A general strategy toward the rational synthesis of metal tungstate nanostructures using plasma electrolytic oxidation method

NASA Astrophysics Data System (ADS)

Jiang, Yanan; Liu, Baodan; Zhai, Zhaofeng; Liu, Xiaoyuan; Yang, Bing; Liu, Lusheng; Jiang, Xin

2015-11-01

A new method based on conventional plasma electrolytic oxidation (PEO) technology has been developed for the rational synthesis of metal tungstate nanostructures. Using this method, ZnWO4 and NiWO4 nanostructures with controllable morphologies (nanorods, nanosheets and microsheets) and superior crystallinity have been synthesized. It has been found that the morphology diversity of ZnWO4 nanostructures can be selectively tailored through tuning the electrolyte concentration and annealing temperatures, showing obvious advantages in comparison to traditional hydrothermal and sol-gel methods. Precise microscopy analyses on the cross section of the PEO coating and ZnWO4 nanostructures confirmed that the precursors initially precipitated in the PEO coating and its surface during plasma discharge process are responsible for the nucleation and subsequent growth of metal tungstate nanostructures by thermal annealing. The method developed in this work represents a general strategy toward the rational synthesis of metal oxide nanostructures and the formation mechanism of metal tungstate nanostructures fabricated by the PEO method is finally discussed.

Rapid polyether cleavage via extracellular one-electron oxidation by a brown-rot basidiomycete.

PubMed

Kerem, Z; Bao, W; Hammel, K E

1998-09-01

Fungi that cause brown rot of wood are essential biomass recyclers and also the principal agents of decay in wooden structures, but the extracellular mechanisms by which they degrade lignocellulose remain unknown. To test the hypothesis that brown-rot fungi use extracellular free radical oxidants as biodegradative tools, Gloeophyllum trabeum was examined for its ability to depolymerize an environmentally recalcitrant polyether, poly(ethylene oxide) (PEO), that cannot penetrate cell membranes. Analyses of degraded PEOs by gel permeation chromatography showed that the fungus cleaved PEO rapidly by an endo route. 13C NMR analyses of unlabeled and perdeuterated PEOs recovered from G. trabeum cultures showed that a major route for depolymerization was oxidative C---C bond cleavage, a reaction diagnostic for hydrogen abstraction from a PEO methylene group by a radical oxidant. Fenton reagent (Fe(II)/H2O2) oxidized PEO by the same route in vitro and therefore might account for PEO biodegradation if it is produced by the fungus, but the data do not rule out involvement of less reactive radicals. The reactivity and extrahyphal location of this PEO-degrading system suggest that its natural function is to participate in the brown rot of wood and that it may enable brown-rot fungi to degrade recalcitrant organopollutants.

Drop-on-demand drop formation of polyethylene oxide solutions

NASA Astrophysics Data System (ADS)

Yan, Xuejia; Carr, Wallace W.; Dong, Hongming

2011-10-01

The dynamics of drop-on-demand (DOD) drop formation for solutions containing polyethylene oxide (PEO) have been studied experimentally. Using a piezoelectrical actuated inkjet printhead with the nozzle orifice diameter of 53 μm, experiments were conducted for a series of PEO aqueous solutions with molecular weights ranging from 14 to 1000 kg/mol, polydispersity from 1.02 to 2.5, and concentrations from 0.005 to 10 wt. %. The addition of a small amount of PEO can have a significant effect on the DOD drop formation process, increasing breakup time, decreasing primary drop speed, and decreasing the number of satellite drops in some cases. The effects depend on both molecular weight and concentration. At lower molecular weights (14 and 35 kg/mol), the effect of PEO over the dilute solution regime is insignificant even at concentrations large enough that the solution does not fall in the dilute regime. As PEO molecular weight increased, the effects became significant. For monodispersed PEO solutions, breakup time and primary drop speed closely correlated with effective relaxation time but not for polydispersed PEO. Effective relaxation time depended greatly on molecular weight distribution. Viscosity-average molecular weight, used in calculating effective relaxation time for polydispersed PEO solutions, did not adequately account for high molecular fractions in the molecular weight distribution of the polydispersed PEOs. A mixture rule was developed to calculate the effective relaxation times for aqueous solutions containing mixtures of monodispersed PEO, and breakup times and primary drop speeds correlated well with effective relaxation times. For our experiments, DOD drop formation was limited to Deborah number ≲ 23.

Surface Plasmon Resonance Study of the Binding of PEO-PPO-PEO Triblock Copolymer and PEO Homopolymer to Supported Lipid Bilayers.

PubMed

Kim, Mihee; Vala, Milan; Ertsgaard, Christopher T; Oh, Sang-Hyun; Lodge, Timothy P; Bates, Frank S; Hackel, Benjamin J

2018-06-12

Poloxamer 188 (P188), a poly(ethylene oxide)- b-poly(propylene oxide)- b-poly(ethylene oxide) triblock copolymer, protects cell membranes against various external stresses, whereas poly(ethylene oxide) (PEO; 8600 g/mol) homopolymer lacks protection efficacy. As part of a comprehensive effort to elucidate the protection mechanism, we used surface plasmon resonance (SPR) to obtain direct evidence of binding of the polymers onto supported lipid bilayers. Binding kinetics and coverage of P188 and PEO were examined and compared. Most notably, PEO exhibited membrane association comparable to that of P188, evidenced by comparable association rate constants and coverage. This result highlights the need for additional mechanistic understanding beyond simple membrane association to explain the differential efficacy of P188 in therapeutic applications.

Development of porous lamellar poly(L-lactic acid) scaffolds by conventional injection molding process.

PubMed

Ghosh, Satyabrata; Viana, Júlio C; Reis, Rui L; Mano, João F

2008-07-01

A novel fabrication technique is proposed for the preparation of unidirectionally oriented, porous scaffolds by selective polymer leaching from lamellar structures created by conventional injection molding. The proof of the concept is implemented using a 50/50 wt.% poly(L-lactic acid)/poly(ethylene oxide) (PLLA/PEO) blend. With this composition, the PLLA and PEO blend is biphasic, containing a homogeneous PLLA/PEO phase and a PEO-rich phase. The two phases were structured using injection molding into well-defined alternating layers of homogeneous PLLA/PEO phase and PEO-rich phase. Leaching of water-soluble PEO from the PEO-rich phase produces macropores, and leaching of phase-separated PEO from the initially homogeneous PLLA/PEO phase produces micropores in the lamellae. Thus, scaffolds with a macroporous lamellar architecture with microporous walls can be produced. The lamellae are continuous along the flow direction, and a continuous lamellar thickness of less than 1 microm could be achieved. Porosities of 57-74% and pore sizes of around 50-100 microm can be obtained using this process. The tensile elastic moduli of the porous constructs were between 580 and 800 MPa. We propose that this organic-solvent-free method of preparing lamellar scaffolds with good mechanical properties, and the reproducibility associated with the injection molding technique, holds promise for a wide range of guided tissue engineering applications.

Crystallization Behavior of Poly(ethylene oxide) in Vertically Aligned Carbon Nanotube Array.

PubMed

Sheng, Jiadong; Zhou, Shenglin; Yang, Zhaohui; Zhang, Xiaohua

2018-03-27

We investigate the effect of the presence of vertically aligned multiwalled carbon nanotubes (CNTs) on the orientation of poly(ethylene oxide) (PEO) lamellae and PEO crystallinity. The high alignment of carbon nanotubes acting as templates probably governs the orientation of PEO lamellae. This templating effect might result in the lamella planes of PEO crystals oriented along a direction parallel to the long axis of the nanotubes. The presence of aligned carbon nanotubes also gives rise to the decreases in PEO crystallinity, crystallization temperature, and melting temperature due to the perturbation of carbon nanotubes to the crystallization of PEO. These effects have significant implications for controlling the orientation of PEO lamellae and decreasing the crystallinity of PEO and thickness of PEO lamellae, which have significant impacts on ion transport in PEO/CNT composite and the capacitive performance of PEO/CNT composite. Both the decreased PEO crystallinity and the orientation of PEO lamellae along the long axes of vertically aligned CNTs give rise to the decrease in the charge transfer resistance, which is associated with the improvements in the ion transport and capacitive performance of PEO/CNT composite.

Enhancing the protein resistance of silicone via surface-restructuring PEO-silane amphiphiles with variable PEO length

PubMed Central

Rufin, M. A.; Gruetzner, J. A.; Hurley, M. J.; Hawkins, M. L.; Raymond, E. S.; Raymond, J. E.

2015-01-01

Silicones with superior protein resistance were produced by bulk-modification with poly(ethylene oxide) (PEO)-silane amphiphiles that demonstrated a higher capacity to restructure to the surface-water interface versus conventional non-amphiphilic PEO-silanes. The PEO-silane amphiphiles were prepared with a single siloxane tether length but variable PEO segment lengths: α-(EtO)3Si(CH2)2-oligodimethylsiloxane13-block-poly(ethylene oxide)n-OCH3 (n = 3, 8, and 16). Conventional PEO-silane analogues (n = 3, 8 and 16) as well as a siloxane tether-silane (i.e. no PEO segment) were prepared as controls. When surface-grafted onto silicon wafer, PEO-silane amphiphiles produced surfaces that were more hydrophobic and thus more adherent towards fibrinogen versus the corresponding PEO-silane. However, when blended into a silicone, PEO-silane amphiphiles exhibited rapid restructuring to the surface-water interface and excellent protein resistance whereas the PEO-silanes did not. Silicones modified with PEO-silane amphiphiles of PEO segment lengths n = 8 and 16 achieved the highest protein resistance. PMID:26339488

Formation of Ca/P ceramic coatings by Plasma Electrolytic Oxidation (PEO) on Ti6Al4V ELI alloy

NASA Astrophysics Data System (ADS)

Rodriguez-Jaimes, Y.; Naranjo, D. I.; Blanco, S.; García-Vergara, S. J.

2017-12-01

The formation of PEO ceramic coatings on Ti6Al4V ELI alloy was investigated using a phosphate/calcium containing electrolyte at 300 and 400V at 310K for different times. The Plasma Electrolytic Oxidation (PEO) coated specimens were then heat treated at 873 and 1073K for 2 hours. Scanning electron microscopy, Energy Dispersive X-Ray Spectroscopy (EDS) and X-ray diffraction analysis were used to study the composition and the morphology of the ceramic coatings. The corrosion behaviour of the coatings was studied by Electrochemical Impedance Spectroscopy (EIS) in Simulated Body Fluid (SBF). The PEO-treated specimens primarily revealed a porous structure with thickness between 4 and 12μm, according to the voltage and process time used. The coatings are mainly composed of hydroxyapatite; however, as the voltage and anodizing time increase, the Ca/P ratio decreases. Generally, the corrosion resistance of the alloy was improved by the PEO-treated coatings, although the specimens treated at 1073K showed the presence of cracks that reduced the protective effect of the coatings.

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-04-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-05-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

Influence of Plasticizers on the Stability and Release of a Prodrug of Δ9-Tetrahydrocannabinol Incorporated in Poly (Ethylene Oxide) Matrices

PubMed Central

Thumma, Sridhar; ElSohly, Mahmoud A.; Zhang, Shuang-Qing; Gul, Waseem; Repka, Michael A.

2008-01-01

The objective of the present research was to stabilize a heat-labile novel prodrug of Δ9-tetrahydrocannabinol (THC), THC-hemiglutarate (THC-HG), in polyethylene oxide (PEO) [PolyOx® WSR N-80 (PEO N-80), MW 200,000 Daltons] polymeric matrix systems produced by hot-melt fabrication for systemic delivery of THC through the oral transmucosal route. For this purpose, the effects of processing conditions (processing temperature and heating duration), plasticizer type and concentration and storage conditions on the stability of the prodrug were investigated. The selected plasticizers studied included vitamin E succinate (VES), acetyltributyl citrate (ATBC), triethyl citrate (TEC), triacetin and polyethylene glycol 8000 (PEG 8000). Furthermore, the influence of plasticizer concentration on drug release was also studied. The stability of THC-HG in PEO matrices was influenced by all of the aforementioned variables. Films processed at 110 °C for 7 min were found to be favorable for hot-melt processing with a post- processing drug content of 95%, while significant degradation of THC-HG (~42%) was observed in those processed at 200 °C for 15 min. The degradation of the prodrug during hot-melt fabrication and also upon storage was considerably reduced in the presence of the plasticizers investigated, VES being the most effective. Modulation of the microenvironmental pH to an acidic range via incorporation of citric acid in PEO-plasticizer matrices significantly improved the stability of the prodrug, with almost 90% of the theoretical drug remaining as opposed to only 15% remaining in PEO-only matrices when stored at 40 °C for up to 3 months. The release of drug from PEO matrices was influenced both by the plasticizer type and concentration. A faster release resulted from water-soluble plasticizers, PEG 8000 and triacetin, and with increasing concentration. However, a slower release was observed with an increase in concentration of water-insoluble plasticizers, VES and ATBC. PMID:18602993

Dynamics of poly(ethylene oxide) in a blend with poly(methyl methacrylate): a quasielastic neutron scattering and molecular dynamics simulations study.

PubMed

Genix, A-C; Arbe, A; Alvarez, F; Colmenero, J; Willner, L; Richter, D

2005-09-01

In this paper, we have addressed the question of the dynamic miscibility in a blend characterized by very different glass-transition temperatures, Tg, for the components: poly(ethylene oxide) and poly(methyl methacrylate) (PEO/PMMA). The combination of quasielastic neutron scattering with isotopic labeling and fully atomistic molecular dynamics simulations has allowed us to selectively investigate the dynamics of the two components in the picosecond-10 nanoseconds scale at temperatures close and above the Tg of the blend. The main focus was on the PEO component, i.e., that of the lowest Tg, but first we have characterized the dynamics of the other component in the blend and of the pure PEO homopolymer as reference. In the region investigated, the dynamics of PMMA in the blend is strongly affected by the alpha-methyl rotation; an additional process detected in the experimental window 65 K above the blend-Tg can be identified as the merged alphabeta process of this component that shows strong deviations from Gaussian behavior. On the other hand, pure PEO displays entropy driven dynamics up to very large momentum transfers. Such kind of motion seems to freeze when the PEO chains are in the blend. There, we have directly observed a very heterogeneous and moreover confined dynamics for the PEO component. The presence of the hardly moving PMMA matrix leads to the creation of little pockets of mobility where PEO can move. The characteristic size of such confined islands of mobility might be estimated to be of approximately 1 nm. These findings are corroborated by the simulation study, which has been an essential support and guide in our data analysis procedure.

Characterization of compressibility and compactibility of poly(ethylene oxide) polymers for modified release application by compaction simulator.

PubMed

Yang, L; Venkatesh, G; Fassihi, R

1996-10-01

Poly(ethylene oxide) polymers (PEO) appear to have great potential for controlled release applications. These polymers are hydrophilic with good water solubility, low toxicity, and high swelling capacity. As part of formulation optimization for a large-scale solid dosage form production, physicomechanical characterization of PEO was undertaken using a compaction simulator. Heckel plots for all PEOs were constructed, and yield pressures (Py) at different punch velocities were calculated from the linear portion of the plots. Low Py values, increase of Py with increasing punch speed, upward curvature of the plot, and strain rate sensitivity values indicate that the densification process and consolidation mechanism for PEOs of various molecular weights (0.2 x 10(6) to 7 x 10(6)) are identical and follow plastic deformation. PEOs have a high degree of crystallinity (57-85%) and show significant axial recovery (15-25%) upon decompression and ejection. The low Py values (58-78 MPa) and low mean compaction pressures demonstrate that volume reduction (compressibility) under pressure is excellent. However, due to viscoelastic behavior and large axial expansion, tablets of relatively low tensile strength are produced. These observations suggest the need to blend PEO with highly compactible excipients in order to produce tables on a high-speed production press.

Hydrogen Bonding-Mediated Microphase Separation during the Formation of Mesoporous Novolac-Type Phenolic Resin Templated by the Triblock Copolymer, PEO-b-PPO-b-PEO

PubMed Central

Chu, Wei-Cheng; Chiang, Shih-Fan; Li, Jheng-Guang; Kuo, Shiao-Wei

2013-01-01

After blending the triblock copolymer, poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-b-PPO-b-PEO) with novolac-type phenolic resin, Fourier transform infrared spectroscopy revealed that the ether groups of the PEO block were stronger hydrogen bond acceptors for the OH groups of phenolic resin than were the ether groups of the PPO block. Thermal curing with hexamethylenetetramine as the curing agent resulted in the triblock copolymer being incorporated into the phenolic resin, forming a nanostructure through a mechanism involving reaction-induced microphase separation. Mild pyrolysis conditions led to the removal of the PEO-b-PPO-b-PEO triblock copolymer and formation of mesoporous phenolic resin. This approach provided a variety of composition-dependent nanostructures, including disordered wormlike, body-centered-cubic spherical and disorder micelles. The regular mesoporous novolac-type phenolic resin was formed only at a phenolic content of 40–60 wt %, the result of an intriguing balance of hydrogen bonding interactions among the phenolic resin and the PEO and PPO segments of the triblock copolymer. PMID:28788378

The influence of poly(ethylene oxide) and illumination on the copper electrodeposition process onto n-Si(100).

PubMed

Muñoz, Eduardo C; Schrebler, Ricardo S; Cury, Paula K; Suarez, Claudio A; Córdova, Ricardo A; Gómez, Carlos H; Marotti, Ricardo E; Dalchiele, Enrique A

2006-10-26

In this study, we examined the influence of illumination and the presence of poly(ethylene oxide) (PEO) as an additive for the copper electrodeposition process onto n-Si(100). The study was carried out by means of cyclic voltammetry (CV) and the potential steps method, from which the corresponding nucleation and growth mechanism (NGM) were determined. Likewise, a morphologic analysis of the deposits obtained at different potential values by means of atomic force microscopy (AFM) was carried out. In a first stage, Mott-Schottky measurements so as to characterize the energetics of the semiconductor/electrolyte interface were made. Also, parallel capacity measurements were carried out in order to determine the surface state density of the substrate. It was found that when PEO concentration is increased, the number of these surface states decreases. The CV results indicated that the presence of PEO inhibits the photoelectrochemical reaction of oxide formation on the surface of the semiconductor. This allows a decrease in the overpotential associated with the electrodeposition process. The analysis of the j/t transients shows that the NGM corresponds to progressive three-dimensional (3D) diffusional controlled (PN3D(Diff)), which was confirmed by the AFM technique. Neither illumination nor the presence of PEO changes the mechanisms. Their influence is in that they diminish the size of the nuclei and the speed with which these are formed, which produces a more homogeneous electrodeposit.

PEO-PPO-PEO Tri-Block Copolymers for Gene Delivery Applications in Human Regenerative Medicine—An Overview

PubMed Central

Cucchiarini, Magali

2018-01-01

Lineal (poloxamers or Pluronic®) or X-shaped (poloxamines or Tetronic®) amphiphilic tri-block copolymers of poly(ethylene oxide) and poly(propylene oxide) (PEO-PPO-PEO) have been broadly explored for controlled drug delivery in different regenerative medicine approaches. The ability of these copolymers to self-assemble as micelles and to undergo sol-to-gel transitions upon heating has endowed the denomination of “smart” or “intelligent” systems. The use of PEO-PPO-PEO copolymers as gene delivery systems is a powerful emerging strategy to improve the performance of classical gene transfer vectors. This review summarizes the state of art of the application of PEO-PPO-PEO copolymers in both nonviral and viral gene transfer approaches and their potential as gene delivery systems in different regenerative medicine approaches. PMID:29518011

Rheological Characterization of Molten Polymer-Drug Dispersions as a Predictive Tool for Pharmaceutical Hot-Melt Extrusion Processability.

PubMed

Van Renterghem, Jeroen; Vervaet, Chris; De Beer, Thomas

2017-11-01

The aim of this study was to investigate (i) the influence of drug solid-state (crystalline or dissolved in the polymer matrix) on the melt viscosity and (ii) the influence of the drug concentration, temperature and shear rate on polymer crystallization using rheological tests. Poly (ethylene oxide) (PEO) (100.000 g/mol) and physical mixtures (PM) containing 10-20-30-40% (w/w) ketoprofen or 10% (w/w) theophylline in PEO were rheologically characterized. Rheological tests were performed (frequency and temperature sweeps in oscillatory shear as well as shear-induced crystallization experiments) to obtain a thorough understanding of the flow behaviour and crystallization of PEO-drug dispersions. Theophylline did not dissolve in PEO as the complex viscosity (η*) of the drug-polymer mixture increased as compared to that of neat PEO. In contrast, ketoprofen dissolved in PEO and acted as a plasticizer, decreasing η*. Acting as a nucleating agent, theophylline induced the crystallization of PEO upon cooling from the melt. On the other hand, ketoprofen inhibited crystallization upon cooling. Moreover, higher concentrations of ketoprofen in the drug-polymer mixture increasingly inhibited polymer crystallization. However, shear-induced crystallization was observed for all tested mixtures containing ketoprofen. The obtained rheological results are relevant for understanding and predicting HME processability (e.g., barrel temperature selection) and downstream processing such as injection moulding (e.g., mold temperature selection).

Effect upon biocompatibility and biocorrosion properties of plasma electrolytic oxidation in trisodium phosphate electrolytes.

PubMed

Kim, Yu-Kyoung; Park, Il-Song; Lee, Kwang-Bok; Bae, Tae-Sung; Jang, Yong-Seok; Oh, Young-Min; Lee, Min-Ho

2016-03-01

Surface modification to improve the corrosion resistance and biocompatibility of the Mg-Al-Zn-Ca alloy was conducted via plasma electrolytic oxidation (PEO) in an electrolyte that included phosphate. Calcium phosphate can be easily induced on the surface of a PEO coating that includes phosphate in a physiological environment because Ca(2+) ions in body fluids can be combined with PO4 (3-). Cytotoxicity of the PEO coating formed in electrolytes with various amounts of Na3PO4 was identified. In particular, the effects that PEO films have upon oxidative stress and differentiation of osteoblast activity were studied. As the concentration of Na3PO4 in the electrolyte increased, the oxide layer was found to become thicker, which increased corrosion resistance. However, the PEO coating formed in electrolytes with over 0.2 M of added Na3PO4 exhibited more microcracks and larger pores than those formed in smaller Na3PO4 concentrations owing to a large spark discharge. A nonuniform oxide film that included more phosphate caused more cytotoxicity and oxidative stress, and overabundant phosphate content in the oxide layer interrupted the differentiation of osteoblasts. The corrosion resistance of the magnesium alloy and the thickness of the oxide layer were increased by the addition of Na3PO4 in the electrolyte for PEO treatment. However, excessive phosphate content in the oxide layer led to oxidative stress, which resulted in reduced cell viability and activity.

Direct fabrication of ordered mesoporous carbons with super-micropore/small mesopore using mixed triblock copolymers.

PubMed

Li, Peng; Song, Yan; Tang, Zhihong; Yang, Guangzhi; Yang, Junhe

2014-01-01

Ordered mesoporous carbons (OMCs) have been prepared by the strategy of evaporation-induced organic-organic self-assembly method by employing a mixture of amphiphilic triblock copolymers poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) and reverse PPO-PEO-PPO as templates, with soluble in ethanol, low-molecular-weight phenolic resin as precursor, followed by carbonization. It has been found that the as prepared OMCs with porosity that combines super-micropore and small mesopore size distributed from 0.8 to 4 nm, which bridges the pore size from 2 to 3 nm and also for the diversification of the soft-templating synthesis of OMCs. Furthermore, the results showed that the OMCs obtained have mesophase transition from cylindrical p6 mm to centered rectangular c2 mm structure by simply tuning the ratio of PPO-PEO-PPO/PEO-PPO-PEO. Copyright © 2013 Elsevier Inc. All rights reserved.

Enhanced mechanical properties and increased corrosion resistance of a biodegradable magnesium alloy by plasma electrolytic oxidation (PEO).

PubMed

White, Leon; Koo, Youngmi; Neralla, Sudheer; Sankar, Jagannathan; Yun, Yeoheung

2016-06-01

We report the enhanced mechanical properties of AZ31 magnesium alloys by plasma electrolytic oxidation (PEO) coating in NaOH, Na 2 SiO 3 , KF and NaH 2 PO 4 ·2H 2 O containing electrolytes. Mechanical properties including wear resistance, surface hardness and elastic modulus were increased for PEO-coated AZ31 Mg alloys (PEO-AZ31). DC polarization in Hank's solution indicating that the corrosion resistance significantly increased for PEO-coating in KF-contained electrolyte. Based on these results, the PEO coating method shows promising potential for use in biodegradable implant applications where tunable corrosion and mechanical properties are needed.

Characterization of poly(ethylene oxide) as a drug carrier in hot-melt extrusion.

PubMed

Li, Lei; AbuBaker, Omar; Shao, Zezhi J

2006-09-01

Poly(ethylene oxide) (PEO) as a drug carrier in hot-melt extrusion was studied by using a model drug, nifedipine, in a twin-screw extruder. Binary mixtures of PEO and nifedipine have been shown to be amenable to hot-melting at a temperature as low as 70 degrees C, well below nifedipine's melting point (172 degrees C). Hot-stage microscopy provided visual evidence that nifedipine can form a miscible dispersion with PEO at 120 degrees C. Complete loss of nifedipine crystallinity when extrudated at and above 120 degrees C with a drug loading of 20% (w/w) was further confirmed by differential scanning calorimetry (DSC) and X-ray diffraction. Cross-sectional imaging of the extrudates using scanning electron microscopy indicated homogeneous drug distribution inside PEO when the processing temperature was above 120 degrees C. Raman spectroscopy confirmed drug-PEO interactions at a molecular level. Cryo-milled extrudates showed significant improvement in dissolution rate compared to either pure nifedipine or the physical mixture of PEO and nifedipine. A state of supersaturation was achieved after 10-minute release in pH 6.8 phosphate buffer. Finally, stability study demonstrated that the solid dispersion system is chemically stable for at least 3 months under the conditions of both 25 degrees C/60% RH and 40 degrees C/75% RH. Overall, PEO appears to be a promising aid/carrier to solublize poorly soluble drugs through the formation of solid dispersion via hot-melt extrusion, thereby improving dissolution and absorption.

In vitro degradation, hemolysis, and cytocompatibility of PEO/PLLA composite coating on biodegradable AZ31 alloy.

PubMed

Wei, Zhongling; Tian, Peng; Liu, Xuanyong; Zhou, Bangxin

2015-02-01

Magnesium and its alloys have large potential as degradable and absorbable biomaterials because of their mechanical properties and biocompatibility. However, their corrosion resistance is usually inadequate especially in physiological environment, which limits their broad applications in biomedical areas. In this work, plasma electrolytic oxidized/poly(l-lactide) (PEO/PLLA) composite coating was successfully fabricated on biodegradable AZ31 alloy by combing PEO process and sealing with PLLA. The microstructure, elemental composition, and phase composition of the PEO/PLLA composite coating were investigated. The in vitro degradation of the PEO/PLLA composite coating in simulated body fluid (SBF) was also systematically evaluated. The results revealed that the PEO/PLLA composite coating improved the corrosion resistance of AZ31 alloy significantly. The corrosion potential shifted from -1.663V to more positive position -1.317 V and the corrosion current density was reduced with six-order of magnitude. The Mg(2+) ions, hydrogen release, and pH value change of solution caused by degradation were all decreased significantly. Moreover, the PEO process played a critical role in sustaining the integrity of the implant in long-term service. The result of hemolysis test showed that the PEO/PLLA composite coating vested AZ31 alloy a low hemolysis ratio (0.806 ± 0.771)%, which is much lower than the safe value of 5% according to ISO 10993-4. For the cytocompatibility test, compared with bare AZ31 alloy and PEO coating, MC3T3-E1 cells showed much better adhesion and proliferation on the PEO/PLLA composite coating with nearly 4-fold increase of cells after 7-day cultivation, indicating that the PEO/PLLA composite coating has good biocompatibility for biomedical applications. © 2014 Wiley Periodicals, Inc.

High-concentration graphene dispersion stabilized by block copolymers in ethanol.

PubMed

Perumal, Suguna; Lee, Hyang Moo; Cheong, In Woo

2017-07-01

This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion. Copyright © 2017 Elsevier Inc. All rights reserved.

Molecular dynamics simulation study of the structure of poly(ethylene oxide) brushes on nonpolar surfaces in aqueous solution.

PubMed

Bedrov, Dmitry; Smith, Grant D

2006-07-04

The structure of poly(ethylene oxide) (PEO, M(w) = 526) brushes of various grafting density (sigma) on nonpolar graphite and hydrophobic (oily) surfaces in aqueous solution has been studied using atomistic molecular dynamics simulations. Additionally, the influence of PEO-surface interactions on the brush structure was investigated by systematically reducing the strength of the (dispersion) attraction between PEO and the surfaces. PEO chains were found to adsorb strongly to the graphite surface due primarily to the relative strength of dispersion interactions between PEO and the atomically dense graphite compared to those between water and graphite. For the oily surface, PEO-surface and water-surface dispersion interactions are much weaker, greatly reducing the energetic driving force for PEO adsorption. This reduction is mediated to some extent by a hydrophobic driving force for PEO adsorption on the oily surface. Reduction in the strength of PEO-surface attraction results in reduced adsorption of PEO for both surfaces, with the effect being much greater for the graphite surface where the strong PEO-surface dispersion interactions dominate. At high grafting density (sigma approximately 1/R(g)(2)), the PEO density profiles exhibited classical brush behavior and were largely independent of the strength of the PEO-surface interaction. With decreasing grafting density (sigma < 1/R(g)(2)), coverage of the surface by PEO requires an increasingly large fraction of PEO segments resulting in a strong dependence of the PEO density profile on the nature of the PEO-surface interaction.

Modified release from lipid bilayer coated mesoporous silica nanoparticles using PEO–PPO–PEO triblock copolymers [Modified release from lipid bilayer coated mesoporous silica nanoparticles using PEO PPO PEO triblock copolymers

DOE PAGES

Rahman, Masoud; Yu, Erick; Forman, Evan; ...

2014-08-20

Triblock copolymers comprised of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, or trade name Pluronic) interact with lipid bilayers to increase their permeability. Here we demonstrate a novel application of Pluronic L61 and L64 as modification agents in tailoring the release rate of a molecular indicator species from 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayer-coated superparamagnetic Fe 3O 4/mesoporous silica coreshell nanoparticles. Lastly, we show there is a direct relationship between Pluronic concentration and the indicator molecule release, suggesting Pluronic may be useful for the controlled release of drugs from lipid bilayer-coated carriers.

The effect of plasma electrolytic oxidation on the mean stress sensitivity of the fatigue life of the 6082 aluminum alloy

NASA Astrophysics Data System (ADS)

Winter, L.; Morgenstern, R.; Hockauf, K.; Lampke, T.

2016-03-01

In this work the mean stress influence on the high cycle fatigue behavior of the plasma electrolytic oxidized (PEO) 6082 aluminum alloy (AlSi1MgMn) is investigated. The present study is focused on the fatigue life time and the susceptibility of fatigue-induced cracking of the oxide coating and their dependence on the applied mean stress. Systematic work is done comparing conditions with and without PEO treatment, which have been tested using three different load ratios. For the uncoated substrate the cycles to failure show a significant dependence on the mean stress, which is typical for aluminum alloys. With increased load ratio and therefore increased mean stress, the fatigue strength decreases. The investigation confirms the well-known effect of PEO treatment on the fatigue life: The fatigue strength is significantly reduced by the PEO process, compared to the uncoated substrate. However, also the mean stress sensitivity of the fatigue performance is reduced. The fatigue limit is not influenced by an increasing mean stress for the PEO treated conditions. This effect is firstly shown in these findings and no explanation for this effect can be found in literature. Supposedly the internal compressive stresses and the micro-cracks in the oxide film have a direct influence on the crack initiation and growth from the oxide film through the interface and in the substrate. Contrary to these findings, the susceptibility of fatigue-induced cracking of the oxide coating is influenced by the load ratio. At tension-tension loading a large number of cracks, which grow partially just in the aluminum substrate, are present. With decreasing load ratio to alternating tension-compression stresses, the crack number and length increases and shattering of the oxide film is more pronounced due to the additional effective compressive part of the load cycle.

Preparation of Pure and Stable Chitosan Nanofibers by Electrospinning in the Presence of Poly(ethylene oxide)

PubMed Central

Mengistu Lemma, Solomon; Bossard, Frédéric; Rinaudo, Marguerite

2016-01-01

Electrospinning was employed to obtain chitosan nanofibers from blends of chitosans (CS) and poly(ethylene oxide) (PEO). Blends of chitosan (MW (weight-average molecular weight) = 102 kg/mol) and PEO (M (molecular weight) = 1000 kg/mol) were selected to optimize the electrospinning process parameters. The PEO powder was solubilized into chitosan solution at different weight ratios in 0.5 M acetic acid. The physicochemical changes of the nanofibers were determined by scanning electron microscopy (SEM), swelling capacity, and nuclear magnetic resonance (NMR) spectroscopy. For stabilization, the produced nanofibers were neutralized with K2CO3 in water or 70% ethanol/30% water as solvent. Subsequently, repeated washings with pure water were performed to extract PEO, potassium acetate and carbonate salts formed in the course of chitosan nanofiber purification. The increase of PEO content in the blend from 20 to 40 w% exhibited bead-free fibers with average diameters 85 ± 19 and 147 ± 28 nm, respectively. Their NMR analysis proved that PEO and the salts were nearly completely removed from the nanostructure of chitosan, demonstrating that the adopted strategy is successful for producing pure chitosan nanofibers. In addition, the nanofibers obtained after neutralization in ethanol-aqueous solution has better structural stability, at least for six months in aqueous solutions (phosphate buffer (PBS) or water). PMID:27792192

Adsorption of poly(ethylene oxide) on smectite: Effect of layer charge.

PubMed

Su, Chia-Chi; Shen, Yun-Hwei

2009-04-01

The adsorption of polymers on clay is important in many applications. However the mechanisms of poly(ethylene oxide) (PEO) adsorption on smectite is not well elucidated at present. The aim of this study was to investigate the effect of layer charge density on the adsorption of PEO by smectite. The results indicated that both the hydrophobic interaction (between CH(2)CH(2) groups and siloxane surface) and the hydrogen bonding (between ether oxygen of PEO and structure OH of smectite) lead to PEO preferential adsorption on the surface of low-charge smectite. In addition, the delamination of low-charge smectite in water is enhanced upon PEO adsorption presumably due to the hydrophilic ether oxygen of adsorbed PEO.

pH responsiveness of dendrimer-like poly(ethylene oxide)s.

PubMed

Feng, Xiaoshuang; Taton, Daniel; Borsali, Redouane; Chaikof, Elliot L; Gnanou, Yves

2006-09-06

Poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA), two polymers known to form pH-sensitive aggregates through noncovalent interactions, were assembled in purposely designed architecture -a dendrimer-like PEO scaffold carrying short inner PAA chains-to produce unimolecular systems that exhibit pH responsiveness. Because of the particular placement of the PAA chains within the dendrimer-like structure, intermolecular complexation between acrylic acid (AA) and ethylene oxide (EO) units-and thus macroscopic aggregation or even mesoscopic micellization-could be avoided in favor of the sole intramolecular complexation. The sensitivity of such interactions to pH was exploited to generate dendrimer-like PEOs that reversibly shrink and expand with the pH. Such PAA-carrying dendrimer-like PEOs were synthesized in two main steps. First, a fifth-generation dendrimer-like PEO was obtained by combining anionic ring-opening polymerization (AROP) of ethylene oxide from a tris-hydroxylated core and selective branching reactions of PEO chain ends. To this end, an AB(2)C-type branching agent was designed: the latter includes a chloromethyl (A) group for its covalent attachment to the arm ends, two geminal hydroxyls (B(2)) protected in the form of a ketal ring for the growth of subsequent PEO generations by AROP, and a vinylic (C) double bonds for further functionalization of the interior of dendrimer-like PEOs. Reiteration of AROP and derivatization of PEO branches allowed us to prepare a dendrimer-like PEO of fourth generation with a total molar mass of 52,000 g x mol(-1), containing 24 external hydroxyl functions and 21 inner vinylic groups in the interior. A fifth generation of PEO chains was generated from this parent dendrimer-like PEO of fourth generation using a "conventional" AB(2)-type branching agent, and 48 PEO branches could be grown by AROP. The 48 outer hydroxy-end groups of the fifth-generation dendrimer-like PEO obtained were subsequently quantitatively converted into inert benzylic groups using benzyl bromide. The 21 internal vinylic groups carried by the PEO scaffold were then chemically modified in a two-step sequence into bromoester groups. The latter which are atom transfer radical polymerization (ATRP) initiating sites thus served to grow poly(tert-butylacrylate) chains. After a final step of hydrolysis of the tert-butyl ester groups, double, hydrophilic, dendrimer-like PEOs comprising 21 internal junction-attached poly(acrylic acid) (PAA) blocks could be obtained. Dynamic light scattering was used to determine the size of these dendrimer-like species in water and to investigate their response to pH variation: in particular, how the pH-sensitive complexation of EO and AA units affects their overall behavior.

Atomistic simulation of CO2 solubility in poly(ethylene oxide) oligomers

NASA Astrophysics Data System (ADS)

Hong, Bingbing; Panagiotopoulos, Athanassios Z.

2014-06-01

We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO2 in poly(ethylene oxide) oligomers. Poly(ethylene oxide) dimethyl ether, CH3O(CH2CH2O)nCH3 (PEO for short) is a widely applied physical solvent that forms the major organic constituent of a class of novel nanoparticle-based absorbents. Good predictions were obtained for pressure-composition-density relations for CO2 + PEO oligomers (2 ≤ n ≤ 12), using the Potoff force field for PEO [J. Chem. Phys. 136, 044514 (2012)] together with the TraPPE model for CO2 [AIChE J. 47, 1676 (2001)]. Water effects on Henry's constant of CO2 in PEO have also been investigated. Addition of modest amounts of water in PEO produces a relatively small increase in Henry's constant. Dependence of the calculated Henry's constant on the weight percentage of water falls on a temperature-dependent master curve, irrespective of PEO chain length.

Rheological study of the effect of polyethylene oxide (PEO) homopolymer on the gelation of PEO-PPO-PEO triblock copolymer in aqueous solution

NASA Astrophysics Data System (ADS)

Li, Xiaolei; Hyun, Kyu

2018-05-01

The effects of polyethylene oxide (PEO) homopolymer on the gelation behavior of a PEO100-PPO65-PEO100 triblock copolymer (Pluronic F127) were explored in aqueous solution under non-isothermal and isothermal conditions. Under non-isothermal conditions (temperature sweep test), two transition points were observed on increasing temperature, that is, at lower and upper gelation temperatures (LTgel and UTgel, respectively). Between LTgel and UTgel, F127 aqueous solutions maintained a hard gel state. Both molecular weight (MW) and PEO concentration affected these two gelation temperatures. In particular, relative molecular weight (MWrel ≡ molecular weight of PEO homopolymer/PEO segment of F127) affected LTgel. LTgel decreased on increasing PEO concentration at MWrel values of <1, but increased on increasing PEO concentration at MWrel values of >1. On the other hand, UTgel decreased with increasing PEO concentration regardless of MWrel. Under isothermal conditions (fixed temperature between LTgel and UTgel), the effects of PEO homopolymer on the mechanical properties of F127 hard gel were systemically investigated using small and large amplitude oscillatory shear tests. In the linear viscoelastic regime, total intra-cycle stress and elastic intra-cycle stress were similar, and viscous response increased on increasing PEO concentration. However, at large strain amplitudes, hard gels showed intra-cycle stiffening but inter-cycle softening behavior. In addition, on increasing PEO concentrations, viscous nonlinearities underwent strain-rate thickening followed by strain-rate thinning.

Water is a poor solvent for densely grafted poly(ethylene oxide) chains: a conclusion drawn from a self-consistent field theory-based analysis of neutron reflectivity and surface pressure-area isotherm data.

PubMed

Lee, Hoyoung; Kim, Dae Hwan; Witte, Kevin N; Ohn, Kimberly; Choi, Je; Akgun, Bulent; Satija, Sushil; Won, You-Yeon

2012-06-21

By use of a combined experimental and theoretical approach, a model poly(ethylene oxide) (PEO) brush system, prepared by spreading a poly(ethylene oxide)-poly(n-butyl acrylate) (PEO-PnBA) amphiphilic diblock copolymer onto an air-water interface, was investigated. The polymer segment density profiles of the PEO brush in the direction normal to the air-water interface under various grafting density conditions were determined by using the neutron reflectivity (NR) measurement technique. To achieve a theoretically sound analysis of the reflectivity data, we used a data analysis method that utilizes the self-consistent field (SCF) theoretical modeling as a tool for predicting expected reflectivity results for comparison with the experimental data. Using this data analysis technique, we discovered that the effective Flory-Huggins interaction parameter of the PEO brush chains is significantly greater than that corresponding to the θ condition in Flory-Huggins solutions (i.e., χ(PEO-water)(brush chains)/χ(PEO-water)(θ condition) ≈ 1.2), suggesting that contrary to what is more commonly observed for PEO in normal situations (χ(PEO-water)(free chains)/χ(PEO-water)(θ condition) ≈ 0.92), the PEO chains are actually not "hydrophilic" when they exist as polymer brush chains, because of the many body interactions that are forced to be effective in the brush situation. This result is further supported by the fact that the surface pressures of the PEO brush calculated on the basis of the measured χ(PEO-water) value are in close agreement with the experimental surface pressure-area isotherm data. The SCF theoretical analysis of the surface pressure behavior of the PEO brush also suggests that even though the grafted PEO chains experience a poor solvent environment, the PEO brush layer exhibits positive surface pressures, because the hydrophobicity of the PEO brush chains (which favors compression) is insufficient to overcome the opposing effect of the chain conformational entropy (which resists compression).

Soft plasma electrolysis with complex ions for optimizing electrochemical performance

NASA Astrophysics Data System (ADS)

Kamil, Muhammad Prisla; Kaseem, Mosab; Ko, Young Gun

2017-03-01

Plasma electrolytic oxidation (PEO) was a promising surface treatment for light metals to tailor an oxide layer with excellent properties. However, porous coating structure was generally exhibited due to excessive plasma discharges, restraining its performance. The present work utilized ethylenediaminetetraacetic acid (EDTA) and Cu-EDTA complexing agents as electrolyte additives that alter the plasma discharges to improve the electrochemical properties of Al-1.1Mg alloy coated by PEO. To achieve this purpose, PEO coatings were fabricated under an alternating current in silicate electrolytes containing EDTA and Cu-EDTA. EDTA complexes were found to modify the plasma discharging behaviour during PEO that led to a lower porosity than that without additives. This was attributed to a more homogeneous electrical field throughout the PEO process while the coating growth would be maintained by an excess of dissolved Al due to the EDTA complexes. When Cu-EDTA was used, the number of discharge channels in the coating layer was lower than that with EDTA due to the incorporation of Cu2O and CuO altering the dielectric behaviour. Accordingly, the sample in the electrolyte containing Cu-EDTA constituted superior corrosion resistance to that with EDTA. The electrochemical mechanism for excellent corrosion protection was elucidated in the context of equivalent circuit model.

Soft plasma electrolysis with complex ions for optimizing electrochemical performance

PubMed Central

Kamil, Muhammad Prisla; Kaseem, Mosab; Ko, Young Gun

2017-01-01

Plasma electrolytic oxidation (PEO) was a promising surface treatment for light metals to tailor an oxide layer with excellent properties. However, porous coating structure was generally exhibited due to excessive plasma discharges, restraining its performance. The present work utilized ethylenediaminetetraacetic acid (EDTA) and Cu-EDTA complexing agents as electrolyte additives that alter the plasma discharges to improve the electrochemical properties of Al-1.1Mg alloy coated by PEO. To achieve this purpose, PEO coatings were fabricated under an alternating current in silicate electrolytes containing EDTA and Cu-EDTA. EDTA complexes were found to modify the plasma discharging behaviour during PEO that led to a lower porosity than that without additives. This was attributed to a more homogeneous electrical field throughout the PEO process while the coating growth would be maintained by an excess of dissolved Al due to the EDTA complexes. When Cu-EDTA was used, the number of discharge channels in the coating layer was lower than that with EDTA due to the incorporation of Cu2O and CuO altering the dielectric behaviour. Accordingly, the sample in the electrolyte containing Cu-EDTA constituted superior corrosion resistance to that with EDTA. The electrochemical mechanism for excellent corrosion protection was elucidated in the context of equivalent circuit model. PMID:28281672

Polyethylene oxide-polytetrahydrofurane-PEDOT conducting interpenetrating polymer networks for high speed actuators

NASA Astrophysics Data System (ADS)

Plesse, C.; Khaldi, A.; Wang, Q.; Cattan, E.; Teyssié, D.; Chevrot, C.; Vidal, F.

2011-12-01

In recent years, numerous studies on electro-active polymer (EAP) actuators have been reported. One promising technology is the elaboration of electronic conducting polymer-based actuators with interpenetrating polymer network (IPNs) architecture. In this study, the synthesis and characterisation of conducting IPNs for actuator applications is described. The IPNs are synthesised from polyethylene oxide (PEO) and polytetrahydrofurane (PTHF) networks in which the conducting polymer (poly(3,4-ethylenedioxythiophene)) is incorporated. In a first step, PEO/PTHF IPNs were prepared via an 'in situ' process using poly(ethylene glycol) methacrylate and dimethacrylate and hydroxytelechelic PTHF as starting materials. The IPN mechanical properties were examined by DMA and tensile strength tests. N-ethylmethylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI) swollen PEO/PTHF IPNs show ionic conductivities up to 10-3 S cm-1 at 30 °C. In a second step, the conducting IPN actuators were prepared by oxidative polymerisation of 3,4-ethylenedioxithiophene (EDOT) using FeCl3 as an oxidising agent within the PEO/PTHF IPN host matrix. The frequency response performance of the bending conducting IPN actuator was then evaluated. The resulting actuator exhibits a mechanical resonance frequency of up to 125 Hz with 0.75% strain for an applied potential of ± 5 V.

Composition of highly concentrated silicate electrolytes and ultrasound influencing the plasma electrolytic oxidation of magnesium

NASA Astrophysics Data System (ADS)

Simchen, F.; Rymer, L.-M.; Sieber, M.; Lampke, T.

2017-03-01

Magnesium and its alloys are increasingly in use as lightweight construction materials. However, their inappropriate corrosion and wear resistance often prevent their direct practical use. The plasma electrolytic oxidation (PEO) is a promising, environmentally friendly method to improve the surface characteristics of magnesium materials by the formation of oxide coatings. These PEO layers contain components of the applied electrolyte and can be shifted in their composition by increasing the concentration of the electrolyte constituents. Therefore, in contrast to the use of conventional low concentrated electrolytes, the process results in more stable protective coatings, in which electrolyte species are the dominating constitutes. In the present work, the influence of the composition of highly concentrated alkaline silicate electrolytes with additives of phosphate and glycerol on the quality of PEO layers on the magnesium alloy AZ31 was examined. The effect of ultrasound coupled into the electrolyte bath was also considered. The process was monitored by recording the electrical process variables with a transient recorder and by observation of the discharge phenomena on the sample surface with a camera. The study was conducted on the basis of a design of experiments. The effects of the process parameter variation are considered with regard to the coatings thickness, hardness and corrosion resistance. Information about the statistical significance of the effects of the parameters on the considered properties is obtained by an analysis of variance (ANOVA).

Molecular dynamics simulation study of hydrogen bonding in aqueous poly(ethylene oxide) solutions.

PubMed

Smith, G D; Bedrov, D; Borodin, O

2000-12-25

A molecular dynamics simulation study of hydrogen bonding in poly(ethylene oxide) (PEO)/water solutions was performed. PEO-water and water-water hydrogen bonding manifested complex dependence on both composition and temperature. Strong water clustering in concentrated solutions was seen. Saturation of hydrogen bonding at w(p) approximately equal to 0.5 and a dramatic decrease in PEO-water hydrogen bonding with increasing temperature, consistent with experimentally observed closed-loop phase behavior, were observed. Little tendency toward intermolecular bridging of PEO chains by water molecules was seen.

Investigations into the structure of PEO-layers for understanding of layer formation

NASA Astrophysics Data System (ADS)

Friedemann, A. E. R.; Thiel, K.; Haßlinger, U.; Ritter, M.; Gesing, Th. M.; Plagemann, P.

2018-06-01

Plasma electrolytic oxidation (PEO) is a type of high-voltage anodic oxidation process capable of producing a thick oxide layer with a wide variety of structural and chemical properties influenced by the electrolytic system. This process enables the combined adjustment of various characteristics, i.e. the morphology and chemical composition. The procedure facilitates the possibility of generating an individual structure as well as forming a crystalline surface in a single step. A highly porous surface with a high crystalline content consisting of titanium dioxide phases is ensured through the process of plasma electrolytic oxidizing pure titanium. In the present study plasma electrolytic oxidized TiO2-layers were investigated regarding their crystallinity through the layer thickness. The layers were prepared with a high applied voltage of 280 V to obtain a PEO-layer with highly crystalline anatase and rutile amounts. Raman spectroscopy and electron backscatter diffraction (EBSD) were selected to clarify the structure of the oxide layer with regard to its crystallinity and phase composition. The composition of the TiO2-phases is more or less irregularly distributed as a result of the higher energy input on the uppermost side of the layer. Scanning transmission electron microscopy (STEM) provided a deeper understanding of the structure and the effects of plasma discharges on the layer. It was observed that the plasma discharges have a strong influence on crystallite formation on top of the oxide layer and also at the boundary layer to the titanium substrate. Therefore, small crystallites of TiO2 could be detected in these regions. In addition, it was shown that amorphous TiO2 phases are formed around the characteristic pore structures, which allows the conclusion to be drawn that a rapid cooling from the gas phase had to take place in these areas.

Effects of plasma electrolytic oxidation process on the mechanical properties of additively manufactured porous biomaterials.

PubMed

Gorgin Karaji, Zahra; Hedayati, Reza; Pouran, Behdad; Apachitei, Iulian; Zadpoor, Amir A

2017-07-01

Metallic porous biomaterials are recently attracting more attention thanks to the additive manufacturing techniques which help produce more complex structures as compared to conventional techniques. On the other hand, bio-functional surfaces on metallic biomaterials such as titanium and its alloys are necessary to enhance the biological interactions with the host tissue. This study discusses the effect of plasma electrolytic oxidation (PEO), as a surface modification technique to produce bio-functional layers, on the mechanical properties of additively manufactured Ti6Al4V scaffolds based on the cubic unit cell. For this purpose, the PEO process with two different oxidation times was applied on scaffolds with four different values of relative density. The effects of the PEO process were studied by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), optical microscopy as well as static and dynamic (fatigue) mechanical testing under compression. SEM results indicated pore formation on the surface of the scaffolds after oxidation with a thickness of 4.85±0.36μm of the oxide layer after 2min and 9.04±2.27μm after 5min oxidation (based on optical images). The static test results showed the high effect of relative density of porous structure on its mechanical properties. However, oxidation did not influence most of the mechanical properties such as maximum stress, yield stress, plateau stress, and energy absorption, although its effect on the elastic modulus was considerable. Under fatigue loading, none of the scaffolds failed even after 10 6 loading cycles at 70% of their yield stress. Copyright © 2017 Elsevier B.V. All rights reserved.

Degradation of the commercial surfactant nonylphenol ethoxylate by advanced oxidation processes.

PubMed

da Silva, Salatiel Wohlmuth; Klauck, Cláudia Regina; Siqueira, Marco Antônio; Bernardes, Andréa Moura

2015-01-23

Four different oxidation process, namely direct photolysis (DP) and three advanced oxidation processes (heterogeneous photocatalysis - HP, eletrochemical oxidation - EO and photo-assisted electrochemical oxidation - PEO) were applied in the treatment of wastewater containing nonylphenol ethoxylate (NPnEO). The objective of this work was to determine which treatment would be the best option in terms of degradation of NPnEO without the subsequent generation of toxic compounds. In order to investigate the degradation of the surfactant, the processes were compared in terms of UV/Vis spectrum, mineralization (total organic carbon), reaction kinetics, energy efficiency and phytotoxicity. A solution containing NPnEO was prepared as a surrogate of the degreasing wastewater, was used in the processes. The results showed that the photo-assisted processes degrade the surfactant, producing biodegradable intermediates in the reaction. On the other hand, the electrochemical process influences the mineralization of the surfactant. The process of PEO carried out with a 250W lamp and a current density of 10mA/cm(2) showed the best results in terms of degradation, mineralization, reaction kinetics and energy consumption, in addition to not presenting phytotoxicity. Based on this information, this process can be a viable alternative for treating wastewater containing NPnEO, avoiding the contamination of water resources. Copyright © 2014 Elsevier B.V. All rights reserved.

