Polymer scaffold degradation control via chemical control

Science.gov (United States)

Hedberg-Dirk, Elizabeth L.; Dirk, Shawn; Cicotte, Kirsten

2016-01-05

A variety of polymers and copolymers suitable for use as biologically compatible constructs and, as a non-limiting specific example, in the formation of degradable tissue scaffolds as well methods for synthesizing these polymers and copolymers are described. The polymers and copolymers have degradation rates that are substantially faster than those of previously described polymers suitable for the same uses. Copolymers having a synthesis route which enables one to fine tune the degradation rate by selecting the specific stoichiometry of the monomers in the resulting copolymer are also described. The disclosure also provides a novel synthesis route for maleoyl chloride which yields monomers suitable for use in the copolymer synthesis methods described herein.

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.

Comparative experiments on polymer degradation technique of produced water of polymer flooding oilfield

Science.gov (United States)

Chen, Rong; Qi, Mei; Zhang, Guohui; Yi, Chenggao

2018-02-01

The application of polymer flooding technology in oilfields can result in polymer content increased in produced water. This increasing made produced water quality become poor. The efficiency of produced water processing decreased significantly. Processed water quality seriously exceeded criterion’s stipulation. The presence of the polymer in produced water is the main reason for more difficulties in processing of produced water, therefore the polymer degradation technology is a key coefficient in produced water processing for polymer flooding oilfields. We evaluated several physical and chemical polymer degradation methods with the solution of separated water from polymer flooding oilfields and hydrolyzed polyacrylamide. The experiment results can provide a basis for produced water processing technologies application in polymer flooding oilfields.

Polymer Composites Corrosive Degradation: A Computational Simulation

Science.gov (United States)

Chamis, Christos C.; Minnetyan, Levon

2007-01-01

A computational simulation of polymer composites corrosive durability is presented. The corrosive environment is assumed to manage the polymer composite degradation on a ply-by-ply basis. The degradation is correlated with a measured pH factor and is represented by voids, temperature and moisture which vary parabolically for voids and linearly for temperature and moisture through the laminate thickness. The simulation is performed by a computational composite mechanics computer code which includes micro, macro, combined stress failure and laminate theories. This accounts for starting the simulation from constitutive material properties and up to the laminate scale which exposes the laminate to the corrosive environment. Results obtained for one laminate indicate that the ply-by-ply degradation degrades the laminate to the last one or the last several plies. Results also demonstrate that the simulation is applicable to other polymer composite systems as well.

Flow accelerated organic coating degradation

Science.gov (United States)

Zhou, Qixin

Applying organic coatings is a common and the most cost effective way to protect metallic objects and structures from corrosion. Water entry into coating-metal interface is usually the main cause for the deterioration of organic coatings, which leads to coating delamination and underfilm corrosion. Recently, flowing fluids over sample surface have received attention due to their capability to accelerate material degradation. A plethora of works has focused on the flow induced metal corrosion, while few studies have investigated the flow accelerated organic coating degradation. Flowing fluids above coating surface affect corrosion by enhancing the water transport and abrading the surface due to fluid shear. Hence, it is of great importance to understand the influence of flowing fluids on the degradation of corrosion protective organic coatings. In this study, a pigmented marine coating and several clear coatings were exposed to the laminar flow and stationary immersion. The laminar flow was pressure driven and confined in a flow channel. A 3.5 wt% sodium chloride solution and pure water was employed as the working fluid with a variety of flow rates. The corrosion protective properties of organic coatings were monitored inline by Electrochemical Impedance Spectroscopy (EIS) measurement. Equivalent circuit models were employed to interpret the EIS spectra. The time evolution of coating resistance and capacitance obtained from the model was studied to demonstrate the coating degradation. Thickness, gloss, and other topography characterizations were conducted to facilitate the assessment of the corrosion. The working fluids were characterized by Fourier Transform Infrared Spectrometer (FTIR) and conductivity measurement. The influence of flow rate, fluid shear, fluid composition, and other effects in the coating degradation were investigated. We conclude that flowing fluid on the coating surface accelerates the transport of water, oxygen, and ions into the coating, as

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)

Pathways for degradation of plastic polymers floating in the marine environment.

Science.gov (United States)

Gewert, Berit; Plassmann, Merle M; MacLeod, Matthew

2015-09-01

Each year vast amounts of plastic are produced worldwide. When released to the environment, plastics accumulate, and plastic debris in the world's oceans is of particular environmental concern. More than 60% of all floating debris in the oceans is plastic and amounts are increasing each year. Plastic polymers in the marine environment are exposed to sunlight, oxidants and physical stress, and over time they weather and degrade. The degradation processes and products must be understood to detect and evaluate potential environmental hazards. Some attention has been drawn to additives and persistent organic pollutants that sorb to the plastic surface, but so far the chemicals generated by degradation of the plastic polymers themselves have not been well studied from an environmental perspective. In this paper we review available information about the degradation pathways and chemicals that are formed by degradation of the six plastic types that are most widely used in Europe. We extrapolate that information to likely pathways and possible degradation products under environmental conditions found on the oceans' surface. The potential degradation pathways and products depend on the polymer type. UV-radiation and oxygen are the most important factors that initiate degradation of polymers with a carbon-carbon backbone, leading to chain scission. Smaller polymer fragments formed by chain scission are more susceptible to biodegradation and therefore abiotic degradation is expected to precede biodegradation. When heteroatoms are present in the main chain of a polymer, degradation proceeds by photo-oxidation, hydrolysis, and biodegradation. Degradation of plastic polymers can lead to low molecular weight polymer fragments, like monomers and oligomers, and formation of new end groups, especially carboxylic acids.

Degradability of Polymers for Implantable Biomedical Devices

Science.gov (United States)

Lyu, SuPing; Untereker, Darrel

2009-01-01

Many key components of implantable medical devices are made from polymeric materials. The functions of these materials include structural support, electrical insulation, protection of other materials from the environment of the body, and biocompatibility, as well as other things such as delivery of a therapeutic drug. In such roles, the stability and integrity of the polymer, over what can be a very long period of time, is very important. For most of these functions, stability over time is desired, but in other cases, the opposite–the degradation and disappearance of the polymer over time is required. In either case, it is important to understand both the chemistry that can lead to the degradation of polymers as well as the kinetics that controls these reactions. Hydrolysis and oxidation are the two classes of reactions that lead to the breaking down of polymers. Both are discussed in detail in the context of the environmental factors that impact the utility of various polymers for medical device applications. Understanding the chemistry and kinetics allows prediction of stability as well as explanations for observations such as porosity and the unexpected behavior of polymeric composite materials in some situations. In the last part, physical degradation such interfacial delamination in composites is discussed. PMID:19865531

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.

Semiflexible polymer conformation, distribution and migration in microcapillary flows

Energy Technology Data Exchange (ETDEWEB)

Chelakkot, Raghunath; Gompper, Gerhard [Institut fuer Festkoerperforschung, Forschungszentrum Juelich, 52425 Juelich (Germany); Winkler, Roland G [Institute for Advanced Simulation, Forschungszentrum Juelich, 52425 Juelich (Germany)

2011-05-11

The flow behavior of a semiflexible polymer in microchannels is studied using multiparticle collision dynamics, a particle-based hydrodynamic simulation technique. Conformations, distributions, and radial cross-streamline migration are investigated for various bending rigidities, with persistence lengths L{sub p} in the range 0.5 {<=} L{sub p}/L{sub r} {<=} 30. The flow behavior is governed by the competition between a hydrodynamic lift force and steric repulsion from the wall, which lead to migration away from the wall, and a locally varying flow induced orientation, which drives the polymer away from the channel center and towards the wall. The different dependences of these effects on the polymer bending rigidity and the flow velocity results in a complex dynamical behavior. However, a generic effect is the appearance of a maximum in the monomer and the center-of-mass distributions, which occurs at the channel center for small flow velocities, but moves off-center at higher velocities.

Semiflexible polymer conformation, distribution and migration in microcapillary flows

International Nuclear Information System (INIS)

Chelakkot, Raghunath; Gompper, Gerhard; Winkler, Roland G

2011-01-01

The flow behavior of a semiflexible polymer in microchannels is studied using multiparticle collision dynamics, a particle-based hydrodynamic simulation technique. Conformations, distributions, and radial cross-streamline migration are investigated for various bending rigidities, with persistence lengths L p in the range 0.5 ≤ L p /L r ≤ 30. The flow behavior is governed by the competition between a hydrodynamic lift force and steric repulsion from the wall, which lead to migration away from the wall, and a locally varying flow induced orientation, which drives the polymer away from the channel center and towards the wall. The different dependences of these effects on the polymer bending rigidity and the flow velocity results in a complex dynamical behavior. However, a generic effect is the appearance of a maximum in the monomer and the center-of-mass distributions, which occurs at the channel center for small flow velocities, but moves off-center at higher velocities.

Process-induced degradation of bioresorbable PDLGA in bone tissue scaffold production.

Science.gov (United States)

Little, H; Clarke, S A; Cunningham, E; Buchanan, F

2017-12-28

Process-induced degradation of clinically relevant resorbable polymers was investigated for two thermal techniques, filament extrusion followed by fused deposition modelling (FDM). The aim was to develop a clear understanding of the relationship between temperature, processing time and resultant process-induced degradation. This acts to address the current knowledge gap in studies involving thermal processing of resorbable polymers. Poly(DL-lactide-co-glycolide) (PDLGA) was chosen for its clinically relevant resorption properties. Furthermore, a comparative study of controlled thermal exposure was conducted through compression moulding PDLGA at a selected range of temperatures (150-225 °C) and times (0.5-20 min). Differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) were used to characterise thermally induced degradation behaviour. DSC proved insensitive to degradation effects, whereas GPC demonstrated distinct reductions in molecular weight allowing for the quantification of degradation. A near-exponential pattern of degradation was identified. Through the application of statistical chain scission equations, a predictive plot of theoretical degradation was created. Thermal degradation was found to have a significant effect on the molecular weight with a reduction of up to 96% experienced in the controlled processing study. The proposed empirical model may assist prediction of changes in molecular weight, however, accuracy limitations are highlighted for twin-screw extrusion, accredited to high-shear mixing. The results from this study highlight the process sensitivity of PDLGA and proposes a methodology for quantification and prediction, which contributes to efforts in understanding the influence of manufacture on performance of degradable medical implants.

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

Investigation of the required length for fully developed pipe flow with drag-reducing polymer solutions

Science.gov (United States)

Farsiani, Yasaman; Elbing, Brian

2015-11-01

Adding trace amounts of long chain polymers into a liquid flow is known to reduce skin friction drag by up to 80%. While polymer drag reduction (PDR) has been successfully implemented in internal flows, diffusion and degradation have limited its external flow applications. A weakness in many previous PDR studies is that there was no characterization of the polymer being injected into the turbulent boundary layer, which can be accomplished by testing a sample in a pressure-drop tube. An implicit assumption in polymer characterization is that the flow is fully developed at the differential pressure measurement. While available data in the literature shows that the entry length to achieve fully developed flow increases with polymeric solutions, it is unclear how long is required to achieve fully developed flow for non-Newtonian turbulent flows. In the present study, the pressure-drop is measured across a 1.05 meter length section of a 1.04 cm inner diameter pipe. Differential pressure is measured with a pressure transducer for different entry lengths, flow and polymer solution properties. This presentation will present preliminary data on the required entrance length as well as characterization of polymer solution an estimate of the mean molecular weight.

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

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

Field Effect Flow Control in a Polymer T-Intersection Microfluidic Network

Science.gov (United States)

Sniadecki, Nathan J.; Chang, Richard; Beamesderfer, Mike; Lee, Cheng S.; DeVoe, Don L.

2003-01-01

We present a study of induced pressure pumping in a polymer microchannel due to differential electroosmotic flow @OF) rates via field-effect flow control (FEFC). The experimental results demonstrate that the induced pressure pumping is dependent on the distance of the FEFC gate from the cathodic gate. A proposed flow model based on a linearly-decaying zeta potential profile is found to successfully predict experimental trends.

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.

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.

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.

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.

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)

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

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.

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.

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...

Macro-Micro Simulation for Polymer Crystallization in Couette Flow

Directory of Open Access Journals (Sweden)

Chunlei Ruan

2017-12-01

Full Text Available Polymer crystallization in manufacturing is a process where quiescent crystallization and flow-induced crystallization coexists, and heat/mass transfer on a macroscopic level interacts with crystal morphology evolution on a microscopic level. Previous numerical studies on polymer crystallization are mostly concentrated at a single scale; they only calculate macroscale parameters, e.g., temperature and relative crystallinity, or they only predict microstructure details, e.g., crystal morphology and mean size of crystals. The multi-scale numerical works that overcome these disadvantages are unfortunately based on quiescent crystallization, in which flow effects are neglected. The objective of this work is to build up a macro-micro model and a macro-micro algorithm to consider both the thermal and flow effects on the crystallization. Our macro-micro model couples two parts: mass and heat transfer of polymeric flow at the macroscopic level, and nucleation and growth of spherulites and shish-kebabs at the microscopic level. Our macro-micro algorithm is a hybrid finite volume/Monte Carlo method, in which the finite volume method is used at the macroscopic level to calculate the flow and temperature fields, while the Monte Carlo method is used at the microscopic level to capture the development of spherulites and shish-kebabs. The macro-micro model and the macro-micro algorithm are applied to simulate polymer crystallization in Couette flow. The effects of shear rate, shear time, and wall temperature on the crystal morphology and crystallization kinetics are also discussed.

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...

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.

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.

Entangled Polymer Melts in Extensional Flow

DEFF Research Database (Denmark)

Hengeller, Ludovica

Many commercial materials derived from synthetic polymers exhibit a complex response under different processing operations such as fiber formation, injection moulding,film blowing, film casting or coatings. They can be processed both in the solid or in the melted state. Often they may contain two...... or more different polymers in addition to additives, fillers or solvents in order to modify the properties of the final product. Usually, it is also desired to improve the processability. For example the supplement of a high molecular weight component improves the stability in elongational flows....... Understanding the behaviour of polymer melts and solutions in complex non-linearflows is crucial for the design of polymeric materials and polymer processes. Through rheological characterization, in shear and extensional flow, of model polymer systems,i.e. narrow molar mass distribution polymer melts...

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.

Short-term flow induced crystallization in isotactic polypropylene : how short is short?

NARCIS (Netherlands)

Ma, Z.; Balzano, L.; Portale, G.; Peters, G.W.M.

2013-01-01

The so-called "short-term flow" protocol is widely applied in experimental flow-induced crystallization studies on polymers in order to separate the nucleation and subsequent growth processes [Liedauer et al. Int. Polym. Proc. 1993, 8, 236–244]. The basis of this protocol is the assumption that

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.

Degradation of amine-based water treatment polymers during chloramination as N-nitrosodimethylamine (NDMA) precursors.

Science.gov (United States)

Park, Sang-Hyuck; Wei, Shuting; Mizaikoff, Boris; Taylor, Amelia E; Favero, Cedrick; Huang, Ching-Hua

2009-03-01

Recent studies indicated that water treatment polymers such as poly(epichlorohydrin dimethylamine) (polyamine) and poly(diallyldimethylammonium chloride) (polyDADMAC) may form N-nitrosodimethylamine (NDMA) when in contact with chloramine water disinfectants. To minimize such potential risk and improve the polymer products, the mechanisms of how the polymers behave as NDMA precursors need to be elucidated. Direct chloramination of polymers and intermediate monomers in reagent water was conducted to probe the predominant mechanisms. The impact of polymer properties including polymer purity, polymer molecular weight and structure, residual dimethylamine (DMA), and other intermediate compounds involved in polymer synthesis, and reaction conditions such as pH, oxidant dose, and contact time on the NDMA formation potential (NDMA-FP) was investigated. Polymer degradation after reaction with chloramines was monitored at the molecular level using FT-IR and Raman spectroscopy. Overall, polyamines have greater NDMA-FP than polyDADMAC, and the NDMA formation from both polymers is strongly related to polymer degradation and DMA release during chloramination. Polyamines' tertiary amine chain ends play a major role in their NDMA-FP, while polyDADMACs' NDMA-FP is related to degradation of the quaternary ammonium ring group.

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.

Selectivity of radiation-induced processes in hydrocarbons, related polymers and organized polymer systems

International Nuclear Information System (INIS)

Feldman, V.I.; Sukhov, F.F.; Zezin, A.A.; Orlov, A.Yu.

1999-01-01

Fundamental aspects of the selectivity of radiation-induced events in polymers and polymeric systems were considered: (1) The grounds of selectivity of the primary events were analyzed on the basis of the results of studies of model compounds (molecular aspect). Basic results were obtained for hydrocarbon molecules irradiated in low-temperature matrices. The effects of selective localization of the primary events on the radical formation were examined for several polymers irradiated at low and superlow temperatures (77 and 15 K). A remarkable correlation between the properties of prototype ionized molecules (radical cations) and selectivity of the primary bond rupture in the corresponding polymers were found for polyethylene, polystyrene and some other hydrocarbon polymers. The first direct indication of selective localization of primary events at conformational defects was obtained for oriented high-crystalline polyethylene irradiated at 15 K. The significance of dimeric ring association was proved for the radiation chemistry of polystyrene. Specific mechanisms of low-temperature radiation-induced degradation were also analyzed for polycarbonate and poly(alkylene terephthalates). (2) Specific features of the localization of primary radiation-induced events in microheterogeneous polymeric systems were investigated (microstructural aspect). It was found that the interphase processes played an important role in the radiation chemistry of such systems. The interphase electron migration may result in both positive and negative non-additive effects in the formation of radiolysis products. The effects of component diffusion and chemical reactions on the radiation-induced processes in microheterogeneous polymeric systems were studied with the example of polycarbonate - poly(alkylene terephthalate) blends. (3) The effects of restricted molecular motion on the development of the radiation-chemical processes in polymers were investigated (dynamic aspect). In particular, it

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.

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)

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.

The flow properties and presence of crystals in drug-polymer mixtures

DEFF Research Database (Denmark)

Aho, J; Van Renterghem, J; Arnfast, L

2017-01-01

and ibuprofen with polyethylene oxide and methacrylate copolymer (Eudragit(®) E PO) were observed by polarized microscopy simultaneously while measuring their rheological properties within temperature ranges relevant for melt processes, such as hot melt extrusion and fused deposition modeling 3D printing....... The dissolution of solid crystalline matter into the molten polymer and its effects on the rheological parameters showed that the plasticization effect of the drug was highly dependent on the temperature range, and at a temperature high enough, plasticization induced by the small-molecule drugs could enhance...... morphological changes in the drug-polymer and the flow behavior of the drug-polymer mixtures at different temperature ranges and deformation modes....

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)

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

Comparison of the degradation behaviour of fusion-bonded epoxy powder coating systems under flowing and static immersion

International Nuclear Information System (INIS)

Wei, Y.H.; Zhang, L.X.; Ke, W.

2006-01-01

The degradation of three different fusion-bonded epoxy (FBE) powder coating systems under flowing and static immersion condition has been monitored using electrochemical impedance spectroscopy (EIS) when exposed to 3% NaCl aqueous solution at 60 o C. The aim of this project was to determine the impact of flowing condition on the degradation of the protective properties of polymer coatings during exposure to corrosive medium. Using a rotating cylinder apparatus, the immersion tests under the flowing condition were performed. The relative permittivity of coating, ε r =C c δε 0 A, where the coating capacitance C c was calculated from the high frequency data of impedance spectrum, was selected as the index to monitor property variation with immersion time. Experimental results showed that the flowing condition aggravated the deterioration of coatings. The results were interpreted in terms of a model in which flowing condition changes coating/solution interface state and then accelerates the ions to diffuse through the coating. The electrochemical results were in agreement with the final visual observation. The present investigation suggests that flowing test provides an effective accelerating way to evaluate the degradation of coating system

Nonequilibrium thermodynamics of dilute polymer solutions in flow.

Science.gov (United States)

Latinwo, Folarin; Hsiao, Kai-Wen; Schroeder, Charles M

2014-11-07

Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

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.

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...

Radiation induced estane polymer crosslinking

International Nuclear Information System (INIS)

Fletcher, M.; Foster, P.

1997-01-01

The exposure of polymeric materials to radiation has been known to induce the effects of crosslinking and degradation. The crosslinking phenomena comes about when two long chain polymers become linked together by a primary bond that extends the chain and increases the viscosity, molecular weight and the elastic modules of the polymer. This process has been observed in relatively short periods of time with fairly high doses of radiation, on the order of several megarads/hour. This paper address low dose exposure over long periods of time to determine what the radiation effects are on the polymeric binder material in PBX 9501. An experimental sample of binder material without explosives will be placed into a thermal and radiation field produced from a W-48 put mod 0. Another sample will be placed in a thermal environment without the radiation. The following is the test plan that was submitted to the Pantex process. The data presented here will be from the first few weeks of exposure and this test will be continued over the next few years. Subsequent data will hopefully be presented in the next compatibility and aging conference

Controlling hydrophilicity of polymer film by altering gas flow rate in atmospheric-pressure homogeneous plasma

International Nuclear Information System (INIS)

Kang, Woo Seok; Hur, Min; Lee, Jae-Ok; Song, Young-Hoon

2014-01-01

Graphical abstract: - Highlights: • Controlling hydrophilicity of polymer film by varying gas flow rate is proposed in atmospheric-pressure homogeneous plasma treatment. • Without employing additional reactive gas, requiring more plasma power and longer treatment time, hydrophilicity of polyimide films was improved after the low-gas-flow plasma treatment. • The gas flow rate affects the hydrophilic properties of polymer surface by changing the discharge atmosphere in the particular geometry of the reactor developed. • Low-gas-flow induced wettability control suggests effective and economical plasma treatment. - Abstract: This paper reports on controlling the hydrophilicity of polyimide films using atmospheric-pressure homogeneous plasmas by changing only the gas flow rate. The gas flow changed the discharge atmosphere by mixing the feed gas with ambient air because of the particular geometry of the reactor developed for the study, and a low gas flow rate was found to be favorable because it generated abundant nitrogen or oxygen species that served as sources of hydrophilic functional groups over the polymer surface. After low-gas-flow plasma treatment, the polymer surface exhibited hydrophilic characteristics with increased surface roughness and enhanced chemical properties owing to the surface addition of functional groups. Without adding any reactive gases or requiring high plasma power and longer treatment time, the developed reactor with low-gas-flow operation offered effective and economical wettability control of polyimide films

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.

Swift heavy ion induced modification of aliphatic polymers

Energy Technology Data Exchange (ETDEWEB)

Hossain, Umme Habiba

2015-01-15

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{sup 10} - 5 x 10{sup 12} ions/cm{sup 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

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 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

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...

Impact of polymer film thickness and cavity size on polymer flow during embossing : towards process design rules for nanoimprint lithography.

Energy Technology Data Exchange (ETDEWEB)

Schunk, Peter Randall; King, William P. (Georgia Institute of Technology, Atlanta, GA); Sun, Amy Cha-Tien; Rowland, Harry D. (Georgia Institute of Technology, Atlanta, GA)

2006-08-01

This paper presents continuum simulations of polymer flow during nanoimprint lithography (NIL). The simulations capture the underlying physics of polymer flow from the nanometer to millimeter length scale and examine geometry and thermophysical process quantities affecting cavity filling. Variations in embossing tool geometry and polymer film thickness during viscous flow distinguish different flow driving mechanisms. Three parameters can predict polymer deformation mode: cavity width to polymer thickness ratio, polymer supply ratio, and Capillary number. The ratio of cavity width to initial polymer film thickness determines vertically or laterally dominant deformation. The ratio of indenter width to residual film thickness measures polymer supply beneath the indenter which determines Stokes or squeeze flow. The local geometry ratios can predict a fill time based on laminar flow between plates, Stokes flow, or squeeze flow. Characteristic NIL capillary number based on geometry-dependent fill time distinguishes between capillary or viscous driven flows. The three parameters predict filling modes observed in published studies of NIL deformation over nanometer to millimeter length scales. The work seeks to establish process design rules for NIL and to provide tools for the rational design of NIL master templates, resist polymers, and process parameters.

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.

A 3D CFD Simulation and Analysis of Flow-Induced Forces on Polymer Piezoelectric Sensors in a Chinese Liquors Identification E-Nose

Directory of Open Access Journals (Sweden)

Yu Gu

2016-10-01

Full Text Available Chinese liquors can be classified according to their flavor types. Accurate identification of Chinese liquor flavors is not always possible through professional sommeliers’ subjective assessment. A novel polymer piezoelectric sensor electric nose (e-nose can be applied to distinguish Chinese liquors because of its excellent ability in imitating human senses by using sensor arrays and pattern recognition systems. The sensor, based on the quartz crystal microbalance (QCM principle is comprised of a quartz piezoelectric crystal plate sandwiched between two specific gas-sensitive polymer coatings. Chinese liquors are identified by obtaining the resonance frequency value changes of each sensor using the e-nose. However, the QCM principle failed to completely account for a particular phenomenon: we found that the resonance frequency values fluctuated in the stable state. For better understanding the phenomenon, a 3D Computational Fluid Dynamics (CFD simulation using the finite volume method is employed to study the influence of the flow-induced forces to the resonance frequency fluctuation of each sensor in the sensor box. A dedicated procedure was developed for modeling the flow of volatile gas from Chinese liquors in a realistic scenario to give reasonably good results with fair accuracy. The flow-induced forces on the sensors are displayed from the perspective of their spatial-temporal and probability density distributions. To evaluate the influence of the fluctuation of the flow-induced forces on each sensor and ensure the serviceability of the e-nose, the standard deviation of resonance frequency value (SDF and the standard deviation of resultant forces (SDFy in y-direction (Fy are compared. Results show that the fluctuations of Fy are bound up with the resonance frequency values fluctuations. To ensure that the sensor's resonance frequency values are steady and only fluctuate slightly, in order to improve the identification accuracy of Chinese

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.

Shock wave emission from laser-induced cavitation bubbles in polymer solutions.

Science.gov (United States)

Brujan, Emil-Alexandru

2008-09-01

The role of extensional viscosity on the acoustic emission from laser-induced cavitation bubbles in polymer solutions and near a rigid boundary is investigated by acoustic measurements. The polymer solutions consist of a 0.5% polyacrylamide (PAM) aqueous solution with a strong elastic component and a 0.5% carboxymethylcellulose (CMC) aqueous solution with a weak elastic component. A reduction of the maximum amplitude of the shock wave pressure and a prolongation of the oscillation period of the bubble were found in the elastic PAM solution. It might be caused by an increased resistance to extensional flow which is conferred upon the liquid by the polymer additive. In both polymer solutions, however, the shock pressure decays proportionally to r(-1) with increasing distance r from the emission centre.

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.

