of the liberated oligomers. The aim of our work is the creation of new polymers which can be easily controlled by the above three factors. If we can degrade the polymers from the end of the polymer chain, i) we can control several properties of the polymers in the degradation such as degradation source (pH, light,, UV, EB, etc.) and rate of the degradation by changing the structure of the end group; 2) production of oligomers, which may induce a significant problem in terms of bioactivity, can be suppressed because of the depolymerization from the end of the polymers (only the monomer will be liberated). In this project, we investigated to synthesize the end functionalizations of poly({alpha}-methylstyrene) derivatives and their degradation characteristics using temperature, acid and alkaline conditions. To

Graphene-Based Polymer Nanocomposites

Science.gov (United States)

2015-03-31

polymerize in-situ around the fillers or even graft to them [71], thus it overcomes the problem of dramatically increased viscosity of the polymer...filler dispersion, increased polymer viscosity during processing and filler damage due to thermal degradation or strong shear forces [3, 82]. At...123, 124]. Figure 1.12 (a) SEM image of the fracture surface of GO/PVA nanocomposite film [85]. (b) TEM image of a clay reinforced Nylon-6

Biological degradation of plastics: a comprehensive review.

Science.gov (United States)

Shah, Aamer Ali; Hasan, Fariha; Hameed, Abdul; Ahmed, Safia

2008-01-01

Lack of degradability and the closing of landfill sites as well as growing water and land pollution problems have led to concern about plastics. With the excessive use of plastics and increasing pressure being placed on capacities available for plastic waste disposal, the need for biodegradable plastics and biodegradation of plastic wastes has assumed increasing importance in the last few years. Awareness of the waste problem and its impact on the environment has awakened new interest in the area of degradable polymers. The interest in environmental issues is growing and there are increasing demands to develop material which do not burden the environment significantly. Biodegradation is necessary for water-soluble or water-immiscible polymers because they eventually enter streams which can neither be recycled nor incinerated. It is important to consider the microbial degradation of natural and synthetic polymers in order to understand what is necessary for biodegradation and the mechanisms involved. This requires understanding of the interactions between materials and microorganisms and the biochemical changes involved. Widespread studies on the biodegradation of plastics have been carried out in order to overcome the environmental problems associated with synthetic plastic waste. This paper reviews the current research on the biodegradation of biodegradable and also the conventional synthetic plastics and also use of various techniques for the analysis of degradation in vitro.

Real-Time Tracking the Synthesis and Degradation of Albumin in Complex Biological Systems with a near-Infrared Fluorescent Probe.

Science.gov (United States)

Jin, Qiang; Feng, Lei; Zhang, Shui-Jun; Wang, Dan-Dan; Wang, Fang-Jun; Zhang, Yi; Cui, Jing-Nan; Guo, Wen-Zhi; Ge, Guang-Bo; Yang, Ling

2017-09-19

In this study, a novel fluorescent detection system for biological sensing of human albumin (HA) was developed on the basis of the pseudoesterase activity and substrate preference of HA. The designed near-infrared (NIR) fluorescent probe (DDAP) could be effectively hydrolyzed by HA, accompanied by significant changes in both color and fluorescence spectrum. The sensing mechanism was fully investigated by fluorescence spectroscopy, NMR, and mass spectra. DDAP exhibited excellent selectivity and sensitivity toward HA over a variety of human plasma proteins, hydrolases, and abundant biomolecules found in human body. The probe has been successfully applied to measure native HA in diluted plasma samples and the secreted HA in the hepatocyte culture supernatant. DDAP has also been used for fluorescence imaging of HA reabsorption in living renal cells, and the results show that the probe exhibits good cell permeability, low cytotoxicity and high imaging resolution. Furthermore, DDAP has been successfully used for real-time tracking the uptaking and degradation of albumin in ex vivo mouse kidney models for the first time. All these results clearly demonstrated that DDAP-based assay held great promise for real-time sensing and tracking HA in complex biological systems, which would be very useful for basic researches and clinical diagnosis of HA-associated diseases.

Acid-degradable and bioerodible modified polyhydroxylated materials

Energy Technology Data Exchange (ETDEWEB)

Frechet, Jean M. J.; Bachelder, Eric M.; Beaudette, Tristan T.; Broaders, Kyle E.

2017-05-09

Compositions and methods of making a modified polyhydroxylated polymer comprising a polyhydroxylated polymer having reversibly modified hydroxyl groups, whereby the hydroxyl groups are modified by an acid-catalyzed reaction between a polydroxylated polymer and a reagent such as acetals, aldehydes, vinyl ethers and ketones such that the modified polyhydroxylated polymers become insoluble in water but freely soluble in common organic solvents allowing for the facile preparation of acid-sensitive materials. Materials made from these polymers can be made to degrade in a pH-dependent manner. Both hydrophobic and hydrophilic cargoes were successfully loaded into particles made from the present polymers using single and double emulsion techniques, respectively. Due to its ease of preparation, processability, pH-sensitivity, and biocompatibility, of the present modified polyhydroxylated polymers should find use in numerous drug delivery applications.

Polymer research by neutron scattering

International Nuclear Information System (INIS)

Richter, D.

1993-01-01

Polymer physics aims on an understanding of the macroscopic behavior of polymer systems on the basis of their molecular structure and dynamics. For this purpose neutrons serve as a unique probe, allowing a simultaneous investigation of polymer structure and dynamics on a molecular scale. Furthermore, hydrogen deuterium exchange facilitates molecular labeling and offers the possibility to observe selected chains or chain parts in dense systems. Neutron small angle scattering reveals information on the conformation and possible aggregation of polymer chains. Data on linear and star like molecules are shown as examples. High resolution neutron spin-echospectroscopy observes the molecular dynamics of long chain molecules. Results on the large scale motion of chins in polymer melts are presented. finally, experiments on chain relaxation close to the glass transition are displayed. Three distinctly different relaxation processes are revealed. (author)

Investigation of Thermal and Viscoelastic Properties of Polymers Relevant to Hot Melt Extrusion, IV: Affinisol™ HPMC HME Polymers.

Science.gov (United States)

Gupta, Simerdeep Singh; Solanki, Nayan; Serajuddin, Abu T M

2016-02-01

Most cellulosic polymers cannot be used as carriers for preparing solid dispersion of drugs by hot melt extrusion (HME) due to their high melt viscosity and thermal degradation at high processing temperatures. Three HME-grade hydroxypropyl methylcelluloses, namely Affinisol™ HPMC HME 15 cP, Affinisol™ HPMC HME 100 cP, and Affinisol™ HPMC HME 4 M, have recently been introduced by The Dow Chemical Co. to enable the preparation of solid dispersion at lower and more acceptable processing temperatures. In the present investigation, physicochemical properties of the new polymers relevant to HME were determined and compared with that of Kollidon(®) VA 64. Powder X-ray diffraction (PXRD), modulated differential scanning calorimetry (mDSC), thermogravimetric analysis (TGA), moisture sorption, rheology, and torque analysis by melt extrusion were applied. PXRD and mDSC showed that the Affinisol™ polymers were amorphous in nature. According to TGA, the onset of degradation for all polymers was >220°C. The Affinisol™ polymers exhibited less hygroscopicity than Kollidon(®) VA 64 and another HPMC polymer, Methocel™ K100LV. The complex viscosity profiles of the Affinisol™ polymers as a function of temperature were similar. The viscosity of the Affinisol™ polymers was highly sensitive to the shear rate applied, and unlike Kollidon(®) VA 64, the viscosity decreased drastically when the angular frequency was increased. Because of the very high shear rate encountered during melt extrusion, Affinisol™ polymers showed capability of being extruded at larger windows of processing temperatures as compared to that of Kollidon(®) VA 64.

Approaches for Making High Performance Polymer Materials from Commodity Polymers

Institute of Scientific and Technical Information of China (English)

Xu Xi

2004-01-01

A brief surrey of ongoing research work done for improving and enhancing the properties of commodity polymers by the author and author's colleagues is given in this paper. A series of high performance polymers and polymer nanomaterials were successfully prepared through irradiation and stress-induced reactions of polymers and hydrogen bonding. The methods proposed are viable, easy in operation, clean and efficient.1. The effect of irradiation source (UV light, electron beam, γ -ray and microwave), irradiation dose, irradiation time and atmosphere etc. on molecular structure of polyolefine during irradiation was studied. The basic rules of dominating oxidation, degradation and cross-linking reactions were mastered. Under the controlled conditions, cross-linking reactions are prevented, some oxygen containing groups are introduced on the molecular chain of polyolefine to facilitate the interface compatibility of their blends. A series of high performance polymer materials: u-HDPE/PA6,u-HDPE/CaCO3, u-iPP/STC, γ-HDPE/STC, γ-LLDPE/ATH, e-HDPE, e-LLDPE and m-HDPEfilled system were prepared (u- ultraviolet light irradiated, γ- γ-ray irradiated, e- electron beam irradiated, m- microwave irradiated)2. The effect of ultrasonic irradiation, jet and pan-milling on structure and changes in properties of polymers were studied. Imposition of critical stress on polymer chain can cause the scission of bonds to form macroradicals. The macroradicals formed in this way may recombine or react with monomer or other radicals to form linear, branched or cross-linked polymers or copolymers. About 20 kinds of block/graft copolymers have been synthesized from polymer-polymer or polymer-monomer through ultrasonic irradiation.Through jet-milling, the molecular weight of PVC is decreased somewhat, the intensity of its crystalline absorption bonds becomes indistinct. The processability, the yield strength, strength at break and elongation at break of PVC get increased quite a lot after

Engineering a degradable polyurethane intravaginal ring for sustained delivery of dapivirine.

Science.gov (United States)

Kaur, Manpreet; Gupta, Kavita M; Poursaid, Azadeh E; Karra, Prasoona; Mahalingam, Alamelu; Aliyar, Hyder A; Kiser, Patrick F

2011-06-01

We describe the engineering of a degradable intravaginal ring (IVR) for the delivery of the potent HIV-1 reverse transcriptase inhibitor dapivirine. The degradable polymer used in fabricating the device incorporated poly(caprolactone) ester blocks in a poly(tetramethylene ether) glycol ABA type polyurethane backbone. The polymer was designed to maintain its structure for 1 month during usage and then degrade in the environment post-disposal. In vitro release of dapivirine showed zero-order kinetics for up to 1 month and significant levels of drug release into engineered vaginal tissue. The mechanical properties of the degradable IVR were comparable to those of a widely used contraceptive intravaginal ring upon exposure to simulated vaginal conditions. Incubation under simulated vaginal conditions for a month caused minimal degradation with minimal effect on the mechanical properties of the ring and polymer. The cytotoxicity evaluation of the drug-loaded IVRs against Vk2/E6E7 human vaginal epithelial cells, Lactobacillus jensenii, and engineered vaginal tissue constructs showed the degradable polyurethane to be non-toxic. In vitro evaluation of inflammatory potential monitored through the levels of inflammatory cytokines IL-8, IL-1α, IL-6, IL-1β, and MIP-3α when engineered EpiVaginal™ tissue was incubated with the polyurethanes suggested that the degradable polyurethane was comparable to commercial medical grade polyurethane. These results are encouraging for further development of this degradable IVR for topical vaginal delivery of microbicides.

Radiation resistant polymers and coatings for nuclear fuel reprocessing plants

International Nuclear Information System (INIS)

Kamachi Mudali, U.; Mallika, C.; Lawrence, Falix

2014-01-01

Polymer based materials are extensively used in the nuclear industry for the reprocessing of spent fuels in highly radioactive and corrosive environment. Hence, these polymer materials are susceptible to damage by ionizing radiation, resulting in the degradation in properties. Polymers containing aromatic molecules generally possess higher resistance to radiation degradation than the aliphatic polymers. For improving the radiation resistance of polymers various methods are reported in the literature. Among the aromatic polymers, polyetheretherketone (PEEK) has the radiation tolerance up to 10 Mega Grey (MGy). To explore the possibility of enhancing the radiation resistance of PEEK, a study was initiated to develop PEEK - ceramic composites and evaluate the effect of radiation on the properties of the composites. PEEK and PEEK - alumina (micron size) composites were irradiated in a gamma chamber using 60 Co source and the degradation in mechanical, structural, electrical and thermal properties, gel fraction, coefficient of friction and morphology were investigated. The degradation in the mechanical properties owing to radiation could be reduced by adding alumina filler to PEEK. Nano alumina filler was observed to be more effective in suppressing the damage caused by radiation on the polymer, when compared to micron alumina filler. For the protection of aluminium components in the manipulators and the rotors and stators of the motors of the centrifugal extractors employed in the plant from the attack by nitric acid vapour, PEEK coating based on liquid dispersion was developed, which has resistance to radiation, chemicals and wear. The effect of radiation and chemical vapour on the properties of the PEEK coating was estimated. The performance of the coating in the plant was evaluated and the coating was found to give adequate protection to the motors of centrifugal extractors against corrosion. (author)

Degradation of polyethylene microplastics in seawater: Insights into the environmental degradation of polymers.

Science.gov (United States)

Da Costa, João P; Nunes, Ana R; Santos, Patrícia S M; Girão, Ana V; Duarte, Armando C; Rocha-Santos, Teresa

2018-04-06

Microplastic contamination of aquatic environments has become an increasingly alarming problem. These, defined as particles degradation of this material. These results highlight the importance of determining the mechanisms of degradation of microplastics in marine settings and what the implications may be for the environment. Overall, the herein presented results show that a relatively short period of time of accelerated exposure can yield quantifiable chemical and physical impacts on the structural and morphological characteristics of PE pellets.

Study of PP/montmorillonite composite degradation

International Nuclear Information System (INIS)

Baer, Marcia; Granado, Carlos J.F.

2009-01-01

The objective of this work was to produce composites of PP/sodium bentonite and PP/ organophilic bentonite through melt intercalation and analyze the degradation produced by ultraviolet irradiation. The XRD results showed that the samples of nature bentonite had better interaction with de polymer and produced intercalated nanocomposite. The effect of UV irradiation on degradation was observed after 24 hours of exposition. The samples showed the same photoproducts and at the same proportion until 240 hours of UV exposition; with 480 hours the organophilize bentonite composite showed higher degradation than other ones. The superficial cracks increased with degradation time. The degradation occurs due chromophores impurities presented in the samples, thus samples with sodium clay show higher degradation, and organophilic clay contains ammonium salt that contribute to increase the degradation. (author)

Potential of Thermophilic microorganisms for the degradation of synthetic polymers

Energy Technology Data Exchange (ETDEWEB)

Dominguez, A.; Deive, F. J.; Sanroman, M. A.; Longo, M. A.

2009-07-01

Nowadays, synthetic polymers are used in all areas of human activity, mainly due to their high stability against environmental conditions and microbial attack. However, these properties are also a problem from an environmental point of view, and thus it is necessary to find biodegradable synthetic polymers that can be easily removed in nature after disposal, and decomposed into biomass, CO{sub 2} and water. (Author)

Optimization of Polymer-ECM Composite Scaffolds for Tissue Engineering: Effect of Cells and Culture Conditions on Polymeric Nanofiber Mats

Directory of Open Access Journals (Sweden)

Ritu Goyal

2017-01-01

Full Text Available The design of composite tissue scaffolds containing an extracellular matrix (ECM and synthetic polymer fibers is a new approach to create bioactive scaffolds that can enhance cell function. Currently, studies investigating the effects of ECM-deposition and decellularization on polymer degradation are still lacking, as are data on optimizing the stability of the ECM-containing composite scaffolds during prolonged cell culture. In this study, we develop fibrous scaffolds using three polymer compositions, representing slow (E0000, medium (E0500, and fast (E1000 degrading materials, to investigate the stability, degradation, and mechanics of the scaffolds during ECM deposition and decellularization, and during the complete cellularization-decell-recell cycle. We report data on percent molecular weight (% Mw retention of polymeric fiber mats, changes in scaffold stiffness, ECM deposition, and the presence of fibronectin after decellularization. We concluded that the fast degrading E1000 (Mw retention ≤ 50% after 28 days was not sufficiently stable to allow scaffold handling after 28 days in culture, while the slow degradation of E0000 (Mw retention ≥ 80% in 28 days did not allow deposited ECM to replace the polymer support. The scaffolds made from medium degrading E0500 (Mw retention about 60% at 28 days allowed the gradual replacement of the polymer network with cell-derived ECM while maintaining the polymer network support. Thus, polymers with an intermediate rate of degradation, maintaining good scaffold handling properties after 28 days in culture, seem best suited for creating ECM-polymer composite scaffolds.

Preparation of dual-responsive hybrid fluorescent nano probe based on graphene oxide and boronic acid/BODIPY-conjugated polymer for cell imaging

Energy Technology Data Exchange (ETDEWEB)

Khoerunnisa [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Kang, Eun Bi [Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Mazrad, Zihnil Adha Islamy [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Lee, Gibaek [Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); In, Insik [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Department of Polymer Science and Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Park, Sung Young, E-mail: parkchem@ut.ac.kr [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of)

2017-02-01

Here, we report a pH- and thermo-responsive fluorescent nanomaterial of functionalized reduced graphene oxide (rGO) with cross-linked polymer produced via catechol-boronate diol binding mechanism. When conjugated with the hydrophobic dye boron dipyrromethane (BODIPY), this material can act as a dual-responsive nanoplatform for cells imaging. 2-Chloro-3′,4′-dihydroxyacetophenone (CCDP)-quaternized-poly(dimethylaminoethyl methacrylate-co-N-isopropylacrylamide) [C-PDN] was cross-linked with BODIPY and 4-chlorophenyl boronic acid (BA)-quaternized-poly(ethylene glycol)-g-poly(dimethylaminoethyl methacrylate-co-N-isopropylacrylamide) [BB-PPDN]. The GO was then reduced by the catechol group in the cross-linked polymer to synthesize rGO nanoparticles, which able to stabilize the quenching mechanism. This nanoplatform exhibits intense fluorescence at acidic pH and low fluorescence at physiological pH. Confocal laser scanning microscopy (CLSM) images shows bright fluorescence at lysosomal pH and total quench at physiological pH. Therefore, we have successfully developed a promising sensitive bio-imaging probe for identifying cancer cells. - Graphical abstract: [BB-PPDN]-[C-PDN]/rGO nanoparticles with boronic acid-catechol cis-diol binding mechanism toward change in pH demonstrated good biocompatibility and effective quenching for cancer cell detection. - Highlights: • Dual responsive (pH- and thermo) fluorescent nano probe was proposed for cells imaging. • The mechanism was based on cis-diol binding mechanism of boronic acid and catechol. • Reduced graphene oxide was used as quencher on nano-platform. • Detection was controlled dependent on pH based on diol compound of boron chemistry.