PEO of pre-anodized Al-Si alloys: Corrosion properties and influence of sealings

NASA Astrophysics Data System (ADS)

Mohedano, M.; Matykina, E.; Arrabal, R.; Mingo, B.; Pardo, A.

2015-08-01

Voltage-controlled PEO coatings were developed on A356 aluminum alloys (gravity-cast and rheocast) with a pre-anodized layer. The influence of the alloy manufacturing process and the effect of Si-rich phase on the structure and composition of the oxide layers were evaluated using SEM, EDS and XRD. The pre-anodized oxide layer preserves the microstructure of the substrate due to the presence of secondary phases that have a different behavior relative to the matrix during anodizing. PEO coatings consisted of a mixture of α-Al2O3, γ-Al2O3 and mullite. The corrosion behavior and the effectiveness of different sealing techniques based on salts of nickel, cobalt, cerium and phosphonic acid were also studied. Post-treatments improved the hydrophobic properties of the coatings and showed a beneficial effect, significantly increasing the coating impedance and thereby reducing the susceptibility to corrosion.

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.

2007-01-01

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

In situ functionalization and PEO coating of iron oxide nanocrystals using seeded emulsion polymerization.

PubMed

Kloust, Hauke; Schmidtke, Christian; Feld, Artur; Schotten, Theo; Eggers, Robin; Fittschen, Ursula E A; Schulz, Florian; Pöselt, Elmar; Ostermann, Johannes; Bastús, Neus G; Weller, Horst

2013-04-16

Herein we demonstrate that seeded emulsion polymerization is a powerful tool to produce multiply functionalized PEO coated iron oxide nanocrystals. Advantageously, by simple addition of functional surfactants, functional monomers, or functional polymerizable linkers-solely or in combinations thereof-during the seeded emulsion polymerization process, a broad range of in situ functionalized polymer-coated iron oxide nanocrystals were obtained. This was demonstrated by purposeful modulation of the zeta potential of encapsulated iron oxide nanocrystals and conjugation of a dyestuff. Successful functionalization was unequivocally proven by TXRF. Furthermore, the spatial position of the functional groups can be controlled by choosing the appropriate spacers. In conclusion, this methodology is highly amenable for combinatorial strategies and will spur rapid expedited synthesis and purposeful optimization of a broad scope of nanocrystals.

Antibiotics mineralization by electrochemical and UV-based hybrid processes: evaluation of the synergistic effect.

PubMed

Wohlmuth da Silva, Salatiel; Arenhart Heberle, Alan Nelson; Pereira Santos, Alexia; Siqueira Rodrigues, Marco Antônio; Pérez-Herranz, Valentín; Moura Bernardes, Andréa

2018-05-29

Antibiotics are not efficiently removed in conventional wastewater treatments. In fact, different advanced oxidation process (AOPs), including ozone, peroxide, UV radiation, among others, are being investigated in the elimination of microcontaminants. Most of AOPs proved to be efficient on the degradation of antibiotics, but the mineralization is on the one hand not evaluated or on the other hand not high. At this work, the UV-based hybrid process, namely Photo-assisted electrochemical oxidation (PEO), was applied, aiming the mineralization of microcontaminants such as the antibiotics Amoxicillin (AMX), Norfloxacin (NOR) and Azithromycin (AZI). The influence of the individual contributions of electrochemical oxidation (EO) and the UV-base processes on the hybrid process (PEO) was analysed. Results showed that AMX and NOR presented higher mineralization rate under direct photolysis than AZI due to the high absorption of UV radiation. For the EO processes, a low mineralization was found for all antibiotics, what was associated to a mass-transport limitation related to the low concentration of contaminants (200 µg/L). Besides that, an increase in mineralization was found, when heterogeneous photocatalysis and EO are compared, due to the influence of UV radiation, which overcomes the mass-transport limitations. Although the UV-based processes control the reaction pathway that leads to mineralization, the best results to mineralize the antibiotics were achieved by PEO hybrid process. This can be explained by the synergistic effect of the processes that constitute them. A higher mineralization was achieved, which is an important and useful finding to avoid the discharge of microcontaminants in the environment.

Solubilization of docetaxel in poly(ethylene oxide)-block-poly(butylene/styrene oxide) micelles.

PubMed

Elsabahy, Mahmoud; Perron, Marie-Eve; Bertrand, Nicolas; Yu, Ga-Er; Leroux, Jean-Christophe

2007-07-01

Poly(ethylene oxide)-block-poly(styrene oxide) (PEO-b-PSO) and PEO-b-poly(butylene oxide) (PEO-b-PBO) of different chain lengths were synthesized and characterized for their self-assembling properties in water by dynamic/static light scattering, spectrofluorimetry, and transmission electron microscopy. The resulting polymeric micelles were evaluated for their ability to solubilize and protect the anticancer drug docetaxel (DCTX) from degradation. The drug release kinetics as well as the cytotoxicity of the loaded micelles were assessed in vitro. All polymers formed micelles with a highly viscous core at low critical association concentrations (<10 mg/L). Micelle morphology depended on the nature of the hydrophobic block, with PBO- and PSO-based micelles yielding monodisperse spherical and cylindrical nanosized aggregates, respectively. The maximum solubilization capacity for DCTX ranged from 0.7 to 4.2% and was the highest for PSO micelles exhibiting the longest hydrophobic segment. Despite their high affinity for DCTX, PEO-b-PSO micelles were not able to efficiently protect DCTX against hydrolysis under accelerated stability testing conditions. Only PEO-b-PBO bearing 24 BO units afforded significant protection against degradation. In vitro, DCTX was released slower from the latter micelles, but all formulations possessed a similar cytotoxic effect against PC-3 prostate cancer cells. These data suggest that PEO-b-P(SO/BO) micelles could be used as alternatives to conventional surfactants for the solubilization of taxanes.

Sodium Aluminate Concentration Effects on Microstructure and Corrosion Behavior of the Plasma Electrolytic Oxidation Coatings on Pure Titanium

NASA Astrophysics Data System (ADS)

Molaei, Maryam; Fattah-Alhosseini, Arash; Gashti, Seyed Omid

2018-01-01

Sodium aluminate (NaAlO2) concentration was varied in order to understand the influence of the chemical composition of electrolyte on the spark characteristics, microstructure, and corrosion behavior of plasma electrolytic oxidation (PEO) coatings. For this purpose, PEO coatings were formed on the pure titanium substrate surface using solutions of four diverse sodium aluminate concentrations (6, 8, 10, and 12 g/L). The PEO process was carried out at constant time and voltage (180 seconds and 420 V). Studying the microstructures of samples by scanning electron microscope (SEM) and their corrosion behavior in 3.5 wt pct NaCl solutions indicated that the increase in NaAlO2 concentration (up to 10 g/L) led to an increase in uniformity and compactness, thus decreasing the size of micro-pores and increment of corrosion resistance. However, at a certain level of NaAlO2 concentration (12 g/L), large and severe sparks were created on the surface of the sample during the process, worsening the corrosion resistance and microstructure of coating.

Ionic conductivity of β-cyclodextrin-polyethylene-oxide/alkali-metal-salt complex.

PubMed

Yang, Ling-Yun; Fu, Xiao-Bin; Chen, Tai-Qiang; Pan, Li-Kun; Ji, Peng; Yao, Ye-Feng; Chen, Qun

2015-04-20

Highly conductive, crystalline, polymer electrolytes, β-cyclodextrin (β-CD)-polyethylene oxide (PEO)/LiAsF6 and β-CD-PEO/NaAsF6 , were prepared through supramolecular self-assembly of PEO, β-CD, and LiAsF6 /NaAsF6 . The assembled β-CDs form nanochannels in which the PEO/X(+) (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In-situ synthesis of magnetic iron-oxide nanoparticle-nanofibre composites using electrospinning.

PubMed

Burke, Luke; Mortimer, Chris J; Curtis, Daniel J; Lewis, Aled R; Williams, Rhodri; Hawkins, Karl; Maffeis, Thierry G G; Wright, Chris J

2017-01-01

We demonstrate a facile, one-step process to form polymer scaffolds composed of magnetic iron oxide nanoparticles (MNPs) contained within electrospun nano- and micro-fibres of two biocompatible polymers, Poly(ethylene oxide) (PEO) and Poly(vinyl pyrrolidone) (PVP). This was achieved with both needle and free-surface electrospinning systems demonstrating the scalability of the composite fibre manufacture; a 228 fold increase in fibre fabrication was observed for the free-surface system. In all cases the nanoparticle-nanofibre composite scaffolds displayed morphological properties as good as or better than those previously described and fabricated using complex multi-stage techniques. Fibres produced had an average diameter (Needle-spun: 125±18nm (PEO) and 1.58±0.28μm (PVP); Free-surface electrospun: 155±31nm (PEO)) similar to that reported previously, were smooth with no bead defects. Nanoparticle-nanofibre composites were characterised using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS) (Nanoparticle average diameter ranging from 8±3nm to 27±5nm), XRD (Phase of iron oxide nanoparticles identified as magnetite) and nuclear magnetic resonance relaxation measurements (NMR) (T1/T2: 32.44 for PEO fibres containing MNPs) were used to verify the magnetic behaviour of MNPs. This study represents a significant step forward for production rates of magnetic nanoparticle-nanofibre composite scaffolds by the electrospinning technique. Copyright © 2016 Elsevier B.V. All rights reserved.

Polyethylene oxide hydration in grafted layers

NASA Astrophysics Data System (ADS)

Dormidontova, Elena; Wang, Zilu

Hydration of water soluble polymers is one of the key-factors defining their conformation and properties, similar to biopolymers. Polyethylene oxide (PEO) is one of the most important biomedical-applications polymers and is known for its reverse temperature solubility due to hydrogen bonding with water. As in many practical applications PEO chains are grafted to surfaces, e.g. of nanoparticles or planar surfaces, it is important to understand PEO hydration in such grafted layers. Using atomistic molecular dynamic simulations we investigate the details of molecular conformation and hydration of PEO end-grafted to gold surfaces. We analyze polymer and water density distribution as a function of distance from the surface for different grafting densities. Based on a detailed analysis of hydrogen bonding between polymer and water in grafted PEO layers, we will discuss the extent of PEO hydration and its implication for polymer conformation, mobility and layer properties. This research is supported by NSF (DMR-1410928).

Preparation, properties and biological application of pH-sensitive poly(ethylene oxide) (PEO) hydrogels grafted with acrylic acid(AAc) using gamma-ray irradiation

NASA Astrophysics Data System (ADS)

Nho, Young Chang; Mook Lim, Youn; Moo Lee, Young

2004-09-01

pH-sensitive hydrogels were studied as a drug carrier for the protection of insulin from the acidic environment of the stomach before releasing it in the small intestine. In this study, hydrogels based on poly(ethylene oxide) (PEO) networks grafted with acrylic acid (AAc) were prepared via a two-step process. PEO hydrogels were prepared by γ-ray irradiation, and then grafting by AAc monomer onto the PEO hydrogels with the subsequent irradiation (radiation dose: 5-20 kGy, dose rate: 2.15 kGy/h). These grafted hydrogels showed a pH-sensitive swelling behavior. The grafted hydrogels were used as a carrier for the drug delivery systems for the controlled release of insulin. The in vitro drug release behaviors of these hydrogels were examined by quantification analysis with a UV/VIS spectrophotometer. Insulin was loaded into freeze-dried hydrogels (7 mm×3 mm×2.5 mm) and administrated orally to healthy and diabetic Wistar rats. The oral administration of insulin-loaded hydrogels to Wistar rats decreased the blood glucose levels obviously for at least 4 h due to the absorption of insulin in the gastrointestinal tract.

Effects of CH3OH Addition on Plasma Electrolytic Oxidation of AZ31 Magnesium Alloys

NASA Astrophysics Data System (ADS)

He, Yongyi; Chen, Li; Yan, Zongcheng; Zhang, Yalei

2015-09-01

Plasma electrolytic oxidation (PEO) films on AZ31 magnesium alloys were prepared in alkaline silicate electrolytes (base electrolyte) with the addition of different volume concentrations of CH3OH, which was used to adjust the thickness of the vapor sheath. The compositions, morphologies, and thicknesses of ceramic layers formed with different CH3OH concentrations were determined via X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), and scanning electron microscopy (SEM). Corrosion behavior of the oxide films was evaluated in 3.5 wt.% NaCl solution using potentiodynamic polarization tests. PEO coatings mainly comprised Mg, MgO, and Mg2SiO4. The addition of CH3OH in base electrolytes affected the thickness, pores diameter, and Mg2SiO4 content in the films. The films formed in the electrolyte containing 12% CH3OH exhibited the highest thickness. The coatings formed in the electrolyte containing different concentrations of CH3OH exhibited similar corrosion resistance. The energy consumption of PEO markedly decreased upon the addition of CH3OH to the electrolytes. The result is helpful for energy saving in the PEO process. supported by National Natural Science Foundation of China (No. 21376088), the Project of Production, Education and Research, Guangdong Province and Ministry of Education (Nos. 2012B09100063, 2012A090300015), and Guangzhou Science and Technology Plan Projects of China (No. 2014Y2-00042)

Membranes of Polymers of Intrinsic Microporosity (PIM-1) Modified by Poly(ethylene glycol).

PubMed

Bengtson, Gisela; Neumann, Silvio; Filiz, Volkan

2017-06-05

Until now, the leading polymer of intrinsic microporosity PIM-1 has become quite famous for its high membrane permeability for many gases in gas separation, linked, however, to a rather moderate selectivity. The combination with the hydrophilic and low permeable poly(ethylene glycol) (PEG) and poly(ethylene oxides) (PEO) should on the one hand reduce permeability, while on the other hand enhance selectivity, especially for the polar gas CO₂ by improving the hydrophilicity of the membranes. Four different paths to combine PIM-1 with PEG or poly(ethylene oxide) and poly(propylene oxide) (PPO) were studied: physically blending, quenching of polycondensation, synthesis of multiblock copolymers and synthesis of copolymers with PEO/PPO side chain. Blends and new, chemically linked polymers were successfully formed into free standing dense membranes and measured in single gas permeation of N₂, O₂, CO₂ and CH₄ by time lag method. As expected, permeability was lowered by any substantial addition of PEG/PEO/PPO regardless the manufacturing process and proportionally to the added amount. About 6 to 7 wt % of PEG/PEO/PPO added to PIM-1 halved permeability compared to PIM-1 membrane prepared under similar conditions. Consequently, selectivity from single gas measurements increased up to values of about 30 for CO₂/N₂ gas pair, a maximum of 18 for CO₂/CH₄ and 3.5 for O₂/N₂.

Highly CO2-Selective Gas Separation Membranes Based on Segmented Copolymers of Poly(Ethylene oxide) Reinforced with Pentiptycene-Containing Polyimide Hard Segments.

PubMed

Luo, Shuangjiang; Stevens, Kevin A; Park, Jae Sung; Moon, Joshua D; Liu, Qiang; Freeman, Benny D; Guo, Ruilan

2016-01-27

Poly(ethylene oxide) (PEO)-containing polymer membranes are attractive for CO2-related gas separations due to their high selectivity toward CO2. However, the development of PEO-rich membranes is frequently challenged by weak mechanical properties and a high crystallization tendency of PEO that hinders gas transport. Here we report a new series of highly CO2-selective, amorphous PEO-containing segmented copolymers prepared from commercial Jeffamine polyetheramines and pentiptycene-based polyimide. The copolymers are much more mechanically robust than the nonpentiptycene containing counterparts due to the molecular reinforcement mechanism of supramolecular chain threading and interlocking interactions induced by the pentiptycene structures, which also effectively suppresses PEO crystallization leading to a completely amorphous structure even at 60% PEO weight content. Membrane transport properties are sensitively affected by both PEO weight content and PEO chain length. A nonlinear correlation between CO2 permeability with PEO weight content was observed due to the competition between solubility and diffusivity contributions, whereby the copolymers change from being size-selective to solubility-selective when PEO content reaches 40%. CO2 selectivities over H2 and N2 increase monotonically with both PEO content and chain length, indicating strong CO2-philicity of the copolymers. The copolymer film with the longest PEO sequence (PEO2000) and highest PEO weight content (60%) showed a measured CO2 pure gas permeability of 39 Barrer, and ideal CO2/H2 and CO2/N2 selectivities of 4.1 and 46, respectively, at 35 °C and 3 atm, making them attractive for hydrogen purification and carbon capture.

Microhardness and wear resistance of PEO-coated 5754 aluminum alloy

NASA Astrophysics Data System (ADS)

Vyaliy, I. E.; Egorkin, V. S.; Sinebryukhov, S. L.; Minaev, A. N.; Gnedenkov, S. V.

2017-09-01

We present results of the study aimed at assessing the effect of duty cycle (D) during plasma electrolytic oxidation (PEO) on protective properties of the coatings produced on 5754 aluminum alloy. It is shown that increasing the duty cycle of a microsecond current pulses leads to increased hardness and reduced abrasive wear of the PEO-layers, improving mechanical properties. The obtained data allowed confirming, that increasing the amount of energy consumed for coating growth leads to the formation of thicker PEO-layers with improved tribological properties. The effect of duty cycle during plasma electrolytic oxidation on protective properties of the produced coatings was assessed.

Poly(ethylene oxide) Chains Are Not ``Hydrophilic'' When They Exist As Polymer Brush Chains

NASA Astrophysics Data System (ADS)

Lee, Hoyoung; Kim, Dae Hwan; Witte, Kevin N.; Ohn, Kimberly; Choi, Je; Kim, Kyungil; Meron, Mati; Lin, Binhua; Akgun, Bulent; Satija, Sushil; Won, You-Yeon

2012-02-01

By using a combined experimental and theoretical approach, a model poly(ethylene oxide) (PEO) brush system, prepared by spreading a poly(ethylene oxide)-poly(n-butyl acrylate) (PEO-PnBA) amphiphilic diblock copolymer onto an air-water interface, was investigated. The polymer segment density profiles of the PEO brush in the direction normal to the air-water interface under various grafting density conditions were determined from combined X-ray and neutron reflectivity data. In order to achieve a theoretically sound analysis of the reflectivity data, we developed a new data analysis method that uses the self-consistent field theoretical modeling as a tool for predicting expected reflectivity results for comparison with the experimental data. Using this new data analysis method, we discovered that the effective Flory-Huggins interaction parameter of the PEO brush chains is significantly greater than that corresponding to the theta condition, suggesting that contrary to what is more commonly observed for PEO in normal situations, the PEO chains are actually not ``hydrophilic'' when they exist as polymer brush chains, because of the many body interactions forced to be effective in the brush situation.

β-NMR measurements of molecular-scale lithium-ion dynamics in poly(ethylene oxide)-lithium-salt thin films

NASA Astrophysics Data System (ADS)

McKenzie, Iain; Cortie, David L.; Harada, Masashi; Kiefl, Robert F.; Levy, C. D. Philip; MacFarlane, W. Andrew; McFadden, Ryan M. L.; Morris, Gerald D.; Ogata, Shin-Ichi; Pearson, Matthew R.; Sugiyama, Jun

2017-06-01

β -detected NMR (β -NMR) has been used to study the molecular-scale dynamics of lithium ions in thin films of poly(ethylene oxide) (PEO) containing either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium trifluoroacetate (LiTFA) salts at monomer-to-salt ratios (EO/Li) of 8.3. The results are compared with previous β -NMR measurements on pure PEO and PEO with lithium triflate (LiOTf) at the same loading [McKenzie et al., J. Am. Chem. Soc. 136, 7833 (2014)]. Activated hopping of 8Li+ was observed in all of the films above ˜250 K, with the hopping parameters strongly correlated with the ionicity of the lithium salt rather than the polymer glass transition temperature. The pre-exponential factor increases exponentially with ionicity, while the activation energy for hopping increases approximately linearly, going from 6.3 ±0.2 kJ mol-1 in PEO:LiTFA to 17.8 ±0.2 kJ mol-1 in PEO:LiTFSI. The more rapid increase in the pre-exponential factor outweighs the effect of the larger activation energy and results in 8Li+ hopping being fastest in PEO followed by PEO:LiTFSI, PEO:LiOTf, and PEO:LiTFA.

β-NMR measurements of molecular-scale lithium-ion dynamics in poly(ethylene oxide)-lithium-salt thin films.

PubMed

McKenzie, Iain; Cortie, David L; Harada, Masashi; Kiefl, Robert F; Levy, C D Philip; MacFarlane, W Andrew; McFadden, Ryan M L; Morris, Gerald D; Ogata, Shin-Ichi; Pearson, Matthew R; Sugiyama, Jun

2017-06-28

β-detected NMR (β-NMR) has been used to study the molecular-scale dynamics of lithium ions in thin films of poly(ethylene oxide) (PEO) containing either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium trifluoroacetate (LiTFA) salts at monomer-to-salt ratios (EO/Li) of 8.3. The results are compared with previous β-NMR measurements on pure PEO and PEO with lithium triflate (LiOTf) at the same loading [McKenzie et al., J. Am. Chem. Soc. 136, 7833 (2014)]. Activated hopping of 8 Li + was observed in all of the films above ∼250 K, with the hopping parameters strongly correlated with the ionicity of the lithium salt rather than the polymer glass transition temperature. The pre-exponential factor increases exponentially with ionicity, while the activation energy for hopping increases approximately linearly, going from 6.3±0.2 kJ mol -1 in PEO:LiTFA to 17.8±0.2 kJ mol -1 in PEO:LiTFSI. The more rapid increase in the pre-exponential factor outweighs the effect of the larger activation energy and results in 8 Li + hopping being fastest in PEO followed by PEO:LiTFSI, PEO:LiOTf, and PEO:LiTFA.

Detection of Nisin and Fibrinogen Adsorption on Poly(ethylene Oxide) Coated Polyurethane Surfaces by Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS)

PubMed Central

Schilke, Karl F.; McGuire, Joseph

2011-01-01

Stable, pendant polyethylene oxide (PEO) layers were formed on medical-grade Pellethane® and Tygon® polyurethane surfaces, by adsorption and gamma-irradiation of PEO-polybutadiene-PEO triblock surfactants. Coated and uncoated polyurethanes were challenged individually or sequentially with nisin (a small polypeptide with antimicrobial activity) and/or fibrinogen, and then analyzed with time-of-flight secondary ion mass spectrometry (TOF-SIMS). Data reduction by robust principal components analysis (PCA) allowed detection of outliers, and distinguished adsorbed nisin and fibrinogen. Fibrinogen-contacted surfaces, with or without nisin, were very similar on uncoated polymer surfaces, consistent with nearly complete displacement or coverage of previously-adsorbed nisin by fibrinogen. In contrast, nisin-loaded PEO layers remained essentially unchanged upon challenge with fibrinogen, suggesting that the adsorbed nisin is stabilized within the pendant PEO layer, while the peptide-loaded PEO layer retains its ability to repel large proteins. Coatings of PEO loaded with therapeutic polypeptides on medical polymers have the potential to be used to produce anti-fouling and biofunctional surfaces for implantable or blood-contacting devices. PMID:21440897

Characterization of coatings formed on AZX magnesium alloys by plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Anawati, Anawati; Gumelar, Muhammad Dikdik

2018-05-01

Plasma Electrolytic Oxidation (PEO) is an electrochemical anodization process which involves the application of a high voltage to create intense plasma on a metal surface to form a ceramic type of oxide. The resulted coating exhibits high wear resistance and good corrosion barrier which are suitable to enhance the performance of biodegradable Mg alloys. In this work, the role of alloying element Ca in modifying the characteristics of PEO layer formed on AZ61 series magnesium alloys was investigated. PEO treatment was conducted on AZ61, AZX611, and AZX612 alloys in 0.5 M Na3PO4 solution at a constant current of 200 A/m2 at 25°C for 8 min. The resulted coatings were characterized by field emission-scanning electron microscope (FESEM), X-ray diffraction spectroscopy (XRD), and X-ray fluorescence spectroscopy (XRF), as well as hardness test. The presence of alloying element Ca in the AZ61 alloys accelerated the PEO coatings formation without altering the coating properties significantly. The coating formed on AZX specimen was slightly thicker ( 14-17 µm) than that of formed onthe AZ specimens ( 13 µm). Longer exposure time to plasma discharge was the reason for faster thickening of the coating layer on AZX specimen. XRD detected a similar crystalline oxide phase of Mg3(PO4)2 in the oxide formed on all of the specimens. Zn was highly incorporated in the coatings with a concentration in the range 24-30 wt%, as analyzed by XRF. Zn compound might exist in amorphous phases. The microhardness test on the coatings revealed similar average hardness 124 HVon all of the specimens.

Synthesis and energy applications of oriented metal oxide nanoporous films

NASA Astrophysics Data System (ADS)

Wu, Qingliu

This dissertation mainly addresses the synthesis of well-ordered mesoporous titania thin films by dip coating with PEO-PPO-PEO triblock copolymer surfactant template P123. Because P123 is composed of poly(ethylene oxide) [PEO] and poly(propylene oxide) [PPO] blocks, concentrations of ingredients are adjusted to tune the films' wall thickness, pore size and mesophase. Structural changes are consistent with partitioning of species among PEO blocks, PPO blocks, and the PEO/PPO interface. Titanates localize near PEO and increase wall thickness (by 5 nm to 7 nm). Depending on aging temperature, PPG either swells the PPO cores (when it is hydrophobic) or introduces large (>200 nm) voids (when it is hydrophilic but phase separates during heating). 1-butanol localizes at the PEO/PPO interface to favor a 3D hexagonal mesostructure. In another approach, anodizing Ti foils yields vertically aligned titania nanotubes arrays with exceptional stabilities as anodes in lithium ion batteries; they maintain capacities of 130-230 mAhg-1 over 200 cycles. No microstructural changes are induced by battery cycling and good electrical contact is maintained. A diffusion induced stress model suggests that thin-walled nanotubes arrays should be stable under testing conditions, and that ordered hexagonal columnar pore arrays should have both high charge/discharge rates and low stress development. KEY WORDS: materials synthesis, porous, thin film, alternative energy, self-assembly

Novel "anchor modification" of polymeric biomaterial surfaces by the utilization of cyclodextrin inclusion complex supramolecules.

PubMed

Zhao, Xiaobin; Courtney, James M

2009-07-01

In this article, a novel approach for the surface modification of polymeric biomaterials by the utilization of supramolecules was studied. The supramolecules selected were cyclodextrin inclusion complexes (CICs). The biomaterial selected for surface modification was plasticized poly (vinyl chloride) (PVC-P). Results indicate that when the CICs were blended into PVC-P, they tend to migrate and "anchor" on the surface to achieve a remarkable protein-resistant surface, with improved blood compatibility. In comparison with a physical mixture of cyclodextrins and a "guest" molecule, such as poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO and PPO-PEO-PPO for PVC-P modification, CICs modified PVC-P are more consistent in processing and achieve reproducible surface characteristics. Based on this study, a novel "anchor modification" was proposed regarding CICs modified surface. This "anchor modification" is likely to reduce plasticizer extraction from PVC-P and also can be utilized for the modification of polymers other than PVC-P.

Molecular arrangement of symmetric and non-symmetric triblock copolymers of poly(ethylene oxide) and poly(isobutylene) at the air/water interface.

PubMed

Fuchs, Christian; Hussain, Hazrat; Schwieger, Christian; Schulz, Matthias; Binder, Wolfgang H; Kressler, Jörg

2015-01-01

The behavior of a series of amphiphilic triblock copolymers of poly(ethylene oxide) (PEO) and poly(isobutylene) (PIB); including both symmetric (same degree of polymerization (DP) of the terminal PEO blocks) PEOm-b-PIBn-b-PEOm and non-symmetric (different DP of the terminal PEO blocks) PEOm-b-PIBn-b-PEOz, is investigated at the air/water interface by measuring surface pressure vs mean molecular area isotherms (π vs mmA), Langmuir-Blodgett (LB) technique, and infrared reflection-absorption spectroscopy (IRRAS). The block copolymer (PEO32-b-PIB160-b-PEO32) with longer PEO segments forms a stable monolayer and the isotherm reveals a pseudo-plateau starting at π∼5.7 mN/m, also observed in the IRRAS, which is assigned to the pancake-to-brush transition related to the PEO dissolution into the subphase and subsequent PEO brush dehydration. Another plateau is observed at π∼40 mN/m, which is attributed to the film collapse due to multilayer formation. The pancake-to-brush transition could not be observed for samples with smaller PEO chains. The isotherms for block copolymers, with short PEO chains, both symmetric (PEO3-b-PIBn-b-PEO3) and non-symmetric (PEO12-b-PIBn-b-PEO3), reveal another transition at π∼20-25 mN/m. This is interpreted to be due to the conformational transition from a folded state where the middle PIB block is anchored to the water surface at both ends by the terminal hydrophilic segments to an unfolded state with PIB anchored to the water surface at one end. It is assumed that this transition involves the removal of PEO3 chains from the water surface in case of non-symmetric PEO12-b-PIB85-b-PEO3 and in case of symmetric, probably one PEO3 of each PEO3-b-PIB85-b-PEO3 chain. Because of the weaker interaction of the short PEO3 chains with the water surface as compared with the relatively longer PEO12 chains, the film of PEO3-b-PIB85-b-PEO3 collapses at much lower surface pressure after the transition as compared with the PEO12-b-PIB85-b-PEO3. The AFM images reveal the formation of microdomains of almost uniform height (6-7 nm) in LB films of PEO3-b-PIB85-b-PEO3 and PEO12-b-PIB85-b-PEO3 after transferring onto silicon surfaces. These domains are assumed to be the mesomorphic domains of ordered and folded PIB chains. Copyright © 2014 Elsevier Inc. All rights reserved.

Comprehensive two-dimensional liquid chromatographic analysis of poloxamers.

PubMed

Malik, Muhammad Imran; Lee, Sanghoon; Chang, Taihyun

2016-04-15

Poloxamers are low molar mass triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), having number of applications as non-ionic surfactants. Comprehensive one and two-dimensional liquid chromatographic (LC) analysis of these materials is proposed in this study. The separation of oligomers of both types (PEO and PPO) is demonstrated for several commercial poloxamers. This is accomplished at the critical conditions for one of the block while interaction for the other block. Reversed phase LC at CAP of PEO allowed for oligomeric separation of triblock copolymers with regard to PPO block whereas normal phase LC at CAP of PPO renders oligomeric separation with respect to PEO block. The oligomeric separation with regard to PEO and PPO are coupled online (comprehensive 2D-LC) to reveal two-dimensional contour plots by unconventional 2D IC×IC (interaction chromatography) coupling. The study provides chemical composition mapping of both PEO and PPO, equivalent to combined molar mass and chemical composition mapping for several commercial poloxamers. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of PEO molecular weight on the miscibility and dynamics in epoxy/PEO blends.

PubMed

Lu, Shoudong; Zhang, Rongchun; Wang, Xiaoliang; Sun, Pingchuan; Lv, Weifeng; Liu, Qingjie; Jia, Ninghong

2015-11-01

In this work, the effect of poly(ethylene oxide) (PEO) molecular weight in blends of epoxy (ER) and PEO on the miscibility, inter-chain weak interactions and local dynamics were systematically investigated by multi-frequency temperature modulation DSC and solid-state NMR techniques. We found that the molecular weight (M(w)) of PEO was a crucial factor in controlling the miscibility, chain dynamics and hydrogen bonding interactions between PEO and ER. A critical PEO molecular weight (M(crit)) around 4.5k was found. PEO was well miscible with ER when the molecular weight was below M(crit), where the chain motion of PEO was restricted due to strong inter-chain hydrogen bonding interactions. However, for the blends with high molecular weight PEO (M(w) > M(crit)), the miscibility between PEO and ER was poor, and most of PEO chains were considerably mobile. Finally, polarization inversion spin exchange at magic angle (PISEMA) solid-state NMR experiment further revealed the different mobility of the PEO in ER/PEO blends with different molecular weight of PEO at molecular level. Based on the DSC and NMR results, a tentative model was proposed to illustrate the miscibility in ER/PEO blends.

Acceleration of Crystal Growth of Amorphous Griseofulvin by Low-Concentration Poly(ethylene oxide): Aspects of Crystallization Kinetics and Molecular Mobility.

PubMed

Shi, Qin; Zhang, Chen; Su, Yuan; Zhang, Jie; Zhou, Dongshan; Cai, Ting

2017-07-03

This study aims to investigate the crystallization behavior and molecular dynamics of amorphous griseofulvin (GSF) in the presence of low-concentration poly(ethylene oxide) (PEO). We observe that the addition of 3% w/w PEO remarkably increases the crystal growth rate of GSF by two orders of magnitude in both the supercooled liquid and glassy states. The liquid dynamics of amorphous GSF in the presence and absence of PEO are characterized by dielectric spectroscopy. With an increase of the PEO content, the α-relaxation times of the systems decrease, indicating the increase of global molecular mobility. The couplings between molecular mobility and crystallization kinetics of GSF systems show strong time-dependences below T g . The overlapping of α-relaxation times of GSF in presence and absence of PEO as a function of T g /T suggest the "plasticization" effect of PEO additives. However, the crystallization kinetics of amorphous GSF containing low-concentration PEO do not overlap with those of pure GSF on a T g /T scale. The remarkable accelerating effect of crystal growth of amorphous GSF by low-concentration PEO can be partially attributed to the increase of global mobility. The high segmental mobility of PEO is expected to strongly affect the crystal growth rates of GSF. These findings are relevant for understanding and predicting the physical stability of amorphous pharmaceutical solid dispersions.

Dielectric and mechanical investigations on the hydrophilicity and hydrophobicity of polyethylene oxide modified on a silicon surface

DOE PAGES

Shang, Jing; Hong, Kunlun; Wang, Tao; ...

2016-10-02

Here, polyethylene oxide (PEO) has been widely used in biomedical fields. The antibiofouling property of the PEO-modified surface has been extensively investigated but is far from being fully understood. A series of PEOs with narrowly distributed molecular weight (M w), synthesized with the technique of high vacuum anionic polymerization, have been successfully grafted onto the surface of silicon wafers. The power-law relationship between the thickness of the monolayer versus the M w of the grafted PEO shows a scaling of 0.3, indicating compact condensing of the chains. The static contact angles show higher hydrophobicity for the layer of PEO withmore » higher M w, which can be attributed to the closely packed conformation of the chains with high density. The frequency shift of the contact resonance indicates that the Young’s modulus decreases and the loss factor increases with the increase in the M w of PEO and the thickness of the PEO layers. Dielectric spectroscopy of bare or PEO-grafted wafers in the aqueous solutions reveals an interfacial polarization, which results from compositional and structural changes in the interface layer and depends on temperatures and salt concentrations. At a given grafting density, the PEO chains are swollen in pure water, demonstrating hydrophilic behavior, whereas they collapse in salt solutions, showing hydrophobic characteristics.« less

Determination of the surface area of smectite in water by ethylene oxide chain adsorption.

PubMed

Yuang, Paul-Cheng; Shen, Yun-Hwei

2005-05-15

This study investigates the feasibility of using ethylene oxide (EO) chain adsorption to determine the surface area of smectite in water. Experimental results indicate that high-molecular-weight poly(ethylene oxide) (PEO) should be used to provide reasonable estimations for monolayer capacity of PEO on smectite. The surface areas of smectites in water are calculated from the monolayer capacity of PEO adsorbed on smectite by taking the area per EO unit as 8.05 A(2). The method measures the actual surface area of smectite exposed when dispersed in water, which is important to applications of smectite under aqueous conditions.

Protein resistance efficacy of PEO-silane amphiphiles: Dependence on PEO-segment length and concentration

PubMed Central

Rufin, Marc A.; Barry, Mikayla E.; Adair, Paige A.; Hawkins, Melissa L.; Raymond, Jeffery E.; Grunlan, Melissa A.

2016-01-01

In contrast to modification with conventional PEO-silanes (i.e. no siloxane tether), silicones with dramatically enhanced protein resistance have been previously achieved via bulk-modification with poly (ethylene oxide) (PEO)-silane amphiphiles α-(EtO)3Si(CH2)2-oligodimethylsiloxane13-block-PEOn-OCH3 when n = 8 and 16 but not when n = 3. In this work, their efficacy was evaluated in terms of optimal PEO-segment length and minimum concentration required in silicone. For each PEO-silane amphiphile (n = 3, 8, and 16), five concentrations (5, 10, 25, 50, and 100 μmol per 1 g silicone) were evaluated. Efficacy was quantified in terms of the modified silicones’ abilities to undergo rapid, water-driven surface restructuring to form hydrophilic surfaces as well as resistance to fibrinogen adsorption. Only n = 8 and 16 were effective, with a lower minimum concentration in silicone required for n = 8 (10 μmol per 1 g silicone) versus n = 16 (25 μmol per 1 g silicone). Statement of Significance Silicone is commonly used for implantable medical devices, but its hydrophobic surface promotes protein adsorption which leads to thrombosis and infection. Typical methods to incorporate poly(ethylene oxide) (PEO) into silicones have not been effective due to the poor migration of PEO to the surface-biological interface. In this work, PEO-silane amphiphiles – comprised of a siloxane tether (m = 13) and variable PEO segment lengths (n = 3, 8, 16) – were blended into silicone to improve its protein resistance. The efficacy of the amphiphiles was determined to be dependent on PEO length. With the intermediate PEO length (n = 8), water-driven surface restructuring and resulting protein resistance was achieved with a concentration of only 1.7 wt%. PMID:27090588

Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

PubMed

Sun, Che-Nan; Zawodzinski, Thomas A; Tenhaeff, Wyatt E; Ren, Fei; Keum, Jong Kahk; Bi, Sheng; Li, Dawen; Ahn, Suk-Kyun; Hong, Kunlun; Rondinone, Adam J; Carrillo, Jan-Michael Y; Do, Changwoo; Sumpter, Bobby G; Chen, Jihua

2015-03-28

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

Molecular dynamics simulation study of solvent effects on conformation and dynamics of polyethylene oxide and polypropylene oxide chains in water and in common organic solvents.

PubMed

Hezaveh, Samira; Samanta, Susruta; Milano, Giuseppe; Roccatano, Danilo

2012-03-28

In this paper, the conformation and dynamics properties of polyethylene oxide (PEO) and polypropylene oxide (PPO) polymer chains at 298 K have been studied in the melt and at infinite dilution condition in water, methanol, chloroform, carbon tetrachloride, and n-heptane using molecular dynamics simulations. The calculated density of PEO melt with chain lengths of n = 2, 3, 4, 5 and, for PPO, n = 7 are in good agreement with the available experimental data. The conformational properties of PEO and PPO show an increasing gauche preference for the O-C-C-O dihedral in the following order water>methanol>chloroform>carbon tetrachloride = n-heptane. On the contrary, the preference for trans conformation has a maximum in carbon tetrachloride and n-heptane followed in the order by chloroform, methanol, and water. The PEO conformational preferences are in qualitative agreement with results of NMR studies. PEO chains formed different types of hydrogen bonds with polar solvent molecules. In particular, the occurrence of bifurcated hydrogen bonding in chloroform was also observed. Radii of gyration of PEO chains of length larger than n = 9 monomers showed a good agreement with light scattering data in water and in methanol. For the shorter chains the observed deviations are probably due to the enhanced hydrophobic effects caused by the terminal methyl groups. For PEO the fitting of end-to-end distance distributions with the semi-flexible chain model at 298 K provided persistence lengths of 0.375 and 0.387 nm in water and methanol, respectively. Finally, the radius of gyration of Pluronic P85 turned out to be 2.25 ± 0.4 nm at 293 K in water in agreement with experimental data.

Molecular dynamics simulation study of solvent effects on conformation and dynamics of polyethylene oxide and polypropylene oxide chains in water and in common organic solvents

NASA Astrophysics Data System (ADS)

Hezaveh, Samira; Samanta, Susruta; Milano, Giuseppe; Roccatano, Danilo

2012-03-01

In this paper, the conformation and dynamics properties of polyethylene oxide (PEO) and polypropylene oxide (PPO) polymer chains at 298 K have been studied in the melt and at infinite dilution condition in water, methanol, chloroform, carbon tetrachloride, and n-heptane using molecular dynamics simulations. The calculated density of PEO melt with chain lengths of n = 2, 3, 4, 5 and, for PPO, n = 7 are in good agreement with the available experimental data. The conformational properties of PEO and PPO show an increasing gauche preference for the O-C-C-O dihedral in the following order water>methanol>chloroform>carbon tetrachloride = n-heptane. On the contrary, the preference for trans conformation has a maximum in carbon tetrachloride and n-heptane followed in the order by chloroform, methanol, and water. The PEO conformational preferences are in qualitative agreement with results of NMR studies. PEO chains formed different types of hydrogen bonds with polar solvent molecules. In particular, the occurrence of bifurcated hydrogen bonding in chloroform was also observed. Radii of gyration of PEO chains of length larger than n = 9 monomers showed a good agreement with light scattering data in water and in methanol. For the shorter chains the observed deviations are probably due to the enhanced hydrophobic effects caused by the terminal methyl groups. For PEO the fitting of end-to-end distance distributions with the semi-flexible chain model at 298 K provided persistence lengths of 0.375 and 0.387 nm in water and methanol, respectively. Finally, the radius of gyration of Pluronic P85 turned out to be 2.25 ± 0.4 nm at 293 K in water in agreement with experimental data.

Blends of POSS-PEO(n=4)(8) and high molecular weight poly(ethylene oxide) as solid polymer electrolytes for lithium batteries.

PubMed

Zhang, Hanjun; Kulkarni, Sunil; Wunder, Stephanie L

2007-04-12

Solid polymer electrolyte blends were prepared with POSS-PEO(n=4)8 (3K), poly(ethylene oxide) (PEO(600K)), and LiClO4 at different salt concentrations (O/Li = 8/1, 12/1, and 16/1). POSS-PEO(n=4)8/LiClO4 is amorphous at all O/Li investigated, whereas PEO(600K) is amorphous only for O/Li = 8/1 and semicrystalline for O/Li = 12/1 and 16/1. The tendency of PEO(600K) to crystallize limited the amount of POSS-PEO(n=4)(8) that could be incorporated into the blends, so that the greatest incorporation of POSS-PEO(n=4)(8) occurred for O/Li = 8/1. Blends of POSS-PEO(n=4)(8)/PEO(600K)/LiClO4 (O/Li = 8/1 and 12/1) microphase separated into two amorphous phases, a low T(g) phase of composition 85% POSS-PEO(n=4)(8)/15% PEO(600K) and a high T(g) phase of composition 29% POSS-PEO(n=4)(8)/71% PEO(600K). For O/Li = 16/1, the blends contained crystalline (pure PEO(600K)), and two amorphous phases, one rich in POSS-PEO(n=4)(8) and one rich in PEO(600K). Microphase, rather than macrophase separation was believed to occur as a result of Li(+)/ether oxygen cross-link sites. The conductivity of the blends depended on their composition. As expected, crystallinity decreased the conductivity of the blends. For the amorphous blends, when the low T(g) (80/20) phase was the continuous phase, the conductivity was intermediate between that of pure PEO(600K) and POSS-PEO(n=4)(8). When the high T(g) (70/30, 50/50, 30/70, and 20/80) phase was the continuous phase, the conductivity of the blend and PEO(600K) were identical, and lower than that for the POSS-PEO(n=4)(8) over the whole temperature range (10-90 degrees C). This suggests that the motions of the POSS-PEO(n=4)(8) were slowed down by the dynamics of the long chain PEO(600K) and that the minor, low Tg phase was not interconnected and thus did not contribute to enhanced conductivity. At temperatures above T(m) of PEO(600K), addition of the POSS-PEO(n=4)(8) did not result in conductivity improvement. The highest RT conductivity, 8 x 10(-6) S/cm, was obtained for a 60% POSS-PEO(n=4)(8)/40% PEO(600K)/LiClO4 (O/Li = 12/1) blend.

Anomalous Micellization of Pluronic Block Copolymers

NASA Astrophysics Data System (ADS)

Leonardi, Amanda; Ryu, Chang Y.

2014-03-01

Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in- situ formed lanthanide complexes

NASA Astrophysics Data System (ADS)

Wang, Yige; Wang, Li; Li, Huanrong; Liu, Peng; Qin, Dashan; Liu, Binyuan; Zhang, Wenjun; Deng, Ruiping; Zhang, Hongjie

2008-03-01

Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data.

PEO based polymer composite with added acetamide, NaI/I2 as gel polymer electrolyte for dye sensitized solar cell applications

NASA Astrophysics Data System (ADS)

Narasimha Rao, B.; Padma suvarna, R.; Giribabu, L.; Raghavender, M.; kumar, V. Ramesh

2018-02-01

Poly (ethylene oxide) (PEO) based gel polymer electrolytes (GPEs) with added acetamide, NaI/I2 have been prepared for dye-sensitized solar cells application (DSSC). The Dye-sensitized solar cell investigated the performance of the optimized gel polymer electrolyte. GPEs synthesized by adding up of acetamide with different wt% in poly (ethylene oxide) (PEO) and poly (ethylene glycol) dimethyl ether (PEGDME) with NaI/I2. A maximum power conversion efficiency of 5.92% is achieved for PEO/PEGDME with 10 wt% acetamide in the photovoltaic performance under 100 mW/cm2 illumination and it exhibits maximum ionic conductivity (σ = 2.81×10-3 S/cm) among all electrolytes, compared to PEO without acetamide (η = 4.35%). The gain in open circuit voltage (Voc) was observed for GPEs due to the decrease in the recombination effect and electron lifetime increases by the addition of acetamide on the PEO. The fill factor (FF) is increased due to the growth in the ionic conductivity and amorphous nature of the GPE increases by the addition of acetamide on the PEO.

Modification of graphene oxide with amphiphilic double-crystalline block copolymer polyethylene-b-poly(ethylene oxide) with assistance of supercritical CO2 and its further functionalization.

PubMed

Zheng, Xiaoli; Xu, Qun; He, Linghao; Yu, Ning; Wang, Shanshan; Chen, Zhimin; Fu, JianWei

2011-05-19

Graphene oxide (GO) sheets were noncovalently modified with an amphiphilic double-crystalline block copolymer, polyethylene-b-poly(ethylene oxide) (PE-b-PEO) with assistance of supercritical CO(2) (SC CO(2)) in this work. The resulting PE-b-PEO/GO nanohybrids were characterized by transmission electron microscopy (TEM), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), and Raman spectra. Distinct morphologies of PE-b-PEO decorating on the surface of GO were obtained in different solvent systems and at different SC CO(2) pressures. We found that the solvent system and the SC CO(2) have significant influence on the crystallization, aggregation, or assembly behaviors of PE-b-PEO molecular chains on the GO sheets. The formation mechanism of the distinct nanohybrid structures is attributed to a relevant easy heteronucleation and the limited crystal growth of the block polymer on the surface of GO. The resulting modified GO sheets could find a broad spectrum of applications not only in producing graphene-based nanocomposites but also being used as a template to fabricate multifunctional structures due to the unique properties of PE-b-PEO. As a proof-of-concept, we further decorated the GO sheets with the as-prepared Au nanoparticles (Au NPs) and CdTe nanoparticles (CdTe NPs) with PE-b-PEO as the interlinker. Using the thiol-terminated PE-b-PEO as an interlinker, Au NPs can be densely assembled on the surface of GO via robust Au-S bonds. Furthermore, the photoluminescence quenching of CdTe NPs was more notable for PE-b-PEO/GO-CdTe hybrid compared to the GO-CdTe hybrid, suggesting that the electron transfer from the CdTe NPs to the GO sheets was enhanced with the PE-b-PEO interlinker. The availability of these affordable graphene-based multifunctional structures and their fundamental properties will open up new opportunities for nanoscience and nanotechnology and accelerate their applications. © 2011 American Chemical Society

Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

PubMed

Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger

2016-05-01

Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transparent and conductive polyethylene oxide film by the introduction of individualized single-walled carbon nanotubes.

PubMed

Jung, Yong Chae; Muramatsu, Hiroyuki; Park, Ki Chul; Shimamoto, Daisuke; Kim, Jin Hee; Hayashi, Takuya; Song, Sung Moo; Kim, Yoong Ahm; Endo, Morinobu; Dresselhaus, Mildred S

2009-12-16

It is demonstrated that an optically transparent and electrically conductive polyethylene oxide (PEO) film is fabricated by the introduction of individualized single-walled carbon nanotubes (SWNTs). The incorporated SWNTs in the PEO film sustain their intrinsic electronic and optical properties and, in addition, the intrinsic properties of the polymer matrix are retained. The individualized SWNTs with smaller diameter provide high transmittance as well as good electrical conductivity in PEO films. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid nanowire ion-to-electron transducers for integrated bioelectronic circuitry (Conference Presentation)

NASA Astrophysics Data System (ADS)

Carrad, Damon J.; Mostert, Bernard; Meredith, Paul; Micolich, Adam P.

2016-09-01

A key task in bioelectronics is the transduction between ionic/protonic signals and electronic signals at high fidelity. This is a considerable challenge since the two carrier types exhibit intrinsically different physics. We present our work on a new class of organic-inorganic transducing interface utilising semiconducting InAs and GaAs nanowires directly gated with a proton transporting hygroscopic polymer consisting of undoped polyethylene oxide (PEO) patterned to nanoscale dimensions by a newly developed electron-beam lithography process [1]. Remarkably, we find our undoped PEO polymer electrolyte gate dielectric [2] gives equivalent electrical performance to the more traditionally used LiClO4-doped PEO [3], with an ionic conductivity three orders of magnitude higher than previously reported for undoped PEO [4]. The observed behaviour is consistent with proton conduction in PEO. We attribute our undoped PEO-based devices' performance to the small external surface and high surface-to-volume ratio of both the nanowire conducting channel and patterned PEO dielectric in our devices, as well as the enhanced hydration afforded by device processing and atmospheric conditions. In addition to studying the basic transducing mechanisms, we also demonstrate high-fidelity ionic to electronic conversion of a.c. signals at frequencies up to 50 Hz. Moreover, by combining complementary n- and p-type transducers we demonstrate functional hybrid ionic-electronic circuits can achieve logic (NOT operation), and with some further engineering of the nanowire contacts, potentially also amplification. Our device structures have significant potential to be scaled towards realising integrated bioelectronic circuitry. [1] D.J. Carrad et al., Nano Letters 14, 94 (2014). [2] D.J. Carrad et al., Manuscript in preparation (2016). [3] S.H. Kim et al., Advanced Materials 25, 1822 (2013). [4] S.K. Fullerton-Shirey et al., Macromolecules 42, 2142 (2009).

Enhancement of the optical, thermal and electrical properties of PEO/PAM:Li polymer electrolyte films doped with Ag nanoparticles

NASA Astrophysics Data System (ADS)

Morsi, M. A.; El-Khodary, Sherif A.; Rajeh, A.

2018-06-01

Both lithium bromide (LiBr) and biosynthesized silver nanoparticles (Ag NPs) with average size 2-30 nm have been incorporated into the polymeric matrix of polyethylene oxide and polyacrylamide (PEO/PAM) blend by the casting method. FT-IR analysis indicates the formation of hydrogen bond between the blend components. Also, LiBr and Ag NPs interact with the functional groups of PEO/PAM matrix. The results of XRD analysis depict the semi-crystalline nature of these polymer samples and the degree of crystallinity is decreased due to the addition process. The values of optical energy gap from UV-Vis. data are decreased from 3.55 eV for blend to 3.26 for the nanocomposite sample in the indirect transition. LiBr/Ag NPs assist the improvement of the thermal stability of the PEO/PAM blend, as evidenced by TGA and DTA techniques. Upon the addition of LiBr and Ag NPs, an improvement for the conductivity, dielectric permittivity (έ) and dielectric loss (ἕ) of PEO/PAM solid polymer electrolytes are observed. It's clear that the improvement of the electrical conductivity and dielectric parameters for PEO/PAM: Li+/Ag NPs polymer electrolyte system makes it as a promising candidate for solid-state Li battery applications.

On the structural and impedance characteristics of Li- doped PEO, using n-butyl lithium in hexane as dopant

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

Anand, P. B., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in; Jayalekshmi, S., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in

2014-01-28

Nowadays polymer based solid state electrolytes for applications in rechargeable battery systems are highly sought after materials, pursued extensively by various research groups worldwide. Numerous methods are discussed in literature to improve the fundamental properties like electrical conductivity, mechanical stability and interfacial stability of polymer based electrolytes. The application of these electrolytes in Li-ion cells is still in the amateur state, due to low ionic conductivity, low lithium transport number and the processing difficulties. The present work is an attempt to study the effects of Li doping on the structural and transport properties of the polymer electrolyte, poly-ethelene oxide (PEO)more » (Molecular weight: 200,000). Li doped PEO was obtained by treating PEO with n-Butyllithium in hexane for different doping concentrations. Structural characterization of the samples was done by XRD and FTIR techniques. Impedance measurements were carried out to estimate the ionic conductivity of Li doped PEO samples. It is seen that, the crystallinity of the doped PEO decreases on increasing the doping concentration. XRD and FTIR studies support this observation. It is inferred that, ionic conductivity of the sample is increasing on increasing the doping concentration since less crystallinity permits more ionic transport. Impedance measurements confirm the results quantitatively.« less

Dynamics of a poly(ethylene oxide) tracer in a poly(methyl methacrylate) matrix: remarkable decoupling of local and global motions.