Radiation effects on polymer materials. Ionizing radiation induces degradation or improvement? (2) Gas evolution by irradiation

International Nuclear Information System (INIS)

Sasuga, Tsuneo

2005-01-01

The present article reviews gas evolution from organic polymers induced by ionizing radiations, focusing on gamma-ray irradiation of PE (polyethylene) and PP (polypropylene)-model compounds at temperatures from -77 to 55degC. In the polyolefins, the main gas evolved by irradiation is hydrogen with G-value of 3-4 at room temperatures and G(H 2 ) is 1.8 at 77K. For PE, G(H 2 ) is higher for the low-density PE than for higher-density PE. For the halogenated polymers as PVC, etc., evolved gas is hydrogen halogenated: G(HCl)=6.8 for PVC. For the case where the irradiation is accompanied with the oxidation of polymers, the de-oxygenation and formation of carboxylic radicals are remarkably high and known to emit a bad smell which depends on the thickness of oxidized layers. In conclusion, the gas evolution can be estimated by considering the molecular structure of polymer materials. (S.Ohno)

The Use of Radiation-Induced Degradation in Controlling Molecular Weights of Polysaccharides : The Effect of Humidity

International Nuclear Information System (INIS)

Sen, M.

2006-01-01

Better understanding of chemistry of radiation-induced degradation is becoming of increasing importance on account of the utilization of polymeric materials in a variety of radiation environments as well as beneficial uses of degraded polymers. It is very well known that polysaccharides in dry form or in solution degrade when exposed to ionizing radiation. In this study degrading effect of radiation has been considered from the point of view of controlling the molecular weights of kappa- and iota-carrageenans and sodium alginate irradiated under varying environmental conditions. The humidity equilibrated polymer samples kept over saturated aqueous salt solutions of NaCl, NaNO 3 and MgCl 2 were irradiated in a Gammacell 220 at room temperature. The degradation was investigated in detail by a careful Gel Permeation Chromatographic analysis of their respective molecular weights before and after irradiation Alexander-Charlesby-Ross equation was used in determining their radiation-chemical yields. Degradation yield is the highest for dry irradiated kappa- (G(S) = 0.73) and iota-carrageenans (G(S) = 2.43) and with small amount of water taken up from surrounding humidity degradation becomes less pronounced and G(S) values show a decrease down to G(S) = 0.16 and 0.87 at 75 % relative humidity, respectively. At very high water contents degradation effect again becomes more effective. Sodium alginate has fount to be less sensitive to the effect of humidity. When there is small amount of water in the polysaccharide structure, it is unlikely to expect an indirect effect of radiation. The water located in between the polymer chains however can give enough mobility to kappa and iota karrageenans chains, plastifying effect, which may enhance the radical-radical combinations thus lowering the rate of degradation hence reducing G(S) values

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.

IR Laser-Induced Degradation of Poly(vinyl acetate): Novel Thermal Reactions in the Solid Polymers

Czech Academy of Sciences Publication Activity Database

Kupčík, Jaroslav; Blazevska-Gilev, J.; Pola, Josef

2005-01-01

Roč. 26, č. 5 (2005), s. 386-389 ISSN 1022-1336 R&D Projects: GA ČR(CZ) GA104/04/2028 Institutional research plan: CEZ:AV0Z40720504 Keywords : laser ablation * laser-induced polymers * poly(vinyl acetate) Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.126, year: 2005

Fluctuation-induced long-range interactions in polymer systems

International Nuclear Information System (INIS)

Semenov, A N; Obukhov, S P

2005-01-01

We discover a new universal long-range interaction between solid objects in polymer media. This polymer-induced interaction is directly opposite to the van der Waals attraction. The predicted effect is deeply related to the classical Casimir interactions, providing a unique example of universal fluctuation-induced repulsion rather than normal attraction. This universal repulsion comes from the subtracted soft fluctuation modes in the ideal counterpart of the real polymer system. The effect can also be interpreted in terms of subtracted (ghost) large-scale polymer loops. We establish the general expressions for the energy of polymer-induced interactions for arbitrary solid particles in a concentrated polymer system. We find that the correlation function of the polymer density in a concentrated solution of very long chains follows a scaling law rather than an exponential decay at large distances. These novel universal long-range interactions can be of importance in various polymer systems. We discuss the ways to observe/simulate these fluctuation-induced effects

Degradation of Fluorotelomer-Based Polymers Contributes to the Global Occurrence of Fluorotelomer Alcohol and Perfluoroalkyl Carboxylates: A Combined Dynamic Substance Flow and Environmental Fate Modeling Analysis.

Science.gov (United States)

Li, Li; Liu, Jianguo; Hu, Jianxin; Wania, Frank

2017-04-18

Using coupled dynamic substance flow and environmental fate models, CiP-CAFE and BETR-Global, we investigated whether the degradation of side-chain fluorotelomer-based polymers (FTPs), mostly in waste stocks (i.e., landfills and dumps), serves as a long-term source of fluorotelomer alcohols (FTOHs) and perfluoroalkyl carboxylates (PFCAs) to the global environment. The modeling results indicate that, in the wake of the worldwide transition from long-chain to short-chain products, in-use stocks of C8 FTPs will peak and decline afterward, while the in-use stocks of C6 FTPs, and the waste stocks of both FTPs will generally grow. FTP degradation in waste stocks is making an increasing contribution to FTOH generation, the bulk of which readily migrates from waste stocks and degrades into PFCAs in the environment; the remaining part of the generated FTOHs degrade in waste stocks, which makes those stocks reservoirs that slowly release PFCAs into the environment over the long run because of the low leaching rate and extreme persistence of PFCAs. Short-chain FTPs have higher relative release rates of PFCAs from waste stocks than long-chain ones. Estimates of in-use and waste stocks of FTPs were more sensitive to the selected lifespan of finished products, while those of the emissions of FTOHs and PFCAs were more sensitive to the degradation half-life of FTPs in waste stocks. Our preliminary calculations highlight the need for environmentally sound management of obsolete FTP-containing products into the foreseeable future.

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.

Carbon-13 Labeling Used to Probe Cure and Degradation Reactions of High- Temperature Polymers

Science.gov (United States)

Meador, Mary Ann B.; Johnston, J. Christopher

1998-01-01

High-temperature, crosslinked polyimides are typically insoluble, intractible materials. Consequently, in these systems it has been difficult to follow high-temperature curing or long-term degradation reactions on a molecular level. Selective labeling of the polymers with carbon-13, coupled with solid nuclear magnetic resonance spectrometry (NMR), enables these reactions to be followed. We successfully employed this technique to provide insight into both curing and degradation reactions of PMR-15, a polymer matrix resin used extensively in aircraft engine applications.

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

Diffusion of drag-reducing polymer solutions within a rough-walled turbulent boundary layer

Science.gov (United States)

Elbing, Brian R.; Dowling, David R.; Perlin, Marc; Ceccio, Steven L.

2010-04-01

The influence of surface roughness on diffusion of wall-injected, drag-reducing polymer solutions within a turbulent boundary layer was studied with a 0.94 m long flat-plate test model at speeds of up to 10.6 m s-1 and Reynolds numbers of up to 9×106. The surface was hydraulically smooth, transitionally rough, or fully rough. Mean concentration profiles were acquired with planar laser induced fluorescence, which was the primary flow diagnostic. Polymer concentration profiles with high injection concentrations (≥1000 wppm) had the peak concentration shifted away from the wall, which was partially attributed to a lifting phenomenon. The diffusion process was divided into three zones—initial, intermediate, and final. Studies of polymer injection into a polymer ocean at concentrations sufficient for maximum drag reduction indicated that the maximum initial zone length is of the order of 100 boundary layer thicknesses. The intermediate zone results indicate that friction velocity and roughness height are important scaling parameters in addition to flow and injection conditions. Lastly, the current results were combined with those in Petrie et al. ["Polymer drag reduction with surface roughness in flat-plate turbulent boundary layer flow," Exp. Fluids 35, 8 (2003)] to demonstrate that the influence of polymer degradation increases with increased surface roughness.

FT-IR study of gamma-radiation induced degradation of polyvinyl alcohol (PVA) and PVA/humic acids blends

International Nuclear Information System (INIS)

Ilcin, M.; Hola, O.; Bakajova, B.; Kucerik, J.

2010-01-01

Samples of pure polyvinyl alcohol (PVA) and PVA doped with humic acids were exposed to gamma radiation. Gamma rays induced the degradation of the pure polymer. Degradation changes were observed using ATR FT-IR equipment. Dehydration, double bond creation, and their subsequent oxidation (surrounding atmosphere was air) were found out. Also, other degradation reactions (e.g. chain scission, cyclization) occur simultaneously. Formation of C=C and C=O bonds is apparent from FT-IR spectra. In contrast the presence of humic acids in the PVA sample showed stabilizing effect on PVA structure within the concentration range 0.5-10%. (author)

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.

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.

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.

The effects of slit-like confinement on flow-induced polymer deformation

Science.gov (United States)

Ghosal, Aishani; Cherayil, Binny J.

2017-08-01

This paper is broadly concerned with the dynamics of a polymer confined to a rectangular slit of width D and deformed by a planar elongational flow of strength γ ˙ . It is interested, more specifically, in the nature of the coil-stretch transition that such polymers undergo when the flow strength γ ˙ is varied, and in the degree to which this transition is affected by the presence of restrictive boundaries. These issues are explored within the framework of a finitely extensible Rouse model that includes pre-averaged surface-mediated hydrodynamic interactions. Calculations of the chain's steady-state fractional extension x using this model suggest that different modes of relaxation (which are characterized by an integer p) exert different levels of control on the coil-stretch transition. In particular, the location of the transition (as identified from the graph of x versus the Weissenberg number Wi, a dimensionless parameter defined by the product of γ ˙ and the time constant τp of a relaxation mode p) is found to vary with the choice of τp. In particular, when τ1 is used in the definition of Wi, the x vs. Wi data for different D lie on a single curve, but when τ3 is used instead (with τ3 > τ1) the corresponding data lie on distinct curves. These findings are in close qualitative agreement with a number of experimental results on confinement effects on DNA stretching in electric fields. Similar D-dependent trends are seen in our calculated force vs. Wi data, but force vs. x data are essentially D-independent and lie on a single curve.

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.

Electrochemical degradation of the chloramphenicol at flow reactor

International Nuclear Information System (INIS)

Rezende, Luis Gustavo P.; Prado, Vania M. do; Rocha, Robson S.; Beati, Andre A.G.F.; Sotomayor, Maria del Pilar T.; Lanza, Marcos R.V.

2010-01-01

This paper reports a study of electrochemical degradation of the chloramphenicol antibiotic in aqueous medium using a flow-by reactor with DSA anode. The process efficiency was monitored by chloramphenicol concentration analysis with liquid chromatography (HPLC) during the experiments. Analysis of Total Organic Carbon (TOC) was performed to estimate the degradation degree and Ion Chromatography (IC) was performed to determinate inorganic ions formed during the electrochemical degradation process. In electrochemical flow-by reactor, 52% of chloramphenicol was degraded, with 12% TOC reduction. IC analysis showed the production of chloride ions (25 mg L -1 ), nitrate ions (6 mg L -1 ) and nitrite ions (4.5 mg L -1 ). (author)

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)

Branched multifunctional polyether polyketals: variation of ketal group structure enables unprecedented control over polymer degradation in solution and within cells.

Science.gov (United States)

Shenoi, Rajesh A; Narayanannair, Jayaprakash K; Hamilton, Jasmine L; Lai, Benjamin F L; Horte, Sonja; Kainthan, Rajesh K; Varghese, Jos P; Rajeev, Kallanthottathil G; Manoharan, Muthiah; Kizhakkedathu, Jayachandran N

2012-09-12

Multifunctional biocompatible and biodegradable nanomaterials incorporating specific degradable linkages that respond to various stimuli and with defined degradation profiles are critical to the advancement of targeted nanomedicine. Herein we report, for the first time, a new class of multifunctional dendritic polyether polyketals containing different ketal linkages in their backbone that exhibit unprecedented control over degradation in solution and within the cells. High-molecular-weight and highly compact poly(ketal hydroxyethers) (PKHEs) were synthesized from newly designed α-epoxy-ω-hydroxyl-functionalized AB(2)-type ketal monomers carrying structurally different ketal groups (both cyclic and acyclic) with good control over polymer properties by anionic ring-opening multibranching polymerization. Polymer functionalization with multiple azide and amine groups was achieved without degradation of the ketal group. The polymer degradation was controlled primarily by the differences in the structure and torsional strain of the substituted ketal groups in the main chain, while for polymers with linear (acyclic) ketal groups, the hydrophobicity of the polymer may play an additional role. This was supported by the log P values of the monomers and the hydrophobicity of the polymers determined by fluorescence spectroscopy using pyrene as the probe. A range of hydrolysis half-lives of the polymers at mild acidic pH values was achieved, from a few minutes to a few hundred days, directly correlating with the differences in ketal group structures. Confocal microscopy analyses demonstrated similar degradation profiles for PKHEs within live cells, as seen in solution and the delivery of fluorescent marker to the cytosol. The cell viability measured by MTS assay and blood compatibility determined by complement activation, platelet activation, and coagulation assays demonstrate that PKHEs and their degradation products are highly biocompatible. Taken together, these data

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.

Effect of dose on radiation-induced conductivity in polymers

International Nuclear Information System (INIS)

Tyutnev, A.P.; Saenko, V.S.; Pozhidaev, E.D.; Ikhsanov, R.Sh.

2007-01-01

Numerical simulation of radiation-induced conductivity in polymers upon long-term irradiation on the basis of the generalized Rose-Fowler-Vaisberg model, which allows for both dipolar carrier transport and generation of radiation traps during irradiation, was performed. The unusual properties of radiation-induced conductivity, such as the appearance of a maximum on current transients, the absence of a steady state, and a substantial difference between these curves for the first and subsequent irradiation, are rationalized in terms of the formation of free radicals, the major feature of radiolysis in the chemical aspect. This interpretation does not require the involvement of degradation or crosslinking processes, unlike other interpretations that appear in the literature. With the use of low-density polyethylene as an example, it was shown that radiation-induced conductivity both upon pulse and continuous irradiation can satisfactorily be described with the unified set of parameters of the generalized Rose-Fowler-Vaisberg model [ru

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.

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.

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.

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.

Dynamics of polymers in elongational flow studied by the neutron spin-echo technique

International Nuclear Information System (INIS)

Rheinstaedter, Maikel C.; Sattler, Rainer; Haeussler, Wolfgang; Wagner, Christian

2010-01-01

The nanoscale fluctuation dynamics of semidilute high molecular weight polymer solutions of polyethylenoxide (PEO) in D 2 O under non-equilibrium flow conditions were studied by the neutron spin-echo technique. The sample cell was in contraction flow geometry and provided a pressure driven flow with a high elongational component that stretched the polymers most efficiently. Neutron scattering experiments in dilute polymer solutions are challenging because of the low polymer concentration and corresponding small quasi-elastic signals. A relaxation process with relaxation times of about 10 ps was observed, which shows anisotropic dynamics with applied flow.

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

Modification of near-wall coherent structures in polymer drag reduced flow: simulation

Science.gov (United States)

Dubief, Yves; White, Christopher; Shaqfeh, Eric; Moin, Parviz; Lele, Sanjiva

2002-11-01

Polymer drag reduced flows are investigated through direct numerical simulations of viscoelastic flows. The solver for the viscoelastic model (FENE-P) is based on higher-order finite difference schemes and a novel implicit time integration method. Its robustness allows the simulation of all drag reduction (DR) regimes from the onset to the maximum drag reduction (MDR). It also permits the use of realistic polymer length and concentration. The maximum polymer extension in our simulation matches that of a polystyrene molecule of 10^6 molecular weight. Two distinct regimes of polymer drag reduced flows are observed: at low drag reduction (LDR, DR< 40-50%), the near-wall structure is essentially similar to Newtonian wall turbulence whereas the high drag reduction regime (HDR, DR from 40-50% to MDR) shows significant differences in the organization of the coherent structures. The 3D information provided by numerical simulations allows the determination of the interaction of polymers and near-wall coherent structures. To isolate the contribution of polymers in the viscous sublayer, the buffer and the outer region of the flow, numerical experiments are performed where the polymer concentration is varied in the wall-normal direction. Finally a mechanism of polymer drag reduction derived from our results and PIV measurements is discussed.

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.

Oxygen- and water-induced degradation of an inverted polymer solar cell: the barrier effect

DEFF Research Database (Denmark)

Vesterager Madsen, Morten; Norrman, Kion; Krebs, Frederik C

2011-01-01

The work focuses on the degradation of performance induced by both water and oxygen in an inverted geometry organic photovoltaic device with emphasis on the accumulated barrier effect of the layers comprising the layer stack. By studying the exchange of oxygen in the zinc oxide (ZnO) layer...... in the humid atmosphere, correlating well with a long observed lifetime in the same atmosphere.© 2011 Society of Photo-Optical Instrumentation Engineers....

Evaluation of Maltose-Induced Chemical Degradation at the Interface of Bilayer Tablets.

Science.gov (United States)

Matsuzaki, Naoya; Yamamoto, Yousuke; Murayama, Daisuke; Katakawa, Yoshifumi; Mimura, Hisashi; Kimura, Shin-Ichiro; Iwao, Yasunori; Itai, Shigeru

2017-01-01

Fixed dose combination tablets consisting of mirabegron (MB) and solifenacin succinate (SS) were developed and formulated into bilayer tablets in the current study. The results of a chemical stability study showed that the original formulation for the tablets led to a significant increase of unknown degradants in the SS layer. Two compatibility studies were conducted to simulate the interface between the MB and SS layers, and the results revealed that the degradants only formed in the presence of both active pharmaceutical ingredients (APIs), and that the presence of maltose in the SS layer was critical to inducing degradation. High resolution mass spectroscopy coupled with high performance liquid chromatography was used to determine the chemical structures of the degradants, which were identified to MB derivatives bearing one or two sugar units. These findings therefore suggested that the degradation of the API could be attributed to the addition of sugar units from maltose to MB under the acidic conditions caused by SS. With this in mind, we developed a new formulation by replacing maltose with hydroxypropyl cellulose as a polymer-type binder. The results showed that this formulation suppressed the formation of the degradants. The results of this study have shown that chemical degradation can occur at the interface of bilayer tablets and that an alternative strategy is available to formulate more stable MB/SS bilayer tablets.

PIV measurement of turbulent mixing layer flow with polymer additives

International Nuclear Information System (INIS)

Ning, T; Guo, F; Chen, B; Zhang, X

2009-01-01

Turbulent mixing layer flow with polymer additives was experimentally investigated by PIV in present paper. The velocity ratio between high and low speed is 4:1 and the Reynolds number for pure water case based on the velocity differences of two steams and hydraulic diameter of the channel ranges from 14667∼73333. Flow field and turbulent quantities of turbulent mixing layer with 200ppm polymer additives were measured and compared with pure water mixing layer flow. It is shown that the dynamic development of mixing layer is greatly influenced by polymer addictives. The smaller vortices are eliminated and the coherent structure is much clearer. Similar with pure water case, Reynolds stress and vorticity still concentrate in a coniform area of central part of mixing layer and the width will increase with the Reynolds number increasing. However, compared with pure water case, the coniform width of polymer additives case is larger, which means the polymer additives will lead to the diffusion of coherent structure. The peak value of vorticity in different cross section will decrease with the development of mixing layer. Compared with pure water case, the vorticity is larger at the beginning of the mixing layer but decreases faster in the case with polymer additives.

Enhanced tolerance to stretch-induced performance degradation of stretchable MnO2-based supercapacitors.

Science.gov (United States)

Huang, Yan; Huang, Yang; Meng, Wenjun; Zhu, Minshen; Xue, Hongtao; Lee, Chun-Sing; Zhi, Chunyi

2015-02-04

The performance of many stretchable electronics, such as energy storage devices and strain sensors, is highly limited by the structural breakdown arising from the stretch imposed. In this article, we focus on a detailed study on materials matching between functional materials and their conductive substrate, as well as enhancement of the tolerance to stretch-induced performance degradation of stretchable supercapacitors, which are essential for the design of a stretchable device. It is revealed that, being widely utilized as the electrode material of the stretchable supercapacitor, metal oxides such as MnO2 nanosheets have serious strain-induced performance degradation due to their rigid structure. In comparison, with conducting polymers like a polypyrrole (PPy) film as the electrochemically active material, the performance of stretchable supercapacitors can be well preserved under strain. Therefore, a smart design is to combine PPy with MnO2 nanosheets to achieve enhanced tolerance to strain-induced performance degradation of MnO2-based supercapacitors, which is realized by fabricating an electrode of PPy-penetrated MnO2 nanosheets. The composite electrodes exhibit a remarkable enhanced tolerance to strain-induced performance degradation with well-preserved performance over 93% under strain. The detailed morphology and electrochemical impedance variations are investigated for the mechanism analyses. Our work presents a systematic investigation on the selection and matching of electrode materials for stretchable supercapacitors to achieve high performance and great tolerance to strain, which may guide the selection of functional materials and their substrate materials for the next-generation of stretchable electronics.

X-ray induced degradation of DNA in Aspergillus nidulans cells comparative analysis of UV- and X-ray induced DNA degradation

International Nuclear Information System (INIS)

Zinchenko, V.V.; Babykin, M.M.

1980-01-01

Irradiating cells of Aspergillus nidulans of the wild type in the logarythmical growth phase with X-rays leads to a certain retention in DNA synthesis. This period is characterized by an insignificant fermentative DNA degradation connected with a process of its repair. There is no direct dependence between the radiation dose and the level of DNA degradation. The investigation of X-ray induced DNA degradation in a number of UVS-mutants permits to show the existence of two branches of DNA degradation - dependent and independent of the exogenic energy source. The dependence of DNA degradation on albumen synthesis prior to irradiation and after it, is demonstrated. It is supposed that the level of X-ray induced DNA degradation is determined by two albumen systems, one of which initiates degradation and the other terminates it. The comparative analysis of UV and X-ray induced DNA degradation is carried out

Polymer fragmentation in extensional flow

Energy Technology Data Exchange (ETDEWEB)

Maroja, Armando M.; Oliveira, Fernando A.; Ciesla, Michal; Longa, Lech

2001-06-01

In this paper we present an analysis of fragmentation of dilute polymer solutions in extensional flow. The transition rate is investigated both from theoretical and computational approaches, where the existence of a Gaussian distribution for the breaking bonds has been controversial. We give as well an explanation for the low fragmentation frequency found in DNA experiments.

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

Effect of sulphuric acid concentration on electroosmotic flow through polymer electrolyte membranes in PEM fuel cells. Paper no. IGEC-1-061

International Nuclear Information System (INIS)

Karimi, G.; Li, X.

2005-01-01

Polymer electrolyte membrane (PEM) fuel cells are highly efficient and environmentally clean, and hence one of the most promising power sources for both stationary and mobile applications. The operations of PEM fuel cells are complicated by the electroosmotic flow of water from anode to cathode through the polymer electrolyte membrane leading to the membrane dehydration and fuel cell performance degradations. In this study, electro osmotic flow in polymer electrolyte membranes is modeled by incorporating the electro kinetic effects in the presence of euphoric acid. The governing Poisson-Boatman and the Nervier-Stokes equations were solved numerically for a single membrane pore to determine the electro osmotic flow distributions through the membrane over a wide range of acid concentrations. The presence of euphoric acid modifies the protons distribution in the membrane and hence alters the driving force for electroosmotic drag. Numerical results indicate that the electro osmotic flow increases steadily with acid concentration. The water transport due to electro osmosis is almost doubled at 2 M acid concentration compared with that of non-doped membrane. The value of electroosmotic drag coefficient however falls steadily with acid concentration due to the presence of a larger number of protons in the electrolyte. (author)

Flow-induced coalescence: arbitrarily mobile interface model and choice of its parameters

Czech Academy of Sciences Publication Activity Database

Fortelný, Ivan; Jůza, Josef

2015-01-01

Roč. 60, č. 10 (2015), s. 628-635 ISSN 0032-2725 R&D Projects: GA ČR GAP106/11/1069 Institutional support: RVO:61389013 Keywords : flow-induced coalescence * polymer blends * interface mobility Subject RIV: BK - Fluid Dynamics Impact factor: 0.718, year: 2015

Study on Mechanism of Viscoelastic Polymer Transient Flow in Porous Media

Directory of Open Access Journals (Sweden)

Huiying Zhong

2017-01-01

Full Text Available Oil recovery, including conventional and viscous oil, can be improved significantly by flooding with polymer solutions. This chemical flooding method can increase oil production, and it can improve the macrodisplacement efficiency and microsweep efficiencies. In this study, we establish physical models that include the dead-end and complex models based on the pore-network pattern etched into glass, using the snappyHexMesh solver in OpenFOAM. These models capture the complexity and topology of porous media geometry. We establish a mathematical model for transient flows of viscoelastic polymers using computational fluid dynamics simulations, and we study the distributions of pressure and velocity for different elasticity scenarios and different flooding process. The results demonstrate that the pressure difference increases as the relaxation time decreases, before the flow reaches its steady state. For a steady flow, elasticity can give rise to an additional pressure difference, which increases with increasing elasticity. Thus, the characteristics of pressure difference vary before and after the flow becomes steady; this phenomenon is very important. Velocity contours become more widely spaced with elasticity increase. This suggests that elasticity of the polymer solutions contributes to the microsweep efficiency. The results of the study provide the necessary theoretical foundation for laboratory experiments and development of methods for polymer flooding and can be helpful for the design and selection of polymers for polymer flooding.

Use of radiation-induced polymers as temporary or permanent diverting agent

International Nuclear Information System (INIS)

Knight, B.L.; Rhudy, J.S.; Gogarty, W.B.

1975-01-01

Temporary or permanent permeability reduction or plugging of porous medium to the flow of fluids is effected by treating, preferably by injecting under pressure into the pores, the porous medium with an aqueous solution containing a water-soluble polymer obtained as a product of radiation-induced polymerization of acrylamide and/or methacrylamide and acrylic acid, methacrylic acid, and/or alkali metal salts thereof. The polymer has sufficient properties to effect substantial permeability reduction of the porous medium. The polymerization is preferably carried out in 10 to 60 percent aqueous monomer solution with gamma radiation. A mixture of monomers, before radiation preferably contain 25 to 99 percent acrylamide and 75 to 1 percent sodium acrylate. Permeability can be restored by subsequently treating the porous medium with a chemical to break down the polymer, e.g., hydrazine hypochlorite solution, strong mineral acids, or bases. (U.S.)

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

Radiation processing of polymer emulsion, (4). Radiation-induced emulsion polymerization of methyl methacrylate at low temperature

Energy Technology Data Exchange (ETDEWEB)

Makuuchi, Keizo; Katakai, Akio; Ito, Hiroshi; Hayakawa, Naohiro; Araki, Kunio (Japan Atomic Energy Research Inst., Takasaki, Gunma. Takasaki Radiation Chemistry Research Establishment)

1983-06-01

Methyl methacrylate was polymerized in emulsion by Co-60 ..gamma..-rays below 19 deg C in a batch reactor by using sodium lauryl sulfate as emulsifier. The conversion-time curves of the polymerization system showed two rate regions, i.e., a fact conversion rate in early stage, and a much slower rate in latter stage. The change in rate occurred at about 70 % conversion. The molecular weight of product polymer decreased with increasing conversion during the course of polymerization in latter stage, in contrast to the behavior in early stage. The distribution of the monomer in emulsion in latter stage was evaluated by nuclear magnetic resonance technique. The decrease of the molecular weight with conversion is due to the radiation-induced degradation of product polymer accelerated by the monomers absorbed in the polymer particles.