New method to access hyperbranched polymers with uniform structure via one-pot polymerization of inimer in microemulsion.

Science.gov (United States)

Min, Ke; Gao, Haifeng

2012-09-26

A facile approach is presented for successful synthesis of hyperbranched polymers with high molecular weight and uniform structure by a one-pot polymerization of an inimer in a microemulsion. The segregated space in the microemulsion confined the inimer polymerization and particularly the polymer-polymer reaction within discrete nanoparticles. At the end of polymerization, each nanoparticle contained one hyperbranched polymer that had thousands of inimer units and low polydispersity. The hyperbranched polymers were used as multifunctional macroinitiators for synthesis of "hyper-star" polymers. When a degradable inimer was applied, the hyper-stars showed fast degradation into linear polymer chains with low molecular weight.

Modelling degradation of bioresorbable polymeric medical devices

CERN Document Server

Pan, J

2015-01-01

The use of bioresorbable polymers in stents, fixation devices and tissue engineering is revolutionising medicine. Both industry and academic researchers are interested in using computer modelling to replace some experiments which are costly and time consuming. This book provides readers with a comprehensive review of modelling polymers and polymeric medical devices as an alternative to practical experiments. Chapters in part one provide readers with an overview of the fundamentals of biodegradation. Part two looks at a wide range of degradation theories for bioresorbable polymers and devices.

Plastic Degradation and Its Environmental Implications with Special Reference to Poly(ethylene terephthalate

Directory of Open Access Journals (Sweden)

Elena P. Ivanova

2012-12-01

Full Text Available With increasing global consumption and their natural resistance to degradation, plastic materials and their accumulation in the environment is of increasing concern. This review aims to present a general overview of the current state of knowledge in areas that relate to biodegradation of polymers, especially poly(ethylene terephthalate (PET. This includes an outline of the problems associated with plastic pollution in the marine environment, a description of the properties, commercial manufacturing and degradability of PET, an overview of the potential for biodegradation of conventional polymers and biodegradable polymers already in production.

Some plutonium IV polymers properties in Purex process

International Nuclear Information System (INIS)

Scoazec, H.; Pasquiou, J.Y.; Germain, M.

1990-01-01

The metabolism of plutonium polymers in fuel reprocessing using the Purex process with tributylphosphate as solvent, and its practical consequence in real operation conditions are examined. Precipitation with dibutylphosphoric acid, a solvent degradation product, occurs both in extraction and stripping units when polymers are present. (author)

Oxidative degradation of acid doped polybenzimidazole membranes and fuel cell durability in the presence of ferrous ions

DEFF Research Database (Denmark)

Liao, Jianhui; Yang, Jingshuai; Li, Qingfeng

2013-01-01

Phosphoric acid doped polybenzimidazole membranes have been explored as proton exchange membranes for high temperature polymer electrolyte membrane fuel cells. Long-term durability of the membrane is of critical concern and has been evaluated by accelerated degradation tests under Fenton conditions...... of the polymer. Fuel cell durability tests with contaminations of ferrous ions did show considerable performance degradation, however, primarily due to the catalyst deterioration rather than the membrane degradation........ In this study effects of phosphoric acid and ferrous ions were investigated by measurements of the weight loss, intrinsic viscosity and size exclusion chromatography (SEC) of the polymer membranes. Ferrous ions resulted in, as expected, catalytic formation of peroxide radicals and hence the accelerated polymer...

Primitive chain network simulations of probe rheology.

Science.gov (United States)

Masubuchi, Yuichi; Amamoto, Yoshifumi; Pandey, Ankita; Liu, Cheng-Yang

2017-09-27

Probe rheology experiments, in which the dynamics of a small amount of probe chains dissolved in immobile matrix chains is discussed, have been performed for the development of molecular theories for entangled polymer dynamics. Although probe chain dynamics in probe rheology is considered hypothetically as single chain dynamics in fixed tube-shaped confinement, it has not been fully elucidated. For instance, the end-to-end relaxation of probe chains is slower than that for monodisperse melts, unlike the conventional molecular theories. In this study, the viscoelastic and dielectric relaxations of probe chains were calculated by primitive chain network simulations. The simulations semi-quantitatively reproduced the dielectric relaxation, which reflects the effect of constraint release on the end-to-end relaxation. Fair agreement was also obtained for the viscoelastic relaxation time. However, the viscoelastic relaxation intensity was underestimated, possibly due to some flaws in the model for the inter-chain cross-correlations between probe and matrix chains.

Probing Rubber Cross-Linking Generation of Industrial Polymer Networks at Nanometer Scale.

Science.gov (United States)

Gabrielle, Brice; Gomez, Emmanuel; Korb, Jean-Pierre

2016-06-23

We present improved analyses of rheometric torque measurements as well as (1)H double-quantum (DQ) nuclear magnetic resonance (NMR) buildup data on polymer networks of industrial compounds. This latter DQ NMR analysis allows finding the distribution of an orientation order parameter (Dres) resulting from the noncomplete averaging of proton dipole-dipole couplings within the cross-linked polymer chains. We investigate the influence of the formulation (filler and vulcanization systems) as well as the process (curing temperature) ending to the final polymer network. We show that DQ NMR follows the generation of the polymer network during the vulcanization process from a heterogeneous network to a very homogeneous one. The time variations of microscopic Dres and macroscopic rheometric torques present power-law behaviors above a threshold time scale with characteristic exponents of the percolation theory. We observe also a very good linear correlation between the kinetics of Dres and rheometric data routinely performed in industry. All these observations confirm the description of the polymer network generation as a critical phenomenon. On the basis of all these results, we believe that DQ NMR could become a valuable tool for investigating in situ the cross-linking of industrial polymer networks at the nanometer scale.

Preparation and characterization of high performance Schiff-base liquid crystal diepoxide polymer

International Nuclear Information System (INIS)

Liu Huan; Fu Zien; Xu Kai; Cai Hualun; Liu Xin; Chen Mingcai

2012-01-01

Graphical abstract: The specific effects of highly conjugated Schiff-base moiety on thermal properties of the Schiff-base epoxy polymer were proposed first by us. From the point of view of structure-properties relationship, it can be considered that owing to the presence of the Schiff-base group, the high performance liquid crystal diepoxide polymer displayed improved thermal stability. Highlights: ► In this work, we first proposed that specific effects of highly conjugated Schiff-base moiety on thermal properties of the Schiff-base epoxy polymer. ► As one aim of this study, the thermal and thermal-oxidative stabilities of the thermosets were studied by TGA under nitrogen and under air. ► The second aim of this study was to further understand the thermal degradation mechanism. ► For thermal degradation mechanism of this polymer under nitrogen, TG-IR was used to investigate volatile components, and SEM/EDS was used to explore morphologies and chemical components of the residual char. ► From the point of view of structure-properties relationship, it can be considered that owing to the presence of the Schiff-base group, the high performance liquid crystal diepoxide polymer displayed the improved thermal stability. - Abstract: A novel Schiff-base liquid crystal diepoxide polymer was prepared via a thermal copolymerization of a Schiff-base epoxy monomer (PBMBA) with a diamine co-monomer (MDA). We first proposed that specific effects of highly conjugated Schiff-base moiety on thermal properties of the Schiff-base epoxy polymer (PBMBA/MDA). Thermal degradation behavior of the polymer was characterized using thermogravimetric analysis (TGA) under nitrogen and under air, respectively. Thermogravimetric data obtained from TGA under nitrogen and under air reveal that PBMBA/MDA exhibits higher thermal stability compared with bisphenol-A type epoxy polymer (DGEBA/MDA) and other mesogene-containing epoxy polymer. It is worth pointing out that the outstanding residual

Characterization and in vitro degradation of poly(2,3-(1,4-diethyl tartrate)-co-2,3-isopropyliden tartrate).

Science.gov (United States)

Schliecker, Gesine; Schmidt, Carsten; Fuchs, Stefan; Kissel, Thomas

2004-07-23

In the present study, a less known polyester based on tartaric acid was characterized with respect to its degradation mechanism. Poly(2,3-(1,4-diethyl tartrate)-co-2,3-isopropyliden tartrate) (PTA) differs from commonly used biodegradable polyesters, such as poly(lactides-co-glycolides) (PLGA) by the presence of additional cleavable bonds in the polymer side chains. This modification results in different polymer properties and influences polymer degradation. The hydrolytic degradation of PTA was studied in parallel to PLGA using disc-shape matrices, which were obtained by compression-molding. The discs were incubated in pH 7.4 phosphate buffer solution at 37 degrees C. The degraded samples were characterized for percentage mass loss, water absorption, decay of molecular weight and change in glass transition temperature. The results demonstrate that the degradation of PTA proceeds via bulk erosion similar to PLGA. However, the degradation of PTA implants is characterized by a rapid mass loss within a short period of time appearing after a definite lag phase without remarkable mass loss. This makes the polymer promising for pulsatile drug release systems.

Deformation and degradation of polymers in ultra-high-pressure liquid chromatography

NARCIS (Netherlands)

Uliyanchenko, E.; van der Wal, S.; Schoenmakers, P.J.

2011-01-01

Ultra-high-pressure liquid chromatography (UHPLC) using columns packed with sub-2 μm particles has great potential for separations of many types of complex samples, including polymers. However, the application of UHPLC for the analysis of polymers meets some fundamental obstacles. Small particles

Characterization of biodegradable polymers irradiated with swift heavy ions

International Nuclear Information System (INIS)

Salguero, N.G.; Grosso, M.F. del; Durán, H.; Peruzzo, P.J.; Amalvy, J.I.

2012-01-01

In view of their application as biomaterials, there is an increasing interest in developing new methods to induce controlled cell adhesion onto polymeric materials. The critical step in all these methods involves the modification of polymer surfaces, to induce cell adhesion, without changing theirs degradation and biocompatibility properties. In this work two biodegradable polymers, polyhydroxybutyrate (PHB) and poly-L-lactide acid (PLLA) were irradiated using carbon and sulfur beams with different energies and fluences. Pristine and irradiated samples were degradated by immersion in a phosphate buffer at pH 7.0 and then characterized. The analysis after irradiation and degradation showed a decrease in the contact angle values and changes in their crystallinity properties.

Characterization of biodegradable polymers irradiated with swift heavy ions

Energy Technology Data Exchange (ETDEWEB)

Salguero, N.G. [Gerencia de Investigacion y Aplicaciones, TANDAR-CNEA, Av. Gral. Paz 1499 (B1650KNA) San Martin, Buenos Aires (Argentina); Grosso, M.F. del, E-mail: delgrosso@tandar.cnea.gov.ar [Gerencia de Investigacion y Aplicaciones, TANDAR-CNEA, Av. Gral. Paz 1499 (B1650KNA) San Martin, Buenos Aires (Argentina); CONICET, Av. Rivadavia 1917 C1033AAJ CABA (Argentina); Duran, H. [CONICET, Av. Rivadavia 1917 C1033AAJ CABA (Argentina); Gerencia de Desarrollo Tecnologico y Proyectos Especiales, CNEA, Av. Gral. Paz 1499 (B1650KNA) San Mart Latin-Small-Letter-Dotless-I Acute-Accent n, Buenos Aires (Argentina); Escuela de Ciencia y Tecnologia, H. Yrigoyen 3100, CP 1650, San Martin, UNSAM (Argentina); Peruzzo, P.J. [CICPBA - Grupo de Materiales y Nanomateriales Polimericos, Instituto de Investigaciones Fisicoquimicas Teoricas y Aplicadas (INIFTA), CCT La Plata CONICET - Universidad Nacional de La Plata, La Plata (Argentina); Amalvy, J.I. [CICPBA - Grupo de Materiales y Nanomateriales Polimericos, Instituto de Investigaciones Fisicoquimicas Teoricas y Aplicadas (INIFTA), CCT La Plata CONICET - Universidad Nacional de La Plata, La Plata (Argentina); Facultad de Ingenieria, Universidad Nacional de La Plata, Calle 116 y 48 (B1900TAG), La Plata (Argentina); Departamento de Ingenieria Quimica, Facultad Regional La Plata, Universidad Tecnologica Nacional, 60 y 124 (1900), La Plata (Argentina); and others

2012-02-15

In view of their application as biomaterials, there is an increasing interest in developing new methods to induce controlled cell adhesion onto polymeric materials. The critical step in all these methods involves the modification of polymer surfaces, to induce cell adhesion, without changing theirs degradation and biocompatibility properties. In this work two biodegradable polymers, polyhydroxybutyrate (PHB) and poly-L-lactide acid (PLLA) were irradiated using carbon and sulfur beams with different energies and fluences. Pristine and irradiated samples were degradated by immersion in a phosphate buffer at pH 7.0 and then characterized. The analysis after irradiation and degradation showed a decrease in the contact angle values and changes in their crystallinity properties.

Quercetin as natural stabilizing agent for bio-polymer

Energy Technology Data Exchange (ETDEWEB)

Morici, Elisabetta [Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Università di Palermo, 90128 Palermo (Italy); Arrigo, Rossella; Dintcheva, Nadka Tzankova [Dipartimento di Ingegneria Civile, Ambientale, Aerospaziale, dei Materiali, Università di Palermo, 90128 Palermo (Italy)

2014-05-15

The introduction of antioxidants in polymers is the main way to prevent or delay the degradation process. In particular natural antioxidants receive attention in the food industry also because of their presumed safety. In this work bio-polymers, i.e. a commercial starch-based polymer (Mater-Bi®) and a bio-polyester (PLA), and a bio-polyether (PEO) were additivated with quercetin, a natural flavonoid antioxidants, in order to formulate bio-based films for ecosustainable packaging and outdoor applications. The photo-oxidation behavior of unstabilized and quercetin stabilized films was analyzed and compared with the behavior of films additivated with a commercial synthetic light stabilizer. The quercetin is able to slow down the photo-degradation rate of all bio-polymeric films investigated in similar way to the synthetic stabilizer.

Quercetin as natural stabilizing agent for bio-polymer

Science.gov (United States)

Morici, Elisabetta; Arrigo, Rossella; Dintcheva, Nadka Tzankova

2014-05-01

The introduction of antioxidants in polymers is the main way to prevent or delay the degradation process. In particular natural antioxidants receive attention in the food industry also because of their presumed safety. In this work bio-polymers, i.e. a commercial starch-based polymer (Mater-Bi®) and a bio-polyester (PLA), and a bio-polyether (PEO) were additivated with quercetin, a natural flavonoid antioxidants, in order to formulate bio-based films for ecosustainable packaging and outdoor applications. The photo-oxidation behavior of unstabilized and quercetin stabilized films was analyzed and compared with the behavior of films additivated with a commercial synthetic light stabilizer. The quercetin is able to slow down the photo-degradation rate of all bio-polymeric films investigated in similar way to the synthetic stabilizer.

Quercetin as natural stabilizing agent for bio-polymer

International Nuclear Information System (INIS)

Morici, Elisabetta; Arrigo, Rossella; Dintcheva, Nadka Tzankova

2014-01-01

The introduction of antioxidants in polymers is the main way to prevent or delay the degradation process. In particular natural antioxidants receive attention in the food industry also because of their presumed safety. In this work bio-polymers, i.e. a commercial starch-based polymer (Mater-Bi®) and a bio-polyester (PLA), and a bio-polyether (PEO) were additivated with quercetin, a natural flavonoid antioxidants, in order to formulate bio-based films for ecosustainable packaging and outdoor applications. The photo-oxidation behavior of unstabilized and quercetin stabilized films was analyzed and compared with the behavior of films additivated with a commercial synthetic light stabilizer. The quercetin is able to slow down the photo-degradation rate of all bio-polymeric films investigated in similar way to the synthetic stabilizer

Chemical degradation of proton conducting perflurosulfonic acid ionomer membranes studied by solid-state nuclear magnetic resonance spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Ghassemzadeh, L. [Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstrasse 1, D-70569 Stuttgart (Germany); Institut fuer Physikalische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Marrony, M. [European Institute for Energy Research, Emmy-Noether-Strasse 11, D-76131 Karlsruhe (Germany); Barrera, R. [Edison, Via Giorgio La Pira, 2, I-10028 Trofarello (Italy); Kreuer, K.D.; Maier, J. [Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstrasse 1, D-70569 Stuttgart (Germany); Mueller, K. [Institut fuer Physikalische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany)

2009-01-15

The degradation of two different types of perfluorinated polymer membranes, Nafion and Hyflon Ion, has been examined by solid-state {sup 19}F and {sup 13}C NMR spectroscopy. This spectroscopic technique is demonstrated to be a valuable tool for the study of the membrane structure and its alterations after in situ degradation in a fuel cell. The structural changes in different parts of the polymers are clearly distinguished, which provides unique insight into details of the degradation processes. The experimental NMR spectra prove that degradation mostly takes place within the polymer side chains, as reflected by the intensity losses of NMR signals associated with SO{sub 3}H, CF{sub 3}, OCF{sub 2} and CF groups. The integral degree of degradation is found to decrease with increasing membrane thickness while for a given thickness, Hyflon Ion appears to degrade less than Nafion. (author)

Water and UV degradable lactic acid polymers

Science.gov (United States)

Bonsignore, P.V.; Coleman, R.D.