PubMed

Haley, Jeffrey C; Lodge, Timothy P

2005-06-15

The tracer diffusion coefficient of unentangled poly(ethylene oxide) (PEO, M=1000 gmol) in a matrix of poly(methyl methacrylate) (PMMA, M=10 000 gmol) has been measured over a temperature range from 125 to 220 degrees C with forced Rayleigh scattering. The dynamic viscosities of blends of two different high molecular weight PEO tracers (M=440 000 and 900 000 gmol) in the same PMMA matrix were also measured at temperatures ranging from 160 to 220 degrees C; failure of time-temperature superposition was observed for these systems. The monomeric friction factors for the PEO tracers were extracted from the diffusion coefficients and the rheological relaxation times using the Rouse model. The friction factors determined by diffusion and rheology were in good agreement, even though the molecular weights of the tracers differed by about three orders of magnitude. The PEO monomeric friction factors were compared with literature data for PEO segmental relaxation times measured directly with NMR. The monomeric friction factors of the PEO tracer in the PMMA matrix were found to be from two to six orders of magnitude greater than anticipated based on direct measurements of segmental dynamics. Additionally, the PEO tracer terminal dynamics are a much stronger function of temperature than the corresponding PEO segmental dynamics. These results indicate that the fastest PEO Rouse mode, inferred from diffusion and rheology, is completely separated from the bond reorientation of PEO detected by NMR. This result is unlike other blend systems in which global and local motions have been compared.

Self-healing effect of the protective inhibitor-containing coatings on Mg alloys

NASA Astrophysics Data System (ADS)

Gnedenkov, A. S.; Sinebryukhov, S. L.; Mashtalyar, D. V.; Gnedenkov, S. V.

2017-09-01

The method of self-healing coating formation on the surface of magnesium alloys on the base of plasma electrolytic oxidation (PEO) with subsequent impregnation of the obtained layer with inhibitor has been suggested. The protective and electrochemical properties of such coatings have been described. Localised Scanning Electrochemical Methods were used for determining the kinetics and mechanism of the self-healing process. The treatment with the solution containing inhibitor enables us to increase the protective properties of the PEO-coating in 30 times in the corrosion-active environment.

Green electrospun grape seed extract-loaded silk fibroin nanofibrous mats with excellent cytocompatibility and antioxidant effect.

PubMed

Lin, Si; Chen, Mengxia; Jiang, Huayue; Fan, Linpeng; Sun, Binbin; Yu, Fan; Yang, Xingxing; Lou, Xiangxin; He, Chuanglong; Wang, Hongsheng

2016-03-01

Silk fibroin (SF) from Bombyx mori has an excellent biocompatibility and thus be widely applied in the biomedical field. Recently, various SF-based composite nanofibers have been developed for more demanding applications. Additionally, grape seed extract (GSE) has been demonstrated to be powerful on antioxidation. In the present study, we dedicate to fabricate a GSE-loaded SF/polyethylene oxide (PEO) composite nanofiber by green electrospinning. Our results indicated the successful loading of GSE into the SF/PEO composite nanofibers. The introduction of GSE did not affect the morphology of the SF/PEO nanofibers and GSE can be released from the nanofibers with a sustained manner. Furthermore, comparing with the raw SF/PEO nanofibrous mats, the GSE-loaded SF/PEO nanofibrous mats significantly enhanced the proliferation of the skin fibroblasts and also protected them against the damage from tert-butyl hydroperoxide-induced oxidative stress. All these findings suggest a promising potential of this novel GSE-loaded SF/PEO composite nanofibrous mats applied in skin care, tissue regeneration and wound healing. Copyright © 2015 Elsevier B.V. All rights reserved.

Filamentous, mixed micelles of triblock copolymers enhance tumor localization of indocyanine green in a murine xenograft model

PubMed Central

Kim, Tae Hee; Mount, Christopher W; Dulken, Benjamin W; Ramos, Jenelyn; Fu, Caroline J; Khant, Htet A; Chiu, Wah; Gombotz, Wayne R; Pun, Suzie H

2012-01-01

Polymeric micelles formed by the self-assembly of amphiphilic block copolymers can be used to encapsulate hydrophobic drugs for tumor-delivery applications. Filamentous carriers with high aspect ratios offer potential advantages over spherical carriers, including prolonged circulation times. In this work, mixed micelles comprised of poly (ethylene oxide)-poly-[(R)-3-hydroxybutyrate]-poly (ethylene oxide) (PEO-PHB-PEO) and Pluronic F-127 (PF-127) were used to encapsulate a near-infrared fluorophore. The micelle formulations were assessed for tumor accumulation after tail vein injection to xenograft tumor-bearing mice by non-invasive optical imaging. The mixed micelle formulation that facilitated the highest tumor accumulation was shown by cryo-electron microscopy to be filamentous in structure compared to spherical structures of pure PF-127 micelles. In addition, increased dye loading efficiency and dye stability was attained in this mixed micelle formulation compared to pure PEO-PHB-PEO micelles. Therefore, the optimized PEO-PHB-PEO/PF-127 mixed micelle formulation offers advantages for cancer delivery over micelles formed from the individual copolymer components. PMID:22118658

The influence of polymer architecture on the assembly of poly(ethylene oxide) grafted C60 fullerene clusters in aqueous solution: a molecular dynamics simulation study.

PubMed

Hooper, Justin B; Bedrov, Dmitry; Smith, Grant D

2009-03-28

The effect of polymer architecture on the aggregation behavior of C60 fullerenes tethered with a single chain of poly(ethylene oxide) (PEO) in aqueous solution has been investigated using coarse-grained, implicit solvent molecular dynamics simulations. The PEO-grafted fullerenes were comprised of a single tether of 60 repeat units represented as a linear polymer, a three-arm star (20 repeat units/arm) or a six-arm star (10 repeat units/arm). Additionally, the influence of arm length on self-assembly of the PEO-fullerene conjugates was investigated for the three-arm stars. Self-assembly is driven by favorable fullerene-fullerene and fullerene-PEO interactions. Our simulations reveal that it should be possible to control the size and geometry of the self-assembled fullerene aggregates in water through variation of PEO architecture and PEO molecular weight. We found that aggregate size and shape could be understood qualitatively in terms of the packing parameter concept that has been employed for diblock polymer and surfactant self-assembly. Higher molecular weight PEO (longer arms) and more compact PEO (more arms for the same molecular weight) resulted in greater steric repulsion between fullerenes, engendering greater aggregate surface curvature and hence the formation of smaller, more spherically shaped aggregates. Finally, weak attractive interactions between PEO and the fullerenes were found to play an important role in determining aggregate shape, size and the dynamics of self-assembly.

Formation of a Spinel Coating on AZ31 Magnesium Alloy by Plasma Electrolytic Oxidation

NASA Astrophysics Data System (ADS)

Sieber, Maximilian; Simchen, Frank; Scharf, Ingolf; Lampke, Thomas

2016-03-01

Plasma electrolytic oxidation (PEO) is a common means for the surface modification of light metals. However, PEO of magnesium substrates in dilute electrolytes generally leads to the formation of coatings consisting of unfavorable MgO magnesium oxide. By incorporation of electrolyte components, the phase constitution of the oxide coatings can be modified. Coatings consisting exclusively of MgAl2O4 magnesium-aluminum spinel are produced by PEO in an electrolyte containing hydroxide, aluminate, and phosphate anions. The hardness of the coatings is 3.5 GPa on Martens scale on average. Compared to the bare substrate, the coatings reduce the corrosion current density in dilute sodium chloride solution by approx. one order of magnitude and slightly shift the corrosion potential toward more noble values.

Effects of Current Density on Microstructure and Corrosion Property of Coating on AZ31 Mg Alloy Processed via Plasma Electrolytic Oxidation

NASA Astrophysics Data System (ADS)

Lee, Kang Min; Einkhah, Feryar; Sani, Mohammad Ali Faghihi; Ko, Young Gun; Shin, Dong Hyuk

The effects of the current density on the micro structure and the corrosion property of the coating on AZ31 Mg alloy processed by the plasma electrolytic oxidation (PEO) were investigated. The present coatings were produced in an acid electrolyte containing K2ZrF6 with three different current densities, i.e., 100, 150, and 200 mA/cm2. From the microstructural observations, as the applied current density was increased, the diameter of micro-pores formed by the plasma discharges with high temperature increased. The coatings on AZ31 Mg alloy were mainly composed of MgO, ZrO2, MgF2, and Mg2Zr5O12 phases. The results of potentiodynamic polarization clearly showed that the PEO-treated AZ31 Mg alloy applied at 100 mA/cm2 of current density exhibited better corrosion properties than the others.

Nanostructure of propylammonium nitrate in the presence of poly(ethylene oxide) and halide salts

NASA Astrophysics Data System (ADS)

Stefanovic, Ryan; Webber, Grant B.; Page, Alister J.

2018-05-01

Nanoscale structure of protic ionic liquids is critical to their utility as molecular electrochemical solvents since it determines the capacity to dissolve salts and polymers such as poly(ethylene oxide) (PEO). Here we use quantum chemical molecular dynamics simulations to investigate the impact of dissolved halide anions on the nanostructure of an archetypal nanostructured protic ionic liquid, propylammonium nitrate (PAN), and how this impacts the solvation of a model PEO polymer. At the molecular level, PAN is nanostructured, consisting of charged/polar and uncharged/nonpolar domains. The charged domain consists of the cation/anion charge groups, and is formed by their electrostatic interaction. This domain solvophobically excludes the propyl chains on the cation, which form a distinct, self-assembled nonpolar domain within the liquid. Our simulations demonstrate that the addition of Cl- and Br- anions to PAN disrupts the structure within the PAN charged domain due to competition between nitrate and halide anions for the ammonium charge centre. This disruption increases with halide concentration (up to 10 mol. %). However, at these concentrations, halide addition has little effect on the structure of the PAN nonpolar domain. Addition of PEO to pure PAN also disrupts the structure within the charged domain of the liquid due to hydrogen bonding between the charge groups and the terminal PEO hydroxyl groups. There is little other association between the PEO structure and the surrounding ionic liquid solvent, with strong PEO self-interaction yielding a compact, coiled polymer morphology. Halide addition results in greater association between the ionic liquid charge centres and the ethylene oxide components of the PEO structure, resulting in reduced conformational flexibility, compared to that observed in pure PAN. Similarly, PEO self-interactions increase in the presence of Cl- and Br- anions, compared to PAN, indicating that the addition of halide salts to PAN decreases its utility as a molecular solvent for polymers such as PEO.

In vitro degradation behavior and cytocompatibility of biodegradable AZ31 alloy with PEO/HT composite coating.

PubMed

Tian, Peng; Liu, Xuanyong; Ding, Chuanxian

2015-04-01

Biodegradable magnesium-based implants have attracted much attention recently in orthopedic applications because of their good mechanical properties and biocompatibility. However, their rapid degradation in vivo will not only reduce their mechanical strength, but also induce some side effects, such as local alkalization and gas cavity, which may lead to a failure of the implant. In this work, a hydroxyapatite (HA) layer was prepared on plasma electrolytic oxidization (PEO) coating by hydrothermal treatment (HT) to fabricate a PEO/HT composite coating on biodegradable AZ31 alloy. The in vitro degradation behaviors of all samples were evaluated in simulated body fluid (SBF) and their surface cytocompatibility was also investigated by evaluating the adhesion and proliferation of osteoblast cells (MC3T3-E1). The results showed that the HA layer consisted of a dense inner layer and a needle-like outer layer, which successfully sealed the PEO coating. The in vitro degradation tests showed that the PEO/HT composite coating improved the corrosion resistance of AZ31 alloy in SBF, presenting nearly no severe local alkalization and hydrogen evolution. The lasting corrosion resistance of the PEO/HT composite coating may attribute to the new hydroxyapatite formation during the degradation process. Moreover, compared with AZ31 alloy and PEO coating, PEO/HT composite coating was more suitable for cells adhesion and proliferation, indicating improved surface cytocompatibility. The results show that the PEO/HT composite coating is promising as protective coating on biodegradable magnesium-based implants to enhance their corrosion resistance as well as improve their surface cytocompatibility for orthopedic applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation, characterization, in vitro drug release, and cellular interactions of tailored paclitaxel releasing polyethylene oxide films for drug-coated balloons.

PubMed

Anderson, Jordan A; Lamichhane, Sujan; Remund, Tyler; Kelly, Patrick; Mani, Gopinath

2016-01-01

Drug-coated balloons (DCBs) are used to treat various cardiovascular diseases. Currently available DCBs carry drug on the balloon surface either solely or using different carriers. Several studies have shown that a significant amount of drug is lost in the blood stream during balloon tracking to deliver only a sub-therapeutic level of drug at the treatment site. This research is focused on developing paclitaxel (PAT) loaded polyethylene oxide (PEO) films (PAT-PEO) as a controlled drug delivery carrier for DCBs. An array of PAT-PEO films were developed in this study to provide tailored release of >90% of drug only at specific time intervals, which is the time frame required for carrying out balloon-based therapy. The characterizations of PAT-PEO films using SEM, FTIR, and DSC showed that the films developed were homogenous and the PAT was molecularly dispersed in the PEO matrix. Mechanical tests showed that most PAT-PEO films developed were flexible and ductile, with yield and tensile strengths not affected after PAT incorporation. The viability, proliferation, morphology, and phenotype of smooth muscle cells (SMCs) interacted with control-PEO and PAT-PEO films were investigated. All control-PEO and PAT-PEO films showed a significant inhibitory effect on the growth of SMCs, with the degree of inhibition strongly dependent on the w/v% of the polymer used. The PAT-PEO coating was produced on the balloons. The integrity of PAT-PEO coating was well maintained without any mechanical defects occurring during balloon inflation or deflation. The drug release studies showed that only 15% of the total PAT loaded was released from the balloons within the initial 1min (typical balloon tracking time), whereas 80% of the PAT was released between 1min and 4min (typical balloon treatment time). Thus, this study demonstrated the use of PEO as an alternate drug delivery system for the balloons. Atherosclerosis is primarily responsible for cardiovascular diseases (CVDs) in millions of patients every year. Drug-coated balloons (DCBs) are commonly used to treat various CVDs. However, in several currently used DCBs, a significant amount of drug is lost in the blood stream during balloon tracking to deliver only a sub-therapeutic level of drug at the treatment site. In this study, paclitaxel containing polyethylene oxide (PEO) films were developed to provide unique advantages including drug release profiles specifically tailored for balloon-based therapy, homogeneous films with molecularly dispersed drug, flexible and ductile films, and exhibits significant inhibitory effect on smooth muscle cell growth. Thus, this study demonstrated the use of PEO as an alternate drug delivery platform for DCBs to improve its efficacy. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effect of DC Plasma Electrolytic Oxidation on Surface Characteristics and Corrosion Resistance of Zirconium

PubMed Central

Sowa, Maciej

2018-01-01

Zr is a valve metal, the biocompatibility of which is at least on par with Ti. Recently, numerous attempts of the formation of bioactive coatings on Zr by plasma electrolytic oxidation (PEO) in solutions that were based on calcium acetate and calcium β-glycerophosphate were made. In this study, the direct current (DC) PEO of commercially pure zirconium in the solutions that contained Ca(H2PO2)2, Ca(HCOO)2, and Mg(CH3COO)2 was investigated. The treatment was conducted at 75 mA/cm2 up to 200, 300, or 400 V. Five process stages were discerned. The treatment at higher voltages resulted in the formation of oxide layers that had Ca/P or (Mg+Ca)/P ratios that were close to that of hydroxyapatite (Ca/P = 1.67), determined by SEM/EDX. The corrosion resistance studies were performed using electrochemical impedance spectroscopy (EIS) and DC polarization methods. R(Q[R(QR)]) circuit model was used to fit the EIS data. In general, the coatings that were obtained at 200 V were the most corrosion resistant, however, they lacked the porous structure, which is typical for PEO coatings, and is sought after in the biomedical applications. The treatment at 400 V resulted in the formation of the coatings that were more corrosion resistant than those that were obtained at 300 V. This was determined mainly by the prevailing plasma regime at the given process voltage. The pitting resistance of Zr was also improved by the treatment, regardless of the applied process conditions. PMID:29751530

Electrochemical Impedance and Polarization Corrosion Studies of Tantalum Surface Modified by DC Plasma Electrolytic Oxidation

PubMed Central

Sowa, Maciej

2018-01-01

Tantalum has recently become an actively researched biomaterial for the bone reconstruction applications because of its excellent corrosion resistance and successful clinical records. However, a bare Ta surface is not capable of directly bonding to the bone upon implantation and requires some method of bioactivation. In this study, this was realized by direct current (DC) plasma electrolytic oxidation (PEO). Susceptibility to corrosion is a major factor determining the service-life of an implant. Therefore, herein, the corrosion resistance of the PEO coatings on Ta was investigated in Ringer’s solution. The coatings were formed by galvanostatic anodization up to 200, 300 and 400 V, after which the treatment was conducted potentiostatically until the total process time amounted to 5 min. Three solutions containing Ca(H2PO2)2, Ca(HCOO)2 and Mg(CH3COO)2 were used in the treatment. For the corrosion characterization, electrochemical impedance spectroscopy and potentiodynamic polarization techniques were chosen. The coatings showed the best corrosion resistance at voltages low enough so that the intensive sparking was absent, which resulted in the formation of thin films. The impedance data were fitted to the equivalent electrical circuits with two time constants, namely R(Q[R(QR)]) and R(Q[R(Q[RW])]). The inclusion of W in the circuit helped to fit the low-frequency part of the samples PEO-ed at 400 V, hinting at the important role of diffusion in the corrosion resistance of the PEO coatings described in the research. PMID:29614014

Interchain coupled chain dynamics of poly(ethylene oxide) in blends with poly(methyl methacrylate): coupling model analysis.

PubMed

Ngai, K L; Wang, Li-Min

2011-11-21

Quasielastic neutron scattering and molecular dynamics simulation data from poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends found that for short times the self-dynamics of PEO chain follows the Rouse model, but at longer times past t(c) = 1-2 ns it becomes slower and departs from the Rouse model in dependences on time, momentum transfer, and temperature. To explain the anomalies, others had proposed the random Rouse model (RRM) in which each monomer has different mobility taken from a broad log-normal distribution. Despite the success of the RRM, Diddens et al. [Eur. Phys. Lett. 95, 56003 (2011)] extracted the distribution of friction coefficients from the MD simulations of a PEO/PMMA blend and found that the distribution is much narrower than expected from the RRM. We propose a simpler alternative explanation of the data by utilizing alone the observed crossover of PEO chain dynamics at t(c). The present problem is just a special case of a general property of relaxation in interacting systems, which is the crossover from independent relaxation to coupled many-body relaxation at some t(c) determined by the interaction potential and intermolecular coupling/constraints. The generality is brought out vividly by pointing out that the crossover also had been observed by neutron scattering from entangled chains relaxation in monodisperse homopolymers, and from the segmental α-relaxation of PEO in blends with PMMA. The properties of all the relaxation processes in connection with the crossover are similar, despite the length scales of the relaxation in these systems are widely different.

Interchain coupled chain dynamics of poly(ethylene oxide) in blends with poly(methyl methacrylate): Coupling model analysis

NASA Astrophysics Data System (ADS)

Ngai, K. L.; Wang, Li-Min

2011-11-01

Quasielastic neutron scattering and molecular dynamics simulation data from poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends found that for short times the self-dynamics of PEO chain follows the Rouse model, but at longer times past tc = 1-2 ns it becomes slower and departs from the Rouse model in dependences on time, momentum transfer, and temperature. To explain the anomalies, others had proposed the random Rouse model (RRM) in which each monomer has different mobility taken from a broad log-normal distribution. Despite the success of the RRM, Diddens et al. [Eur. Phys. Lett. 95, 56003 (2011)] extracted the distribution of friction coefficients from the MD simulations of a PEO/PMMA blend and found that the distribution is much narrower than expected from the RRM. We propose a simpler alternative explanation of the data by utilizing alone the observed crossover of PEO chain dynamics at tc. The present problem is just a special case of a general property of relaxation in interacting systems, which is the crossover from independent relaxation to coupled many-body relaxation at some tc determined by the interaction potential and intermolecular coupling/constraints. The generality is brought out vividly by pointing out that the crossover also had been observed by neutron scattering from entangled chains relaxation in monodisperse homopolymers, and from the segmental α-relaxation of PEO in blends with PMMA. The properties of all the relaxation processes in connection with the crossover are similar, despite the length scales of the relaxation in these systems are widely different.

Molecular dynamics study of the diffusivity of a hydrophobic drug Cucurbitacin B in pseudo-poly(ethylene oxide-b-caprolactone) micelle environments.

PubMed

Razavilar, Negin; Choi, Phillip

2014-07-08

Isobaric-isothermal molecular dynamics simulation was used to study the diffusion of a hydrophobic drug Cucurbitacin B (CuB) in pseudomicelle environments consisting of poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) swollen by various amounts of water. Two PEO-b-PCL configurations, linear and branched, with the same total molecular weight were used. For the branched configuration, the block copolymer contained one linear block of PEO with the same molecular weight as that of the PEO block used in the linear configuration but with one end connecting to three PCL blocks with the same chain length, hereafter denoted PEO-b-3PCL. Regardless of the configuration, the simulation results showed that the diffusivity of CuB was insensitive to the water concentration up to ∼8 wt % while that of water decreased with an increasing water concentration. The diffusivity of CuB (10(-8) cm(2)/s) was 3 orders of magnitude lower than that of water (10(-5) cm(2)/s). This is attributed to the fact that CuB relied on the wiggling motion of the block copolymers to diffuse while water molecules diffused via a hopping mechanism. The rates at which CuB and water diffused into PEO-b-PCL were twice those in PEO-b-3PCL because the chain mobility and the degree of swelling are higher and there are fewer intermolecular hydrogen bonds in the case of PEO-b-PCL. The velocity autocorrelation functions of CuB show that the free volume holes formed by PEO-b-3PCL are more rigid than those formed by PEO-b-PCL, making CuB exhibit higher-frequency collision motion in PEO-b-3PCL than in PEO-b-PCL, and the difference in frequency is insensitive to water concentration.

Polystyrene-block-poly(ethylene oxide) copolymers as templates for stacked, spherical large-mesopore silica coatings: dependence of silica pore size on the PS/PEO ratio

PubMed Central

Magnacca, Giuliana; Jadhav, Sushilkumar A; Scalarone, Dominique

2016-01-01

Summary Large-mesopore silica films with a narrow pore size distribution and high porosity have been obtained by a sol–gel reaction of a silicon oxide precursor (TEOS) and using polystyrene-block-poly(ethylene oxide) (PS-b-PEO) copolymers as templates in an acidic environment. PS-b-PEO copolymers with different molecular weight and composition have been studied in order to assess the effects of the block length on the pore size of the templated silica films. The changes in the morphology of the porous systems have been investigated by transmission electron microscopy and a systematic analysis has been carried out, evidencing the dependence between the hydrophilic/hydrophobic ratio of the two polymer blocks and the size of the final silica pores. The obtained results prove that by tuning the PS/PEO ratio, the pore size of the templated silica films can be easily and finely predicted. PMID:27826520

Formyl-ended heterobifunctional poly(ethylene oxide): synthesis of poly(ethylene oxide) with a formyl group at one end and a hydroxyl group at the other end.

PubMed

Nagasaki, Y; Kutsuna, T; Iijima, M; Kato, M; Kataoka, K; Kitano, S; Kadoma, Y

1995-01-01

Well-defined poly(ethylene oxide) (PEO) with a formyl group at one end and a hydroxyl group at the other terminus was synthesized by the anionic ring opening polymerization of ethylene oxide (EO) with a new organometallic initiator possessing an acetal moiety, potassium 3,3-diethoxypropyl alkoxide. Hydrolysis of the acetal moiety produced a formyl group-terminated heterobifunctional PEO with a hydroxyl group at the other end.

Study on Microstructure and Electrochemical Corrosion Behavior of PEO Coatings Formed on Aluminum Alloy

NASA Astrophysics Data System (ADS)

Xiang, N.; Song, R. G.; Li, H.; Wang, C.; Mao, Q. Z.; Xiong, Y.

2015-12-01

Plasma electrolytic oxidation (PEO) treated 6063 aluminum alloy was applied in a silicate- and borate-based alkaline solution. The microstructure and electrochemical corrosion behavior were studied by scanning electron microscopy, electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization techniques. The results showed that the silicate-based PEO coating was of a denser structure compared with that of borate-based PEO coating. In addition, the silicate-based PEO coating was composed of more phased (Al9Si) than borate-based PEO coating. The results of corrosion test indicated that the silicate-based PEO coating provided a superior protection to 6063 aluminum alloy substrate, while borate-based PEO coating with a porous structure showed an inferior conservancy against corrosive electrolyte. Furthermore, the EIS tests proved that both coatings were capable to resist the aggressive erosion in 0.5 M NaCl solution after 72 h of immersion. However, the borate-based PEO coating could not provide sufficient protection to the substrate after 72-h immersion in 1 M NaCl solution.

Morphology and conductivity of PEO-based polymers having various end functional groups

NASA Astrophysics Data System (ADS)

Jung, Ha Young; Mandal, Prithwiraj; Park, Moon Jeong

Poly(ethylene oxide) (PEO)-based polymers have been considered most promising candidates of polymer electrolytes for lithium batteries owing to the high ionic conductivity of PEO/lithium salt complexes. This positive aspect prompted researchers to investigate PEO-containing block copolymers prepared by linking mechanically robust block to PEO covalently. Given that the microphase separation of block copolymers can affect both mechanical properties and ion transport properties, various strategies have been reported to tune the morphology of PEO-containing block copolymers. In the present study, we describe a simple means for modulating the morphologies of PEO-based block copolymers with an aim to improve ion transport properties. By varying terminal groups of PEO in block copolymers, the disordered morphology can be readily transformed into ordered lamellae or gyroid phases, depending on the type and number density of end group. In particular, the existence of terminal groups resulted in a large reduction in crystallinity of PEO chains and thereby increasing room temperature ionic conductivity.

W-containing oxide layers obtained on aluminum and titanium by PEO as catalysts in thiophene oxidation

NASA Astrophysics Data System (ADS)

Rudnev, V. S.; Lukiyanchuk, I. V.; Vasilyeva, M. S.; Morozova, V. P.; Zelikman, V. M.; Tarkhanova, I. G.

2017-11-01

W-containing oxide layers fabricated on titanium and aluminum alloys by Plasma electrolytic oxidation (PEO) have been tested in the reaction of the peroxide oxidation of thiophene. Samples with two types of coatings have been investigated. Coatings I contained tungsten oxide in the matrix and on the surface of amorphous silica-titania or silica-alumina layers, while coatings II comprised crystalline WO3 and/or Al2(WO4)3. Aluminum-supported catalyst containing a smallest amount of transition metals in the form of tungsten oxides and manganese oxides in low oxidation levels showed high activity and stability.

Achieving surface chemical and morphologic alterations on tantalum by plasma electrolytic oxidation.

PubMed

Goularte, Marcelo Augusto Pinto Cardoso; Barbosa, Gustavo Frainer; da Cruz, Nilson Cristino; Hirakata, Luciana Mayumi

2016-12-01

Search for materials that may either replace titanium dental implants or constitute an alternative as a new dental implant material has been widely studied. As well, the search for optimum biocompatible metal surfaces remains crucial. So, the aim of this work is to develop an oxidized surface layer on tantalum using plasma electrolytic oxidation (PEO) similar to those existing on oral implants been marketed today. Cleaned tantalum samples were divided into group 1 (control) and groups 2, 3, and 4 (treated by PEO for 1, 3, and 5 min, respectively). An electrolytic solution diluted in 1-L deionized water was used for the anodizing process. Then, samples were washed with anhydrous ethyl alcohol and dried in the open air. For complete anodic treatment disposal, the samples were immersed in acetone altogether, taken to the ultrasonic tank for 10 min, washed again in distilled water, and finally air-dried. For the scanning electron microscopy (SEM) analysis, all samples were previously coated with gold; the salt deposition analysis was conducted with an energy-dispersive X-ray spectroscopy (EDS) system integrated with the SEM unit. SEM images confirmed the changes on tantalum strips surface according to different exposure times while EDS analysis confirmed increased salt deposition as exposure time to the anodizing process also increased. PEO was able to produce both surface alteration and salt deposition on tantalum strips similar to those existing on oral implants been marketed today.

Apatite grown in niobium by two-step plasma electrolytic oxidation.

PubMed

Pereira, Bruno Leandro; Lepienski, Carlos Maurício; Mazzaro, Irineu; Kuromoto, Neide Kazue

2017-08-01

Plasma electrolytic oxidation (PEO) of niobium plates were done electrochemically in two steps with electrolytes containing phosphorous and calcium being observed the formation of crystalline apatite. All samples were submitted to a first step of PEO using an electrolyte containing phosphate ions. The second oxidization step was made using three different electrolytes. Some samples were oxidized by PEO in electrolyte containing calcium, while in other samples it was used two mixtures of phosphoric acid and calcium acetate monohydrate solutions. Three different surface layers were obtained. The morphology and chemical composition of the films were analyzed by scanning electronic microscopy (SEM), and energy dispersive spectroscopy (EDS) respectively. It was observed that all samples submitted to two-step oxidation shown porous surface and a calcium and phosphorus rich layer. Average surface roughness (Ra) was measured by a profilometer remaining in the sub-micrometric range. The contact angle by sessile drop technique, using 1μL of distilled water was performed with an optical goniometer. It was verified a higher hydrophilicity in all surfaces compared to the polished niobium. Orthorhombic Nb 2 O 5 was identified by XRD in the oxide layer. Crystalline apatite was identified by XRD in surfaces after the second oxidation made with the Ca-rich electrolyte and a mixture of an electrolyte richer in Ca compared to P. These results indicate that a two-step oxidized niobium surface present great features for applications in the osseointegration processes: favorable chemical composition that increase the biocompatibility, the formation of crystalline niobium pentoxide (orthorhombic), high hydrophilicity and formation of crystalline calcium phosphate (apatite) under adequate electrolyte composition. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular dynamics simulations of poly (ethylene oxide) hydration and conformation in solutions

NASA Astrophysics Data System (ADS)

Dahal, Udaya; Dormidontova, Elena

Polyethylene oxide (PEO) is one of the most actively used polymers, especially in biomedical applications due to its high hydrophilicity, biocompatibility and potency to inhibit protein adsorption. PEO solubility and conformation in water depends on its capability to form hydrogen bonds. Using atomistic molecular dynamics simulations we investigated the details of water packing around PEO chain and characterized the type and lifetime of hydrogen bonds in aqueous and mixed solvent solutions. The observed polymer chain conformation varies from an extended coil in pure water to collapsed globule in hexane and a helical-like conformation in pure isobutyric acid or isobutyric acid -water mixture in agreement with experimental observations. We'll discuss the implications of protic solvent arrangement and stability of hydrogen bonds on PEO chain conformation and mobility. This research is supported by NSF (DMR-1410928).

Polyethylene Oxide (PEO) and Polyethylene Glycol (PEG) Polymer Sieving Matrix for RNA Capillary Electrophoresis

PubMed Central

Yamaguchi, Yoshinori; Li, Zhenqing; Zhu, Xifang; Liu, Chenchen; Zhang, Dawei; Dou, Xiaoming

2015-01-01

The selection of sieving polymer for RNA fragments separation by capillary electrophoresis is imperative. We investigated the separation of RNA fragments ranged from 100 to 10,000 nt in polyethylene glycol (PEG) and polyethylene oxide (PEO) solutions with different molecular weight and different concentration. We found that the separation performance of the small RNA fragments (<1000 nt) was improved with the increase of polymer concentration, whereas the separation performance for the large ones (>4000 nt) deteriorated in PEG/PEO solutions when the concentration was above 1.0%/0.6%, respectively. By double logarithmic plot of mobility and RNA fragment size, we revealed three migration regimes for RNA in PEG (300-500k) and PEO (4,000k). Moreover, we calculated the smallest resolvable nucleotide length (N min) from the resolution length analysis. PMID:25933347

Miscibility of poly(lactic acid) and poly(ethylene oxide) solvent polymer blends and nanofibers made by solution blow spinning

USDA-ARS?s Scientific Manuscript database

The miscibility of blends of poly(lactic acid) (PLA) and poly(ethylene oxide) (PEO) was studied in polymer solutions by dilute solution viscometry and in solution blow spun nanofibers by microscopy (SEM, TEM) and by thermal and spectral analysis. Three blends of PLA and PEO were solution blended in...

Comparison between Cellulose Nanocrystal and Cellulose Nanofibril Reinforced Poly(ethylene oxide) Nanofibers and Their Novel Shish-Kebab-Like Crystalline Structures

Treesearch

Xuezhu Xu; Haoran Wang; Long Jiang; Xinnan Wang; Scott A. Payne; J.Y. Zhu; Ruipeng Li

2014-01-01

Poly(ethylene oxide) (PEO) nanofiber mats were produced by electrospinning. Biobased cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) as reinforcement nanofillers were also added to the polymer to produce composite nanofiber mats. The effects of the two cellulose nanofillers on the rheological properties of the PEO solutions and the microstructure,...

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Antibacterial electrospun chitosan-polyethylene oxide nanocomposite mats containing ZIF-8 nanoparticles.

PubMed

Kohsari, Iraj; Shariatinia, Zahra; Pourmortazavi, Seied Mahdi

2016-10-01

Antimicrobial chitosan-polyethylene oxide (CS-PEO) nanofiber mats loaded with 3, 5 and 10% (w/w) of zeolitic imidazolate framework-8 nanoparticles (ZIF-8 NPs, ∼60nm diameter) were developed by electrospinning technique. The CS-PEO-GA-3% ZIF-8 NPs crosslinked with glutaraldehyde (GA) vapor was also prepared. The electrospun mats were characterized by various analysis including FE-SEM, EDAX, elemental mapping, FT-IR, contact angle, TGA/DSC as well as tensile strength analysis. The nanofibers had average diameters within the range ∼70-120nm. Antimicrobial activities of the CS-PEO and CS-PEO-3% ZIF-8 mats were evaluated by the viable cell-counting method for determining their effectiveness in reducing or halting the growth of Staphylococcus aureus and Escherichia coli bacteria so that the CS-PEO mat containing 3% ZIF-8 revealed 100% bactericidal activity against both kinds of bacteria. The crosslinked CS-PEO-GA-3% ZIF-8 NPs sample was less thermally stable but more hydrophilic than its related non-crosslinked mat reflecting there was no need to crosslink the fibers using a chemical crosslinker having adverse effects. The highest hydrophobicity and appropriate thermal and tensile properties of CS-PEO-3% ZIF-8 NPs among those of the mats including 5 and 10% ZIF-8 NPs suggested that the mentioned mat is the most suitable sample for food coating applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Plasma Electrolytic Oxidation of Titanium Implant Surfaces: Microgroove-Structures Improve Cellular Adhesion and Viability.

PubMed

Hartjen, Philip; Hoffmann, Alexia; Henningsen, Anders; Barbeck, Mike; Kopp, Alexander; Kluwe, Lan; Precht, Clarissa; Quatela, Olivia; Gaudin, Robert; Heiland, Max; Friedrich, Reinhard E; Knipfer, Christian; Grubeanu, Daniel; Smeets, Ralf; Jung, Ole

2018-01-01

Plasma electrolytic oxidation (PEO) is an established electrochemical treatment technique that can be used for surface modifications of metal implants. In this study we to treated titanium implants with PEO, to examine the resulting microstructure and to characterize adhesion and viability of cells on the treated surfaces. Our aim was to identify an optimal surface-modification for titanium implants in order to improve soft-tissue integration. Three surface-variants were generated on titanium alloy Ti6Al4V by PEO-treatment. The elemental composition and the microstructures of the surfaces were characterized using energy dispersive X-ray spectroscopy, scanning electron microscopy and profilometry. In vitro cytocompatibility of the surfaces was assessed by seeding L929 fibroblasts onto them and measuring the adhesion, viability and cytotoxicity of cells by means of live/dead staining, XTT assay and LDH assay. Electron microscopy and profilometry revealed that the PEO-surface variants differed largely in microstructure/topography, porosity and roughness from the untreated control material as well as from one another. Roughness was generally increased after PEO-treatment. In vitro, PEO-treatment led to improved cellular adhesion and viability of cells accompanied by decreased cytotoxicity. PEO-treatment provides a promising strategy to improve the integration of titanium implants with surrounding tissues. Copyright© 2018, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

Relationship between morphological change and crystalline phase transitions of polyethylene-poly(ethylene oxide) diblock copolymers, revealed by the temperature-dependent synchrotron WAXD/SAXS and infrared/Raman spectral measurements.

PubMed

Weiyu, Cao; Tashiro, Kohji; Hanesaka, Makoto; Takeda, Shinichi; Masunaga, Hiroyasu; Sasaki, Sono; Takata, Masaki

2009-02-26

The phase transition behaviors of low-molecular-weight polyethylene-poly(ethylene oxide) (PE-b-PEO) diblock copolymers with the monomeric units of PE/PEO = 17/40 and 39/86 have been successfully investigated through the temperature-dependent measurements of wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), infrared and Raman spectra, as well as thermal analysis. These diblock copolymers had been believed to show only order-to-disorder transition of lamellar morphology in a wide temperature region, but it has been found here for the first time that this copolymer clearly exhibits the three stages of transitions among lamella, gyroid, cylinder, and spherical phases in the heating and cooling processes. The WAXD and IR/Raman spectral measurements allowed us to relate these morphological changes to the microscopic changes in the aggregation states of PEO and PE segments. In the low-temperature region the PEO segments form the monoclinic crystal of (7/2) helical chain conformation and the PE segments of planar-zigzag form take the orthorhombic crystalline phase. These crystalline lamellae of PEO and PE segments are alternately stacked with the long period of 165 Angstroms. In a higher temperature region, where the PEO crystalline parts are on the way of melting but the PE parts are still in the orthorhombic phase, the gyroid morphology is detected in the SAXS data. By heating further, the gyroid morphology changes to the hexagonally packed cylindrical morphology, where the orthorhombic phase of PE segments is gradually disordered because of thermally activated molecular motion and finally transforms to the pseudohexagonal or rotator phase. Once the PE segments are perfectly melted, the higher-order structure changes from the cylinder to the spherical morphology. These morphological transitions might relate to the thermally activated motions of two short chain segments of the diblock copolymer, although the details of the transition mechanism are unclear at the present stage.

Effect of critical molecular weight of PEO in epoxy/EPO blends as characterized by advanced DSC and solid-state NMR

NASA Astrophysics Data System (ADS)

Wang, Xiaoliang; Lu, Shoudong; Sun, Pingchuan; Xue, Gi

2013-03-01

The differential scanning calorimetry (DSC) and solid state NMR have been used to systematically study the length scale of the miscibility and local dynamics of the epoxy resin/poly(ethylene oxide) (ER/PEO) blends with different PEO molecular weight. By DSC, we found that the diffusion behavior of PEO with different Mw is an important factor in controlling these behaviors upon curing. We further employed two-dimensional 13C-{1H}PISEMA NMR experiment to elucidate the possible weak interaction and detailed local dynamics in ER/PEO blends. The CH2O group of PEO forms hydrogen bond with hydroxyl proton of cured-ER ether group, and its local dynamics frozen by such interaction. Our finding indicates that molecular weight (Mw) of PEO is a crucial factor in controlling the miscibility, chain dynamics and hydrogen bonding interaction in these blends.

Molecular dynamics simulation study of the role of evenly spaced poly(ethylene oxide) tethers on the aggregation of C60 fullerenes in water.

PubMed

Bedrov, Dmitry; Smith, Grant D; Li, Liwei

2005-06-07

The aggregation behavior of C60 fullerenes and C60 fullerenes with six symmetrically tethered poly(ethylene oxide) oligomers [(PEO)-6-C60] in aqueous solutions has been studied using implicit solvent molecular dynamics simulations. Our simulations reveal that while the attraction between two (PEO)-6-C60 fullerenes in aqueous solution is stronger and longer range than that between two bare C60 fullerenes, the (PEO)-6-C60 fullerenes do not phase-separate in water but rather aggregate in chain-like clusters at concentrations where unmodified fullerenes completely phase-separate.

Effect of Eutectic Concentration on Conductivity in PEO:LiX Based Solid Polymer Electrolytes

NASA Astrophysics Data System (ADS)

Zhan, Pengfei; Ganapatibhotla, Lalitha; Maranas, Janna

Polyethylene oxide (PEO) and lithium salt based solid polymer electrolytes (SPEs) have been widely proposed as a substitution for the liquid electrolyte in Li-ion batteries. As salt concentration varies, these systems demonstrate rich phase behavior. Conductivity as a function of salt concentration has been measured for decades and various concentration dependences have been observed. A PEO:LiX mixture can have one or two conductivity maximums, while some mixtures with salt of high ionic strength will have higher conductivity as the salt concentration decrease. The factors that affect the conductivity are specific for each sample. The universal factor that affects conductivity is still not clear. In this work, we measured the conductivity of a series of PEO:LiX mixtures and statistical analysis shows conductivity is affected by the concentration difference from the eutectic concentration (Δc). The correlation with Δc is stronger than the correlation with glass transition temperature. We believe that at the eutectic concentration, during the solidification process, unique structures can form which aid conduction. Currently at Dow Chemical.

Influences of urea and sodium nitrite on surface coating of plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Yeh, Shang-Chun; Tsai, Dah-Shyang; Guan, Sheng-Yong; Chou, Chen-Chia

2015-11-01

Urea and sodium nitrite are generally viewed as nitridation additives in the electrolyte for plasma electrolytic oxidation (PEO) of aluminum alloys. We study the influences of these two convenient chemicals in presence of sodium aluminate and find very different effects on film growth. Urea addition enhances the nitrogen content of PEO layer, diminishes the layer thickness, increases the porosity, interferes with the α-alumina formation, and promotes precipitation in the electrolyte. Hence, the electrolytic urea content ought to be maintained less than 45 g dm-3. On the other hand, sodium nitrite behaves like an oxidation additive, more than a nitridation additive. NaNO2 addition effectively introduces nitrogen in the PEO layer at low concentration, yet the nitrogen content of oxide layer decreases with increasing NaNO2 concentration. The effects of NaNO2, such as increasing layer thickness, reducing porosity, promoting α-alumina formation are attributed to oxidation enhancement, not because of nitridation.

Comblike poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers as anti-infection surface modifying agents.

PubMed

Mai-ngam, Katanchalee

2006-05-01

A series of structurally well-defined poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers that undergo surface induced self assembly on hydrophobic biomaterial surfaces were synthesized and characterized. The surfactant polymers consist of low molecular weight (Mw) chitosan backbone with hydrophilic poly(ethylene oxide) (PEO) and hydrophobic hexyl pendant groups. Chitosan was depolymerized by nitrous acid deaminative cleavage. Hexanal and aldehyde-terminated PEO chains were simultaneously attached to low Mw chitosan hydrochloride via reductive amination. The surfactant polymers were prepared with various ratios of the two side chains. The molecular composition of the surfactant polymers was determined by FT-IR and 1H NMR. Surface active properties at the air-water interface were determined by Langmuir film balance measurements. The surfactant polymers with PEO/hexyl ratios of 1:3.0 and 1:14.4 were used as surface modifying agents to investigate their anti-infection properties. E. coli adhesion on Silastic surface was decreased significantly by the surfactant polymer with PEO/hexyl 1:3.0. Surface growth of adherent E. coli was effectively suppressed by both tested surfactant polymers.

Crystallization, Crystal Orientation and Morphology of Poly(ethylene oxide) under 1D Defect-Free Nanoscale Confinement

NASA Astrophysics Data System (ADS)

Hsiao, Ming-Siao; Zheng, Joseph X.; van Horn, Ryan M.; Quirk, Roderic P.; Thomas, Edwin L.; Lotz, Bernard; Cheng, Stephen Z. D.

2009-03-01

One-dimensional (1-D) defect-free nanoscale confinement is created by growing single crystals of PS-b-PEO block copolymers in dilute solution. Those defect-free, 1-D confined lamellae having different PEO layer thicknesses in PS-b-PEO lamellar single crystals (or crystal mats) were used to study the polymer recrystallization and crystal orientation evolution as a function of recrystallization temperature (Trx) because the Tg^PS is larger than Tm^PEO in the PS-b-PEO single crystal. The results are summarized as follows. First, by the combination of electron diffraction and known PEO crystallography, the crystallization of PEO only takes place at Trx<-5^oC. Meanwhile a unique tilted PEO orientation is formed at Trx >-5^oC after self-seeding. The origin of the formation of tilted chains in the PEO crystal will be addressed. Second, from the analysis of 2D WAXD patterns of crystal mats, it is shown that the change in PEO c-axis orientation from homogeneous at low Trx to homeotropic at higher Trx transitions sharply, within 1^oC. The mechanism inducing this dramatic change in crystal orientation will be investigated in detail.

Novel nanodisperse composite cathode for rechargeable lithium/polymer batteries

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

Striebel, K.A.; Wen, S.J.; Ghantous, D.I.

1997-05-01

A novel approach to the design of a composite positive electrode for lithium/polymer cells based on a polyethylene oxide (PEO) polymer, manganese (II), and lithium hydroxide has been discovered. A chemical reaction leading to a stable suspension occurs when the precursor salts are added directly to a polymer solution. The electrode film is cast directly and then vacuum-dried with no calcination step. The film is amorphous as-prepared and has been named the nanodisperse composite cathode, or NCC. Film characterization with x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy indicates that the Mn (II) has been oxidized to Mn (IV), whichmore » forms a complex with the PEO. This leads to highly disperse Mn sites within the polymer matrix and highly mobile Li ions within the PEO. Cells have been assembled with NCC films, PEO-LiN(SO{sub 2}CF{sub 3}){sub 2} electrolyte and lithium metal, and cycled at 85 to 105 C at current densities of 0.2 mA/cm{sup 2} between the voltage limits of 3.5 and 2.0 V. Discharge capacities as high as 340 mAh/g-cathode film have been achieved on the first half-cycle. The discharge capacity declines consistently during a formation process to steady values as high as 50 mAh/g-cathode. This cathode capacity is equivalent to an active material capacity of 150 mAh/g in a composite cathode at a loading of 30 weight percent. The synthesis process for the NCC is simple, should be relatively easy to scale up, and should lead to an extremely useful composite cathode for a lithium polymer battery.« less

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

DOE PAGES

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; ...

2015-11-03

We studied the dynamics of water in polyethylene oxide (PEO)/LiCl solution with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. Furthermore, the measured diffusion coefficient of interfacial water remained 5–10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li +. Detailed analysis of MD trajectories suggests that Li + is favorably found at the surface of the hydration layer, and the probability to find the caged Li + configuration formed by themore » PEO is lower than for the noncaged Li +-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li + hydration complexes. Moreover, performing the MD simulation with different ions (Na + and K +) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.« less

Nano-web structures constructed with a cellulose acetate/lithium chloride/polyethylene oxide hybrid: modeling, fabrication and characterization.

PubMed

Broumand, Atefeh; Emam-Djomeh, Zahra; Khodaiyan, Faramarz; Mirzakhanlouei, Sasan; Davoodi, Driush; Moosavi-Movahedi, Ali A

2015-01-22

Electrospun nano-web structures (ENWSs) were successfully fabricated from ionized binary solution of cellulose(Mn30)/polyethylene oxide(Mn200) (CA/PEO of 0.5-1.5). Final concentration of polymers was 12% (w/v) in the solution, and lithium chloride was used as ionizing agent. Response surface methodology (RSM) was applied to the optimize fabrication of ENWSs. Results of multiple linear regression analysis revealed that the solution properties and ENWSs morphology were strongly influenced by CA/PEO. An increase in PEO amount increased the viscosity which is a function of molecular weight, and as a result raised the entanglement of polymeric solution but decreased the surface tension that all support nanofibers fabrication. The size of nanofibers decreased with reducing PEO and LiCl concentration. Increasing the content of LiCl promoted the electrical conductivity (EC) value; however, junction zones were formed. The overall optimum region was found to be at combined level of 1.5% CA/PEO and 0.49% (w/v) LiCl. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

NASA Astrophysics Data System (ADS)

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; Jalarvo, Niina H.; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S.; Do, Changwoo

2015-11-01

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li+ . Detailed analysis of MD trajectories suggests that Li+ is favorably found at the surface of the hydration layer, and the probability to find the caged Li+ configuration formed by the PEO is lower than for the noncaged Li+-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li+ hydration complexes. Performing the MD simulation with different ions (Na+ and K+ ) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide.

PubMed

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O; Jalarvo, Niina H; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S; Do, Changwoo

2015-11-06

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li(+). Detailed analysis of MD trajectories suggests that Li(+) is favorably found at the surface of the hydration layer, and the probability to find the caged Li(+) configuration formed by the PEO is lower than for the noncaged Li(+)-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li(+) hydration complexes. Performing the MD simulation with different ions (Na(+) and K(+)) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

S-containing copolymer as cathode material in poly(ethylene oxide)-based all-solid-state Li-S batteries

NASA Astrophysics Data System (ADS)

Gracia, Ismael; Ben Youcef, Hicham; Judez, Xabier; Oteo, Uxue; Zhang, Heng; Li, Chunmei; Rodriguez-Martinez, Lide M.; Armand, Michel

2018-06-01

Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solid-state Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g-1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

Electroactive semi-interpenetrating polymer networks architecture with tunable IR reflectivity

NASA Astrophysics Data System (ADS)

Chevrot, C.; Teyssié, D.; Verge, P.; Goujon, L.; Tran-Van, F.; Vidal, F.; Aubert, P. H.; Peralta, S.; Sauques, L.

2011-04-01

A promising alternative of multi-layered devices showing electrochromic properties results from the design of a self-supported semi-interpenetrating polymer network (semi-IPN) including an electronic conductive polymer (ECP) formed within. The formation of the ECP in the network has already been described by oxidative polymerization using iron trichloride as an oxidant and leading to conducting semi-IPN with mixed electronic and ionic conductivities as well as convenient mechanical properties. This presentation relates to the elaboration of such semi-IPN using polyethyleneoxide (PEO) network or a PEO/NBR (Nitrile Butadiene Rubber) IPN in which a linear poly (3,4-ethylenedioxythiophene) (PEDOT) is formed symmetrically and selectively as very thin layers very next to the two main faces of the film matrix. PEO/PEDOT semi-IPNs lead to interesting optical reflective properties in the IR between 0.8 and 25 μm. Reflectance contrasts up to 35 % is observed when, after swelling in an ionic liquid, a low voltage is applied between the two main faces of the film. However the low flexibility and brittleness of the film and a slow degradation in air at temperature up from 60°C prompted to replace the PEO matrix by a flexible PEO/NBR IPN one. Indeed, the combination of NBR and PEO in an IPN leads to materials possessing flexible properties, good ionic conductivity at 25°C as well as a better resistance to thermal ageing. Finally, NBR/PEO/PEDOT semi-IPNs allow observing comparable reflectance contrast in the IR range than those shown by PEO/PEDOT semi-IPNs.

Prediction of the solubility of cucurbitacin drugs in self-associating poly(ethylene oxide)-b-poly(alpha-benzyl carboxylate epsilon-caprolactone) block copolymer with different tacticities using molecular dynamics simulation.

PubMed

Patel, Sarthak K; Lavasanifar, Afsaneh; Choi, Phillip

2010-01-01

Molecular dynamics (MD) simulation was used to investigate the solubility of two hydrophobic drugs Cucurbitacin B (CuB) and Cucurbitacin I (CuI) in poly(ethylene oxide)-b-poly(alpha-benzyl carboxylate epsilon-caprolactone) (PEO-b-PBCL) block copolymers with different tacticities. In particular, di-block copolymer with three different tacticities viz. PEO-b-iPBCL, PEO-b-sPBCL, and PEO-b-aPBCL were used. The solubility was quantified by calculating the corresponding Flory-Huggins interaction parameters (chi) using random binary mixture models with 10wt% of drug. The tacticity of the di-block copolymer was found to influence significantly the solubility of two drugs in it. In particular, based on MD simulation results, only PEO-b-sPBCL exhibited solubility while the other two did not. Given the fact that the drugs were shown to be soluble in PEO-b-PBCL experimentally, it is predicted that the tacticity of the di-block copolymer synthesized in experiment is syndiotactic. This predication matches well with the dominant ring opening polymerization of cyclic lactones to syndiotactic polymers by stannous octoate as catalyst used to prepare PEO-b-PBCL block copolymers in our previous experiments. The simulation results showed that the solubility of the drugs in PEO-b-sPBCL is attributed to the favorable intra-molecular interaction of the di-block copolymer and favorable intermolecular interaction between the di-block copolymer and the drugs. Radial distribution function analysis provides useful insights into the nature and type of the intermolecular interactions.