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

Thermal/chemical degradation of ceramic cross-flow filter materials

Energy Technology Data Exchange (ETDEWEB)

Alvin, M.A.; Lane, J.E.; Lippert, T.E.

1989-11-01

This report summarizes the 14-month, Phase 1 effort conducted by Westinghouse on the Thermal/Chemical Degradation of Ceramic Cross-Flow Filter Materials program. In Phase 1 expected filter process conditions were identified for a fixed-bed, fluid-bed, and entrained-bed gasification, direct coal fired turbine, and pressurized fluidized-bed combustion system. Ceramic cross-flow filter materials were also selected, procured, and subjected to chemical and physical characterization. The stability of each of the ceramic cross-flow materials was assessed in terms of potential reactions or phase change as a result of process temperature, and effluent gas compositions containing alkali and fines. In addition chemical and physical characterization was conducted on cross-flow filters that were exposed to the METC fluid-bed gasifier and the New York University pressurized fluidized-bed combustor. Long-term high temperature degradation mechanisms were proposed for each ceramic cross-flow material at process operating conditions. An experimental bench-scale test program is recommended to be conducted in Phase 2, generating data that support the proposed cross-flow filter material thermal/chemical degradation mechanisms. Papers on the individual subtasks have been processed separately for inclusion on the data base.

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

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

KAUST Repository

Heumueller, Thomas

2014-08-01

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 polymer is used. We show that the light-induced traps are in the bulk of the active layer and we find a direct correlation between their presence and the open-circuit voltage loss in devices made with amorphous polymers. Solar cells made with crystalline polymers do not show characteristic open circuit voltage losses, even though light-induced traps are also present in these devices. This indicates that crystalline materials are more resistant against the influence of traps on device performance. Recent work on crystalline materials has shown there is an energetic driving force for charge carriers to leave amorphous, mixed regions of bulk heterojunctions, and charges are dominantly transported in pure, ordered phases. This energetic landscape allows efficient charge generation as well as extraction and also may benefit the stability against light-induced traps. This journal is © the Partner Organisations 2014.

Superhydrophobic and polymer drag reduction in turbulent Taylor-Couette flow

Science.gov (United States)

Rajappan, Anoop; McKinley, Gareth H.

2017-11-01

We use a custom-built Taylor-Couette apparatus (radius ratio η = 0.75) to study frictional drag reduction by dilute polymer solutions and superhydrophobic (SH) surfaces in turbulent flows for 15000 analysis. We also investigate drag reduction by dilute polymer solutions, and show that natural biopolymers from plant mucilage can be an inexpensive and effective alternative to synthetic polymers in drag reduction applications, approaching the same maximum drag reduction asymptote. Finally we explore combinations of the two methods - one arising from wall slip and the other due to changes in turbulence dynamics in the bulk flow - and find that the two effects are not additive; interestingly, the effectiveness of polymer drag reduction is drastically reduced in the presence of an SH coating on the wall. This study was financially supported by the Office of Naval Research (ONR) through Contract No. 3002453814.

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.

Coating flexible probes with an ultra fast degrading polymer to aid in tissue insertion.

Science.gov (United States)

Lo, Meng-chen; Wang, Shuwu; Singh, Sagar; Damodaran, Vinod B; Kaplan, Hilton M; Kohn, Joachim; Shreiber, David I; Zahn, Jeffrey D

2015-04-01

We report a fabrication process for coating neural probes with an ultrafast degrading polymer to create consistent and reproducible devices for neural tissue insertion. The rigid polymer coating acts as a probe insertion aid, but resorbs within hours post-implantation. Despite the feasibility for short term neural recordings from currently available neural prosthetic devices, most of these devices suffer from long term gliosis, which isolates the probes from adjacent neurons, increasing the recording impedance and stimulation threshold. The size and stiffness of implanted probes have been identified as critical factors that lead to this long term gliosis. Smaller, more flexible probes that match the mechanical properties of brain tissue could allow better long term integration by limiting the mechanical disruption of the surrounding tissue during and after probe insertion, while being flexible enough to deform with the tissue during brain movement. However, these small flexible probes inherently lack the mechanical strength to penetrate the brain on their own. In this work, we have developed a micromolding method for coating a non-functional miniaturized SU-8 probe with an ultrafast degrading tyrosine-derived polycarbonate (E5005(2K)). Coated, non-functionalized probes of varying dimensions were reproducibly fabricated with high yields. The polymer erosion/degradation profiles of the probes were characterized in vitro. The probes were also mechanically characterized in ex vivo brain tissue models by measuring buckling and insertion forces during probe insertion. The results demonstrate the ability to produce polymer coated probes of consistent quality for future in vivo use, for example to study the effects of different design parameters that may affect tissue response during long term chronic intra-cortical microelectrode neural recordings.

Degradation of polyethylene induced by plasma in oxidizing atmospheres

International Nuclear Information System (INIS)

Colin, E.; Olayo, M.G.; Cruz, G.J.

2002-01-01

The garbage of polyethylene is not easily degradable in normal environmental conditions . The indiscriminate use of this polymer and the enormous quantity of garbage which is generated carries a damage to the environment due to its long life as waste. The objective of this work is to study the conditions in which can be carried out the degradation of polyethylene. A form of accelerating the degradation is exposing it to plasma with reactive atmospheres. In this work a study of surface modification of polyethylene by plasmas with discharges of direct current of oxygen and nitrogen is presented. (Author)

Flow and Failure in Extension of Monodisperse Polymer Melts

DEFF Research Database (Denmark)

Rasmussen, Henrik K.

is commonly referred to be of either brittle (e.g. cohesive type) or of liquid (e.g. necking type) nature. Here the focus will be on monodisperse polymers, to study numerically the sample flow dynamics in dual wind-up extensional rheometers. The computations are within the ideas of the microstructural......It is well known that failure or rupture phenomenon appears in the extension of polymer melts. These appear not only as failure in extension rheometers, but also as sharkskin, developments of holes in thin polymeric films etc. Sometime these ruptures appear spontaneous as well. The rupture...... 'interchain pressure' theory based on the molecular stress function constitutive model for the polymer melt flow. The purpose is twofold. Primarily to present to what extend the experimentally observed failure, appearing during or after (e.g. as a spontaneous failure) extension, can be explained within...

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).

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene in flow system, 8

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Ito, Masayuki; Machi, Sueo; Okamoto, Jiro.

1982-02-01

Seeded copolymerization of tetrafluoroethylene with propylene by radiation was carried out in a flow apparatus with pipe reactor at a pressure of 30 kg/cm 2 , a temperature of 40 0 C, a propylene fraction in monomer gas of 0.1, and at various dose rates. Amounts of dissolved monomer in latex increases in proportion to the polymer concentration, however, it becomes lower than that in equilibrium as polymerization proceeds. Propylene fraction in the dissolved monomer decreases with reaction time. Polymer concentration in latex increases accelerately with reaction time, and polymerization rate increases and tends to level off when the polymer concentration exceeds 100 g/l-H 2 O at higher dose rate. Polymerization rate is proportional to the 0.6 power of the dose rate at the polymer concentration of 50 g/l-H 2 O, and the power factor decreases from 0.46 to 0.39 with increasing the concentration from 100 to 150 g/l-H 2 O. Molecular weight of the polymer is proportional to the -0.17 power of the dose rate. The dose rate effects are explained by considering both first-order termination by degradative chain transfer to propylene and second-order termination by recombination. (author)

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.

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

Glycocalyx Degradation Induces a Proinflammatory Phenotype and Increased Leukocyte Adhesion in Cultured Endothelial Cells under Flow.

Directory of Open Access Journals (Sweden)

Karli K McDonald

Full Text Available Leukocyte adhesion to the endothelium is an early step in the pathogenesis of atherosclerosis. Effective adhesion requires the binding of leukocytes to their cognate receptors on the surface of endothelial cells. The glycocalyx covers the surface of endothelial cells and is important in the mechanotransduction of shear stress. This study aimed to identify the molecular mechanisms underlying the role of the glycocalyx in leukocyte adhesion under flow. We performed experiments using 3-D cell culture models, exposing human abdominal aortic endothelial cells to steady laminar shear stress (10 dynes/cm2 for 24 hours. We found that with the enzymatic degradation of the glycocalyx, endothelial cells developed a proinflammatory phenotype when exposed to uniform steady shear stress leading to an increase in leukocyte adhesion. Our results show an up-regulation of ICAM-1 with degradation compared to non-degraded controls (3-fold increase, p<0.05 and we attribute this effect to a de-regulation in NF-κB activity in response to flow. These results suggest that the glycocalyx is not solely a physical barrier to adhesion but rather plays an important role in governing the phenotype of endothelial cells, a key determinant in leukocyte adhesion. We provide evidence for how the destabilization of this structure may be an early and defining feature in the initiation of atherosclerosis.

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.

Degradation of ground ice in a changing climate: the potential impact of groundwater flow

Science.gov (United States)

de Grandpré, I.; Fortier, D.; Stephani, E.

2011-12-01

Climate changes affecting the North West portion of Canada alter the thermal state of the permafrost and promote ground ice degradation. Melting of ground ice leads to greater water flow into the ground and to significant hydraulic changes (i.e. drainage of peatland and lakes, triggering of thermokarst and new groundwater flow patterns). Road infrastructures built on permafrost are particularly sensitive to permafrost degradation. Road construction and maintenance induce heat flux into the ground by the increase of solar radiation absorption (comparing to natural ground), the increase of snow cover on side slopes, the infiltration of water in embankment material and the migration of surface water in the active layer. The permafrost under the roads is therefore submitted to a warmer environment than in natural ground and his behavior reflects how the permafrost will act in the future with the global warming trend. The permafrost degradation dynamic under a road was studied at the Beaver Creek (Yukon) experimental site located on the Alaska Highway. Permafrost was characterized as near-zero Celcius and highly susceptible to differential thaw-settlement due to the ground ice spatial distribution. Ice-rich cryostructures typical of syngenetic permafrost (e.g. microlenticular) were abundant in the upper and lower cryostratigraphic units of fine-grained soils (Units 1, 2A, and 2C). The middle ice-poor silt layer (Unit 2B) characterized by porous cryostructure comprised the top of a buried ice-wedge network extending several meters in the underlying layers and susceptible to degradation by thermo-erosion. These particular features of the permafrost at the study site facilitated the formation of taliks (unfrozen zones) under the road which leaded to a greater water flow. We believe that water flow is promoting an acceleration of permafrost degradation by advective heat transfer. This process remains poorly studied and quantified in permafrost environment. Field data on

The mechanism of fracture for entangled polymer liquids in extensional flow

DEFF Research Database (Denmark)

Huang, Qian; Yu, Liyun; Wingstrand, Sara Lindeblad

In uniaxial extensional flow of entangled polymer liquids, different rupture modes may happen, including necking and fracture. Malkin andPetrie [1] proposed a ''master curve'' dividing the flow behavior into four zones based on the stretch rate: (I) Flow zone; (II) Transition zone; (III) Rubbery...... curve in Zone IV. However, with faster rate, a constant critical strain is observed, which is not shown in the original master curve. The value of the constant critical strain seems to be related to themaximum stretch ratio of the polymer chain (determined by Me), but not influenced by Z. The results...

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.

Swift Heavy Ion Induced Modification of Aliphatic Polymers

OpenAIRE

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 I...

A Constitutive Model for Flow-Induced Anisotropic Behavior of Viscoelastic Complex Fluids

International Nuclear Information System (INIS)

Zhu, H.; De Kee, D.

2008-01-01

Flow-induced structural anisotropy could result when a complex fluid system is removed from equilibrium by means of hydrodynamic forces. In this paper, a general theory is developed to model flow induced anisotropic behavior of complex viscoelastic systems, e.g. polymer solutions/melts and suspensions. The rheological properties are characterized by viscosity and relaxation time tensors. We consider a second-rank tensor as a measure of the microstructure. We consider the effect of the flow on the structural changes: i.e. the evolution of the microstructure tensor is governed by a relaxation-type differential equation. We also propose that the viscosity and the relaxation time tensors depend on the second-rank microstructure tensor. That is as the microstructure tensor changes with the applied rate of deformation, the viscosity and relaxation time tensors evolve accordingly. As an example we consider elongational flow of two complex fluids

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.

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.

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.

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...

Modification of polymer blends by irradiation

International Nuclear Information System (INIS)

Zuchowska, D.; Zagorski, Z.P.

1999-01-01

Modification of polymers, especially of polyolefin-elastomer blends (e. g. ethylene/propylene/diene terpolymer, ethylene propylene copolymer, ethylene/vinyl acetate copolymer etc.), by irradiation with a beam of fast electrons is discussed. Irradiation of polymer blends usually results in enhanced interactions between the constituents, caused among other things, by grafting induced at the polymer interphase. As a result, mechanical properties are affected to an extent depending on the proportion and type of constituent polymers, stabilizer content and radiation dose. Breaking strength (σ) relative elongation at break (ε) and melt flow rate (MFR), were examined for a triblock styrene/butadiene/styrene (SBS) copolymer, polypropylene (PP), and a PP-SBS blend (50:50 by wt.). In PP, the content of the crystal phase was determined. Irradiation was found to make SBS crosslink, as a result, σ rose by 25% and ε remained unaffected. PP was found to become degraded upon irradiation (MFR rose as much as 16 times), thereby σ and ε decreased considerably. In pure PP, the content of the crystal phase was found to increase. The variations of σ and ε in the irradiated PP-SBS blend follow a tendency similar to that in the SBS copolymer examined. This fact suggests the SBS copolymer to have a decisive effect on the macroscopic properties of the PP-SBS blend. (author)

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...

Flow boundary conditions for chain-end adsorbing polymer blends.

Science.gov (United States)

Zhou, Xin; Andrienko, Denis; Delle Site, Luigi; Kremer, Kurt

2005-09-08

Using the phenol-terminated polycarbonate blend as an example, we demonstrate that the hydrodynamic boundary conditions for a flow of an adsorbing polymer melt are extremely sensitive to the structure of the epitaxial layer. Under shear, the adsorbed parts (chain ends) of the polymer melt move along the equipotential lines of the surface potential whereas the adsorbed additives serve as the surface defects. In response to the increase of the number of the adsorbed additives the surface layer becomes thinner and solidifies. This results in a gradual transition from the slip to the no-slip boundary condition for the melt flow, with a nonmonotonic dependence of the slip length on the surface concentration of the adsorbed ends.

Numerical Simulation of Polymer Injection in Turbulent Flow Past a Circular Cylinder

KAUST Repository

Richter, David; Shaqfeh, Eric S. G.; Iaccarino, Gianluca

2011-01-01

Using a code developed to compute high Reynolds number viscoelastic flows, polymer injection from the upstream stagnation point of a circular cylinder is modeled at Re = 3900. Polymer stresses are represented using the FENE-P constitutive equations. By increasing polymer injection rates within realistic ranges, significant near wake stabilization is observed. Rather than a turbulent detached shear layer giving way to a chaotic primary vortex (as seen in Newtonian flows at high Re), a much more coherent primary vortex is shed, which possesses an increased core pressure as well as a reduced level of turbulent energy. © 2011 American Society of Mechanical Engineers.

MLKL forms disulfide bond-dependent amyloid-like polymers to induce necroptosis.

Science.gov (United States)

Liu, Shuzhen; Liu, Hua; Johnston, Andrea; Hanna-Addams, Sarah; Reynoso, Eduardo; Xiang, Yougui; Wang, Zhigao

2017-09-05

Mixed-lineage kinase domain-like protein (MLKL) is essential for TNF-α-induced necroptosis. How MLKL promotes cell death is still under debate. Here we report that MLKL forms SDS-resistant, disulfide bond-dependent polymers during necroptosis in both human and mouse cells. MLKL polymers are independent of receptor-interacting protein kinase 1 and 3 (RIPK1/RIPK3) fibers. Large MLKL polymers are more than 2 million Da and are resistant to proteinase K digestion. MLKL polymers are fibers 5 nm in diameter under electron microscopy. Furthermore, the recombinant N-terminal domain of MLKL forms amyloid-like fibers and binds Congo red dye. MLKL mutants that cannot form polymers also fail to induce necroptosis efficiently. Finally, the compound necrosulfonamide conjugates cysteine 86 of human MLKL and blocks MLKL polymer formation and subsequent cell death. These results demonstrate that disulfide bond-dependent, amyloid-like MLKL polymers are necessary and sufficient to induce necroptosis.

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

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.

Extensional Strain Hardening Induced by π -π Interactions in Barely Entangled Polymer Chains: The Curious Case of Poly(4-vinylbiphenyl)

Science.gov (United States)

López-Barrón, Carlos R.; Zhou, Huaxing

2017-12-01

Aromatic π -π interactions between phenyl groups of adjacent chains in poly(4-vinylbiphenyl) (PVBP) have profound effects on the dynamics of this polymer. We report two unexpected nonlinear viscoelastic responses of PVBP when subjected to uniaxial flow. One is the unprecedented observation of extensional strain hardening (SH) in a barely entangled polymer melt. An even more intriguing finding is that SH of lightly (or even barely) entangled melts occurs at strain rates one order of magnitude below the coil-stretch transition predicted by Rouse theory (ɛ˙ H=0.5 /τR ).We postulate that this behavior is due to a molecular rearrangement mechanism (supported by x-ray diffraction measurements) that involves flow-induced π -π stacking of the phenyl groups, which results in an enhancement of the friction coefficient between polymer chains.

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

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

The use of radiation-induced graft polymerization for modification of polymer track membranes

International Nuclear Information System (INIS)

Shtanko, N.I.; Kabanov, V.Ya.; Apel, P.Yu.; Yoshida, M.

1999-01-01

Track membranes (TM) made of poly(ethylene terephtalate) (PET) and polypropylene (PP) films have a number of peculiarities as compared with other ones. They have high mechanical strength at a low thickness, narrow pore size distribution, low content of extractables. However, TM have some disadvantages such as low chemical resistance in alkaline media (PET TM), the low water flow rate due to the hydrophobic nature of their surface. The use of radiation-induced graft polymerization makes it possible to improve the basic characteristics of TM. In this communication our results on the modification of PET and PP TM are presented. The modified membranes were prepared by radiation-induced graft polymerization from the liquid phase. Three methods of grafting were used: (a) the direct method in argon atmosphere; (b) the pre-irradiation of TM in air followed by grafting in argon atmosphere; (c) pre-irradiation in vacuum followed by grafting in vacuum without contacting oxygen. The aim of the work was to investigate some properties of TM modified by grafted poly(methylvinyl pyridine) (PMVP) and poly(N-isopropylacrylamide) (PNIPAAM). It was shown that the modification of TM with hydrophilic polymer results in the growth of the water flow rate. In the past few years many works have been devoted to the synthesis of new polymers - the so-called 'intelligent' materials - such as PNIPAAM. However, it is very difficult to make thin membranes of this polymer. Recently, it has been proposed to manufacture composite membranes by grafting stimulus-responsive polymers onto TM. Following this principle, we prepared thermosensitive membranes by the radiation-induced graft polymerization of N-isopropylacrylamide (NIPAAM) onto PET TM. PET TM with the pore size of about 1 μm and pore density of 10 6 cm -2 were first inserted into a solution of NIPAAM containing inhibitor of homopolymerization (CuCl 2 ) and then exposed to the γ-rays from a 60 Co source. The transport properties of the

The use of radiation-induced graft polymerization for modification of polymer track membranes

Science.gov (United States)

Shtanko, N. I.; Kabanov, V. Ya.; Apel, P. Yu.; Yoshida, M.

1999-05-01

Track membranes (TM) made of poly(ethylene terephtalate) (PET) and polypropylene (PP) films have a number of peculiarities as compared with other ones. They have high mechanical strength at a low thickness, narrow pore size distribution, low content of extractables. However, TM have some disadvantages such as low chemical resistance in alkaline media (PET TM), the low water flow rate due to the hydrophobic nature of their surface. The use of radiation-induced graft polymerization makes it possible to improve the basic characteristics of TM. In this communication our results on the modification of PET and PP TM are presented. The modified membranes were prepared by radiation-induced graft polymerization from the liquid phase. Three methods of grafting were used: (a) the direct method in argon atmosphere; (b) the pre-irradiation of TM in air followed by grafting in argon atmosphere; (c) pre-irradiation in vacuum followed by grafting in vacuum without contacting oxygen. The aim of the work was to investigate some properties of TM modified by grafted poly(methylvinyl pyridine) (PMVP) and poly(N-isopropylacrylamide) (PNIPAAM). It was shown that the modification of TM with hydrophilic polymer results in the growth of the water flow rate. In the past few years many works have been devoted to the synthesis of new polymers - the so-called "intelligent" materials - such as PNIPAAM. However, it is very difficult to make thin membranes of this polymer. Recently, it has been proposed to manufacture composite membranes by grafting stimulus-responsive polymers onto TM. Following this principle, we prepared thermosensitive membranes by the radiation-induced graft polymerization of N-isopropylacrylamide (NIPAAM) onto PET TM. PET TM with the pore size of about 1 μm and pore density of 10 6 cm -2 were first inserted into a solution of NIPAAM containing inhibitor of homopolymerization (CuCl 2) and then exposed to the γ-rays from a 60Co source. The transport properties of the grafted

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.

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.

Enhancing emerging organic compound degradation: applying chaotic flow to managed aquifer recharge

Science.gov (United States)

Rodríguez-Escales, Paula; Fernandez-Garcia, Daniel; Drechsel, Johannes; Folch, Albert; Sanchez-Vila, Xavier

2017-04-01

The coupling of Managed Aquifer Recharge with soil aquifer remediation treatment, by placing a reactive layer containing organic matter at the bottom of the infiltration pond, is a promising technology to improve the rate of degradation of EOCs. Its success is based on assuming that recharged water and groundwater get well mixed, which is not always true. It has been demonstrated that mixing can be enhanced by inducing chaotic advection through extraction-injection engineering. In this work we analyze how chaotic advection might enhance the spreading of redox conditions with the final aim of improving degradation of a mix of benzotriazoles: benzotriazole, 5-methyl-benzotriazole, and 5-chloro-benzotriazole. The first two compounds are better degraded under aerobic conditions whereas the third one under nitrate reducing conditions. We developed a reactive transport model that describes how a recharged water rich in organic matter mixes with groundwater, how this organic matter is oxidized by different electron acceptors, and how the benzotriazoles are degraded attending for the redox state. The model was tested in different scenarios of recharge, both in homogenous and in heterogenous media. It was found that chaotic flow increases the spreading of the plume of recharged water. Consequently, different redox conditions coexist at a given time within the area affected by recharge, facilitating the degradation of EOCs.

Redox Active Transition Metal ions Make Melanin Susceptible to Chemical Degradation Induced by Organic Peroxide.

Science.gov (United States)

Zadlo, Andrzej; Pilat, Anna; Sarna, Michal; Pawlak, Anna; Sarna, Tadeusz

2017-12-01

With aging, retinal pigment epithelium melanosomes, by fusion with the age pigment lipofuscin, form complex granules called melanolipofuscin. Lipofuscin granules may contain oxidized proteins and lipid hydroperoxides, which in melanolipofuscin could chemically modify melanin polymer, while transition metal ions present in melanin can accelerate such oxidative modifications. The aim of this research was to examine the effect of selected transition metal ions on melanin susceptibility to chemical modification induced by the water-soluble tert-butyl hydroperoxide used as an oxidizing agent. Synthetic melanin obtained by DOPA autooxidation and melanosomes isolated from bovine retinal pigment epithelium were analyzed. To monitor tert-butyl hydroperoxide-induced oxidative changes of DMa and BMs, electron paramagnetic resonance spectroscopy, UV-vis absorption spectroscopy, dynamic light scattering, atomic force microscopy and electron paramagnetic resonance oximetry were employed. These measurements revealed that both copper and iron ions accelerated chemical degradation induced by tert-butyl hydroperoxide, while zinc ions had no effect. Strong prooxidant action was detected only in the case of melanosomes and melanin degraded in the presence of iron. It can be postulated that similar chemical processes, if they occur in situ in melanolipofuscin granules of the human retinal pigment epithelium, would modify antioxidant properties of melanin and its reactivity.

Electroosmotic Flow in Mixed Polymer Brush-Grafted Nanochannels

Directory of Open Access Journals (Sweden)

Qianqian Cao

2016-12-01

Full Text Available Mixed polymer brush-grafted nanochannels—where two distinct species of polymers are alternately grafted on the inner surface of nanochannels—are an interesting class of nanostructured hybrid materials. By using a coarse-grained molecular dynamics simulation method, we are able to simulate the electrokinetic transport dynamics of the fluid in such nanochannels as well as the conformational behaviors of the mixed polymer brush. We find that (1 the brush adopts vertically-layered and longitudinally-separated structures due to the coupling of electroosmotic flow (EOF and applied electric field; (2 the solvent quality affects the brush conformations and the transport properties of the EOF; (3 the EOF flux non-monotonically depends on the grafting density, although the EOF velocity in the central region of the channel monotonically depends on the grafting density.

Aging and low-flow degradation of auxilary feedwater pumps

International Nuclear Information System (INIS)

Adams, M.L.

1992-01-01

This paper documents the results of research done under the auspices of the Nuclear Regulatory Commission Nuclear Plant Aging Research Program. It examines the degradation imparted to safety related Auxiliary Feedwater System pumps at nuclear plants due to the low flow operation. The Auxiliary Feedwater (AFW) System is normally a stand-by system. As such it is operated most often in the test mode. Since few plants are equipped with full flow test loops, most testing is accomplished at minimum flow conditions in pump by-pass lines. It is the vibration and hydraulic forces generated at low flow conditions that have been shown to be the major causes of AFW pump aging and degradation. The wear can be manifested in a number of ways, such as impeller or diffuser breakage, thrust bearing and/or balance device failure due to excessive loading, cavitation damage on such stage impellers, increase seal leakage or failure, sear injection piping failure, shaft or coupling breakage, and rotating element seizure

Aging and low-flow degradation of auxiliary feedwater pumps

International Nuclear Information System (INIS)

Adams, M.L.

1991-01-01

This paper documents the results of research done under the auspices of the Nuclear Regulatory Commission Nuclear Plant Aging Research Program. It examines the degradation imparted to safety Auxiliary Feedwater System pumps at nuclear plants due to the low flow operation. The Auxiliary Feedwater (AFW) System is normally a stand-by system. As such it is operated most often in the test mode. Since few plants are equipped with full flow test loops, most testing is accomplished at minimum flow conditions in pump by-pass lines. It is the vibration and hydraulic forces generated at low flow conditions that have been shown to be the major causes of AFW pump aging and degradation. The wear can be manifested in a number of ways, such as impeller or diffuser breakage, thrust bearing and/or balance device failure due to excessive loading, cavitation damage on such stage impellers, increase seal leakage or failure, sear injection piping failure, shaft or coupling breakage, and rotating element seizure

An advanced tube wear and fatigue workstation to predict flow induced vibrations of steam generator tubes

International Nuclear Information System (INIS)

Gay, N.; Baratte, C.; Flesch, B.