1996-10-08

A water and UV light degradable copolymer is described made from monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene glycol, propylene glycol, P-dioxanone, 1,5 dioxepan-2-one, 1,4-oxathialan-2-one, 1,4-dioxide and mixtures thereof. These copolymers are useful for waste disposal and agricultural purposes. Also disclosed is a water degradable blend of polylactic acid or modified polylactic acid and high molecular weight polyethylene oxide wherein the high molecular weight polyethylene oxide is present in the range of from about 2 by weight to about 50% by weight, suitable for films. A method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures thereof to an agricultural site is also disclosed.

Polymers for enhanced oil recovery: fundamentals and selection criteria.

Science.gov (United States)

Rellegadla, Sandeep; Prajapat, Ganshyam; Agrawal, Akhil

2017-06-01

With a rising population, the demand for energy has increased over the years. As per the projections, both fossil fuel and renewables will remain as major energy source (678 quadrillion BTU) till 2030 with fossil fuel contributing 78% of total energy consumption. Hence, attempts are continuously made to make fossil fuel production more sustainable and cheaper. From the past 40 years, polymer flooding has been carried out in marginal oil fields and have proved to be successful in many cases. The common expectation from polymer flooding is to obtain 50% ultimate recovery with 15 to 20% incremental recovery over secondary water flooding. Both naturally derived polymers like xanthan gum and synthetic polymers like partially hydrolyzed polyacrylamide (HPAM) have been used for this purpose. Earlier laboratory and field trials revealed that salinity and temperature are the major issues with the synthetic polymers that lead to polymer degradation and adsorption on the rock surface. Microbial degradation and concentration are major issues with naturally derived polymers leading to loss of viscosity and pore throat plugging. Earlier studies also revealed that polymer flooding is successful in the fields where oil viscosity is quite higher (up to 126 cp) than injection water due to improvement in mobility ratio during polymer flooding. The largest successful polymer flood was reported in China in 1990 where both synthetic and naturally derived polymers were used in nearly 20 projects. The implementation of these projects provides valuable suggestions for further improving the available processes in future. This paper examines the selection criteria of polymer, field characteristics that support polymer floods and recommendation to design a large producing polymer flooding.

Nanoscale thermal-mechanical probe determination of 'softening transitions' in thin polymer films

International Nuclear Information System (INIS)

Zhou Jing; Berry, Brian; Douglas, Jack F; Karim, Alamgir; Snyder, Chad R; Soles, Christopher

2008-01-01

We report a quantitative study of the softening behavior of glassy polystyrene (PS) films at length scales on the order of 100 nm using nano-thermomechanometry (nano-TM), an emerging scanning probe technique in which a highly doped silicon atomic force microscopy (AFM) tip is resistively heated on the surface of a polymer film. The apparent 'softening temperature' T s of the film is found to depend on the logarithm of the square root of the thermal ramping rate R. This relation allows us to estimate a quasi-equilibrium (or zero rate) softening transition temperature T s0 by extrapolation. We observe marked shifts of T s0 with decreasing film thickness, but the nature of these shifts, and even their sign, depend strongly on both the thermal and mechanical properties of the supporting substrate. Finite element simulations suggest that thin PS films on rigid substrates with large thermal conductivities lead to increasing T s0 with decreasing film thickness, whereas softer, less thermally conductive substrates promote reductions in T s0 . Experimental observations on a range of substrates confirm this behavior and indicate a complicated interplay between the thermal and mechanical properties of the thin PS film and the substrate. This study directly points to relevant factors for quantitative measurements of thermophysical properties of materials at the nanoscale using this nano-TM based method.

Increased radiation degradation in methyl methacrylate copolymers

International Nuclear Information System (INIS)

Helbert, J.N; Wagner, G.E.; Caplan, P.J.; Poindexter, E.H.

1975-01-01

The effect of polar substituents at the quaternary carbon on degradation processes in several polymers and 10 to 20 percent copolymers of methyl methacrylate was explored. EPR was used to monitor radiation degradation products and to determine radiation G values. Irradiations were carried out at 77 0 K in a gamma irradiator at a dose rate of 0.3 Mrad/hr. (U.S.)

Structural Characterization of Polymer-Clay Nanocomposites Prepared by Co-Precipitation Using EPR Techniques

Directory of Open Access Journals (Sweden)

Udo Kielmann

2014-02-01

Full Text Available Polymer-clay nanocomposites (PCNCs containing either a rubber or an acrylate polymer were prepared by drying or co-precipitating polymer latex and nanolayered clay (synthetic and natural suspensions. The interface between the polymer and the clay nanoparticles was studied by electron paramagnetic resonance (EPR techniques by selectively addressing spin probes either to the surfactant layer (labeled stearic acid or the clay surface (labeled catamine. Continuous-wave (CW EPR studies of the surfactant dynamics allow to define a transition temperature T* which was tentatively assigned to the order-disorder transition of the surfactant layer. CW EPR studies of PCNC showed that completely exfoliated nanoparticles coexist with agglomerates. HYSCORE spectroscopy in PCNCs showed couplings within the probe −assigned with DFT computations− and couplings with nuclei of the environment, 1H and 23Na for the surfactant layer probe, and 29Si, 7Li, 19F and 23Na for the clay surface probe. Analysis of these couplings indicates that the integrity of the surfactant layer is conserved and that there are sizeable ionic regions containing sodium ions directly beyond the surfactant layer. Simulations of the very weak couplings demonstrated that the HYSCORE spectra are sensitive to the composition of the clay and whether or not clay platelets stack.

Photoluminescence in conjugated polymers

International Nuclear Information System (INIS)

Furst, J.E.; Laugesen, R.; Dastoor, P.; McNeill, C.

2002-01-01

Full text: Conjugated polymers combine the electronic and optical properties of semiconductors with the processability of polymers. They contain a sequence of alternate single and double carbon bonds so that the overlap of unhybridised p z orbitals creates a delocalised ρ system which gives semiconducting properties with p-bonding (valence) and p* -antibonding (conduction) bands. Photoluminesence (PL) in conjugated polymers results from the radiative decay of singlet excitons confined to a single chain. The present work is the first in a series of studies in our laboratory that will characterize the optical properties of conjugated polymers. The experiment involves the illumination of thin films of conjugated polymer with UV light (I=360 nm) and observing the subsequent fluorescence using a custom-built, fluorescence spectrometer. Photoluminesence spectra provide basic information about the structure of the polymer film. A typical spectrum is shown in the accompanying figure. The position of the first peak is related to the polymer chain length and resolved multiple vibronic peaks are an indication of film structure and morphology. We will also present results related to the optical degradation of these materials when exposed to air and UV light

A phenomenological constitutive model for the nonlinear viscoelastic responses of biodegradable polymers

KAUST Repository

Khan, Kamran

2012-11-09

We formulate a constitutive framework for biodegradable polymers that accounts for nonlinear viscous behavior under regimes with large deformation. The generalized Maxwell model is used to represent the degraded viscoelastic response of a polymer. The large-deformation, time-dependent behavior of viscoelastic solids is described using an Ogden-type hyperviscoelastic model. A deformation-induced degradation mechanism is assumed in which a scalar field depicts the local state of the degradation, which is responsible for the changes in the material\\'s properties. The degradation process introduces another timescale (the intrinsic material clock) and an entropy production mechanism. Examples of the degradation of a polymer under various loading conditions, including creep, relaxation and cyclic loading, are presented. Results from parametric studies to determine the effects of various parameters on the process of degradation are reported. Finally, degradation of an annular cylinder subjected to pressure is also presented to mimic the effects of viscoelastic arterial walls (the outer cylinder) on the degradation response of a biodegradable stent (the inner cylinder). A general contact analysis is performed. As the stiffness of the biodegradable stent decreases, stress reduction in the stented viscoelastic arterial wall is observed. The integration of the proposed constitutive model with finite element software could help a designer to predict the time-dependent response of a biodegradable stent exhibiting finite deformation and under complex mechanical loading conditions. © 2012 Springer-Verlag Wien.

Degradation of plastic carrier bags in the marine environment.

Science.gov (United States)

O'Brine, Tim; Thompson, Richard C

2010-12-01

There is considerable concern about the hazards that plastic debris presents to wildlife. Use of polymers that degrade more quickly than conventional plastics presents a possible solution to this problem. Here we investigate breakdown of two oxo-biodegradable plastics, compostable plastic and standard polyethylene in the marine environment. Tensile strength of all materials decreased during exposure, but at different rates. Compostable plastic disappeared from our test rig between 16 and 24 weeks whereas approximately 98% of the other plastics remained after 40 weeks. Some plastics require UV light to degrade. Transmittance of UV through oxo-biodegradable and standard polyethylene decreased as a consequence of fouling such that these materials received ∼ 90% less UV light after 40 weeks. Our data indicate that compostable plastics may degrade relatively quickly compared to oxo-biodegradable and conventional plastics. While degradable polymers offer waste management solutions, there are limitations to their effectiveness in reducing hazards associated with plastic debris. Copyright © 2010 Elsevier Ltd. All rights reserved.

The micro thermal analysis of polymers

International Nuclear Information System (INIS)

Grandy, David Brian

2002-01-01

This study is concerned with the development of micro-thermal analysis as a technique for characterising heterogeneous polymers. It is divided into two main parts. In the first part, the use of miniature Wollaston wire near-field thermal probes mounted in an atomic force microscope (AFM) to carry out highly localised thermal analysis (L-TA) of amorphous and semi-crystalline polymers is investigated. Here, the temperature of the probe sensor or tip is scanned over a pre-selected temperature range while in contact with the surface of a sample. It is thereby used to heat a volume of material of the order of several cubic micrometres. The effect of the glass transition, cold crystallisation, melting and degree of crystallinity on L-TA measurements is investigated. The materials used are poly(ethylene terephthalate), polystyrene and fluorocarbon-coated poly(butylene terephthalate). The primary measurements are the micro- or localised analogues of thermomechanical analysis (L-TMA) and differential thermal analysis (L-DTA). The effect of applying a sinusoidal modulation to the temperature of the probe is also investigated. In the second part, conventional ultra-sharp inert AFM probes are used, in conjunction with a variable-temperature microscope stage, to conduct variable-temperature mechanical property-based imaging of phase-separated polymer blends and copolymers. Here, the temperature of the whole sample is varied and the temperature of the probe tip remains essentially the same as that of the sample. The primary AFM imaging mode is pulsed force mode (PFM-AFM). This is an intermittent contact (IC) method in which a mechanical modulation is applied to the probe cantilever. The methodology is demonstrated on a model 50:50 blend of polystyrene and poly(methyl methacrylate) (PS-PMMA) and three segmented polyurethane (SPU) elastomers containing different chain extenders. In doing so, it is shown that PFM-AFM imaging can be carried out successfully over a temperature range

In Vivo Biological Evaluation of High Molecular Weight Multifunctional Acid-Degradable Polymeric Drug Carriers with Structurally Different Ketals.

Science.gov (United States)

Shenoi, Rajesh A; Abbina, Srinivas; Kizhakkedathu, Jayachandran N

2016-11-14

Understanding the influence of degradable chemical moieties on in vivo degradation, tissue distribution, and excretion is critical for the design of novel biodegradable drug carriers. Polyketals have recently emerged as a promising therapeutic delivery platform due to their ability to degrade under mild acidic intracellular compartments and generation of nontoxic degradation products. However, the effect of chemical structure of the ketal groups on the in vivo degradation, biodistribution, and pharmacokinetics of water-soluble ketal-containing polymers has not been explored. In the present work, we synthesized high molecular weight, water-soluble biodegradable hyperbranched polyglycerols (BHPGs) through the incorporation of structurally different ketal groups into the main chain of highly biocompatible polyglycerols. BHPGs showed pH and ketal group structure dependent degradation in buffer solutions. When the polymers were intravenously administered in mice, a strong dependence of in vivo degradation, biodistribution, and clearance on the ketal group structure was observed. All the BHPGs demonstrated degradation and clearance in vivo, with minimal tissue accumulation. Interestingly, an unanticipated degradation behavior of BHPGs with structurally different ketal groups was observed in vivo in comparison to their degradation in buffer solutions. BHPGs with cyclohexyl ketal (CHK) and cyclopentyl ketal (CPK) groups degraded much faster and were cleared from circulation much rapidly, while BHPG with glycerol hydroxy butanone ketal (GHBK) group degraded at a much slower rate and exhibited similar plasma half-life as that of nondegradable HPG. BHPG-GHBK also showed significantly lower tissue accumulation than nondegradable HPG after 30 days of administration. The difference in in vivo degradation may be attributed to the difference in hydrophobic characteristics of different ketal containing polymers, which may change their interaction with proteins and cells in vivo

Application of positron annihilation to polymer and development of a radioisotopes-based pulsed slow positron beam apparatus

International Nuclear Information System (INIS)

Suzuki, Takenori

2004-01-01

Positrons injected into polymer behave as nanometer probes, which can detect the size and amount of intermolecular spaces among polymer structures. Although positrons can probe the characteristics of polymer, they induce a radiation effect on polymer samples. At low temperature, the radiation effect induces free electrons, which can be trapped in a shallow potential created among intermolecular structures after freezing molecular motions. These trapped electrons can be released after the disappearance of the shallow potential due to the reappearance of molecular motion above the relaxation temperature. Thus, positrons can be used as a probe for relaxation studies. Coincidence of Doppler broadening spectroscopy (CDBS) can improve the S/N ratio to 10 7 , which makes it possible to detect trace elements, since CDBS can separate the high-momentum component of core electrons. A pulsed slow positron beam apparatus is necessary for measuring holes in the polymer film and allows the measurement of the characteristics of thin film coated on semiconductors used widely in electronics industries. (author)

Reducing burn-in voltage loss in polymer solar cells by increasing the polymer crystallinity

KAUST Repository

Heumueller, Thomas; Mateker, William R.; Sachs-Quintana, I. T.; Vandewal, Koen; Bartelt, Jonathan A.; Burke, Timothy M.; Ameri, Tayebeh; Brabec, Christoph J.; McGehee, Michael D.

2014-01-01

In order to commercialize polymer solar cells, the fast initial performance losses present in many high efficiency materials will have to be managed. This burn-in degradation is caused by light-induced traps and its characteristics depend on which

Influence of processing and intrinsic polymer parameters on photochemical stability of polythiophene thin films

DEFF Research Database (Denmark)

Vesterager Madsen, Morten; Tromholt, Thomas; Böttiger, Arvid P.L.

2012-01-01

shielding effects were shown to have a negligible effect on the photochemical degradation rate. The results obtained in this work advance the understanding of polymer stability and will help improve the design of materials used for polymer solar cells resulting in longer lifetimes, which will push......Intrinsic polymer parameters such as regio-regularity, molecular weight, and crystallinity play an important role when studying polymer stability. 18 different batches of poly-3-hexyl-thiophene (P3HT) were degraded in a solar simulator (AM1.5G, 1000 W/m2) and the degradation kinetics were monitored....... The results suggest that the radical reaction responsible for the photodegradation takes place at terminal thiophene rings exposed at points were the conjugation is broken. This proposed mechanism is supported by the fact that stability scales with regio-regularity following the ratio of head...

Mechanical Degradation Onset of Polyethylene Oxide Used as a Hydrosoluble Model Polymer for Enhanced Oil Recovery Seuil de dégradation mécanique de solutions de polymères utilisés en récupération assistée des hydrocarbures

Directory of Open Access Journals (Sweden)

Dupas A.

2013-02-01

Full Text Available Water soluble polymers such as polyacrylamide are used in polymer flooding, which is an advanced technique of Enhanced Oil Recovery (EOR. It aims at improving crude oil displacement in reservoir by pushing it with a viscous injected fluid. Polymer flood is challenged by mechanical degradation of long macromolecules during intense flows. Many studies reported that above a critical extensional rate hbox{$varepsilon^{mathrm{cdot }}_{mathrm{c}}$} ε c · , polymer chains can break and lose their rheological properties. The molecular weight (M dependence of hbox{$varepsilon^{mathrm{cdot }}_{mathrm{c}}$} ε c · for dilute solutions in laminar flows was shown to follow a power law: hbox{$varepsilon^{mathrm{cdot }}_{mathrm{c}}$} ε c · ≈ Mw–k. An experimental study has been performed to investigate the onset of mechanical degradation in both laminar and turbulent flows and for both dilute and semi dilute polyethylene oxide aqueous solutions. It reveals that the exponent k strongly depends on the concentration and flow regimes and also on solvent quality. Results show that mechanical degradation mainly affects long chains, that it is favoured at high concentrations, under poor solvent conditions. They also evidence that the extensional viscosity at low strain rates decreases to the same extent as shear viscosities due to mechanical degradation. However, the decrease of the extensional viscous properties at high strain rates is much more pronounced. Les polymères hydrosolubles comme les polyacrylamides peuvent être utilisés en récupération assistée des hydrocarbures (Enhanced Oil Recovery (EOR par injection de polymère. Cette technique vise à augmenter la production de brut en le poussant du réservoir vers un puits producteur à l’aide d’une solution de polymère suffisamment visqueuse. Les polymères utilisés à cet effet ont des masses moléculaires supérieures à 106 g/mol, ce qui les rend sensibles à la dégradation. En raison

Degradation in tensile properties of aromatic polymers by electron beam irradiation

International Nuclear Information System (INIS)

Sasuga, T.; Hayakawa, N.; Yoshida, K.; Hagiwara, M.