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

Polymer-surfactant complex formation and its effect on turbulent wall shear stress.

PubMed

Suksamranchit, Siriluck; Sirivat, Anuvat; Jamieson, Alexander M

2006-02-01

Turbulent drag reduction in Couette flow was investigated in terms of a decrease in wall shear stress for aqueous solutions of a nonionic polymer, poly(ethylene oxide) (PEO), a cationic surfactant, hexadecyltrimethylammonium chloride (HTAC), and their mixtures. Consistent with literature data, drag reduction was observed for PEO solutions above a critical molecular weight, 0.91 x 10(5) < Mc < 3.04 x 10(5) g/mol. Maximum drag reduction occurred at an optimum concentration, c(PEO)*, which scales inversely with molecular weight, and the % maximum drag reduction increases with molecular weight. For aqueous HTAC solutions, wall shear stress decreased with increasing HTAC concentration and leveled off at an optimum concentration, c(HTAC)*, comparable to the critical micelle concentration. For HTAC/PEO mixtures, the critical PEO molecular weight for drag reduction decreases, interpreted as due to an increase in hydrodynamic volume because of binding of HTAC micelles to PEO. Consistent with this interpretation, at fixed PEO concentration, maximum drag reduction was observed at an optimum HTAC concentration, c(HTAC/PEO)*, comparable to the maximum binding concentration, MBC. Also, with HTAC concentration fixed at the MBC, the optimum PEO concentration for drag reduction, c(PEO/HTAC)*, decreases relative to that, c(PEO)*, in the absence of HTAC.

Preparation, characterization, and application of Ti/TiO2-NTs/Sb-SnO2 electrode in photo-electrochemical treatment of industrial effluents under mild conditions.

PubMed

Subba Rao, Anantha N; Venkatarangaiah, Venkatesha T

2018-04-01

Ti/TiO 2 -NTs/Sb-SnO 2 electrode was prepared by gradient pulsed electrodeposition, and its electrochemical properties were evaluated. The catalytic activity and reusability of the electrode were tested by electrochemical oxidation (EO) and photoelectrochemical oxidation (PEO) of organics present in textile industry wastewater (TWW) and coffee bean processing industry wastewater (CWW). COD removal of ~ 41% was achieved after 5-h electrolysis under a constant applied current density of 30 mA cm -2 for TWW and 50 mA cm -2 for CWW. Nearly 14 and 18% increment in COD removal was observed under PEO for TWW and CWW, respectively. The turbidity of TWW reduced from 15 to ~ 3 NTU and the turbidity of CWW reduced from 27 to ~ 3 NTU by both EO and PEO. The % COD removal observed after 5-h electrolysis remained consistent for 7 repeated cycles; however, the catalytic activity of the electrode reduced gradually. These results suggested that the Ti/TiO 2 -NTs/Sb-SnO 2 can be a potential electrode for the treatment of industrial wastewater.

Synthesis and characterization of α-MoO{sub 3} nanobelt composite positive electrode materials for lithium battery application

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

Nadimicherla, Reddeppa; State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, and School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070; Chen, Wen

2015-06-15

Graphical abstract: (a) TEM image of MoO{sub 3}/PEO nanobelts composite, (b) CV curves of MoO{sub 3}/PEO nanobelts composite. - Highlights: • α-MoO{sub 3} and PEO surfactant MoO{sub 3} nanobelts were synthesized by solvothermal method. • The capacity retention of 12.5 wt% PEO surfactant MoO{sub 3} nanobelts is 88.78%. • The specific capacity of 12.5 wt% PEO surfactant MoO{sub 3} nanobelts is 352 mAh g{sup −1}. • MoO{sub 3}/PEO nanobelts composite material demonstrates good cycling stability as cathode. - Abstract: α-MoO{sub 3} and PEO surfactant MoO{sub 3} nanobelts were synthesized by a solvothermal method. The morphology and nanostructure of samples weremore » characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Bare α-MoO{sub 3} and 12.5 wt% PEO surfactant MoO{sub 3} nanobelts have an initial specific capacities of 279 and 352 mAh g{sup −1}, respectively, at constant current density 30 mA g{sup −1} with potential range of 1.5–4.0 V vs. Li/Li{sup +}. While MoO{sub 3} is modified by the intercalation of PEO, it is effectively shielded against electrostatic interaction between the MoO{sub 3} interlayer and Li{sup +} ions. We reported positive material, a nanocomposite of MoO{sub 3} coated with polyethylene oxide. It presents good cycling stability due to existence of the conductive and protective polyethylene oxide coating and the nanobelt morphology of MoO{sub 3}. The polyethylene oxide acts as a conducting matrix, a binder and an active material, as well as a volume change buffer agent, which holds the MoO{sub 3} particles in place during the discharge cycles. The cyclic voltammograms of the 12.5 wt% PEO surfactant MoO{sub 3} nanobelt composite displayed better cyclic performance compared with pure MoO{sub 3} nanobelts. The specific capacity of the pure MoO{sub 3} nanobelts and 12.5 wt% PEO surfactant MoO{sub 3} nanobelts exhibit as 199 mAh g{sup −1} and 225 mAh g{sup −1}, respectively, after 9 cycles, suggesting that the stability of surfactant material is worthy.« less

High efficiency solid state dye sensitized solar cells with graphene-polyethylene oxide composite electrolytes.

PubMed

Akhtar, M Shaheer; Kwon, Soonji; Stadler, Florian J; Yang, O Bong

2013-06-21

Novel and highly effective composite electrolytes were prepared by combining the two dimensional graphene (Gra) and polyethylene oxide (PEO) for the solid electrolyte of dye sensitized solar cells (DSSCs). Gra sheets were uniformly coated by the polymer layer through the ester carboxylate bonding between oxygenated species on Gra sheets and PEO. The Gra-PEO composite electrolyte showed the large scale generation of iodide ions in a redox couple. From rheological analysis, the decrease in viscosity after the addition of LiI and I2 in the Gra-PEO electrolyte might be explained by the dipolar interactions being severely disrupted by the ionic interactions of Li(+), I(-), and I3(-) ions. A composite electrolyte with 0.5 wt% Gra presented a higher ionic conductivity (3.32 mS cm(-1)) than those of PEO and other composite electrolytes at room temperature. A high overall conversion efficiency (∼5.23%) with a very high short circuit current (JSC) of 18.32 mA cm(-2), open circuit voltage (VOC) of 0.592 V and fill factor (FF) of 0.48 was achieved in DSSCs fabricated with the 0.5 wt% Gra-PEO composite electrolyte. This enhanced photovoltaic performance might be attributed to the large scale formation of iodide ions in the redox electrolyte and the relatively high ionic conductivity.

Nanoscale confinement effects on the relaxation dynamics in networks of diglycidyl ether of bisphenol-A and low-molecular-weight poly(ethylene oxide).

PubMed

Kalogeras, Ioannis M; Stathopoulos, Andreas; Vassilikou-Dova, Aglaia; Brostow, Witold

2007-03-22

Thermoplastic poly(ethylene oxide) (PEO) (Mw(PEO) approximately 4000) has been used to prepare thermosetting nanocomposites incorporating diglycidyl ether of bisphenol A (DGEBA) epoxy oligomer. Blends with various PEO/DGEBA weight ratios were cured using stoichiometric portions of 4,4'-diaminodiphenylmethane. The resulting semi-interpenetrating polymer networks were studied by several techniques. Nanoscale confinement effects, thermal (glass transition, melting and crystallization temperatures) and structural features of our materials are similar to those for networks with much higher Mw(PEO) and different curing agents; however, the polyether crystallization onset occurs in our case at a lower PEO concentration; shorter PEO chains organize themselves more easily into crystalline domains. Very low estimates of the k parameter of the Gordon-Taylor equation, used to fit the compositional dependences of the dielectric and calorimetric glass transition temperatures, and a strong plasticization of the motion of the glyceryl segments (beta-relaxation) in the epoxy resin were observed. These illustrate an intensified weakening in the strength of the intermolecular interactions in the modified networks, as compared to the high strength of the self-association of hydroxyls in the neat resin. The significance of hydrogen-bonding interactions between the components for obtaining structurally homogeneous thermoset-i-thermoplastic networks is discussed.

Differences in the adsorption behaviour of poly(ethylene oxide) copolymers onto model polystyrene nanoparticles assessed by isothermal titration microcalorimetry correspond to the biological differences.

PubMed

Stolnik, S; Heald, C R; Garnett, M G; Illum, L; Davis, S S

2005-01-01

The adsorption behaviour of a tetrafunctional copolymer of poly (ethylene oxide)-poly (propylene oxide) ethylene diamine (commercially available as Poloxamine 908) and a diblock copolymer of poly (lactic acid)-poly (ethylene oxide) (PLA/PEG 2:5) onto a model colloidal drug carrier (156 nm sized polystyrene latex) is described. The adsorption isotherm, hydrodynamic thickness of the adsorbed layers and enthalpy of the adsorption were assessed. The close similarity in the conformation of the poly (ethylene oxide) (PEO) chains (molecular weight 5,000 Da) in the adsorbed layers of these two copolymers was demonstrated by combining the adsorption data with the adsorbed layer thickness data. In contrast, the results from isothermal titration microcalorimetry indicated a distinct difference in the interaction of the copolymers with the polystyrene colloid surface. Poloxamine 908 adsorption to polystyrene nanoparticles is dominated by an endothermic heat effect, whereas, PLA/PEG 2:5 adsorption is entirely an exothermic process. This difference in adsorption behaviour could provide an explanation for differences in the biodistribution of Poloxamine 908 and PLA/PEG 2:5 coated polystyrene nanoparticles observed in previous studies. A comparison with the interaction enthalpy for several other PEO-containing copolymers onto the same polystyrene colloid was made. The results demonstrate the importance of the nature of the anchoring moiety on the interaction of the adsorbing copolymer with the colloid surface. An endothermic contribution is found when an adsorbing molecule contains a poly (propylene oxide) (PPO) moiety (e.g. Poloxamine 908), whilst the adsorption is exothermic (i.e. enthalpy driven) for PEO copolymers with polylactide (PLA/PEG 2:5) or alkyl moieties.

Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

PubMed

Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

2017-10-04

We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

Adsorption energies of poly(ethylene oxide)-based surfactants and nanoparticles on an air-water surface.

PubMed

Zell, Zachary A; Isa, Lucio; Ilg, Patrick; Leal, L Gary; Squires, Todd M

2014-01-14

The self-assembly of polymer-based surfactants and nanoparticles on fluid-fluid interfaces is central to many applications, including dispersion stabilization, creation of novel 2D materials, and surface patterning. Very often these processes involve compressing interfacial monolayers of particles or polymers to obtain a desired material microstructure. At high surface pressures, however, even highly interfacially active objects can desorb from the interface. Methods of directly measuring the energy which keeps the polymer or particles bound to the interface (adsorption/desorption energies) are therefore of high interest for these processes. Moreover, though a geometric description linking adsorption energy and wetting properties through the definition of a contact angle can be established for rigid nano- or microparticles, such a description breaks down for deformable or aggregating objects. Here, we demonstrate a technique to quantify desorption energies directly, by comparing surface pressure-density compression measurements using a Wilhelmy plate and a custom-microfabricated deflection tensiometer. We focus on poly(ethylene oxide)-based polymers and nanoparticles. For PEO-based homo- and copolymers, the adsorption energy of PEO chains scales linearly with molecular weight and can be tuned by changing the subphase composition. Moreover, the desorption surface pressure of PEO-stabilized nanoparticles corresponds to the saturation surface pressure for spontaneously adsorbed monolayers, yielding trapping energies of ∼10(3) k(B)T.

Microstructural study of a nitroxide-mediated poly(ethylene oxide)/polystyrene block copolymer (PEO-b-PS) by electrospray tandem mass spectrometry.

PubMed

Girod, Marion; Phan, Trang N T; Charles, Laurence

2008-08-01

Electrospray ionization tandem mass spectrometry has been used to characterize the microstructure of a nitroxide-mediated poly(ethylene oxide)/polystyrene block copolymer, called SG1-capped PEO-b-PS. The main dissociation route of co-oligomers adducted with lithium or silver cation was observed to proceed via the homolytic cleavage of a C-ON bond, aimed at undergoing reversible homolysis during nitroxide mediated polymerization. This cleavage results in the elimination of the terminal SG1 end-group as a radical, inducing a complete depolymerization process of the PS block from the so-formed radical cation. These successive eliminations of styrene molecules allowed a straightforward determination of the PS block size. An alternative fragmentation pathway of the radical cation was shown to provide structural information on the junction group between the two blocks. Proposed dissociation mechanisms were supported by accurate mass measurements. Structural information on the SG1 end-group could be reached from weak abundance fragment ions detected in the low m/z range of the MS/MS spectrum. Amongst fragments typically expected from PS dissociation, only beta ions were produced. Moreover, specific dissociation of the PEO block was not observed to occur in MS/MS, suggesting that these rearrangement reactions do not compete effectively with dissociations of the odd-electron fragment ions. Information about the PEO block length and the initiated end-group were obtained in MS(3) experiments.

Physicochemical properties of film-coated melt-extruded pellets.

PubMed

Young, Chistopher R; Crowley, Michael; Dietzsch, Caroline; McGinity, James W

2007-02-01

The purpose of this study was to investigate the physicochemical properties of poly(ethylene oxide) (PEO) and guaifenesin containing beads prepared by a melt-extrusion process and film-coated with a methacrylic acid copolymer. Solubility parameter calculations, thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), modulated differential scanning calorimetry (MDSC), X-ray powder diffraction (XRPD) and high performance liquid chromatography (HPLC) were used to determine drug/polymer miscibility and/or the thermal processibility of the systems. Powder blends of guaifenesin, PEO and functional excipients were processed using a melt-extrusion and spheronization technique and then film-coated in a fluidized bed apparatus. Solubility parameter calculations were used to predict miscibility between PEO and guaifenesin, and miscibility was confirmed by SEM and observation of a single melting point for extruded drug/polymer blends during MDSC investigations. The drug was stable following melt-extrusion as determined by TGA and HPLC; however, drug release rate from pellets decreased upon storage in sealed HDPE containers with silica desiccants at 40 degrees C/75% RH. The weight loss on drying, porosity and tortuosity determinations were not influenced by storage. Recrystallization of guaifenesin and PEO was confirmed by SEM and XRPD. Additionally, the pellets exhibited a change in adhesion behaviour during dissolution testing. The addition of ethylcellulose to the extruded powder blend decreased and stabilized the drug release rate from the thermally processed pellets. The current study also demonstrated film-coating to be an efficient process for providing melt-extruded beads with pH-dependent drug release properties that were stable upon storage at accelerated conditions.

Conjugation of arginine-glycine-aspartic acid peptides to poly(ethylene oxide)-b-poly(epsilon-caprolactone) micelles for enhanced intracellular drug delivery to metastatic tumor cells.

PubMed

Xiong, Xiao-Bing; Mahmud, Abdullah; Uludağ, Hasan; Lavasanifar, Afsaneh

2007-03-01

An arginine-glycine-aspartic acid (RGD) containing model peptide was conjugated to the surface of poly(ethylene oxide)-block-poly(epsilon-caprolactone) (PEO-b-PCL) micelles as a ligand that can recognize adhesion molecules overexpressed on the surface of metastatic cancer cells, that is, integrins, and that can enhance the micellar delivery of encapsulated hydrophobic drug into a tumor cell. Toward this goal, PEO-b-PCL copolymers bearing acetal groups on the PEO end were synthesized, characterized, and assembled to polymeric micelles. The acetal group on the surface of the PEO-b-PCL micelles was converted to reactive aldehyde under acidic condition at room temperature. An RGD-containing linear peptide, GRGDS, was conjugated on the surface of the aldehyde-decorated PEO-b-PCL micelles by incubation at room temperature. A hydrophobic fluorescent probe, that is, DiI, was physically loaded in prepared polymeric micelles to imitate hydrophobic drugs loaded in micellar carrier. The cellular uptake of DiI loaded GRGDS-modified micelles by melanoma B16-F10 cells was investigated at 4 and 37 degrees C by fluorescent spectroscopy and confocal microscopy techniques and was compared to the uptake of DiI loaded valine-PEO-b-PCL micelles (as the irrelevant ligand decorated micelles) and free DiI. GRGDS conjugation to polymeric micelles significantly facilitated the cellular uptake of encapsulated hydrophobic DiI most probably by intergrin-mediated cell attachment and endocytosis. The results indicate that acetal-terminated PEO-b-PCL micelles are amenable for introducing targeting moieties on the surface of polymeric micelles and that RGD-peptide conjugated PEO-b-PCL micelles are promising ligand-targeted carriers for enhanced drug delivery to metastatic tumor cells.

Laboratory Investigations for the Role of Flushing Media in Diamond Drilling of Marble

NASA Astrophysics Data System (ADS)

Bhatnagar, A.; Khandelwal, Manoj; Rao, K. U. M.

2011-05-01

Marble is used as a natural stone for decorative purposes from ages. Marble is a crystalline rock, composed predominantly of calcite, dolomite or serpentine. The presence of impurities imparts decorative pattern and colors. The diamond-based operations are extensively used in the mining and processing of marble. Marble is mined out in the form of blocks of cuboids shape and has to undergo extensive processing to make it suitable for the end users. The processing operation includes slabbing, sizing, polishing, etc. Diamond drilling is also commonly used for the exploration of different mineral deposits throughout the world. In this paper an attempt has been made to enhance the performance of diamond drilling on marble rocks by adding polyethylene-oxide (PEO) in the flushing water. The effect of PEO added with the drilling water was studied by varying different machine parameters and flushing media concentration in the laboratory. The responses were rate of penetration and torque at bit-rock interface. Different physico-mechanical properties of marble were also determined. It was found that flushing water added with PEO can substantially enhance the penetration rates and reduce the torque developed at the bit-rock interface as compared to plain flushing water.

Effect of KOH to Na2SiO3 Ratio on Microstructure and Hardness of Plasma Electrolytic Oxidation Coatings on AA 6061 Alloy

NASA Astrophysics Data System (ADS)

Sharma, Ashutosh; Jang, Yong-Joo; Jung, Jae Pil

2017-10-01

In this study, plasma electrolytic oxidation (PEO) process has been employed to fabricate alumina coatings on AA 6061 aluminum alloy from an electrolyte containing water glass (Na2SiO3) and alkali (KOH). The effect of deposition time and the alkali to water glass (KOH: Na2SiO3) composition ratio on the coating morphology and properties are studied. The different phases of the oxide layer and microstructure are investigated by x-ray diffraction, scanning electron microscopy, and atomic force microscopy. The results indicate that initially γ-Al2O3 forms in the coating, and as the processing time is increased from 5 to 60 minutes, α-Al2O3 phase becomes prominent. Further, higher the content of Na2SiO3, higher is the hardness and coating growth rate due to the formation of stable α-Al2O3 and Al-Si-O phase. It has been reported that the optimum properties of the PEO coatings can be obtained at a ratio of KOH: Na2SiO3 ≈ 15:10 followed by 10:10.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

PubMed

Lundberg, Pontus; Lee, Bongjae F; van den Berg, Sebastiaan A; Pressly, Eric D; Lee, Annabelle; Hawker, Craig J; Lynd, Nathaniel A

2012-11-20

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

Development of a Polarizable Force Field for Molecular Dynamics Simulations of Poly (Ethylene Oxide) in Aqueous Solution.

PubMed

Starovoytov, Oleg N; Borodin, Oleg; Bedrov, Dmitry; Smith, Grant D

2011-06-14

We have developed a quantum chemistry-based polarizable potential for poly(ethylene oxide) (PEO) in aqueous solution based on the APPLE&P polarizable ether and the SWM4-DP polarizable water models. Ether-water interactions were parametrized to reproduce the binding energy of water with 1,2-dimethoxyethane (DME) determined from high-level quantum chemistry calculations. Simulations of DME-water and PEO-water solutions at room temperature using the new polarizable potentials yielded thermodynamic properties in good agreement with experimental results. The predicted miscibility of PEO and water as a function of the temperature was found to be strongly correlated with the predicted free energy of solvation of DME. The developed nonbonded force field parameters were found to be transferrable to poly(propylene oxide) (PPO), as confirmed by capturing, at least qualitatively, the miscibility of PPO in water as a function of the molecular weight.

Characterization of Microstructure and Wear Resistance of PEO Coatings Containing Various Microparticles on Ti6Al4V Alloy

NASA Astrophysics Data System (ADS)

Li, Xinyi; Dong, Chaofang; Zhao, Qing; Pang, Yu; Cheng, Fasong; Wang, Shuaixing

2018-02-01

Titania-based composite coatings were prepared by plasma electrolytic oxidation (PEO) treatment of Ti6Al4V alloy in electrolyte with α-Al2O3, Cr2O3 or h-BN microparticles in suspension. The microstructure, composition of PEO composite coatings were analyzed by SEM, EDS and XRD. The wear resistance of composite ceramic coatings was studied by ball-on-disk wear test at ambient temperature and 300 °C. The results showed that the addition of microparticles accelerated the growth rate of PEO coating and changed the microstructure and composition of PEO coating. PEO coating was porous and mainly composed of rutile-TiO2, anatase-TiO2 and Al2TiO5. PEO/α-Al2O3 (Cr2O3 or h-BN) composite coating only had small micropores and appeared some α-Al2O3 (Cr2O3 or h-BN) phase. Besides, the addition of α-Al2O3 (Cr2O3 or h-BN) microparticles greatly improved the wear resistance of PEO coating. At ambient temperature, abrasive wear dominated the wear behavior of PEO coating, but abrasive wear and adhesive peel simultaneously happened at 300 °C. Whether at ambient temperature or 300 °C, PEO composite coating had better wear resistance than PEO coating. Besides, PEO/h-BN composite coating outperformed other composite coatings regardless of the temperature.

Corrosion behaviors and effects of corrosion products of plasma electrolytic oxidation coated AZ31 magnesium alloy under the salt spray corrosion test

NASA Astrophysics Data System (ADS)

Wang, Yan; Huang, Zhiquan; Yan, Qin; Liu, Chen; Liu, Peng; Zhang, Yi; Guo, Changhong; Jiang, Guirong; Shen, Dejiu

2016-08-01

The effects of corrosion products on corrosion behaviors of AZ31 magnesium alloy with a plasma electrolytic oxidation (PEO) coating were investigated under the salt spray corrosion test (SSCT). The surface morphology, cross-sectional microstructure, chemical and phase compositions of the PEO coating were determined using scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction analysis (XRD), respectively. Further, the corrosion process of the samples under the SSCT was examined in a non-aqueous electrolyte (methanol) using electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit. The results show that the inner layer of the coating was destroyed firstly and the corrosion products have significant effects on the corrosion behaviors of the coating. The results above are discussed and an electrochemical corrosion model is proposed in the paper.

Molecular Dynamics Simulations of Strain-Induced Phase Transition of Poly(ethylene oxide) in Water.

PubMed

Donets, Sergii; Sommer, Jens-Uwe

2018-01-11

We study the dilute aqueous solutions of poly(ethylene oxide) (PEO) oligomers that are subject to an elongating force dipole acting on both chain ends using atomistic molecular dynamics. By increasing the force, liquid-liquid demixing can be observed at room temperature far below the lower critical solution temperature. For forces above 35 pN, fibrillar nanostructures are spontaneously formed related to a decrease in hydrogen bonding between PEO and water. Most notable is a rapid decrease in the bifurcated hydrogen bonds during stretching, which can also be observed for isolated single chains. The phase-segregated structures display signs of chain ordering, but a clear signature of the crystalline order is not obtained during the simulation time, indicating a liquid-liquid phase transition induced by chain stretching. Our results indicate that the solvent quality of the aqueous solution of PEO depends on the conformational state of the chains, which is most likely related to the specific hydrogen-bond-induced solvation of PEO in water. The strain-induced demixing of PEO opens the possibility to obtain polymer fibers with low energy costs because crystallization starts via the strain-induced demixing in the extended state only.

Morphology of a highly asymmetric double crystallizable poly(ɛ-caprolactone-b-ethylene oxide) block copolymer

NASA Astrophysics Data System (ADS)

Li, Liangbin; Meng, Fenghua; Zhong, Zhiyuan; Byelov, Dmytro; de Jeu, Wim H.; Feijen, Jan

2007-01-01

The morphology of a highly asymmetric double crystallizable poly(ɛ-caprolactone-b-ethylene oxide) (PCL-b-PEO) block copolymer has been studied with in situ simultaneously small and wide-angle x-ray scattering as well as atomic force microscopy. The molecular masses Mn of the PCL and PEO blocks are 24 000 and 5800, respectively. X-ray scattering and rheological measurements indicate that no microphase separation occurs in the melt. Decreasing the temperature simultaneously triggers off a crystallization of PCL and microphase separation between the PCL and PEO blocks. Coupling and competition between microphase separation and crystallization results in a morphology of PEO spheres surrounded by PCL partially crystallized in lamella. Further decreasing temperature induces the crystallization of PEO spheres, which have a preferred orientation due to the confinements from hard PCL crystalline lamella and from soft amorphous PCL segments in different sides. The final morphology of this highly asymmetric block copolymer is similar to the granular morphology reported for syndiotactic polypropylene and other (co-) polymers. This implies a similar underlying mechanism of coupling and competition of various phase transitions, which is worth further exploration.

Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers.

PubMed

Chintapalli, Mahati; Timachova, Ksenia; Olson, Kevin R; Banaszak, Michał; Thelen, Jacob L; Mecham, Sue J; DeSimone, Joseph M; Balsara, Nitash P

2017-06-07

Incipient microphase separation is observed by wide angle X-ray scattering (WAXS) in short chain multiblock copolymers consisting of perfluoropolyether (PFPE) and poly(ethylene oxide) (PEO) segments. Two PFPE-PEO block copolymers were studied; one with dihydroxyl end groups and one with dimethyl carbonate end groups. Despite having a low degree of polymerization (N ∼ 10), these materials exhibited significant scattering intensity, due to disordered concentration fluctuations between their PFPE-rich and PEO-rich domains. The disordered scattering intensity was fit to a model based on a multicomponent random phase approximation to determine the value of the interaction parameter, χ, and the radius of gyration, R g . Over the temperature range 30-90 °C, the values of χ were determined to be very large (∼2-2.5), indicating a high degree of immiscibility between the PFPE and PEO blocks. In PFPE-PEO, due to the large electron density contrast between the fluorinated and non-fluorinated block and the high value of χ, disordered scattering was detected at intermediate scattering angles, (q ∼ 2 nm -1 ) for relatively small polymer chains. Our ability to detect concentration fluctuations was enabled by both a relatively large value of χ and significant scattering contrast.

Insight into fast ion migration kinetics of a new hybrid single Li-ion conductor based on aluminate complexes for solid-state Li-ion batteries.

PubMed

Feng, Yancong; Tan, Rui; Zhao, Yan; Gao, Rongtan; Yang, Luyi; Yang, Jinlong; Li, Hao; Zhou, Guofu; Chen, Haibiao; Pan, Feng

2018-03-29

A novel hybrid single Li-ion conductor (SLIC) for a Li-ion solid electrolyte was prepared by mixing aluminate complexes-polyethylene glycol (LiAl-PEG) and polyethylene oxide (PEO) for solid-state Li-ion batteries. The LiAl-PEG/PEO blend possesses high thermal stability and electrochemical stability with an oxidation decomposition voltage up to 4.8 V. Notably, this hybrid SLIC exhibits not only excellent Li-ion migration kinetics, but also good ionic conductivity as high as 4.0 × 10-5 and 2.6 × 10-4 S cm-1 at 30 and 100 °C, respectively, which is much higher than previously reported SLICs. Importantly, by the combination of molecular dynamics simulations and experiment measurements, the mechanisms of Li-ion migration across the SLIC (LiAl-PEG), the salt-in-polymer (LiClO4/PEO) and the optimized SLIC (LiAl-PEG/PEO) were systematically investigated for the first time. The new hopping transport mechanism was verified for the SLIC system at the nanoscale. As for the hybrid SLIC, PEO chains enhance the segmental mobility of the ether-chains bonded with Al atoms, improve the ionicity, and provide extra ionic paths for Li transfer, resulting in the optimized Li-ion migration kinetics of LiAl-PEG/PEO.

Improving educational objectives of the Industrial and Management Systems Engineering programme at Kuwait University

NASA Astrophysics Data System (ADS)

Aldowaisan, Tariq; Allahverdi, Ali

2016-05-01

This paper describes the process of developing programme educational objectives (PEOs) for the Industrial and Management Systems Engineering programme at Kuwait University, and the process of deployment of these PEOs. Input of the four constituents of the programme, faculty, students, alumni, and employers, is incorporated in the development and update of the PEOs. For each PEO an assessment process is employed where performance measures are defined along with target attainment levels. Results from assessment tools are compared with the target attainment levels to measure performance with regard to the PEOs. The assessment indicates that the results meet or exceed the target attainment levels of the PEOs' performance measures.

Nanostructure and Dynamics of Ionic and Non-Ionic PEO-Containing Polyureas

NASA Astrophysics Data System (ADS)

Chuayprakong, Sunanta; Runt, James

2013-03-01

A series of polyethylene oxide (PEO) - based diamines with molecular weights ranging from 250 - 6000 g/mol were polymerized in solution with 4,4'-methylene diphenyl diisocyanate (MDI). In addition, PEO soft segment diamines where modified to incorporate ionomeric species and also polymerized with MDI. The role of PEO soft segment molecular weight and the presence of ionic species on nanoscale segregation and cation conductivity were explored. The former was investigated using small-angle X-ray scattering and atomic force microscopy. Dielectric relaxation spectroscopy was used to investigate polymer and ion dynamics. Local environment and hydrogen bonding were identified by using FTIR spectroscopy.

Sound Absorption Characteristics of Aluminum Foams Treated by Plasma Electrolytic Oxidation

PubMed Central

Jin, Wei; Liu, Jiaan; Wang, Zhili; Wang, Yonghua; Cao, Zheng; Liu, Yaohui; Zhu, Xianyong

2015-01-01

Open-celled aluminum foams with different pore sizes were fabricated. A plasma electrolytic oxidation (PEO) treatment was applied on the aluminum foams to create a layer of ceramic coating. The sound absorption coefficients of the foams were measured by an impedance tube and they were calculated by a transfer function method. The experimental results show that the sound absorption coefficient of the foam increases gradually with the decrease of pore size. Additionally, when the porosity of the foam increases, the sound absorption coefficient also increases. The PEO coating surface is rough and porous, which is beneficial for improvement in sound absorption. After PEO treatment, the maximum sound absorption of the foam is improved to some extent. PMID:28793653

Investigation of Tb 3+ ion fluorescence properties in γ-irradiated poly(ethylene oxide)-TbCl 3 blended systems

NASA Astrophysics Data System (ADS)

Cho, Myung D.; Okamoto, Yoshiyuki

1995-05-01

Degradation of polymers by γ-irradiation using Tb 3+ ion as a fluorescence probe was investigated. When poly(ethylene oxide) blended with TbCl 3 films were γ-irradiated in air, the fluorescence intensity of Tb 3+ was found to be greatly increased and the molecular weights of PEO were decreased. These results suggest that radiolysis caused chain degradation of PEO and produced carbonyl groups at the end of the cleaved polymer chain. The chromophore moiety produced transfers energy to Tb 3+ ion located within the non-irradiative energy trasfer distance. It is suggested that blended films of PEO with Tb 3+ may be used as convenient and fast detectors of γ-irradiation doses.

Growth mechanism changes in pseudo-dewetted monolayer poly(ethylene oxide) crystallization

NASA Astrophysics Data System (ADS)

Zhu, Dun-Shen; Chen, Er-Qiang; Shi, An-Chang; Cheng, Stephen

2006-03-01

Crystal growth mechanism changes have been observed in pseudo-dewetted monolayers of low molecular weight (LMW) (PEO) on freshly cleaved hydrophilic mica surfaces [HPEO(4250) which have -OH groups at both ends and MHPEO(4700) which has one -OH and one -OCH3 as end groups]. X-ray scattering reflectivity measurements show a wetted monolayer of molten PEO with a thickness of ˜ 4.5 nm on the mica surface. Non-adsorbed PEO droplets sit on top of the wetted monolayer. A two-step process for PEO single crystal growth under isothermal conditions was identified utilizing in-situ atomic force microscopy at different crystallization temperatures (Tx). In the first step, the crystal grows within the droplet which supplies the molten PEO that participates in the crystal formation. In this second-step, the wetted monolayer at the growth front is depleted by about 1.5 - 2.5 nm. The growing crystal lateral sizes obey a power law of t^α (t: time). At a high Tx of 63 C for MHPEO(4700), the growth behavior obeys r t (α = 1). While in the case of HPEO(4250), its growth behavior follows r t^0.5 (α = 0.5) in the whole Tx range. With decreasing Tx, the growth of MHPEO(4700) falls into a scaling law of r t^α (0.5 < α < 1).

7Li NMR spectroscopy and ion conduction mechanism in mesoporous silica (SBA-15) composite poly(ethylene oxide) electrolyte

NASA Astrophysics Data System (ADS)

Reddy, M. Jaipal; Chu, Peter P.

A composite of mesoporous silica (SBA-15) with a polyethylene oxide (PEO) polymer electrolyte is examined for use in various electrochemical devices. Incorporation of SBA-15 in a PEO:LiClO 4 polymer electrolyte facilitates salt dissociation, enhances ion conductivity, and improves miscibility between organic and inorganic moieties. Optimized conductivity is found at 10 wt.% SBA-15 composition, above this concentration the conductivity is reduced due to aggregation of a SBA-15:Li rich phase. Heating above melt temperature of PEO allows more of the polymer segments to interact with SBA-15. This results in a greater degree of disorder upon cooling, and the ion conductivity is enhanced. A 7Li MAS NMR study reveals three types of lithium-ion coordination. Two major types of conduction mechanism can be identified: one through conventional amorphous PEO; a second via hopping in a sequential manner by replacing the nearby vacancies ('holes') on the surface (both interior and exterior) of the SBA-15 channels.

Drug delivery using novel nanoplexes against a Salmonella mouse infection model

NASA Astrophysics Data System (ADS)

Ranjan, A.; Pothayee, N.; Seleem, M.; Jain, N.; Sriranganathan, N.; Riffle, J. S.; Kasimanickam, R.

2010-03-01

A novel methodology for incorporating gentamicin into macromolecular complexes with anionic homo- and block copolymers via cooperative electrostatic interactions is described. Block copolymers of poly(ethylene oxide- b-sodium acrylate) (PEO- b-PAA- +Na) or poly(ethylene oxide- b-sodium methacrylate) (PEO- b-PMA- +Na) were blended with PAA- Na+ and complexed with the polycationic antibiotic gentamicin. Gentamicin nanoplexes made with PEO- b-PMA- +Na/PAA- +Na (PMPG) and analogous nanoplexes with PEO- b-PAA- +Na/PAA- +Na (PAPG) had mean intensity average diameters of 120 and 90 nm, zeta potentials of -17 and -11 mv, and incorporated 26% and 23% by weight of gentamicin, respectively. Gentamicin release rates at physiological pH from nanoplexes were relatively slow. PAPG and PMPG as drug delivery systems for treating murine salmonellosis at doses similar to the free gentamicin experiments resulted in reduced numbers of viable bacteria in the liver and spleen. Polymeric nanoplexes developed by this methodology can potentially improve targeting of intracellular pathogens.

Stability and effectiveness against bacterial adhesion of poly(ethylene oxide) coatings in biological fluids.

PubMed

Roosjen, Astrid; de Vries, Joop; van der Mei, Henny C; Norde, Willem; Busscher, Henk J

2005-05-01

Poly(ethylene oxide) (PEO) coatings have been shown to reduce the adhesion of different microbial strains and species and thus are promising as coatings to prevent biomaterial-centered infection of medical implants. Clinically, however, PEO coatings are not yet applied, as little is known about their stability and effectiveness in biological fluids. In this study, PEO coatings coupled to a glass substratum through silyl ether bonds were exposed for different time intervals to saliva, urine, or phosphate-buffered saline (PBS) as a reference at 37 degrees C. After exposure, the effectiveness of the coatings against bacterial adhesion was assessed in a parallel plate flow chamber. The coatings appeared effective against Staphylococcus epidermidis adhesion for 24, 48, and 0.5 h in PBS, urine, and saliva, respectively. Using XPS and contact-angle measurements, the variations in effectiveness could be attributed to conditioning film formation. The overall short stability results from hydrolysis of the coupling of the PEO chains to the substratum. (c) 2005 Wiley Periodicals, Inc.

In Situ Nanocalorimetric Investigations of Plasma Assisted Deposited Poly(ethylene oxide)-like Films by Specific Heat Spectroscopy.

PubMed

Madkou, Sherif; Melnichu, Iurii; Choukourov, Andrei; Krakovsky, Ivan; Biederman, Hynek; Schönhals, Andreas

2016-04-28

In recent years, highly cross-linked plasma polymers have started to unveil their potential in numerous biomedical applications in thin-film form. However, conventional diagnostic methods often fail due to their diverse molecular dynamics conformations. Here, glassy dynamics and the melting transition of thin PEO-like plasma assisted deposited (ppPEO) films (thickness 100 nm) were in situ studied by a combination of specific heat spectroscopy, utilizing a pJ/K sensitive ac-calorimeter chip, and composition analytical techniques. Different cross-linking densities were obtained by different plasma powers during the deposition of the films. Glassy dynamics were observed for all values of the plasma power. It was found that the glassy dynamics slows down with increasing the plasma power. Moreover, the underlying relaxation time spectra broaden indicating that the molecular motions become more heterogeneous with increasing plasma power. In a second set of the experiment, the melting behavior of the ppPEO films was studied. The melting temperature of ppPEO was found to decrease with increasing plasma power. This was explained by a decrease of the order in the crystals due to formation of chemical defects during the plasma process.

Crystal orientation of PEO confined within the nanorod templated by AAO nanochannels.

PubMed

Liu, Chien-Liang; Chen, Hsin-Lung

2018-06-18

The orientation of poly(ethylene oxide) (PEO) crystallites developed in the nanochannels of anodic aluminum oxide (AAO) membrane has been investigated. PEO was filled homogeneously into the nanochannels in the melt state, and the crystallization confined within the PEO nanorod thus formed was allowed to take place subsequently at different temperatures. The effects of PEO molecular weight (MPEO), crystallization temperature (Tc) and AAO channel diameter (DAAO) on the crystal orientation attained in the nanorod were revealed by 2-D wide angle X-ray scattering (WAXS) patterns. In the nanochannels with DAAO = 23 nm, the crystallites formed from PEO with the lowest MPEO (= 3400 g mol-1) were found to adopt a predominantly perpendicular orientation with the crystalline stems aligning normal to the channel axis irrespective of Tc (ranging from -40 to 20 °C). Increasing MPEO or decreasing Tc tended to induce the development of the tilt orientation characterized by the tilt of the (120) plane by 45° from the channel axis. In the case of the highest MPEO (= 95 000 g mol-1) studied, both perpendicular and tilt orientations coexisted irrespective of Tc. Coexistent orientation was always observed in the channels with a larger diameter (DAAO = 89 nm) irrespective of MPEO and Tc. Compared with the previous results of the crystal orientation attained in nanotubes templated by the preferential wetting of the channel walls by PEO, the window of the perpendicular crystal orientation in the nanorod was much narrower due to its weaker confinement effect imposed on the crystal growth than that set by the nanotube.

Novel self-associating poly(ethylene oxide)-b-poly(epsilon-caprolactone) based drug conjugates and nano-containers for paclitaxel delivery.

PubMed

Shahin, Mostafa; Lavasanifar, Afsaneh

2010-04-15

Poly(ethylene oxide)-block-poly(epsilon-caprolactone) (PEO-b-PCL) copolymers bearing paclitaxel (PTX) side groups on PCL (PEO-b-P(CL-PTX) were synthesized and assembled to particles of 123 nm average diameter. At 20% (w/w) PTX to polymer conjugation, PEO-b-P(CL-PTX) demonstrated only 5.0 and 6.7% PTX release after 72 h incubation at pH 7.4 and 5.0, respectively, but revealed signs of chain cleavage at pH 5.0. The cytotoxicity of PEO-b-P(CL-PTX) against MDA-MB-435 cancer cells increased as incubation time was raised from 72 to 96 h (IC(50) of 680 and 475 ng/mL, respectively), but it was still significantly lower than the cytotoxicity of free PTX (IC(50) of 3.5 ng/mL at 72 h). In further studies, micelles of PEO-b-PCL and those bearing benzyl or PTX on PCL were used for physical encapsulation of PTX, where maximum level of loading was achieved by PEO-b-P(CL-PTX) (2.22%, w/w). The release of PTX from this carrier was rapid; however. The in vitro cytotoxicity of physically loaded PTX was independent of carrier and similar to that of free PTX. This was attributed to the low concentration of polymers which fell below their critical micellar concentration in the cytotoxicity study. The results point to the potential of chemically tailored PEO-b-PCL for optimum PTX solubilization and delivery. Copyright 2010 Elsevier B.V. All rights reserved.

Evidence of formation of site-selective inclusion complexation between beta-cyclodextrin and poly(ethylene oxide)-block-poly(propylene oxide)- block-poly(ethylene oxide) copolymers.

PubMed

Tsai, Chi-Chun; Zhang, Wen-Bin; Wang, Chien-Lung; Van Horn, Ryan M; Graham, Matthew J; Huang, Jing; Chen, Yongming; Guo, Mingming; Cheng, Stephen Z D

2010-05-28

A series of inclusion complexes of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-b-PPO-b-PEO) with beta-cyclodextrin (beta-CD) was prepared. Their formation, structure, and dynamics were investigated by solution two-dimensional rotating-frame Overhauser effect spectroscopy (2D ROESY) and one-dimensional (1D) and 2D solid-state (13)C NMR. The inclusion complexes between the PEO-b-PPO-b-PEO copolymers and the beta-CDs were formed in aqueous solution and detected by 2D ROESY. The high efficiency of cross polarization and spin diffusion experiments in (13)C solid-state NMR showed that the mobility of the PPO blocks dramatically decreases after beta-CD complexation, indicating that they are selectively incorporated onto the PPO blocks. The hydrophobic cavities of beta-CD restrict the PPO block mobility, which is evidence of the formation of inclusion complexes in the solid state. The 2D wide-line separation NMR experiments suggested that beta-CDs only thread onto the PPO blocks while forming the inclusion complexes. The stoichiometry of inclusion complexes was studied using (1)H NMR, and a 3:1 (PO unit to beta-CD) was found for all inclusion complexes, which indicated that the number of threaded beta-CDs was only dependent on the molecular weight of the PPO blocks. 1D wide angle x-ray diffraction studies demonstrated that the beta-CD in the inclusion complex formed a channel-like structure that is different from the pure beta-CD crystal structure.

Evidence of formation of site-selective inclusion complexation between β-cyclodextrin and poly(ethylene oxide)-block-poly(propylene oxide)- block-poly(ethylene oxide) copolymers

NASA Astrophysics Data System (ADS)

Tsai, Chi-Chun; Zhang, Wen-Bin; Wang, Chien-Lung; Van Horn, Ryan M.; Graham, Matthew J.; Huang, Jing; Chen, Yongming; Guo, Mingming; Cheng, Stephen Z. D.

2010-05-01

A series of inclusion complexes of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-b-PPO-b-PEO) with β-cyclodextrin (β-CD) was prepared. Their formation, structure, and dynamics were investigated by solution two-dimensional rotating-frame Overhauser effect spectroscopy (2D ROESY) and one-dimensional (1D) and 2D solid-state C13 NMR. The inclusion complexes between the PEO-b-PPO-b-PEO copolymers and the β-CDs were formed in aqueous solution and detected by 2D ROESY. The high efficiency of cross polarization and spin diffusion experiments in C13 solid-state NMR showed that the mobility of the PPO blocks dramatically decreases after β-CD complexation, indicating that they are selectively incorporated onto the PPO blocks. The hydrophobic cavities of β-CD restrict the PPO block mobility, which is evidence of the formation of inclusion complexes in the solid state. The 2D wide-line separation NMR experiments suggested that β-CDs only thread onto the PPO blocks while forming the inclusion complexes. The stoichiometry of inclusion complexes was studied using H1 NMR, and a 3:1 (PO unit to β-CD) was found for all inclusion complexes, which indicated that the number of threaded β-CDs was only dependent on the molecular weight of the PPO blocks. 1D wide angle x-ray diffraction studies demonstrated that the β-CD in the inclusion complex formed a channel-like structure that is different from the pure β-CD crystal structure.

Microstructures and Properties of Plasma Electrolytic Oxidized Ti Alloy (Ti-6Al-4V) for Bio-implant Application

NASA Astrophysics Data System (ADS)

Kumari, Renu; Blawert, Carsten; Majumdar, J. Dutta

2016-02-01

In the present study, plasma electrolytic oxidation (PEO) of Ti6Al4V has been performed in an electrolyte containing 20 g/L of Na2SiO3, 10 g/L of Na3PO4, 2 g/L of KOH, and 5 g/L of hydroxyapatite at an optimum constant potential of 430 V for 10 minutes. Followed by PEO treatment, surface roughness was measured using non-contact optical profilometer. A detailed characterization of microstructure, composition and phase analysis was carried out using scanning electron microscopy, energy-dispersive X-ray spectroscopic analysis, Fourier-transform infrared, and X-ray diffraction study. The mechanical properties of the surface have been evaluated by measuring nano-hardness and wear resistance. The effect of surface modification on corrosion resistance property has also been evaluated in Hank's solution. Finally, wettability and bioactivity test have been also performed. PEO developed a thick (150 μm) porous (35 pct) oxide film on the surface of Ti-6Al-4V consisting of anatase, rutile, and SiO2. The nano-hardness of the PEO-treated surface is increased to 8 ± 0.5 GPa as compared to 2 ± 0.4 GPa of the as-received Ti-6Al-4V. Wear and corrosion resistance were improved following oxidation. There is an improvement in wettability in terms of decrease in contact angle from 60 ± 1.5 to 45 ± 1 deg. Total surface energy and its polar component were also increased significantly on PEO-treated surface as compared to the as-received Ti6Al4V.

Combined Effect of Long Processing Time and Na2SiF6 on the Properties of PEO Coatings Formed on AZ91D

NASA Astrophysics Data System (ADS)

Rehman, Zeeshan Ur; Koo, Bon Heun

2016-08-01

In this study, protective ceramic coatings were prepared on AZ91D magnesium alloy by plasma electrolytic oxidation (PEO) to improve the corrosion and mechanical properties of AZ91D magnesium alloy. The process was conducted in silicate-fluoride-based electrolyte solution. It was found that the average micro-hardness of the coating was significantly increased with an increase in the PEO processing time. The highest value of the average micro-hardness ~1271.2 HV was recorded for 60-min processing time. The phase analysis of the coatings indicated that they were mainly composed of Mg2SiO4, MgO, and MgF2 phases. The surface and cross-sectional study demonstrated that porosity was largely reduced with processing time, together with the change in pore geometry from irregular to spherical shape. The results of the polarization test in 3.5 wt.% NaCl solution revealed that aggressive corrosion took place for 5-min sample; however, the corrosion current was noticeably decreased to 0.43 × 10-7 A/cm2 for the 60-min-coated sample. The superior nobility and hardness for long processing time are suggested to be due to the dense and highly thick coating, coupled with the presence of MgF2 phase.

Production of chitosan-based non-woven membranes using the electrospinning process

NASA Astrophysics Data System (ADS)

Pakravan Lonbani, Mehdi

Chitosan is a modified natural polymer mainly produced from chitin, one of the most abundant organic materials in the world. Highly porous chitosan mats present the specific physicochemical properties of the base material and also benefit from the physical characteristics of nanoporous membranes. Electrospinning is a novel technique developed long time ago and revisited recently that can generate polymeric fibers with nanometric size. The ultimate purpose of this work is to fabricate microporous non-woven chitosan membranes for wound healing dressings and heavy metal ion removal from drinking water. In this dissertation, two approaches have been utilized to prepare chitosan-based nanofibers; blending and co-axial electrospinning of chitosan solution with a readily electrospinnable solution, i.e. an aqueous solution of polyethylene oxide (PEO). Consequently, understanding the phase behavior and miscibility of aqueous acidic solutions of chitosan and PEO and their blends is of crucial importance, as any phase separation occurring during the electrospinning process greatly changes the morphology and physico-mechanical properties of the final products. First we employed the rheological approach on a well-known aqueous PEO solution to develop the experimental protocol. By comparing these critical points with that obtained from other experimental techniques, we showed that rheological measurements can sensitively detect early stages of phase separation. Subsequently the method was applied to 50 wt% aqueous acetic acid solutions of PEO, chitosan and their blends at different ratios. These solutions showed a lower critical solution temperature (LCST) phase diagram that is attributed to the existence of hydrogen bonds between active groups on chitosan and PEO backbone and the solvent. Critical decomposition temperatures for binodal and spinodal points were estimated from isochronal temperature sweep experiments. The obtained binodal temperatures confirmed that chitosan/PEO solutions are miscible and stable at moderate temperatures and phase separate at higher temperatures of 60-75 °C. Then, we intended to obtain a thorough understanding of chitosan/PEO solution properties that lead to a successful electrospinning process, i.e. continuous and stable, and which produces defect free uniform beadless nanofibers. The effect of blend composition and acetic acid concentration on properties such as surface tension and conductivity and, ultimately, on electrospinnability were investigated. A highly deacetylated chitosan (DDA=97.5 %) in 50% acetic acid was used, which is the maximum deacetylated chitosan grade that has been reported for the preparation of electrospun chitosan-based nanofibers. The rheological characteristics of the chitosan/PEO solutions as a controlling parameter in the electrospinning process were examined and their relationships to electrospinnability presented. As we showed that chitosan/PEO solutions are miscible and stable at moderate temperatures, a modified electrospinning set up to electrospin at temperatures of 25-70 °C was designed to achieve content as high as 90 wt% of chitosan in beadless chitosan/PEO nanofibers of 60-80 nm in diameter. It was also found that increasing chitosan/PEO ratio from 50/50 to 90/10 led to a remarkable diameter reduction from 123 to 63 nm at room temperature. Additionally, we found that moderate process temperatures help to stabilize the electrospinning process of these solutions and produce beadless nanofibers. However, at higher temperatures, the electrospun jet became unstable and beaded fiber morphology was obtained. This phenomena occurs closely at the temperature range of phase separation, previously determined by rheology studies. Therefore, temperature-induced phase separation of these solutions is considered as the reason for that observation. On the other hand, an FTIR study at room temperature on cast films and nanofibers of chitosan/PEO blends at room temperature showed the presence of hydrogen bonding interactions between chitosan and PEO that could be an another indication of miscibility between these two polymers in solution at moderate temperatures. Finally, in order to remove the blending step, reducing the amount of chitosan used and also to put chitosan right on the outer surface of the nanofibers for further related applications, a co-axial electrospinning technique was employed. By using a one-step co-axial electrospinning process, for the first time core-shell structured PEO-chitosan nanofibers from aqueous solutions were produced in which chitosan is located at the shell (outer layer) and PEO at the core (inner layer). Uniform sized defect-free nanofibers of 100-190 nm diameter were produced. The core-shell nanostructure and existence of chitosan on the shell layer were confirmed by TEM images obtained before and after washing the PEO content with water. The presence of chitosan on the surface of the composite nanofibers was further supported by XPS studies. Bulk and local compositional analysis is performed by thermal gravimetry (TGA) and Fourier transform infrared spectroscopy (FTIR) techniques, respectively, to examine the homogeneity of the nanofibers. Additionally, it was shown that hollow chitosan nanofibers could be obtained by PEO washing of the co-axial PEO/chitosan nanofibers, which could also be of great interest in applications such as blood purification in hemodialysis.

Effect of the voltage pulse frequency on the structure of TiO2 coatings grown by plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Torres-Cerón, D. A.; Gordillo-Delgado, F.; Moya-Betancourt, S. N.