1997-01-01

Flow induced tube vibration damage is a major concern for designers and operators of nuclear power plant steam generators (SG). The operating flow-induced vibrational behaviour has to be estimated accurately to allow a precise evaluation of the new safety margins in order to optimize the maintenance policy. For this purpose, an industrial 'Tube Wear and Fatigue Workstation', called 'GEVIBUS Workstation' and based on an advanced methodology for predictive analysis of flow-induced vibration of tube bundles subject to cross-flow has been developed at Electricite de France. The GEVIBUS Workstation is an interactive processor linking modules as: thermalhydraulic computation, parametric finite element builder, interface between finite element model, thermalhydraulic code and vibratory response computations, refining modelling of fluid-elastic and random forces, linear and non-linear dynamic response and the coupled fluid-structure system, evaluation of tube damage due to fatigue and wear, graphical outputs. Two practical applications are also presented in the paper; the first simulation refers to an experimental set-up consisting of a straight tube bundle subject to water cross-flow, while the second one deals with an industrial configuration which has been observed in some operating steam generators i.e., top tube support plate degradation. In the first case the GEVIBUS predictions in terms of tube displacement time histories and phase planes have been found in very good agreement with experiment. In the second application the GEVIBUS computation showed that a tube with localized degradation is much more stable than a tube located in an extended degradation zone. Important conclusions are also drawn concerning maintenance. (author)

Chemical modifications of polymer films induced by high energy heavy ions

International Nuclear Information System (INIS)

Zhu Zhiyong; Sun Youmei; Liu Changlong; Liu Jie; Jin Yunfan

2002-01-01

Polymer films including polyethylene terephthalate (PET), polystyrene (PS) and polycarbonate (PC) were irradiated at room temperature with ions of 35 MeV/u 40 Ar, 25 MeV/u 84 Kr, 15.1 MeV/u 136 Xe and 11.4 MeV/u 238 U to fluences ranging from 9x10 9 to 5.5x10 12 ions/cm 2 . The radiation-induced chemical changes of the materials were investigated by Fourier-transform infrared (FTIR) and ultraviolet/visible spectroscopies. It is found that the absorbance in the ultraviolet and visible range induced by all irradiations follows a linear relationship with fluence. The radiation-induced absorbance normalized to one particle increases slowly with increasing of electronic energy loss below about 8 keV/nm followed by a sharp increase up to about 15 keV/nm above which saturation is reached. FTIR measurements reveal that the materials suffer serious degradation through bond breaking. The absorbance of the typical infrared bands decays exponentially with increase of ion fluence and the bond-disruption cross-section shows a sigmoid variation with electronic energy loss. In PET loss of crystallinity is attributed to the configuration transformation of the ethylene glycol residue from trans into the gauche. Alkyne end groups are induced in all the materials above certain electronic energy loss threshold, which is found to be about 0.8 keV/nm for PS and 0.4 keV/nm for PC. The production cross-section of alkyne end group increases with increasing of electronic energy loss and shows saturation at high electronic energy loss values. It is concluded that not only the physical processes but also the chemical processes of the energy deposition determine the modification of polymer

Flow behavior of polymers during the roll-to-roll hot embossing process

International Nuclear Information System (INIS)

Deng, Yujun; Yi, Peiyun; Peng, Linfa; Lai, Xinmin; Lin, Zhongqin

2015-01-01

The roll-to-roll (R2R) hot embossing process is a recent advancement in the micro hot embossing process and is capable of continuously fabricating micro/nano-structures on polymers, with a high efficiency and a high throughput. However, the fast forming of the R2R hot embossing process limits the time for material flow and results in complicated flow behavior in the polymers. This study presents a fundamental investigation into the flow behavior of polymers and aims towards the comprehensive understanding of the R2R hot embossing process. A three-dimensional (3D) finite element (FE) model based on the viscoelastic model of polymers is established and validated for the fabrication of micro-pyramids using the R2R hot embossing process. The deformation and recovery of micro-pyramids on poly(vinyl chloride) (PVC) film are analyzed in the filling stage and the demolding stage, respectively. Firstly, in the analysis of the filling stage, the temperature distribution on the PVC film is discussed. A large temperature gradient is observed along the thickness direction of the PVC film and the temperature of the top surface is found to be higher than that of the bottom surface, due to the poor thermal conductivity of PVC. In addition, creep strains are demonstrated to depend highly on the temperature and are also observed to concentrate on the top layer of the PVC film because of high local temperature. In the demolding stage, the recovery of the embossed micro-pyramids is obvious. The cooling process is shown to be efficient for the reduction of recovery, especially when the mold temperature is high. In conclusion, this research advances the understanding of the flow behavior of polymers in the R2R hot embossing process and might help in the development of the highly accurate and highly efficient fabrication of microstructures on polymers. (paper)

Radiation-induced polymerization and radiation effect on polymers

International Nuclear Information System (INIS)

Seguchi, Tadao

1977-12-01

The processes of radiation-induced polymerization of monomers and also radiation effects on polymers have been studied by instrumental analyses of electron spin resonance (ESR), nuclear magnetic resonance (NMR) and electron microscopy. In radiation-induced polymerization, graft-copolymerization and absorbed state polymerization were taken up. For graft-copolymerization, monomers such as methylmethacrylate and butadiene were made to react with irradiated polyethylene, and behaviors of the initiating radicals and propagating radicals were followed under the reaction by ESR. For absorbed state polymerization, acrylonitrile/zeolite and methylmethacrylate/zeolite were chosen. Absorbed monomers were irradiated at 77 0 K and polymerized at room temperature. Active species and the concentrations were measured by ESR and the yields of polymer were observed by NMR. In radiation effect on polymers, polyvinylfluoride, polyvinylidenfluoride and polytetrafluoroethylene were taken up. Active species trapped in the polymer matrixes were identified and decay and reactivity of the species were also studied. On the basis of information from the electron microscopy and x-ray analysis, radiation effects on these polymers are described. In polytetrafluoroethylene produced by radiation polymerization, the relation between morphology and polymerization conditions and also the process of crystallization during polymerization were studied. (auth.)

Studies of positron induced luminescence from polymers

International Nuclear Information System (INIS)

Xu, J.; Hulett, L.D. Jr.; Lewis, T.A.; Tolk, N.H.

1994-01-01

Light emission from polymers (anthracene dissolved in polystryrene) induced by low-energy positrons and electrons has been studied. Results indicate a clear difference between optical emissions under positron and electron bombardment. The positron-induced luminescence spectrum is believed to be generated by both collisional and annihilation processes

Photo-isomerization induced rapid photo-degradation of optical nonlinearity in cyano substituted stilbene derivative doped poled polymer

International Nuclear Information System (INIS)

Yan Jieyun; Liu Liying; Ji Liyong; Ye Mingxin; Xu Lei; Wang Wencheng

2004-01-01

We found that, although alpha'-cyano-4'-nitro-4-N, N-dimethylaminostilbene has larger hyperpolarizability than that of conventional 4'-N, N-dimethylamino-nitrostilbene, the addition of the cyano group makes it much more easy to photo-isomerize, thus destroying the molecular ordering in poled chromophore doped polymers. Experimental evidence was obtained by monitoring the second-harmonic generation intensity, UV-Vis absorption spectrum, and FTIR spectrum. The photo-isomerization reaction process was monitored by optical pump induced absorption anisotropy measurement. Comparisons with the behaviour of a azobenzene dye are also made

Modification of a Turbulent Boundary Layer within a Homogeneous Concentration of Drag reducing Polymer Solution

Science.gov (United States)

Farsiani, Yasaman; Elbing, Brian

2017-11-01

High molecular weight polymer solutions in wall-bounded flows can reduce the local skin friction by as much as 80%. External flow studies have typical focused on injection of polymer within a developing turbulent boundary layer (TBL), allowing the concentration and drag reduction level to evolve with downstream distance. Modification of the log-law region of the TBL is directly related to drag reduction, but recent results suggest that the exact behavior is dependent on flow and polymer properties. Weissenberg number and the viscosity ratio (ratio of solvent viscosity to the zero-shear viscosity) are concentration dependent, thus the current study uses a polymer ocean (i.e. a homogenous concentration of polymer solution) with a developing TBL to eliminate uncertainty related to polymer properties. The near-wall modified TBL velocity profiles are acquired with particle image velocimetry. In the current presentation the mean velocity profiles and the corresponding flow (Reynolds number) and polymer (Weissenberg number, viscosity ratio, and length ratio) properties are reported. Note that the impact of polymer degradation on molecular weight will also be quantified and accounted for when estimating polymer properties This work was supported by NSF Grant 1604978.

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

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

Oriented nanofibers embedded in a polymer matrix

Science.gov (United States)

Barrera, Enrique V. (Inventor); Lozano, Karen (Inventor); Rodriguez-Macias, Fernando J. (Inventor); Chibante, Luis Paulo Felipe (Inventor); Stewart, David Harris (Inventor)

2011-01-01

A method of forming a composite of embedded nanofibers in a polymer matrix is disclosed. The method includes incorporating nanofibers in a plastic matrix forming agglomerates, and uniformly distributing the nanofibers by exposing the agglomerates to hydrodynamic stresses. The hydrodynamic said stresses force the agglomerates to break apart. In combination or additionally elongational flow is used to achieve small diameters and alignment. A nanofiber reinforced polymer composite system is disclosed. The system includes a plurality of nanofibers that are embedded in polymer matrices in micron size fibers. A method for producing nanotube continuous fibers is disclosed. Nanofibers are fibrils with diameters of 100 nm, multiwall nanotubes, single wall nanotubes and their various functionalized and derivatized forms. The method includes mixing a nanofiber in a polymer; and inducing an orientation of the nanofibers that enables the nanofibers to be used to enhance mechanical, thermal and electrical properties. Orientation is induced by high shear mixing and elongational flow, singly or in combination. The polymer may be removed from said nanofibers, leaving micron size fibers of aligned nanofibers.

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.

Effect of drag-reducing polymers on Tubing Performance Curve (TPC) in vertical gas-liquid flows

NARCIS (Netherlands)

Shoeibi Omrani, P.; Veltin, J.; Turkenburg, D.H.

2014-01-01

This paper discusses the effect of drag reducing polymers on the Tubing Performance Curve (TPC) of vertical air-water flows at near atmospheric conditions. The effect of polymer concentration, liquid and gas flow rates on the pressure drop curve (Tubing Performance Curve) was investigated

Effect of short-chain branching on interfacial polymer structure and dynamics under shear flow.

Science.gov (United States)

Jeong, Sohdam; Kim, Jun Mo; Cho, Soowon; Baig, Chunggi

2017-11-22

We present a detailed analysis on the effect of short-chain branches on the structure and dynamics of interfacial chains using atomistic nonequilibrium molecular dynamics simulations of confined polyethylene melts in a wide range of shear rates. The intrinsically fast random motions of the short branches constantly disturb the overall chain conformation, leading to a more compact and less deformed chain structure of the short-chain branched (SCB) polymer against the imposed flow field in comparison with the corresponding linear polymer. Moreover, such highly mobile short branches along the backbone of the SCB polymer lead to relatively weaker out-of-plane wagging dynamics of interfacial chains, with highly curvy backbone structures in the intermediate flow regime. In conjunction with the contribution of short branches (as opposed to that of the backbone) to the total interfacial friction between the chains and the wall, the SCB polymer shows a nearly constant behavior in the degree of slip (d s ) with respect to shear rate in the weak-to-intermediate flow regimes. On the contrary, in the strong flow regime where irregular chain rotation and tumbling dynamics occur via intensive dynamical collisions between interfacial chains and the wall, an enhancement effect on the chain detachment from the wall, caused by short branches, leads to a steeper increase in d s for the SCB polymer than for the linear polymer. Remarkably, the SCB chains at the interface exhibit two distinct types of rolling mechanisms along the backbone, with a half-dumbbell mesoscopic structure at strong flow fields, in addition to the typical hairpin-like tumbling behavior displayed by the linear chains.

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.

Performance of intact and partially degraded concrete barriers in limiting fluid flow

International Nuclear Information System (INIS)

Walton, J.C.; Seitz, R.R.

1991-07-01

Concrete barriers will play a critical role in the long-term isolation of low-level radioactive wastes. Over time the barriers will degrade, and in many cases, the fundamental processes controlling performance of the barriers will be different for intact and degraded conditions. This document examines factors controlling fluid flow through intact and degraded concrete disposal facilities. Simplified models are presented fro predicting build up of fluid above a vault; fluid flow through and around intact vaults, through flaws in coatings/liners applied to a vault, and through cracks in a concrete vault; and the influence of different backfill materials around the outside of the vault. Example calculations are presented to illustrate the parameters and processes that influence fluid flow. 46 refs., 49 figs., 2 tabs

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

An In Vitro Comparative Study of Intracanal Fluid Motion and Wall Shear Stress Induced by Ultrasonic and Polymer Rotary Finishing Files in a Simulated Root Canal Model

OpenAIRE

Koch, Jon; Borg, John; Mattson, Abby; Olsen, Kris; Bahcall, James

2012-01-01

Objective. This in vitro study compared the flow pattern and shear stress of an irrigant induced by ultrasonic and polymer rotary finishing file activation in an acrylic root canal model. Flow visualization analysis was performed using an acrylic canal filled with a mixture of distilled water and rheoscopic fluid. The ultrasonic and polymer rotary finishing file were separately tested in the canal and activated in a static position and in a cyclical axial motion (up and down). Particle moveme...

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

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.

Hydrolytic degradation of poly(ethylene oxide)-block-polycaprolactone worm micelles.

Science.gov (United States)

Geng, Yan; Discher, Dennis E

2005-09-21

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 polycaprolactone hydrolysis, with distinct mechanism and kinetics from that which occurs in bulk material.

Model for Stress-induced Protein Degradation in Lemna minor1

Science.gov (United States)

Cooke, Robert J.; Roberts, Keith; Davies, David D.

1980-01-01

Transfer of Lemna minor fronds to adverse or stress conditions produces a large increase in the rate of protein degradation. Cycloheximide partially inhibits stress-induced protein degradation and also partially inhibits the protein degradation which occurs in the absence of stress. The increased protein degradation does not appear to be due to an increase in activity of soluble proteolytic enzymes. Biochemical evidence indicates that stress, perhaps acting via hormones, affects the permeability of certain membranes, particularly the tonoplast. A general model for stress-induced protein degradation is presented in which changes in membrane properties allow vacuolar proteolytic enzymes increased access to cytoplasmic proteins. PMID:16661588

Flash nano-precipitation of polymer blends: a role for fluid flow?

Science.gov (United States)

Grundy, Lorena; Mason, Lachlan; Chergui, Jalel; Juric, Damir; Craster, Richard V.; Lee, Victoria; Prudhomme, Robert; Priestley, Rodney; Matar, Omar K.

2017-11-01

Porous structures can be formed by the controlled precipitation of polymer blends; ranging from porous matrices, with applications in membrane filtration, to porous nano-particles, with applications in catalysis, targeted drug delivery and emulsion stabilisation. Under a diffusive exchange of solvent for non-solvent, prevailing conditions favour the decomposition of polymer blends into multiple phases. Interestingly, dynamic structures can be `trapped' via vitrification prior to thermodynamic equilibrium. A promising mechanism for large-scale polymer processing is flash nano-precipitation (FNP). FNP particle formation has recently been modelled using spinodal decomposition theory, however the influence of fluid flow on structure formation is yet to be clarified. In this study, we couple a Navier-Stokes equation to a Cahn-Hilliard model of spinodal decomposition. The framework is implemented using Code BLUE, a massively scalable fluid dynamics solver, and applied to flows within confined impinging jet mixers. The present method is valid for a wide range of mixing timescales spanning FNP and conventional immersion precipitation processes. Results aid in the fabrication of nano-scale polymer particles with tuneable internal porosities. EPSRC, UK, MEMPHIS program Grant (EP/K003976/1), RAEng Research Chair (OKM), PETRONAS.

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

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.

Effect of polymer additives on transition in pipe flow

Energy Technology Data Exchange (ETDEWEB)

Castro, W; Squire, W

1967-09-01

Small amounts of long-chain, water-soluble polymers have a marked effect on turbulent flow resulting in appreciable reduction of turbulent friction. The maximum reduction in pipe flow resistance is obtained at such low concentrations that the density and viscosity are not altered appreciably. The minimum friction curve varies as Re-2/3 and appears to be the same for all effective additives tested. The transition process is affected by these additives. Quantitative results are presented showing a reduction in the intensity of the turbulent flashes and the fraction of the time the flow is turbulent at a given Reynolds number. (13 refs.)

Solvent-annealing-induced nanowetting in templates: towards tailored polymer nanostructures.

Science.gov (United States)

Chen, Jiun-Tai; Lee, Chih-Wei; Chi, Mu-Huan; Yao, I-Chun

2013-02-25

We study the solvent-annealing-induced nanowetting in templates using porous anodic aluminum oxide membranes. The morphology of polystyrene and poly(methyl methacrylate) nanostructures can be controlled, depending on whether the swollen polymers are in the partial or complete wetting regimes, which are characterized by the spreading coefficient. When the swollen polymers are in the partial wetting regime, polymers wet the nanopores by capillary action, resulting in the formation of polymer nanorods. When the swollen polymers are in the complete wetting regime, polymers form wetting layers in the nanopores, resulting in the formation of polymer nanotubes. The solubility parameters of polymers and solvents are also used to predict the wetting behavior of swollen polymers in cylindrical geometry. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Modeling Day-to-day Flow Dynamics on Degradable Transport Network

Science.gov (United States)

Gao, Bo; Zhang, Ronghui; Lou, Xiaoming

2016-01-01

Stochastic link capacity degradations are common phenomena in transport network which can cause travel time variations and further can affect travelers’ daily route choice behaviors. This paper formulates a deterministic dynamic model, to capture the day-to-day (DTD) flow evolution process in the presence of degraded link capacity degradations. The aggregated network flow dynamics are driven by travelers’ study of uncertain travel time and their choice of risky routes. This paper applies the exponential-smoothing filter to describe travelers’ study of travel time variations, and meanwhile formulates risk attitude parameter updating equation to reflect travelers’ endogenous risk attitude evolution schema. In addition, this paper conducts theoretical analyses to investigate several significant mathematical characteristics implied in the proposed DTD model, including fixed point existence, uniqueness, stability and irreversibility. Numerical experiments are used to demonstrate the effectiveness of the DTD model and verify some important dynamic system properties. PMID:27959903

Global Assessment of Human-induced Soil Degradation (GLASOD)

NARCIS (Netherlands)

Oldeman, L.R.; Hakkeling, R.T.A.; Sombroek, W.G.; Batjes, N.H.

2014-01-01

The GLASOD project (1987-1990) has produced a world map of human-induced soil degradation. Data were complied in cooperation with a large number of soil scientists throughout the world, using uniform Guidelines and international correlation. The status of soil degradation was mapped within loosely

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.

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.

Improvement of the cold flow characteristics of biodiesel containing dissolved polymer wastes using acetone

Directory of Open Access Journals (Sweden)

Pouya Mohammadi

2014-03-01

Full Text Available Due to the fast fossil fuel depletion and at the same time global warming phenomenon anticipated for the next coming years, the necessity of developing alternative fuels e.g. biofuels (i.e. bioethanol, biodiesel, biogas and etc. has turned into an important concern. Recently, the application of the bio-solvency properties of biodiesel for recycling waste polymers has been highlighted. However, the impact of polymer dissolution on cold flow characteristics of biodiesel was never investigated. The present study was set to explore the impact of different solvents in stabilizing biodiesel-polymer solution. Among them, acetone was proved to be the best fuel stabilizer. Subsequently, cold flow characteristic i.e. cloud point, of the biodiesel-polymer-acetone fuel was found to have improved (decreased due to the inclusion of acetone. Finally, flash point analysis of the fuel blends containing acetone was done to ensured high safety of the fuel blend by dramatically increasing the flash point values of biodiesel-polymer fuel blends.

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

Radiation stress relieving of polymer articles

International Nuclear Information System (INIS)

Frisch, D.C.; Weber, W.

1982-01-01

A method of rapidly relieving stress in an extruded or molded polymer article is disclosed. The method can be used in the preparation of printed circuit boards. An article comprised of the polymer is exposed to electromagnetic radiation, for a time period sufficient to absorb enough energy to stress relieve the polymer against stress cracking therein. Exposure occurs at one or more ranges of frequencies which are capable of being absorbed by the polymer and which are effective for stress relieving without or substantially without causing heat induced softening or flowing of the polymer. The electromagnetic radiation is selected from the ranges of infrared, microwave or ultraviolet radiation

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...

Constitutive and ligand-induced TCR degradation

DEFF Research Database (Denmark)

von Essen, Marina; Bonefeld, Charlotte Menné; Siersma, Volkert

2004-01-01

Modulation of TCR expression levels is a central event during T cell development and activation, and it probably plays an important role in adjusting T cell responsiveness. Conflicting data have been published on down-regulation and degradation rates of the individual TCR subunits, and several di...... to the lysosomes. Similar results were obtained in studies of primary human Vbeta8+ T cells stimulated with superantigen. Based on these results, the simplest model for TCR internalization, sorting, and degradation is proposed.......Modulation of TCR expression levels is a central event during T cell development and activation, and it probably plays an important role in adjusting T cell responsiveness. Conflicting data have been published on down-regulation and degradation rates of the individual TCR subunits, and several...... divergent models for TCR down-regulation and degradation have been suggested. The aims of this study were to determine the rate constants for constitutive and ligand-induced TCR degradation and to determine whether the TCR subunits segregate or are processed as an intact unit during TCR down...

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.

Study of the degradation process of polyimide induced by high energetic ion irradiation

International Nuclear Information System (INIS)

Severin, Daniel

2008-01-01

The dissertation focuses on the radiation hardness of Kapton under extreme radiation environment conditions. To study ion-beam induced modifications, Kapton foils were irradiated at the GSI linear accelerator UNILAC using several projectiles (e.g. Ti, Mo, Au, and U) within a large fluence regime (1 x 10 10 -5 x 10 12 ions/cm 2 ). The irradiated Kapton foils were analysed by means of infrared and UV/Vis spectroscopy, tensile strength measurement, mass loss analysis, and dielectric relaxation spectroscopy. For testing the radiation stability of Kapton at the cryogenic operation temperature (5-10 K) of the superconducting magnets, additional irradiation experiments were performed at the Grand Accelerateur National d' Ions Lourds (GANIL, France) focusing on the online analysis of the outgassing process of small volatile degradation fragments. The investigations of the electrical properties analysed by dielectric relaxation spectroscopy exhibit a different trend: high fluence irradiations with light ions (e.g. Ti) lead to a slight increase of the conductivity, whereas heavy ions (e.g. Sm, Au) cause a drastic change already in the fluence regime of nonoverlapping tracks (5 x 10 10 ions/cm 2 ). Online analysis of the outgassing process during irradiation at cryogenic temperatures shows the release of a variety of small gaseous molecules (e.g. CO, CO 2 , and short hydro carbons). Also a small amount of large polymer fragments is identified. The results allow the following conclusions which are of special interest for the application of Kapton as insulating material in a high-energetic particle radiation environment. a) The material degradation measured with the optical spectroscopy and tensile strength tests are scalable with the dose deposited by the ions. The high correlation of the results allows the prediction of the mechanical degradation with the simple and non-destructive infrared spectroscopy. The degradation curve points to a critical material degradation which

Study of the degradation process of polyimide induced by high energetic ion irradiation

Energy Technology Data Exchange (ETDEWEB)

Severin, Daniel

2008-09-19

The dissertation focuses on the radiation hardness of Kapton under extreme radiation environment conditions. To study ion-beam induced modifications, Kapton foils were irradiated at the GSI linear accelerator UNILAC using several projectiles (e.g. Ti, Mo, Au, and U) within a large fluence regime (1 x 10{sup 10}-5 x 10{sup 12} ions/cm{sup 2}). The irradiated Kapton foils were analysed by means of infrared and UV/Vis spectroscopy, tensile strength measurement, mass loss analysis, and dielectric relaxation spectroscopy. For testing the radiation stability of Kapton at the cryogenic operation temperature (5-10 K) of the superconducting magnets, additional irradiation experiments were performed at the Grand Accelerateur National d' Ions Lourds (GANIL, France) focusing on the online analysis of the outgassing process of small volatile degradation fragments. The investigations of the electrical properties analysed by dielectric relaxation spectroscopy exhibit a different trend: high fluence irradiations with light ions (e.g. Ti) lead to a slight increase of the conductivity, whereas heavy ions (e.g. Sm, Au) cause a drastic change already in the fluence regime of nonoverlapping tracks (5 x 10{sup 10} ions/cm{sup 2}). Online analysis of the outgassing process during irradiation at cryogenic temperatures shows the release of a variety of small gaseous molecules (e.g. CO, CO{sub 2}, and short hydro carbons). Also a small amount of large polymer fragments is identified. The results allow the following conclusions which are of special interest for the application of Kapton as insulating material in a high-energetic particle radiation environment. a) The material degradation measured with the optical spectroscopy and tensile strength tests are scalable with the dose deposited by the ions. The high correlation of the results allows the prediction of the mechanical degradation with the simple and non-destructive infrared spectroscopy. The degradation curve points to a

A study on the life extension of polymer materials under radiation environment

Energy Technology Data Exchange (ETDEWEB)

Park, K. J.; Park, S. W.; Cho, S. H.; Hong, S. S

2000-12-01

The object of this study is to improve the stability and the economic profit by reducing the radiation-induced degradation rate of polymer material used under the radiation environment. So far, the resistance to radiation-induced oxidation of a polymer has been improved by the stabilizers. They can play an important role in the anti-oxidants that interrupt the radical-mediated oxidation chain reaction. The stabilization effect could be larger than that achieved in an inert-atmosphere irradiation. Stabilization is a function of stabilizer concentration up to a certain threshold, but it is not further improved above this concentration. Beyond the threshold, the rate of radiation-induced oxidation goes up to the rate that is characteristic for the unstabilized polymer. To make up for this weakness, a technique depositing a thin layer of diamond-like carbon (DLC) on the polymer surface was developed for protecting the radiation-induced oxidation in the air.

A study on the life extension of polymer materials under radiation environment

International Nuclear Information System (INIS)

Park, K. J.; Park, S. W.; Cho, S. H.; Hong, S. S.

2000-12-01

The object of this study is to improve the stability and the economic profit by reducing the radiation-induced degradation rate of polymer material used under the radiation environment. So far, the resistance to radiation-induced oxidation of a polymer has been improved by the stabilizers. They can play an important role in the anti-oxidants that interrupt the radical-mediated oxidation chain reaction. The stabilization effect could be larger than that achieved in an inert-atmosphere irradiation. Stabilization is a function of stabilizer concentration up to a certain threshold, but it is not further improved above this concentration. Beyond the threshold, the rate of radiation-induced oxidation goes up to the rate that is characteristic for the unstabilized polymer. To make up for this weakness, a technique depositing a thin layer of diamond-like carbon (DLC) on the polymer surface was developed for protecting the radiation-induced oxidation in the air

Laser-induced damage study of polymer PMMA

International Nuclear Information System (INIS)

Mansour, N.