1985-01-01

Electron beam irradiation effects of ten kinds of polymers containing various aromatic rings linked by functional groups in the main chain (aromatic polymer) were studied with reference to change in tensile properties. The polymers studied were polyimides 'Kapton H', and 'UPILEX', polyetherimide 'ULTEM', polyamides 'A-Film' and 'APH-50 (nomex type paper)', poly-ether-ether-ketone 'PEEK', polyarylate 'U-Polymer', polysulphones 'Udel-Polysulphone' and 'PES', and modified poly(phenylene oxide) 'NORYL'. Irradiation was carried out by use of electron beam at a dose rate of 5 x 10 3 Gy s -1 at room temperature. The elongation at break was the most severely influenced by the irradiation and it decreased with increasing dose. The order of radiation resistivity which was evaluated from the dose required for the elongation to become 50% and 20% of the initial value was as follows: Polyimide > PEEK > polyamide > polyetherimide > polyarylate > polysulphone, poly(phenylene oxide). Based on the above experimental results, an order is proposed for the radiation stability of the aromatic repeating units composing the main chain. (author)

Radiation effects in polymers for plastic scintillation detectors

International Nuclear Information System (INIS)

Pla-Dalmau, A.; Bross, A.D.; Hurlbut, C.R.; Moser, S.W.

1994-01-01

Recent developments in both scintillating plastic optical fibers and photon detection devices have spawned new applications for plastic scintillator detectors. This renewed attention has encouraged research that addresses the radiation stability of plastic scintillators. The optical quality of the polymer degrades with exposure to ionizing radiation and thus the light yield of the detector decreases. A complete understanding of all the mechanisms contributing to this radiation-induced degradation of the polymer can lead to techniques that will extend the radiation stability of these materials. Various radiation damage studies have been performed under different atmospheres and dose rates. Currently, the use of additives to preserve the optical properties of the polymer matrix under radiation is being investigated. The authors discuss the effect of certain antioxidants, plasticizers, and cross-linking agents on the radiation resilience of plastic scintillators

Interaction between a high purity magnesium surface and PCL and PLA coatings during dynamic degradation

International Nuclear Information System (INIS)

Chen Ying; Song Yang; Zhang Shaoxiang; Li Jianan; Zhao Changli; Zhang Xiaonong

2011-01-01

In this study, polycaprolactone (PCL) and polylactic acid (PLA) coatings were prepared on the surface of high purity magnesium (HPMs), respectively, and electrochemical and dynamic degradation tests were used to investigate the degradation behaviors of these polymer-coated HPMs. The experimental results indicated that two uniform and smooth polymer films with thicknesses between 15 and 20 μm were successfully prepared on the HPMs. Electrochemical tests showed that both PCL-coated and PLA-coated HPMs had higher free corrosion potentials (E corr ) and smaller corrosion currents (I corr ) in the modified simulated body fluid (m-SBF) at 37 0 C, compared to those of the uncoated HPMs. Dynamic degradation tests simulating the flow conditions in coronary arteries were carried out on a specific test platform. The weight of the specimens and the pH over the tests were recorded to characterize the corrosion performance of those samples. The surfaces of the specimens after the dynamic degradation tests were also examined. The data implied that there was a special interaction between HPM and its polymer coatings during the dynamic degradation tests, which undermined the corrosion resistance of the coated HPMs. A model was proposed to illustrate the interaction between the polymer coatings and HPM. This study also suggested that this reciprocity may also exist on the implanted magnesium stents coated with biodegradable polymers, which is a potential obstacle for the further development of drug-eluting magnesium stents.

Interaction between a high purity magnesium surface and PCL and PLA coatings during dynamic degradation

Energy Technology Data Exchange (ETDEWEB)

Chen Ying; Song Yang; Zhang Shaoxiang; Li Jianan; Zhao Changli; Zhang Xiaonong, E-mail: xnzhang@sjtu.edu.cn [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China)

2011-04-15

In this study, polycaprolactone (PCL) and polylactic acid (PLA) coatings were prepared on the surface of high purity magnesium (HPMs), respectively, and electrochemical and dynamic degradation tests were used to investigate the degradation behaviors of these polymer-coated HPMs. The experimental results indicated that two uniform and smooth polymer films with thicknesses between 15 and 20 {mu}m were successfully prepared on the HPMs. Electrochemical tests showed that both PCL-coated and PLA-coated HPMs had higher free corrosion potentials (E{sub corr}) and smaller corrosion currents (I{sub corr}) in the modified simulated body fluid (m-SBF) at 37 {sup 0}C, compared to those of the uncoated HPMs. Dynamic degradation tests simulating the flow conditions in coronary arteries were carried out on a specific test platform. The weight of the specimens and the pH over the tests were recorded to characterize the corrosion performance of those samples. The surfaces of the specimens after the dynamic degradation tests were also examined. The data implied that there was a special interaction between HPM and its polymer coatings during the dynamic degradation tests, which undermined the corrosion resistance of the coated HPMs. A model was proposed to illustrate the interaction between the polymer coatings and HPM. This study also suggested that this reciprocity may also exist on the implanted magnesium stents coated with biodegradable polymers, which is a potential obstacle for the further development of drug-eluting magnesium stents.

A novel bio-degradable polymer stabilized Ag/TiO2 nanocomposites and their catalytic activity on reduction of methylene blue under natural sun light.

Science.gov (United States)

Geetha, D; Kavitha, S; Ramesh, P S

2015-11-01

In the present work we defined a novel method of TiO2 doped silver nanocomposite synthesis and stabilization using bio-degradable polymers viz., chitosan (Cts) and polyethylene glycol (PEG). These polymers are used as reducing agents. The instant formation of AgNPs was analyzed by visual observation and UV-visible spectrophotometer. TiO2 nanoparticles doped at different concentrations viz., 0.03, 0.06 and 0.09mM on PEG/Cts stabilized silver (0.04wt%) were successfully synthesized. This study presents a simple route for the in situ synthesis of both metal and polymer confined within the nanomaterial, producing ternary hybrid inorganic-organic nanomaterials. The results reveal that they have higher photocatalytic efficiencies under natural sun light. The synthesized TiO2 doped Ag nanocomposites (NCs) were characterized by SEM/EDS, TEM, XRD, FTIR and DLS with zeta potential. The stability of Ag/TiO2 nanocomposite is due to the high negative values of zeta potential and capping of constituents present in the biodegradable polymer which is evident from zeta potential and FT-IR studies. The XRD and EDS pattern of synthesized Ag/TiO2 NCs showed their crystalline structure, with face centered cubic geometry oriented in (111) plane. AFM and DLS studies revealed that the diameter of stable Ag/TiO2 NCs was approximately 35nm. Moreover the catalytic activity of synthesize Ag/TiO2 NCs in the reduction of methylene blue was studied by UV-visible spectrophotometer. The synthesized Ag/TiO2 NCs are observed to have a good catalytic activity on the reduction of methylene blue by bio-degradable which is confirmed by the decrease in absorbance maximum value of methylene blue with respect to time using UV-vis spectrophotometer. The significant enhancement in the photocatalytic activity of Ag/TiO2 nanocomposites under sun light irradiation can be ascribed to the effect of noble metal Ag by acting as electron traps in TiO2 band gap. Copyright © 2015. Published by Elsevier Inc.

Radiolytic degradation and stability of polycarbonate

International Nuclear Information System (INIS)

Araujo, E.S. de.

1993-01-01

The radiolytic stability of polycarbonate was studied using national commercial additives, employed in the photo and thermo-oxidative stabilization of polymers. Among several additives tested only two showed the efficiency to radiolytic protection: one quencher and one radical scavenger. It was derived a linear relation that provides by slope of the straight line the degree of degradation (scissions), G, and the factors of radiolytic protection P (degree of protection) and CE (capture of energy) conferred by radioprotector additive easily. Therefore the method developed in this work (viscosity) to study the molecular degradation and stability of polymers is a simply and precise method. The synergic mixture of two additives (1% of weight total) confers at polycarbonate excellent radiolytic protection of 98% (20 - 40 kGy) reducing the G value of 16.7 to only 0.4. (author). 69 refs, 31 figs, 17 tabs

Degradability of polylactide films by commercial microbiological preparations for household composters

Directory of Open Access Journals (Sweden)

Morawska Magda

2017-09-01

Full Text Available Environmentally friendly polymers such as polylactide are increasingly becoming available for use in packaging applications. The main advantages of polylactide packaging are evident. Polylactide is based on renewable resources and can be degraded in compost or soil. The studies on degradability of polylactide (PLA films by commercial preparation of mixture of multi-active saprophytic soil microorganisms, bacteria, actinomycetes and fungi have been done. Unmodified PLA film, metalized co-extruded PLA film and modified by silicon oxide PLA film were incubated in the liquid nutritious medium (TSB prepared to support the growth of microorganisms. The degradability of polylactide films was examined by macro and microscopic observations of surface, changes of mass and crystallinity of polymer samples before and after incubation. The obtained results indicate that the degradation of polylactide was accelerated by the presence of a biological vaccine. It was found that PLA degradation in the inoculated TSB broth was a result of both: enzymatic and chemical hydrolysis.

Direct measurement of the microscale conductivity of conjugated polymer monolayers

DEFF Research Database (Denmark)

Bøggild, Peter; Grey, Francois; Hassenkam, T.

2000-01-01

The in-plane conductivity of conjugated polymer monolayers is mapped here for the first time on the microscale using a novel scanning micro four-point probe (see Figure). The probe allows the source, drain, and voltage electrodes to be positioned within the same domain and the mapping results...

Surfactant-Polymer Interaction for Improved Oil Recovery; FINAL

International Nuclear Information System (INIS)

Gabitto, Jorge; Mohanty, Kishore K.

2002-01-01

The goal of this research was to use the interaction between a surfactant and a polymer for efficient displacement of tertiary oil by improving slug integrity, oil solubility in the displacing fluid and mobility control. Surfactant-polymer flooding has been shown to be highly effective in laboratory-scale linear floods. The focus of this proposal is to design an inexpensive surfactant-polymer mixture that can efficiently recover tertiary oil by avoiding surfactant slug degradation and viscous/heterogeneity fingering

Modeling the effect of probe force on length measurements on polymer parts

DEFF Research Database (Denmark)

Mohammadi, Ali; Sonne, Mads Rostgaard; Dalla Costa, Giuseppe

2016-01-01

Measurement uncertainty at micrometer level is in the future going to be very common in dimensional measurements on polymer parts. Accurate dimensional measurement of polymer parts is becoming a key and common practice in the industry, especially when micrometer tolerances are required. When cond...

In vivo integrity of polymer-coated gold nanoparticles

Science.gov (United States)

Kreyling, Wolfgang G.; Abdelmonem, Abuelmagd M.; Ali, Zulqurnain; Alves, Frauke; Geiser, Marianne; Haberl, Nadine; Hartmann, Raimo; Hirn, Stephanie; de Aberasturi, Dorleta Jimenez; Kantner, Karsten; Khadem-Saba, Gülnaz; Montenegro, Jose-Maria; Rejman, Joanna; Rojo, Teofilo; de Larramendi, Idoia Ruiz; Ufartes, Roser; Wenk, Alexander; Parak, Wolfgang J.

2015-07-01

Inorganic nanoparticles are frequently engineered with an organic surface coating to improve their physicochemical properties, and it is well known that their colloidal properties may change upon internalization by cells. While the stability of such nanoparticles is typically assayed in simple in vitro tests, their stability in a mammalian organism remains unknown. Here, we show that firmly grafted polymer shells around gold nanoparticles may degrade when injected into rats. We synthesized monodisperse radioactively labelled gold nanoparticles (198Au) and engineered an 111In-labelled polymer shell around them. Upon intravenous injection into rats, quantitative biodistribution analyses performed independently for 198Au and 111In showed partial removal of the polymer shell in vivo. While 198Au accumulates mostly in the liver, part of the 111In shows a non-particulate biodistribution similar to intravenous injection of chelated 111In. Further in vitro studies suggest that degradation of the polymer shell is caused by proteolytic enzymes in the liver. Our results show that even nanoparticles with high colloidal stability can change their physicochemical properties in vivo.

Probe based manipulation and assembly of nanowires into organized mesostructures

Science.gov (United States)

Reynolds, K.; Komulainen, J.; Kivijakola, J.; Lovera, P.; Iacopino, D.; Pudas, M.; Vähäkangas, J.; Röning, J.; Redmond, G.

2008-12-01

A convenient approach to patterning inorganic and organic nanowires using a novel probe manipulator is presented. The system utilizes an electrochemically etched tungsten wire probe mounted onto a 3D actuator that is directed by a 3D controller. When it is engaged by the user, the movement of the probe and the forces experienced by the tip are simultaneously reported in real time. Platinum nanowires are manipulated into organized mesostructures on silicon chip substrates. In particular, individual nanowires are systematically removed from aggregates, transferred to a chosen location, and manipulated into complex structures in which selected wires occupy specific positions with defined orientations. Rapid prototyping of complex mesostructures, by pushing, rotating and bending conjugated polymer, i.e., polyfluorene, nanowires into various configurations, is also achieved. By exploiting the strong internal axial alignment of polymer chains within the polyfluorene nanowires, mesostructures tailored to exhibit distinctly anisotropic optical properties, such as birefringence and photoluminescence dichroism, are successfully assembled on fused silica substrates.

Probe based manipulation and assembly of nanowires into organized mesostructures

International Nuclear Information System (INIS)

Reynolds, K; Lovera, P; Iacopino, D; Redmond, G; Komulainen, J; Pudas, M; Vaehaekangas, J; Kivijakola, J; Roening, J

2008-01-01

A convenient approach to patterning inorganic and organic nanowires using a novel probe manipulator is presented. The system utilizes an electrochemically etched tungsten wire probe mounted onto a 3D actuator that is directed by a 3D controller. When it is engaged by the user, the movement of the probe and the forces experienced by the tip are simultaneously reported in real time. Platinum nanowires are manipulated into organized mesostructures on silicon chip substrates. In particular, individual nanowires are systematically removed from aggregates, transferred to a chosen location, and manipulated into complex structures in which selected wires occupy specific positions with defined orientations. Rapid prototyping of complex mesostructures, by pushing, rotating and bending conjugated polymer, i.e., polyfluorene, nanowires into various configurations, is also achieved. By exploiting the strong internal axial alignment of polymer chains within the polyfluorene nanowires, mesostructures tailored to exhibit distinctly anisotropic optical properties, such as birefringence and photoluminescence dichroism, are successfully assembled on fused silica substrates.

The effect of mechanical loads on the degradation of aliphatic biodegradable polyesters.

Science.gov (United States)

Li, Ying; Chu, Zhaowei; Li, Xiaoming; Ding, Xili; Guo, Meng; Zhao, Haoran; Yao, Jie; Wang, Lizhen; Cai, Qiang; Fan, Yubo

2017-06-01

Aliphatic biodegradable polyesters have been the most widely used synthetic polymers for developing biodegradable devices as alternatives for the currently used permanent medical devices. The performances during biodegradation process play crucial roles for final realization of their functions. Because physiological and biochemical environment in vivo significantly affects biodegradation process, large numbers of studies on effects of mechanical loads on the degradation of aliphatic biodegradable polyesters have been launched during last decades. In this review article, we discussed the mechanism of biodegradation and several different mechanical loads that have been reported to affect the biodegradation process. Other physiological and biochemical factors related to mechanical loads were also discussed. The mechanical load could change the conformational strain energy and morphology to weaken the stability of the polymer. Besides, the load and pattern could accelerate the loss of intrinsic mechanical properties of polymers. This indicated that investigations into effects of mechanical loads on the degradation should be indispensable. More combination condition of mechanical loads and multiple factors should be considered in order to keep the degradation rate controllable and evaluate the degradation process in vivo accurately. Only then can the degradable devise achieve the desired effects and further expand the special applications of aliphatic biodegradable polyesters.

Effect of chemical functionalization on the electrochemical properties of conducting polymers. Modification of polyaniline by diazonium ion coupling and subsequent reductive degradation

Energy Technology Data Exchange (ETDEWEB)

Acevedo, Diego F.; Rivarola, Claudia R.; Miras, Maria C. [Departamento de Quimica, Universidad Nacional de Rio Cuarto, Ruta Nacional 8, Km 601, X5804ZAB, Rio Cuarto, Cordoba (Argentina); Barbero, Cesar A., E-mail: cbarbero@exa.unrc.edu.a [Departamento de Quimica, Universidad Nacional de Rio Cuarto, Ruta Nacional 8, Km 601, X5804ZAB, Rio Cuarto, Cordoba (Argentina)

2011-04-01

The electrochemical properties of polyaniline (PANI) can be altered by coupling the polymer with aryldiazonium ions. The ions are synthesized by diazotization of aromatic primary amines (1-aminoanthraquinone, sulphadiazine and 4-cyanoaniline) bearing functional groups which are then linked to the polyaniline backbone. All materials produced are electroactive, suggesting that the reaction involves coupling of the diazonium ion with the aromatic rings and not nucleophilic substitution by the aminic nitrogen of PANI on the aryl cations. The electrochemical properties of the modified polymers are different to those of PANI, likely due to electronic and steric effects of the attached groups. Reductive degradation of the azo linkages, using dithionite ion, removes the attached moieties leaving primary amino groups attached to the polyaniline backbone. In that way, the effect of the attached groups on the electrochemical properties of PANI is eliminated. FTIR spectroscopy measurement of the different polymers supports the proposed mechanism. Using the method a polymer containing redox (anthraquinone) groups, which could be used for charge storage, is obtained. Additionally a material containing sulphadiazine moieties, which can be released in vivo by bacterial activity, is also produced. The molecule is a well-known sulfa drug with bacteriostatic activity. The reaction sequence seems to be of general application to modify polyanilines, by attaching functional groups, and then to produce a PANI backbone bearing primary amino groups. Evidence is presented on the kinetic control of attached group removal.