2017-12-01

Plasma Electrolytic Oxidation (PEO) is used to synthetize titanium dioxide (TiO2) ceramic coatings with the appropriate selection of an electrolyte. The dimension of the micro-cavities and the particle size at the surface can be controlled through the pulse frequency of the voltage that is applied between the electrodes. The change of surface morphology can increase the surface area-to-volume ratio. In this work, PEO of an ASME SB-265 titanium substrate (20×20×1mm) was made in a water solution containing 8g/L Na3PO4 and 0.4g/L NaOH. Hence, the coatings were fabricated using voltage pulses of 340V for 10 minutes with a 10% duty cycle and frequencies of 1000, 1500 and 2000Hz. According to the X-ray diffractograms of the obtained samples, the sintering process at 500°C during 1 hour generated Anatase titanium dioxide porous coatings. The grain size decreased approximately from 29nm for 1000 and 1500Hz pulse frequencies until 21nm for 2000Hz. On the other hand, from the micrographs of scanning electron microscopy was possible to see the uniform formation of the micro-cavities with the largest diameter, 900nm, for the lowest frequency value used in PEO.

Field Effect Transistor Behavior in Electrospun Polyaniline/Polyethylene Oxide Demonstrated

NASA Technical Reports Server (NTRS)

Mueller, Carl H.; Theofylaktos, Onoufrios; Robinson, Daryl C.; Miranda, Felix A.

2004-01-01

Novel transistors and logic devices based on nanotechnology concepts are under intense development. The potential for ultra-low-power circuitry makes nanotechnology attractive for applications such as digital electronics and sensors. For NASA applications, nanotechnology offers tremendous opportunities for increased onboard data processing, and thus autonomous decisionmaking ability, and novel sensors that detect and respond to environmental stimuli with little oversight requirements. Polyaniline/polyethylene oxide (PANi/PEO) nanofibers are of interest because they have electrical conductivities that can be changed from insulating to metallic by varying the doping levels and conformations of the polymer chain. At the NASA Glenn Research Center, we have observed field effect transistor (FET) behavior in electrospun PANi/PEO nanofibers doped with camphorsulfonic acid. The nanofibers were deposited onto Au electrodes, which had been prepatterned onto oxidized silicon substrates. The preceding scanning electron image shows the device used in the transistor measurements. Saturation channel currents are observed at surprisingly low source/drain voltages (see the following graph). The hole mobility in the depletion regime is 1.4x10(exp -4)sq cm/V sec, whereas the one-dimensional charge density (at zero gate bias) is calculated to be approximately 1 hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (approx.10(exp -3) S/cm). Reducing or eliminating the PEO content in the fiber is expected to enhance device parameters. Electrospinning is thus proposed as a simple method of fabricating one-dimensional polymer FET's.

Synthetic polymers and biomembranes. How do they interact? Atomistic molecular dynamics simulation study of PEO in contact with a DMPC lipid bilayer.

PubMed

Pal, Sandeep; Milano, Giuseppe; Roccatano, Danilo

2006-12-28

The understanding of interactions of poly(ethylene glycol) (PEG) or poly(ethylene oxide) (PEO) with biological interfaces has important technological application in industry and in medicine. In this paper, structural and dynamical properties of PEO at the dimyristoylphospatidylcholine (DMPC) bilayer/water interface have been investigated by molecular dynamics (MD) and steered molecular dynamics (SMD) simulations. The structural properties of a PEO chain in bulk water, at the water/vacuum interface, and in the presence of the membrane were compared with available experimental data. The presence of a barrier for the PEO penetration into the DMPC bilayer has been found. A qualitative estimation of the barrier provided a value equal to approximately 19 kJ/mol, that is, 7 times the value of kT at 310 K.

Unimpeded permeation of water through biocidal graphene oxide sheets anchored on to 3D porous polyolefinic membranes

NASA Astrophysics Data System (ADS)

Mural, Prasanna Kumar S.; Jain, Shubham; Kumar, Sachin; Madras, Giridhar; Bose, Suryasarathi

2016-04-01

3D porous membranes were developed by etching one of the phases (here PEO, polyethylene oxide) from melt-mixed PE/PEO binary blends. Herein, we have systematically discussed the development of these membranes using X-ray micro-computed tomography. The 3D tomograms of the extruded strands and hot-pressed samples revealed a clear picture as to how the morphology develops and coarsens over a function of time during post-processing operations like compression molding. The coarsening of PE/PEO blends was traced using X-ray micro-computed tomography and scanning electron microscopy (SEM) of annealed blends at different times. It is now understood from X-ray micro-computed tomography that by the addition of a compatibilizer (here lightly maleated PE), a stable morphology can be visualized in 3D. In order to anchor biocidal graphene oxide sheets onto these 3D porous membranes, the PE membranes were chemically modified with acid/ethylene diamine treatment to anchor the GO sheets which were further confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and surface Raman mapping. The transport properties through the membrane clearly reveal unimpeded permeation of water which suggests that anchoring GO on to the membranes does not clog the pores. Antibacterial studies through the direct contact of bacteria with GO anchored PE membranes resulted in 99% of bacterial inactivation. The possible bacterial inactivation through physical disruption of the bacterial cell wall and/or reactive oxygen species (ROS) is discussed herein. Thus this study opens new avenues in designing polyolefin based antibacterial 3D porous membranes for water purification.3D porous membranes were developed by etching one of the phases (here PEO, polyethylene oxide) from melt-mixed PE/PEO binary blends. Herein, we have systematically discussed the development of these membranes using X-ray micro-computed tomography. The 3D tomograms of the extruded strands and hot-pressed samples revealed a clear picture as to how the morphology develops and coarsens over a function of time during post-processing operations like compression molding. The coarsening of PE/PEO blends was traced using X-ray micro-computed tomography and scanning electron microscopy (SEM) of annealed blends at different times. It is now understood from X-ray micro-computed tomography that by the addition of a compatibilizer (here lightly maleated PE), a stable morphology can be visualized in 3D. In order to anchor biocidal graphene oxide sheets onto these 3D porous membranes, the PE membranes were chemically modified with acid/ethylene diamine treatment to anchor the GO sheets which were further confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and surface Raman mapping. The transport properties through the membrane clearly reveal unimpeded permeation of water which suggests that anchoring GO on to the membranes does not clog the pores. Antibacterial studies through the direct contact of bacteria with GO anchored PE membranes resulted in 99% of bacterial inactivation. The possible bacterial inactivation through physical disruption of the bacterial cell wall and/or reactive oxygen species (ROS) is discussed herein. Thus this study opens new avenues in designing polyolefin based antibacterial 3D porous membranes for water purification. Electronic supplementary information (ESI) available: SEM micrographs of porous PE with and without maleated PE, X-ray micro-computed tomogram of porous extruded PE, FTIR spectra of GO, XPS wide spectra of untreated and GO immobilized PE and Raman spectra of PE and GO. See DOI: 10.1039/c6nr01356b

Effect of poly(ethylene oxide) homopolymer and two different poly(ethylene oxide-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymers on morphological, optical, and mechanical properties of nanostructured unsaturated polyester.

PubMed

Builes, Daniel H; Hernández-Ortiz, Juan P; Corcuera, Ma Angeles; Mondragon, Iñaki; Tercjak, Agnieszka

2014-01-22

Novel nanostructured unsaturated polyester resin-based thermosets, modified with poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and two poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) block copolymers (BCP), were developed and analyzed. The effects of molecular weights, blocks ratio, and curing temperatures on the final morphological, optical, and mechanical properties were reported. The block influence on the BCP miscibility was studied through uncured and cured mixtures of unsaturated polyester (UP) resins with PEO and PPO homopolymers having molecular weights similar to molecular weights of the blocks of BCP. The final morphology of the nanostructured thermosetting systems, containing BCP or homopolymers, was investigated, and multiple mechanisms of nanostructuration were listed and explained. By considering the miscibility of each block before and after curing, it was determined that the formation of the nanostructured matrices followed a self-assembly mechanism or a polymerization-induced phase separation mechanism. The miscibility between PEO or PPO blocks with one of two phases of UP matrix was highlighted due to its importance in the final thermoset properties. Relationships between the final morphology and thermoset optical and mechanical properties were examined. The mechanisms and physics behind the morphologies lead toward the design of highly transparent, nanostructured, and toughened thermosetting UP systems.

High-compactness coating grown by plasma electrolytic oxidation on AZ31 magnesium alloy in the solution of silicate-borax

NASA Astrophysics Data System (ADS)

Shen, M. J.; Wang, X. J.; Zhang, M. F.

2012-10-01

A ceramic coating was formed on the surface of AZ31 magnesium alloy by plasma electrolytic oxidation (PEO) in the silicate solution with and without borax doped. The composition, morphology, elements and roughness as well as mechanical property of the coating were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and reciprocal-sliding tribometer. The results show that the PEO coating is mainly composed of magnesia. When using borax dope, boron element is permeating into the coating and the boron containing phase exist in the form of amorphous. In addition, the microhardness and compactness of the PEO coating are improved significantly due to doped borax.

Molecular Dynamics Simulations of Poly(ethylene oxide) Grafted onto Silica Immersed in Melt of Homopolymers.

PubMed

Benková, Zuzana; Cordeiro, M Natália D S

2015-09-22

Tuning of surface properties plays an important role in applications ranging from material engineering to biomedicine/chemistry. The interactions of chains grafted to a solid support and exposed to a matrix of chemically identical chains represent an intriguing issue. In this work, the behavior of poly(ethylene oxide) (PEO) chains grafted irreversibly onto an amorphous silica and immersed in the matrix of free PEO chains of different polymerization degree is studied using molecular dynamics simulations. The density distributions of grafted and free PEO chains, the height of the grafted layer, overlap parameters, and orientation order parameters depend not only on the grafting density but also on the length of free chains which confirm the entropic nature of the interactions between the grafted and free chains. In order to achieve a complete expulsion of the free chains from the grafted layer, a grafting density as high as 3.5 nm(-2) is necessary. Free PEO chains of 9 monomers leave the grafted layer at lower grafting densities than the longer PEO chains of 18 monomers in contrast with the theoretical predictions. The height of the grafted layer evolves with the grafting density in the presence of free chains in qualitative agreement with the theoretical phase diagram.

Glucose-Responsive Hybrid Nanoassemblies in Aqueous Solutions: Ordered Phenylboronic Acid within Intermixed Poly(4-hydroxystyrene)-block-poly(ethylene oxide) Block Copolymer.

PubMed

Matuszewska, Alicja; Uchman, Mariusz; Adamczyk-Woźniak, Agnieszka; Sporzyński, Andrzej; Pispas, Stergios; Kováčik, Lubomír; Štěpánek, Miroslav

2015-12-14

Coassembly behavior of the double hydrophilic block copolymer poly(4-hydroxystyrene)-block-poly(ethylene oxide) (PHOS-PEO) with three amphiphilic phenylboronic acids (PBA) differing in hydrophobicity, 4-dodecyloxyphenylboronic acid (C12), 4-octyloxyphenylboronic acid (C8), and 4-isobutoxyphenylboronic acid (i-Bu) was studied in alkaline aqueous solutions and in mixtures of NaOHaq/THF by spin-echo (1)H NMR spectroscopy, dynamic and electrophoretic light scattering, and SAXS. The study reveals that only the coassembly of C12 with PHOS-PEO provides spherical nanoparticles with intermixed PHOS and PEO blocks, containing densely packed C12 micelles. NMR measurements have shown that spatial proximity of PHOS-PEO and C12 leads to the formation of ester bonds between -OH of PHOS block and hydroxyl groups of -B(OH)2. Due to the presence of PBA moieties, the release of compounds with 1,2- or 1,3-dihydroxy groups loaded in the coassembled PHOS-PEO/PBA nanoparticles by covalent binding to PBA can be triggered by addition of a surplus of glucose that bind to PBA competitively. The latter feature has been confirmed by fluorescence measurements using Alizarin Red as a model compound. Nanoparticles were proved to exhibit swelling in response to glucose as detected by light scattering.

Hydrophilic PEO-PDMS for microfluidic applications

NASA Astrophysics Data System (ADS)

Yao, Mingjin; Fang, Ji

2012-02-01

Polydimethylsiloxane (PDMS) is a popularly used nontoxic and biocompatible material in microfluidic systems, which is relatively cheap and does not break easily like glass. The simple fabrication, optical transparency and elastomeric property make PDMS a handy material to work with. In order to develop different applications of PDMS in microfluidics and bioengineering, it is necessary to modify the PDMS surface nature to improve wetting characteristics, and to have a better control in nonspecific binding of proteins and cells, as well as to increase adhesion. At the moment, the hydrophilic surface modification performance of PDMS is known to recover its hydrophobicity shortly after oxidation modification, which is not stable in the long term (Owen and Smith 1994 J. Adhes. Sci. Technol. 8 1063-75). This paper presents a long-term stable hydrophilic surface modification processing of PDMS. The poly(dimethylsiloxane-ethylene oxide polymeric) (PDMS-b-PEO) is used in this project as a surfactant additive to be added into the PDMS base and the curing agent mixture during polymerization and to create hydrophilic PEO-PDMS. The contact angle can be controlled at 21.5-80.9° with the different mixing ratios and the hydrophilicity will remain stable for two months and then slightly varied later. We also investigate the bonding conditions of the modified PDMS to a silicon wafer and a glass wafer. To demonstrate its applications, we designed a device which consists of microchannels on a silicon wafer, and PEO-PDMS is utilized as a cover sheet. The capillary function was investigated under the different contact angles of PED-PDMS and with different aspect ratios of microchannels. All of the processes and testing data are presented in detail. This easy and cost-effective modified PDMS with a good bonding property can be widely used in the capillary device and systems, and microfluidic devices for fluid flow control of the microchannels in biological, chemical, medical applications.

Silica-F127 nanohybrid-encapsulated manganese oxide nanoparticles for optimized T1 magnetic resonance relaxivity

NASA Astrophysics Data System (ADS)

Wei Hsu, Benedict You; Wang, Miao; Zhang, Yu; Vijayaragavan, Vimalan; Wong, Siew Yee; Yuang-Chi Chang, Alex; Bhakoo, Kishore Kumar; Li, Xu; Wang, John

2013-12-01

To properly engineer MnO nanoparticles (MONPs) of high r1 relaxivity, a nanohybrid coating consisting of silica and F127 (PEO106PPO70PEO106) is designed to encapsulate MONPs. Achieved by an interfacial templating scheme, the nanohybrid encapsulating layer is highly permeable and hydrophilic to allow for an optimal access of water molecules to the encapsulated manganese oxide core. Hence, the efficacy of MONPs as MRI contrast agents is significantly improved, as demonstrated by an enhancement of the MR signal measured with a pre-clinical 7.0 T MRI scanner. The nanohybrid encapsulation strategy also confers high colloidal stability to the hydrophobic MONPs by the surface decoration of PEO chains and a small overall diameter (<100 nm) of the PEO-SiO2 nanohybrid-encapsulated MONPs (PEOMSNs). The PEOMSNs are not susceptible to Mn-ion leaching, and their biocompatibility is affirmed by a low toxicity profile. Moreover, these hybrid nanocapsules exhibit a nano-rattle structure, which would favor the facile loading of various therapeutic reagents for theranostic applications.To properly engineer MnO nanoparticles (MONPs) of high r1 relaxivity, a nanohybrid coating consisting of silica and F127 (PEO106PPO70PEO106) is designed to encapsulate MONPs. Achieved by an interfacial templating scheme, the nanohybrid encapsulating layer is highly permeable and hydrophilic to allow for an optimal access of water molecules to the encapsulated manganese oxide core. Hence, the efficacy of MONPs as MRI contrast agents is significantly improved, as demonstrated by an enhancement of the MR signal measured with a pre-clinical 7.0 T MRI scanner. The nanohybrid encapsulation strategy also confers high colloidal stability to the hydrophobic MONPs by the surface decoration of PEO chains and a small overall diameter (<100 nm) of the PEO-SiO2 nanohybrid-encapsulated MONPs (PEOMSNs). The PEOMSNs are not susceptible to Mn-ion leaching, and their biocompatibility is affirmed by a low toxicity profile. Moreover, these hybrid nanocapsules exhibit a nano-rattle structure, which would favor the facile loading of various therapeutic reagents for theranostic applications. Electronic supplementary information (ESI) available: Fig. S1-S6. See DOI: 10.1039/c3nr04378a

Preparation, process optimization and characterization of core-shell polyurethane/chitosan nanofibers as a potential platform for bioactive scaffolds.

PubMed

Maleknia, Laleh; Dilamian, Mandana; Pilehrood, Mohammad Kazemi; Sadeghi-Aliabadi, Hojjat; Hekmati, Amir Houshang

2018-06-01

In this paper, polyurethane (PU), chitosan (Cs)/polyethylene oxide (PEO), and core-shell PU/Cs nanofibers were produced at the optimal processing conditions using electrospinning technique. Several methods including SEM, TEM, FTIR, XRD, DSC, TGA and image analysis were utilized to characterize these nanofibrous structures. SEM images exhibited that the core-shell PU/Cs nanofibers were spun without any structural imperfections at the optimized processing conditions. TEM image confirmed the PU/Cs core-shell nanofibers were formed apparently. It that seems the inclusion of Cs/PEO to the shell, did not induce the significant variations in the crystallinity in the core-shell nanofibers. DSC analysis showed that the inclusion of Cs/PEO led to the glass temperature of the composition increased significantly compared to those of neat PU nanofibers. The thermal degradation of core-shell PU/Cs was similar to PU nanofibers degradation due to the higher PU concentration compared to other components. It was hypothesized that the core-shell PU/Cs nanofibers can be used as a potential platform for the bioactive scaffolds in tissue engineering. Further biological tests should be conducted to evaluate this platform as a three dimensional scaffold with the capabilities of releasing the bioactive molecules in a sustained manner.

A Facile Methodology for the Development of a Printable and Flexible All-Solid-State Rechargeable Battery.

PubMed

De, Bibekananda; Yadav, Amit; Khan, Salman; Kar, Kamal K

2017-06-14

Development of printable and flexible energy storage devices is one of the most promising technologies for wearable electronics in textile industry. The present work involves the design of a printable and flexible all-solid-state rechargeable battery for wearable electronics in textile applications. Copper-coated carbon fiber is used to make a poly(ethylene oxide) (PEO)-based polymer nanocomposite for a flexible and conductive current collector layer. Lithium iron phosphate (LiFePO 4 ) and titanium dioxide (TiO 2 ) are utilized to prepare the cathode and anode layers, respectively, with PEO and carbon black composites. The PEO- and Li salt-based solid composite separator layer is utilized for the solid-state and safe electrolyte. Fabrication of all these layers and assembly of them through coating on fabrics are performed in the open atmosphere without using any complex processing, as PEO prevents the degradation of the materials in the open atmosphere. The performance of the battery is evaluated through charge-discharge and open-circuit voltage analyses. The battery shows an open-circuit voltage of ∼2.67 V and discharge time ∼2000 s. It shows similar performance at different repeated bending angles (0° to 180°) and continuous bending along with long cycle life. The application of the battery is also investigated for printable and wearable textile applications. Therefore, this printable, flexible, easily processable, and nontoxic battery with this performance has great potential to be used in portable and wearable textile electronics.

Comparison of mechanical properties of multi-walled carbon nanotube and graphene nanosheet/polyethylene oxide composites plasticized with lithium triflate

NASA Astrophysics Data System (ADS)

Jurkane, A.; Gaidukov, S.

2017-10-01

A strong engineering interest in nanostructured conducting polymers and its composite materials have been widely used to build various sensor devices, electronic interconnect devices, fuel cells and batteries. Preparation of polymeric nano-composites with finely controlled structure, especially, at nano-scale, is still one of the most perspective modification ways of the properties of polymeric composites. Multi-walled carbon nanotube (MWCNT)/polyethylene oxide (PEO) and graphene nanosheets (GR)/PEO composites and composite of MWCNT/GR/PEO were prepared by solution casting and hot-pressing method. Composites were plasticized by 5% of Lithium triflate (LiTrifl), which play role of additional ion source in conducting polymer composite. Mechanical tensile tests were performed to evaluate nanoparticles influence on the mechanical strength of the conductive polymer composite materials. Difference of tensile tests of prepared composition can be seen from tensile tests data curves. The results of tensile tests indicated that the nanoparticles can provide PEO/5%LiTrifl composite with stiffening effects at rather low filler content (at least 0.05% by volume).

Simulated glass transition of poly(ethylene oxide) bulk and film: a comparative study.

PubMed

Wu, Chaofu

2011-09-29

Stepwise cooling molecular dynamics (MD) simulations have been carried out on the bulk and film models for poly(ethylene oxide) (PEO) to understand glass transition of amorphous polymer films. Three types of properties--density, energy, and dynamics--are computed and plotted against the temperature for the two systems. It has been confirmed that all these properties can reveal glass transition in both PEO bulk and film systems. All the determined glass transition temperatures (T(g)'s) drop in the same order of magnitude to the experimental data available. Among various methods, the T(g)'s obtained from the density and energy data are close to each other if the same space regions are defined, which can suggest the same free volume theory, and dynamic T(g)'s obtained from mean-squared displacements (MSDs) are highest, which can suggest the kinetic theory for structural relaxation. Consistently, all these T(g)'s obtained using different methods show that the T(g)'s of PEO film are lower than those of PEO bulk. The free surface layers of polymer films dictate this offset. © 2011 American Chemical Society

Effects of Alloying Element Ca on the Corrosion Behavior and Bioactivity of Anodic Films Formed on AM60 Mg Alloys

PubMed Central

Anawati, Anawati; Asoh, Hidetaka; Ono, Sachiko

2016-01-01

Effects of alloying element Ca on the corrosion behavior and bioactivity of films formed by plasma electrolytic oxidation (PEO) on AM60 alloys were investigated. The corrosion behavior was studied by conducting electrochemical tests in 0.9% NaCl solution while the bioactivity was evaluated by soaking the specimens in simulated body fluid (SBF). Under identical anodization conditions, the PEO film thicknesses increased with increasing Ca content in the alloys, which enhanced the corrosion resistance in NaCl solution. Thicker apatite layers grew on the PEO films of Ca-containing alloys because Ca was incorporated into the PEO film and because Ca was present in the alloys. Improvement of corrosion resistance and bioactivity of the PEO-coated AM60 by alloying with Ca may be beneficial for biodegradable implant applications. PMID:28772371

In situ investigation of supercritical CO2 assisted impregnation of drugs into a polymer by high pressure FTIR micro-spectroscopy.

PubMed

Champeau, M; Thomassin, J-M; Jérôme, C; Tassaing, T

2015-02-07

An original experimental set-up combining a FTIR micro-spectrometer with a high pressure cell has been built in order to analyze in situ the impregnation of a solute into microscopic polymer samples, such as fibers or films, subjected to supercritical CO2. Thanks to this experimental set-up, key factors governing the impregnation process can be simultaneously followed such as the swelling of the polymeric matrix, the CO2 sorption, the kinetics of impregnation and the drug loading into the matrix. Moreover, the solute/polymer interactions and the speciation of the solute can be analyzed. We have monitored in situ the impregnation of aspirin and ketoprofen into PEO (Polyethylene Oxide) platelets at T = 40 °C and P = 5; 10 and 15 MPa. The kinetics of impregnation of aspirin was quicker than the one of ketoprofen and the final drug loading was also higher in the case of aspirin. Whereas the CO2 sorption and the PEO swelling remain constant when PEO is just subjected to CO2 under isobaric conditions, we noticed that both parameters can increase while the drug impregnates PEO. Coupling these results with DSC measurements, we underlined the plasticizing effect of the drug that also leads to a decrease in the crystallinity of PEO in situ thus favoring the sorption of CO2 molecules into the matrix and the swelling of the matrix. The plasticizing effect increases with the drug loading. Finally, the speciation of drugs was investigated considering the shift of the carboxyl bands of the drugs. Both drugs were found to be mainly homogeneously dispersed into PEO.

Hydroxypropyl-β-CD vs. its α-homologue for a 3D modified polyrotaxane network formation and properties: the relationship between modified CD and polymer revealed through comparison.

PubMed

Li, Zhao; Zheng, Zhen; Su, Shan; Yu, Lin; Wang, Xinling

2016-09-14

The threading mechanism of the hydroxypropyl-cyclodextrin (Hy-CD)/tetrahedron-like poly(ethylene glycol) (tetra-PEG) based host-guest complex and the relationship between Hy-CD and poly(ethylene oxide) (PEO) in the three-dimensional modified polyrotaxane (PR) formed by the complex were revealed through the comparison between Hy-β-CD/tetra-PEG and Hy-α-CD/tetra-PEG based systems from the macroscopic material view to the microscopic molecular view. The complexation between Hy-CD and tetra-PEG in water experiences a threading-dethreading-rethreading process which is controlled by the intermolecular interaction intensity or molecular hindrance depending on the feed ratio of Hy-CD to tetra-PEG. In the 3D modified PR, the methyl group of the Hy part on one Hy-CD can insert into the cavity of the adjacent Hy-CD and interacts with both the interior surface of the cavity and the PEO segment within the cavity if the cavity of Hy-CD is large enough. The threaded Hy-CD in the PR straightens the chain of PEO and suppresses the segment motion of the PEO. With the decrease of the cavity size of Hy-CD, the degree of suppression on the segment motion of PEO increases. Hy-CD threaded on the PEO chain can also deform when the 3D modified PR is compressed, and the degree of deformation increases with the increase of the cavity size of Hy-CD. These results of the modified CD/PEG based complex system set it apart from the unmodified CD/PEG based one, and reveal the structure-property relationship of this new type of Hy-CD/tetra-PEG based 3D modified PR material.

Mechanical properties of PEO-coatings on the surface of magnesium alloy MA8 modified by TiN nanoparticles

NASA Astrophysics Data System (ADS)

Imshinetsky, Igor M.; Mashtalyar, Dmitriy V.; Sunebryukhov, Sergey L.; Gnedenkov, Sergey V.

2017-09-01

The methods to form protective coatings by the plasma electrolytic oxidation method (PEO) in the electrolytic system containing nanosized particles of titanium nitride has been develoted. Tribological and morfological studies of the composite coatings have been carried out. It has been established that the microhardness of the coating with nanoparticles concentration of 3 g/l increases by 2 folds, while the wear resistance - by 2.2 fold, as compared to respective values for the PEO-coating formed in the electrolyte without nanoparticles.

An evaluation of the effects of PEO/PEG molecular weights on extruded alumina rods

NASA Astrophysics Data System (ADS)

Bolger, Nancy Beth

1998-12-01

Alumina rods were piston extruded from bodies containing polyethylene glycols (PEGs) and polyethylene oxides (PEOs) with molecular weights ranging from 1,300 to 3,800,000 g/mol. A blend of aluminas possessing different particle size distributions was evaluated with regard to its extrusion pressure by varying the amount of PEG/PEO addition. Behavior exhibited by the alumina blend was dependent upon the additive that was used. The higher molecular weight binders with average molecular weight of 200,000 g/mol and 3,350,000 g/mol displayed the most severe behaviors of near dilatant and dilatant respectively. Physical properties of the green and fired states, as well as the binder burnout, were investigated with the changing additions. Correlation between the green and fired strengths and the changing molecular weights were examined. The additive present influenced the surface properties of the rods, which affected the green strengths. The highest average molecular weight polyethylene glycols showed higher green strengths, while the lowest green strengths were observed for the high molecular weight polyethylene oxides. Fired strengths generally ranged from approximately 12,000 psi to 16,000 psi for additive batches. Alumina pellets containing twelve separate combinations of polyethylene glycol with polyethylene oxide were dry pressed. Physical properties of the green and fired states were examined. Statistical analysis was performed upon the data and seven combinations of polyethylene glycol with polyethylene oxide were deemed significant. These combinations in conjunction with the same alumina blend were then piston extruded. The addition of polyethylene glycol reduced the near dilatant behavior exhibited by the 200,000 g/mol average molecular weight polyethylene oxide. Dilatant behavior was completely eliminated from the 3,350,000 g/mol average molecular weight polyethylene oxide batches. Physical properties of the green and fired states were again investigated with the changing additions. Polyethylene oxide, in combination with polyethylene glycol, did show an increase in green strength versus the polyethylene oxide alone. Strengths were still lower than those displayed by the polyethylene glycols alone. Reductions or degradations in molecular weight of the polymers due to mixing and extrusion processes may account for lower green strength of bodies, especially those containing polyethylene oxides.

Electrical Characterization of Polyaniline/polyethylene Oxide Nanofibers for Field Effect Transistors

NASA Technical Reports Server (NTRS)

Mueller, Carl H.; Theofylaktos, Noulie; Pinto, Nicholas J.; Robinson, Daryl C.; Miranda, Felix A.

2002-01-01

Nanofibers comprised of polyaniline/polyethylene oxide (PANI/PEO) are being developed for novel logic devices. We report the electrical conductivity of PANI/PEO nanofibers with diameters in the 100 to 200 nm range. We measured conductivity values of approx. 0.3 to 1.0 S/cm, which is higher than the values reported for thicker nanofibers, but less than the bulk value of PANI. The electrical measurements were performed by depositing the fibers on pre-electroded, oxidized silicon (Si) substrates. The excellent adherence of the nanofibers to the SiO2 as well as the gold (Au) electrodes may be useful in the design of future devices.

The influence of guaifenesin and ketoprofen on the properties of hot-melt extruded polyethylene oxide films.

PubMed

Crowley, Michael M; Fredersdorf, Anke; Schroeder, Britta; Kucera, Shawn; Prodduturi, Suneela; Repka, Michael A; McGinity, James W

2004-08-01

Films containing polyethylene oxide (PEO) and a model drug, either guaifenesin (GFN) or ketoprofen (KTP), were prepared by hot-melt extrusion. The thermal properties of the hot-melt extruded films were investigated using differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) was used to examine the surface morphology of the films, and wide angle X-ray diffraction (XRD) was used to investigate the crystalline properties of the polymer, drugs and physical mixtures as well as the solid state structure of the films. The stability of the polymer was studied using gel permeation chromatography. The mechanical properties, including percent elongation and tensile strength of the films, were determined on an Instron according to American Society for Testing Materials (ASTM) procedures. The Hansen solubility parameter was calculated using the Hoftyzer or van Krevelen method to estimate the likelihood of drug--polymer miscibility. Both GFN and KTP were stable during the extrusion process. Melting points corresponding to the crystalline drugs were not observed in the films. Crystallization of GFN on the surface of the film was observed at all concentrations studied, however KTP crystallization did not occur until reaching the 15% level. Guaifenesin and ketoprofen were found to decrease drive load, increase PEO stability and plasticize the polymer during extrusion. The Hansen solubility parameters predicted miscibility between PEO and KTP and poor miscibility between PEO and GFN. The predictions of the solubility parameters were in agreement with the XRD and SEM results. The percent elongation decreased with increasing GFN concentrations and significantly increased with increasing levels of KTP. Both GFN and KTP decreased the tensile strength of the extruded film.

Molecular dynamics simulation of interactions between a sodium dodecyl sulfate micelle and a poly(ethylene oxide) polymer.

PubMed

Shang, Barry Z; Wang, Zuowei; Larson, Ronald G

2008-03-13

We have performed atomistic molecular dynamics simulations of an anionic sodium dodecyl sulfate (SDS) micelle and a nonionic poly(ethylene oxide) (PEO) polymer in aqueous solution. The micelle consisted of 60 surfactant molecules, and the polymer chain lengths varied from 20 to 40 monomers. The force field parameters for PEO were adjusted by using 1,2-dimethoxymethane (DME) as a model compound and matching its hydration enthalpy and conformational behavior to experiment. Excellent agreement with previous experimental and simulation work was obtained through these modifications. The simulated scaling behavior of the PEO radius of gyration was also in close agreement with experimental results. The SDS-PEO simulations show that the polymer resides on the micelle surface and at the hydrocarbon-water interface, leading to a selective reduction in the hydrophobic contribution to the solvent-accessible surface area of the micelle. The association is mainly driven by hydrophobic interactions between the polymer and surfactant tails, while the interaction between the polymer and sulfate headgroups on the micelle surface is weak. The 40-monomer chain is mostly wrapped around the micelle, and nearly 90% of the monomers are adsorbed at low PEO concentration. Simulations were also performed with multiple 20-monomer chains, and gradual addition of polymer indicates that about 120 monomers are required to saturate the micelle surface. The stoichiometry of the resulting complex is in close agreement with experimental results, and the commonly accepted "beaded necklace" structure of the SDS-PEO complex is recovered by our simulations.

Synthesis and Properties of Highly Dispersed Ionic Silica–Poly(ethylene oxide) Nanohybrids

PubMed Central

2013-01-01

We report an ionic hybrid based on silica nanoparticles as the anion and amine-terminated poly(ethylene oxide) (PEO) as a cation. The charge on the nanoparticle anion is carried by the surface hydroxyls. SAXS and TEM reveal an exceptional degree of dispersion of the silica in the polymer and high degree of order in both thin film and bulk forms. In addition to better dispersion, the ionic hybrid shows improved flow characteristics compared to silica/PEO mixtures in which the ionic interactions are absent. PMID:23351113

The dynamics of solvation dictates the conformation of polyethylene oxide in aqueous, isobutyric acid and binary solutions.

PubMed

Dahal, Udaya R; Dormidontova, Elena E

2017-04-12

Polymers hydrogen-bonding with solvent represent an important broad class of polymers, properties of which depend on solvation. Using atomistic molecular dynamics simulations with the OPLS/AA force field we investigate the effect of hydrogen bonding on PEO conformation and chain mobility by comparing its behavior in isobutyric acid and aqueous solutions. In agreement with experimental data, we found that in isobutyric acid PEO forms a rather rigid extended helical structure, while in water it assumes a highly flexible coil conformation. We show that the difference in PEO conformation and flexibility is the result of the hydrogen bond stability and overall solvent dynamics near PEO. Isobutyric acid forms up to one hydrogen bond per repeat unit of PEO and interacts with PEO for a prolonged period of time, thereby stabilizing the helical structure of the polymer and reducing its segmental mobility. In contrast, water forms on average 1.2 hydrogen bonds per repeat unit of PEO (with 60% of water forming a single hydrogen bond and 40% of water forming two hydrogen bonds) and resides near PEO for a noticeably shorter time than isobutyric acid, leading to the well-documented high segmental mobility of PEO in water. We also analyze PEO conformation, hydrogen bonding and segmental mobility in binary water/isobutyric acid solutions and find that in the phase separated region PEO resides in the isobutyric-rich phase forming about 25% of its hydrogen bonds with isobutyric acid and 75% with water. We show that the dynamics of solvation affects the equilibrium properties of macromolecules, such as conformation, and by mixing of hydrogen bond-donating solvents one can significantly alter both polymer conformation and its local dynamics.

PLA/CS/Nifedipine Nanocomposite Films: Properties and the In Vitro Release of Nifedipine

NASA Astrophysics Data System (ADS)

Trang, Nguyen Thi Thu; Chinh, Nguyen Thuy; Giang, Nguyen Vu; Thanh, Dinh Thi Mai; Lam, Tran Dai; Hoang, Thai

2016-07-01

The polylactic acid (PLA)/chitosan (CS) films containing a drug, nifedipine (NIF), in the presence of polyethylene oxide (PEO) as a compatibilizer were prepared by the solution method. This method has not been used to form films containing four components (PLA, CS, NIF, PEO) up to now. The CS, PEO, and NIF contents are 25 wt.%, 6-8 wt.%, and 10-50 wt.% in comparison with PLA weight, respectively. Fourier transform infrared spectroscopy (FTIR), thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC), and field emission scanning electron microscopy (FESEM) were used to characterize the interactions, properties, and morphology of the PLA/CS/PEO/NIF films. The FTIR, TGA, and DSC results show that NIF carried by PLA/CS/PEO films and PLA, CS, NIF had better interaction and were more compatible when using PEO. The surface morphology of PLA/CS/PEO/NIF films was similar to that of PLA/CS/PEO films. Moreover, this was the first time drug loading and NIF release content from PLA/CS/PEO films were determined by the ultraviolet-visible (UV-Vis) spectroscopy method. The drug loading of PLA/CS/PEO/NIF films was from 80.99% to 93.61%. The in vitro NIF release studies were carried out in pH 2, 6.8, and 7.4 solutions corresponding to the pH of stomach, colon, and duodenum regions in the human body, respectively. The NIF release content in different pH solutions is in the order: pH 2 > pH 6.8 > pH 7.4 and increases when there is increasing NIF loading. The PLA/CS/PEO films are potential materials to apply for long-circulating systems for NIF delivery.

Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

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

Sakamoto, Y.; Ishii, Y.; Kawasaki, S., E-mail: kawasaki.shinji@nitech.ac.jp

2016-07-06

Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

Failure Analysis of Alumina Reinforced Aluminum Microtruss and Tube Composites

NASA Astrophysics Data System (ADS)

Chien, Hsueh Fen (Karen)

The energy absorption capacity of cellular materials can be dramatically increased by applying a structural coating. This thesis examined the failure mechanisms of alumina reinforced 3003 aluminum alloy microtrusses and tubes. Alumina coatings were produced by hard anodizing and by plasma electrolytic oxidation (PEO). The relatively thin and discontinuous oxide coating at the hinge acted as a localized weak spot which triggered a chain reaction of failure, including oxide fracture, oxide spallation, oxide penetration to the aluminum core and severe local plastic deformation of the core. For the PEO microtrusses, delamination occurred within the oxide coating resulting in a global strut buckling failure mode. A new failure mode for the anodized tubes was observed: (i) axisymmetric folding of the aluminum core, (ii) longitudinal fracture, and (iii) alumina pulverization. Overall, the alumina coating enhanced the buckling resistance of the composites, while the aluminum core supported the oxide during the damage propagation.

Mesoporous CeO2 nanoparticles synthesized by an inverse miniemulsion technique and their catalytic properties in methane oxidation

NASA Astrophysics Data System (ADS)

Nabih, Nermeen; Schiller, Renate; Lieberwirth, Ingo; Kockrick, Emanuel; Frind, Robert; Kaskel, Stefan; Weiss, Clemens K.; Landfester, Katharina

2011-04-01

Cerium(IV) oxide nanoparticles were synthesized using an inverse miniemulsion technique with cerium nitrate hexahydrate as precursor. The resulting nanocrystallites are as small as 5 nm with a specific surface area of 158 m2 g - 1 after calcination at 400 °C. With the addition of cetyltrimethylammonium bromide (CTAB) or (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)) triblock copolymers (PEO-PPO-PEO) as template in the miniemulsion droplets, the specific surface area can be increased up to 255 m2 g - 1. The miniemulsions were characterized by dynamic light scattering (DLS) and the obtained oxides were examined by x-ray diffraction (XRD), nitrogen sorption (BET and BJH), and transmission electron microscopy (TEM). The catalytic activity of the resulting ceria was investigated for the temperature-programmed oxidation (TPO) of methane.

The role of cathodic current in PEO of aluminum: Influence of cationic electrolyte composition on the transient current-voltage curves and the discharges optical emission spectra

NASA Astrophysics Data System (ADS)

Rogov, A. B.; Shayapov, V. R.

2017-02-01

In this paper, the influence of cationic electrolytes composition on electrical and optical responses of plasma electrolytic oxidation process of A1050 aluminum alloy under alternating polarization is considered. The electrolytes consist of 0.1 M boric acid with addition of one of the following hydroxides: LiOH, NaOH, KOH, tetraethylammonium hydroxide, Ca(OH)2 up to pH value 9.2. Coatings microstructure, elemental and phase compositions were studied by SEM, EDS and XRD. It was shown that the hysteresis of anodic current-voltage curve (specific feature of "Soft sparking" PEO) was clear observed in the presence of sodium and potassium cations. It was found that composition of microdischarges plasma is also affected by the nature of the cations. It was shown that there are a number of reciprocal processes, which take place under anodic and cathodic polarization.

Study of the pluronic-silica interaction in synthesis of mesoporous silica under mild acidic conditions.

PubMed

Sundblom, Andreas; Palmqvist, Anders E C; Holmberg, Krister

2010-02-02

The interaction between silica and poly(ethylene oxide) (PEO) in water may appear trivial and it is generally stated that hydrogen bonding is responsible for the attraction. However, a literature search shows that there is not a consensus with respect to the mechanism behind the attractive interaction. Several papers claim that only hydrogen bonding is not sufficient to explain the binding. The silica-PEO interaction is interesting from an academic perspective and it is also exploited in the preparation of mesoporous silica, a material of considerable current interest. This study concerns the very early stage of synthesis of mesoporous silica under mild acidic conditions, pH 2-5, and the aim is to shed light on the interaction between silica and the PEO-containing structure directing agent. The synthesis comprises two steps. An organic silica source, tetraethylorthosilicate (TEOS), is first hydrolyzed and Pluronic P123, a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer, is subsequently added at different time periods following the hydrolysis of TEOS. It is shown that the interaction between the silica and the Pluronic is dependent both on the temperature and on the time between onset of TEOS hydrolysis and addition of the copolymer. The results show that the interaction is mainly driven by entropy. The effect of the synthesis temperature and of the time between hydrolysis and addition of the copolymer on the final material is also studied. The material with the highest degree of mesoorder was obtained when the reaction was performed at 20 degrees C and the copolymer was added 40 h after the start of TEOS hydrolysis. It is claimed that the reason for the good ordering of the silica is that whereas particle formation under these conditions is fast, the rate of silica condensation is relatively low.

Poly(ethylene oxide)-Assisted Macromolecular Self-Assembly of Lignin in ABS Matrix for Sustainable Composite Applications

DOE PAGES

Akato, Kokouvi M.; Tran, Chau D.; Chen, Jihua; ...

2015-11-05

Here we report the compatibilization of biomass-derived lignin polymer in acrylonitrile butadiene styrene (ABS) thermoplastic matrix without loss of mechanical properties via poly(ethylene oxide) (PEO)-mediated macromolecular self-assembly. ABS was blended with lignin in different concentrations, and blends with 10 wt % PEO (relative to lignin) were prepared. The relative tensile strength improved slightly at low lignin content but diminished rapidly as the lignin content was increased. However, the inclusion of PEO as an interfacial adhesion promoter helped avoid deleterious effects. Dynamic mechanical analysis showed that PEO plasticized the hard phase and thus lowered the activation energy (E a) for itsmore » relaxation but caused stiffening of the soft phase and increased its E a. Microscopy revealed that incorporating lignin in ABS led to the statistical dispersion of discrete lignin domains (300–1000 nm) which, after PEO addition, were reduced to smaller interconnected particles (200–500 nm). The lignin-extended partially renewable ABS resins showed shear-thinning behavior and reduced viscosity compared to neat ABS. The preferred lignin-loaded compositions reinforced with 20 vol % chopped carbon fibers exhibited mechanical performances (77–80 MPa) equivalent to those of reinforced ABS materials reportedly used in 3D printing applications. In conclusion, this approach could lower the cost of ABS while reducing its carbon footprint.« less

Self-organization of poly(ethylene oxide) on the surface of aqueous salt solutions.

PubMed

Fuchs, Christian; Hussain, Hazrat; Amado, Elkin; Busse, Karsten; Kressler, Joerg

2015-01-01

It is demonstrated that stable Langmuir films of poly(ethylene oxide) (PEO) can be formed up to surface pressures of 30 mN m(-1) when potassium carbonate K2CO3 is added to the aqueous subphase. Generally, PEO homopolymer cannot stay on the water surface at a surface pressure ≥10 mN m(-1) due to its high water solubility. To prepare stable monolayer films, PEO can be modified with hydrophobic moieties. However, by exploiting the salting out effect by adding certain salts (K2CO3 or MgSO4) into the aqueous subphase, not only very stable films but also unusual self-organization can be achieved by the PEO homopolymer on the surface of the aqueous solution. Thus, a series of OH-terminated PEOs is found to form a stable monolayer at K2CO3 concentrations of 2 M and above in the aqueous subphase, and the stability of the film increases with an increase in K2CO3 concentration. Hysteresis experiments are also carried out. During the phase transition induced by progressive compression, self-organization into well-defined domains with sizes in the micrometer range are observed, and with further compression and holding of the film for 30 min and above the microdomains transform into a crystalline morphology as visualized by Brewster angle microscopy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biodegradable copolymers carrying cell-adhesion peptide sequences.

PubMed

Proks, Vladimír; Machová, Lud'ka; Popelka, Stepán; Rypácek, Frantisek

2003-01-01

Amphiphilic block copolymers are used to create bioactive surfaces on biodegradable polymer scaffolds for tissue engineering. Cell-selective biomaterials can be prepared using copolymers containing peptide sequences derived from extracellular-matrix proteins (ECM). Here we discuss alternative ways for preparation of amphiphilic block copolymers composed of hydrophobic polylactide (PLA) and hydrophilic poly(ethylene oxide) (PEO) blocks with cell-adhesion peptide sequences. Copolymers PLA-b-PEO were prepared by a living polymerisation of lactide in dioxane with tin(II)2-ethylhexanoate as a catalyst. The following approaches for incorporation of peptides into copolymers were elaborated. (a) First, a side-chain protected Gly-Arg-Gly-Asp-Ser-Gly (GRGDSG) peptide was prepared by solid-phase peptide synthesis (SPPS) and then coupled with delta-hydroxy-Z-amino-PEO in solution. In the second step, the PLA block was grafted to it via a controlled polymerisation of lactide initiated by the hydroxy end-groups of PEO in the side-chain-protected GRGDSG-PEO. Deprotection of the peptide yielded a GRGDSG-b-PEO-b-PLA copolymer, with the peptide attached through its C-end. (b) A protected GRGDSG peptide was built up on a polymer resin and coupled with Z-carboxy-PEO using a solid-phase approach. After cleavage of the delta-hydroxy-PEO-GRGDSG copolymer from the resin, polymerisation of lactide followed by deprotection of the peptide yielded a PLA-b-PEO-b-GRGDSG block copolymer, in which the peptide is linked through its N-terminus.

Insights into the use of polyethylene oxide in energy storage/conversion devices: a critical review

NASA Astrophysics Data System (ADS)

Arya, Anil; Sharma, A. L.

2017-11-01

In this review, the latest updates in poly (ethylene oxide) based electrolytes are summarized. The ultimate goal of researchers globally is towards the development of free-standing solid polymeric separators for energy storage devices. This single free-standing solid polymeric separator may replace the liquid and separator (organic/inorganic) used in existing efficient/smart energy technology. As an example, polyethylene oxide (PEO) consists of an electron donor-rich group which provides coordinating sites to the cation for migration. Owing to this exclusive structure, PEO exhibits some remarkable properties, such as a low glass transition temperature, excellent flexibility, and the ability to make complexation with various metal salts which are unattainable by another polymer host. Hence, the PEO is an emerging candidate that has been most examined or is currently under consideration for application in energy storage devices. This review article first provides a detailed study of the PEO properties, characteristics of the constituents of the polymer electrolyte, and suitable approaches for the modification of polymer electrolytes. Then, the synthesization and characterizations techniques are outlined. The structures, characteristics, and performance during charge-discharge of four types of electrolyte/separators (liquid, plasticized, and dispersed and intercalated electrolyte) are highlighted. The suitable ion transport mechanism proposed by researchers in different renowned groups have been discussed for the better understanding of the ion dynamics in such systems.

High-resolution Kendrick Mass Defect Analysis of Poly(ethylene oxide)-based Non-ionic Surfactants and Their Degradation Products.

PubMed

Fouquet, Thierry; Shimada, Haruo; Maeno, Katsuyuki; Ito, Kanako; Ozeki, Yuka; Kitagawa, Shinya; Ohtani, Hajime; Sato, Hiroaki

2017-09-01

Matrix assisted laser desorption ionization (MALDI) high-resolution mass spectrometry (HRMS) and the recently introduced high-resolution Kendrick mass defect (HRKMD) analysis are combined to thoroughly characterize non-ionic surfactants made of a poly(ethylene oxide) (PEO) core capped by esters of fatty acids. A PEO monostearate surfactant is first analyzed as a proof of principle of the HRKMD analysis conducted with a fraction of EO as the base unit (EO/X with X being an integer) in lieu of EO for a regular KMD analysis. Data visualization is greatly enhanced and the distributions detected in the MALDI mass spectrum are assigned to a pristine (H, OH)-PEO as well as mono- and di-esterified PEO chains with palmitate and stearate end-groups in HRKMD plots computed with EO/45. The MALDI-HRMS/HRKMD analysis is then successfully applied to the more complex case of ethoxylated hydrogenated castor oil (EHCO) found to contain a large number of hydrogenated ricinoleate moieties (up to 14) in its HRKMD plot computed with EO/43, departing from the expected triglyceride structure. The exhaustiveness of the MALDI-HRMS/HRKMD strategy is validated by comparing the so-obtained fingerprints with results from alternative techniques (electrospray ionization MS, size exclusion and liquid adsorption chromatography, ion mobility spectrometry). Finally, aged non-ionic surfactants formed upon hydrolytic degradation are analyzed by MALDI-HRMS/HRKMD to easily assign the degradation products and infer the associated degradation routes. In addition to the hydrolysis of the ester groups observed for EHCO, chain scissions and new polar end-groups are observed in the HRKMD plot of PEO monostearate arising from a competitive oxidative ageing.

Release mechanisms of acetaminophen from polyethylene oxide/polyethylene glycol matrix tablets utilizing magnetic resonance imaging.

PubMed

Tajiri, Tomokazu; Morita, Shigeaki; Sakamoto, Ryosaku; Suzuki, Masazumi; Yamanashi, Shigeyuki; Ozaki, Yukihiro; Kitamura, Satoshi

2010-08-16

Release mechanism of acetaminophen (AAP) from extended-release tablets of hydrogel polymer matrices containing polyethylene oxide (PEO) and polyethylene glycol (PEG) were achieved using flow-through cell with magnetic resonance imaging (MRI). The hydrogel forming abilities are observed characteristically and the layer thickness which is corresponding to the diffusion length of AAP has a good correlation with the drug release profiles. In addition, polymeric erosion contribution to AAP releasing from hydrogel matrix tablets was directly quantified using size-exclusion chromatography (SEC). The matrix erosion profile indicates that the PEG erosion kinetic depends primarily on the composition ratio of PEG to PEO. The present study has confirmed that the combination of in situ MRI and SEC should be well suited to investigate the drug release mechanisms of hydrogel matrix such as PEO/PEG. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Structural Evolution of Low-Molecular-Weight Poly(ethylene oxide)-block-polystyrene Diblock Copolymer Thin Film

PubMed Central

Huang, Xiaohua

2013-01-01

The structural evolution of low-molecular-weight poly(ethylene oxide)-block-polystyrene (PEO-b-PS) diblock copolymer thin film with various initial film thicknesses on silicon substrate under thermal annealing was investigated by atomic force microscopy, optical microscopy, and contact angle measurement. At film thickness below half of the interlamellar spacing of the diblock copolymer (6.2 nm), the entire silicon is covered by a polymer brush with PEO blocks anchored on the Si substrate due to the substrate-induced effect. When the film is thicker than 6.2 nm, a dense polymer brush which is equal to half of an interlamellar layer was formed on the silicon, while the excess material dewet this layer to form droplets. The droplet surface was rich with PS block and the PEO block crystallized inside the bigger droplet to form spherulite. PMID:24302862

Fibrin-polyethylene oxide interpenetrating polymer networks: new self-supported biomaterials combining the properties of both protein gel and synthetic polymer.

PubMed

Akpalo, E; Bidault, L; Boissière, M; Vancaeyzeele, C; Fichet, O; Larreta-Garde, V

2011-06-01

Interpenetrating polymer network (IPN) architectures were conceived to improve the mechanical properties of a fibrin gel. Conditions allowing an enzymatic reaction to create one of the two networks in IPN architecture were included in the synthesis pathway. Two IPN series were carried out, starting from two polyethylene oxide (PEO) network precursors leading to different cross-linking densities of the PEO phase. The fibrin concentration varied from 5 to 20 wt.% in each series. The behavior of these materials during dehydration/hydration cycles was also studied. The mechanical properties of the resulting IPN were characterized in the wet and dry states. These self-supported biomaterials combine the properties of both a protein gel and a synthetic polymer. Finally, cells were grown on PEO/fibrin IPN, indicating that they are non-cytotoxic. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Microstructure, nickel suppression and mechanical characteristics of electropolished and photoelectrocatalytically oxidized biomedical nickel titanium shape memory alloy.