2001-01-01

This article presents the results of bulk laser-induced damage measurements in polymer PMMA at 532 nm and 1064 nm for nanosecond laser pulses. The damage thresholds were measured for focused spot sizes ranging over two orders of magnitude. In this work, self-focusing effects were verified to be absent by measurements of breakdown thresholds using both linearly and circularly polarized light. At both 1064 nm and 532 nm, the dependence of the breakdown field, E B , on the spot size, ω, was empirically determined to be E B = C/√ω, where C depends on the wavelength. The extracted value for C(λ) at 1064 nm is larger by a factor of 5 than at 532 nm. Possible reasons for this strong dispersion and mechanism for laser-induced damage in polymer materials will be discussed

Statistical Investigation on Coherent Vortex Structure in Turbulent Drag Reducing Channel Flow with Blown Polymer Solution

International Nuclear Information System (INIS)

Ishitsuka, Shota; Motozawa, Masaaki; Kawaguchi, Yasuo; Iwamoto, Kaoru; Ando, Hirotomo; Senda, Tetsuya

2011-01-01

Coherent vortex structure in turbulent drag-reducing channel flow with blown polymer solution from the wall was investigated. As a statistical analysis, we carried out Galilean decomposition, swirling strength and linear stochastic estimation of the PIV data obtained by the PIV measurement in x – y plane. Reynolds number based on bulk velocity and channel height was set to 40000. As a result, the angle of shear layer that cleared up by using Galilean decomposition becomes small in the drag-reducing flow. Q3 events were observed near the shear layer. In addition, as a result of linear stochastic estimation (LSE) based on swirling strength, we confirmed that the velocity under the vortex core is strong in the water flow. This result shows Q2 (ejection) are dominant in the water flow. However, in the drag-reducing flow with blown polymer solution, the velocity above the vortex core become strong, that is, Q4 (sweep) events are relatively strong around the vortex core. This is the result of Q4 events to come from the channel center region because the polymer solution does not exist in this region. The typical structure like this was observed in the drag -reducing flow with blown polymer solution from the wall.

Constitutive Curve and Velocity Profile in Entangled Polymers during Start-Up of Steady Shear Flow

KAUST Repository

Hayes, Keesha A.

2010-05-11

Time-dependent shear stress versus shear rate, constitutive curve, and velocity profile measurements are reported in entangled polymer solutions during start-up of steady shear flow. By combining confocal microscopy and particle image velocimetry (PIV), we determine the time-dependent velocity profile in polybutadiene and polystyrene solutions seeded with fluorescent 150 nm silica and 7.5 μm melamine particles. By comparing these profiles with time-dependent constitutive curves obtained from experiment and theory, we explore the connection between transient nonmonotonic regions in the constitutive curve for an entangled polymer and its susceptibility to unstable flow by shear banding [Adams et al. Phys. Rev. Lett. 2009, 102, 067801-4]. Surprisingly, we find that even polymer systems which exhibit transient, nonmonotonic shear stress-shear rate relationships in bulk rheology experiments manifest time-dependent velocity profiles that are decidedly linear and show no evidence of unstable flow. We also report that interfacial slip plays an important role in the steady shear flow behavior of entangled polymers at shear rates above the reciprocal terminal relaxation time but has little, if any, effect on the shape of the velocity profile. © 2010 American Chemical Society.

Polymer electrolyte fuel cells: flow field for efficient air operation

Energy Technology Data Exchange (ETDEWEB)

Buechi, F N; Tsukada, A; Haas, O; Scherer, G G [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

A new flow field was designed for a polymer electrolyte fuel cell stack with an active area of 200 cm{sup 2} for operation at low air stoichiometry and low air over pressure. Optimum of gas flow and channel dimensions were calculated based on the required pressure drop in the fluid. Single cells and a bi-cell stack with the new flow field show an improved current/voltage characteristic when operated at low air stoichiometries as compared to that of the previous non optimized design. (author) 4 figs., 3 refs.

Thermal spraying of polyethylene-based polymers: Processing and characterization

Science.gov (United States)

Otterson, David Mark

This research explores the development of a flame-spray process map as it relates to polymers. This work provides a more complete understanding of the thermal history of the coating material from injection, to deposition and finally to cooling. This was accomplished through precise control of the processing conditions during deposition. Mass flow meters were used to monitor air and fuel flows as they were systematically changed, while temperatures were simultaneously monitored along the length of the flame. A process model was then implemented that incorporated this information along with measured particle velocities, particle size distribution, the polymer's melting temperature and its enthalpy of melting. This computational model was then used to develop a process map that described particle softening, melting and decomposition phenomena as a function of particle size and standoff distance. It demonstrated that changes in particle size caused significant variations in particle states achieved in-flight. A series of experiments were used to determine the range of spray parameters within which a cohesive coating without visible signs of degradation could be sprayed. These results provided additional information that complimented the computational processing map. The boundaries established by these results were the basis for a Statistical Design of Experiments that tested the effects that subtle processing changes had on coating properties. A series of processing maps were developed that combined the computational and the experimental results to describe the manner in which processing parameters interact to determine the degree of melting, polymer degradation and coating porosity. Strong interactions between standoff distance and traverse rate can cause the polymer to degrade and form pores in the coating. A clear picture of the manner in which particle size and standoff distance interact to determine particle melting was provided by combining the computational

Visualization study of flow in axial flow inducer.

Science.gov (United States)

Lakshminarayana, B.

1972-01-01

A visualization study of the flow through a three ft dia model of a four bladed inducer, which is operated in air at a flow coefficient of 0.065, is reported in this paper. The flow near the blade surfaces, inside the rotating passages, downstream and upstream of the inducer is visualized by means of smoke, tufts, ammonia filament, and lampblack techniques. Flow is found to be highly three dimensional, with appreciable radial velocity throughout the entire passage. The secondary flows observed near the hub and annulus walls agree with qualitative predictions obtained from the inviscid secondary flow theory.

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)

A micromotor based on polymer single crystals and nanoparticles: toward functional versatility

Science.gov (United States)

Liu, Mei; Liu, Limei; Gao, Wenlong; Su, Miaoda; Ge, Ya; Shi, Lili; Zhang, Hui; Dong, Bin; Li, Christopher Y.

2014-07-01

We report a multifunctional micromotor fabricated by the self-assembly technique using multifunctional materials, i.e. polymer single crystals and nanoparticles, as basic building blocks. Not only can this micromotor achieve autonomous and directed movement, it also possesses unprecedented functions, including enzymatic degradation-induced micromotor disassembly, sustained release and molecular detection.We report a multifunctional micromotor fabricated by the self-assembly technique using multifunctional materials, i.e. polymer single crystals and nanoparticles, as basic building blocks. Not only can this micromotor achieve autonomous and directed movement, it also possesses unprecedented functions, including enzymatic degradation-induced micromotor disassembly, sustained release and molecular detection. Electronic supplementary information (ESI) available: Experimental section, Fig. S1-S8 and Video S1-S4. See DOI: 10.1039/c4nr02593h

PIV measurement of turbulent bubbly mixing layer flow with polymer additives

International Nuclear Information System (INIS)

Ning, T; Guo, F; Chen, B; Zhang, X

2009-01-01

Based on experimental investigation of single-phase turbulent mixing layer flow with polymer additives, bubbly mixing layer was experimentally investigated by PIV. The velocity ratio between high and low speed is 4:1 and the Reynolds number based on the velocity difference of two steams and hydraulic diameter of the channel ranges is 73333. Gas bubbles with about 0.5% gas fraction were injected into pure water mixing layer with/without polymer additives from three different parts at the end of the splitter plate. The comparison between single phase and bubbly mixing layer shows clearly that the dynamic development of mixing layer is great influenced by the bubble injection. Similar with single phase, the Reynolds stress and vorticity still concentrate in a coniform area of central mixing flow field part and the width will increase with increasing the Reynolds number. Mean Reynolds stress will decrease with bubble injection in high Reynolds numbers and the decreasing of Reynolds stress with polymer additives is much more than pure water case.

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.

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.

Fluid Flow Programming in Paper-Derived Silica-Polymer Hybrids.

Science.gov (United States)

Dubois, Christelle; Herzog, Nicole; Rüttiger, Christian; Geißler, Andreas; Grange, Eléonor; Kunz, Ulrike; Kleebe, Hans-Joachim; Biesalski, Markus; Meckel, Tobias; Gutmann, Torsten; Gallei, Markus; Andrieu-Brunsen, Annette

2017-01-10

In paper-based devices, capillary fluid flow is based on length-scale selective functional control within a hierarchical porous system. The fluid flow can be tuned by altering the paper preparation process, which controls parameters such as the paper grammage. Interestingly, the fiber morphology and nanoporosity are often neglected. In this work, porous voids are incorporated into paper by the combination of dense or mesoporous ceramic silica coatings with hierarchically porous cotton linter paper. Varying the silica coating leads to significant changes in the fluid flow characteristics, up to the complete water exclusion without any further fiber surface hydrophobization, providing new approaches to control fluid flow. Additionally, functionalization with redox-responsive polymers leads to reversible, dynamic gating of fluid flow in these hybrid paper materials, demonstrating the potential of length scale specific, dynamic, and external transport control.

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.

Simple kinetic model of ion induced gas emission from polymers

Czech Academy of Sciences Publication Activity Database

Hnatowicz, Vladimír

2004-01-01

Roč. 215, 1/2 (2004), s. 162-168 ISSN 0168-583X R&D Projects: GA ČR GA106/03/0514; GA AV ČR IAA5011301 Institutional research plan: CEZ:AV0Z1048901 Keywords : polymers * ion irradiation * degradation Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 0.997, year: 2004

Radiation-induced structural transitions in composite materials with strong interaction of polymer components

International Nuclear Information System (INIS)

Zaikin, Yu.A.; Koztaeva, U.P.

2002-01-01

In earlier papers the internal friction (IF) method was applied to studies of structural relaxation in different types of polymer-based composite materials (glass-cloth, paper-based and foiled laminates impregnated by epoxy and phenolic resins) irradiated by 2 MeV electrons in the dose range of 0.1-50.0 MGy. Selectivity and high sensibility of the internal friction method allowed to distinguish glassy transitions in different structural components of the composites. The relaxation processes observed were identified and attributed to structural alterations in the polymer filler, the binder and the boundary layers. It was shown that changes in the parameters of relaxation maximums during irradiation can be considered as quantitative characteristics for the degree of radiation-induced degradation or cross-linking of polymer molecules. This paper deals with specific features of IF spectra in paper-based laminates where both the filler fibers and the binder are strongly interacting polymers. Anisotropy of viscous and elastic properties is very weak for this kind of materials, so that IF measurements give nearly the same result independently on the filler fiber orientation in the sample. The main reasons for it are the rigid chain structure of fillers (polyethylene-terephthalate and cellulose) and the good adhesion strengthened by diffusion of the epoxy or phenolic binder to defect regions of the filler.The IF temperature dependence observed in paper-based laminates is represented by superposition of two very broad relaxation maximums associated with transitions from glassy to high-elastic state in structural components, each based on one of the polymers. The inflection points characteristic for IF temperature dependence in paper-based laminates give a reason to treat them as a superposition of α-peaks associated with transitions from glassy to high-elastic state in structural components of a composite based on the binder and the filler, respectively. Another

The influence of the PDMS technique in the study of the induced modifications of polymers used in nuclear environment

International Nuclear Information System (INIS)

Nsouli, B.

1995-01-01

The PDMS technique (Particle Induced Desorption Mass Spectrometry) combined with a TOF detection (Time of Flight) is the main tool used in this study of polymer degradation in nuclear environment. Ar 3+ ions with a 9 MeV energy have been used to induce the secondary ion emission, and the study was devoted to two stresses typical of this type of environment. The first part of the work concerned with the structural modifications induced by gamma irradiation on ion exchange resin, used for nuclear effluents reprocessing, namely the poly(4-vinylpyridine), or P-4PV. For such a material, the negative fragment emission is particularly sensitive to structural modifications. Difficult physical measurements in such an insoluble and infusible material (IR, UV - Vis, EPR, TGA, dielectric measurements) became consistent after the degradation mechanisms were elucidated. These effects, interpreted in terms of scissions and recombinations, enabled us to explicit different modes of energy deposition, and shed light on some discrepancies between SIMS and PDMS. The second part of the study is devoted to the thermal ageing of an elastomer, used in fabrication of valve gaskets submitted to high temperatures. First of all, we studied the constituents of the polymeric material, i. e. copolymer, homo polymers, and also additives. This last component proved useful to analyze, as a superficial lubricant layer can mask the conformational rearrangements which seem to occur after few hours of thermal treatment (PE blocks are prevailing at the surface). Here too, the PDMS information is important to account for static SIMS and ESCA results, as its probed layer thickness lies in-between. (author)

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)

Gas-liquid hybrid discharge-induced degradation of diuron in aqueous solution.

Science.gov (United States)

Feng, Jingwei; Zheng, Zheng; Luan, Jingfei; Li, Kunquan; Wang, Lianhong; Feng, Jianfang

2009-05-30

Degradation of diuron in aqueous solution by gas-liquid hybrid discharge was investigated for the first time. The effect of output power intensity, pH value, Fe(2+) concentration, Cu(2+) concentration, initial conductivity and air flow rate on the degradation efficiency of diuron was examined. The results showed that the degradation efficiency of diuron increased with increasing output power intensity and increased with decreasing pH values. In the presence of Fe(2+), the degradation efficiency of diuron increased with increasing Fe(2+) concentration. The degradation efficiency of diuron was decreased during the first 4 min and increased during the last 10 min with adding of Cu(2+). Decreasing the initial conductivity and increasing the air flow rate were favorable for the degradation of diuron. Degradation of diuron by gas-liquid hybrid discharge fitted first-order kinetics. The pH value of the solution decreased during the reaction process. Total organic carbon removal rate increased in the presence of Fe(2+) or Cu(2+). The generated Cl(-1), NH(4)(+), NO(3)(-), oxalic acid, acetic acid and formic acid during the degradation process were also detected. Based on the detected Cl(-1) and other intermediates, a possible degradation pathway of diuron was proposed.

Viscoelastic Flow Modelling for Polymer Flooding

Science.gov (United States)

de, Shauvik; Padding, Johan; Peters, Frank; Kuipers, Hans; Multi-scale Modelling of Multi-phase Flows Team

2015-11-01

Polymer liquids are used in the oil industry to improve the volumetric sweep and displacement efficiency of oil from a reservoir. Surprisingly, it is not only the viscosity but also the elasticity of the displacing fluid that determine the displacement efficiency. The main aim of our work is to obtain a fundamental understanding of the effect of fluid elasticity, by developing an advanced computer simulation methodology for the flow of non-Newtonian fluids through porous media. We simulate a 3D unsteady viscoelastic flow through a converging diverging geometry of realistic pore dimension using computational fluid dynamics (CFD).The primitive variables velocity, pressure and extra stresses are used in the formulation of models. The viscoelastic stress part is formulated using a FENE-P type of constitutive equation, which can predict both shear and elongational stress properties during this flow. A Direct Numerical Simulation (DNS) approach using Finite volume method (FVM) with staggered grid has been applied. A novel second order Immersed boundary method (IBM) has been incorporated to mimic porous media. The effect of rheological parameters on flow characteristics has also been studied. The simulations provide an insight into 3D flow asymmetry at higher Deborah numbers. Micro-Particle Image Velocimetry experiments are carried out to obtain further insights. These simulations present, for the first time, a detailed computational study of the effects of fluid elasticity on the imbibition of an oil phase.

Numerical predictions and measurements of Reynolds normal stresses in turbulent pipe flow of polymers

Energy Technology Data Exchange (ETDEWEB)

Resende, P.R. [Centro de Estudos de Fenomenos de Transporte, DEMEGI, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto (Portugal)]. E-mail: resende@fe.up.pt; Escudier, M.P. [Department of Engineering, University of Liverpool, Brownlow Street, Liverpool L69 3GH (United Kingdom)]. E-mail: escudier@liv.ac.uk; Presti, F [Department of Engineering, University of Liverpool, Brownlow Street, Liverpool L69 3GH (United Kingdom); Pinho, F.T. [Centro de Estudos de Fenomenos de Transporte, DEM, Universidade do Minho Campus de Azurem, 4800-058 Guimaraes (Portugal)]. E-mail: fpinho@dem.uminho.pt; Cruz, D.O.A. [Departamento de Engenharia Mecanica, Universidade Federal do Para-UFPa Campus Universitario do Guama, 66075-900 Belem, Para (Brazil)]. E-mail: doac@ufpa.br

2006-04-15

An anisotropic low Reynolds number k-{epsilon} turbulence model has been developed and its performance compared with experimental data for fully-developed turbulent pipe flow of four different polymer solutions. Although the predictions of friction factor, mean velocity and turbulent kinetic energy show only slight improvements over those of a previous isotropic model [Cruz, D.O.A., Pinho, F.T., Resende, P.R., 2004. Modeling the new stress for improved drag reduction predictions of viscoelastic pipe flow. J. Non-Newt. Fluid Mech. 121, 127-141], the new turbulence model is capable of predicting the enhanced anisotropy of the Reynolds normal stresses that accompanies polymer drag reduction in turbulent flow.

Numerical predictions and measurements of Reynolds normal stresses in turbulent pipe flow of polymers

International Nuclear Information System (INIS)

Resende, P.R.; Escudier, M.P.; Presti, F; Pinho, F.T.; Cruz, D.O.A.

2006-01-01

An anisotropic low Reynolds number k-ε turbulence model has been developed and its performance compared with experimental data for fully-developed turbulent pipe flow of four different polymer solutions. Although the predictions of friction factor, mean velocity and turbulent kinetic energy show only slight improvements over those of a previous isotropic model [Cruz, D.O.A., Pinho, F.T., Resende, P.R., 2004. Modeling the new stress for improved drag reduction predictions of viscoelastic pipe flow. J. Non-Newt. Fluid Mech. 121, 127-141], the new turbulence model is capable of predicting the enhanced anisotropy of the Reynolds normal stresses that accompanies polymer drag reduction in turbulent flow

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...

Field-effect Flow Control in Polymer Microchannel Networks

Science.gov (United States)

Sniadecki, Nathan; Lee, Cheng S.; Beamesderfer, Mike; DeVoe, Don L.

2003-01-01

A new Bio-MEMS electroosmotic flow (EOF) modulator for plastic microchannel networks has been developed. The EOF modulator uses field-effect flow control (FEFC) to adjust the zeta potential at the Parylene C microchannel wall. By setting a differential EOF pumping rate in two of the three microchannels at a T-intersection with EOF modulators, the induced pressure at the intersection generated pumping in the third, field-free microchannel. The EOF modulators are able to change the magnitude and direction of the pressure pumping by inducing either a negative or positive pressure at the intersection. The flow velocity is tracked by neutralized fluorescent microbeads in the microchannels. The proof-of-concept of the EOF modulator described here may be applied to complex plastic ,microchannel networks where individual microchannel flow rates are addressable by localized induced-pressure pumping.

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.

Entangled Polymer Melts in Extensional Flow: Synthesis, Rheology, Neutron Scattering

DEFF Research Database (Denmark)

Dorokhin, Andriy

This thesis contains 5 chapters and reprints in Appendices, combined of both published and unpublished materials. The first chapter is an introduction to the goals, methods and problem identification of the project of the entangled polymer melts in extensional flow, which is aimed to shed some li...

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

Synthesis and characterization of partially fluorinated poly(acryl) ionomers for polymer electrolyte membrane fuel cells and ESR-spectroscopic investigation of the radically induced degradation of model compounds; Synthese und Charakterisierung teilfluorierter Poly(acryl)-Ionomere als Polymerelektrolytmembranen fuer Brennstoffzellen und ESR-spektroskopische Untersuchung der radikalinduzierten Degradation von Modellverbindungen

Energy Technology Data Exchange (ETDEWEB)

Schoenberger, Frank

2008-07-09

this work deals with the EPR-spectroscopic investigation of radically induced degradation reactions of model compounds which represent structural units of poly(aryl) ionomers prepared in the first part of this work. These model compounds are exposed to hydroxyl and hydroperoxyl radicals in a flow cell, which are generated directly by photolysis of hydrogen peroxide in the cavity of an ESR spectrometer. By using this experimental setup different parameters (such as concentration of hydroxyl radicals, monomer concentration, flow rate, and pH value) are varied systematically and their influences in terms of the observed product formation of the aromatic model compounds with the hydroxyl radicals are estimated. Conclusions in terms of possible radical reactions of the poly(aryl) ionomer can be drawn from these investigations and information of avoidable structural features (e.g. type of the end groups of the ionomers) and avoidable conditions (e.g. inhomogeneities of pH values in the membrane) are obtained. (orig.)

Lifetimes of organic photovoltaics: Using TOF-SIMS and ¹⁸O₂ isotopic labelling to characterise chemical degradation mechanisms

DEFF Research Database (Denmark)

Norrman, K.; Krebs, Frederik C

2006-01-01

The lifetimes of organic photovoltaic cells based on conjugated polymer materials were studied. The device geometry was glass:ITO:PEDOT:PSS:C-12-PSV:C-60:aluminium. To characterise and elucidate the parts of the degradation mechanisms induced by molecular oxygen, 1802 isotopic labelling was emplo......The lifetimes of organic photovoltaic cells based on conjugated polymer materials were studied. The device geometry was glass:ITO:PEDOT:PSS:C-12-PSV:C-60:aluminium. To characterise and elucidate the parts of the degradation mechanisms induced by molecular oxygen, 1802 isotopic labelling...

Biostable scaffolds of polyacrylate polymers implanted in the articular cartilage induce hyaline-like cartilage regeneration in rabbits.

Science.gov (United States)

Sancho-Tello, María; Forriol, Francisco; Martín de Llano, José J; Antolinos-Turpin, Carmen; Gómez-Tejedor, José A; Gómez Ribelles, José L; Carda, Carmen

2017-07-05

To study the influence of scaffold properties on the organization of in vivo cartilage regeneration. Our hypothesis was that stress transmission to the cells seeded inside the pores of the scaffold or surrounding it, which is highly dependent on the scaffold properties, determines the differentiation of both mesenchymal cells and dedifferentiated autologous chondrocytes. 4 series of porous scaffolds made of different polyacrylate polymers, previously seeded with cultured rabbit chondrocytes or without cells, were implanted in cartilage defects in rabbits. Subchondral bone was injured during the surgery to allow blood to reach the implantation site and fill the scaffold pores. At 3 months after implantation, excellent tissue regeneration was obtained, with a well-organized layer of hyaline-like cartilage at the condylar surface in most cases of the hydrophobic or slightly hydrophilic series. The most hydrophilic material induced the poorest regeneration. However, no statistically significant difference was observed between preseeded and non-preseeded scaffolds. All of the materials used were biocompatible, biostable polymers, so, in contrast to some other studies, our results were not perturbed by possible effects attributable to material degradation products or to the loss of scaffold mechanical properties over time due to degradation. Cartilage regeneration depends mainly on the properties of the scaffold, such as stiffness and hydrophilicity, whereas little difference was observed between preseeded and non-preseeded scaffolds.

In vivo degradation characteristics of poly (β-propiolactone) prepared by radiation-induced polymerization at low temperature

International Nuclear Information System (INIS)

Asano, Masaharu; Yoshida, Masaru; Kaetsu, Isao

1987-01-01

The polymerization rate of β-propiolactone (PL) by irradiation at -78deg C in vacuo inceased markedly with the irradiation dose of up to 50 kGy and then gradually increased at an irradiation dose of up to 200 kGy. The yields of poly(PL) obtained at irradiation doses of 50 and 200 kGy were 22 and 25%, respectively. The polymer was shaped into a cylindrical form with high rigidity and density by pressing at 200 kg/cm 2 in a range of 50deg C to 75deg C. The in vivo degradation of cylindrical specimens was checked by implanting subcutaneously in the back of male Wistar rats. The degrees of in vivo degradation of poly(PL) obtained at 5, 10, 50, 100, 160, and 200 kGy irradiations were 5, 9, 25, 34, 37, and 40%, respectively. The viscosity (η sp /c value) of these polymers showed a decrease tendency with an increase in the irradiation dose. From the relationship between the η sp /c value and the in vivo degradation, it was found that the degree of in vivo degradation had a inflection point at a η sp /c value of 0.4 dl/g (30 kGy irradiation). That is, the in vivo degradation of poly(PL) with η sp /c values below 0.4 dl/g (above 30 kGy irradiation) was markedly accelerated by a slight decrease of viscosity, but such an acceleration was not remarkable at η sp /c values aboves 0.4 dl/g (below 30 kGy irradiation). This may be primarily attributed to the scssion of polymer chains during the irradiation polymerization. The data of X-ray diffraction patterns and DSC curves also showed that the in vivo degradation is influenced by a change in the crystallinity or by a decrease in the melting point of poly(PL). (author)

Induced helical backbone conformations of self-organizable dendronized polymers.

Science.gov (United States)

Rudick, Jonathan G; Percec, Virgil

2008-12-01

information to rationalize function as retrostructural analysis. Retrostructural analysis validates our hypothesis that the self-assembling dendrons induce a helical backbone conformation in cylindrical self-organizable dendronized polymers. This helical conformation mediates unprecedented functions. Self-organizable dendronized polymers have emerged as powerful building blocks for nanoscience by virtue of their dimensions and ability to self-organize. Discrete cylindrical and spherical structures with well-defined dimensions can be visualized and manipulated individually. More importantly, they provide a robust framework for elucidating functions available only at the nanoscale. This Account will highlight structures and functions generated from self-organizable dendronized polymers that enable integration of the nanoworld with its macroscopic universe. Emphasis is placed on those structures and functions derived from the induced helical backbone conformation of cylindrical self-organizable dendronized polymers.

Radiation-induced degradation of pollutants

International Nuclear Information System (INIS)

Proksch, E.

1988-01-01

This article outlines the fundamentals of radiation-induced degradation of noxious substances in drinking water and waste water and discusses the relevant literature. Radiation methods present a number of advantages and disadvantages, which should carefully be considered in each case. In many cases, there seems to be merit in combining the radiation method with other techniques, as e.g. ozone treatement and biodegradation. 30 refs., 3 figs. (Author)

Radiation processing of polymer emulsion, (4)

International Nuclear Information System (INIS)

Makuuchi, Keizo; Katakai, Akio; Ito, Hiroshi; Hayakawa, Naohiro; Araki, Kunio

1983-01-01

Methyl methacrylate was polymerized in emulsion by Co-60 γ-rays below 19 deg C in a batch reactor by using sodium lauryl sulfate as emulsifier. The conversion-time curves of the polymerization system showed two rate regions, i.e., a fact conversion rate in early stage, and a much slower rate in latter stage. The change in rate occurred at about 70 % conversion. The molecular weight of product polymer decreased with increasing conversion during the course of polymerization in latter stage, in contrast to the behavior in early stage. The distribution of the monomer in emulsion in latter stage was evaluated by nuclear magnetic resonance technique. The decrease of the molecular weight with conversion is due to the radiation-induced degradation of product polymer accelerated by the monomers absorbed in the polymer particles. (author)

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.