Effect of chemical functionalization on the electrochemical properties of conducting polymers. Modification of polyaniline by diazonium ion coupling and subsequent reductive degradation

International Nuclear Information System (INIS)

Acevedo, Diego F.; Rivarola, Claudia R.; Miras, Maria C.; Barbero, Cesar A.

2011-01-01

The electrochemical properties of polyaniline (PANI) can be altered by coupling the polymer with aryldiazonium ions. The ions are synthesized by diazotization of aromatic primary amines (1-aminoanthraquinone, sulphadiazine and 4-cyanoaniline) bearing functional groups which are then linked to the polyaniline backbone. All materials produced are electroactive, suggesting that the reaction involves coupling of the diazonium ion with the aromatic rings and not nucleophilic substitution by the aminic nitrogen of PANI on the aryl cations. The electrochemical properties of the modified polymers are different to those of PANI, likely due to electronic and steric effects of the attached groups. Reductive degradation of the azo linkages, using dithionite ion, removes the attached moieties leaving primary amino groups attached to the polyaniline backbone. In that way, the effect of the attached groups on the electrochemical properties of PANI is eliminated. FTIR spectroscopy measurement of the different polymers supports the proposed mechanism. Using the method a polymer containing redox (anthraquinone) groups, which could be used for charge storage, is obtained. Additionally a material containing sulphadiazine moieties, which can be released in vivo by bacterial activity, is also produced. The molecule is a well-known sulfa drug with bacteriostatic activity. The reaction sequence seems to be of general application to modify polyanilines, by attaching functional groups, and then to produce a PANI backbone bearing primary amino groups. Evidence is presented on the kinetic control of attached group removal.

Synthesis and photocatalytic activity of TiO2/conjugated polymer complex nanoparticles

Institute of Scientific and Technical Information of China (English)

Shi Xiong Min; Fang Wang; Lei Feng; Yong Chun Tong; Zi Rong Yang

2008-01-01

A photocatalyst of nanometer TiO2/conjugated polymer complex was successfully synthesized and characterized by spectroscopic methods and photocatalytic experiments. The complex photocatalyst could be activated by absorbing both ultraviolet and visible light (λ=190-800nm). Methylene blue (MB) could be degraded more efficiently on the complex photocatalyst than on the TiO2 under natural light. The conjugated polymer played a promoting role in the photocatalytic degradation of MB. The calcination temperature had an important effect in degradation of dye and could be summarized as 260℃＞300℃＞340℃＞220℃＞180℃.

Degradation of oxo-biodegradable plastic by Pleurotus ostreatus.

Science.gov (United States)

da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Nunes, Mateus Dias; da Silva, Marliane de Cássia Soares; Kasuya, Maria Catarina Megumi

2013-01-01

Growing concerns regarding the impact of the accumulation of plastic waste over several decades on the environmental have led to the development of biodegradable plastic. These plastics can be degraded by microorganisms and absorbed by the environment and are therefore gaining public support as a possible alternative to petroleum-derived plastics. Among the developed biodegradable plastics, oxo-biodegradable polymers have been used to produce plastic bags. Exposure of this waste plastic to ultraviolet light (UV) or heat can lead to breakage of the polymer chains in the plastic, and the resulting compounds are easily degraded by microorganisms. However, few studies have characterized the microbial degradation of oxo-biodegradable plastics. In this study, we tested the capability of Pleurotus ostreatus to degrade oxo-biodegradable (D2W) plastic without prior physical treatment, such as exposure to UV or thermal heating. After 45 d of incubation in substrate-containing plastic bags, the oxo-biodegradable plastic, which is commonly used in supermarkets, developed cracks and small holes in the plastic surface as a result of the formation of hydroxyl groups and carbon-oxygen bonds. These alterations may be due to laccase activity. Furthermore, we observed the degradation of the dye found in these bags as well as mushroom formation. Thus, P. ostreatus degrades oxo-biodegradable plastics and produces mushrooms using this plastic as substrate.

Degradation of oxo-biodegradable plastic by Pleurotus ostreatus.

Directory of Open Access Journals (Sweden)

José Maria Rodrigues da Luz

Full Text Available Growing concerns regarding the impact of the accumulation of plastic waste over several decades on the environmental have led to the development of biodegradable plastic. These plastics can be degraded by microorganisms and absorbed by the environment and are therefore gaining public support as a possible alternative to petroleum-derived plastics. Among the developed biodegradable plastics, oxo-biodegradable polymers have been used to produce plastic bags. Exposure of this waste plastic to ultraviolet light (UV or heat can lead to breakage of the polymer chains in the plastic, and the resulting compounds are easily degraded by microorganisms. However, few studies have characterized the microbial degradation of oxo-biodegradable plastics. In this study, we tested the capability of Pleurotus ostreatus to degrade oxo-biodegradable (D2W plastic without prior physical treatment, such as exposure to UV or thermal heating. After 45 d of incubation in substrate-containing plastic bags, the oxo-biodegradable plastic, which is commonly used in supermarkets, developed cracks and small holes in the plastic surface as a result of the formation of hydroxyl groups and carbon-oxygen bonds. These alterations may be due to laccase activity. Furthermore, we observed the degradation of the dye found in these bags as well as mushroom formation. Thus, P. ostreatus degrades oxo-biodegradable plastics and produces mushrooms using this plastic as substrate.

Degradation of Oxo-Biodegradable Plastic by Pleurotus ostreatus

Science.gov (United States)

da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Nunes, Mateus Dias; da Silva, Marliane de Cássia Soares; Kasuya, Maria Catarina Megumi

2013-01-01

Growing concerns regarding the impact of the accumulation of plastic waste over several decades on the environmental have led to the development of biodegradable plastic. These plastics can be degraded by microorganisms and absorbed by the environment and are therefore gaining public support as a possible alternative to petroleum-derived plastics. Among the developed biodegradable plastics, oxo-biodegradable polymers have been used to produce plastic bags. Exposure of this waste plastic to ultraviolet light (UV) or heat can lead to breakage of the polymer chains in the plastic, and the resulting compounds are easily degraded by microorganisms. However, few studies have characterized the microbial degradation of oxo-biodegradable plastics. In this study, we tested the capability of Pleurotus ostreatus to degrade oxo-biodegradable (D2W) plastic without prior physical treatment, such as exposure to UV or thermal heating. After 45 d of incubation in substrate-containing plastic bags, the oxo-biodegradable plastic, which is commonly used in supermarkets, developed cracks and small holes in the plastic surface as a result of the formation of hydroxyl groups and carbon-oxygen bonds. These alterations may be due to laccase activity. Furthermore, we observed the degradation of the dye found in these bags as well as mushroom formation. Thus, P. ostreatus degrades oxo-biodegradable plastics and produces mushrooms using this plastic as substrate. PMID:23967057

Evaluation of atmospheric solid analysis probe ionization coupled to ion mobility mass spectrometry for characterization of poly(ether ether ketone) polymers

Energy Technology Data Exchange (ETDEWEB)

Cossoul, Emilie; Hubert-Roux, Marie; Sebban, Muriel [Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex (France); Churlaud, Florence [Arkema, Centre d’Etude de Recherche et Développement, 27470 Serquigny (France); Oulyadi, Hassan [Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex (France); Afonso, Carlos, E-mail: carlos.afonso@univ-rouen.fr [Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex (France)

2015-01-26

Highlights: • Solvent free approach. • Production of intact small oligomers of PEEK with ASAP ionization. • Comparison of the MS/MS spectra from M{sup +}· and [M + H]{sup +} precursor ions. • Identification of end-groups using tandem mass spectrometry. - Abstract: Recently, the interest of the coupling between atmospheric solid analysis probe (ASAP) and ion mobility–mass spectrometry has been revealed in the field of polymers. This method associates a direct ionization technique with a bi-dimensional separation method. Poly(ether ether ketones) (PEEK) belong to the family of the poly(aryl ether ketones) (PAEK) which are high performance aromatic polymers usually used in aerospace, electronics and nuclear industries. PEEK are important commercial thermoplastics with excellent chemical resistance and good mechanical properties. Because of their low solubility, few structural characterization studies of PEEK have been reported. In mass spectrometry, only MALDI-TOF analyses for polymer synthesis monitoring have been described with the use of strong acids such as sulfuric acid. This work demonstrates that ASAP is particularly efficient for analysis of PEEK in a solvent free approach with the production of intact small oligomers (n ≤ 2). Five types of PEEK oligomers with different end-groups were evidenced. With MALDI-TOF, the same end-groups with almost the same relative abundance were obtained which support the hypothesis that the oligomers detected in ASAP are intact small oligomers and not fragments or pyrolysis products. This is particularly interesting as generally the ASAP analysis of polymers yields pyrolysis products with the loss of end-group information. The end-groups assignments have been confirmed by tandem mass spectrometry (MS/MS) experiments on the M{sup +}· molecular ions, which allowed highlighting some specific neutral or radical losses as well as two diagnostic product ions. Thus, ASAP-IM/MS/MS proves to be a fast and efficient

Molecular dynamics modeling of polymer flammability

International Nuclear Information System (INIS)

Nyden, M.R.; Brown, J.E.; Lomakin, S.M.

1992-01-01

Molecular dynamic simulations were used to identify factors which promote char formation during the thermal degradation of polymers. Computer movies based on these simulations, indicate that cross-linked model polymers tend to undergo further cross-linking when burned, eventually forming a high molecular weight, thermally stable char. This paper reports that the prediction was confirmed by char yield measurements made on γ and e - -irradiated polyethylene and chemically cross-linked poly(methyl methacrylate)

Future of radiation processing of polymers

International Nuclear Information System (INIS)

Chapiro, A.; Tabata, Y.; Stannett, V.; Dole, M.; Dobo, J.; Charlesby, A.

1990-01-01

The present development of radiation processing in the polymer field including well established technologies, with large scale productions and substantial markets, such as: crosslinking; curing of monomer-polymer formulations; sterilization of plastic supplies; are discussed. The manufacture of sophisticated devices with low volume production but large added value: electronic devices; resistors and several promising applications for which only small commercial productions are on stream today: chain degradation; polymerization; graft copolymerization, are reviewed. (author)

Multifunctional PHPMA-Derived Polymer for Ratiometric pH Sensing, Fluorescence Imaging, and Magnetic Resonance Imaging.

Science.gov (United States)

Su, Fengyu; Agarwal, Shubhangi; Pan, Tingting; Qiao, Yuan; Zhang, Liqiang; Shi, Zhengwei; Kong, Xiangxing; Day, Kevin; Chen, Meiwan; Meldrum, Deirdre; Kodibagkar, Vikram D; Tian, Yanqing

2018-01-17

In this paper, we report synthesis and characterization of a novel multimodality (MRI/fluorescence) probe for pH sensing and imaging. A multifunctional polymer was derived from poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and integrated with a naphthalimide-based-ratiometric fluorescence probe and a gadolinium-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid complex (Gd-DOTA complex). The polymer was characterized using UV-vis absorption spectrophotometry, fluorescence spectrofluorophotometry, magnetic resonance imaging (MRI), and confocal microscopy for optical and MRI-based pH sensing and cellular imaging. In vitro labeling of macrophage J774 and esophageal CP-A cell lines shows the polymer's ability to be internalized in the cells. The transverse relaxation time (T 2 ) of the polymer was observed to be pH-dependent, whereas the spin-lattice relaxation time (T 1 ) was not. The pH probe in the polymer shows a strong fluorescence-based ratiometric pH response with emission window changes, exhibiting blue emission under acidic conditions and green emission under basic conditions, respectively. This study provides new materials with multimodalities for pH sensing and imaging.

Polypeptoids from N -Substituted Glycine N -Carboxyanhydrides: Hydrophilic, Hydrophobic, and Amphiphilic Polymers with Poisson Distribution

KAUST Repository

Fetsch, Corinna

2011-09-13

Preparation of defined and functional polymers has been one of the hottest topics in polymer science and drug delivery in the recent decade. Also, research on (bio)degradable polymers gains more and more interest, in particular at the interface of these two disciplines. However, in the majority of cases, combination of definition, functionality and degradability, is problematic. Here we present the preparation and characterization (MALDI-ToF MS, NMR, GPC) of nonionic hydrophilic, hydrophobic, and amphiphilic N-substituted polyglycines (polypeptoids), which are expected to be main-chain degradable and are able to disperse a hydrophobic model compound in aqueous media. Polymerization kinetics suggest that the polymerization is well controlled with strictly linear pseudo first-order kinetic plots to high monomer consumption. Moreover, molar mass distributions of products are Poisson-type and molar mass can be controlled by the monomer to initiator ratio. The presented polymer platform is nonionic, backbone degradable, and synthetically highly flexible and may therefore be valuable for a broad range of applications, in particular as a biomaterial. © 2011 American Chemical Society.

Polypeptoids from N -Substituted Glycine N -Carboxyanhydrides: Hydrophilic, Hydrophobic, and Amphiphilic Polymers with Poisson Distribution

KAUST Repository

Fetsch, Corinna; Grossmann, Arlett; Holz, Lisa; Nawroth, Jonas F.; Luxenhofer, Robert

2011-01-01

Preparation of defined and functional polymers has been one of the hottest topics in polymer science and drug delivery in the recent decade. Also, research on (bio)degradable polymers gains more and more interest, in particular at the interface of these two disciplines. However, in the majority of cases, combination of definition, functionality and degradability, is problematic. Here we present the preparation and characterization (MALDI-ToF MS, NMR, GPC) of nonionic hydrophilic, hydrophobic, and amphiphilic N-substituted polyglycines (polypeptoids), which are expected to be main-chain degradable and are able to disperse a hydrophobic model compound in aqueous media. Polymerization kinetics suggest that the polymerization is well controlled with strictly linear pseudo first-order kinetic plots to high monomer consumption. Moreover, molar mass distributions of products are Poisson-type and molar mass can be controlled by the monomer to initiator ratio. The presented polymer platform is nonionic, backbone degradable, and synthetically highly flexible and may therefore be valuable for a broad range of applications, in particular as a biomaterial. © 2011 American Chemical Society.

Hydrolytic Degradation of Poly (ethylene oxide)-block-Polycaprolactone Worm Micelles

OpenAIRE

Geng, Yan; Discher, Dennis E.

2005-01-01

Spherical micelles and nanoparticles made with degradable polymers have been of great interest for therapeutic application, but degradation induced changes in a spherical morphology can be subtle and mechanism/kinetics appears poorly understood. Here, we report the first preparation of giant and flexible worm micelles self-assembled from degradable copolymer poly (ethylene oxide)-block-polycaprolactone. Such worm micelles spontaneously shorten to generate spherical micelles, triggered by poly...

In Vitro Degradation of PHBV Scaffolds and nHA/PHBV Composite Scaffolds Containing Hydroxyapatite Nanoparticles for Bone Tissue Engineering

Directory of Open Access Journals (Sweden)

Naznin Sultana

2012-01-01

Full Text Available This paper investigated the long-term in vitro degradation properties of scaffolds based on biodegradable polymers and osteoconductive bioceramic/polymer composite materials for the application of bone tissue engineering. The three-dimensional porous scaffolds were fabricated using emulsion-freezing/freeze-drying technique using poly(hydroxybutyrate-co-hydroxyvalerate (PHBV which is a natural biodegradable and biocompatible polymer. Nanosized hydroxyapatite (nHA particles were successfully incorporated into the PHBV scaffolds to render the scaffolds osteoconductive. The PHBV and nHA/PHBV scaffolds were systematically evaluated using various techniques in terms of mechanical strength, porosity, porous morphology, and in vitro degradation. PHBV and nHA/PHBV scaffolds degraded over time in phosphate-buffered saline at 37°C. PHBV polymer scaffolds exhibited slow molecular weight loss and weight loss in the in vitro physiological environment. Accelerated weight loss was observed in nHA incorporated PHBV composite scaffolds. An increasing trend of crystallinity was observed during the initial period of degradation time. The compressive properties decreased more than 40% after 5-month in vitro degradation. Together with interconnected pores, high porosity, suitable mechanical properties, and slow degradation profile obtained from long-term degradation studies, the PHBV scaffolds and osteoconductive nHA/PHBV composite scaffolds showed promises for bone tissue engineering application.

Resolving Properties of Polymers and Nanoparticle Assembly through Coarse-Grained Computational Studies.

Energy Technology Data Exchange (ETDEWEB)

Grest, Gary S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2017-09-01

Coupled length and time scales determine the dynamic behavior of polymers and polymer nanocomposites and underlie their unique properties. To resolve the properties over large time and length scales it is imperative to develop coarse grained models which retain the atomistic specificity. Here we probe the degree of coarse graining required to simultaneously retain significant atomistic details a nd access large length and time scales. The degree of coarse graining in turn sets the minimum length scale instrumental in defining polymer properties and dynamics. Using polyethylene as a model system, we probe how the coarse - graining scale affects the measured dynamics with different number methylene group s per coarse - grained beads. Using these models we simulate polyethylene melts for times over 500 ms to study the viscoelastic properties of well - entangled polymer melts and large nanoparticle assembly as the nanoparticles are driven close enough to form nanostructures.

Formation of microscopic particles during the degradation of different polymers.