PubMed

Chu, C L; Guo, C; Sheng, X B; Dong, Y S; Lin, P H; Yeung, K W K; Chu, Paul K

2009-07-01

A new surface modification protocol encompassing an electropolishing pretreatment (EP) and subsequent photoelectrocatalytic oxidation (PEO) has been developed to improve the surface properties of biomedical nickel titanium (NiTi) shape memory alloy (SMA). Electropolishing is a good way to improve the resistance to localized breakdown of NiTi SMA whereas PEO offers the synergistic effects of advanced oxidation and electrochemical oxidation. Our results indicate that PEO leads to the formation of a sturdy titania film on the EP NiTi substrate. There is an Ni-free zone near the top surface and a graded interface between the titania layer and NiTi substrate, which bodes well for both biocompatibility and mechanical stability. In addition, Ni ion release from the NiTi substrate is suppressed, as confirmed by the 10-week immersion test. The modulus and hardness of the modified NiTi surface increase with larger indentation depths, finally reaching plateau values of about 69 and 3.1GPa, respectively, which are slightly higher than those of the NiTi substrate but much lower than those of a dense amorphous titania film. In comparison, after undergoing only EP, the mechanical properties of NiTi exhibit an inverse change with depth. The deformation mechanism is proposed and discussed. Our results indicate that surface modification by dual EP and PEO can notably suppress Ni ion release and improve the biocompatibility of NiTi SMA while the surface mechanical properties are not compromised, making the treated materials suitable for hard tissue replacements.

Optimization of neural network for ionic conductivity of nanocomposite solid polymer electrolyte system (PEO-LiPF 6-EC-CNT)

NASA Astrophysics Data System (ADS)

Johan, Mohd Rafie; Ibrahim, Suriani

2012-01-01

In this study, the ionic conductivity of a nanocomposite polymer electrolyte system (PEO-LiPF 6-EC-CNT), which has been produced using solution cast technique, is obtained using artificial neural networks approach. Several results have been recorded from experiments in preparation for the training and testing of the network. In the experiments, polyethylene oxide (PEO), lithium hexafluorophosphate (LiPF 6), ethylene carbonate (EC) and carbon nanotubes (CNT) are mixed at various ratios to obtain the highest ionic conductivity. The effects of chemical composition and temperature on the ionic conductivity of the polymer electrolyte system are investigated. Electrical tests reveal that the ionic conductivity of the polymer electrolyte system varies with different chemical compositions and temperatures. In neural networks training, different chemical compositions and temperatures are used as inputs and the ionic conductivities of the resultant polymer electrolytes are used as outputs. The experimental data is used to check the system's accuracy following the training process. The neural network is found to be successful for the prediction of ionic conductivity of nanocomposite polymer electrolyte system.

Electrochemical and biological characterization of coatings formed on Ti-15Mo alloy by plasma electrolytic oxidation.

PubMed

Kazek-Kęsik, Alicja; Krok-Borkowicz, Małgorzata; Pamuła, Elżbieta; Simka, Wojciech

2014-10-01

β-Type titanium alloys are considered the future materials for bone implants. To improve the bioactivity of Ti-15Mo, the surface was modified using the plasma electrolytic oxidation (PEO) process. Tricalcium phosphate (TCP, Ca3PO4), wollastonite (CaSiO3) and silica (SiO2) were selected as additives in the anodizing bath to enhance the bioactivity of the coatings formed during the PEO process. Electrochemical analysis of the samples was performed in Ringer's solution at 37°C. The open-circuit potential (EOCP) as a function of time, corrosion potential (ECORR), corrosion current density (jCORR) and polarization resistance (Rp) of the samples were determined. Surface modification improved the corrosion resistance of Ti-15Mo in Ringer's solution. In vitro studies with MG-63 osteoblast-like cells were performed for 1, 3 and 7 days. After 24h, the cells were well adhered on the entire surfaces, and their number increased with increasing culture time. The coatings formed in basic solution with wollastonite exhibited better biological performance compared with the as-ground sample. Copyright © 2014 Elsevier B.V. All rights reserved.

In-situ grown MgO-ZnO ceramic coating with high thermal emittance on Mg alloy by plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Li, Hang; Lu, Songtao; Qin, Wei; Wu, Xiaohong

2017-07-01

Intense solar radiation and internal heat generation determine the equilibrium temperature of an in-orbit spacecraft. Thermal control coatings with low solar absorptance and high thermal emittance effectively maintain the thermal equilibrium within safe operating limits for exposed, miniaturized and highly integrated components. A novel ceramic coating with high thermal emittance and good adhesion was directly prepared on the Mg substrate using an economical process of controlled plasma electrolytic oxidation (PEO) in the electrolyte containing ZnSO4. XRD and XPS results showed that this coating was mainly composed of the MgO phase as well as an unusual ZnO crystalline phase. The adhesive strength between the coating and substrate determined by a pull-off test revealed an excellent adhesion. Thermal and optical properties test revealed that the coating exhibited a high infrared emittance of 0.88 (2-16 μm) and low solar absorptance of 0.35 (200-2500 nm). The result indicated that the formation of ZnO during the PEO process played an important role in the improvement of the coating emittance. The process developed provides a simple surface method for improving the thermal emittance of Mg alloy, which presents a promising application prospect in the thermal management of the spacecraft.

Sequential and competitive adsorption of peptides at pendant PEO layers.

PubMed

Wu, Xiangming; Ryder, Matthew P; McGuire, Joseph; Snider, Joshua L; Schilke, Karl F

2015-06-01

Earlier work provided direction for development of responsive drug delivery systems based on modulation of the structure, amphiphilicity, and surface density of bioactive peptides entrapped within pendant polyethylene oxide (PEO) brush layers. In this work, we describe the sequential and competitive adsorption behavior of such peptides at pendant PEO layers. Three cationic peptides were used for this purpose: the arginine-rich, amphiphilic peptide WLBU2, a peptide chemically identical to WLBU2 but of scrambled sequence (S-WLBU2), and the non-amphiphilic peptide poly-L-arginine (PLR). Optical waveguide lightmode spectroscopy (OWLS) was used to quantify the rate and extent of peptide adsorption and elution at surfaces coated with PEO. UV spectroscopy and time-of-flight secondary ion mass spectrometry (TOF-SIMS) were used to quantify the extent of peptide exchange during the course of sequential and competitive adsorption. Circular dichroism (CD) was used to evaluate conformational changes after adsorption of peptide mixtures at PEO-coated silica nanoparticles. Results indicated that amphiphilic peptides are able to displace adsorbed, non-amphiphilic peptides in PEO layers, while non-amphiphilic peptides were not able to displace more amphiphilic peptides. In addition, peptides of greater amphiphilicity dominated the adsorption at the PEO layer from mixtures with less amphiphilic or non-amphiphilic peptides. Copyright © 2015 Elsevier B.V. All rights reserved.

Insights on Li-TFSI diffusion in polyethylene oxide for battery applications

NASA Astrophysics Data System (ADS)

Molinari, Nicola; Mailoa, Jonathan; Kozinsky, Boris; Robert Bosch LLC Collaboration

Improving the energy density, safety and efficiency of lithium-ion (Li-ion) batteries is crucial for the future of energy storage and applications such as electric cars. A key step in the research of next-generation solid polymeric electrolyte materials is understanding the diffusion mechanism of Li-ion in polyethylene oxide (PEO) in order to guide the design of electrolytes materials with high Li-ion diffusion while, ideally, suppress counter-anion movement. In this work we use computer simulations to investigate this long-standing problem at a fundamental level. The system under study has Li-TFSI concentration and PEO chain length that are representative of practical application specifications; the interactions of the molecular model are described via the PCFF+ all-atom force-field. Validation of the model is performed by comparing trends against experiments for diffusivity and conductivity as a function of salt concentration. The analysis of Li-TFSI molecular dynamics trajectories reveals that 1. for high Li-TFSI concentration a significant fraction of Li-ion is coordinated by only TFSI and consistently move less than PEO-coordinated Li-ion, 2. PEO chain motion is key in enabling Li-ion movement. Robert Bosch LLC.

Controlling the Degradation of Bioresorbable Polymers

NASA Astrophysics Data System (ADS)

Moritz, Istvan; Crowley, Brian; Brundage, Elizabeth; Rende, Deniz; Ozisik, Rahmi

Bioresorbable polymers play a vital role in the development of implantable materials that are used in surgical procedures, controlled drug delivery systems; and tissue engineering scaffolds. The half-life of common bioresorbable polymers ranges from 3 to over 12 months and slow bioresorption rates of these polymers restrict their use to a limited set of applications. The use of embedded enzymes was previously proposed to control the degradation rate of bioresorbable polymers, and was shown to decrease average degradation time to about 0.5 months. In this study, electromagnetic actuation of iron oxide magnetic nanoparticles embedded in an encapsulant polymer, poly(ethyleneoxide), PEO, was employed to initiate enzyme assisted degradation of bioresorbable polymer poly(caprolactone), PCL. Results indicate that the internal temperature of iron oxide magnetic nanoparticle doped PEO samples can be increased via an alternating magnetic field, and temperature increase depends strongly on nanoparticle concentration and magnetic field parameters. The temperature achieved is sufficient to relax the PEO matrix and to enable the diffusion of enzymes from PEO to a surrounding PCL matrix. Current studies are directed at measuring the degradation rate of PCL due to the diffused enzyme. This material is based upon work supported by the National Science Foundation under Grant No. CMMI-1538730.

Tuning of the Morphology and Optoelectronic Properties of ZnO/P3HT/P3HT- b-PEO Hybrid Films via Spray Deposition Method.

PubMed

Wang, Kun; Bießmann, Lorenz; Schwartzkopf, Matthias; Roth, Stephan V; Müller-Buschbaum, Peter

2018-06-20

The self-assembly of amphiphilic diblock copolymers yields the possibility of using them as a template for tailoring the film morphologies of sol-gel chemistry-derived inorganic electron transport materials, such as mesoporous ZnO and TiO 2 . However, additional steps including etching and backfilling are required for the common bulk heterojunction fabrication process when using insulating diblock copolymers. Here, we use the conducting diblock copolymer poly(3-hexylthiophene)- block-poly(ethylene oxide) (P3HT- b-PEO) in which P3HT acts as charge carrier transport material and light absorber, whereas PEO serves as a template for ZnO synthesis. The initial solution is subsequently spray-coated to obtain the hybrid film. Scanning electron microscopy and grazing-incidence small-angle X-ray scattering measurements reveal a significant change in the morphology of the hybrid films during deposition. Optoelectronic properties illustrate the improved charge separation and charge transfer process. Both the amount of the diblock copolymer and the annealing temperature play an important role in tuning the morphology and the optoelectronic properties. Hybrid films being sprayed from a solution with the ratio of ω ZnO , ω P3HT , and ω P3HT- b-PEO of 2:1:1 and subsequent annealing at 80 °C show the most promising morphology combined with an optimal photoluminescence quenching. Thus, the presented simple, reagent- and energy-saving fabrication method provides a promising approach for a large-scale preparation of bulk heterojunction P3HT/ZnO films on flexible substrates.

Inter and Intra Molecular Phase Separation Environment Effects on PI-PEO Block Copolymers for Batteries and Fuel Cells

NASA Technical Reports Server (NTRS)

Xue, Chen-Chen; Meador, Mary Ann B.; Eby, R. K.; Cheng, Stephen Z. D.; Ge, Jason J.; Cubon, Valerie A.

2002-01-01

Rod-coil molecules have been introduced as a novel type of block copolymers with unique microstructure due to their ability to self-assemble to various ordered morphologies on a nanometer length scale. These molecules, comprised two homo polymers joined together at one end, microphase separate into ordered, periodic arrays of spheres, cylinders in the bulk state and or solution. To get ordered structure in a reasonable scale, additional force field are applied, such as mechanical shearing, electric field and magnetic field. Recently, progress has made it a possible to develop a new class of polyimides (PI)-Polyethylene oxide (PEO) that are soluble in polar organic solvents. The solvent-soluble PI-PEO has a wide variety of applications in microelectronics, since these PI-PEO films exhibit a high degree of thermal and chemical stability. In this paper, we report the self-assembled ordered structure of PI-PEO molecules formed from concentrate solution.

Efficient Transport Networks in a Dual Electron/Lithium-Conducting Polymeric Composite for Electrochemical Applications.

PubMed

McDonald, Michael B; Hammond, Paula T

2018-05-09

In this work, an all-functional polymer material composed of the electrically conductive poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) and lithium-conducting poly(ethylene oxide) (PEO) was developed to form a dual conductor for three-dimensional electrodes in electrochemical applications. The composite exhibits enhanced ionic conductivity (∼10 -4 S cm -1 ) and, counterintuitively, electronic conductivity (∼45 S cm -1 ) with increasing PEO proportion, optimal at a monomer ratio of 20:1 PEO:PEDOT. Microscopy reveals a unique morphology, where PSS interacts favorably with PEO, destabilizing PEDOT to associate into highly branched, interconnected networks that allow for more efficient electronic transport despite relatively low concentrations. Thermal and X-ray techniques affirm that the PSS-PEO domain suppresses crystallinity, explaining the high ionic conductivity. Electrochemical experiments in lithium cell environments indicate stability as a function of cycling and improved overpotential due to dual transport characteristics despite known issues with both individual components.

Mesoscopic simulation of a micellar poly(N-isopropyl acrylamide)-b-(polyethylene oxide) copolymer system

NASA Astrophysics Data System (ADS)

Bautista-Reyes, Rubén; Soto-Figueroa, César; Vicente, Luis

2016-05-01

In this article we studied the micellar formation of poly(N-isopropyl acrylamide)-b-polyethylene oxide (PNIPAM-b-PEO) copolymers in an aqueous system. From molecular simulations the dependence on temperature of the Flory-Huggins interaction parameter χ for PNIPAM and PEO in water is obtained and compared with available experimental results and values from other theoretical calculations. By means of dissipative particle dynamics (DPD) we then simulated the coil-globule transition for PNIPAM chains in water with a transition temperature of around 305 K. The simulations for PNIPAM-b-PEO copolymers showed that at room temperature the chains are miscible in an aqueous phase but with a temperature increase the system turns into micelles at T  =  305 K. The change in micelle anisotropy due to a different ratio PNIPAM/PEO of chains is also analyzed. What is observed is that for large PEO the large number of dissolved PEO chains gives a large corona size and the micelle is not spherical but obloide and as the number of PNIPAM is increased the micelle acquires a spherical shape. As an important application we considered the system micelle-water/anionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate [BMIM]+[PF6]-). By increasing the temperature of the system from 306 K it is shown that at T  =  345 K there is a transfer of the micelle from water to the ionic liquid phase and this was due to the change in the relative affinity of PEO to water and ionic liquid expressed by the change in χ. All the simulation outcomes are qualitatively consistent with experimental results and thus to our knowledge we give the first set of χ values for the interaction between PNIPAM and water in a wide range of temperature values.

Melt Extrusion of High-Dose Co-Amorphous Drug-Drug Combinations : Theme: Formulation and Manufacturing of Solid Dosage Forms Guest Editors: Tony Zhou and Tonglei Li.

PubMed

Arnfast, Lærke; Kamruzzaman, Md; Löbmann, Korbinian; Aho, Johanna; Baldursdottir, Stefania; Rades, Thomas; Rantanen, Jukka

2017-12-01

Many future drug products will be based on innovative manufacturing solutions, which will increase the need for a thorough understanding of the interplay between drug material properties and processability. In this study, hot melt extrusion of a drug-drug mixture with minimal amount of polymeric excipient was investigated. Using indomethacin-cimetidine as a model drug-drug system, processability of physical mixtures with and without 5% (w/w) of polyethylene oxide (PEO) were studied using Differential Scanning Calorimetry (DSC) and Small Amplitude Oscillatory Shear (SAOS) rheometry. Extrudates containing a co-amorphous glass solution were produced and the solid-state composition of these was studied with DSC. Rheological analysis indicated that the studied systems display viscosities higher than expected for small molecule melts and addition of PEO decreased the viscosity of the melt. Extrudates of indomethacin-cimetidine alone displayed amorphous-amorphous phase separation after 4 weeks of storage, whereas no phase separation was observed during the 16 week storage of the indomethacin-cimetidine extrudates containing 5% (w/w) PEO. Melt extrusion of co-amorphous extrudates with low amounts of polymer was found to be a feasible manufacturing technique. Addition of 5% (w/w) polymer reduced melt viscosity and prevented phase separation.

Plasma electrolytic oxidation treatment mode influence on corrosion properties of coatings obtained on Zr-1Nb alloy in silicate-phosphate electrolyte

NASA Astrophysics Data System (ADS)

Farrakhov, R. G.; Mukaeva, V. R.; Fatkullin, A. R.; Gorbatkov, M. V.; Tarasov, P. V.; Lazarev, D. M.; Babu, N. Ramesh; Parfenov, E. V.

2018-01-01

This research is aimed at improvement of corrosion properties for Zr-1Nb alloy via plasma electrolytic oxidation (PEO). The coatings obtained in DC, pulsed unipolar and pulsed bipolar modes were assessed using SEM, XRD, PDP and EIS techniques. It was shown that pulsed unipolar mode provides the PEO coatings having promising combination of the coating thickness, surface roughness, porosity, corrosion potential and current density, and charge transfer resistance, all contributing to corrosion protection of the zirconium alloy for advanced fuel cladding applications.

Investigation of absorptance and emissivity of thermal control coatings on Mg–Li alloys and OES analysis during PEO process

PubMed Central

Yao, Zhongping; Xia, Qixing; Ju, Pengfei; Wang, Jiankang; Su, Peibo; Li, Dongqi; Jiang, Zhaohua

2016-01-01

Thermal control ceramic coatings on Mg–Li alloys have been successfully prepared in silicate electrolyte system by plasma electrolytic oxidation (PEO) method. The PEO coatings are mainly composed of crystallized Mg2SiO4 and MgO, which have typical porous structure with some bulges on the surface; OES analysis shows that the plasma temperature, which is influenced by the technique parameters, determines the formation of the coatings with different crystalline phases and morphologies, combined with “quick cooling effect” by the electrolyte; and the electron concentration is constant, which is related to the electric spark breakdown, determined by the nature of the coating and the interface of coating/electrolyte. Technique parameters influence the coating thickness, roughness and surface morphology, but do not change the coating composition in the specific PEO regime, and therefore the absorptance (αS) and emissivity (ε) of the coatings can be adjusted by the technique parameters through changing thickness and roughness in a certain degree. The coating prepared at 10 A/dm2, 50 Hz, 30 min and 14 g/L Na2SiO3 has the minimum value of αS (0.35) and the maximum value of ε (0.82), with the balance temperature of 320 K. PMID:27383569

Unusual large-pitch banding in poly(L-lactic acid): Effects of composition and geometry confinement

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

Woo, Eamor M.; Lugito, Graecia; Hsieh, Ya-Ting

2014-02-24

Lamellar patterns and orientations in blends of two crystalline polymers: poly(ethylene oxide) (PEO) and low-molecular-weight poly(L-lactic acid) (PLLA) were investigated using polarizing light optical microscopy (POM), and atomic and scanning electron microscopy (AFM, SEM). Specific etching off of PEO was used to reveal the complex earlier-grown PLLA lamellae patterns with various PEO content in blends. Banding of extremely long pitch (50 μm) in crystallized PLLA spherulites was induced by two kinetic factors: geometry confinement by top cover and introduction of diluent such as PEO. The mechanisms and correlation among the lamellar assembly, ring bands, and cracks are exemplified. Lamellar patternsmore » and ring-band types in blends were found to vary with respect to not only blend compositions, but also confinement of top-cover.« less

Application of molecular dynamics simulation to predict the compatability between water-insoluble drugs and self-associating poly(ethylene oxide)-b-poly(epsilon-caprolactone) block copolymers.

PubMed

Patel, Sarthak; Lavasanifar, Afsaneh; Choi, Phillip

2008-11-01

In the present work, molecular dynamics (MD) simulation was applied to study the solubility of two water-insoluble drugs, fenofibrate and nimodipine, in a series of micelle-forming PEO-b-PCL block copolymers with combinations of blocks having different molecular weights. The solubility predictions based on the MD results were then compared with those obtained from solubility experiments and by the commonly used group contribution method (GCM). The results showed that Flory-Huggins interaction parameters computed by the MD simulations are consistent with the solubility data of the drug/PEO-b-PCL systems, whereas those calculated by the GCM significantly deviate from the experimental observation. We have also accounted for the possibility of drug solubilization in the PEO block of PEO-b-PCL.

Giant surfactants of poly(ethylene oxide)- b-polystyrene-(molecular nanoparticle): nanoparticle-driven self-assembly with sub-10-nm nanostructures in thin films

NASA Astrophysics Data System (ADS)

Hsu, Chih-Hao; Lin, Zhiwei; Dong, Xue-Hui; Hsieh, I.-Fan; Cheng, Stephen Z. D.

2014-03-01

Giant surfactants are built upon precisely attaching shape- and volume-persistent molecular nanoparticles (MNP) to polymeric flexible tails. The unique class of self-assembling materials, giant surfactants, has been demonstrated to form self-assembled ordered nanostructures, and their self-assembly behaviors are remarkably sensitive to primary chemical structures. In this work, two sets of giant surfactants with functionalized MNP attached to diblock copolymer tails were studied in thin films. Carboxylic acid-functionalized [60]fullerene (AC60) tethered with PEO- b-PS (PEO-PS-AC60) represents an ABA' (hydrophilic-hydrophobic-hydrophilic) giant surfactant, and fluoro-functionalized polyhedral oligomeric silsesquioxane (FPOSS) tethered with PEO- b-PS (PEO-PS-FPOSS) represents an ABC (hydrophilic-hydrophobic-omniphobic) one. The dissimilar chemical natures of the MNPs result in different arrangement of MNPs in self-assembled structures, the dispersion of AC60 in PEO domain and the single domain of FPOSS. Moreover, the chemically bonded MNPs could induce the originally disordered small molecular PEO- b-PS to form ordered cylindrical and lamellar structure, as evidenced by TEM and GISAXS, leading to sub-10-nm nanostructures of copolymer in the thin film state.

Structure and dynamics of water in mixed solutions including laponite and PEO

NASA Astrophysics Data System (ADS)

Morikubo, Satoshi; Sekine, Yurina; Ikeda-Fukazawa, Tomoko

2011-01-01

To investigate the structure and dynamics of water in mixed solutions including laponite clay particles and poly(ethylene oxide) (PEO), we measured the Raman spectra of the mixed solutions in the temperature range 283-313 K. The results show that the vibrational energies of the O-H stretching modes in the mixed solutions depend on the water content and temperature. The energy shifts of the O-H stretching modes are attributed to changes in the water structure. By applying a structural model of bulk water to the spectra in the O-H stretching region, the local structures of water in the solutions were analyzed. The result shows that the formation probability of hydrogen bonds in the solutions decreases as the water content decreases. Laponite and PEO have effects to disrupt the network structure of hydrogen bonds between water molecules. Further, it was found that laponite and PEO cause increase in the strength of hydrogen bonds of surrounding water,although the strength of the hydrogen bonds increases with the order water-laponite < water-water < water-PEO. It is concluded that water in laponite-PEO mixed solutions has a less-networked structure with strong hydrogen bonds compared with bulk water.

Controlling interlayer interactions in vanadium pentoxide-poly(ethylene oxide) nanocomposites for enhanced magnesium-ion charge transport and storage

NASA Astrophysics Data System (ADS)

Perera, Sanjaya D.; Archer, Randall B.; Damin, Craig A.; Mendoza-Cruz, Rubén; Rhodes, Christopher P.

2017-03-01

Rechargeable magnesium batteries provide the potential for lower cost and improved safety compared with lithium-ion batteries, however obtaining cathode materials with highly reversible Mg-ion capacities is hindered by the high polarizability of divalent Mg-ions and slow solid-state Mg-ion diffusion. We report that incorporating poly(ethylene oxide) (PEO) between the layers of hydrated vanadium pentoxide (V2O5) xerogels results in significantly improved reversible Mg-ion capacities. X-ray diffraction and high resolution transmission electron microscopy show that the interlayer spacing between V2O5 layers was increased by PEO incorporation. Vibrational spectroscopy supports that the polymer interacts with the V2O5 lattice. The V2O5-PEO nanocomposite exhibited a 5-fold enhancement in Mg-ion capacity, improved stability, and improved rate capabilities compared with V2O5 xerogels. The Mg-ion diffusion coefficient of the nanocomposite was increased compared with that of V2O5 xerogels which is attributed to enhanced Mg-ion mobility due to the shielding interaction of PEO with the V2O5 lattice. This study shows that beyond only interlayer spacing, the nature of interlayer interactions of Mg-ions with V2O5, PEO, and H2O are key factors that affect Mg-ion charge transport and storage in layered materials. The design of layered materials with controlled interlayer interactions provides a new approach to develop improved cathodes for magnesium batteries.

Study of Polydiacetylene-Poly (Ethylene Oxide) Electrospun Fibers Used as Biosensors

PubMed Central

Alam, A K M Mashud; Yapor, Janet P.; Reynolds, Melissa M.; Li, Yan Vivian

2016-01-01

Polydiacetylene (PDA) is an attractive conjugated material for use in biosensors due to its unique characteristic of undergoing a blue-to-red color change in response to external stimuli. 10,12-Pentacosadiynoic acid (PCDA) and poly (ethylene oxide) (PEO) were used in this study to develop fiber composites via an electrospinning method at various mass ratios of PEO to PCDA, solution concentrations, and injection speeds. The PEO-PDA fibers in blue phase were obtained via photo-polymerization upon UV-light irritation. High mass ratios of PEO to PCDA, low polymer concentrations of spinning solution, and low injection speeds promoted fine fibers with small diameters and smooth surfaces. The colorimetric transition of the fibers was investigated when the fibers were heated at temperatures ranging from 25 °C to 120 °C. A color switch from blue to red in the fibers was observed when the fibers were heated at temperatures greater than 60 °C. The color transition was more sensitive in the fibers made with a low mass ratio of PEO to PCDA due to high fraction of PDA in the fibers. The large diameter fibers also promoted the color switch due to high reflectance area in the fibers. All of the fibers were analyzed using Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC) and compared before and after the color change occurred. The colorimetric transitional mechanism is proposed to occur due to conformational changes in the PDA macromolecules. PMID:28773326

Study of Polydiacetylene-Poly (Ethylene Oxide) Electrospun Fibers Used as Biosensors.

PubMed

Alam, A K M Mashud; Yapor, Janet P; Reynolds, Melissa M; Li, Yan Vivian

2016-03-16

Polydiacetylene (PDA) is an attractive conjugated material for use in biosensors due to its unique characteristic of undergoing a blue-to-red color change in response to external stimuli. 10,12-Pentacosadiynoic acid (PCDA) and poly (ethylene oxide) (PEO) were used in this study to develop fiber composites via an electrospinning method at various mass ratios of PEO to PCDA, solution concentrations, and injection speeds. The PEO-PDA fibers in blue phase were obtained via photo-polymerization upon UV-light irritation. High mass ratios of PEO to PCDA, low polymer concentrations of spinning solution, and low injection speeds promoted fine fibers with small diameters and smooth surfaces. The colorimetric transition of the fibers was investigated when the fibers were heated at temperatures ranging from 25 °C to 120 °C. A color switch from blue to red in the fibers was observed when the fibers were heated at temperatures greater than 60 °C. The color transition was more sensitive in the fibers made with a low mass ratio of PEO to PCDA due to high fraction of PDA in the fibers. The large diameter fibers also promoted the color switch due to high reflectance area in the fibers. All of the fibers were analyzed using Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC) and compared before and after the color change occurred. The colorimetric transitional mechanism is proposed to occur due to conformational changes in the PDA macromolecules.

Modeling and simulation of Li-ion conduction in poly(ethylene oxide)

NASA Astrophysics Data System (ADS)

Gitelman, L.; Israeli, M.; Averbuch, A.; Nathan, M.; Schuss, Z.; Golodnitsky, D.

2007-12-01

Polyethylene oxide (PEO) containing a lithium salt (e.g., LiI) serves as a solid polymer electrolyte (SPE) in thin-film batteries and its ionic conductivity is a key parameter of their performance. We model and simulate Li + ion conduction in a single PEO molecule. Our simplified stochastic model of ionic motion is based on an analogy between protein channels of biological membranes that conduct Na +, K +, and other ions, and the PEO helical chain that conducts Li + ions. In contrast with protein channels and salt solutions, the PEO is both the channel and the solvent for the lithium salt (e.g., LiI). The mobile ions are treated as charged spherical Brownian particles. We simulate Smoluchowski dynamics in channels with a radius of ca. 0.1 nm and study the effect of stretching and temperature on ion conductivity. We assume that each helix (molecule) forms a random angle with the axis between these electrodes and the polymeric film is composed of many uniformly distributed oriented boxes that include molecules with the same direction. We further assume that mechanical stretching aligns the molecular structures in each box along the axis of stretching (intra-box alignment). Our model thus predicts the PEO conductivity as a function of the stretching, the salt concentration and the temperature. The computed enhancement of the ionic conductivity in the stretch direction is in good agreement with experimental results. The simulation results are also in qualitative agreement with recent theoretical and experimental results.

Understanding the surface properties and rheology of a silica suspension mediated by a comb-type poly(acrylic acid)/poly(ethylene oxide) (PAA/PEO) copolymer: effect of salinity.

PubMed

Yang, Dingzheng; Yan, Bin; Xiang, Li; Xu, Haolan; Wang, Xiaogang; Zeng, Hongbo

2018-06-13

Understanding the surface properties and rheology of colloidal suspensions in the presence of polymer additives with high salinity are of great importance in formulating construction materials and optimizing process conditions in the mining and petroleum industry. In this work, the surface properties and rheology of a model spherical silica aqueous suspension mediated by a comb-type poly(acrylic acid)/poly(ethylene oxide) (PAA/PEO) copolymer at various salt concentrations have been investigated. Adsorption measurements using a Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) align well with zeta potential tests and show that polymer adsorption on silica surfaces is enhanced at high salinity (i.e., 3 M NaCl) than at low salinity (i.e., 1 mM NaCl) due to the suppression of the electrical double layer. Surface Forces Apparatus (SFA) measurements reveal that for interactions between two mica surfaces (the basal plane of which has a similar structure as silica) at a high polymer concentration (e.g., 2 wt%), steric repulsion dominates in 1 mM NaCl while bridging attraction is observed in 3 M NaCl. Surface force measurements agree with rheological results on silica suspensions with 0.5 to 2 wt% of PAA/PEO addition, which shows a significant decrease in yield stress in 1 mM NaCl due to steric repulsion but an insignificant variation in yield stress in 3 M NaCl due to attractive bridging interactions. This work provides useful information regarding the surface properties and rheological properties of comb-type polymer-mediated silica suspensions under different salinity conditions, with implications on designing and processing complex colloidal suspensions with polymer additives for various applications.

Unimpeded permeation of water through biocidal graphene oxide sheets anchored on to 3D porous polyolefinic membranes.

PubMed

Mural, Prasanna Kumar S; Jain, Shubham; Kumar, Sachin; Madras, Giridhar; Bose, Suryasarathi

2016-04-21

3D porous membranes were developed by etching one of the phases (here PEO, polyethylene oxide) from melt-mixed PE/PEO binary blends. Herein, we have systematically discussed the development of these membranes using X-ray micro-computed tomography. The 3D tomograms of the extruded strands and hot-pressed samples revealed a clear picture as to how the morphology develops and coarsens over a function of time during post-processing operations like compression molding. The coarsening of PE/PEO blends was traced using X-ray micro-computed tomography and scanning electron microscopy (SEM) of annealed blends at different times. It is now understood from X-ray micro-computed tomography that by the addition of a compatibilizer (here lightly maleated PE), a stable morphology can be visualized in 3D. In order to anchor biocidal graphene oxide sheets onto these 3D porous membranes, the PE membranes were chemically modified with acid/ethylene diamine treatment to anchor the GO sheets which were further confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and surface Raman mapping. The transport properties through the membrane clearly reveal unimpeded permeation of water which suggests that anchoring GO on to the membranes does not clog the pores. Antibacterial studies through the direct contact of bacteria with GO anchored PE membranes resulted in 99% of bacterial inactivation. The possible bacterial inactivation through physical disruption of the bacterial cell wall and/or reactive oxygen species (ROS) is discussed herein. Thus this study opens new avenues in designing polyolefin based antibacterial 3D porous membranes for water purification.

Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers.

PubMed

Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie

2013-09-05

This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

Nanoparticle-Reinforced Associative Network Hydrogels

PubMed Central

Agrawal, Sarvesh K.; Sanabria-DeLong, Naomi; Tew, Gregory N.; Bhatia, Surita R.

2009-01-01

ABA triblock copolymers in solvents selective for the midblock are known to form associative micellar gels. We have modified the structure and rheology of ABA triblock copolymer gels comprising poly(lactide)-poly(ethylene oxide)-poly(lactide) (PLA-PEO-PLA) through addition of a clay nanoparticle, laponite. Addition of laponite particles resulted in additional junction points in the gel via adsorption of the PEO corona chains onto the clay surfaces. Rheological measurements showed that this strategy led to a significant enhancement of the gel elastic modulus with small amounts of nanoparticles. Further characterization using SAXS and DLS confirmed that nanoparticles increase the intermicellar attraction and result in aggregation of PLA-PEO-PLA micelles. PMID:18947244

Temperature-responsive magnetite/PEO-PPO-PEO block copolymer nanoparticles for controlled drug targeting delivery.

PubMed

Chen, Shu; Li, Ying; Guo, Chen; Wang, Jing; Ma, Junhe; Liang, Xiangfeng; Yang, Liang-Rong; Liu, Hui-Zhou

2007-12-04

In this study, temperature-responsive magnetite/polymer nanoparticles were developed from iron oxide nanoparticles and poly(ethyleneimine)-modified poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer. The particles were characterized by TEM, XRD, DLS, VSM, FTIR, and TGA. A typical product has an approximately 20 nm magnetite core and an approximately 40 nm hydrodynamic diameter with a narrow size distribution and is superparamagnetic with large saturation magnetization (51.34 emu/g) at room temperature. The most attractive feature of the nanoparticles is their temperature-responsive volume-transition property. DLS results indicated that their average hydrodynamic diameter underwent a sharp decrease from 45 to 25 nm while evaluating the temperature from 20 to 35 degrees C. The temperature-dependent evolution of the C-O stretching band in the FTIR spectra of the aqueous nanoparticles solution revealed that thermo-induced self-assembly of the immobilized block copolymers occurred on the magnetite solid surfaces, which is accompanied by a conformational change from a fully extended state to a highly coiled state of the copolymer. Consequently, the copolymer shell could act as a temperature-controlled "gate" for the transit of guest substance. The uptake and release of both hydrophobic and hydrophilic model drugs were well controlled by switching the transient opening and closing of the polymer shell at different temperatures. A sustained release of about 3 days was achieved in simulated human body conditions. In primary mouse experiments, drug-entrapped magnetic nanoparticles showed good biocompatibility and effective therapy for spinal cord damage. Such intelligent magnetic nanoparticles are attractive candidates for widespread biomedical applications, particularly in controlled drug-targeting delivery.

Quantitative control of poly(ethylene oxide) surface antifouling and biodetection through azimuthally enhanced grating coupled-surface plasmon resonance sensing

NASA Astrophysics Data System (ADS)

Sonato, Agnese; Silvestri, Davide; Ruffato, Gianluca; Zacco, Gabriele; Romanato, Filippo; Morpurgo, Margherita

2013-12-01

Grating Coupled-Surface Plasmon reflectivity measurements carried out under azimuth and polarization control (GC-SPR φ ≠ 0°) were used to optimize the process of gold surface dressing with poly(ethylene oxide) (PEO) derivatives of different molecular weight, with the final goal to maximize the discrimination between specific and non-specific binding events occurring at the surface. The kinetics of surface deposition of thiol-ending PEOs (0.3, 2 and 5 kDa), introduced as antifouling layers, was monitored. Non-specific binding events upon immersion of the surfaces into buffers containing either 0.1% bovine serum albumin or 1% Goat Serum, were evaluated as a function of polymer size and density. A biorecognition event between avidin and biotin was then monitored in both buffers at selected low and high polymer surface densities and the contribution of analyte and fouling elements to the signal was precisely quantified. The 0.3 kDa PEO film was unable to protect the surface from non-specific interactions at any tested density. On the other hand, the 2 and 5 kDa polymers at their highest surface densities guaranteed full protection from non-specific interactions from both buffers. These densities were reached upon a long deposition time (24-30 h). The results pave the way toward the application of this platform for the detection of low concentration and small dimension analytes, for which both non-fouling and high instrumental sensitivity are fundamental requirements.

Synthesis, morphology and dynamics of polyureas and their lithium ionomers

NASA Astrophysics Data System (ADS)

Chuayprakong, Sunanta

Electrolytes currently used in commercial lithium ion batteries have led to leakage and safety issues. Solvent-free solid polymer electrolytes (SPEs) offering high energy density are promising materials for lithium battery applications. SPEs require high modulus to separate the electrodes and suppress lithium dendrite growth. Microphase separation of the hard segments in amorphous polyureas (PUs) yields materials with higher moduli than typical low glass transition temperature (Tg) polymers. In this dissertation, several families of solution polymerized polyether-based PU ionomers were synthesized and their thermal, morphology and dynamic properties characterized as a function of chemical composition. In the initial phase of this investigation, polyethylene oxide (PEO) diamines (with molecular weights = 200, 600, 1050, 2000, 3000 and 6000 g/mol) were polymerized with 4,4' methylene diphenyl diisocyanate (MDI). PUs with 200 and 600 g/mol PEO soft segments are amorphous and single phase. The amorphous PU having 1050 g/mol PEO segments exhibits a small degree of phase separation, as demonstrated by X-ray scattering. PUs with 2000, 3000 and 6000 g/mol PEO soft segments are semicrystalline and their melting points and degrees of crystallinity are lower than those of the precursor PEO diamines due to their attachment to rigid hard segments. Even though polypropylene oxide (PPO) does not dissolve cations as efficiently as PEO, PPO is not crystallizable and was chosen to create a second family of amorphous PUs. PPO-containing diamines ((Jeff400 (MW = 400 g/mol) and Jeff2000 (MW = 2000 g/mol)) and MDI were chosen as the neutral soft segment and the hard segment, respectively. 2,5-diaminobenzene sulfonate was successfully synthesized and used for preparing ionomers. The amount of ionic species in these ionomers was varied and quantified using 1H-NMR. Single Tgs were observed and they increased with increasing ionic content. No X-ray scattering peaks corresponding to microphase separation of hard and soft segments were detected, nor were ordered hydrogen bonded carbonyl bands in FTIR spectra, demonstrating that the Jeff400 PUs are single phase. Using dielectric relaxation spectroscopy (DRS), segmental relaxation temperatures also increase with increasing ionic species content.. Increasing the number of ionic groups increases the hard segment content, which results in higher DSC Tgs and slower fmaxs for the segmental relaxation processes. For the non-ionic and all of the ionic Jeff2000 PU samples that contain some nonionic soft segments, low temperature Tgs were observed that arise from microphase separated soft phases. X-ray scattering peaks related to microphase separation and ordered hydrogen bonded carbonyl bands were observed, reinforcing the conclusion of hard/soft segment segregation. The DRS segmental relaxation is associated with soft phase relaxation, with some of the ion dipoles participating in this process for the ionic samples. The ionomers could not be dialyzed due to water insolubility, but were purified by multiple precipitation in deionize water. Nevertheless, the findings suggest that the observed conductivity primarily arises from ionic impurities. A third family of PU ionomers was synthesized using an amorphous polypropylene oxide-b- polyethylene oxide-b-polypropylene oxide diamine (ED900, MW = 900 g/mol, 68% EO) and 2,5-diaminobenzene sulfonate. Hexamethylene diisocyanate was utilized as the hard segment as its high packing efficiency is known to facilitate microphase separation. The non-ionic ED900 PU and its ionomers with various ion contents were successfully synthesized. Low Tgs due to segregation of soft segments, X-ray scattering peaks related to microphase separation between segments, and ordered hydrogen bonded carbonyl bands were detected. Tapping mode atomic force microscopy was also used to explore the morphology of these microphase separated materials. DRS segmental relaxations are associated with soft phase. These materials were extensively dialyzed and their low conductivities suggest that the lithium ions are primarily trapped in hard domains.

Cascade synthesis of a gold nanoparticle-network polymer composite

DOE PAGES

Grubjesic, Simonida; Ringstrand, Bryan Scott; Jungjohann, Katherine L.; ...

2015-11-02

In this paper, the multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO 117-PPO 47-PEO 117 and [AuCl 4] -. The reaction sequence begins with the auto-reduction of aqueous [AuCl 4] - by PEO 117-PPO 47-PEO 117 which leads to both the production of Au NPs and the free radical initiated polymerization and crosslinking of the acrylate endderivatized PEO 117-PPO 47-PEO 117 to yield a network polymer. Optical spectroscopy andmore » TEM monitored the reduction of [AuCl 4] -, formation of large aggregated Au NPs and oxidative etching into a final state of dispersed, spherical Au NPs. ATR/FT-IR spectroscopy and thermal analysis confirms acrylate crosslinking to yield the polymer network. X-ray scattering (SAXS and WAXS) monitored the evolution of the multilamellar structured mesophase and revealed the presence of semi-crystalline PEO confined within the water layers. The hydrogel could be reversibly swollen without loss of the well-entrained Au NPs with full recovery of composite structure. Finally, optical spectroscopy shows a notable red shift (Δλ~ 45 nm) in the surface plasmon resonance between swollen and contracted states, demonstrating solvent-mediated modulation of the internal NP packing arrangement.« less

Computational studies on self-assembled paclitaxel structures: templates for hierarchical block copolymer assemblies and sustained drug release.

PubMed

Guo, Xin D; Tan, Jeremy P K; Kim, Sung H; Zhang, Li J; Zhang, Ying; Hedrick, James L; Yang, Yi Y; Qian, Yu

2009-11-01

Paclitaxel-loaded poly(ethylene oxide)-b-poly(lactide) (PEO-b-PLA) systems have been observed to assemble into fiber structures with remarkably different properties using different chirality and molecular weight of PLA segments. In this study, dissipative particle dynamics (DPD) simulations were carried out to elaborate the microstructures and properties of pure paclitaxel and paclitaxel-loaded PEO-b-PLA systems. Paclitaxel molecules formed ribbon or fiber like structures in water. With the addition of PEO-b-PDLA, PEO-b-PLLA and their stereocomplex, paclitaxel acted as a template and polymer molecules assembled around the paclitaxel structure to form core/shell structured fibers having a PEO shell. For PEO19-b-PDLA27 and PEO19-b-PLLA27 systems, PLA segments and paclitaxel molecules were distributed homogeneously in the core of fibers based on the hydrophobic interactions. In the stereocomplex formulation, paclitaxel molecules were more concentrated in the inner PLA stereocomplex core, which led to slower release of paclitaxel. By increasing the length of PLA segments (e.g. 8,16,22 and 27), the crystalline structure of paclitaxel was gradually weakened and destroyed, which was further proved by X-ray diffraction studies. All the simulation results agreed well with experimental data, suggesting that the DPD simulations may provide a powerful tool for designing drug delivery systems.

Simulation study of the lithium ion transport mechanism in ternary polymer electrolytes: the critical role of the segmental mobility.

PubMed

Diddens, Diddo; Heuer, Andreas

2014-01-30

We present an extensive molecular dynamics (MD) simulation study of the lithium ion transport in ternary polymer electrolytes consisting of poly(ethylene oxide) (PEO), lithium-bis(trifluoromethane)sulfonimide (LiTFSI), and the ionic liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethane)sulfonimide (PYR13TFSI). In particular, we focus on two different strategies by which the ternary electrolytes can be devised, namely by (a) adding the ionic liquid to PEO20LiTFSI and (b) substituting the PEO chains in PEO20LiTFSI by the ionic liquid. To grasp the changes of the overall lithium transport mechanism, we employ an analytical, Rouse-based cation transport model (Maitra et al. Phys. Rev. Lett. 2007, 98, 227802), which has originally been devised for binary PEO-based electrolytes. This model distinguishes three different microscopic transport mechanisms, each quantified by an individual time scale. In the course of our analysis, we extend this mathematical description to account for an entirely new transport mechanism, namely, the TFSI-supported diffusion of lithium ions decoupled from the PEO chains, which emerges for certain stoichiometries. We find that the segmental mobility plays a decisive role in PEO-based polymer electrolytes. That is, whereas the addition of the ionic liquid to PEO20LiTFSI plasticizes the polymer network and thus also increases the lithium diffusion, the amount of free, mobile ether oxygens reduces when substituting the PEO chains by the ionic liquid, which compensates the plasticizing effect. In total, our observations allow us to formulate some general principles about the lithium ion transport mechanism in ternary polymer electrolytes. Moreover, our insights also shed light on recent experimental observations (Joost et al. Electrochim. Acta 2012, 86, 330).

PS-b-PEO/Silica Films with Regular and Reverse Mesostructures of Large Characteristic Length Scales Prepared by Solvent Evaporation-Induced Self-Assembly

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

YU,KUI; BRINKER,C. JEFFREY; HURD,ALAN J.

2000-11-22

Since the discovery of surfactant-templated silica by Mobil scientists in 1992, mesostructured silica has been synthesized in various forms including thin films, powders, particles, and fibers. In general, mesostructured silica has potential applications, such as in separation, catalysis, sensors, and fluidic microsystems. In respect to these potential applications, mesostructured silica in the form of thin films is perhaps one of the most promising candidates. The preparation of mesostructured silica films through preferential solvent evaporation-induced self-assembly (EISA) has recently received much attention in the laboratories. However, no amphiphile/silica films with reverse mesophases have ever been made through this EISA procedure. Furthermore,more » templates employed to date have been either surfactants or poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymers, such as pluronic P-123, both of which are water-soluble and alcohol-soluble. Due to their relatively low molecular weight, the templated silica films with mesoscopic order have been limited to relatively small characteristic length scales. In the present communication, the authors report a novel synthetic method to prepare mesostructured amphiphilic/silica films with regular and reverse mesophases of large characteristic length scales. This method involves evaporation-induced self-assembly (EISA) of amphiphilic polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymers. In the present study, the PS-b-PEO diblocks are denoted as, for example, PS(215)-b-PEO(100), showing that this particular sample contains 215 S repeat units and 100 EO repeat units. This PS(215)-b-PEO(100) diblock possesses high molecular weight and does not directly mix with water or alcohol. To the authors knowledge, no studies have reported the use of water-insoluble and alcohol-insoluble amphiphilic diblocks as structure-directing agents in the synthesis of mesostructured silica films through EISA. It is believed that the present system is the first to yield amphiphile/silica films with regular and reverse mesophases, as well as curved multi-bilayer mesostructures, through EISA. The ready formation of the diblock/silica films with multi-bilayer vesicular mesostructures is discussed.« less

Formation of protective composite coatings with the use of solution of TFE telomers

NASA Astrophysics Data System (ADS)

Mashtalyar, D. V.; Gnedenkov, S. V.; Sinebryukhov, S. L.; Nadaraia, K. V.; Kiryukhin, D. P.; Kushch, P. P.; Kichigina, G. A.; Buznik, V. M.

2017-09-01

This paper presents the method of fabricate and the results of investigation of electrochemical properties and wettability of the composite coatings obtained on the magnesium alloy by plasma electrolytic oxidation (PEO) and the use of the solution of tetrafluoroethylene (TFE) telomers. The fluoropolymer-containing coatings decrease corrosion current density, increase contact angle in comparison with the base PEO-coating and the bare alloy.

Secondary Li battery incorporating 12-Crown-4 ether

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan (Inventor); Distefano, Salvador (Inventor)

1992-01-01

A rechargeable lithium battery which utilizes a polyethylene oxide (PEO) solid polymeric electrolyte complexed with a lithium salt is disclosed. The conductivity is increased an order of magnitude and interfacial charge transfer resistance is substantially decreased by incorporating a minor amount of 12-Crown-4 ether in the PEO-lithium salt solid electrolyte film. Batteries containing the improved electrolyte permit operation at a lower temperature with improved efficiency.

Novel Elastomeric Membranes Developed for Polymer Electrolytes in Lithium Batteries

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Maryann B.; Kinder, James D.; Bennett, William R.

2005-01-01

Lithium-based polymer batteries for aerospace applications need to be highly conductive from -70 to 70 C. State-of-the-art polymer electrolytes are based on polyethylene oxide (PEO) because of the ability of its ether linkages to solvate lithium ions. Unfortunately, PEO has a tendency to form crystalline regions below 60 C, dramatically lowering conductivity below this temperature. PEO has acceptable ionic conductivities (10(exp -4) to 10(exp -3) S/cm) above 60 C, but it is not mechanically strong. The room-temperature conductivity of PEO can be increased by adding solvent or plasticizers, but this comes at the expense of thermal and mechanical stability. One of NASA Glenn Research Center s objectives in the Polymer Rechargeable System program (PERS) is to develop novel polymer electrolytes that are highly conductive at and below room temperature without added solvents or plasticizers.

Hydrogen Bond Induces Hierarchical Self-Assembly in Liquid-Crystalline Block Copolymers.

PubMed

Huang, Shuai; Pang, Linlin; Chen, Yuxuan; Zhou, Liming; Fang, Shaoming; Yu, Haifeng

2018-03-01

Microphase-separated structures of block copolymers (BCs) with a size of sub-10 nm are usually obtained by hydrogen-bond-induced self-assembly of BCs through doping with small molecules as functional additives. Here, fabrication of hierarchically self-assembled sub-10 nm structures upon microphase separation of amphiphilic liquid-crystalline BCs (LCBCs) at the existence of hydrogen bonds but without any dopants is reported. The newly introduced urethane groups in the side chain of the hydrophobic block of LCBCs interact with the ether groups of the hydrophilic poly(ethylene oxide) (PEO) block, leading to imperfect crystallization of the PEO blocks. Both crystalline and amorphous domains coexist in the separated PEO phase, enabling a lamellar structure to appear inside the PEO nanocylinders. This provides an elegant method to fabricate controllable sub-10 nm microstructures in well-defined polymer systems without the introduction of any dopants. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular dynamics studies of polyethylene oxide and polyethylene glycol: hydrodynamic radius and shape anisotropy.

PubMed

Lee, Hwankyu; Venable, Richard M; Mackerell, Alexander D; Pastor, Richard W

2008-08-01

A revision (C35r) to the CHARMM ether force field is shown to reproduce experimentally observed conformational populations of dimethoxyethane. Molecular dynamics simulations of 9, 18, 27, and 36-mers of polyethylene oxide (PEO) and 27-mers of polyethylene glycol (PEG) in water based on C35r yield a persistence length lambda = 3.7 A, in quantitative agreement with experimentally obtained values of 3.7 A for PEO and 3.8 A for PEG; agreement with experimental values for hydrodynamic radii of comparably sized PEG is also excellent. The exponent upsilon relating the radius of gyration and molecular weight (R(g) proportional, variantM(w)(upsilon)) of PEO from the simulations equals 0.515 +/- 0.023, consistent with experimental observations that low molecular weight PEG behaves as an ideal chain. The shape anisotropy of hydrated PEO is 2.59:1.44:1.00. The dimension of the middle length for each of the polymers nearly equals the hydrodynamic radius R(h)obtained from diffusion measurements in solution. This explains the correspondence of R(h) and R(p), the pore radius of membrane channels: a polymer such as PEG diffuses with its long axis parallel to the membrane channel, and passes through the channel without substantial distortion.

Resistance of poly(ethylene oxide)-silane monolayers to the growth of polyelectrolyte multilayers.

PubMed

Buron, Cédric C; Callegari, Vincent; Nysten, Bernard; Jonas, Alain M

2007-09-11

The ability of poly(ethylene oxide)-silane (PEO-silane) monolayers grafted onto silicon surfaces to resist the growth of polyelectrolyte multilayers under various pH conditions is assessed for different pairs of polyelectrolytes of varying molar mass. For acidic conditions (pH 3), the PEO-silane monolayers exhibit good polyelectrolyte repellency provided the polyelectrolytes bear no moieties that are able to form hydrogen bonds with the ether groups of the PEO chains. At basic pH, PEO-silane monolayers undergo substantial hydrolysis leading to the formation of negatively charged defects in the monolayers, which then play the role of adsorption sites for the polycation. Once the polycation is adsorbed, multilayer growth ensues. Because this is defect-driven growth, the multilayer is not continuous and is made of blobs or an open network of adsorbed strands. For such conditions, the molar mass of the polyelectrolyte plays a key role, with polyelectrolyte chains of larger molar mass adsorbing on a larger number of defects, resulting in stronger anchoring of the polyelectrolyte complex on the surfaces and faster subsequent growth of the multilayer. For polyelectrolytes of sufficiently low molar mass at pH 9, the growth of the multilayer can nevertheless be prevented for as much as five cycles of deposition.