Solvent-assisted polymer micro-molding

Institute of Scientific and Technical Information of China (English)

HAN LuLu; ZHOU Jing; GONG Xiao; GAO ChangYou

2009-01-01

The micro-molding technology has played an important role in fabrication of polymer micro-patterns and development of functional devices.In such a process,suitable solvent can swell or dissolve the polymer films to decrease their glass transition temperature (Tg) and viscosity and thereby improve flowing ability.Consequently,it is easy to obtain the 2D and 3D patterns with high fidelity by the solvent-assisted micro-molding.Compared with the high temperature molding,this technology overcomes some shortcomings such as shrinking after cooling,degradation at high temperature,difficulty in processing some functional materials having high Tg,etc.It can be applied to making patterns not only on polymer monolayers but also on polyelectrolyte multilayers.Moreover,the compressioninduced patterns on the multilayers are chemically homogenous but physically heterogeneous.In this review,the controlling factors on the pattern quality are also discussed,including materials of the mold,solvent,pressure,temperature and pattern density.

Modeling material-degradation-induced elastic property of tissue engineering scaffolds.

Science.gov (United States)

Bawolin, N K; Li, M G; Chen, X B; Zhang, W J

2010-11-01

The mechanical properties of tissue engineering scaffolds play a critical role in the success of repairing damaged tissues/organs. Determining the mechanical properties has proven to be a challenging task as these properties are not constant but depend upon time as the scaffold degrades. In this study, the modeling of the time-dependent mechanical properties of a scaffold is performed based on the concept of finite element model updating. This modeling approach contains three steps: (1) development of a finite element model for the effective mechanical properties of the scaffold, (2) parametrizing the finite element model by selecting parameters associated with the scaffold microstructure and/or material properties, which vary with scaffold degradation, and (3) identifying selected parameters as functions of time based on measurements from the tests on the scaffold mechanical properties as they degrade. To validate the developed model, scaffolds were made from the biocompatible polymer polycaprolactone (PCL) mixed with hydroxylapatite (HA) nanoparticles and their mechanical properties were examined in terms of the Young modulus. Based on the bulk degradation exhibited by the PCL/HA scaffold, the molecular weight was selected for model updating. With the identified molecular weight, the finite element model developed was effective for predicting the time-dependent mechanical properties of PCL/HA scaffolds during degradation.

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

Low Permeable Hydrocarbon Polymer Electrolyte Membrane for Vanadium Redox Flow Battery.

Science.gov (United States)

Jung, Ho-Young; Moon, Geon-O; Jung, Seunghun; Kim, Hee Tak; Kim, Sang-Chai; Roh, Sung-Hee

2017-04-01

Polymer electrolyte membrane (PEM) confirms the life span of vanadium redox flow battery (VRFB). Products from Dupont, Nafion membrane, is mainly used for PEM in VRFB. However, permeation of vanadium ion occurs because of Nafion’s high permeability. Therefore, the efficiency of VRFB decreases and the prices becomes higher, which hinders VRFB’s commercialization. In order to solve this problem, poly(phenylene oxide) (PPO) is sulfonated for the preparation of low-priced hydrocarbon polymer electrolyte membrane. sPPO membrane is characterized by fundamental properties and VRFB cell test.

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.

Influence of composition of functional additives and deformation modes on flow behavior of polymer composite materials

Science.gov (United States)

Onoprienko, N. N.; Rahimbaev, Sh M.

2018-03-01

The paper presents the results of the influence of composition of functional water-soluble polymers and viscosity of domestic and foreign one-percent water solution polymer on flow parameters of cement and polymer test. It also gives the results of rheogoniometry of Eunice Granit tile adhesive used for large-size plates from natural stone and ceramic granite.

Two-phase flow degradation on Fukushima-Daiichi Unit 2 RCIC turbine performance

International Nuclear Information System (INIS)

Lopez, Hector; Erkan, Nejdet; Okamoto, Koji

2016-01-01

After the Fukushima accident, several investigation reports, including experiments and simulations have been done for each of the affected units to completely understand the accident progression and use their results to improve the knowledge of severe accident management and the severe codes performance. In Unit 2, the major uncertainties are related with the reactor core isolation cooling (RCIC) system performance during the accident progression especially focused in the RCIC turbine, which is assumed to work in two-phase flow. The main objective of this study is to analyze the RCIC turbine performance under two-phase flow scenarios under the assumption that the power produced by the turbine is lower than expected due to the liquid phase in the flow. A degradation coefficient quantifying the turbine power reduction is developed as a function of the flow quality by using the sonic speed reduction at critical flow conditions principle obtained by applying the non-homogeneous equilibrium model (NHEM). The degradation coefficient was applied to RELAP/ScdapSIM severe accident code showing a drastic reduction of the turbine-generated power during two-phase flow and obtaining a RCIC system behavior closer to the Tokyo electric power company (TEPCO) investigation report conclusions. (author)

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.

Changes in Flow and Transport Patterns in Fen Peat as a Result of Soil Degradation

Science.gov (United States)

Liu, Haojie; Janssen, Manon; Lennartz, Bernd

2016-04-01

The preferential movement of water and transport of substances play an important role in soils and are not yet fully understood especially in degraded peat soils. In this study, we aimed at deducing changes in flow and transport patterns in the course of soil degradation as resulting from peat drainage, using titanium dioxide (TiO2) as a dye tracer. The dye tracer experiments were conducted on columns of eight types of differently degraded peat soils from three sites taken both in vertical and horizontal directions. The titanium dioxide suspension (average particle size of 0.3 μm; 10 g l-1) was applied in a pulse of 40 mm to each soil core. Twenty-four hours after the application of the tracer, cross sections of the soil cores were prepared for photo documentation. In addition, the saturated hydraulic conductivity (Ks) was determined. Preferential flow occurred in all investigated peat types. From the stained soil structural elements, we concluded that undecomposed plant remains are the major preferential flow pathways in less degraded peat. For more strongly degraded peat, bio-pores, such as root and earthworm channels, operated as the major transport domain. Results show that Ks and the effective pore network in less degraded peat soils are anisotropic. With increasing peat degradation, the Ks and cross section of effective pore network decreased. The results also indicate a strong positive relationship between Ks and number of macropores as well as pore continuity. Hence, we conclude that changes in flow and transport pathways as well as Ks with an increasing peat degradation are due to the disintegration of the peat forming plant material and decrement of number and continuity of macropores after drainage.

Mass transport aspects of polymer electrolyte fuel cells under two-phase flow conditions

Energy Technology Data Exchange (ETDEWEB)

Kramer, D.

2007-03-15

This well-illustrated, comprehensive dissertation by Dr. Ing. Denis Kramer takes an in-depth look at polymer electrolyte fuel cells (PEFC) and the possibilities for their application. First of all, the operating principles of polymer electrolyte fuel cells are described and discussed, whereby thermodynamics aspects and loss mechanisms are examined. The mass transport diagnostics made with respect to the function of the cells are discussed. Field flow geometry, gas diffusion layers and, amongst other things, liquid distribution, the influence of flow direction and the low-frequency behaviour of air-fed PEFCs are discussed. Direct methanol fuel cells are examined, as are the materials chosen. The documentation includes comprehensive mathematical and graphical representations of the mechanisms involved.

Photo-induced Mass Transport through Polymer Networks

Science.gov (United States)

Meng, Yuan; Anthamatten, Mitchell

2014-03-01

Among adaptable materials, photo-responsive polymers are especially attractive as they allow for spatiotemporal stimuli and response. We have recently developed a macromolecular network capable of photo-induced mass transport of covalently bound species. The system comprises of crosslinked chains that form an elastic network and photosensitive fluorescent arms that become mobile upon irradiation. We form loosely crosslinked polymer networks by Michael-Addition between multifunctional thiols and small molecule containing acrylate end-groups. The arms are connected to the network by allyl sulfide, that undergoes addition-fragmentation chain transfer (AFCT) in the presence of free radicals, releasing diffusible fluorophore. The networks are loaded with photoinitiator to allow for spatial modulation of the AFCT reactions. FRAP experiments within bulk elastomers are conducted to establish correlations between the fluorophore's diffusion coefficient and experimental variables such as network architecture, temperature and UV intensity. Photo-induced mass transport between two contacted films is demonstrated, and release of fluorophore into a solvent is investigated. Spatial and temporal control of mass transport could benefit drug release, printing, and sensing applications.

Total-dose radiation-induced degradation of thin film ferroelectric capacitors

International Nuclear Information System (INIS)

Schwank, J.R.; Nasby, R.D.; Miller, S.L.; Rodgers, M.S.; Dressendorfer, P.V.

1990-01-01

Thin film PbZr y Ti 1-y O 3 (PZT) ferroelectric memories offer the potential for radiation-hardened, high-speed nonvolatile memories with good retention and fatigue properties. In this paper we explore in detail the radiation hardness of PZT ferroelectric capacitors. Ferroelectric capacitors were irradiated using x-ray and Co-60 sources to dose levels up to 16 Mrad(Si). The capacitors were characterized for their memory properties both before and after irradiation. The radiation hardness was process dependent. Three out of four processes resulted in capacitors that showed less than 30% radiation-induced degradation in retained polarization charge and remanent polarization after irradiating to 16 Mrad(Si). On the other hand, one of the processes showed significant radiation-induced degradation in retained polarization charge and remanent polarization at dose levels above 1 Mrad(Si). The decrease in retained polarization charge appears to be due to an alteration of the switching characteristics of the ferroelectric due to changes in the internal fields. The radiation-induced degradation is recoverable by a postirradiation biased anneal and can be prevented entirely if devices are cycled during irradiation. The authors have developed a model to simulate the observed degradation

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.

A highly energy-efficient flow-through electro-Fenton process for organic pollutants degradation

International Nuclear Information System (INIS)

Ma, Liang; Zhou, Minghua; Ren, Gengbo; Yang, Weilu; Liang, Liang

2016-01-01

Highlights: • A highly energy-efficient flow-through electro-Fenton reactor was designed. • It had high H 2 O 2 yield and low energy consumption for organic pollutants degradation. • The effect of operational parameters was optimized and possible process mechanism was studied. • The novel system performed wide practicability and potential for organic pollutants degradation. - Abstract: A highly energy-efficient flow-through Electro-Fenton (E-Fenton) reactor for oxidation of methylene blue (MB) from aqueous solution was designed using a perforated DSA as anode and the graphite felt modified by carbon black and polytetrafluoroethylene (PTFE) as cathode for the in situ generation of H 2 O 2 . The modified cathode had a high H 2 O 2 production with low energy consumption, which was characterized by scanning electron microscopy (SEM), nitrogen adsorption-desorption study and contact angle. The flow-through E-Fenton system was compared to the flow-by and regular one, and confirmed to be best on MB removal and TOC degradation. The operational parameters such as current density, pH, Fe 2+ concentration and flow rate were optimized. The MB and TOC removal efficiency of the effluents could keep above 90% and 50%, respectively, and the energy consumption was 23.0 kWh/kgTOC at the current density of 50 mA, pH 3, 0.3 mM Fe 2+ , and the flow rate of 7 mL/min. ·OH was proved to be the main oxidizing species in this system. After 5 times operation, the system, especially cathode, still showed good stability. Five more organic pollutants including orange II (OG), tartrazine, acetylsalicylic acid (ASA), tetracycline (TC) and 2,4-dichlorophen (2,4-DCP) were investigated and the electric energy consumption (EEC) was compared with literatures. All results demonstrated that this flow-through E-Fenton system was energy-efficient and potential for degradation of organic pollutants.

High resolution optical spectroscopy of air-induced electrical instabilities in n-type polymer semiconductors.

Science.gov (United States)

Di Pietro, Riccardo; Sirringhaus, Henning

2012-07-03

We use high-resolution charge-accumulation optical spectroscopy to measure charge accumulation in the channel of an n-type organic field-effect transistor. We monitor the degradation of device performance in air, correlate the onset voltage shift with the reduction of charge accumulated in the polymer semiconductor, and explain the results in view of the redox reaction between the polymer, water and oxygen in the accumulation layer. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Use of radiation-induced polymers in cement slurries

International Nuclear Information System (INIS)

Knight, B.L.; Rhudy, J.S.; Gogarty, W.B.

1976-01-01

Water loss from cement slurries is reduced by incorporating within a cement slurry a polymer obtained as a product of radiation-induced polymerization of acrylamide and/or methacrylamide and acrylic acid, methacrylic acid, and/or alkali metal salts thereof. The polymerization is preferably carried out in 10-60 percent aqueous monomer solution with gamma radiation. The aqueous monomer solution preferably contains 25-99 percent acrylamide and 75-1 percent sodium acrylate. The polymer can be present in concentration of about 0.001 to about 3.0 weight percent, based on the aqueous phase of the slurry

Hydroxyl radical induced degradation of salicylates in aerated aqueous solution

International Nuclear Information System (INIS)

Szabó, László; Tóth, Tünde; Homlok, Renáta; Rácz, Gergely; Takács, Erzsébet; Wojnárovits, László

2014-01-01

Ionizing radiation induced degradation of acetylsalicylic acid, its hydrolysis product salicylic acid and a salicylic acid derivative 5-sulpho-salicylic acid, was investigated in dilute aqueous solutions by UV–vis spectrophotometry, HPLC separation and diode-array or MS/MS detection, chemical oxygen demand, total organic carbon content and by Vibrio fischeri toxicity measurements. Hydroxyl radicals were shown to degrade these molecules readily, and first degradation products were hydroxylated derivatives in all cases. Due to the by-products, among them hydrogen peroxide, the toxicity first increased and then decreased with the absorbed dose. With prolonged irradiation complete mineralization was achieved. - Highlights: • In OH induced reactions of salicylates first products are hydroxylated derivatives. • With prolonged irradiation dihydroxy derivatives also form. • In aerated solutions the one-electron oxidant OH induces 3–4 oxidations. • Toxicity first increases and then decreases with dose mainly due to H 2 O 2 formation. • The toxicity in tap water is smaller than in pure water

Fabrication of polymer-alloy based on polytetrafluoroethylene by radiation-crosslinking

International Nuclear Information System (INIS)

Oshima, A.; Asano, S.; Hyunga, T.; Ichizuri, S.; Washio, M.

2003-01-01

Perfluoropolymer such as polytetrafluoroethylene (PTFE), tetrafluoroethylene co-perfluoroalkylvinylether (PFA) and tetrafluoroethylene-co-hexafluoropropylene (FFP) have been classified to be a typical polymer of radiation-induced degradation. However, we confirmed that the crosslinking of PTFE, PFA and FEP proceed by irradiation under selective condition where oxygen-free and high temperature above the melting temperature of them. In this study, fabrication of polymer-alloy based on PTFE has been demonstrated by radiation-crosslinking techniques. The polymer alloy, which was PTFE fine powder contained with other polymeric materials, was obtained by electron beams irradiation under oxygen-free atmosphere. Characterization of polymer-alloy based on PTFE has been studied by various measurements such as solid state 19F- and 13C-NMR spectroscopy, thermal analysis (DSC, TGA)

Flow-induced crystallization of a nano composite of poly(butylene adipate-co-terephthalate)/montmorillonite

International Nuclear Information System (INIS)

Bonel, Alan B.; Rego, Bruna T.; Beatrice, Cesar A.G.; Marini, Juliano; Bretas, Rosario E.S.

2011-01-01

Poly(butylene adipate-co-terephthalate) (PBAT) with 5wt% of an organically modified montmorillonite with polar surfactant was prepared by melt blending in a co-rotational twin-screw extruder at 160 degree C. 100rpm and 1 kg/h. Both pure polymer and nano composite were characterized by wide measurements. The study of the flow-induced crystallization was also done by rheological measurements, monitoring the viscosity as a function of time. The nano clay's lamellas were intercalated in the polymer m loss moduli of the nano composite, at low frequencies, showed that the particles of the nano clay were well dispersed and distributed thru the PBAT matrix. Finally, the presence of the nano clay's particles reduced the induction tim crystals growth, due to the strong interactions with the PBAT chains. (author)

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.

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene in flow system, 10

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Ito, Masayuki; Okamoto, Jiro; Machi, Sueo.

1982-02-01

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene by continuous operation was carried out using a flow apparatus with tank type reactor of 5 liter under a constant pressure of 30 kg/cm 2 , a temperature of 40 0 C, and a propylene fraction in monomer gas of 0.1. The polymer concentration in latex reaches to steady value after two times longer operation than mean residence time of latex in the reactor. The steady polymer concentration increases accelerately with increase of the mean residence time. The polymer concentrations and the polymerization rates are 33, 70, 164 g/l-H 2 O and 35.1, 40.0, 49.5 g/h.l-H 2 O, respectively, obtained at the mean residence times of 0.94, 1.75 and 3.31 hour. The results are consistent with those in semi-batch operation under the same reaction conditions. The amounts of dissolved monomer in latex tends to decrease with decreasing the mean residence time. This shows that monomer supply by diffusion from gas phase to latex is not enough in shorter residence time of latex in the reactor. (author)

Agglomerated polymer monoliths with bimetallic nano-particles as flow-through micro-reactors

International Nuclear Information System (INIS)

Floris, P.; Twamley, B.; Nesterenko, P.N.; Paull, B.; Connolly, D.

2012-01-01

Polymer monoliths in capillary format have been prepared as solid supports for the immobilisation of platinum/palladium bimetallic nano-flowers. Optimum surface coverage of nano-flowers was realised by photografting the monoliths with vinyl azlactone followed by amination with ethylenediamine prior to nano-particle immobilisation. Field emission SEM imaging was used as a characterisation tool for evaluating nano-particle coverage, together with BET surface area analysis to probe the effect of nano-particle immobilisation upon monolith morphology. Ion exchange chromatography was also used to confirm the nature of the covalent attachment of nano-flowers on the monolithic surface. In addition, EDX and ICP analyses were used to quantify platinum and palladium on modified polymer monoliths. Finally the catalytic properties of immobilised bimetallic Pd/Pt nano-flowers were evaluated in flow-through mode, exploiting the porous interconnected flow-paths present in the prepared monoliths (pore diameter ∼ 1-2 μm). Specifically, the reduction of Fe (III) to Fe (II) and the oxidation of NADH to NAD+ were selected as model redox reactions. The use of a porous polymer monolith as an immobilisation substrate (rather than aminated micro-spheres) eliminated the need for a centrifugation step after the reaction. (author)

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...

Preventing light-induced degradation in multicrystalline silicon

Science.gov (United States)

Lindroos, J.; Boulfrad, Y.; Yli-Koski, M.; Savin, H.

2014-04-01

Multicrystalline silicon (mc-Si) is currently dominating the silicon solar cell market due to low ingot costs, but its efficiency is limited by transition metals, extended defects, and light-induced degradation (LID). LID is traditionally associated with a boron-oxygen complex, but the origin of the degradation in the top of the commercial mc-Si brick is revealed to be interstitial copper. We demonstrate that both a large negative corona charge and an aluminum oxide thin film with a built-in negative charge decrease the interstitial copper concentration in the bulk, preventing LID in mc-Si.

Land Tenure Induced Deforestation and Environmental Degradation ...

African Journals Online (AJOL)

Land Tenure Induced Deforestation and Environmental Degradation in Ethiopia: The Case of Arbagugu State Forest Development and Protection Project (A ... The objective of this paper is to explore the cause and impact of this overarching problem by focusing on Arbagugu State Forest Development and Protection Project, ...

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

Study of the flow development of polymer solutions through capillaries

International Nuclear Information System (INIS)

Perez-Gonzalez, J.; De Vargas, L.; Tejero, M.

1991-01-01

Flow experiments through capillaries with semirigid and rigid polymers in aqueous solutions were carried out in order to study the dependence of the flow development on the molecular conformation and the length to diameter ratio (L/D), of the capillary at relatively low shear rates. It was found that the apparent viscosity has a strong dependence upon the ratio L/D for a given shear rate, although an asymptotic value is reached. This dependence was reflected in the non-linearity of Bagley's plots. The asymptotic value was attained at lower L/D values for semirigid molecules than for rigid ones, showing the influence of the molecular conformation on the flow field development due to the different modes of relaxation for each type of molecule. (Author)

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

Aromatic polymers of increased resistance to flow and molecular weight obtained by irradiation

International Nuclear Information System (INIS)

Staniland, P.A.; Jarrett, G.

1976-01-01

Aromatic polymers of increased resistance to flow and increased molecular weight are obtained by irradiation using β rays or gamma rays at temperatures up to 400 0 C of an aromatic polymer whose molecular chains comprise benzenoid groups and bivalent linking groups, and where irradiation is gamma rays by heating subsequent to irradiation at 200 0 C to 400 0 C. The polymeric materials having increased molecular weight are useful for coating non-cooking surfaces of cookware

Radiation induced degradation of dyes-An overview

International Nuclear Information System (INIS)

Rauf, M.A.; Ashraf, S. Salman

2009-01-01

Synthetic dyes are a major part of our life. Products ranging from clothes to leather accessories to furniture all depend on extensive use of organic dyes. An unfortunate side effect of extensive use of these chemicals is that huge amounts of these potentially carcinogenic compounds enter our water supplies. Various advanced oxidation processes (AOPs) including the use of high-energy radiation have been developed to degrade these compounds. In this review, dye decoloration and degradation as a result of its exposure to high energy radiation such as gamma radiation and pulsed electron beam are discussed in detail. The role of various transient species such as ·H, ·OH and e aq - are taken into account as reported by various researchers. Literature citations in this area show that e aq - is very effective in decolorization but is less active in the further degradation of the products formed. The degradation of the dyes is initiated exclusively by ·OH attack on electron-rich sites of the dye molecules. Additionally, various parameters that affect the efficiency of radiation induced degradation of dyes, such as effect of radiation dose, oxygen, pH, hydrogen peroxide, added ions and dye classes are also reviewed and summarized. Lastly, pilot plant application of radiation for wastewater treatment is briefly discussed.

Electric field induced dewetting at polymer/polymer interfaces

NARCIS (Netherlands)

Lin, Z.Q.; Kerle, T.; Russell, T.P.; Schäffer, E.; Steiner, U

2002-01-01

External electric fields were used to amplify interfacial fluctuations in the air/polymer/polymer system where one polymer dewets the other. Two different hydrodynamic regimes were found as a function of electric field strength. If heterogeneous nucleation leads to the formation of holes before the

Creep-induced anisotropy in covalent adaptable network polymers.

Science.gov (United States)

Hanzon, Drew W; He, Xu; Yang, Hua; Shi, Qian; Yu, Kai

2017-10-11

Anisotropic polymers with aligned macromolecule chains exhibit directional strengthening of mechanical and physical properties. However, manipulating the orientation of polymer chains in a fully cured thermoset is almost impossible due to its permanently crosslinked nature. In this paper, we demonstrate that rearrangeable networks with bond exchange reactions (BERs) can be utilized to tailor the anisotropic mechanical properties of thermosetting polymers. When a constant force is maintained at BER activated temperatures, the malleable thermoset creeps in the direction of stress, and macromolecule chains align themselves in the same direction. The aligned polymer chains result in an anisotropic network with a stiffer mechanical behavior in the direction of creep, while with a more compliant behavior in the transverse direction. The degree of network anisotropy is proportional to the amount of creep strain. A multi-length scale constitutive model is developed to study the creep-induced anisotropy of thermosetting polymers. The model connects the micro-scale BER kinetics, orientation of polymer chains, and directional mechanical properties of network polymers. Without any fitting parameters, it is able to predict the evolution of creep strain at different temperatures and anisotropic stress-strain behaviors of CANs after creep. Predictions on the chain orientation are verified by molecular dynamics (MD) simulation. Based on parametric studies, it is shown that the influences of creep time and temperature on the network anisotropy can be generalized into a single parameter, and the evolution of directional modulus follows an Arrhenius type time-temperature superposition principle (TTSP). The presented work provides a facile approach to transform isotropic thermosets into anisotropic ones using simple heating, and their directional properties can be readily tailored by the processing conditions.

Radiation degradation of poly(olefin sulphone)s - Fundamental research to practical applications

International Nuclear Information System (INIS)

Bowden, M.J.; O'Donnell, J.H.

1985-01-01

The degradation of poly(olefin sulphone)s by high energy radiation, particularly by γ-rays and electron beams, provides an example of the application of fundamental science to high technology industry. Scientific interest in the radiation degradation of these polymers was first aroused by the discovery that they underwent highly specific bond scission in the backbone chain as the primary result of absorption of high energy radiation and in fact they were the first polymers in which such an effect had been demonstrated. This conclusion was initially based mainly on evidence from electron spin resonance spectroscopy and was subsequently verified by studies of molecular weight changes. These studies showed that the poly(olefin sulphone)s not only degraded by main chain scission but were also among the most radiation-sensitive polymers known. The extremely high sensitivity of poly(olefin sulphone)s to radiation-induced main-chain scission has found application in the field of microelectronics. Electron beam writing on poly(olefin sulphone) films is used to produce lithographic masks for the manufacture of integrated circuits on silicon wafers. Poly(1-butene sulphone) (PBS) is currently used in the production of a substantial proportion of the masks for the industry. The fundamental aspects of the radiation degradation of poly(olefin sulphone)s and the practical applications to high technology are reviewed. (author)

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.