Science.gov (United States)

Lambert, Scott; Wagner, Martin

2016-10-01

This study investigated the formation and size distribution of microscopic plastic particles during the degradation of different plastic materials. Particle number concentrations in the size range 30 nm-60 μm were measured by nanoparticle tracking analysis (NTA) and Coulter Counter techniques. Each of the plastics used exhibited a measureable increase in the release of particles into the surrounding solution, with polystyrene (PS) and polylactic acid (PLA) generating the highest particle concentrations. After 112 d, particle concentrations ranged from 2147 particles ml(-1) in the control (C) to 92,465 particles ml(-1) for PS in the 2-60 μm size class; 1.2 × 10(5) particles ml(-1) (C) to 11.6 × 10(6) for PLA in the 0.6-18 μm size class; and 0.2 × 10(8) particles ml(-1) (C) to 6.4 × 10(8) particles ml(-1) for PS in the 30-2000 nm size class (84 d). A classification of samples based on principal component analysis showed a separation between the different plastic types, with PLA clustering individually in each of the three size classes. In addition, particle size distribution models were used to examine more closely the size distribution data generated by NTA. Overall, the results indicate that at the beginning of plastic weathering processes chain scission at the polymer surface causes many very small particles to be released into the surrounding solution and those concentrations may vary between plastic types. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemical stabilization of polymers: Implications for dermal exposure to additives.

Science.gov (United States)

Bartsch, N; Girard, M; Schneider, L; Weijgert, V Van De; Wilde, A; Kappenstein, O; Vieth, B; Hutzler, C; Luch, A

2018-04-16

Technical benefits of additives in polymers stand in marked contrast to their associated health risks. Here, a multi-analyte method based on gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) was developed to quantify polymer additives in complex matrices such as low-density polyethylene (LDPE) and isolated human skin layers after dermal exposure ex vivo. That way both technical aspects and dermal exposure were investigated. The effects of polymer additivation on the material were studied using the example of LDPE. To this end, a tailor-made polymer was applied in aging studies that had been furnished with two different mixtures of phenol- and diarylamine-based antioxidants, plasticizers and processing aids. Upon accelerated thermo-oxidative aging of the material, the formation of LDPE degradation products was monitored with attenuated total reflectance-Fourier transformed infrared (ATR-FTIR) spectroscopy. Compared to pure LDPE, a protective effect of added antioxidants could be observed on the integrity of the polymer. Further, thermo-oxidative degradation of the additives and its kinetics were investigated using LDPE or squalane as matrix. The half-lives of additives in both matrices revealed significant differences between the tested additives as well as between LDPE and squalane. For instance, 2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol (Antioxidant 2246) showed a half-life 12 times lower when incorporated in LDPE as compared to squalane. As a model for dermal exposure of consumers, human skin was brought into contact with the tailor-made LDPE containing additives ex vivo in static Franz diffusion cells. The skin was then analyzed for additives and decomposition products. This study proved 10 polymer additives of diverse pysicochemical properties and functionalities to migrate out of the polymer and eventually overcome the intact human skin barrier during contact. Moreover, their individual distribution within

A review on mechanical considerations for chronically-implanted neural probes

Science.gov (United States)

Lecomte, Aziliz; Descamps, Emeline; Bergaud, Christian

2018-06-01

This review intends to present a comprehensive analysis of the mechanical considerations for chronically-implanted neural probes. Failure of neural electrical recordings or stimulation over time has shown to arise from foreign body reaction and device material stability. It seems that devices that match most closely with the mechanical properties of the brain would be more likely to reduce the mechanical stress at the probe/tissue interface, thus improving body acceptance. The use of low Young’s modulus polymers instead of hard substrates is one way to enhance this mechanical mimetism, though compliance can be achieved through a variety of means. The reduction of probe width and thickness in comparison to a designated length, the use of soft hydrogel coatings and the release in device tethering to the skull, can also improve device compliance. Paradoxically, the more compliant the device, the more likely it will fail during the insertion process in the brain. Strategies have multiplied this past decade to offer partial or temporary stiffness to the device to overcome this buckling effect. A detailed description of the probe insertion mechanisms is provided to analyze potential sources of implantation failure and the need for a mechanically-enhancing structure. This leads us to present an overview of the strategies that have been put in place over the last ten years to overcome buckling issues. Particularly, great emphasis is put on bioresorbable polymers and their assessment for neural applications. Finally, a discussion is provided on some of the key features for the design of mechanically-reliable, polymer-based next generation of chronic neuroprosthetic devices.

Sago Starch-Mixed Low-Density Polyethylene Biodegradable Polymer: Synthesis and Characterization

Directory of Open Access Journals (Sweden)

Md Enamul Hoque

2013-01-01

Full Text Available This research focuses on synthesis and characterization of sago starch-mixed LDPE biodegradable polymer. Firstly, the effect of variation of starch content on mechanical property (elongation at break and Young’s modulus and biodegradability of the polymer was studied. The LDPE was combined with 10%, 30%, 50%, and 70% of sago for this study. Then how the cross-linking with trimethylolpropane triacrylate (TMPTA and electron beam (EB irradiation influence the mechanical and thermal properties of the polymer was investigated. In the 2nd study, to avoid overwhelming of data LDPE polymer was incorporated with only 50% of starch. The starch content had direct influence on mechanical property and biodegradability of the polymer. The elongation at break decreased with increase of starch content, while Young’s modulus and mass loss (i.e., degradation were found to increase with increase of starch content. Increase of cross-linker (TMPTA and EB doses also resulted in increased Young’s modulus of the polymer. However, both cross-linking and EB irradiation processes rendered lowering of polymer’s melting temperature. In conclusion, starch content and modification processes play significant roles in controlling mechanical, thermal, and degradation properties of the starch-mixed LDPE synthetic polymer, thus providing the opportunity to modulate the polymer properties for tailored applications.

CLASSIFICATION OF BIODEGRADABLE POLYMERS

Directory of Open Access Journals (Sweden)

I. I. Karpunin

2015-01-01

Full Text Available The executed investigations have made it possible to ascertain that a morphological structure of starch granules mainly determine technological peculiarities of starch isolation from raw material, its modification and its later use. Morphological structure of starch granules primarily depends on type of plant starch-containing raw material which has been used for its isolation. Class of raw material exerts a strong impact on the shape and size of the granules. Linear “light” amylose chains and “heavy” amylopectin branch chains form a starch granule ultrastructure. X-ray research has proved that starch granules are characterized by presence of interlacing amorphous and crystalline regions. In this case polymer orientation using stretching of the obtained end product influences on its physical and mechanical  indices which are increasing due to polymer orientation. For the purpose of packaging orientation of polymer films can solve such important problems as significant improvement of operational properties, creation of  thermosetting film materials, improvement of qualitative indices of the recycled film.Results of the conducted research have proved the fact that it is necessary to make changes in technology in order to increase biological degradability of the recycled packaging made from polymers and improve physical and mechanical indices. In this regard film production technology presupposes usage of such substances as stark and others which are characterized by rather large presence of branch chains of molecules and interlacing amorphous and crystalline regions. Such approach makes it possible to obtain after-use package which is strong and quickly degradable by micro-organisms.

A phenomenological constitutive model for the nonlinear viscoelastic responses of biodegradable polymers

KAUST Repository

Khan, Kamran; El Sayed, Tamer S.

2012-01-01

We formulate a constitutive framework for biodegradable polymers that accounts for nonlinear viscous behavior under regimes with large deformation. The generalized Maxwell model is used to represent the degraded viscoelastic response of a polymer

A statistical design of experiments for optimizing the MALDI-TOF-MS sample preparation of polymers. An application in the assessment of the thermo-mechanical degradation mechanisms of poly (ethylene terephthalate)

International Nuclear Information System (INIS)

Badia, J.D.; Stroemberg, E.; Ribes-Greus, A.; Karlsson, S.

2011-01-01

The sample preparation procedure for MALDI-TOF MS of polymers is addressed in this study by the application of a statistical Design of Experiments (DoE). Industrial poly (ethylene terephthalate) (PET) was chosen as model polymer. Different experimental settings (levels) for matrixes, analyte/matrix proportions and concentrations of cationization agent were considered. The quality parameters used for the analysis were signal-to-noise ratio and resolution. A closer inspection of the statistical results provided the study not only with the best combination of factors for the MALDI sample preparation, but also with a better understanding of the influence of the different factors, individually or in combination, to the signal. The application of DoE for the improvement of the MALDI measure of PET stated that the best combination of factors and levels was the following: matrix (dithranol), proportion analyte/matrix/cationization agent (1/15/1, V/V/V), and concentration of cationization agent (2 g L -1 ). In a second part, multiple processing by means of successive injection cycles was used to simulate the thermo-mechanical degradation effects on the oligomeric distribution of PET under mechanical recycling. The application of MALDI-TOF-MS showed that thermo-mechanical degradation primarily affected initially predominant cyclic species. Several degradation mechanisms were proposed, remarking intramolecular transesterification and hydrolysis. The ether links of the glycol unit in PET were shown to act as potential reaction sites, driving the main reactions of degradation.

Hot melt extrusion versus spray drying: hot melt extrusion degrades albendazole.

Science.gov (United States)

Hengsawas Surasarang, Soraya; Keen, Justin M; Huang, Siyuan; Zhang, Feng; McGinity, James W; Williams, Robert O

2017-05-01

The purpose of this study was to enhance the dissolution properties of albendazole (ABZ) by the use of amorphous solid dispersions. Phase diagrams of ABZ-polymer binary mixtures generated from Flory-Huggins theory were used to assess miscibility and processability. Forced degradation studies showed that ABZ degraded upon exposure to hydrogen peroxide and 1 N NaOH at 80 °C for 5 min, and the degradants were albendazole sulfoxide (ABZSX), and ABZ impurity A, respectively. ABZ was chemically stable following exposure to 1 N HCl at 80 °C for one hour. Thermal degradation profiles show that ABZ, with and without Kollidon ® VA 64, degraded at 180 °C and 140 °C, respectively, which indicated that ABZ could likely be processed by thermal processing. Following hot melt extrusion, ABZ degraded up to 97.4%, while the amorphous ABZ solid dispersion was successfully prepared by spray drying. Spray-dried ABZ formulations using various types of acids (methanesulfonic acid, sulfuric acid and hydrochloric acid) and polymers (Kollidon ® VA 64, Soluplus ® and Eudragit ® E PO) were studied. The spray-dried ABZ with methanesulfonic acid and Kollidon ® VA 64 substantially improved non-sink dissolution in acidic media as compared to bulk ABZ (8-fold), physical mixture of ABZ:Kollidon ® VA 64 (5.6-fold) and ABZ mesylate salt (1.6-fold). No degradation was observed in the spray-dried product for up to six months and less than 5% after one-year storage. In conclusion, amorphous ABZ solid dispersions in combination with an acid and polymer can be prepared by spray drying to enhance dissolution and shelf-stability, whereas those made by melt extrusion are degraded.

Radiation Processing of Natural Polymers for Industrial Applications

International Nuclear Information System (INIS)

Hegazy, E.A.

2008-01-01

Radiation induced degradation technology is a new and promising application of ionizing radiation to develop viscose, pulp, paper, food preservation, pharmaceutical production, and natural bioactive agents industries. Controlling the degree of degradation, uniform molecular weight distribution, saving achieved in the chemicals (used in conventional methods) on a cost basis, and environmentally friendly process are the beneficial effects of using radiation technology in these industries. However, for some development countries such technology is not economic. Therefore, a great effort should be done to reduce the cost required for such technologies. One of the principle factors for reducing the cost is achieving the degradation at low irradiation doses. The addition of some additives such as potassium per-sulfate (KPS), ammonium per-sulfate (APS), or H 2 O 2 to natural polymers (carboxy-methylcellulose (CMC), chitosan, carrageenan and Na-alginate) during irradiation process accelerates their degradation. The highest degradation rate of polysaccharides obtained when APS was used. The end product of irradiated CMC, chitosan, carrageenan and Na-alginate may be used as food additive or benefited in agricultural purposes. On the other hand, radiation crosslinking of PAAm or PNIPAAm is affected by the presence of natural polymer like CMC-Na and carrageenan due to their degradability which could be controlled according to its concentration in the bulk medium and irradiation dose. Accordingly, the gel content, thermo-sensitivity (LCST) and swelling properties of PNIPAAm based natural polymers could be controlled. The swelling of the prepared copolymer hydrogels was investigated for its possible use in personal care articles particularly diapers or as carriers for drug delivery systems. The prepared crosslinked copolymers possessed high and fast swelling properties in simulated urine media and the swelling ratios of CMC-Na /PAAm gels in urine are acceptable for diaper

Chitin Degradation In Marine Bacteria

DEFF Research Database (Denmark)

Paulsen, Sara; Machado, Henrique; Gram, Lone

2015-01-01

Introduction: Chitin is the most abundant polymer in the marine environment and the second most abundant in nature. Chitin does not accumulate on the ocean floor, because of microbial breakdown. Chitin degrading bacteria could have potential in the utilization of chitin as a renewable carbon...... and nitrogen source in the fermentation industry.Methods: Here, whole genome sequenced marine bacteria were screened for chitin degradation using phenotypic and in silico analyses.Results: The in silico analyses revealed the presence of three to nine chitinases in each strain, however the number of chitinases...... chitin regulatory system.Conclusions: This study has provided insight into the ecology of chitin degradation in marine bacteria. It also served as a basis for choosing a more efficient chitin degrading production strain e.g. for the use of chitin waste for large-scale fermentations....

The key microorganisms for anaerobic degradation of pentachlorophenol in paddy soil as revealed by stable isotope probing

Energy Technology Data Exchange (ETDEWEB)

Tong, Hui [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Liu, Chengshuai [State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550009 (China); Li, Fangbai, E-mail: cefbli@soil.gd.cn [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Luo, Chunling [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Chen, Manjia; Hu, Min [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China)

2015-11-15

Highlights: • SIP suggested that Dechloromonas can mineralize PCP in soil. • Methanosaeta and Methanocella acquired PCP-derived carbon. • Lactate enhanced microbial degradation of PCP in soil. - Abstract: Pentachlorophenol (PCP) is a common residual persistent pesticide in paddy soil and has resulted in harmful effect on soil ecosystem. The anaerobic microbial transformation of PCP, therefore, has been received much attentions, especially the functional microbial communities for the reductive transformation. However, the key functional microorganisms for PCP mineralization in the paddy soil still remain unknown. In this work, DNA-based stable isotope probing (SIP) was applied to explore the key microorganisms responsible for PCP mineralization in paddy soil. The SIP results indicated that the dominant bacteria responsible for PCP biodegradation belonged to the genus Dechloromonas of the class β-Proteobacteria. In addition, the increased production of {sup 13}CH{sub 4} and {sup 13}CO{sub 2} indicated that the addition of lactate enhanced the rate of biodegradation and mineralization of PCP. Two archaea classified as the genera of Methanosaeta and Methanocella of class Methanobacteria were enriched in the heavy fraction when with lactate, whereas no archaea was detected in the absence of lactate. These findings provide direct evidence for the species of bacteria and archaea responsible for anaerobic PCP or its breakdown products mineralization and reveal a new insight into the microorganisms linked with PCP degradation in paddy soil.

The key microorganisms for anaerobic degradation of pentachlorophenol in paddy soil as revealed by stable isotope probing

International Nuclear Information System (INIS)

Tong, Hui; Liu, Chengshuai; Li, Fangbai; Luo, Chunling; Chen, Manjia; Hu, Min

2015-01-01

Highlights: • SIP suggested that Dechloromonas can mineralize PCP in soil. • Methanosaeta and Methanocella acquired PCP-derived carbon. • Lactate enhanced microbial degradation of PCP in soil. - Abstract: Pentachlorophenol (PCP) is a common residual persistent pesticide in paddy soil and has resulted in harmful effect on soil ecosystem. The anaerobic microbial transformation of PCP, therefore, has been received much attentions, especially the functional microbial communities for the reductive transformation. However, the key functional microorganisms for PCP mineralization in the paddy soil still remain unknown. In this work, DNA-based stable isotope probing (SIP) was applied to explore the key microorganisms responsible for PCP mineralization in paddy soil. The SIP results indicated that the dominant bacteria responsible for PCP biodegradation belonged to the genus Dechloromonas of the class β-Proteobacteria. In addition, the increased production of 13 CH 4 and 13 CO 2 indicated that the addition of lactate enhanced the rate of biodegradation and mineralization of PCP. Two archaea classified as the genera of Methanosaeta and Methanocella of class Methanobacteria were enriched in the heavy fraction when with lactate, whereas no archaea was detected in the absence of lactate. These findings provide direct evidence for the species of bacteria and archaea responsible for anaerobic PCP or its breakdown products mineralization and reveal a new insight into the microorganisms linked with PCP degradation in paddy soil

Swift heavy ion induced modification of aliphatic polymers

International Nuclear Information System (INIS)

Hossain, Umme Habiba

2015-01-01

In this thesis, the high energy heavy ion induced modification of aliphatic polymers is studied. Two polymer groups, namely polyvinyl polymers (PVF, PVAc, PVA and PMMA) and fluoropolymers (PVDF, ETFE, PFA and FEP) were used in this work. Polyvinyl polymers were investigated since they will be used as insulating materials in the superconducting magnets of the new ion accelerators of the planned International Facility for Antiproton and Ion Research (FAIR) at the GSI Helmholtz-Centre of Heavy Ion Research (GSI) in Darmstadt. In order to study ion-beam induced degradation, all polymer foils were irradiated at the GSI linear accelerator UNILAC using several projectiles (U, Au, Sm, Xe) and experimentation sites (beam lines X0 and M3) over a large fluence regime (1 x 10 10 - 5 x 10 12 ions/cm 2 ). Five independent techniques, namely infrared (FT-IR) and ultraviolet-visible (UV-Vis) spectroscopy, residual gas analysis (RGA), thermal gravimetric analysis (TGA), and mass loss analysis (ML), were used to analyze the irradiated samples. FT-IR spectroscopy revealed that ion irradiation led to the decrease of characteristic band intensities showing the general degradation of the polymers, with scission of side groups and the main backbone. As a consequence of the structural modification, new bands appeared. UV-Vis transmission analysis showed an absorption edge shift from the ultraviolet region towards the visible region indicating double bond and conjugated double bond formation. On-line massspectrometric residual gas analysis showed the release of small gaseous fragment molecules. TGA analysis gave evidence of a changed thermal stability. With ML analysis, the considerable mass loss was quantified. The results of the five complementary analytical methods show how heavy ion irradiation changes the molecular structure of the polymers. Molecular degradation mechanisms are postulated. The amount of radiation damage is found to be sensitive to the used type of ionic species. While

Polymer-Based Surfaces Designed to Reduce Biofilm Formation: From Antimicrobial Polymers to Strategies for Long-Term Applications.