Conformation and hydration of surface grafted and free polyethylene oxide chains in solutions

NASA Astrophysics Data System (ADS)

Dahal, Udaya; Wang, Zilu; Dormidontova, Elena

Due to the wide application of polyethylene oxide (PEO), ranging from biomedicine to fuel cells, it is one of the most studied polymers in the scientific world. In order to elucidate detailed molecular-level insights on the impact of surface grafting on PEO conformation, we performed atomistic molecular dynamics simulations of PEO chains in solution and grafted to a flat gold surface in different solvents. We examined the hydration as well as conformation of the free chain compared to the grafted polymer in pure water and mixed solvents. We find that grafted chains are stiffer and have a stronger tendency to form helical structures in isobutyric acid or mixture of isobutyric acid and water solution than the free chains in corresponding solutions. For grafted chains exposed to pure water the random coil conformation is retained at low grafting density, but becomes stretched and more dehydrated as the grafting density or temperature increases. This research is supported by NSF (DMR-1410928).

Toxicity effects of nickel electroplating effluents treated by photoelectrooxidation in the industries of the Sinos River Basin.

PubMed

Benvenuti, T; Rodrigues, Mas; Arenzon, A; Bernardes, A M; Zoppas-Ferreira, J

2015-05-01

The Sinos river Basin is an industrial region with many tanneries and electroplating plants in southern Brazil. The wastewater generated by electroplating contains high loads of salts and metals that have to be treated before discharge. After conventional treatment, this study applied an advanced oxidative process to degrade organic additives in the electroplating bright nickel baths effluent. Synthetic rinsing water was submitted to physical-chemical coagulation for nickel removal. The sample was submitted to ecotoxicity tests, and the effluent was treated by photoelectrooxidation (PEO). The effects of current density and treatment time were evaluated. The concentration of total organic carbon (TOC) was 38% lower. The toxicity tests of the effluent treated using PEO revealed that the organic additives were partially degraded and the concentration that is toxic for test organisms was reduced.

Ion conducting polymers and polymer blends for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

Multiscale Molecular Dynamics Simulations of Model Hydrophobically Modified Ethylene Oxide Urethane Micelles.

PubMed

Yuan, Fang; Larson, Ronald G

2015-09-24

The flower-like micelles of various aggregation numbers of a model hydrophobically modified ethylene oxide urethane (HEUR) molecule, C16E45C16, and their corresponding starlike micelles, containing the surfactants C16E22 and C16E23, were studied by atomistic and coarse-grained molecular dynamic (MD) simulations. We used free energies from umbrella sampling to calculate the size distribution of micelle sizes and the average time for escape of a hydrophobic group from the micelle. Using the coarse-grained MARTINI force field, the most probable size of the model HEUR molecule was thereby determined to be about 80 hydrophobes per micelle and the average hydrophobe escape time to be about 0.1 s, both of which are consistent with previous experimental studies. Atomistic simulations reveal that hydrogen bond formation and the mean lifetime of hydration waters of the poly(ethylene oxide) (or PEO) groups are location-dependent in the HEUR micelle, with PEO groups immediately adjacent to the C16 groups forming the fewest hydrogen bonds with water and having hydration waters with longer lifetimes than those of the PEO groups located further away from the C16 groups.

Development of FDR-AF (Frictional Drag Reduction Anti-Fouling) Marine Coating

NASA Astrophysics Data System (ADS)

Lee, Inwon; Park, Hyun; Chun, Ho Hwan; GCRC-SOP Team

2013-11-01

In this study, a novel skin-friction reducing marine paint has been developed by mixing fine powder of PEO(PolyEthyleneOxide) with SPC (Self-Polishing Copolymer) AF (Anti-Fouling) paint. The PEO is well known as one of drag reducing agent to exhibit Toms effect, the attenuation of turbulent flows by long chain polymer molecules in the near wall region. The frictional drag reduction has been implemented by injecting such polymer solutions to liquid flows. However, the injection holes have been a significant obstacle to marine application. The present PEO-containing marine paint is proposed as an alternative to realize Toms effect without any hole on the ship surface. The erosion mechanism of SPC paint resin and the subsequent dissolution of PEO enable the controlled release of PEO solution from the coating. Various tests such as towing tank drag measurement of flat plate and turbulence measurement in circulating water tunnel demonstrated over 10% frictional drag reduction compared with conventional AF paint. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) through GCRC-SOP(No. 2011-0030013).

Molecular Simulation Evaluation of Macromolecular Transport through Nanofiltration Membranes

NASA Astrophysics Data System (ADS)

Almodovar Arbelo, Noelia; Boudouris, Bryan; Corti, David

A hybrid Monte Carlo and Molecular Dynamics simulation technique was implemented to elucidate the equilibrium behavior and transport properties of a model macromolecule as it navigated across a nanoporous polymer thin film (i.e., a nanofiltration membrane). The model linear homopolymer chosen was one that had interactions that were representative of poly(ethylene oxide) (PEO) due to the known interactions of PEO with solution molecules when a PEO chain is dissolved in an aqueous environment. The structural rearrangements of the PEO chain as it passes through the nanopore under an imposed chemical potential gradient was quantified as a function of solvent quality, polymer chain length, nanopore diameter and shape, and PEO-nanopore wall interactions. Thus, these computational studies provide a more detailed picture of the underlying physical mechanisms that drive macromolecular transport through nanopores, and, in particular, how dimensionally-large macromolecules (i.e., with large radii of gyration) enter and move through dimensionally-small pores (i.e., small radii nanopores). The insights gained from these studies will aid in the development of more cost-effective water purification systems in separation technologies for myriad industrial applications.

Controlling domain orientation of liquid crystalline block copolymer in thin films through tuning mesogenic chemical structures

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

Xie, He-Lou; Li, Xiao; Ren, Jiaxing

Controlling the macroscopic orientation of nanoscale periodic structures of amphiphilic liquid crystalline block copolymers (LC BCPs) is important to a variety of technical applications (e.g., lithium conducting polymer electrolytes). To study LC BCP domain orientation, a series of LC BCPs containing a poly(ethylene oxide) (PEO) block as a conventional hydrophilic coil block and LC blocks containing azobenzene mesogens is designed and synthesized. LC ordering in thin films of the BCP leads to the formation of highly ordered, microphase-separated nanostructures, with hexagonally arranged PEO cylinders. Substitution on the tail of the azobenzene mesogen is shown to control the orientation of themore » PEO cylinders. When the substitution on the mesogenic tails is an alkyl chain, the PEO cylinders have a perpendicular orientation to the substrate surface, provided the thin film is above a critical thickness value. In contrast, when the substitution on the mesogenic tails has an ether group the PEO cylinders assemble parallel to the substrate surface regardless of the film thickness value.« less

Toxicity evaluation of methoxy poly(ethylene oxide)-block-poly(ε-caprolactone) polymeric micelles following multiple oral and intraperitoneal administration to rats.

PubMed

Binkhathlan, Ziyad; Qamar, Wajhul; Ali, Raisuddin; Kfoury, Hala; Alghonaim, Mohammed

2017-09-01

Methoxy poly(ethylene oxide)- block -poly(ɛ-caprolactone) (PEO- b -PCL) copolymers are amphiphilic and biodegradable copolymers designed to deliver a variety of drugs and diagnostic agents. The aim of this study was to synthesize PEO- b -PCL block copolymers and assess the toxic effects of drug-free PEO- b -PCL micelles after multiple-dose administrations via oral or intraperitoneal (ip) administration in rats. Assembly of block copolymers was achieved by co-solvent evaporation method. To investigate the toxicity profile of PEO- b -PCL micelles, sixty animals were divided into two major groups: The first group received PEO- b -PCL micelles (100 mg/kg) by oral gavage daily for seven days, while the other group received the same dose of micelles by ip injections daily for seven days. Twenty-four hours following the last dose, half of the animals from each group were sacrificed and blood and organs (lung, liver, kidneys, heart and spleen) were collected. Remaining animals were observed for further 14 days and was sacrificed at the end of the third week, and blood and organs were collected. None of the polymeric micelles administered caused any significant effects on relative organ weight, animal body weight, leucocytes count, % lymphocytes, liver and kidney toxicity markers and organs histology. Although the dose of copolymers used in this study is much higher than those used for drug delivery, it did not cause any significant toxic effects in rats. Histological examination of all the organs confirmed the nontoxic nature of the micelles.

Composition-dependent damping and relaxation dynamics in miscible polymer blends above glass transition temperature by anelastic spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Xuebang; Shang, Shuying; Xu, Qiaoling; Liu, Changsong; Zhu, Zhengang; Zhang, Guangzhao

2008-07-01

Anelastic spectroscopy is used to study the composition dependence of the damping and molecular relaxation dynamics in miscible poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends above the glass transition temperature. The ultrahigh damping peak of the relaxation type is shown to be associated with the liquid-liquid transition of PMMA. A higher PEO concentration leads to a higher damping performance and a lower transition temperature. The decreasing activation energy with increasing PEO concentration indicates a drastic increase in molecular mobility. Moreover, the relaxation time reveals a transition from the Vogel-Fulcher-Tamman behavior to the Arrhenius behavior due to the intermolecular guest-host interactions.

An all-solid-state lithium/polyaniline rechargeable cell

NASA Astrophysics Data System (ADS)

Li, Changzhi; Peng, Xinsheng; Zhang, Borong; Wang, Baochen

1992-07-01

The performance of an all-solid-state cell having a lithium negative electrode, a modified polyethylene oxide (PEO)-epoxy resin (ER) electrolyte, and a polyaniline (PAn) positive electrode has been studied using cyclic voltammetry, charge/discharge cycling, and polarization curves at various temperatures. The redox reaction of the PAn electrode at the PAn/modified PEO-ER interface exhibits good reversibility. At 50-80 C, the Li/PEO-ER-LiClO4/PAn cell shows more than 40 charge/discharge cycles, 90 percent charge/discharge efficiency, and 54 W h kg discharge energy density (on PAn weight basis) at 50 micro-A between 2 and 4 V. The polarization performance of the battery improves steadily with increase in temperature.

Electrospinning and stabilization of chitosan nanofiber mats

NASA Astrophysics Data System (ADS)

Grimmelsmann, N.; Grothe, T.; Homburg, S. V.; Ehrmann, A.

2017-10-01

Chitosan is of special interest for biotechnological and medical applications due to its antibacterial, antifungal and other intrinsic physical and chemical properties. The biopolymer can, e.g., be used for biotechnological purposes, as a filter medium, in medical products, etc. In all these applications, the inner surface should be maximized to increase the contact area with the filtered medium etc. and thus the chitosan’s efficacy. Chitosan dissolves in acidic solutions, opposite to neutral water. Electrospinning is possible, e.g., by co-spinning with PEO (poly(ethylene oxide)). Tests with different chitosan:PEO ratios revealed that higher PEO fractions resulted in better spinnability and more regular fibre mats, but make stabilization of the fibre structure more challenging.

Present status of solid state photoelectrochemical solar cells and dye sensitized solar cells using PEO-based polymer electrolytes

NASA Astrophysics Data System (ADS)

Singh, Pramod Kumar; Nagarale, R. K.; Pandey, S. P.; Rhee, H. W.; Bhattacharya, Bhaskar

2011-06-01

Due to energy crises in the future, much effort is being directed towards alternate sources. Solar energy is accepted as a novel substitute for conventional sources of energy. Out of the long list of various types of solar cells available on the market, solid state photoelectrochemical solar cells (SSPECs) and dye sensitized solar cells (DSSCs) are proposed as an alternative to costly crystalline solar cell. This review provides a common platform for SSPECs and DSSCs using polymer electrolyte, particularly on polyethylene oxide (PEO)-based polymer electrolytes. Due to numerous advantageous properties of PEO, it is frequently used as an electrolyte in both SSPECs as well as DSSCs. In DSSCs, so far high efficiency (more than 11%) has been obtained only by using volatile liquid electrolyte, which suffers many disadvantages, such as corrosion, leakage and evaporation. The PEO-based solid polymer proves its importance and could be used to solve the problems stated above. The recent developments in SSPECs and DSSCs using modified PEO electrolytes by adding nano size inorganic fillers, blending with low molecular weight polymers and ionic liquid (IL) are discussed in detail. The role of ionic liquid in modifying the electrical, structural and photoelectrochemical properties of PEO polymer electrolytes is also described.

Restricted lithium ion dynamics in PEO-based block copolymer electrolytes measured by high-field nuclear magnetic resonance relaxation

NASA Astrophysics Data System (ADS)

Huynh, Tan Vu; Messinger, Robert J.; Sarou-Kanian, Vincent; Fayon, Franck; Bouchet, Renaud; Deschamps, Michaël

2017-10-01

The intrinsic ionic conductivity of polyethylene oxide (PEO)-based block copolymer electrolytes is often assumed to be identical to the conductivity of the PEO homopolymer. Here, we use high-field 7Li nuclear magnetic resonance (NMR) relaxation and pulsed-field-gradient (PFG) NMR diffusion measurements to probe lithium ion dynamics over nanosecond and millisecond time scales in PEO and polystyrene (PS)-b-PEO-b-PS electrolytes containing the lithium salt LiTFSI. Variable-temperature longitudinal (T1) and transverse (T2) 7Li NMR relaxation rates were acquired at three magnetic field strengths and quantitatively analyzed for the first time at such fields, enabling us to distinguish two characteristic time scales that describe fluctuations of the 7Li nuclear electric quadrupolar interaction. Fast lithium motions [up to O (ns)] are essentially identical between the two polymer electrolytes, including sub-nanosecond vibrations and local fluctuations of the coordination polyhedra between lithium and nearby oxygen atoms. However, lithium dynamics over longer time scales [O (10 ns) and greater] are slower in the block copolymer compared to the homopolymer, as manifested experimentally by their different transverse 7Li NMR relaxation rates. Restricted dynamics and altered thermodynamic behavior of PEO chains anchored near PS domains likely explain these results.

Roles of nonpolar and polar intermolecular interactions in the improvement of the drug loading capacity of PEO-b-PCL with increasing PCL content for two hydrophobic Cucurbitacin drugs.

PubMed

Patel, Sarthak K; Lavasanifar, Afsaneh; Choi, Phillip

2009-09-14

Molecular dynamics (MD) simulation was used to study the roles of nonpolar and polar intermolecular interactions in the improvement of the drug loading capacity of poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PEO-b-PCL) with increasing PCL content for two water insoluble anticancer drugs: Cucurbitacin B (CuB) and Cucurbitacin I (CuI). In particular, random binary mixture models containing 10-12 wt % drug and remaining PEO-b-PCL with three different PCL/PEO (w/w) ratios (0.5, 1, and 2) were used to calculate their Flory-Huggins interaction parameters (chi). The MD simulation results show that, for both CuB and CuI, the computed chi decreases (i.e., affinity increases) with increasing PCL/PEO ratio. Such results are consistent with our experimental observation that increasing the PCL/PEO (w/w) ratio from 1 to 4.8 significantly increases the drug loading capacity of micelles formed by PEO-b-PCL for both drugs. Analysis of the energy data shows that increasing affinity (loading) at higher PCL/PEO ratio is attributed to the increase in favorable polar interactions and to the formation of additional hydrogen bonds (H-bonds) between the drugs and the PCL block rather than to the increase in the hydrophobic characteristics of the diblock copolymer as one would normally expect. In fact, the nonpolar intermolecular interactions became more unfavorable at higher PCL/PEO ratio. Analysis of the radial distribution functions of the model mixtures indicates that at high PCL/PEO ratio, multiple H-bond sites on the PCL block interacted with single H-bond sites on the drug molecules. However, at low PCL/PEO ratio, only single H-bonds formed between various H-bond sites on the drug molecules and those of the PCL and PEO blocks. It seems that formation of H-bonds between multiple H-bond sites on the PCL block and single H-bond sites on the drug molecules is responsible for inducing drug/PEO-b-PCL affinity. The finding also explains the experimental observation that release rates of both drugs decrease with increasing PCL/PEO ratio and that the decrease in the release rate of CuB is more pronounced than that of CuI. Our simulation results show that the number of H-bonds formed between CuB and the PCL block is much higher than that of CuI at high PCL/PEO ratio.

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

NASA Astrophysics Data System (ADS)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-05-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

NASA Astrophysics Data System (ADS)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-04-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

Macroscopic lateral heterogeneity observed in a laterally mobile immiscible mixed polyelectrolyte-neutral polymer brush

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

Lee, Hoyoung; Tsouris, Vasilios; Lim, Yunho

We studied mixed poly(ethylene oxide) (PEO) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes. The question we attempted to answer was: when the chain grafting points are laterally mobile, how will this lateral mobility influence the structure and phase behavior of the mixed brush? Three different model mixed PEO/PDMAEMA brush systems were prepared: (1) a laterally mobile mixed brush by spreading onto the air–water interface a mixture of poly(ethylene oxide)–poly(n-butyl acrylate) (PEO–PnBA) and poly(2-(dimethylamino)ethyl methacrylate)–poly(n-butyl acrylate) (PDMAEMA–PnBA) diblock copolymers (the specific diblock copolymers used will be denoted as PEO 113–PnBA 100 and PDMAEMA 118–PnBA 100, where the subscripts refer to the number-average degreesmore » of polymerization of the individual blocks), (2) a mobility-restricted (inseparable) version of the above mixed brush prepared using a PEO–PnBA–PDMAEMA triblock copolymer (denoted as PEO 113–PnBA 89–PDMAEMA 120) having respective brush molecular weights matched with those of the diblock copolymers, and (3) a different laterally mobile mixed PEO and PDMAEMA brush prepared from a PEO 113–PnBA 100 and PDMAEMA 200–PnBA 103 diblock copolymer combination, which represents a further more height-mismatched mixed brush situation than described in (1). These three mixed brush systems were investigated by surface pressure–area isotherm and X-ray (XR) reflectivity measurements. These experimental data were analyzed within the theoretical framework of a continuum self-consistent field (SCF) polymer brush model. The combined experimental and theoretical results suggest that the mobile mixed brush derived using the PEO 113–PnBA 100 and PDMAEMA 118–PnBA 100 combination (i.e., mixed brush System #1) undergoes a lateral macroscopic phase separation at high chain grafting densities, whereas the more height-mismatched system (System #3) is only microscopically phase separated under comparable brush density conditions even though the lateral mobility of the grafted chains is unrestricted. The macroscopic phase separation observed in the laterally mobile mixed brush system is in contrast with the microphase separation behavior commonly observed in two-dimensional laterally mobile charged small molecule mixtures. Further study is needed to determine the detailed morphologies of the macro- and microphase-separated mixed PEO/PDMAEMA brushes.« less

Molecular-Level Control of Ciclopirox Olamine Release from Poly(ethylene oxide)-Based Mucoadhesive Buccal Films: Exploration of Structure-Property Relationships with Solid-State NMR.

PubMed

Urbanova, Martina; Gajdosova, Marketa; Steinhart, Miloš; Vetchy, David; Brus, Jiri

2016-05-02

Mucoadhesive buccal films (MBFs) provide an innovative way to facilitate the efficient site-specific delivery of active compounds while simultaneously separating the lesions from the environment of the oral cavity. The structural diversity of these complex multicomponent and mostly multiphase systems as well as an experimental strategy for their structural characterization at molecular scale with atomic resolution were demonstrated using MBFs of ciclopirox olamine (CPX) in a poly(ethylene oxide) (PEO) matrix as a case study. A detailed description of each component of the CPX/PEO films was followed by an analysis of the relationships between each component and the physicochemical properties of the MBFs. Two distinct MBFs were identified by solid-state NMR spectroscopy: (i) at low API (active pharmaceutical ingredient) loading, a nanoheterogeneous solid solution of CPX molecularly dispersed in an amorphous PEO matrix was created; and (ii) at high API loading, a pseudoco-crystalline system containing CPX-2-aminoethanol nanocrystals incorporated into the interlamellar space of a crystalline PEO matrix was revealed. These structural differences were found to be closely related to the mechanical and physicochemical properties of the prepared MBFs. At low API loading, the polymer chains of PEO provided sufficient quantities of binding sites to stabilize the CPX that was molecularly dispersed in the highly amorphous semiflexible polymer matrix. Consequently, the resulting MBFs were soft, with low tensile strength, plasticity, and swelling index, supporting rapid drug release. At high CPX content, however, the active compounds and the polymer chains simultaneously cocrystallized, leaving the CPX to form nanocrystals grown directly inside the spherulites of PEO. Interfacial polymer-drug interactions were thus responsible not only for the considerably enhanced plasticity of the system but also for the exclusive crystallization of CPX in the thermodynamically most stable polymorphic form, Form I, which exhibited reduced dissolution kinetics. The bioavailability of CPX olamine formulated as PEO-based MBFs can thus be effectively controlled by inducing the complete dispersion and/or microsegregation and nanocrystallization of CPX olamine in the polymer matrix. Solid-state NMR spectroscopy is an efficient tool for exploring structure-property relationships in these complex pharmaceutical solids.

Performance comparison of hybrid resistive switching devices based on solution-processable nanocomposites

NASA Astrophysics Data System (ADS)

Rajan, Krishna; Roppolo, Ignazio; Bejtka, Katarzyna; Chiappone, Annalisa; Bocchini, Sergio; Perrone, Denis; Pirri, Candido Fabrizio; Ricciardi, Carlo; Chiolerio, Alessandro

2018-06-01

The present work compares the influence of different polymer matrices on the performance of planar asymmetric Resistive Switching Devices (RSDs) based on silver nitrate and Ionic Liquid (IL). PolyVinyliDene Fluoride-HexaFluoroPropylene (PVDF-HFP), PolyEthylene Oxide (PEO), PolyMethyl MethAcrylate (PMMA) and a blend of PVDF-HFP and PEO were used as matrices and compared. RSDs represent perhaps the most promising electron device to back the More than Moore development, and our approach through functional polymers enables low temperature processing and gives compatibility towards flexible/stretchable/wearable equipment. The switching mechanism in all the four sample families is explained by means of a filamentary conduction. A huge difference in the cyclability and the On/Off ratio is experienced when changing the active polymers and explained based on the polymer crystallinity degree and general morphology of the prepared nanocomposite. It is worth noting that all the RSDs discussed here present good switching behaviour with reasonable endurance. The current study displays one of the most cost-effective and effortless ways to produce an RSD based on solution-processable materials.

Preparation and Characterization of Single Ion Conductors from High Surface Area Fumed Silica

NASA Technical Reports Server (NTRS)

Zhang, H.; Maitra, P.; Liu, B.; Wunder, S. L.; Lin, H.-P.; Salomon, M.; Hagedorn, Norman H. (Technical Monitor)

2002-01-01

Anions that can form dissociative salts with Li(+) have been prepared and covalently attached to high surface area fumed silica. When blended with polyethylene oxide (PEO), the functionalized fumed silica suppresses the crystallization of the PEO, provides dimensional stability, and serves as a single ion conductor. Since functionalized fumed silica is easily dispersed in common polar solvents, it can be incorporated in both the polymer electrolyte and the electrodes.

Magnetic Nanocomposites and Their Incorporation into Higher Order Biosynthetic Functional Architectures

DOE PAGES

Watt, John; Collins, Aaron M.; Vreeland, Erika C.; ...

2018-01-17

A magnetically active Fe 3O 4/poly(ethylene oxide)-block-poly(butadiene) (PEO-b-PBD) nanocomposite is formed by the encapsulation of magnetite nanoparticles with a short-chain amphiphilic block copolymer. This material is then incorporated into the self-assembly of higher order polymer architectures, along with an organic pigment, to yield biosynthetic, bifunctional optical and magnetically active Fe 3O 4/bacteriochlorophyll c/PEO-b-PBD polymeric chlorosomes.

Evolution processes of the corrosion behavior and structural characteristics of plasma electrolytic oxidation coatings on AZ31 magnesium alloy

NASA Astrophysics Data System (ADS)

Chen, Dong; Wang, Ruiqiang; Huang, Zhiquan; Wu, Yekang; Zhang, Yi; Wu, Guorui; Li, Dalong; Guo, Changhong; Jiang, Guirong; Yu, Shengxue; Shen, Dejiu; Nash, Philip

2018-03-01

Evolution processes of the corrosion behavior and structural characteristics of the plasma electrolytic oxidation (PEO) coated AZ31 magnesium alloy were investigated by using scanning electron microscope (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), potentio-dynamic polarization curves and electrochemical impedance spectroscopy (EIS) measurements. Detached coating samples were fabricated by an electrochemical method and more details of the internal micro-structure of coatings were clearly observed on the fractured cross-section morphologies of the samples compared to general polished cross-section morphologies. Evolution mechanisms of the coating corrosion behavior in relation to the evolution of micro-structural characteristics were discussed in detail.

Investigation of ionic conduction in PEO-PVDF based blend polymer electrolytes

NASA Astrophysics Data System (ADS)

Patla, Subir Kumar; Ray, Ruma; Asokan, K.; Karmakar, Sanat

2018-03-01

We investigate the effect of blend host polymer on solid polymer electrolyte (SPE) films doped with ammonium iodide (NH4I) salt using a variety of experimental techniques. Structural studies on the composite SPEs show that the blending of Poly(ethylene oxide) (PEO)-Poly(vinylidene fluoride) (PVDF) polymers in a suitable ratio enhances the amorphous fraction of the polymer matrix and facilitates fast ion conduction through it. We observe that the addition of a small amount of PVDF in the PEO host polymer enhances the ion - polymer interaction leading to more ion dissociation. As a result, the effective number of mobile charge carriers within the polymer matrix increases. Systematic investigation in these blend SPEs shows that the maximum conductivity (1.01 × 10-3 S/cm) is obtained for PEO - rich (80 wt. % PEO, 20 wt. % PVDF) composites at 35 wt. % NH4I concentration at room temperature. Interestingly, at higher salt concentrations (above 35 wt. %), the conductivity is found to decrease in this system. The reduction of conductivity at higher salt concentrations is the consequence of decrease in the carrier concentration due to the formation of an ion pair and ion aggregates. PVDF-rich compositions (20 wt. % PEO and 80 wt. % PVDF), on the other hand, show a very complex porous microstructure. We also observe a much lower ionic conductivity (maximum ˜ 10-6 S/cm at 15 wt. % salt) in these composite systems relative to PEO-rich composites.

Single-Molecule Tracking Study of the Permeability and Transverse Width of Individual Cylindrical Microdomains in Solvent-Swollen Polystyrene-block-poly(ethylene oxide) Films.

PubMed

Sapkota, Dol Raj; Tran-Ba, Khanh-Hoa; Elwell-Cuddy, Trevor; Higgins, Daniel A; Ito, Takashi

2016-12-01

Understanding the properties of solvent-swollen block copolymer (BCP) microdomains is important for better solvent-based control of microdomain morphology, orientation, and permeability. In this study, single-molecule tracking (SMT) was explored to assess the permeability and transverse width of individual cylindrical microdomains in solvent-swollen polystyrene-block-poly(ethylene oxide) (PS-b-PEO) films. PS-b-PEO films comprising shear-elongated cylindrical PEO microdomains were prepared by sandwiching its benzene or tetrahydrofuran (THF) solution between two glass substrates. SMT measurements were performed at different drying times to investigate the effects of solvent evaporation on the microdomain properties. SMT data showed one-dimensional (1D) motions of single fluorescent molecules (sulforhodamine B) based on their diffusion within the cylindrical microdomains. Microdomain permeability and transverse width were assessed from the single-molecule diffusion coefficients (D SMT ) and transverse variance of the 1D trajectories (σ δ 2 ), respectively. The D SMT and σ δ 2 values from individual 1D trajectories were widely distributed with no evidence of correlation on a single molecule basis, possibly because the individual microdomains in a film were swollen to different extents. On average, microdomain permeability (D) and effective radius (r) gradually decreased within the first 3 days of drying due to solvent evaporation, and changed negligibly thereafter. PS-b-PEO films prepared from THF solutions exhibited larger changes in D and r as compared with those from benzene solutions due to the better swelling of the PEO microdomains by THF. Importantly, changes in D were more prominent than those in r, suggesting that the permeability of the PEO microdomains is very susceptible to the presence of solvent. These results reveal the unique capability of SMT to assess the properties of individual cylindrical microdomains in a solvent-swollen BCP film.

Competitive adsorption of surfactants and polymers at the free water surface. A computer simulation study of the sodium dodecyl sulfate-poly(ethylene oxide) system.

PubMed

Darvas, Mária; Gilányi, Tibor; Jedlovszky, Pál

2011-02-10

Competitive adsorption of a neutral amphiphilic polymer, namely poly(ethylene oxide) (PEO) and an ionic surfactant, i.e., sodium dodecyl sulfate (SDS), is investigated at the free water surface by computer simulation methods at 298 K. The sampled equilibrium configurations are analyzed in terms of the novel identification of the truly interfacial molecules (ITIM) method, by which the intrinsic surface of the aqueous phase (i.e., its real surface corrugated by the capillary waves) instead of an ideally flat surface approximating its macroscopic surface plane, can be taken into account. In the simulations, the surface density of SDS is gradually increased from zero up to saturation, and the structural, dynamical, and energetic aspects of the gradual squeezing out of the PEO chains from the surface are analyzed in detail. The obtained results reveal that this squeezing out occurs in a rather intricate way. Thus, in the presence of a moderate amount of SDS the majority of the PEO monomer units, forming long bulk phase loops in the absence of SDS, are attracted to the surface of the solution. This synergistic effect of SDS of moderate surface density on the adsorption of PEO is explained by two factors, namely by the electrostatic attraction between the ionic groups of the surfactant and the moderately polar monomer units of the polymer, and by the increase of the conformational entropy of the polymer chain in the presence of the surfactant. This latter effect, thought to be the dominant one among the above two factors, also implies the formation of similar polymer/surfactant complexes at the interface than what are known to exist in the bulk phase of the solution. Finally, in the presence of a large amount of SDS the more surface active surfactant molecules gradually replace the PEO monomer units at the interfacial positions, and squeezing out the PEO molecules from the surface in a monomer unit by monomer unit manner.

Single-molecule tracking study of the permeability and transverse width of individual cylindrical microdomains in solvent-swollen polystyrene- block-poly(ethylene oxide) films

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

Sapkota, Dol Raj; Tran-Ba, Khanh-Hoa; Elwell-Cuddy, Trevor

Understanding the properties of solvent-swollen block copolymer (BCP) microdomains is important for better solvent-based control of microdomain morphology, orientation, and permeability. In this study, single-molecule tracking (SMT) was explored to assess the permeability and transverse width of individual cylindrical microdomains in solvent-swollen polystyrene- block-poly(ethylene oxide) (PS-b-PEO) films. PS-b-PEO films comprising shear-elongated cylindrical PEO microdomains were prepared by sandwiching its benzene or tetrahydrofuran (THF) solution between two glass substrates. In this paper, SMT measurements were performed at different drying times to investigate the effects of solvent evaporation on the microdomain properties. SMT data showed one-dimensional (1D) motions of single fluorescent moleculesmore » (sulforhodamine B) based on their diffusion within the cylindrical microdomains. Microdomain permeability and transverse width were assessed from the single-molecule diffusion coefficients (D SMT) and transverse variance of the 1D trajectories (σ δ 2), respectively. The D SMT and σ δ 2 values from individual 1D trajectories were widely distributed with no evidence of correlation on a single molecule basis, possibly because the individual microdomains in a film were swollen to different extents. On average, microdomain permeability (D) and effective radius (r) gradually decreased within the first 3 days of drying due to solvent evaporation, and changed negligibly thereafter. PS-b-PEO films prepared from THF solutions exhibited larger changes in D and r as compared with those from benzene solutions due to the better swelling of the PEO microdomains by THF. Importantly, changes in D were more prominent than those in r, suggesting that the permeability of the PEO microdomains is very susceptible to the presence of solvent. Finally, these results reveal the unique capability of SMT to assess the properties of individual cylindrical microdomains in a solvent-swollen BCP film.« less

Single-molecule tracking study of the permeability and transverse width of individual cylindrical microdomains in solvent-swollen polystyrene- block-poly(ethylene oxide) films

DOE PAGES

Sapkota, Dol Raj; Tran-Ba, Khanh-Hoa; Elwell-Cuddy, Trevor; ...

2016-11-04

Understanding the properties of solvent-swollen block copolymer (BCP) microdomains is important for better solvent-based control of microdomain morphology, orientation, and permeability. In this study, single-molecule tracking (SMT) was explored to assess the permeability and transverse width of individual cylindrical microdomains in solvent-swollen polystyrene- block-poly(ethylene oxide) (PS-b-PEO) films. PS-b-PEO films comprising shear-elongated cylindrical PEO microdomains were prepared by sandwiching its benzene or tetrahydrofuran (THF) solution between two glass substrates. In this paper, SMT measurements were performed at different drying times to investigate the effects of solvent evaporation on the microdomain properties. SMT data showed one-dimensional (1D) motions of single fluorescent moleculesmore » (sulforhodamine B) based on their diffusion within the cylindrical microdomains. Microdomain permeability and transverse width were assessed from the single-molecule diffusion coefficients (D SMT) and transverse variance of the 1D trajectories (σ δ 2), respectively. The D SMT and σ δ 2 values from individual 1D trajectories were widely distributed with no evidence of correlation on a single molecule basis, possibly because the individual microdomains in a film were swollen to different extents. On average, microdomain permeability (D) and effective radius (r) gradually decreased within the first 3 days of drying due to solvent evaporation, and changed negligibly thereafter. PS-b-PEO films prepared from THF solutions exhibited larger changes in D and r as compared with those from benzene solutions due to the better swelling of the PEO microdomains by THF. Importantly, changes in D were more prominent than those in r, suggesting that the permeability of the PEO microdomains is very susceptible to the presence of solvent. Finally, these results reveal the unique capability of SMT to assess the properties of individual cylindrical microdomains in a solvent-swollen BCP film.« less

Aqueous self-assembly of poly(ethylene oxide)-block-poly(ε-caprolactone) (PEO-b-PCL) copolymers: disparate diblock copolymer compositions give rise to nano- and meso-scale bilayered vesicles

NASA Astrophysics Data System (ADS)

Qi, Wei; Ghoroghchian, P. Peter; Li, Guizhi; Hammer, Daniel A.; Therien, Michael J.

2013-10-01

Nanoparticles formed from diblock copolymers of FDA approved PEO and PCL have generated considerable interest as in vivo drug delivery vehicles. Herein, we report the synthesis of the most extensive family PEO-b-PCL copolymers that vary over the largest range of number-average molecular weights (Mn: 3.6-57k), PEO weight fractions (fPEO: 0.08-0.33), and PEO chain lengths (0.75-5.8k) reported to date. These polymers were synthesized in order to establish the full range of aqueous phase behaviours of these diblock copolymers and to specifically identify formulations that were able to generate bilayered vesicles (polymersomes). Cryogenic transmission electron microscopy (cryo-TEM) was utilized in order to visualize the morphology of these structures upon aqueous self-assembly of dry polymer films. Nanoscale polymersomes were formed from PEO-b-PCL copolymers over a wide range of PEO weight fractions (fPEO: 0.14-0.27) and PEO molecular weights (0.75-3.8k) after extrusion of aqueous suspensions. Comparative morphology diagrams, which describe the nature of self-assembled structures as a function of diblock copolymer molecular weight and PEO weight fraction, show that in contrast to micron-scale polymersomes, which form only from a limited range of PEO-b-PCL diblock copolymer compositions, a multiplicity of PEO-b-PCL diblock copolymer compositions are able to give rise to nanoscale vesicles. These data underscore that PEO-b-PCL compositions that spontaneously form micron-sized polymersomes, as well as those that have previously been reported to form polymersomes via a cosolvent fabrication system, provide only limited insights into the distribution of PEO-b-PCL diblocks that give rise to nanoscale vesicles. The broad range of polymersome-forming PEO-b-PCL compositions described herein suggest the ability to construct extensive families of nanoscale vesicles of varied bilayer thickness, providing the ability to tune the timescales of vesicle degradation and encapsulant release based on the intended in vivo application.Nanoparticles formed from diblock copolymers of FDA approved PEO and PCL have generated considerable interest as in vivo drug delivery vehicles. Herein, we report the synthesis of the most extensive family PEO-b-PCL copolymers that vary over the largest range of number-average molecular weights (Mn: 3.6-57k), PEO weight fractions (fPEO: 0.08-0.33), and PEO chain lengths (0.75-5.8k) reported to date. These polymers were synthesized in order to establish the full range of aqueous phase behaviours of these diblock copolymers and to specifically identify formulations that were able to generate bilayered vesicles (polymersomes). Cryogenic transmission electron microscopy (cryo-TEM) was utilized in order to visualize the morphology of these structures upon aqueous self-assembly of dry polymer films. Nanoscale polymersomes were formed from PEO-b-PCL copolymers over a wide range of PEO weight fractions (fPEO: 0.14-0.27) and PEO molecular weights (0.75-3.8k) after extrusion of aqueous suspensions. Comparative morphology diagrams, which describe the nature of self-assembled structures as a function of diblock copolymer molecular weight and PEO weight fraction, show that in contrast to micron-scale polymersomes, which form only from a limited range of PEO-b-PCL diblock copolymer compositions, a multiplicity of PEO-b-PCL diblock copolymer compositions are able to give rise to nanoscale vesicles. These data underscore that PEO-b-PCL compositions that spontaneously form micron-sized polymersomes, as well as those that have previously been reported to form polymersomes via a cosolvent fabrication system, provide only limited insights into the distribution of PEO-b-PCL diblocks that give rise to nanoscale vesicles. The broad range of polymersome-forming PEO-b-PCL compositions described herein suggest the ability to construct extensive families of nanoscale vesicles of varied bilayer thickness, providing the ability to tune the timescales of vesicle degradation and encapsulant release based on the intended in vivo application. Electronic supplementary information (ESI) available: Materials and methods, characterization data. See DOI: 10.1039/c3nr03250g

Li+ transport in poly(ethylene oxide) based electrolytes: neutron scattering, dielectric spectroscopy, and molecular dynamics simulations.

PubMed

Do, Changwoo; Lunkenheimer, Peter; Diddens, Diddo; Götz, Marion; Weiss, Matthias; Loidl, Alois; Sun, Xiao-Guang; Allgaier, Jürgen; Ohl, Michael

2013-07-05

The dynamics of Li(+) transport in polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imde mixtures are investigated by combining neutron spin-echo (NSE) and dielectric spectroscopy with molecular dynamics (MD) simulations. The results are summarized in a relaxation time map covering wide ranges of temperature and time. The temperature dependence of the dc conductivity and the dielectric α relaxation time is found to be identical, indicating a strong coupling between both. The relaxation times obtained from the NSE measurements at 0.05 Å(-1)

Li+ Transport in Poly(Ethylene Oxide) Based Electrolytes: Neutron Scattering, Dielectric Spectroscopy, and Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Do, Changwoo; Lunkenheimer, Peter; Diddens, Diddo; Götz, Marion; Weiß, Matthias; Loidl, Alois; Sun, Xiao-Guang; Allgaier, Jürgen; Ohl, Michael

2013-07-01

The dynamics of Li+ transport in polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imde mixtures are investigated by combining neutron spin-echo (NSE) and dielectric spectroscopy with molecular dynamics (MD) simulations. The results are summarized in a relaxation time map covering wide ranges of temperature and time. The temperature dependence of the dc conductivity and the dielectric α relaxation time is found to be identical, indicating a strong coupling between both. The relaxation times obtained from the NSE measurements at 0.05Å-1

Plasma electrolytic oxidation of Titanium Aluminides

NASA Astrophysics Data System (ADS)

Morgenstern, R.; Sieber, M.; Grund, T.; Lampke, T.; Wielage, B.

2016-03-01

Due to their outstanding specific mechanical and high-temperature properties, titanium aluminides exhibit a high potential for lightweight components exposed to high temperatures. However, their application is limited through their low wear resistance and the increasing high-temperature oxidation starting from about 750 °C. By the use of oxide ceramic coatings, these constraints can be set aside and the possible applications of titanium aluminides can be extended. The plasma electrolytic oxidation (PEO) represents a process for the generation of oxide ceramic conversion coatings with high thickness. The current work aims at the clarification of different electrolyte components’ influences on the oxide layer evolution on alloy TNM-B1 (Ti43.5Al4Nb1Mo0.1B) and the creation of compact and wear resistant coatings. Model experiments were applied using a ramp-wise increase of the anodic potential in order to show the influence of electrolyte components on the discharge initiation and the early stage of the oxide layer growth. The production of PEO layers with technically relevant thicknesses close to 100 μm was conducted in alkaline electrolytes with varying amounts of Na2SiO3·5H2O and K4P2O7 under symmetrically pulsed current conditions. Coating properties were evaluated with regard to morphology, chemical composition, hardness and wear resistance. The addition of phosphates and silicates leads to an increasing substrate passivation and the growth of compact oxide layers with higher thicknesses. Optimal electrolyte compositions for maximum coating hardness and thickness were identified by statistical analysis. Under these conditions, a homogeneous inner layer with low porosity can be achieved. The frictional wear behavior of the compact coating layer is superior to a hard anodized layer on aluminum.

Viscoelastic Properties, Ionic Conductivity, and Materials Design Considerations for Poly(styrene-b-ethylene oxide-b-styrene)-Based Ion Gel Electrolytes

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

Zhang, Sipei; Lee, Keun Hyung; Sun, Jingru

2013-03-07

The viscoelastic properties and ionic conductivity of ion gels based on the self-assembly of a poly(styrene-b-ethylene oxide-b-styrene) (SOS) triblock copolymer (M{sub n,S} = 3 kDa, M{sub n,O} = 35 kDa) in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMI][TFSA]) were investigated over the composition range of 10-50 wt % SOS and the temperature range of 25-160 C. The poly(styrene) (PS) end-blocks associate into micelles, whereas the poly(ethylene oxide) (PEO) midblocks are well-solvated by this ionic liquid. The ion gel with 10 wt % SOS melts at 54 C, with the longest relaxation time exhibiting a similar temperature dependence to that of themore » viscosity of bulk PS. However, the actual values of the gel relaxation time are more than 4 orders of magnitude larger than the relaxation time of bulk PS. This is attributed to the thermodynamic penalty of pulling PS end-blocks through the PEO/[EMI][TFSA] matrix. Ion gels with 20-50 wt % SOS do not melt and show two plateaus in the storage modulus over the temperature and frequency ranges measured. The one at higher frequencies is that of an entangled network of PEO strands with PS cross-links; the modulus displays a quadratic dependence on polymer weight fraction and agrees with the prediction of linear viscoelastic theory assuming half of the PEO chains are elastically effective. The frequency that separates the two plateaus, {omega}{sub c}, reflects the time scale of PS end-block pull-out. The other plateau at lower frequencies is that of a congested micelle solution with PS cores and PEO coronas, which has a power law dependence on domain spacing similar to diblock melts. The ionic conductivity of the ion gels is compared to PEO homopolymer solutions at similar polymer concentrations; the conductivity is reduced by a factor of 2.1 or less, decreases with increasing PS volume fraction, and follows predictions based on a simple obstruction model. Our collective results allow the formulation of basic design considerations for optimizing the mechanical properties, thermal stability, and ionic conductivity of these gels.« less

Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer.

PubMed

Huang, Weihuan; Luo, Chunxia; Zhang, Jilin; Han, Yanchun

2007-03-14

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared. When the film thickness exceeds another definite value (12.0 nm), the crystallization of PEO dominates the surface morphology. For films with thickness between these two values, microphase separation and crystallization can simultaneously occur.

Room temperature performance of 4 V aqueous hybrid supercapacitor using multi-layered lithium-doped carbon negative electrode

NASA Astrophysics Data System (ADS)

Makino, Sho; Yamamoto, Rie; Sugimoto, Shigeyuki; Sugimoto, Wataru

2016-09-01

Water-stable multi-layered lithium-doped carbon (LixC6) negative electrode using poly(ethylene oxide) (PEO)-lithium bis(trifluoromethansulfonyl)imide (LiTFSI) polymer electrolyte containing N-methyl-N-propylpiperidinium bis(trifluoromethansulfonyl)imide (PP13TFSI) ionic liquid was developed. Electrochemical properties at 60 °C of the aqueous hybrid supercapacitor using activated carbon positive electrode and a multi-layered LixC6 negative electrode (LixC6 | PEO-LiTFSI | LTAP) without PP13TFSI exhibited performance similar to that using Li anode (Li | PEO-LiTFSI | LTAP). A drastic decrease in ESR was achieved by the addition of PP13TFSI to PEO-LiTFSI, allowing room temperature operation. The ESR of the multi-layered LixC6 negative electrode with PEO-LiTFSI-PP13TFSI at 25 °C was 801 Ω cm2, which is 1/6 the value of the multi-layered Li negative electrode with PEO-LiTFSI (5014 Ω cm2). Charge/discharge test of the aqueous hybrid supercapacitor using multi-layered LixC6 negative electrode with PEO-LiTFSI-PP13TFSI at 25 °C afforded specific capacity of 20.6 mAh (g-activated carbon)-1 with a working voltage of 2.7-3.7 V, and good long-term capability up to 3000 cycles. Furthermore, an aqueous hybrid supercapacitor consisting of a high capacitance RuO2 nanosheet positive electrode and multi-layered LixC6 negative electrode with PEO-LiTFSI-PP13TFSI showed specific capacity of 196 mAh (g-RuO2)-1 and specific energy of 625 Wh (kg-RuO2)-1 in 2.0 M acetic acid-lithium acetate buffered solution at 25 °C.

Features of the corrosion protection of aluminium alloys by creation of hydrophobic coatings

NASA Astrophysics Data System (ADS)

Sinebryukhov, S. L.; Gnedenkov, S. V.; Egorkin, V. S.; Vyaliy, I. E.

2017-09-01

Results of the study of hydrophobic layers on aluminum alloy, which underwent plasma electrolytic oxidation (PEO) and subsequent deposition of the hydrophobic agent have been described. Coatings formed by deposition of dispersion of the hydrophobic agent containing SiO2 nanoparticles on the surface of the PEO-layer are characterized by high contact angles and inhibitive properties. The formed composite layers were found to be characterized with hydrophobicity and high barrier properties.

Lyotropic Phase Behavior of Polybutadiene-Poly(ethylene oxide) Diblock Copolymers in Ionic Liquids

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

Simone, Peter M.; Lodge, Timothy P.

2008-08-26

The lyotropic phase behavior of three poly(1,2-butadiene-b-ethylene oxide) diblock copolymers (PB-PEO) with different monomer volume fractions has been studied in two different ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF{sub 6}]), across the complete concentration range. The ordered microstructures present in the solutions were characterized via small-angle X-ray scattering (SAXS). The phase diagrams for the PB-PEO/ionic liquid solutions include regions corresponding to the classical copolymer microstructures: body-centered-cubic lattices of spheres, hexagonally ordered cylinders, and lamellae. Additionally, the phase diagrams also include wide regions of coexisting microstructures and regions apparently corresponding to a disordered network microstructure. The phase behavior ofmore » the PB-PEO copolymers in both ionic liquids was comparable to their previously reported aqueous solution behavior. The temperature dependence of the phase diagrams was very modest, indicative of a highly segregated system. The level of solvent selectivity was also investigated via cryogenic transmission electron microscopy (cryo-TEM) on dilute solutions. On the basis of the morphology of the dilute solution copolymer aggregate structures in the ionic liquid solvents, and on the structural length scales of the concentrated solutions, it was concluded that for PB-PEO [BMI][PF{sub 6}] behaves as a more selective solvent than [EMI][TFSI].« less

Selective laser melting porous metallic implants with immobilized silver nanoparticles kill and prevent biofilm formation by methicillin-resistant Staphylococcus aureus.

PubMed

van Hengel, Ingmar A J; Riool, Martijn; Fratila-Apachitei, Lidy E; Witte-Bouma, Janneke; Farrell, Eric; Zadpoor, Amir A; Zaat, Sebastian A J; Apachitei, Iulian

2017-09-01

Implant-associated infection and limited longevity are two major challenges that orthopedic devices need to simultaneously address. Additively manufactured porous implants have recently shown tremendous promise in improving bone regeneration and osseointegration, but, as any conventional implant, are threatened by infection. In this study, we therefore used rational design and additive manufacturing in the form of selective laser melting (SLM) to fabricate porous titanium implants with interconnected pores, resulting in a 3.75 times larger surface area than corresponding solid implants. The SLM implants were biofunctionalized by embedding silver nanoparticles in an oxide surface layer grown using plasma electrolytic oxidation (PEO) in Ca/P-based electrolytes. The PEO layer of the SLM implants released silver ions for at least 28 days. X-ray diffraction analysis detected hydroxyapatite on the SLM PEO implants but not on the corresponding solid implants. In vitro and ex vivo assays showed strong antimicrobial activity of these novel SLM PEO silver-releasing implants, without any signs of cytotoxicity. The rationally designed SLM porous implants outperformed solid implants with similar dimensions undergoing the same biofunctionalization treatment. This included four times larger amount of released silver ions, two times larger zone of inhibition, and one additional order of magnitude of reduction in numbers of CFU in an ex vivo mouse infection model. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modulating the Release Kinetics of Paclitaxel from Membrane-Covered Stents Using Different Loading Strategies

PubMed Central

Sydow-Plum, Georg; Haidar, Ziyad S.; Merhi, Yahye; Tabrizian, Maryam

2008-01-01

Membrane-covered Express2TM Monorail® stents composed of chitosan (CH) blended with polyethylene oxide (PEO) in 70:30% wt (CH-PEO) were coated with a monolayer of hyaluronic acid (HA). This significantly improved the resistance to platelet adhesion and demonstrated excellent mechanical properties, resisting the harsh conditions during stent crimping and subsequent inflation. CH-PEO/HA membrane was then combined with a paclitaxel (Pac) delivery system via three different approaches for comparison of release profiles of Pac. The activity of Pac in these systems was confirmed since its presence in the membrane significantly decreased cell viability of U937 macrophages. Presented results are promising for applications requiring different release patterns of hydrophobic drugs.

Effects of 12-crown-4 ether on the electrochemical performance of CoO2 and TiS2 cathodes in Li polymer electrolyte cells

NASA Technical Reports Server (NTRS)

Nagasubramanian, G.; Attia, Alan I.; Halpert, G.

1992-01-01

The effect of adding 12-crown-4 ether (12Cr4) to the polyethylene oxide (PEO) electrolyte on the electrochemical properties of cells with Li(x)CoO2 or TiS2 as the cathode was investigated. The polymer electrolyte films were: (1) PEO, LiBF4; (2) PEO, LiBF4 with 12Cr4; (3) Li(x)CoO2, PEO, and LiBF4; and (4) Li(x)CoO2, PEO, LiBF4, and 12Cr4. It was found that, although 12Cr4 improved the cell performance over cells without 12Cr4 in the shallow c/d cycles (cyclic voltammetric behavior), it did not seem to prolong the active life of the cell. The cells with CoO2 as the cathode failed after a few c/d cycles, while similar cells with TiS2 did not fail even after 12 c/d cycles. The probable cause of failure in the case of CoO2 is ascribed to the instability of the CoO2 cathode.

Chemically Realistic Tetrahedral Lattice Models for Polymer Chains: Application to Polyethylene Oxide.

PubMed

Dietschreit, Johannes C B; Diestler, Dennis J; Knapp, Ernst W

2016-05-10

To speed up the generation of an ensemble of poly(ethylene oxide) (PEO) polymer chains in solution, a tetrahedral lattice model possessing the appropriate bond angles is used. The distance between noncovalently bonded atoms is maintained at realistic values by generating chains with an enhanced degree of self-avoidance by a very efficient Monte Carlo (MC) algorithm. Potential energy parameters characterizing this lattice model are adjusted so as to mimic realistic PEO polymer chains in water simulated by molecular dynamics (MD), which serves as a benchmark. The MD data show that PEO chains have a fractal dimension of about two, in contrast to self-avoiding walk lattice models, which exhibit the fractal dimension of 1.7. The potential energy accounts for a mild hydrophobic effect (HYEF) of PEO and for a proper setting of the distribution between trans and gauche conformers. The potential energy parameters are determined by matching the Flory radius, the radius of gyration, and the fraction of trans torsion angles in the chain. A gratifying result is the excellent agreement of the pair distribution function and the angular correlation for the lattice model with the benchmark distribution. The lattice model allows for the precise computation of the torsional entropy of the chain. The generation of polymer conformations of the adjusted lattice model is at least 2 orders of magnitude more efficient than MD simulations of the PEO chain in explicit water. This method of generating chain conformations on a tetrahedral lattice can also be applied to other types of polymers with appropriate adjustment of the potential energy function. The efficient MC algorithm for generating chain conformations on a tetrahedral lattice is available for download at https://github.com/Roulattice/Roulattice .

Effects of salt and nanoparticles on the segmental motion of poly(ethylene oxide) in its crystalline and amorphous phases: 2H and 7Li NMR studies.