Monitoring the Erosion of Hydrolytically-Degradable Nanogels via Multiangle Light Scattering Coupled to Asymmetrical Flow Field-Flow Fractionation

Science.gov (United States)

Smith, Michael H.; South, Antoinette B.; Gaulding, Jeffrey C.; Lyon, L. Andrew

2009-01-01

We describe the synthesis and characterization of degradable nanogels that display bulk erosion under physiologic conditions (pH = 7.4, 37 °C). Erodible poly(N-isopropylmethacrylamide) nanogels were synthesized by copolymerization with N,O-(dimethacryloyl)hydroxylamine, a cross-linker previously used in the preparation of non-toxic and biodegradable bulk hydrogels. To monitor particle degradation, we employed multiangle light scattering and differential refractometry detection following asymmetrical flow field-flow fractionation. This approach allowed the detection of changes in nanogel molar mass and topology as a function of both temperature and pH. Particle erosion was evident from both an increase in nanogel swelling and a decrease in scattering intensity as a function of time. Following these analyses, the samples were recovered for subsequent characterization by direct particle tracking, which yields hydrodynamic size measurements and enables number density determination. Additionally, we confirmed the conservation of nanogel stimuli-responsivity through turbidity measurements. Thus, we have demonstrated the synthesis of degradable nanogels that erode under conditions and on timescales that are relevant for many drug delivery applications. The combined separation and light scattering detection method is demonstrated to be a versatile means to monitor erosion and should also find applicability in the characterization of other degradable particle constructs. PMID:20000662

Degradation of Mcl-1 through GSK-3β Activation Regulates Apoptosis Induced by Bufalin in Non-Small Cell Lung Cancer H1975 Cells

Directory of Open Access Journals (Sweden)

Xiao-hong Kang

2017-04-01

Full Text Available Background/Aims: Mcl-1, an anti-apoptotic Bcl-2 family member, is often overexpressed in non-small cell lung cancer (NSCLC. Bufalin has been reported to induce apoptosis in various tumor cells. However, there is no report showing that bufalin could downregulate Mcl-1 expression in NSCLC. Methods: Cell proliferation was analyzed by cell counting kit-8 (CCK-8 assay in H1975 cells. Cell apoptosis was detected by flow cytometry. Mcl-1 mRNA was detected by RT-PCR. The expression of apoptosis-associated proteins in H1975 cells was detected by western blotting. The levels of Mcl-1 ubiquitination and NOXA were analyzed by Immunoprecipitation assay. Results: Cell growth was inhibited by bufalin in a time and dose-dependent manner. Bufalin induced apoptosis in NSCLC cells by activating caspase cascades and downregulating Mcl-1 expression. However, overexpression of Mcl-1 diminished bufalin-induced apoptosis. Furthermore, bufalin did not reduce Mcl-1 mRNA expression in H1975 cells, but strongly promoted Mcl-1 protein degradation. Proteasome inhibitor MG132 markedly prevented the degradation of Mcl-1 and blocked bufalin-induced Mcl-1 reduction. Bufalin did not significantly affect NOXA protein levels, but downregulated the expression of p-GSK-3β. GSK-3 inhibitor and GSK-3β siRNA resulted in increased levels of Mcl-1 and reversed the bufalin-induced Mcl-1 degradation. Conclusion: Bufalin induced cell apoptosis in H1975 cells may be through downregulation of Mcl-1. Proteasomal degradation of Mcl-1 via GSK-3β activation was involved in bufalin-induced apoptosis.

Embrittlement of MISSE 5 Polymers After 13 Months of Space Exposure

Science.gov (United States)

Guo, Aobo; Yi, Grace T.; Ashmead, Claire C.; Mitchell, Gianna G.; deGroh, Kim K.

2012-01-01

Understanding space environment induced degradation of spacecraft materials is essential when designing durable and stable spacecraft components. As a result of space radiation, debris impacts, atomic oxygen interaction, and thermal cycling, the outer surfaces of space materials degrade when exposed to low Earth orbit (LEO). The objective of this study was to measure the embrittlement of 37 thin film polymers after LEO space exposure. The polymers were flown aboard the International Space Station and exposed to the LEO space environment as part of the Materials International Space Station Experiment 5 (MISSE 5). The samples were flown in a nadir-facing position for 13 months and were exposed to thermal cycling along with low doses of atomic oxygen, direct solar radiation and omnidirectional charged particle radiation. The samples were analyzed for space-induced embrittlement using a bend-test procedure in which the strain necessary to induce surface cracking was determined. Bend-testing was conducted using successively smaller mandrels to apply a surface strain to samples placed on a semi-suspended pliable platform. A pristine sample was also tested for each flight sample. Eighteen of the 37 flight samples experienced some degree of surface cracking during bend-testing, while none of the pristine samples experienced any degree of cracking. The results indicate that 49 percent of the MISSE 5 thin film polymers became embrittled in the space environment even though they were exposed to low doses (approx.2.75 krad (Si) dose through 127 mm Kapton) of ionizing radiation.

Impact of drag reducing polymers on the onset of instability in a pipe with reverse flow

Science.gov (United States)

Shashank, H. J.; Sreenivas, K. R.

2014-11-01

The objective of this study is to understand the mechanism by which drag reducing polymer (DRP) additives modify turbulent flow, so as to reduce turbulent drag. Reverse flow in a pipe occurs when the fluid close to the wall moves in an opposite direction to that of the core fluid. Reverse flow is established by using a piston-cylinder mechanism, the programmed motion of which imparts a known impulse to the fluid. When the piston is stopped at the end of the stroke, fluid inertia makes the core of the flow to continue in the same direction. In order to conserve mass, reverse flow is established close to the wall. An inflection point is thus formed, leading to flow instability above a critical Reynolds number. Dye and streak flow visualization experiments are performed to highlight the impact of DRP additives (polyethylene oxide, PEO, dissolved in water). The time of onset of the instability and the wavelength of the observed instability are studied in systems with and without DRP additives. This study will provide further insight into the phenomenon of turbulent polymer drag reduction.

Targeting Neutrophil Protease-Mediated Degradation of Tsp-1 to Induce Metastatic Dormancy

Science.gov (United States)

2017-10-01

AWARD NUMBER: W81XWH-16-1-0615 TITLE: Targeting Neutrophil Protease-Mediated Degradation of Tsp-1 to Induce Metastatic Dormancy PRINCIPAL...29 Sep 2017 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Targeting Neutrophil Protease-Mediated Degradation of Tsp-1 to Induce Metastatic Dormancy...infection or cigarette smoke enhanced pulmonary metastasis from breast cancer in humans and mice. Similarly, autoimmune arthritis, characterized by

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.

Differentiation-inducing factor-1 induces cyclin D1 degradation through the phosphorylation of Thr286 in squamous cell carcinoma

International Nuclear Information System (INIS)

Mori, Jun; Takahashi-Yanaga, Fumi; Miwa, Yoshikazu; Watanabe, Yutaka; Hirata, Masato; Morimoto, Sachio; Shirasuna, Kanemitsu; Sasaguri, Toshiyuki

2005-01-01

Differentiation-inducing factors (DIFs) are morphogens which induce cell differentiation in Dictyostelium. We reported that DIF-1 and DIF-3 inhibit proliferation and induce differentiation in mammalian cells. In this study, we investigated the effect of DIF-1 on oral squamous cell carcinoma cell lines NA and SAS, well differentiated and poorly differentiated cell lines, respectively. Although DIF-1 did not induce the expression of cell differentiation makers in these cell lines, it inhibited the proliferation of NA and SAS in a dose-dependent manner by restricting the cell cycle in the G 0 /G 1 phase. DIF-1 induced cyclin D1 degradation, but this effect was prevented by treatment with lithium chloride and SB216763, the inhibitors of glycogen synthase kinase-3β (GSK-3β). Depletion of endogenous GSK-3β by RNA interference also attenuated the effect of DIF-1 on cyclin D1 degradation. Therefore, we investigated the effect of DIF-1 on GSK-3β and found that DIF-1 dephosphorylated GSK-3β on Ser 9 and induced the nuclear translocation of GSK-3β, suggesting that DIF-1 activated GSK-3β. Then, we examined the effect of DIF-1 on cyclin D1 mutants (Thr286Ala, Thr288Ala, and Thr286/288Ala). We revealed that Thr286Ala and Thr286/288Ala mutants were highly resistant to DIF-1-induced degradation compared with wild-type cyclin D1, indicating that the phosphorylation of Thr 286 was critical for cyclin D1 degradation induced by DIF-1. These results suggest that DIF-1 induces degradation of cyclin D1 through the GSK-3β-mediated phosphorylation of Thr 286

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

Calcitonin Gene-Related Peptide Induces HIV-1 Proteasomal Degradation in Mucosal Langerhans Cells.

Science.gov (United States)

Bomsel, Morgane; Ganor, Yonatan

2017-12-01

The neuroimmune dialogue between peripheral neurons and Langerhans cells (LCs) within mucosal epithelia protects against incoming pathogens. LCs rapidly internalize human immunodeficiency virus type 1 (HIV-1) upon its sexual transmission and then trans -infect CD4 + T cells. We recently found that the neuropeptide calcitonin gene-related peptide (CGRP), secreted mucosally from peripheral neurons, inhibits LC-mediated HIV-1 trans -infection. In this study, we investigated the mechanism of CGRP-induced inhibition, focusing on HIV-1 degradation in LCs and its interplay with trans -infection. We first show that HIV-1 degradation occurs in endolysosomes in untreated LCs, and functionally blocking such degradation with lysosomotropic agents results in increased trans -infection. We demonstrate that CGRP acts via its cognate receptor and at a viral postentry step to induce faster HIV-1 degradation, but without affecting the kinetics of endolysosomal degradation. We reveal that unexpectedly, CGRP shifts HIV-1 degradation from endolysosomes toward the proteasome, providing the first evidence for functional HIV-1 proteasomal degradation in LCs. Such efficient proteasomal degradation significantly inhibits the first phase of trans -infection, and proteasomal, but not endolysosomal, inhibitors abrogate CGRP-induced inhibition. Together, our results establish that CGRP controls the HIV-1 degradation mode in LCs. The presence of endogenous CGRP within innervated mucosal tissues, especially during the sexual response, to which CGRP contributes, suggests that HIV-1 proteasomal degradation predominates in vivo Hence, proteasomal, rather than endolysosomal, HIV-1 degradation in LCs should be enhanced clinically to effectively restrict HIV-1 trans -infection. IMPORTANCE During sexual transmission, HIV-1 is internalized and degraded in LCs, the resident antigen-presenting cells in mucosal epithelia. Yet during trans -infection, infectious virions escaping degradation are transferred

Redox active polymers and colloidal particles for flow batteries

Science.gov (United States)

Gavvalapalli, Nagarjuna; Moore, Jeffrey S.; Rodriguez-Lopez, Joaquin; Cheng, Kevin; Shen, Mei; Lichtenstein, Timothy

2018-05-29

The invention provides a redox flow battery comprising a microporous or nanoporous size-exclusion membrane, wherein one cell of the battery contains a redox-active polymer dissolved in the non-aqueous solvent or a redox-active colloidal particle dispersed in the non-aqueous solvent. The redox flow battery provides enhanced ionic conductivity across the electrolyte separator and reduced redox-active species crossover, thereby improving the performance and enabling widespread utilization. Redox active poly(vinylbenzyl ethylviologen) (RAPs) and redox active colloidal particles (RACs) were prepared and were found to be highly effective redox species. Controlled potential bulk electrolysis indicates that 94-99% of the nominal charge on different RAPs is accessible and the electrolysis products are stable upon cycling. The high concentration attainable (>2.0 M) for RAPs in common non-aqueous battery solvents, their electrochemical and chemical reversibility, and their hindered transport across porous separators make them attractive materials for non-aqueous redox flow batteries based on size-selectivity.

Flow-induced vibration -- 1994. PVP-Volume 273

International Nuclear Information System (INIS)

Au-Yang, M.K.; Fujita, K.

1994-01-01

Flow-induced vibration is a subject of practical interest to many engineering disciplines, including the power generation, process, and petrochemical industries. In the nuclear industry, flow-induced vibration reaches a higher level of concern because of safety issues and the huge cost associated with down time and site repair. Not surprisingly, during the last 25 years a tremendous amount of effort has been spent in the study of flow-induced vibration phenomena related to nuclear plant components, notably nuclear steam generator tube banks and nuclear fuel bundles. Yet, in spite of this concentrated effort, the industry is still not free from flow-induced vibration-related problems. This explains why in this volume almost half of the papers address the issue of cross-flow induced vibration in tube bundles, with applications to the nuclear steam generator and nuclear fuel bundles in mind. Unlike 10 or 15 years ago, when flow-induced vibration studies almost always involved experimentation and empirical studies, the advent of high-speed computers has enabled numerical calculation and simulation of this complex phenomenon to take place. Separate abstracts were prepared for 27 papers in this volume

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)

Precision Polymer Design in Microstructured Flow Reactors: Improved Control and First Upscale at Once

OpenAIRE

Junkers, Thomas

2017-01-01

Continuous flow synthesis techniques have in recent years conquered laboratory scale synthesis, yet within the field of precision polymer synthesis its use is still not fully established despite the large advantages that can be gained from switching from classical batch-wise chemistry to flow chemistry, often already by using relatively simple chip-based or cheap tubular micro- and mesoscaled reactors. Translating a polymerization from batch to continuous flow marks not only a mere change in ...

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.

Electrohydrodynamics in nanochannels coated by mixed polymer brushes: effects of electric field strength and solvent quality

Science.gov (United States)

Cao, Qianqian; Tian, Xiu; You, Hao

2018-04-01

We examine the electrohydrodynamics in mixed polymer brush-coated nanochannels and the conformational dynamics of grafted polymers using molecular dynamics simulations. Charged (A) and neutral polymers (B) are alternately grafted on the channel surfaces. The effects of the electric field strength and solvent quality are addressed in detail. The dependence of electroosmotic flow characteristics and polymer conformational behavior on the solvent quality is influenced due to the change of the electric field strength. The enhanced electric field induces a collapse of the neutral polymer chains which adopt a highly extended conformation along the flow direction. However, the thickness of the charged polymer layer is affected weakly by the electric field, and even a slight swelling is identified for the A-B attraction case, implying the conformational coupling between two polymer species. Furthermore, the charged polymer chains incline entirely towards the electric field direction oppositely to the flow direction. More importantly, unlike the neutral polymer chains, the shape factor of the charged polymer chains, which is used to describe the overall shape of polymer chains, is reduced significantly with increasing the electric field strength, corresponding to a more coiled structure.

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...

A new modified-serpentine flow field for application in high temperature polymer electrolyte fuel cell

DEFF Research Database (Denmark)

Singdeo, Debanand; Dey, Tapobrata; Gaikwad, Shrihari

2017-01-01

field design is proposed and its usefulness for the fuel cell applications are evaluated in a high-temperature polymer electrolyte fuel cell. The proposed geometry retains some of the features of serpentine flow field such as multiple bends, while modifications are made in its in-plane flow path...

LASER INDUCED SELECTIVE ACTIVATION UTILIZING AUTO-CATALYTIC ELECTROLESS PLATING ON POLYMER SURFACE

DEFF Research Database (Denmark)

Zhang, Yang; Nielsen, Jakob Skov; Tang, Peter Torben

2009-01-01

. Characterization of the deposited copper layer was used to select and improve laser parameters. Several types of polymers with different melting points were used as substrate. Using the above mentioned laser treatment, standard grades of thermoplastic materials such as ABS, SAN, PE, PC and others have been......This paper presents a new method for selective micro metallization of polymers induced by laser. An Nd: YAG laser was employed to draw patterns on polymer surfaces using a special set-up. After subsequent activation and auto-catalytic electroless plating, copper only deposited on the laser tracks....... Induced by the laser, porous and rough structures are formed on the surface, which favours the palladium attachment during the activation step prior to the metallization. Laser focus detection, scanning electron microscopy (SEM) and other instruments were used to analyze the topography of the laser track...

Radiation induced degradation of DNA in photodynamic therapy of cancer

International Nuclear Information System (INIS)

Ion, Rodica; Scarlat, F.; Niculescu, V.I.R.; Scarlat, Fl.; Gunaydin, Keriman

2001-01-01

DNA is a critical cellular target for oxidative processes induced by physical and chemical stresses. It is known that the direct effect of ionizing radiation on DNA results mainly in base ionization and may lead to mutation, carcinogenesis and cell death. The degradation of DNA induced by laser and ionizing radiation (electron and photon beam) is analyzed in this paper. The ionizing radiation degradation of DNA is a radical process. A series of lesions among the major base degradation product has been measured in isolated DNA exposed to gamma radiation in aerated aqueous solution. Degradation can be accounted for by the formation of hydroxyl radicals upon radiolysis of water (indirect effect). The production of DNA damage by ionizing radiation involves two mechanisms, direct and indirect effects. Direct effect leads to ionization and excitation of DNA molecules, while indirect effect is due to the interaction of reactive species, in particular of OH radicals produced by water radiolysis, with targets in DNA. The relative contribution of the two mechanisms in damaging DNA depends on the type of radiation. Single strand breaks and base damage seem to be mainly produced by the attack of hydroxyl radicals on DNA, whereas double strand breaks result predominantly of direct energy deposition. The four bases are degraded in high yield. Direct effect has been mimicked by photo-induced electron abstraction from the bases producing their radical cation. The base damage may also occur from the formation of radical cation of purine and pyrimidine components. When DNA is irradiated in solution, single strand breaks are mainly due to the abstraction of an H atom from the 4 ' position of 2 ' -deoxyribose by the attack of OH radicals produced by water radiolysis. Quantification of the modified bases showed the guanine is the preferential target. Ionizing radiation induces several types of DNA modifications, including chain breaks, DNA-protein cross-links, oxidized DNA bases

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.

HD domain of SAMHD1 influences Vpx-induced degradation at a post-interaction step

Energy Technology Data Exchange (ETDEWEB)

Kang, Jian; Hou, Jingwei; Zhao, Ke; Yu, Xiao-Fang; Du, Juan, E-mail: jdu@jlu.edu.cn

2016-02-12

Primate SAMHD1 proteins are potent inhibitors of viruses, including retroviruses such as HIV-1, HIV-2, and SIV. Vpx, a distinctive viral protein expressed by HIV-2 and some SIVs, induces SAMHD1 degradation by forming a Vpx-DCAF1-based ubiquitin ligase complex. Either the N- or the C-terminus of SAMHD1 is critical for Vpx-induced degradation, depending on the types of SAMHD1 and Vpx proteins. However, it was not fully understood whether other regions of SAMHD1 also contribute to its depletion by Vpx. In the present study, we report that SAMHD1 from chicken (SAMHD1{sub GG}) was not degraded by SIVmac Vpx, in contrast with results for human SAMHD1 (SAMHD1{sub HS}). Results regarding to SAMHD1{sub HS} and SAMHD1{sub GG} fusion proteins supported previous findings that the C-terminus of SAMHD1{sub HS} is essential for Vpx-induced degradation. Internal domain substitution, however, revealed that the HD domain also contributes to Vpx-mediated SAMHD1 degradation. Interestingly, the HD domain influenced Vpx-mediated SAMHD1 degradation without affecting Vpx-SAMHD1 interaction. Therefore, our findings revealed that factors in addition to Vpx-SAMHD1 binding influence the efficiency of Vpx-mediated SAMHD1 degradation. - Highlights: • SAMHD1{sub GG} from chicken could not be depleted by SIVmac Vpx. • The C-terminus of human SAMHD1{sub HS} is critical for its degradation by Vpx. • The HD domain is essential for Vpx-induced degradation of SAMHD1{sub HS}. • Altering the HD domain does not affect Vpx-SAMHD1 interaction.

Radiation processing of natural polymers for industrial and agricultural applications

International Nuclear Information System (INIS)

Hegazy, El-Sayed A.; AbdEl-Rehim, H.; Diaa, D.A.; El-Barbary, 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 efforts 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 (carboxymethylcellulose (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

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)

Trends in Polymer and Particle Characterization by Microfluidic Field-Flow Fractionation Methods: Science or Business?

Czech Academy of Sciences Publication Activity Database

Janča, Josef; Sobota, Jaroslav

2014-01-01

Roč. 19, 16 May (2014), s. 296-308 ISSN 1023-666X R&D Projects: GA MŠk(CZ) LO1212 Institutional support: RVO:68081731 Keywords : Asymmetrical flow FFF * Electrical FFF * Field-flow fractionation * Flow FFF * Microelectrical FFF * Microfluidic channels * Microthermal FFF * Miniaturization and resolution * Polymers and particles separation * Sedimentation FFF * Technical benefits of microchannels * Thermal FFF Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.264, year: 2014

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

Biosensor-based real-time monitoring of paracetamol photocatalytic degradation.

Science.gov (United States)

Calas-Blanchard, Carole; Istamboulié, Georges; Bontoux, Margot; Plantard, Gaël; Goetz, Vincent; Noguer, Thierry

2015-07-01

This paper presents for the first time the integration of a biosensor for the on-line, real-time monitoring of a photocatalytic degradation process. Paracetamol was used as a model molecule due to its wide use and occurrence in environmental waters. The biosensor was developed based on tyrosinase immobilization in a polyvinylalcohol photocrosslinkable polymer. It was inserted in a computer-controlled flow system installed besides a photocatalytic reactor including titanium dioxide (TiO2) as photocatalyst. It was shown that the biosensor was able to accurately monitor the paracetamol degradation with time. Compared with conventional HPLC analysis, the described device provides a real-time information on the reaction advancement, allowing a better control of the photodegradation process. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Anomalies in the coil-stretch transition of flexible polymers

Science.gov (United States)

Ghosal, Aishani; Cherayil, Binny J.

2018-03-01

The flow-induced coil-stretch transition of high molecular weight polymers has generally been held to be of first order. But evidence of significant slowing down in the rate at which the polymers relax to equilibrium in the vicinity of the transition suggests that the thermodynamic character of the transition may be less clear-cut. The above slowing down effect is actually characteristic of a second-order transition, and it points to the existence of a broad spectrum of conformational states in the transition region, analogous to the existence of fluctuations of all length scales at a critical point. In this paper, using a path integral approach based on a free-draining finitely extensible chain model, we calculate various polymer properties as a function of elongational flow as a way of exploring different statistical mechanical details of the coil-stretch transition. These properties include the molecular weight dependence of the flow-extension curve of the polymer, the distribution of its steady-state end-to-end distances, and the characteristic relaxation time τR of these distances. Among other findings, our calculations indicate that the coil-stretch transition is discontinuous in the N → ∞ limit, that the effective free energy of the chain is unimodal at all values of the flow, becoming broad and flat in the immediate vicinity of the transition, and that the ratio of τR to the Rouse relaxation time increases abruptly at the transition before eventually reaching a plateau value at large flow strengths. These aspects of the coil-stretch transition place it among a larger class of unconventional nominally first-order single chain transitions that include the adsorption transition of surface-tethered polymers and the escape transition of compressed polymers.

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....

Gamma Irradiation Induced Degradation of Orange Peels

Directory of Open Access Journals (Sweden)

Jaime Saucedo Luna

2012-08-01

Full Text Available In this study, gamma irradiation induced degradation of orange peels (OP was investigated. The lignocellulosic biomass degradation was carried out at doses of 0 (control, 600, 1800 and 3500 kGy using a Co-60 gamma radiation source. The samples were tested for total and reducing sugars. The concentrations of total sugars ranged from 0.530 g∙g⁻¹ in control sample to 0.382 g∙g⁻¹ of dry weight in the sample which received the highest radiation dose. The reducing sugars content varying from 0.018 to 0.184 g∙g⁻¹ of dry weight with the largest rise occurring in the sample irradiated at 3500 kGy. The concentrations of sucrose, glucose and fructose were determined. The changes generated in physico-chemical properties were determined by Fourier Transform Infrared Spectroscopy (FTIR and termogravimetric analysis (TG-DTG. The results show that OP was affected, but not significantly, which suggests that lignocellulose and sugars profiles were partially degraded after gamma irradiation.

Numerical study of viscoelastic polymer flow in simplified pore structures using stabilised finite element model

Energy Technology Data Exchange (ETDEWEB)

Qi, M.; Wegner, J.; Ganzer, L. [Technische Univ. Clausthal, Clausthal-Zellerfeld (Germany). ITE

2013-08-01

Polymer flooding, as an EOR method, has become one of the most important driving forces after water flooding. The conventional believe is that polymer flooding can only improve sweep efficiency, but it has no contribution to residual oil saturation reduction. However, experimental studies indicated that polymer solution can also improve displacement efficiency and decrease residual oil saturation. To get a better understanding of the mechanism to increase the microscopic sweep efficiency and the displacement efficiency, theoretical studies are required. In this paper, we studied the viscoelasticity effect of polymer by using a numerical simulator, which is based on Finite Element Analysis. Since it is showed experimentally that the first normal stress difference of viscoelastic polymer solution is higher than the second stress difference, the Oldroyd-B model was selected as the constitutive equation in the simulation. Numerical modelling of Oldroyd-B viscoelastic fluids is notoriously difficult. Standard Galerkin finite element methods are prone to numerical oscillations, and there is no convergence as the elasticity of fluid increases. Therefore, we use a stabilised finite element model. In order to verify our model, we first built up a model with the same geometry and fluid properties as presented in literature and compared the results. Then, with the tested model we simulated the effect of viscoelastic polymer fluid on dead pores in three simplified pore structures, which are contraction structure, expansion structure and expansion-contraction structure. Correspondingly, the streamlines and velocity contours of polymer solution, with different Reynolds numbers (Re) and Weissenberg numbers (We), flowing in these three structures are showed. The simulation results indicate that the viscoelasticity of polymer solution is the main contribution to increase the micro-scale sweep efficiency. With higher elasticity, the velocity of polymer solution is getting bigger at

A study on the life extension of polymer materials under radiation environment

International Nuclear Information System (INIS)

Park, K. J; Park, S. W.; Jung, K. S.; Cho, S. H.; Seo, H. S.

2001-12-01

The object of this project is to improve the stability and the economics by reducing the radiation-induced oxidation as a factor of degradation of polymer materials used under the radiation environment. In order to attain the objective of this study and to check the effect of diamond-like carbon(DLC) coating on the anti-oxidation reaction, polymer specimens such as ABS, Acryl, Polycarbonate, Polyethylene, Polypropylene, PVC coating DLC thin layer were exposed to high-level gamma radiation, and their irradiation effects were investigated. A plasma-enhanced chemical vapor deposition method was adopted in fabricating a DLC thin film on the polymer specimens, which were irradiated with the non-DLC film deposited specimens under the gamma radiation emitted from Co-60 source from 1x10 5 to 1x10 8 rads exposure. According to the characterization of irradiated specimens from the elapsed time of minimum 4 hours to a maximum of 105 days after the irradiation, the DLC deposition on the polymer surface was revealed to contribute to the improvement on the resistance of the radiation-induced oxidation in this study

Development of partially biodegradable foams from PP/HMSPP blends with natural and synthetic polymers

International Nuclear Information System (INIS)

Cardoso, Elizabeth Carvalho Leite

2014-01-01

Polymers are used in various application and in different industrial areas providing enormous quantities of wastes in environment. Among diverse components of residues in landfills are polymeric materials, including Polypropylene, which contribute with 20 to 30% of total volume of solid residues. As polymeric materials are immune to microbial degradation, they remain in soil and in landfills as a semi-permanent residue. Environmental concerning in litter reduction is being directed to renewable polymers development for manufacturing of polymeric foams. Foamed polymers are considered future materials, with a wide range of applications; high density structural foams are specially used in civil construction, in replacement of metal, woods and concrete with a final purpose of reducing materials costs. At present development, it was possible the incorporation of PP/HMSPP polymeric matrix blends with sugarcane bagasse, PHB and PLA, in structural foams production. Thermal degradation at 100, 120 and 160 deg C temperatures was not enough to induce biodegradability. Gamma irradiation degradation, at 50, 100, 200 and 500 kGy showed effective for biodegradability induction. Irradiated bagasse blends suffered surface erosion, in favor of water uptake and consequently, a higher biodegradation in bulk structure. (author)

Physical degradation of proteins in well-defined fluid flows studied within a four-roll apparatus.