Science.gov (United States)

Riga, Esther K; Vöhringer, Maria; Widyaya, Vania Tanda; Lienkamp, Karen

2017-10-01

Contact-active antimicrobial polymer surfaces bear cationic charges and kill or deactivate bacteria by interaction with the negatively charged parts of their cell envelope (lipopolysaccharides, peptidoglycan, and membrane lipids). The exact mechanism of this interaction is still under debate. While cationic antimicrobial polymer surfaces can be very useful for short-term applications, they lose their activity once they are contaminated by a sufficiently thick layer of adhering biomolecules or bacterial cell debris. This layer shields incoming bacteria from the antimicrobially active cationic surface moieties. Besides discussing antimicrobial surfaces, this feature article focuses on recent strategies that were developed to overcome the contamination problem. This includes bifunctional materials with simultaneously presented antimicrobial and protein-repellent moieties; polymer surfaces that can be switched from an antimicrobial, cell-attractive to a cell-repellent state; polymer surfaces that can be regenerated by enzyme action; degradable antimicrobial polymers; and antimicrobial polymer surfaces with removable top layers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tribology of natural fiber polymer composites

CERN Document Server

Chand, N

2008-01-01

Environmental concerns are driving demand for bio-degradable materials such as plant-based natural fiber reinforced polymer composites. These composites are fast replacing conventional materials in many applications, especially in automobiles, where tribology (friction, lubrication and wear) is important. This book covers the availability and processing of natural fiber polymer composites and their structural, thermal, mechanical and, in particular, tribological properties.Chapter 1 discusses sources of natural fibers, their extraction and surface modification. It also reviews the ther

Statistical optimization and artificial neural network modeling for acridine orange dye degradation using in-situ synthesized polymer capped ZnO nanoparticles.

Science.gov (United States)

Dhiman, Nitesh; Markandeya; Singh, Amrita; Verma, Neeraj K; Ajaria, Nidhi; Patnaik, Satyakam

2017-05-01

ZnO NPs were synthesized by a prudent green chemistry approach in presence of polyacrylamide grafted guar gum polymer (pAAm-g-GG) to ensure uniform morphology, and functionality and appraised for their ability to degrade photocatalytically Acridine Orange (AO) dye. These ZnO@pAAm-g-GG NPs were thoroughly characterized by various spectroscopic, XRD and electron microscopic techniques. The relative quantity of ZnO NPs in polymeric matrix has been estimated by spectro-analytical procedure; AAS and TGA analysis. The impact of process parameters viz. NP's dose, contact time and AO dye concentration on percentage photocatalytic degradation of AO dyes were evaluated using multivariate optimizing tools, Response Surface Methodology (RSM) involving Box-Behnken Design (BBD) and Artificial Neural Network (ANN). Congruity of the BBD statistical model was implied by R 2 value 0.9786 and F-value 35.48. At RSM predicted optimal condition viz. ZnO@pAAm-g-GG NP's dose of 0.2g/L, contact time of 210min and AO dye concentration 10mg/L, a maximum of 98% dye degradation was obtained. ANOVA indicated appropriateness of the model for dye degradation owing to "Prob.>F" less than 0.05 for variable parameters. We further, employed three layers feed forward ANN model for validating the BBD process parameters and suitability of our chosen model. The evaluation of Levenberg-Marquardt algorithm (ANN1) and Gradient Descent with adaptive learning rate (ANN2) model employed to scrutinize the best method and found experimental values of AO dye degradation were in close to those with predicated value of ANN 2 modeling with minimum error. Copyright © 2017 Elsevier Inc. All rights reserved.

New trends in radiation processing of polymers

International Nuclear Information System (INIS)

Chmielewski, Andrzej G.

2005-01-01

Nowadays, the modification of polymers covers radiation cross-linking, radiation induced polymerization (graft polymerization and curing) and the degradation of polymers. The success of radiation technology for the processing of synthetic polymers can be attributed to two reasons, namely the easiness of processing in various shapes and sizes and, secondly, most of these polymers undergo cross-linking reaction upon exposure to radiation. years, natural polymers are being looked at again with renewed interest because of their unique characteristics like inherent biocompatibility, biodegradability and easy availability. However the recent progress in the field regards development of new processing methods and technical solutions. No other break trough technologies or products based on synthetic polymers are reported recently. The future progress, both from scientific and practical points of view, concerns nanotechnology and natural polymer processing. Overview of the subject, including the works performed in the Institute of the author is presented in the paper. (author)

Driving degradation within biodegradable polymers with embedded nanoparticles

Science.gov (United States)

Gorga, Russell; Firestone, Gabriel; Fontecha, Daniela; Bochinski, Jason; Clarke, Laura

The ability to controllably trigger breaking of chemical bonds enables a substance that has robust material properties during use but can be re-worked or deteriorated upon command. Photothermal heating creates intense local heat at isolated nanoparticle locations within a sample and can result in very different material responses than those achievable with conventional (uniform) heating. In this process, irradiation with visible light resonant with the nanoparticle's surface plasmon resonance results in dramatic local heating of the particles and the surrounding material. This work studies intentional thermal degradation of poly ethyl cyanoacrylate-starch composites doped with metal nanoparticles, and explores differences in degradation speed, efficiency, and resultant mechanical properties when heated via the photothermal effect. This work was supported by the National Science Foundation, Grant #: CMMI-1462966.

In situ analysis of plant tissue underivatized carbohydrates and on-probe enzymatic degraded starch by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry by using carbon nanotubes as matrix.

Science.gov (United States)

Gholipour, Yousef; Nonami, Hiroshi; Erra-Balsells, Rosa

2008-12-15

Underivatized carbohydrates of tulip bulb and leaf tissues were characterized in situ by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) by using carbon nanotubes (CNTs) as matrix. Two sample preparation methods--(i) depositing CNTs on the fresh tissue slices placed on the probe and (ii) locating semitransparent tissues on a dried layer of CNTs on the probe--were examined. Furthermore, practicability of in situ starch analysis by MALDI-TOF MS was examined by detection of glucose originated from on-probe amyloglucosidase-catalyzed degradation of starch on the tissue surface. Besides, CNTs could efficiently desorb/ionize natural mono-, di-, and oligosaccharides extracted from tulip bulb tissues as well as glucose resulting from starch enzymatic degradation in vitro. These results were compared with those obtained by in situ MALDI-TOF MS analysis of similar tissues. Positive ion mode showed superior signal reproducibility. CNTs deposited under semitransparent tissue could also desorb/ionize neutral carbohydrates, leading to nearly complete elimination of matrix cluster signals but with an increase in tissue-originated signals. Furthermore, several experiments were carried out to compare the efficiency of 2,5-dihydroxybenzoic acid, nor-harmane, alpha-cyano-4-hydroxycinnamic acid, and CNTs as matrices for MALDI of neutral carbohydrates from the intact plant tissue surface and for enzymatic tissue starch degradation; these results are discussed in brief. Among matrices studied, the lowest laser power was needed to acquire carbohydrate signals with high signal-to-noise ratio and resolution when CNTs were used.

Trend and future of radiation processing of polymers

International Nuclear Information System (INIS)

Makuuchi, Keizo

2000-01-01

Five Asian countries have been cooperating with Takasaki Radiation Chemistry Research Establishment (TRCRE), Japan, in the field of radiation processing of polymers. The experience of cooperation is summarized. Main processes are polymerization of monomers, cross-linking and degradation of polymers, graft polymerization and curing. The industrial state-of-art of radiation processing in Japan is described. The characteristics of radiation processes are compared with other processes. The future prospect of processing is also described. The growth in cross-linking and degradation are anticipated, whereas graft polymerization and curing are to confront to severe competition with other methods. The possibility of developing new area of radiation processing in Asian counties is pointed out. (A. Yamamoto)

Oxygen diffusion in bilayer polymer films

DEFF Research Database (Denmark)

Poulsen, Lars; Zebger, Ingo; Tofte, Jannik Pentti

2004-01-01

Experiments to quantify oxygen diffusion have been performed on polymer samples in which a film of poly(ethylene-co-norbornene) was cast onto a film of polystyrene which, in turn, was cast onto an oxygen-impermeable substrate. In the technique employed, the time evolution of oxygen transport...... through the film of poly(ethylene-co-norbornene) and into the polystyrene film was monitored using the phosphorescence of singlet oxygen as a spectroscopic probe. To analyze the data, it was necessary to solve Fick's second law of diffusion for both polymer films. Tractable analytical and numerical...

Nanoscopic Studies on Polymer Molecules(STM-other surfaces)

OpenAIRE

Toshio, NISHI; Ken, NAKAJIMA; Takayuki, IKEHARA; Department of Applied Physics, School of Engineering, The University of Tokyo; Department of Applied Physics, School of Engineering, The University of Tokyo; Department of Applied Physics, School of Engineering, The University of Tokyo

1997-01-01

A new field of study in the polymer science and engineering is being opened with the use of scanning tunneling microscope (STM), atomic force microscope (AFM), and scanning probe microscope (SPM). In this short review article several examples are given with comments. They are direct observation of poly(macromonomer), structure of a cross-linking domain of a gel, and observation of topochemically photopolymerizable conjugated aromatic compound. Moreover, nanorheological properties of polymer b...

Quickly updatable hologram images with high performance photorefractive polymer composites

Science.gov (United States)

Tsutsumi, Naoto; Kinashi, Kenji; Nonomura, Asato; Sakai, Wataru

2012-02-01

We present here quickly updatable hologram images using high performance photorefractive (PR) polymer composite based on poly(N-vinyl carbazole) (PVCz). PVCz is one of the pioneer materials for photoconductive polymer. PVCz/7- DCST/CzEPA/TNF (44/35/20/1 by wt) gives high diffraction efficiency of 68 % at E = 45 V/μm with fast response speed. Response speed of optical diffraction is the key parameter for real-time 3D holographic display. Key parameter for obtaining quickly updatable hologram images is to control the glass transition temperature lower enough to enhance chromophore orientation. Object image of the reflected coin surface recorded with reference beam at 532 nm (green beam) in the PR polymer composite is simultaneously reconstructed using a red probe beam at 642 nm. Instead of using coin object, object image produced by a computer was displayed on a spatial light modulator (SLM) is used as an object for hologram. Reflected object beam from a SLM interfered with reference beam on PR polymer composite to record a hologram and simultaneously reconstructed by a red probe beam. Movie produced in a computer was recorded as a realtime hologram in the PR polymer composite and simultaneously clearly reconstructed with a video rate.

Drag reduction behavior of hydrolyzed polyacrylamide/xanthan gum mixed polymer solutions

Institute of Scientific and Technical Information of China (English)

Mehdi Habibpour; Peter E.Clark

2017-01-01

Partially hydrolyzed polyacrylamide (HPAM) as the main component of slickwater fracturing fluid is a shear-sensitive polymer,which suffers from mechanical degradation at turbulent flow rates.Five different concentrations of HPAM as well as mixtures of polyacrylamide/xanthan gum were prepared to investigate the possibility of improving shear stability of HPAM.Drag reduction (DR)measurements were performed in a closed flow loop.For HPAM solutions,the extent of DR increased from 30％ to 67％ with increasing HPAM concentration from 100 to 1000 wppm.All the HPAM solutions suffered from mechanical degradation and loss of DR efficiency over the shearing period.Results indicated that the resistance to shear degradation increased with increasing polymer concentration.DR efficiency of 600 wppm xanthan gum (XG)was 38％,indicating that XG was not as good a drag reducer as HPAM.But with only 6％ DR decline,XG solution exhibited a better shear stability compared to HPAM solutions.Mixed HPAM/XG solutions initially exhibited greater DR (40％ and 55％) compared to XG,but due to shear degradation,DR％ dropped for HPAM/XG solutions.Compared to 200 wppm HPAM solution,addition of XG did not improve the drag reduction efficiency of HPAM/XG mixed solutions though XG slightly improved the resistance against mechanical degradation in HPAM/XG mixed polymer solutions.

Visualizing phase transition behavior of dilute stimuli responsive polymer solutions via Mueller matrix polarimetry.

Science.gov (United States)

Narayanan, Amal; Chandel, Shubham; Ghosh, Nirmalya; De, Priyadarsi

2015-09-15

Probing volume phase transition behavior of superdiluted polymer solutions both micro- and macroscopically still persists as an outstanding challenge. In this regard, we have explored 4 × 4 spectral Mueller matrix measurement and its inverse analysis for excavating the microarchitectural facts about stimuli responsiveness of "smart" polymers. Phase separation behavior of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) and pH responsive poly(N,N-(dimethylamino)ethyl methacrylate) (PDMAEMA) and their copolymers were analyzed in terms of Mueller matrix derived polarization parameters, namely, depolarization (Δ), diattenuation (d), and linear retardance (δ). The Δ, d, and δ parameters provided useful information on both macro- and microstructural alterations during the phase separation. Additionally, the two step action ((i) breakage of polymer-water hydrogen bonding and (ii) polymer-polymer aggregation) at the molecular microenvironment during the cloud point generation was successfully probed via these parameters. It is demonstrated that, in comparison to the present techniques available for assessing the hydrophobic-hydrophilic switch over of simple stimuli-responsive polymers, Mueller matrix polarimetry offers an important advantage requiring a few hundred times dilute polymer solution (0.01 mg/mL, 1.1-1.4 μM) at a low-volume format.

Polymers selection for a liquid inoculant of Azospirillum brasilense ...

African Journals Online (AJOL)

In this study, we used a method of accelerated degradation to select a polymer and a concentration to maintain cell stability of a liquid inoculant based on the strain C16 Azospirillum brasilense. A screening at 45°C was made to compare the protectant effect of five polymers on the viability of the strain (p/v): carrageenan ...

New hyperthermal thermosetting heterocyclic polymers

Science.gov (United States)

Bilow, N.; Landis, A. L.; Miller, L. J.

1970-01-01

Polyimidazopyrrolone polymers, formed by the condensation of aromatic dianhydrides with aromatic tetraamines in various solvents, form moldings that resist degradation in air and retain great strength at 400 to 700 degrees F. The resins have good insulating properties, are easy to mold, and make good protective coatings.

Electronic structure of Pt-Co cathode catalysts in membrane electrolyte assembly observed by X-ray absorption fine structure spectroscopy with different probing depth

International Nuclear Information System (INIS)

Kobayashi, M.; Hidai, S.; Niwa, H.; Harada, Y.; Oshima, M.; Ofuchi, H.; Nakamori, Y.; Aoki, T.

2010-01-01

Electronic structures of Pt-Co cathode and Pt-Ru anode catalysts in membrane electrolyte assemblies (MEAs) for polymer electrolyte fuel cell have been investigated using X-ray absorption near edge structure (XANES) spectroscopy, and the changes of electronic structures accompanied with degradation have been observed by comparison between spectra obtained by fluorescence-yield (FY) and conversion-electron-yield (CEY) methods, probing depths of which are several hundreds μm and ∼100 nm, respectively. The Co K XANES spectra of the as-fabricated MEA show that the Co atoms in the cathode are metallic and oxidized Co ions exist at the interface between the cathode and electrolyte. The spectra of the long-time operated MEA suggest that the oxidation of Co makes progress with degradation of the cathode catalysts. In contrast to the Co K XANES spectra, the line shape of the Ru K XANES spectra is unchanged even after the long-time operation.

Correction of MHS Viscosimetric Constants upon Numerical Simulation of Temperature Induced Degradation Kinetic of Chitosan Solutions

Directory of Open Access Journals (Sweden)

Vincenzo Maria De Benedictis

2016-05-01

Full Text Available The Mark–Houwink–Sakurada (MHS equation allows for estimation of rheological properties, if the molecular weight is known along with good understanding of the polymer conformation. The intrinsic viscosity of a polymer solution is related to the polymer molecular weight according to the MHS equation, where the value of the constants is related to the specific solvent and its concentration. However, MHS constants do not account for other characteristics of the polymeric solutions, i.e., Deacetilation Degree (DD when the solute is chitosan. In this paper, the degradation of chitosan in different acidic environments by thermal treatment is addressed. In particular, two different solutions are investigated (used as solvent acetic or hydrochloric acid with different concentrations used for the preparation of chitosan solutions. The samples were treated at different temperatures (4, 30, and 80 °C and time points (3, 6 and 24 h. Rheological, Gel Permeation Chromatography (GPC, Fourier Transform Infrared Spectroscopy (FT-IR, Differential Scanning Calorimetry (DSC and Thermal Gravimetric Analyses (TGA were performed in order to assess the degradation rate of the polymer backbones. Measured values of molecular weight have been integrated in the simulation of the batch degradation of chitosan solutions for evaluating MHS coefficients to be compared with their corresponding experimental values. Evaluating the relationship between the different parameters used in the preparation of chitosan solutions (e.g., temperature, time, acid type and concentration, and their contribution to the degradation of chitosan backbone, it is important to have a mathematical frame that could account for phenomena involved in polymer degradation that go beyond the solvent-solute combination. Therefore, the goal of the present work is to propose an integration of MHS coefficients for chitosan solutions that contemplate a deacetylation degree for chitosan systems or a more

Double polymer sheathed carbon nanotube supercapacitors show enhanced cycling stability

Science.gov (United States)

Zhao, Wenqi; Wang, Shanshan; Wang, Chunhui; Wu, Shiting; Xu, Wenjing; Zou, Mingchu; Ouyang, An; Cao, Anyuan; Li, Yibin

2015-12-01

Pseudo-materials are effective in boosting the specific capacitance of supercapacitors, but during service their degradation may also be very strong, causing reduced cycling stability. Here, we show that a carbon nanotube sponge grafted by two conventional pseudo-polymer layers in sequence can serve as a porous supercapacitor electrode with significantly enhanced cycling stability compared with single polymer grafting. Creating conformal polymer coatings on the nanotube surface and the resulting double-sheath configuration are important structural factors leading to the enhanced performance. Combining different polymers as double sheaths as reported here might be a potential route to circumvent the dilemma of pseudo-materials, and to simultaneously improve the capacitance and stability for various energy storage devices.Pseudo-materials are effective in boosting the specific capacitance of supercapacitors, but during service their degradation may also be very strong, causing reduced cycling stability. Here, we show that a carbon nanotube sponge grafted by two conventional pseudo-polymer layers in sequence can serve as a porous supercapacitor electrode with significantly enhanced cycling stability compared with single polymer grafting. Creating conformal polymer coatings on the nanotube surface and the resulting double-sheath configuration are important structural factors leading to the enhanced performance. Combining different polymers as double sheaths as reported here might be a potential route to circumvent the dilemma of pseudo-materials, and to simultaneously improve the capacitance and stability for various energy storage devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05978j

Sialylglycan-Assembled Supra-Dots for Ratiometric Probing and Blocking of Human-Infecting Influenza Viruses.

Science.gov (United States)

Wang, Chang-Zheng; Han, Hai-Hao; Tang, Xin-Ying; Zhou, Dong-Ming; Wu, Changfeng; Chen, Guo-Rong; He, Xiao-Peng; Tian, He

2017-08-02

The seasonal outbreak of influenza causes significant morbidity and mortality worldwide because a number of influenza virus (IV) strains have been shown to infect and circulate in humans. Development of effective means to timely monitor as well as block IVs is still a challenging task. Whereas conventional fluorescence probes rely on a fluorimetric change upon recognizing IVs, here we developed simple "Supra-dots" that are formed through the aqueous supramolecular assembly between a blue-emitting polymer dot and red-emitting sialylglycan probes for the ratiometric detection of IVs. Tuning the Förster resonance energy transfer from polymer dots to glycan probes by selective sialylglycan-virus recognition enables the fluorescence ratiometric determination of IVs, whereas the presence of unselective, control viruses quenched the fluorescence of the Supra-dots. Meanwhile, we show that the Supra-dots can effectively inhibit the invasion of a human-infecting IV toward a human cell line, thereby making possible a unique bifunctional, supramolecular probe for influenza theranostics.

Ellipsometry-based combination of isothermal sorption-desorption measurement and temperature programmed desorption technique: A probe for interaction of thin polymer films with solvent vapor

Science.gov (United States)

Efremov, Mikhail Yu.; Nealey, Paul F.

2018-05-01

An environmental chamber equipped with an in situ spectroscopic ellipsometer, programmatic vapor pressure control, and variable temperature substrate holder has been designed for studying polymer coating behavior during an exposure to a solvent vapor and also for probing the residual solvent in the film afterwards. Both sorption-desorption cycle at a constant temperature and temperature programmed desorption (TPD) of the residual solvent manifest themselves as a change of the film thickness. Monitoring of ellipsometric angles of the coating allows us to determine the thickness as a function of the vapor pressure or sample temperature. The solvent vapor pressure is precisely regulated by a computer-controlled pneumatics. TPD spectra are recorded during heating of the film in an oil-free vacuum. The vapor pressure control system is described in detail. The system has been tested on 6-170 nm thick polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) films deposited on silicon substrates. Liquid toluene, water, ethanol, isopropanol, cyclohexane, 1,2-dichloroethane, and chlorobenzene were used to create a vapor atmosphere. Typical sorption-desorption and TPD curves are shown. The instrument achieves sub-monolayer sensitivity for adsorption studies on flat surfaces. Polymer-solvent vapor systems with strong interaction demonstrate characteristic absorption-desorption hysteresis spanning from vacuum to the glass transition pressure. Features on the TPD curves can be classified as either glass transition related film contraction or low temperature broad contraction peak. Typical absorption-desorption and TPD dependencies recorded for the 6 nm thick polystyrene film demonstrate the possibility to apply the presented technique for probing size effects in extremely thin coatings.

Degradation Behaviour of Gamma Irradiated Poly(Acrylic Acid)-graft-Chitosan Superabsorbent Hydrogel

Science.gov (United States)

Ria Barleany, Dhena; Ilhami, Alpin; Yusuf Yudanto, Dea; Erizal

2018-03-01

A series of superabsorbent hydrogels were prepared from chitosan and partially neutralized acrylic acid at room temperature by gamma irradiation technique. The effect of irradiation and chitosan addition to the degradation behaviour of polymer were investigated. The gel content, swelling capacity, Equillibrium Degree of Swelling (EDS), Fourier Transform Infra Red (FTIR), and Scanning Electron Microscopy (SEM) study were also performed. Natural degradation in soil and thermal degradation by using of TGA analysis were observed. The variation of chitosan compositions were 0.5, 1, 1.5, and 2 g and the total irradiation doses were 5, 10, 15, and 20 kGy. The highest water capacity of 583.3 g water/g dry hydrogel was resulted from 5 kGy total irradiation dose and 0,5 g addition of chitosan. From the thermal degradation evaluation by using of TGA analysis showed that irradiation dose did not give a significant influence to the degradation rate. The rate of thermal degradation was ranged between 2.42 to 2.55 mg/min. In the natural test of degradation behaviour by using of soil medium, the hydrogel product with chitosan addition was found to have better degradability compared with the poly(acrylic acid) polymer without chitosan.

Self-Assembly of Telechelic Tyrosine End-Capped PEO Star Polymers in Aqueous Solution.

Science.gov (United States)

Edwards-Gayle, Charlotte J C; Greco, Francesca; Hamley, Ian W; Rambo, Robert P; Reza, Mehedi; Ruokolainen, Janne; Skoulas, Dimitrios; Iatrou, Hermis

2018-01-08

We investigate the self-assembly of two telechelic star polymer-peptide conjugates based on poly(ethylene oxide) (PEO) four-arm star polymers capped with oligotyrosine. The conjugates were prepared via N-carboxy anhydride-mediated ring-opening polymerization from PEO star polymer macroinitiators. Self-assembly occurs above a critical aggregation concentration determined via fluorescence probe assays. Peptide conformation was examined using circular dichroism spectroscopy. The structure of self-assembled aggregates was probed using small-angle X-ray scattering and cryogenic transmission electron microscopy. In contrast to previous studies on linear telechelic PEO-oligotyrosine conjugates that show self-assembly into β-sheet fibrils, the star architecture suppresses fibril formation and micelles are generally observed instead, a small population of fibrils only being observed upon pH adjustment. Hydrogelation is also suppressed by the polymer star architecture. These peptide-functionalized star polymer solutions are cytocompatible at sufficiently low concentration. These systems present tyrosine at high density and may be useful in the development of future enzyme or pH-responsive biomaterials.

Radiation damage of polymers in ultrasonic fields

Energy Technology Data Exchange (ETDEWEB)

Anbalagan, Poornnima

2008-07-01

Radiation damage has always been a topic of great interest in various fields of sciences. In this work, an attempt is made to probe into the effect of subthreshold ultrasonic waves on the radiation damage created by irradiation of deuterons in polymer samples wherein the polymer samples act as model systems. Two equal volumes of radiation damage were produced in a single polymer sample wherein a standing wave of ultrasound was introduced into one. Three polymers namely, Polycarbonate, Polymethylmethacrylate and Polyvinyl chloride were used in this work. Four independent techniques were used to analyze the irradiated samples and visualize the radiation damage. Interferometric measurements give a measure of the refractive index modulation in the irradiated sample. Polymers, being transparent, do not absorb in the visible region of the electromagnetic spectrum. UV-Vis absorption spectroscopy shows absorption peaks in the visible region in irradiated polymer samples. Ion irradiation causes coloration of polymers. The light microscope is used to measure the absorption of white light by the irradiated polymers. Positron annihilation spectroscopy is used to obtain a measure of the open volume created by irradiation in polymers. A comparison between the irradiated region and the region exposed to ultrasonic waves simultaneously with irradiation in a polymer sample shows the polymer specific influence of the ultrasonic standing wave. (orig.)

Radiation damage of polymers in ultrasonic fields

International Nuclear Information System (INIS)

Anbalagan, Poornnima

2008-01-01

Radiation damage has always been a topic of great interest in various fields of sciences. In this work, an attempt is made to probe into the effect of subthreshold ultrasonic waves on the radiation damage created by irradiation of deuterons in polymer samples wherein the polymer samples act as model systems. Two equal volumes of radiation damage were produced in a single polymer sample wherein a standing wave of ultrasound was introduced into one. Three polymers namely, Polycarbonate, Polymethylmethacrylate and Polyvinyl chloride were used in this work. Four independent techniques were used to analyze the irradiated samples and visualize the radiation damage. Interferometric measurements give a measure of the refractive index modulation in the irradiated sample. Polymers, being transparent, do not absorb in the visible region of the electromagnetic spectrum. UV-Vis absorption spectroscopy shows absorption peaks in the visible region in irradiated polymer samples. Ion irradiation causes coloration of polymers. The light microscope is used to measure the absorption of white light by the irradiated polymers. Positron annihilation spectroscopy is used to obtain a measure of the open volume created by irradiation in polymers. A comparison between the irradiated region and the region exposed to ultrasonic waves simultaneously with irradiation in a polymer sample shows the polymer specific influence of the ultrasonic standing wave. (orig.)

The effects of gamma-irradiation on additives in food-contact polymers

Science.gov (United States)

Smith, Christine

A range of antioxidants (BHT, Irganox 1010, 1076, 1330 and Irgafos 168) were incorporated into polymers (polyethylene, polypropylene, polystyrene and polyvinyl chloride) and subjected to increasing doses of gamma-irradiation (1,5,10,20,25,35 and 50 kGy) from a cobalt-60 source.The amount of extractable antioxidant from the stabilised polymers was determined chromatographically and a gradual diminution in the total extractable levels of each antioxidant was observed as irradiation progressed, the extent depending on the nature of both the antioxidant and the polymer 2,6-Di-t-butyl-1,4-benzoquinone was shown to be an extractable degradation product, arising from the effects of gamma-irradiation on the phenolic antioxidants. The extractable degradation product arising from the phosphite antioxidant, Irgafos 168, was identified as tris(2,4-di-t-butylphenyl)phosphate. It was demonstrated using 14C-labelled Irganox 1076 that degradation products formed during gamma-irradiation are becoming covalently bound to the polymer, as a result of radical coupling processes. There is a pronounced increase in the extent of covalent binding from 0.4% before irradiation to a minimum of 12.4% after an exposure to 50 kGy. Evidence has also been presented of covalent binding of the degradation product of Irgafos 168 to the polypropylene matrix, via polymeric radicals formed during irradiation. Finally, the effects of gamma-irradiation on the extent of migration of antioxidants from polyolefins into food simulants was studied. It was found that irradiation leads to a decrease in the extent to which hindered phenolic antioxidants migrate from polyolefins into fatty media, consistent with the reduction in extractable antioxidant levels and the increase in the extent of antioxidant-polymer binding.

Near-field circular polarization probed by chiral polyfluorene

NARCIS (Netherlands)

Savoini, M.; Biagioni, P.; Lakhwani, G.; Meskers, S.C.J.; Duò, L.; Finazzi, M.

2009-01-01

We demonstrate that a high degree of circular polarization can be delivered to the near field (NF) of an aperture at the apex of hollow-pyramid probes for scanning optical microscopy. This result is achieved by analyzing the dichroic properties of an annealed thin polymer film containing a chiral

Mechanisms of Photo Degradation for Layered Silicate-Polycarbonate Nanocomposites

National Research Council Canada - National Science Library

Sloan, James M; Patterson, Philip

2005-01-01

...., lightweight structure, rugged abrasion resistance, and high ballistic impact strength). However, as with any polymer system, these materials are susceptible to degradation over time when exposed to various environmental (i.e...

The scanning probe microscopy study of thin polymer films

International Nuclear Information System (INIS)

Harron, H.R.

1995-08-01

Scanning Tunnelling Microscopy and Atomic Force Microscopy were used systematically to investigate the morphology, uniformity, coverage and structure of the thin films of several commercially important insulating polymers. Despite the poorly conducting nature of the polymer sample, detailed and convincing images of this class of materials were achieved by STM without the need to coat the samples with a conductive layer. The polymer regions of the sample were further investigated by the use of surface profiling with 'line scans'. The fluctuations of the amplitude therein enabled important film characteristics to be assessed. An environmental stage was designed for the STM to enable the effect of various vapour-sample interactions to be observed during the imaging process. Using the data from the environmental stage in addition to the surface profiling with line scans, an insight into the conduction mechanism and image interpretation was gained. Results suggest that the water content of the sample and its immediate surroundings is an important factor in achieving reliable STM images in air. The initial study culminated with the observation by STM alone of the plasticizer induced crystallization of uncoated PC thin films. The 'amorphous' PC films were observed before crystallization and small ordered regions in roughly the same proportion as that predicted by diffraction studies [Prietschk, 1959 and Schnell, 1964] were imaged. This has never been observed by a microscopy technique. Furthermore, images of the crystalline film contained elongated units that were attributed to the lamellae formations that form the basic building blocks of polymer spherulites. The study continued with the AFM imaging of the growth of crystalline entities in a PC film, without the need for harsh sample treatment or metal coating. A method of casting and crystallizing the films was developed such that the growth was predominantly in two dimensions and consequently ideal for observation by

Photochemical stability of electrochromic polymers and devices

DEFF Research Database (Denmark)

Jensen, Jacob; Madsen, Morten Vesterager; Krebs, Frederik C

2013-01-01

The stability of fully printed flexible organic electrochromics based on 11 different conjugated polymers is explored from the fundamental chemical degradation level to the operational device level. The photochemical stability of the electrochromic polymers (ECPs) is studied enabling an analysis ...... based on flexible barrier substrates exhibit increased stability and are indeed viable in devices such as shading elements, light management systems, displays with low switching speed requirements and signage. © 2013 The Royal Society of Chemistry....

Polymer and Additive Mass Spectrometry Literature Review

Energy Technology Data Exchange (ETDEWEB)

Shear, Trevor Allan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-06-06

The use of mass spectrometry in fields related to polymers has increased significantly over the past three decades and will be explored in this literature review. The importance of this technique is highlighted when exploring how polymers degrade, verifying purchased materials, and as internal requirements change. The primary focus will be on four ionization techniques and the triple quadrupole and quadrupole / time-of-flight mass spectrometers. The advantages and limitations of each will also be explored.

Computational analysis for biodegradation of exogenously depolymerizable polymer

Science.gov (United States)

Watanabe, M.; Kawai, F.

2018-03-01

This study shows that microbial growth and decay in a biodegradation process of exogenously depolymerizable polymer are controlled by consumption of monomer units. Experimental outcomes for residual polymer were incorporated in inverse analysis for a degradation rate. The Gauss-Newton method was applied to an inverse problem for two parameter values associated with the microbial population. A biodegradation process of polyethylene glycol was analyzed numerically, and numerical outcomes were obtained.

Stabilization of polymer solutions in the presence of oxidizing agents

Energy Technology Data Exchange (ETDEWEB)

Mendez, A; Serino, A; Jenkins, D; Lichaa, P M

1974-01-01

Many investigators in the field of heavy oil recovery techniques have confirmed the recovery efficiency which, in the miscible displacement method, has utilized polymer solutions as additives to the injection fluids. The viscosity increase of the displacing phase has lowered the mobility ratio with a significant improvement in the sweep efficiency. Recently, others have reported a notable improvement in the recovery of heavy crude by this same method of miscible displacement which causes a mobile fluid bank between the crude and the displacing fluid. There is an intervening oxidation reaction, promoting the in situ formation of surface-active agents on the interface of these 2 fluids. This study describes the effect on degradation of polymer solutions by such oxidizing agents as potassium chromate and potassium permanganate. The degradation of any polymer solution with or without additives is increased materially by an increase in temperature. The presence of NaCl brine is not often of any great significance in the time of gelation, especially with polymers of the polysaccharide type. (18 refs.)

The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells

DEFF Research Database (Denmark)

Heckler, Ilona Maria; Kesters, Jurgen; Defour, Maxime

2016-01-01

]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio...... studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear......The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT) or thiazolo[5,4-d...

The Role of Electron Affinity in Determining Whether Fullerenes Catalyze or Inhibit Photooxidation of Polymers for Solar Cells

KAUST Repository

Hoke, Eric T.

2012-05-21

Understanding the stability and degradation mechanisms of organic solar materials is critically important to achieving long device lifetimes. Here, an investigation of the photodegradation of polymer:fullerene blend fi lms exposed to ambient conditions for a variety of polymer and fullerene derivative combinations is presented. Despite the wide range in polymer stabilities to photodegradation, the rate of irreversible polymer photobleaching in blend fi lms is found to consistently and dramatically increase with decreasing electron affi nity of the fullerene derivative. Furthermore, blends containing fullerenes with the smallest electron affi nities photobleached at a faster rate than fi lms of the pure polymer. These observations can be explained by a mechanism where both the polymer and fullerene donate photogenerated electrons to diatomic oxygen to form the superoxide radical anion which degrades the polymer. © 2012 WILEY-VCH Verlag GmbH & Co.