Science.gov (United States)

Simon, S; Krause, H J; Weber, C; Peukert, W

2011-12-01

In most applications of biotechnology and downstream processing proteins are exposed to fluid stresses in various flow configurations which often lead to the formation of unwanted protein aggregates. In this paper we present physical degradation experiments for proteins under well-defined flow conditions in a four-roll apparatus. The flow field was characterized numerically by computational fluid dynamics (CFD) and experimentally by particle image velocimetry (PIV). The local shear strain rate as well as the local shear and elongation rate was used to characterize the hydrodynamic stress environment acting on the proteins. Lysozyme was used as a model protein and subjected to well-defined fluid stresses in high and low stress environment. By using in situ turbidity measurements during stressing the aggregate formation was monitored directly in the fluid flow. An increase in absorbance at 350 nm was attributed to a higher content of visible particles (>1 µm). In addition to lysozyme, the formation of aggregates was confirmed for two larger proteins (bovine serum albumin and alcohol dehydrogenase). Thus, the presented experimental setup is a helpful tool to monitor flow-induced protein aggregation with high reproducibility. For instance, screening experiments for formulation development of biopharmaceuticals for fill and finish operations can be performed in the lab-scale in a short time-period if the stress distributions in the application are transferred and applied in the four-roll mill. Copyright © 2011 Wiley Periodicals, Inc.

Negative charge induced degradation of PMOSFETs with BF2-implanted p+-poly gate

International Nuclear Information System (INIS)

Lu, C.Y.; Sung, J.M.

1989-01-01

A new degradation phenomenon on thin gate oxide PMOS-FETs with BF 2 implanted p + -poly gate has been demonstrated and investigated. The cause of this type of degradation is a combination of the boron penetration through the gate oxide and charge trap generation due to the presence of fluorine in the gate oxide and some other processing-induced effects. The negative charge-induced degradation other than enhanced boron diffusion has been studied in detail here. The impact of this process-sensitive p + -poly gate structure on deep submicron CMOS process integration has been discussed. (author)

Space environment effects on polymers in low earth orbit

International Nuclear Information System (INIS)

Grossman, E.; Gouzman, I.

2003-01-01

Polymers are widely used in space vehicles and systems as structural materials, thermal blankets, thermal control coatings, conformal coatings, adhesives, lubricants, etc. The low earth orbit (LEO) space environment includes hazards such as atomic oxygen, UV radiation, ionizing radiation (electrons, protons), high vacuum, plasma, micrometeoroids and debris, as well as severe temperature cycles. Exposure of polymers and composites to the space environment may result in different detrimental effects via modification of their chemical, electrical, thermal, optical and mechanical properties as well as surface erosion. The high vacuum induces material outgassing (e.g. low-molecular weight residues, plasticizers and additives) and consequent contamination of nearby surfaces. The present work reviews the LEO space environment constituents and their interactions with polymers. Examples of degradation of materials exposed in ground simulation facilities are presented. The issues discussed include the erosion mechanisms of polymers, formation of contaminants and their interaction with the space environment, and protection of materials from the harsh space environment

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.

Ions-induced nanostructuration: effect of specific ionic adsorption on hydrophobic polymer surfaces.

Science.gov (United States)

Siretanu, Igor; Chapel, Jean-Paul; Bastos-González, Delfi; Drummond, Carlos

2013-06-06

The effect of surface charges on the ionic distribution in close proximity to an interface has been extensively studied. On the contrary, the influence of ions (from dissolved salts) on deformable interfaces has been barely investigated. Ions can adsorb from aqueous solutions on hydrophobic surfaces, generating forces that can induce long-lasting deformation of glassy polymer films, a process called ion-induced polymer nanostructuration, IPN. We have found that this process is ion-specific; larger surface modifications are observed in the presence of water ions and hydrophobic and amphiphilic ions. Surface structuration is also observed in the presence of certain salts of lithium. We have used streaming potential and atomic force microscopy to study the effect of dissolved ions on the surface properties of polystyrene films, finding a good correlation between ionic adsorption and IPN. Our results also suggest that the presence of strongly hydrated lithium promotes the interaction of anions with polystyrene surfaces and more generally with hydrophobic polymer surfaces, triggering then the IPN process.

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)

Structure, deformation, and failure of flow-oriented semicrystalline polymers

NARCIS (Netherlands)

Schrauwen, B.A.G.; Breemen, van L.C.A.; Spoelstra, A.B.; Govaert, L.E.; Peters, G.W.M.; Meijer, H.E.H.

2004-01-01

This study deals with the influence of processing induced crystalline orientation on the macroscopic deformation and failure behavior of thin samples of polyethylene and polypropylene. Distribution and structure of flow-induced orientations were characterized by optical microscopy, X-ray diffraction

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...

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...

Peclet number analysis of cross-flow in porous gas diffusion layer of polymer electrolyte membrane fuel cell (PEMFC).

Science.gov (United States)

Suresh, P V; Jayanti, Sreenivas

2016-10-01

Adoption of hydrogen economy by means of using hydrogen fuel cells is one possible solution for energy crisis and climate change issues. Polymer electrolyte membrane (PEM) fuel cell, which is an important type of fuel cells, suffers from the problem of water management. Cross-flow is induced in some flow field designs to enhance the water removal. The presence of cross-flow in the serpentine and interdigitated flow fields makes them more effective in proper distribution of the reactants on the reaction layer and evacuation of water from the reaction layer than diffusion-based conventional parallel flow fields. However, too much of cross-flow leads to flow maldistribution in the channels, higher pressure drop, and membrane dehydration. In this study, an attempt has been made to quantify the amount of cross-flow required for effective distribution of reactants and removal of water in the gas diffusion layer. Unit cells containing two adjacent channels with gas diffusion layer (GDL) and catalyst layer at the bottom have been considered for the parallel, interdigitated, and serpentine flow patterns. Computational fluid dynamics-based simulations are carried out to study the reactant transport in under-the-rib area with cross-flow in the GDL. A new criterion based on the Peclet number is presented as a quantitative measure of cross-flow in the GDL. The study shows that a cross-flow Peclet number of the order of 2 is required for effective removal of water from the GDL. Estimates show that this much of cross-flow is not usually produced in the U-bends of Serpentine flow fields, making these areas prone to flooding.

A liquid crystal polymer membrane MEMS sensor for flow rate and flow direction sensing applications

International Nuclear Information System (INIS)

Kottapalli, A G P; Tan, C W; Olfatnia, M; Miao, J M; Barbastathis, G; Triantafyllou, M

2011-01-01

The paper reports the design, fabrication and experimental results of a liquid crystal polymer (LCP) membrane-based pressure sensor for flow rate and flow direction sensing applications. Elaborate experimental testing results demonstrating the sensors' performance as an airflow sensor have been illustrated and validated with theory. MEMS sensors using LCP as a membrane structural material show higher sensitivity and reliability over silicon counterparts. The developed device is highly robust for harsh environment applications such as atmospheric wind flow monitoring and underwater flow sensing. A simple, low-cost and repeatable fabrication scheme has been developed employing low temperatures. The main features of the sensor developed in this work are a LCP membrane with integrated thin film gold piezoresistors deposited on it. The sensor developed demonstrates a good sensitivity of 3.695 mV (ms −1 ) −1 , large operating range (0.1 to >10 ms −1 ) and good accuracy in measuring airflow with an average error of only 3.6% full-scale in comparison with theory. Various feasible applications of the developed sensor have been demonstrated with experimental results. The sensor was tested for two other applications—in clinical diagnosis for breath rate, breath velocity monitoring, and in underwater applications for object detection by sensing near-field spatial flow pressure

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.

Drag reduction by polymer addition in single and two-phase gas-liquid flows in pipelines

Energy Technology Data Exchange (ETDEWEB)

Bizotto, Vanessa Cristina; Paes, Diogo Melo; Franca, Fernando de Almeida [Universidade Estadual de Campinas, SP (Brazil). Centro de Estudos de Petroleo. LabPetro]. E-mails: vanessa@cepetro.unicamp.br; diogopaes10@hotmail.com; Sabadini, Edvaldo [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica]. E-mails: sabadini@iqm.unicamp.br; ffranca@fem.unicamp.br

2008-07-01

Turbulence mechanisms, as the eddies formation frequency and size, promote energy dissipation that appears as pressure drop in pipe flows. Adding minute amounts of polymers - ppm - of high molecular weight to the solution can lead to the reduction of the viscous dissipation. The formed macromolecules interact with the eddies, cause the eddies coherence breakdown, damp the energy transport and reduces the pressure drop. This phenomenon is known as the hydrodynamic drag reduction (DR, for short). Thus, for a given pipe flow rate there is decrease in pressure head, which is a desired operating strategy when transporting liquids. Studies on the hydrodynamic drag reduction in polymeric systems have been carried out in collaboration by the Chemistry Institute and the Petroleum Laboratory - LabPetro, UNICAMP. These studies have allowed microscopic approaches to the engineering scales, tackling the most usual processes - single phase flows, as well as gas-liquid two-phase flows in pipelines, which are quite common in the chemical and the petroleum industries. Tests conducted in the Chemistry Institute comprised over-the-bench experimentations made with a rotational double-gap type rheometer. These quick performed tests used small amount of polymers, and provided information on the additive concentration, the drag reduction and the solution mechanical stability along a turbulent shearing process. The results indicated that 17% is the limiting drag reduction achieved when a 2 ppm aqueous solution of polyacrylamide - PAM - was tested. These tests, besides giving preliminary estimations, are limited in terms of engineering application due to the low shearing rates applied by the viscometer. The tests performed at LabPetro comprised pressure drop measurements in actual pipe flows, both water single and air-water two-phase flows, using the previous knowledge acquired with the viscometer tests. In the former case, the Prandtl-von Karman map has been drawn to show the %DR in terms

Relaxation model of radiation-induced conductivity in polymers

Science.gov (United States)

Zhutayeva, Yu. R.; Khatipov, S. A.

1999-05-01

The paper suggests a relaxation model of radiation-induced conductivity (RIC) in polymers. According to the model, the transfer of charges generated in the polymer volume by ionizing radiation takes place with the participation of molecular relaxation processes. The mechanism of electron transport consists in the transfer of the charge directly between traps when they draw close to one another due to the rotation of macromolecule segments. The numerical solutions of the corresponding kinetic equations for different distribution functions Q( τ) of the times of molecular relaxation and for different functions of the probability P( τ, τ') of charge transfer in the `overlapping' regions of the diffusion spheres of the segments are analyzed. The relaxation model provides an explanation of the non-Arrhenius behavior of the RIC temperature dependence, the power dependence of RIC on the dose rate with a power index in the interval 0.5-1.0, the appearance of maxima in the curves of the RIC temporal dependence and their irreversible character in the region of large dose rates (more than 1 Gy/s). The model can be used for interpreting polymer RIC in conditions of kinetic mobility of macromolecules.

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

Hydrophobic coating of microfluidic chips structured by SU-8 polymer for segmented flow operation

International Nuclear Information System (INIS)

Schumacher, J T; Grodrian, A; Metze, J; Kremin, C; Hoffmann, M

2008-01-01

We present a hydrophobization procedure for SU-8-based microfluidic chips on borofloat substrates. Different layouts of gold electrodes passivated by the polymer have been investigated. The chips are used for segmented flow in a two-fluid mode that requires a distinct hydrophobicity of the channel walls which is generated by the use of specific silane. In this paper we describe the production and silanization of the chips and demonstrate segmented flow operation

Parallelized system for biopolymer degradation studies through automated microresonator measurement in liquid flow

DEFF Research Database (Denmark)

Casci Ceccacci, Andrea; Morelli, Lidia; Bosco, Filippo

2015-01-01

setup unit, the system allows high-throughput measurements of resonance frequency over microresonator arrays under controlled flow conditions. We here demonstrate the acquisition of statistical data on biopolymer films degradation under enzymatic reaction over a large sample of micromechanical......In this work we present a novel automated system which allows the study of enzymatic degradation of biopolymer films coated on micromechanical resonators. The system combines an optical readout based on Blu-Ray technology with a software-controlled scanning mechanism. Integrated with a microfluidic...

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.

Degradation of polyethylene induced by plasma in oxidizing atmospheres; Degradacion de polietileno inducido por plasma en atmosferas oxidantes

Energy Technology Data Exchange (ETDEWEB)

Colin, E.; Olayo, M.G.; Cruz, G.J. [Facultad de Quimica, UAEM, Av. Tollocan y Colon, 50000 Toluca (Mexico)

2002-07-01

The garbage of polyethylene is not easily degradable in normal environmental conditions . The indiscriminate use of this polymer and the enormous quantity of garbage which is generated carries a damage to the environment due to its long life as waste. The objective of this work is to study the conditions in which can be carried out the degradation of polyethylene. A form of accelerating the degradation is exposing it to plasma with reactive atmospheres. In this work a study of surface modification of polyethylene by plasmas with discharges of direct current of oxygen and nitrogen is presented. (Author)

Stabilization of two-phase octanol/water flows inside poly(dimethylsiloxane) microchannels using polymer coatings

NARCIS (Netherlands)

van der Linden, H. J.; Jellema, L. C.; Holwerda, M.; Verpoorte, E.

In this paper we present our first results on the realization of stable water/octanol, two-phase flows inside poly(dimethylsiloxane) (PDMS) microchannels. Native PDMS microchannels were coated with high molecular weight polymers to change the surface properties of the microchannels and thus

Microwave-assisted preparation of carbon nanofiber-functionalized graphite felts as electrodes for polymer-based redox-flow batteries

Science.gov (United States)

Schwenke, A. M.; Janoschka, T.; Stolze, C.; Martin, N.; Hoeppener, S.; Schubert, U. S.

2016-12-01

A simple and fast microwave-assisted protocol to functionalize commercially available graphite felts (GFs) with carbon nanofibers (CNFs) for the application as electrode materials in redox-flow batteries (RFB) is demonstrated. As catalyst for the CNF synthesis nickel acetate is applied and ethanol serves as the carbon source. By the in-situ growth of CNFs, the active surface of the electrodes is increased by a factor of 50, which is determined by the electrochemical double layer capacities of the obtained materials. Furthermore, the morphology of the CNF-coating is investigated by scanning electron microscopy. Subsequently, the functionalized electrodes are applied in a polymer-based redox-flow battery (pRFB) using a TEMPO- and a viologen polymer as active materials. Due to the increased surface area as compared to an untreated graphite felt electrode, the current rating is improved by about 45% at 80 mA cm-2 and, furthermore, a decrease in overpotentials is observed. Thus, using this microwave-assisted synthesis approach, CNF-functionalized composite electrodes are prepared with a very simple protocol suitable for real life applications and an improvement of the overall performance of the polymer-based redox-flow battery is demonstrated.

Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

Energy Technology Data Exchange (ETDEWEB)

Khan, I. John [The State Univ. of New Jersey, Piscataway, NJ (United States); Murthy, N. Sanjeeva [The State Univ. of New Jersey, Piscataway, NJ (United States); Kohn, Joachim [The State Univ. of New Jersey, Piscataway, NJ (United States)

2015-10-30

Voclosporin is a highly potent, new cyclosporine -- a derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. It was selected as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE) and desaminotyrosyl-tyrosine (DT), and the hydrophilic component is poly(ethylene glycol) (PEG). Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide) (PLGA), which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin.

Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

Directory of Open Access Journals (Sweden)

Joachim Kohn

2012-10-01

Full Text Available Voclosporin is a highly potent, new cyclosporine-A derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. We therefore selected it as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE and desaminotyrosyl-tyrosine (DT, and the hydrophilic component is poly(ethylene glycol (PEG. Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide (PLGA, which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin.

Reaction mechanism for radiation-induced degradation of poly(methyl methacrylate) as studied by ESR and ESE

International Nuclear Information System (INIS)

Yoshida, H.; Ichikawa, T.

1991-01-01

Reaction mechanism for the radiation-induced degradation of poly(methyl methacrylate) has been studied based on the ESR and electron spin echo observations of the free radicals in the polymer irradiated with γ-rays. It is indicated that the side-chain radical, -CH 2 -CCH 3 (COOC-radicalH 2 )-, is the precursor for the main-chain scission. This radical transforms into the propagating-type radical, a fingerprint of the main-chain scission, without loss of the total radical concentration. UV illumination converts the side-chain radical into the acyl-type radical, -CH 2 -CCH 3 (-C-radical=O)-, which thermally transforms into the propagating-type radical. The radical of the type, -CH 2 -C-radicalCH 3 -CH 2 -, is suggested as a common, immediate precursor for the main-chain scission with and without the UV illumination, though it has not been detected because of its short life-time. (author) 7 refs.; 2 figs

Parametric analysis of protective grid flow induced vibration

Energy Technology Data Exchange (ETDEWEB)

Ryu, Jooyoung; Eom, Kyongbo; Jeon, Sangyoun; Suh, Jungmin [KEPCO NF Co., Daejeon (Korea, Republic of)

2012-10-15

Protective grid (P-grid) flow-induced vibration in a nuclear power reactor is one of the critical factors for the mechanical integrity of a nuclear fuel. The P-grid is located at the lower most position above the bottom nozzle of the nuclear fuel as shown in Fig. 1, and it is required for not only filtering debris, but also supporting fuel rods. On the other hand, P-grid working conditions installed in a nuclear fuel in a reactor are severe in terms of flow speed, temperature and pressure. Considering such a severe condition of P-grid's functional performance in working environment, excessive vibration could be developed. Furthermore, if the P-grid is exposed to high levels of excessive vibration over a long period of time, fatigue failure could be unavoidable. Therefore, it is important to reduce excessive vibration while maintaining P-grid's own functional performance. KEPCO Nuclear Fuel has developed a test facility - Investigation Flow-induced Vibration (INFINIT) - to study flow-induced vibration caused by flowing coolant at various flow rates. To investigate specific relationships between configuration of P-grid and flow-induced vibration characteristics, several types of the P-grids were tested in INFINIT facility. And, based on the test results through parametric studies, the flow-induced vibration characteristics could be analyzed, and critical design parameters were found.

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).

Pressure drop and flow distribution characteristics of single and parallel serpentine flow fields for polymer electrolyte membrane fuel cells

International Nuclear Information System (INIS)

Baek, Seung Man; Kim, Charn Jung; Jeon, Dong Hyup; Nam, Jin Hyun

2012-01-01

This study numerically investigates pressure drop and flow distribution characteristics of serpentine flow fields (SFFs) that are designed for polymer electrolyte membrane fuel cells, which consider the Poiseuille flow with secondary pressure drop in the gas channel (GC) and the Darcy flow in the porous gas diffusion layer (GDL). The numerical results for a conventional SFF agreed well with those obtained via computational fluid dynamics simulations, thus proving the validity of the present flow network model. This model is employed to characterize various single and parallel SFFs, including multi-pass serpentine flow fields (MPSFFs). Findings reveal that under rib convection (convective flow through GDL under an interconnector rib) is an important transport process for conventional SFFs, with its intensity being significantly enhanced as GDL permeability increases. The results also indicate that under rib convection can be significantly improved by employing MPSFFs as the reactant flow field, because of the closely interlaced structure of GC regions that have different path lengths from the inlet. However, reactant flow rate through GCs proportionally decreases as under rib convection intensity increases, suggesting that proper optimization is required between the flow velocity in GCs and the under rib convection intensity in GDLs

Polymer- and salt-induced toroids of hexagonal DNA.

OpenAIRE

Ubbink, J; Odijk, T

1995-01-01

A model is proposed for polymer- and salt-induced toroidal condensates of DNA, based on a recent theory of the undulation enhancement of the electrostatic interaction in the bulk hexagonal phase of semiflexible polyions. In a continuum approximation, the thermodynamic potential of a monomolecular toroid may be split up in bulk, surface, and curvature contributions. With the help of an approximate analytical minimization procedure, the optimal torus dimensions are calculated as a function of t...

Microscopic theory of light-induced deformation in amorphous side-chain azobenzene polymers.

Science.gov (United States)

Toshchevikov, V; Saphiannikova, M; Heinrich, G

2009-04-16

We propose a microscopic theory of light-induced deformation of side-chain azobenzene polymers taking into account the internal structure of polymer chains. Our theory is based on the fact that interaction of chromophores with the polarized light leads to the orientation anisotropy of azobenzene macromolecules which is accompanied by the appearance of mechanical stress. It is the first microscopic theory which provides the value of the light-induced stress larger than the yield stress. This result explains a possibility for the inscription of surface relief gratings in glassy side-chain azobenzene polymers. For some chemical architectures, elongation of a sample demonstrates a nonmonotonic behavior with the light intensity and can change its sign (a stretched sample starts to be uniaxially compressed), in agreement with experiments. Using a viscoplastic approach, we show that the irreversible strain of a sample, which remains after the light is switched off, decreases with increasing temperature and can disappear at certain temperature below the glass transition temperature. This theoretical prediction is also confirmed by recent experiments.

Study of equivalent retention among different polymer-solvent systems in thermal field-flow fractionation

International Nuclear Information System (INIS)

Kim, Won Suk; Park, Young Hun; Lee, Dai Woon; Moon, Myeong Hee; Yu, Euy Kyung

1998-01-01

An equivalent retention has been experimentally observed in thermal field-flow fractionation (ThFF) for different polymer-solvent systems. It is shown that iso-retention between two sets of polymer-solvent systems can be obtained by adjusting the temperature difference (ΔT) according to the difference in the ration of ordinary diffusion coefficient to thermal diffusion coefficient. This method uses a compensation of field strength (ΔT) in ThFFF at a fixed condition of cold wall temperature. It is applied for the calculation of molecular weight of polymers based on a calibration run of different standards obtained at an adjusted ΔT. The polymer standards used in this study are polystyrene (PS), polymethylmethacrylate (PMMA), and polytetrahydrofuran (PTHF). Three carrier solvents, tetrahydrofuran (THF), methylethylketone (MEK) and ethylacetate (ETAc) were employed. Though the accuracy in the calculation of molecular weight is dependent on the difference in the slope of log λ vs. log M which is related to Mark-Houwink constant a, it shows reasonable agreement within about 6% of relative error in molecular weight calculation for the polymer-solvent systems having similar a value

Constitutive Curve and Velocity Profile in Entangled Polymers during Start-Up of Steady Shear Flow

KAUST Repository

Hayes, Keesha A.; Buckley, Mark R.; Qi, Haibo; Cohen, Itai; Archer, Lynden A.

2010-01-01

-4]. Surprisingly, we find that even polymer systems which exhibit transient, nonmonotonic shear stress-shear rate relationships in bulk rheology experiments manifest time-dependent velocity profiles that are decidedly linear and show no evidence of unstable flow

Nonequilibrium molecular dynamics study of ring polymer melts under shear and elongation flows: A comparison with their linear analogs

Energy Technology Data Exchange (ETDEWEB)

Yoon, Jeongha; Kim, Jinseong; Baig, Chunggi, E-mail: cbaig@unist.ac.kr [Department of Chemical Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798 (Korea, Republic of)

2016-07-15

We present detailed results for the structural and rheological properties of unknotted and unconcatenated ring polyethylene (PE) melts under shear and elongation flows via direct atomistic nonequilibrium molecular dynamics simulations. Short (C{sub 78}H{sub 156}) and long (C{sub 400}H{sub 800}) ring PE melts were subjected to planar Couette flow (PCF) and planar elongational flow (PEF) across a wide range of strain rates from linear to highly nonlinear flow regimes. The results are analyzed in detail through a direct comparison with those of the corresponding linear polymers. We found that, in comparison to their linear analogs, ring melts possess rather compact chain structures at or near the equilibrium state and exhibit a considerably lesser degree of structural deformation with respect to the applied flow strength under both PCF and PEF. The large structural resistance of ring polymers against an external flow field is attributed to the intrinsic closed-loop configuration of the ring and the topological constraint of nonconcatenation between ring chains in the melt. As a result, there appears to be a substantial discrepancy between ring and linear systems in terms of their structural and rheological properties such as chain orientation, the distribution of chain dimensions, viscosity, flow birefringence, hydrostatic pressure, the pair correlation function, and potential interaction energies. The findings and conclusions drawn in this work would be a useful guide in future exploration of the characteristic dynamical and relaxation mechanisms of ring polymers in bulk or confined systems under flowing conditions.

Microchip Flow Cytometer with Integrated Polymer Optical Elements for Measurement of Scattered Light

DEFF Research Database (Denmark)

Wang, Zhenyu; El-Ali, Jamil; Perch-Nielsen, Ivan Ryberg

2004-01-01

channels to form a complete microchip flow cytometer. All the optical elements, the microfluidic system, and the fiber-to-waveguide couplers were defined in one layer of polymer (SU-8, negative photoresist) by standard photolithography. With only one single mask procedure, all the fabrication and packaging...... processes can be finished in one day. Polystyrene beads were measured in the microchip flow cytometer, and three signals (forward scattering, large angle scattering and extinction) were measured simultaneously for each bead. The average intensities of the forward Scattered light and the incident light...

Development and evaluation of a micro-macro algorithm for the simulation of polymer flow

International Nuclear Information System (INIS)

Feigl, Kathleen; Tanner, Franz X.

2006-01-01

A micro-macro algorithm for the calculation of polymer flow is developed and numerically evaluated. The system being solved consists of the momentum and mass conservation equations from continuum mechanics coupled with a microscopic-based rheological model for polymer stress. Standard finite element techniques are used to solve the conservation equations for velocity and pressure, while stochastic simulation techniques are used to compute polymer stress from the simulated polymer dynamics in the rheological model. The rheological model considered combines aspects of reptation, network and continuum models. Two types of spatial approximation are considered for the configuration fields defining the dynamics in the model: piecewise constant and piecewise linear. The micro-macro algorithm is evaluated by simulating the abrupt planar die entry flow of a polyisobutylene solution described in the literature. The computed velocity and stress fields are found to be essentially independent of mesh size and ensemble size, while there is some dependence of the results on the order of spatial approximation to the configuration fields close to the die entry. Comparison with experimental data shows that the piecewise linear approximation leads to better predictions of the centerline first normal stress difference. Finally, the computational time associated with the piecewise constant spatial approximation is found to be about 2.5 times lower than that associated with the piecewise linear approximation. This is the result of the more efficient time integration scheme that is possible with the former type of approximation due to the pointwise incompressibility guaranteed by the choice of velocity-pressure finite element

Birnessite-induced mechanochemical degradation of 2,4-dichlorophenol.

Science.gov (United States)

Nasser, A; Mingelgrin, U

2014-07-01

DCP (2,4-dichlorophenol) is the key-intermediate in the synthesis of some widely used pesticides and is an EPA priority pollutant. The mechanochemical breakdown of DCP loaded on birnessite (δ-MnO2), montmorillonite saturated with Na(+) or Cu(2+) and hematite was investigated. Mechanical force was applied by grinding of mixtures of DCP and the minerals, using mortar and pestle. Grinding of DCP for 5 min with the montmorillonites or with hematite resulted in negligible degradation during grinding, while grinding with birnessite induced the immediate degradation of 90% of the loaded DCP. Incubation for 24h after grinding did result in up to 30% degradation of the DCP loaded on the other minerals tested. HPLC and LC-MS analysis revealed that the transformation of DCP yielded oligomerization products as well as partial dechlorination. DCP degradation on birnessite was accompanied with a substantial increase in the extractability of manganese from the mineral into an acidic aqueous solution, indicating that Mn(IV) in the mineral transformed into Mn(II) and that birnessite served as an electron acceptor in the transformation. The oligomerization and partial dechlorination brought about by grinding, suggest a reduction in bioavailability and toxicity. Copyright © 2013 Elsevier Ltd. All rights reserved.

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