PubMed

Vogel, M; Herbers, C; Koch, B

2008-09-11

We use (2)H NMR to investigate the segmental motion of poly(ethylene oxide) (PEO) in neat and nanocomposite materials that do and do not contain salt. Specifically, in addition to a neat low-molecular-weight PEO, we study mixtures of this polymer with TiO 2 nanoparticles and LiClO 4. To characterize the polymer dynamics over a wide range of time scales, we combine (2)H NMR spin-lattice relaxation, line-shape, and stimulated-echo analyses. The results consistently show that the presence of nanoparticles hardly affects the behavior of the polymer, while addition of salt leads to substantial changes; e.g., it reduces the crystallinity. For neat PEO and a PEO-TiO 2 mixture, stimulated-echo spectroscopy enables measurement of rotational correlation functions for the crystalline phase. Analysis of the decays allows us to determine correlation times, to demonstrate the existence of a nonexponential relaxation, which implies a high complexity of the polymer dynamics in the crystal, and to show that the reorientation can be described as a large-angle jump. For a PEO-TiO 2-LiClO 4 mixture, we use (2)H and (7)Li NMR to study the polymer and the lithium dynamics, respectively. Analysis of the (7)Li spin-lattice relaxation reveals a high lithium ionic mobility in this nanocomposite polymer electrolyte. The (7)Li stimulated-echo decay is well described by a stretched exponential extending over about 6 orders of magnitude, indicating that a broad and continuous distribution of correlation times characterizes the fluctuations of the local lithium ionic environments.

Influence of confinement on polymer-electrolyte relaxational dynamics.

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

Zanotti, J.-M.; Smith, L. J.; Price, D. L.

2004-01-01

Conception and industrial production of viable high specific energy/power batteries is a central issue for the development of non-polluting vehicles. In terms of stored energy and safety, solid-state devices using polymer electrolytes are highly desirable. One of the most studied systems is PEO (polyethylene oxide) complexed by Li salts. Polymer segmental motions and ionic conductivity are closely related. Bulk PEO is actually a biphasic system where an amorphous and a crystalline state (Tm 335 K) coexist. To improve ionic conduction in those systems requires a significant increase of the amorphous phase fraction where lithium conduction is known to mainly takemore » place. Confinement strongly affects properties of condensed matter and in particular the collective phenomena inducing crystallization. Confinement of the polymer matrix is therefore a possible alternative route to the unpractical use of high temperature. Results of a quasi-elastic incoherent neutron scattering study of the influence of confinement on polyethylene oxide (PEO) and (PEO)8Li+[(CF3SO2)2N]- (or (POE)8LiTFSI) dynamics are presented. The nano-confining media is Vycor, a silica based hydrophilic porous glass (characteristic size of the 3D pore network 50 {angstrom}). As expected, the presence of Li salt slows down the bulk polymer dynamics. The confinement also affects dramatically the apparent mean-square displacement of the polymer. Local relaxational PEO dynamics is described KWW model. We also present an alternate model and show how the detailed polymer dynamics (correlation times and local geometry of the motions) can be described without the use of such stretched exponentials so as to access a rheology-related meaningful physical quantity: the monomeric friction coefficient.« less

Polyethylene oxide film coating enhances lithium cycling efficiency of an anode-free lithium-metal battery.

PubMed

Assegie, Addisu Alemayehu; Cheng, Ju-Hsiang; Kuo, Li-Ming; Su, Wei-Nien; Hwang, Bing-Joe

2018-03-29

The practical implementation of an anode-free lithium-metal battery with promising high capacity is hampered by dendrite formation and low coulombic efficiency. Most notably, these challenges stem from non-uniform lithium plating and unstable SEI layer formation on the bare copper electrode. Herein, we revealed the homogeneous deposition of lithium and effective suppression of dendrite formation using a copper electrode coated with a polyethylene oxide (PEO) film in an electrolyte comprising 1 M LiTFSI, DME/DOL (1/1, v/v) and 2 wt% LiNO3. More importantly, the PEO film coating promoted the formation of a thin and robust SEI layer film by hosting lithium and regulating the inevitable reaction of lithium with the electrolyte. The modified electrode exhibited stable cycling of lithium with an average coulombic efficiency of ∼100% over 200 cycles and low voltage hysteresis (∼30 mV) at a current density of 0.5 mA cm-2. Moreover, we tested the anode-free battery experimentally by integrating it with an LiFePO4 cathode into a full-cell configuration (Cu@PEO/LiFePO4). The new cell demonstrated stable cycling with an average coulombic efficiency of 98.6% and capacity retention of 30% in the 200th cycle at a rate of 0.2C. These impressive enhancements in cycle life and capacity retention result from the synergy of the PEO film coating, high electrode-electrolyte interface compatibility, stable polar oligomer formation from the reduction of 1,3-dioxolane and the generation of SEI-stabilizing nitrite and nitride upon lithium nitrate reduction. Our result opens up a new route to realize anode-free batteries by modifying the copper anode with PEO to achieve ever more demanding yet safe interfacial chemistry and control of dendrite formation.

Computationally Guided Design of Polymer Electrolytes for Battery Applications

NASA Astrophysics Data System (ADS)

Wang, Zhen-Gang; Webb, Michael; Savoie, Brett; Miller, Thomas

We develop an efficient computational framework for guiding the design of polymer electrolytes for Li battery applications. Short-times molecular dynamics (MD) simulations are employed to identify key structural and dynamic features in the solvation and motion of Li ions, such as the structure of the solvation shells, the spatial distribution of solvation sites, and the polymer segmental mobility. Comparative studies on six polyester-based polymers and polyethylene oxide (PEO) yield good agreement with experimental data on the ion conductivities, and reveal significant differences in the ion diffusion mechanism between PEO and the polyesters. The molecular insights from the MD simulations are used to build a chemically specific coarse-grained model in the spirit of the dynamic bond percolation model of Druger, Ratner and Nitzan. We apply this coarse-grained model to characterize Li ion diffusion in several existing and yet-to-be synthesized polyethers that differ by oxygen content and backbone stiffness. Good agreement is obtained between the predictions of the coarse-grained model and long-timescale atomistic MD simulations, thus providing validation of the model. Our study predicts higher Li ion diffusivity in poly(trimethylene oxide-alt-ethylene oxide) than in PEO. These results demonstrate the potential of this computational framework for rapid screening of new polymer electrolytes based on ion diffusivity.

Self-Assembly of Telechelic Tyrosine End-Capped PEO Star Polymers in Aqueous Solution.

PubMed

Edwards-Gayle, Charlotte J C; Greco, Francesca; Hamley, Ian W; Rambo, Robert P; Reza, Mehedi; Ruokolainen, Janne; Skoulas, Dimitrios; Iatrou, Hermis

2018-01-08

We investigate the self-assembly of two telechelic star polymer-peptide conjugates based on poly(ethylene oxide) (PEO) four-arm star polymers capped with oligotyrosine. The conjugates were prepared via N-carboxy anhydride-mediated ring-opening polymerization from PEO star polymer macroinitiators. Self-assembly occurs above a critical aggregation concentration determined via fluorescence probe assays. Peptide conformation was examined using circular dichroism spectroscopy. The structure of self-assembled aggregates was probed using small-angle X-ray scattering and cryogenic transmission electron microscopy. In contrast to previous studies on linear telechelic PEO-oligotyrosine conjugates that show self-assembly into β-sheet fibrils, the star architecture suppresses fibril formation and micelles are generally observed instead, a small population of fibrils only being observed upon pH adjustment. Hydrogelation is also suppressed by the polymer star architecture. These peptide-functionalized star polymer solutions are cytocompatible at sufficiently low concentration. These systems present tyrosine at high density and may be useful in the development of future enzyme or pH-responsive biomaterials.

Exploring the Molecular Origins of Bio(in)compatibility: Adhesion Between Proteins and Individual Chains of Poly(ethylene oxide)

NASA Astrophysics Data System (ADS)

Rixman, Monica A.; Ortiz, Christine

2002-03-01

A critical determinant of the biocompatibility of implanted blood-contacting devices is the initial noncovalent adsorption of blood plasma proteins onto the biomaterial surface. Using high-resolution force spectroscopy, we have measured the complex intermolecular interaction forces between individual end-grafted PEO chains and a probe tip covalently bound with human serum albumin, the most abundant blood plasma protein in the human body. On approach, a long-range, nonlinear repulsive force is observed. Upon retraction, however, adhesion between the HSA probe tip and PEO chain occurs, which in many cases is strong enough to allow long-range adhesion and stretching of the individual PEO chains. The known PEO strain-induced conformational transition from the helical (ttg) to the planar (ttt) conformation is clearly observed and seen to shift to lower force values. Statistical analysis of adhesion data, comparison to a variety of control experiments, and theoretical modeling enable us to interpret these experimental results in terms of electrostatic interactions, hydrogen bonding, and steric forces.

Effect of chain topology on crystallization within nanoporous alumina

NASA Astrophysics Data System (ADS)

Yao, Yang; Suzuki, Yasuhito; Sakai, Takamasa; Seiwert, Jan; Frey, Holger; Steinhart, Martin; Butt, Hans-Juergen; Floudas, George

Polymer topology has inevitable influence on the structure, packing, and dynamic of chains. Herein, we investigate for the first time the impact of polymer architecture on crystallization under 2D confinement, the latter provided by nanoporous alumina (AAO). We employ two poly(ethylene oxide) (PEO) star polymers to study the effect of (i) end groups and (ii) molecular weight on polymer crystallization in the bulk and under confinement. Bulk end groups reduce the crystallization/melting temperatures and the corresponding equilibrium melting point. Under confinement, in the absence of catalyst, homogeneous nucleation prevails as with linear PEOs. The homogeneous nucleation temperatures for the star polymers agree with that of linear ones provided that the arm molecular weight is used instead. Long-range dynamics pertinent to star relaxation are affecting the homogeneous nucleation temperature. On the other hand, the segmental dynamics speed up on confinement. In addition to star PEO, we study the effect of another topology, i.e. hyperbranched PEO, on the nucleation mechanism.

TiO2 Nanotube Arrays: Fabricated by Soft-Hard Template and the Grain Size Dependence of Field Emission Performance

NASA Astrophysics Data System (ADS)

Yang, Xuxin; Ma, Pei; Qi, Hui; Zhao, Jingxin; Wu, Qiang; You, Jichun; Li, Yongjin

2017-11-01

Highly ordered TiO2 nanotube (TNT) arrays were successfully synthesized by the combination of soft and hard templates. In the fabrication of them, anodic aluminum oxide membranes act as the hard template while the self-assembly of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) complexed with titanium-tetraisopropoxide (TTIP, the precursor of TiO2) provides the soft template to control the grain size of TiO2 nanotubes. Our results indicate that the field emission (FE) performance depends crucially on the grain size of the calcinated TiO2 which is dominated by the PS-b-PEO and its blending ratio with TTIP. The optimized sample (with the TTIP/PEO ratio of 3.87) exhibits excellent FE performances involving both a low turn-on field of 3.3 V/um and a high current density of 7.6 mA/cm2 at 12.7 V/μm. The enhanced FE properties can be attributed to the low effective work function (1.2 eV) resulted from the smaller grain size of TiO2.

Anomalous Diffusion of Water in Lamellar Membranes Formed by Pluronic Polymers

NASA Astrophysics Data System (ADS)

Zhang, Zhe; Ohl, Michael; Han, Youngkyu; Smith, Gregory; Do, Changwoo; Biology; Soft-Matter Division, Oak Ridge National Laboratory Team; Julich CenterNeutron Science Team

Water diffusion is playing an important role in polymer systems. We calculated the water diffusion coefficient at different layers along z-direction which is perpendicular to the lamellar membrane formed by Pluronic block copolymers (L62: (EO6-PO34-EO6)) with the molecular dynamics simulation trajectories. Water molecules at bulk layers are following the normal diffusion, while that at hydration layers formed by polyethylene oxide (PEO) and hydrophobic layers formed by polypropylene oxide (PPO) are following anomalous diffusion. We find that although the subdiffusive regimes at PEO layers and PPO layers are the same, which is the fractional Brownian motion, however, the dynamics are different, i.e. diffusion at the PEO layers is much faster than that at the PPO layers, and meanwhile it exhibits a normal diffusive approximation within a short time period which is governed by the localized free self-diffusion, but becomes subdiffusive after t >8 ps, which is governed by the viscoelastic medium. The Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy; and Zhe Zhang gratefully acknowledges financial support from Julich Center for Neutron Science.

In Situ Study of Strain-Dependent Ion Conductivity of Stretchable Polyethylene Oxide Electrolyte

PubMed Central

Kelly, Taylor; Ghadi, Bahar Moradi; Berg, Sean; Ardebili, Haleh

2016-01-01

There is a strong need in developing stretchable batteries that can accommodate stretchable or irregularly shaped applications including medical implants, wearable devices and stretchable electronics. Stretchable solid polymer electrolytes are ideal candidates for creating fully stretchable lithium ion batteries mainly due to their mechanical and electrochemical stability, thin-film manufacturability and enhanced safety. However, the characteristics of ion conductivity of polymer electrolytes during tensile deformation are not well understood. Here, we investigate the effects of tensile strain on the ion conductivity of thin-film polyethylene oxide (PEO) through an in situ study. The results of this investigation demonstrate that both in-plane and through-plane ion conductivities of PEO undergo steady and linear growths with respect to the tensile strain. The coefficients of strain-dependent ion conductivity enhancement (CSDICE) for in-plane and through-plane conduction were found to be 28.5 and 27.2, respectively. Tensile stress-strain curves and polarization light microscopy (PLM) of the polymer electrolyte film reveal critical insights on the microstructural transformation of stretched PEO and the potential consequences on ionic conductivity. PMID:26831948

Influence of chain topology on polymer crystallization: poly(ethylene oxide) (PEO) rings vs. linear chains.

PubMed

Zardalidis, George; Mars, Julian; Allgaier, Jürgen; Mezger, Markus; Richter, Dieter; Floudas, George

2016-10-04

The absence of entanglements, the more compact structure and the faster diffusion in melts of cyclic poly(ethylene oxide) (PEO) chains have consequences on their crystallization behavior at the lamellar and spherulitic length scales. Rings with molecular weight below the entanglement molecular weight (M < M e ), attain the equilibrium configuration composed from twice-folded chains with a lamellar periodicity that is half of the corresponding linear chains. Rings with M > M e undergo distinct step-like conformational changes to a crystalline lamellar with the equilibrium configuration. Rings melt from this configuration in the absence of crystal thickening in sharp contrast to linear chains. In general, rings more easily attain their extended equilibrium configuration due to strained segments and the absence of entanglements. In addition, rings have a higher equilibrium melting temperature. At the level of the spherulitic superstructure, growth rates are much faster for rings reflecting the faster diffusion and more compact structure. With respect to the segmental dynamics in their semi-crystalline state, ring PEOs with a steepness index of ∼34 form some of the "strongest" glasses.

Bioactivity and biocompatibility of hydroxyapatite-based bioceramic coatings on zirconium by plasma electrolytic oxidation.

PubMed

Aktuğ, Salim Levent; Durdu, Salih; Yalçın, Emine; Çavuşoğlu, Kültigin; Usta, Metin

2017-02-01

In the present work, hydroxyapatite (HAP)-based plasma electrolytic oxide (PEO) coatings were produced on zirconium at different current densities in a solution containing calcium acetate and β-calcium glycerophosphate by a single step. The phase structure, surface morphology, functional groups, thickness and roughness of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), eddy current method and surface profilometer, respectively. The phases of cubic-zirconia, calcium zirconate and HAP were detected by XRD. The amount of HAP and calcium zirconate increased with increasing current density. The surface of the coatings was very porous and rough. Moreover, bioactivity and biocompatibility of the coatings were analyzed in vitro immersion simulated body fluid (SBF) and MTT (3-(4,5-dimethyl thiazol-2yl)-2,5-diphenyl tetrazolium bromide) assay, hemolysis assay and bacterial formation. The apatite-forming ability of the coatings was evaluated after immersion in SBF up to 28days. After immersion, the bioactivity of HAP-based coatings on zirconium was greater than the ones of uncoated zirconium and zirconium oxide-based surface. The bioactivity of PEO surface on zirconium was significantly improved under SBF conditions. The bacterial adhesion of the coatings decreased with increasing current density. The bacterial adhesion of the coating produced at 0.370A/cm 2 was minimum compared to uncoated zirconium coated at 0.260 and 0.292A/cm 2 . The hemocompatibility of HAP-based surfaces was improved by PEO. The cell attachment and proliferation of the PEO coatings were better than the one of uncoated zirconium according to MTT assay results. Copyright © 2016 Elsevier B.V. All rights reserved.

Li + transport in poly(ethylene oxide) based electrolyte: A combined study of neutron scattering, dielectric spectroscopy, and MD simulation

NASA Astrophysics Data System (ADS)

Do, Changwoo; Lunkenheimer, Peter; Diddens, Diddo; Götz, Marion; Weiß, Matthias; Loidl, Alois; Sun, Xiao-Guang; Allgaier, Jürgen; Ohl, Michael

2013-03-01

Dynamics of Li + transport in polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imde (LiTFSI) mixtures are investigated by combining various experimental techniques (neutron spin-echo and dielectric spectroscopy) with molecular dynamics (MD) simulations. Our results suggest that the characteristic live times within the cages formed by oxygens are mainly determined by the alpha-relaxation which corresponds to local segmental motions of polymers, to a much lesser extent by the main chain relaxation, and not at all by the beta-relaxation or any other faster processes. The significant contribution of Li + hopping process to the ion conductivity is also identified. Subsequently, detailed characteristic length and time scales of various Li + transport processes in solid polymer electrolytes are presented and interpreted.

An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor

NASA Astrophysics Data System (ADS)

Yijing, Yin

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.

Formation of protective composite coatings with the use of SPTFE suspensions

NASA Astrophysics Data System (ADS)

Nadaraia, K. V.; Mashtalyar, D. V.; Sinebryukhov, S. L.; Gnedenkov, S. V.

2017-09-01

The method of protective composite coatings formation with the use of the plasma electrolytic oxidation (PEO) and subsequent treatment in isopropanol or aqueous suspension of the superdispersed polytetrafluoroethylene (SPTFE) have been developed. Morphological, electrochemical and tribological studies, as well as wetting ability of the protective coatings have been carried out. The obtained results corroborated the increase of the corrosion and wear resistance parameters for the polymer-containing coating in comparison with the base PEO-coating and uncoated material.

TSDC (Thermally Stimulated Depolarization Current) Studies of PEO (Poly(Ethylene Oxide)) and PEO Complexed with KSCN.

DTIC Science & Technology

1985-06-01

evaporated onto the resulting films. These films were then cut to form disks about 8 mm in diameter and 0.7 mm thick. While one electrode covered the full...surrounded by a heating coil, inside an airtight chamber. A spring loaded brass electrode presses the sample and the other electrode ." down onto the copper...cylinder. A sapphire disk insulates the lower " lectrodh( from the copper. This arrangement guarantees good thermal contact, arid electrical

Diblock-copolymer-mediated self-assembly of protein-stabilized iron oxide nanoparticle clusters for magnetic resonance imaging.

PubMed

Tähkä, Sari; Laiho, Ari; Kostiainen, Mauri A

2014-03-03

Superparamagnetic iron oxide nanoparticles (SPIONs) can be used as efficient transverse relaxivity (T2 ) contrast agents in magnetic resonance imaging (MRI). Organizing small (D<10 nm) SPIONs into large assemblies can considerably enhance their relaxivity. However, this assembly process is difficult to control and can easily result in unwanted aggregation and precipitation, which might further lead to lower contrast agent performance. Herein, we present highly stable protein-polymer double-stabilized SPIONs for improving contrast in MRI. We used a cationic-neutral double hydrophilic poly(N-methyl-2-vinyl pyridinium iodide-block-poly(ethylene oxide) diblock copolymer (P2QVP-b-PEO) to mediate the self-assembly of protein-cage-encapsulated iron oxide (γ-Fe2 O3 ) nanoparticles (magnetoferritin) into stable PEO-coated clusters. This approach relies on electrostatic interactions between the cationic N-methyl-2-vinylpyridinium iodide block and magnetoferritin protein cage surface (pI≈4.5) to form a dense core, whereas the neutral ethylene oxide block provides a stabilizing biocompatible shell. Formation of the complexes was studied in aqueous solvent medium with dynamic light scattering (DLS) and cryogenic transmission electron microcopy (cryo-TEM). DLS results indicated that the hydrodynamic diameter (Dh ) of the clusters is approximately 200 nm, and cryo-TEM showed that the clusters have an anisotropic stringlike morphology. MRI studies showed that in the clusters the longitudinal relaxivity (r1 ) is decreased and the transverse relaxivity (r2 ) is increased relative to free magnetoferritin (MF), thus indicating that clusters can provide considerable contrast enhancement. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular dynamics simulations of polyamidoamine dendrimers and their complexes with linear poly(ethylene oxide) at different pH conditions: static properties and hydrogen bonding.

PubMed

Tanis, I; Karatasos, K

2009-11-21

Models consisting of an amine-terminated poly(amidoamine) (PAMAM) dendrimer with and without the presence of a linear poly(ethylene oxide) (PEO) chain were studied in aqueous solutions by means of fully atomistic molecular dynamics simulations. Dendrimers of two generations, 3rd and 4th and at different pH conditions were examined, in order to address issues associated with characteristics pertinent to the shape of the dendrimers in the presence or absence of PEO as well as to the volume fraction of the penetrating solvent molecules and counterions as compared to recent experimental studies. In addition, hydrogen-bonding characteristics such as the intensity and the longevity of intra- and intermolecular hydrogen-bonded pairs are examined for the first time in these systems. It was found that the volume fraction of the penetrating solvent molecules increased upon decrease of pH, but no dependence on the size of the molecules was observed. The density of the solvent within the dendritic interior did not exceed that of the bulk, while the corresponding number of counterions entering the dendrimer boundaries exhibited a marked increase between the 3rd and the 4th generation of the dendrimers. Intramolecular hydrogen bonding was favored at high pH conditions, while intermolecular hydrogen bonding between PAMAM and the solvent or the PEO was significantly enhanced upon protonation of the dendrimer's amines. The presence of PEO imparted appreciable changes in the dendrimer's shape particularly in the physiological pH conditions. In addition, it incurred a decrease in intramolecular hydrogen bonding and acted antagonistically to the formation of water/dendrimer hydrogen bonds. The higher degree of hydrogen bonding between PAMAM and PEO was observed at low pH levels, indicating that under these conditions the formed complexes are expected to be more stable. The findings of the present study were found to be in good agreement with the relevant experimental findings where available, thus assessing the role of several structural and conformational details in the manifested behavior and providing further insight of the effects of non-covalent complexation of PAMAM dendrimers with linear poly(ethylene oxide).

Block Copolymer as a Surface Modifier to Monodisperse Patchy Silica Nanoparticles for Superhydrophobic Surfaces.

PubMed

Lou, Shuo; Wang, Junzheng; Yin, Xiaohong; Qu, Wenxiu; Song, Yuexiao; Xin, Feng; Qaraah, Fahim Abdo Ali

2018-06-18

Monodisperse patchy silica nanoparticles (PSNPs) less than 100 nm are prepared based on the seed-regrowth method using a poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO-type block copolymer as a surface modifier. Well-defined patches are controllably synthesized through area-selective deposition of silica onto the surface of seeds. After colloidal PSNPs are further modified with trimethylchlorosilane, the advancing and receding contact angles of water for PSNPs are 168 ± 2° and 167 ± 2°, respectively. The superhydrophobic and transparent coatings on the various types of substrates are obtained by a simple drop-casting procedure. Additionally, almost the same superhydrophobicity can be achieved by using colloidal PSNPs via redispersing the powder of superhydrophobic PSNPs in ethanol.

Formation and photopatterning of nanoporous titania thin films

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

Park, Oun-Ho; Cheng, Joy Y.; Kim, Hyun Suk

2007-06-04

Photopatternable nanoporous titania thin films were generated from mixtures of an organic diblock copolymer, poly(styrene-b-ethylene oxide) (PS-b-PEO), and an oligomeric titanate (OT) prepared from a chelated titanium isopropoxide. The PS-b-PEO templates well-defined microdomains in thin films of the mixtures, which upon thermal treatment at 450 deg. C, become nanopores in titania. Average pore size and porosity are controlled by the molecular weight and loading level of the PS-b-PEO, respectively. Patterns of nanoporous titania were created by selectively exposing UV light on the mixture films. The UV irradiation destroys the chelating bond and induces the cross-linking reaction of the OT. Subsequentmore » wet development followed by thermal treatment gives patterned nanoporous films of anatase phase titania.« less

Supramolecular Systems Behavior at the Air-Water Interface. Molecular Dynamic Simulation Study.

NASA Astrophysics Data System (ADS)

Sandoval, C.; Saavedra, M.; Gargallo, L.; Radić, D.

2008-08-01

Atomistic molecular dynamics simulation (MDS) was development to investigate the structural and dynamic properties of a monolayer of supramolecular systems. The simulations were performed at room temperature, on inclusion complexes (ICs) of α-cyclodextrin (CD) with poly(ethylene-oxide)(PEO), poly(ɛ-caprolactone)(PEC) and poly(tetrahydrofuran)(PTHF). The simulations were carried out for a surface area of 30Å. The trajectories of the MDS show that the system more stable was IC-PEC, being the less stable IC-PEO. The disordered monolayer for the systems was proved by the orientation correlation function and the radial distribution function between the polar groups of ICs and the water molecules. We found that the system IC-PEC was more stable that the systems IC-PTHF and IC-PEO.

A Highly Efficient Sensor Platform Using Simply Manufactured Nanodot Patterned Substrates

PubMed Central

Rasappa, Sozaraj; Ghoshal, Tandra; Borah, Dipu; Senthamaraikannan, Ramsankar; Holmes, Justin D.; Morris, Michael A.

2015-01-01

Block copolymer (BCP) self-assembly is a low-cost means to nanopattern surfaces. Here, we use these nanopatterns to directly print arrays of nanodots onto a conducting substrate (Indium Tin Oxide (ITO) coated glass) for application as an electrochemical sensor for ethanol (EtOH) and hydrogen peroxide (H2O2) detection. The work demonstrates that BCP systems can be used as a highly efficient, flexible methodology for creating functional surfaces of materials. Highly dense iron oxide nanodots arrays that mimicked the original BCP pattern were prepared by an ‘insitu’ BCP inclusion methodology using poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO). The electrochemical behaviour of these densely packed arrays of iron oxide nanodots fabricated by two different molecular weight PS-b-PEO systems was studied. The dual detection of EtOH and H2O2 was clearly observed. The as-prepared nanodots have good long term thermal and chemical stability at the substrate and demonstrate promising electrocatalytic performance. PMID:26290188

The plasma electrolytic oxidation micro-discharge channel model and its microstructure characteristic based on Ti tracer

NASA Astrophysics Data System (ADS)

Gao, Fangyuan; Hao, Li; Li, Guang; Xia, Yuan

2018-02-01

This study focuses on the individual discharge channel of ceramic coating prepared by plasma electrolytic oxidation (PEO), and attempts to reveal the mechanism of breakdown discharge at low voltage. Titanium (Ti) was employed as a substrate with the layer of aluminum deposited on it (aluminized Ti). The shape and microstructure of the discharge channels in PEO coatings were investigated using transmission electron microscope (TEM) and scanning electron microscopy (SEM). A schematic model of the individual discharge channel was proposed based on Ti tracer method. The shape of the discharge channel was mainly cylinder-shaped in the compact coating, with a groove-like oxidation region existed at the coating/substrate interface. In the groove-like oxidation region, the phase composition mainly composed of amorphous and mixed polycrystalline (aluminum titanate and mullite). β-Al2O3 was found in the ceramic coating. TEM morphology showed that nanometer sized micro channels existed in the ceramic coatings.

A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

NASA Astrophysics Data System (ADS)

Rao, B. Narasimha; Suvarna, R. Padma

2016-05-01

Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

Role of hydration and water coordination in micellization of Pluronic block copolymers.

PubMed

Šturcová, Adriana; Schmidt, Pavel; Dybal, Jiří

2010-12-15

Raman, attenuated total reflectance FTIR, near-infrared spectroscopy, and DFT calculations have been used in a study of aqueous solutions of three tri-block copolymers poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) or PEO-PPO-PEO with commercial names Pluronic PE6200, PE6400 and F68. It is shown that the process of micellization as a response to increased temperature is reflected in the hydroxyl stretching region of infrared and Raman spectra, which contains information both about restructuring of water and changes of polymer chains in polymer/water aggregates. Raman spectra exhibit differences between individual Pluronics even at temperatures below the critical micellization temperature (CMT). According to the attenuated total reflection (ATR) FTIR spectra, the same five water coordination types defined by the number of donated/accepted hydrogen bonds are present in interacting water as in bulk water. It indicates that models considering mixed states of water with different hydrogen bonding environments provide appropriate descriptions of bound water both below and above the CMT. Above the CMT, aggregate hydration increases in the order PE6400 < PE6200 < F68, although that does not fully correspond to the EO/PO ratio, and points to the differences in microstructure of aggregates formed by each copolymer. This study relates nanoscale phenomena (hydrophobic and hydrophilic hydration) with the mesoscale phenomenon of micellization. Copyright © 2010 Elsevier Inc. All rights reserved.

Investigation of metallurgical coatings for automotive applications

NASA Astrophysics Data System (ADS)

Su, Jun Feng

Metallurgical coatings have been widely used in the automotive industry from component machining, engine daily running to body decoration due to their high hardness, wear resistance, corrosion resistance and low friction coefficient. With high demands in energy saving, weight reduction and limiting environmental impact, the use of new materials such as light Aluminum/magnesium alloys with high strength-weight ratio for engine block and advanced high-strength steel (AHSS) with better performance in crash energy management for die stamping, are increasing. However, challenges are emerging when these new materials are applied such as the wear of the relative soft light alloys and machining tools for hard AHSS. The protective metallurgical coatings are the best option to profit from these new materials' advantages without altering largely in mass production equipments, machinery, tools and human labor. In this dissertation, a plasma electrolytic oxidation (PEO) coating processing on aluminum alloys was introduced in engine cylinder bores to resist wear and corrosion. The tribological behavior of the PEO coatings under boundary and starve lubrication conditions was studied experimentally and numerically for the first time. Experimental results of the PEO coating demonstrated prominent wear resistance and low friction, taking into account the extreme working conditions. The numerical elastohydrodynamic lubrication (EHL) and asperity contact based tribological study also showed a promising approach on designing low friction and high wear resistant PEO coatings. Other than the fabrication of the new coatings, a novel coating evaluation methodology, namely, inclined impact sliding tester was presented in the second part of this dissertation. This methodology has been developed and applied in testing and analyzing physical vapor deposition (PVD)/ chemical vapor deposition (CVD)/PEO coatings. Failure mechanisms of these common metallurgical hard coatings were systematically studied and summarized via the new testing methodology. Field tests based on the new coating characterization technique proved that this methodology is reliable, effective and economical.

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. II. Dynamical properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2007-10-28

Dynamical properties of polymer electrolytes based on poly(ethylene oxide) (PEO) and ionic liquids of 1-alkyl-3-methylimidazolium cations were calculated by molecular dynamics simulations with previously proposed models [L. T. Costa and M. C. Ribeiro, J. Chem. Phys. 124, 184902 (2006)]. The effect of changing the ionic liquid concentration, temperature, and the 1-alkyl-chain lengths, [1,3-dimethylimidazolium]PF(6) and [1-butyl-3-methylimidazolium]PF(6) ([dmim]PF(6) and [bmim]PF(6)), was investigated. Cation diffusion coefficient is higher than those of anion and oxygen atoms of PEO chains. Ionic mobility in PEO[bmim]PF(6) is higher than in PEO[dmim]PF(6), so that the ionic conductivity kappa of the former is approximately ten times larger than the latter. The ratio between kappa and its estimate from the Nernst-Einstein equation kappa/kappa(NE), which is inversely proportional to the strength of ion pairs, is higher in ionic liquid polymer electrolytes than in polymer electrolytes based on inorganic salts with Li(+) cations. Calculated time correlation functions corroborate previous evidence from the analysis of equilibrium structure that the ion pairs in ionic liquid polymer electrolytes are relatively weak. Structural relaxation at distinct spatial scales is revealed by the calculation of the intermediate scattering function at different wavevectors. These data are reproduced with stretched exponential functions, so that temperature and wavevector dependences of best fit parameters can be compared with corresponding results for polymer electrolytes containing simpler ions.

Biodegradable thermoresponsive polymeric magnetic nanoparticles: a new drug delivery platform for doxorubicin

NASA Astrophysics Data System (ADS)

Andhariya, Nidhi; Chudasama, Bhupendra; Mehta, R. V.; Upadhyay, R. V.

2011-04-01

The use of nanoparticles as drug delivery systems for anticancer therapeutics has great potential to revolutionize the future of cancer therapy. The aim of this study is to construct a novel drug delivery platform comprising a magnetic core and biodegradable thermoresponsive shell of tri-block-copolymer. Oleic acid-coated Fe3O4 nanoparticles and hydrophilic anticancer drug "doxorubicin" are encapsulated with PEO-PLGA-PEO (polyethylene oxide-poly d, l lactide-co-glycolide-polyethylene oxide) tri-block-copolymer. Structural, magnetic, and physical properties of Fe3O4 core are determined by X-ray diffraction, vibrating sample magnetometer, and transmission electron microscopy techniques, respectively. The hydrodynamic size of composite nanoparticles is determined by dynamic light scattering and is found to be 36.4 nm at 25 °C. The functionalization of magnetic core with various polymeric chain molecules and their weight proportions are determined by Fourier transform infrared spectroscopy and thermogravimetric analysis, respectively. Encapsulation of doxorubicin into the polymeric magnetic nanoparticles, its loading efficiency, and kinetics of drug release are investigated by UV-vis spectroscopy. The loading efficiency of drug is 89% with a rapid release for the initial 7 h followed by the sustained release over a period of 36 h. The release of drug is envisaged to occur in response to the physiological temperature by deswelling of thermoresponsive PEO-PLGA-PEO block-copolymer. This study demonstrates that temperature can be exploited successfully as an external parameter to control the release of drug.

High ionic conductivity P(VDF-TrFE)/PEO blended polymer electrolytes for solid electrochromic devices.

PubMed

Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See

2011-08-07

Solid polymer electrolytes with excellent ionic conductivity (above 10(-4) S cm(-1)), which result in high optical modulation for solid electrochromic (EC) devices are presented. The combination of a polar host matrix poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) and a solid plasticized of a low molecular weight poly(ethylene oxide) (PEO) (M(w)≤ 20,000) blended polymer electrolyte serves to enhance both the dissolution of lithium salt and the ionic transport. Calorimetric measurement shows a reduced crystallization due to a better intermixing of the polymers with small molecular weight PEO. Vibrational spectroscopy identifies the presence of free ions and ion pairs in the electrolytes with PEO of M(w)≤ 8000. The ionic dissolution is improved using PEO as a plasticizer when compared to liquid propylene carbonate, evidently shown in the transference number analysis. Ionic transport follows the Arrhenius equation with a low activation energy (0.16-0.2 eV), leading to high ionic conductivities. Solid electrochromic devices fabricated with the blended P(VDF-TrFE)/PEO electrolytes and polyaniline show good spectroelectrochemical performance in the visible (300-800 nm) and near-infrared (0.9-2.4 μm) regions with a modulation up to 60% and fast switching speed of below 20 seconds. The successful introduction of the solid polymer electrolytes with its best harnessed qualities helps to expedite the application of various electrochemical devices. This journal is © the Owner Societies 2011

Molecular dynamics simulation of thermomechanical properties of montmorillonite crystal. 3. montmorillonite crystals with PEO oligomer intercalates.

PubMed

Mazo, Mikhail A; Manevitch, Leonid I; Gusarova, Elena B; Shamaev, Mikhail Yu; Berlin, Alexander A; Balabaev, Nikolay K; Rutledge, Gregory C

2008-03-27

We present the results of molecular dynamics (MD) simulation of the structure and thermomechanical behavior of Wyoming-type Na+-montmorillonite (MMT) with poly(ethylene oxide) (PEO) oligomer intercalates. Periodic boundary conditions in all three directions and simulation cells containing two MMT lamellae [Si248Al8][Al112Mg16]O640[OH]128 oriented parallel to the XY-plane were used. The interlamellar space, or gallery, between neighboring MMT lamellae was populated by 24 Na+ counterions and PEO macromolecules of different lengths, ranging from 2 up to 240 repeat units. We considered three different loadings of PEO within the gallery: 80, 160, and 240 repeat units, corresponding to 13, 23, and 31 wt % PEO based on total mass of the nanocomposite, respectively. In the cases of 13 and 23 wt %, the polymer chains formed one or two well-defined amorphous layers with interlayer distances of 1.35 and 1.8 nm, respectively. We have observed also formation of a wider monolayer gallery with interlayer distances of 1.6 nm. Three-layer PEO films formed in the case of 31 wt % loading. The thermal properties were analyzed over the range 300-400 K, and the isothermal linear compressibility, transversal moduli, and shear moduli were calculated at 300 K. These properties are compared with the results of our simulation of thermal and mechanical properties of MMT crystal with galleries filled by one or two water layers as well as with those of an isolated clay nanoplate.

Photodegradable neutral-cationic brush block copolymers for nonviral gene delivery.

PubMed

Hu, Xianglong; Li, Yang; Liu, Tao; Zhang, Guoying; Liu, Shiyong

2014-08-01

We report on the fabrication of a photodegradable gene-delivery vector based on PEO-b-P(GMA-g-PDMAEMA) neutral-cationic brush block copolymers that possess cationic poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) brushes for DNA compaction, poly(ethylene oxide) (PEO) as a hydrophilic block, and poly(glycidyl methacrylate) (PGMA) as the backbone. The PEO-b-P(GMA-g-PDMAEMA) copolymers were synthesized through the combination of reversible addition-fragmentation transfer (RAFT) polymerization and postmodification. A photocleavable PEO-based macroRAFT agent was first synthesized; next, the PEO-b-PGMA block copolymer was prepared by RAFT polymerization of GMA; this was followed by a click reaction to introduce the RAFT initiators on the side chains of the PGMA block; then, RAFT polymerization of DMAEMA afforded the PEO-b-P(GMA-g-PDMAEMA) copolymer. The obtained neutral-cationic brush block copolymer could effectively complex plasmid DNA (pDNA) into nanoparticles at an N/P ratio (i.e., the number of nitrogen residues per DNA phosphate) of 4. Upon UV irradiation, pDNA could be released owing to cleavage of the pDNA-binding cationic PDMAEMA side chains as well as the nitrobenzyl ester linkages at the diblock junction point. In addition, in vitro gene transfection results demonstrated that the polyplexes could be effectively internalized by cells with good transfection efficiency, and the UV irradiation protocol could considerably enhance the efficiency of gene transfection. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface characterization and corrosion behavior of calcium phosphate-base composite layer on titanium and its alloys via plasma electrolytic oxidation: A review paper.

PubMed

Rafieerad, A R; Ashra, M R; Mahmoodian, R; Bushroa, A R

2015-12-01

In recent years, calcium phosphate-base composites, such as hydroxyapatite (HA) and carbonate apatite (CA) have been considered desirable and biocompatible coating layers in clinical and biomedical applications such as implants because of the high resistance of the composites. This review focuses on the effects of voltage, time and electrolytes on a calcium phosphate-base composite layer in case of pure titanium and other biomedical grade titanium alloys via the plasma electrolytic oxidation (PEO) method. Remarkably, these parameters changed the structure, morphology, pH, thickness and crystallinity of the obtained coating for various engineering and biomedical applications. Hence, the structured layer caused improvement of the biocompatibility, corrosion resistance and assignment of extra benefits for Osseo integration. The fabricated layer with a thickness range of 10 to 20 μm was evaluated for physical, chemical, mechanical and tribological characteristics via XRD, FESEM, EDS, EIS and corrosion analysis respectively, to determine the effects of the applied parameters and various electrolytes on morphology and phase transition. Moreover, it was observed that during PEO, the concentration of calcium, phosphor and titanium shifts upward, which leads to an enhanced bioactivity by altering the thickness. The results confirm that the crystallinity, thickness and contents of composite layer can be changed by applying thermal treatments. The corrosion behavior was investigated via the potentiodynamic polarization test in a body-simulated environment. Here, the optimum corrosion resistance was obtained for the coating process condition at 500 V for 15 min in Ringer solution. This review has been summarized, aiming at the further development of PEO by producing more adequate titanium-base implants along with desired mechanical and biomedical features. Copyright © 2015 Elsevier B.V. All rights reserved.

MesoDyn simulation study on the phase morphologies of Miktoarm PEO-b-PMMA copolymer doped by nanoparticles

NASA Astrophysics Data System (ADS)

Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

2013-03-01

The compatibility of six groups of 12 miktoarm poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers is studied at 270, 298 and 400 K via mesoscopic modeling. The values of the order parameters depend on both the architectures of the block copolymers and the simulation temperature, while the tendency to change of the order parameters at low temperature, such as 270 and 298 K, is nearly the same. However, the values of order parameters of the copolymer in the same group are the same at high temperature, i.e. 400 K. Obviously, temperature has a more obvious effect on long and PEO-rich chains. A study of plain copolymers doped with nanoparticles shows that the microscopic phase is influenced by not only the properties of the nanoparticles, such as the size, number and density, but also the composition and architecture of copolymers. Increasing the size and the number of the nanoparticles used as a dopant plays the most significant role on determining the phase morphologies of the copolymers at lower and higher temperature, respectively. In paricular, the 23141 and 23241-type copolymers, which are both of PEO-rich composition, presents microscopic phase separation as perforated lamallae phase morphologies at 400 K, alternated with PEO and PMMA components.

Preparation of immobilized coating Fenton-like catalyst for high efficient degradation of phenol.

PubMed

Wang, Jiankang; Yao, Zhongping; Wang, Yajing; Xia, Qixing; Chu, Huiya; Jiang, Zhaohua

2017-05-01

In this study, solid acid amorphous Fe 3 O 4 /SiO 2 ceramic coating decorated with sulfur on Q235 carbon steel as Fenton-like catalyst for phenol degradation was successfully prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte containing Na 2 S 2 O 8 as sulfur source. The surface morphology and phase composition were characterized by SEM, EDS, XRD and XPS analyses. NH 3 -TPD was used to evaluate surface acidity of PEO coating. The results indicated that sulfur decorated amorphous Fe 3 O 4 /SiO 2 ceramic coatings with porous structure and higher acid strength had the similar pore size and the surface became more and more uneven with the increase of Na 2 S 2 O 8 in the silicate electrolyte. The Fenton-like catalytic activity of sulfur decorated PEO coatings was also evaluated. In contrast to negligible catalytic activity of sulfur undecorated PEO coating, catalytic activity of sulfur decorated PEO coating was excellent and PEO coating prepared with 3.0 g Na 2 S 2 O 8 had the highest catalytic activity which could degrade 99% of phenol within 8 min under circumneutral pH. The outstanding performance of sulfur decorated PEO coating was attributed to strong acidic microenvironment and more Fe 2+ on the surface. The strong acid sites played a key factor in determining catalytic activity of catalyst. In conclusion, rapid phenol removal under circumneutral pH and easier separation endowed it potential application in wastewater treatment. In addition, this strategy of preparing immobilized solid acid coating could provide guidance for designing Fenton-like catalyst with excellent catalytic activity and easier separation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solution rheology of polyelectrolytes and polyelectrolyte-surfactant systems

NASA Astrophysics Data System (ADS)

Plucktaveesak, Nopparat

The fundamental understanding of polyelectrolytes in aqueous solutions is an important branch of polymer research. In this work, the rheological properties of polyelectrolytes and polyelectrolyte/surfactant systems are studied. Various synthetic poly electrolytes are chosen with varied hydrophobicity. We discuss the effects of adding various surfactants to aqueous solutions of poly(ethylene oxide)-b-poly(propylene oxide)- b-polyethylene oxide)-g-poly(acrylic acid) (PEO-PPO-PAA) in the first chapter. Thermogelation in aqueous solutions of PEO-PPO-PAA is due to micellization caused by aggregation of poly(propylene oxide) (PPO) blocks resulting from temperature-induced dehydration of PPO. When nonionic surfactants with hydrophilic-lipophilic balance (HLB) parameter exceeding 11 or Cn alkylsulfates; n-octyl (C8), n-decyl (C 10) and n-dodecyl (C12) sulfates are added, the gelation threshold temperature (Tgel) of 1.0wt% PEO-PPO-PAA in aqueous solutions increases. In contrast, when nonionic surfactants with HLB below 11 are added, the gelation temperature decreases. On the other hand, alkylsulfates with n = 16 or 18 and poly(ethylene oxide) (PEO) do not affect the Tgel. The results imply that both hydrophobicity and tail length of the added surfactant play important roles in the interaction of PEO-PPO-PAA micelles and the surfactant. In the second chapter, the solution behavior of alternating copolymers of maleic acid and hydrophobic monomer is studied. The alternating structure of monomers with two-carboxylic groups and hydrophobic monomers make these copolymers unique. Under appropriate conditions, these carboxylic groups dissociate leaving charges on the chain. The potentiometric titrations of copolymer solutions with added CaCl2 reveal two distinct dissociation processes corresponding to the dissociation of the two adjacent carboxylic acids. The viscosity data as a function of polymer concentration of poly(isobutylene-alt-sodium maleate), poly(styrene-alt-sodium maleate) and poly(diisobutylene- alt-sodium maleate) show the polyelectrolyte behavior as predicted. However, the viscosity as a function of concentration of sodium maleate based copolymers with 1-alkenes; 1-octene (C8), 1-decene (C10), 1-dodecene (C12) and 1-hexene (C14) exhibit an abnormal scaling power, which might be caused by aggregation of the alkene tails to form micelles. In the last chapter, we report the rheological properties of aqueous solutions of poly(acrylic acid) and oppositely charged surfactant, dodecyl trimethylammonium bromide (C12TAB). The solution viscosity decreases as surfactant is added, partly because the polyelectrolyte wraps around the surface of the spherical surfactant micelles, shortening the effective chain length. The effects of polymer molecular weight, polymer concentration, and polymer charge have been studied with no added salt. The results are compared with the predictions of a simple model based on the scaling theory for the viscosity of dilute and unentangled semidilute polyelectrolyte solutions in good solvent. This model takes into account two effects of added surfactant. The effective chain length of the polyelectrolyte is shortened when a significant fraction of the chain wraps around micelles. Another effect is the change of solution ionic strength resulting from surfactant addition that further lowers the viscosity. The parameters used in this model are independently determined, allowing the model to make a quantitative prediction of solution viscosity with no adjustable parameters. The model is also applied to predict the decrease in viscosity of various polyelectrolyte/oppositely charged surfactant systems reported in literature. The results are in good agreement with experimental data, proving that our model applies to all polyelectrolytes mixed with oppositely charged surfactants that form spherical micelles.

Electrospun-sodiumtetrafluoroborate-polyethylene oxide membranes for solvent-free sodium ion transport in solid state sodium ion batteries

NASA Astrophysics Data System (ADS)

Freitag, K. M.; Walke, P.; Nilges, T.; Kirchhain, H.; Spranger, R. J.; van Wüllen, L.

2018-02-01

Electrospinning is used to fabricate sodium ion conducting fiber membranes composed of polyethylene oxide (PEO), sodium tetrafluoroborate (NaBF4), and succinonitrile (SN) as plasticizer. As compared to conventionally prepared lithium electrolyte membranes with identical composition (PEO:SN:LiBF4), those membranes exhibit conductivities up to 10-4 S cm-1 at 328 K (activation energy ∼36 kJ mol-1, 36:8:1 membrane), which favors such systems as a solid-state electrolyte alternative for batteries. The conduction mechanism is evaluated and the ion mobility are examined. We identified the segment mobility of the polyethylene oxide as the main driving force for the enhanced ion mobility in the membranes. The introduction of SN has only a minor influence on the conductivity and segment mobility at room temperature, but extents the anion and cation mobility to temperatures below ambient. For the 36:8:1 (PEO:SN:NaBF4) membrane we found the highest ion mobility of all membranes under investigation. A comparison of the present sodium membranes with lithium systems of the same composition shows that the overall performance of the sodium systems is comparable. Taking plasticizer-free sodium membranes into account they perform even better than the lithium containing counterparts, and plasticizer-modified membranes show only half an order of magnitude lower conductivities than comparable lithium ones.

Department of Defense Systems Engineering FY 2012 Annual Report

DTIC Science & Technology

2013-03-01

by the Utility Helicopter PMO, is utilizing the latest Defense Acquisition Guidelines and previously approved PEO AVN SEP examples to develop all...efforts. As a whole, all of PEO AVN Program Management Offices understand the importance of systems engineering. They stress the continued use of...established SE guidelines, practices and procedures throughout our acquisition processes. PEO AVN , working with the AMRDEC SE Division, has

Nanoporous Films with Sub-10 nm in Pore Size from Acid-Cleavable Block Copolymers.

PubMed

Li, Yayuan; Xu, Yawei; Cao, Shubo; Zhao, Yongbin; Qu, Ting; Iyoda, Tomokazu; Chen, Aihua

2017-03-01

Nanoporous thin films with pore size of sub-10 nm are fabricated using an acid-cleavable block copolymer (BCP), a benzoic imine junction between poly(ethylene oxide) (PEO) and poly(methacrylate) (PMAAz) bearing an azobenzene side chain (denoted as PEO-bei-PMAAz) as the precursor. After a thermal annealing, the block copolymers are self-assembled to form highly ordered PEO cylinders within a PMAAz matrix normal to the film, even in the case of low BCP molecular weight due to the existing of the liquid crystalline (LC) azobenzene rigid segment. Thus, PMAAz thin films with pore size of ≈7 nm and density of ≈10 12 cm -2 are obtained after removal of the PEO minor phase by breaking the benzoic imine junction under mild acidic conditions. This work enriches the nanoporous polymer films from BCP precursors and introduces the LC property as a functionality which can further enhance the mechanical properties of the films and broaden their applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of non-ionic ABC triblock copolymers: Surface modification of TiO2 suspensions in aqueous and non-aqueous medium

NASA Astrophysics Data System (ADS)

Lerch, Jean-Philippe; Atanase, Leonard Ionut; Riess, Gérard

2017-10-01

A series of non-ionic ABC triblock copolymers, such as poly(butadiene)-b-poly(2-vinylpyrridine)-b-poly(ethylene oxide) (PB-P2VP-PEO) were synthesized by sequential anionic polymerizations. For these copolymers comprising an organo-soluble PB and a water-soluble PEO block, their P2VP middle block has been selected for its anchoring capacity on solid surfaces. The adsorption isotherms on TiO2 were obtained in heptane and in aqueous medium, as selective solvents. In both of these cases, the P2VP middle block provides the surface anchoring, whereas PB and PEO sequences are acting as stabilizing moieties in heptane and water respectively. By extension to ABC triblock copolymers of the scaling theory developed for diblock copolymers, the density of adsorbed chains could be correlated with the molecular characteristics of the PB-P2VP-PEO triblock copolymers. From a practical point a view, it could be demonstrated that these copolymers are efficient dispersing agents for the TiO2 pigments in both aqueous and non-aqueous medium.

Electrochemically oxidized electronic and ionic conducting nanostructured block copolymers for lithium battery electrodes.

PubMed

Patel, Shrayesh N; Javier, Anna E; Balsara, Nitash P

2013-07-23

Block copolymers that can simultaneously conduct electronic and ionic charges on the nanometer length scale can serve as innovative conductive binder material for solid-state battery electrodes. The purpose of this work is to study the electronic charge transport of poly(3-hexylthiophene)-b-poly(ethylene oxide) (P3HT-PEO) copolymers electrochemically oxidized with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt in the context of a lithium battery charge/discharge cycle. We use a solid-state three-terminal electrochemical cell that enables simultaneous conductivity measurements and control over electrochemical doping of P3HT. At low oxidation levels (ratio of moles of electrons removed to moles of 3-hexylthiophene moieties in the electrode), the electronic conductivity (σe,ox) increases from 10(-7) S/cm to 10(-4) S/cm. At high oxidation levels, σe,ox approaches 10(-2) S/cm. When P3HT-PEO is used as a conductive binder in a positive electrode with LiFePO4 active material, P3HT is electrochemically active within the voltage window of a charge/discharge cycle. The electronic conductivity of the P3HT-PEO binder is in the 10(-4) to 10(-2) S/cm range over most of the potential window of the charge/discharge cycle. This allows for efficient electronic conduction, and observed charge/discharge capacities approach the theoretical limit of LiFePO4. However, at the end of the discharge cycle, the electronic conductivity decreases sharply to 10(-7) S/cm, which means the "conductive" binder is now electronically insulating. The ability of our conductive binder to switch between electronically conducting and insulating states in the positive electrode provides an unprecedented route for automatic overdischarge protection in rechargeable batteries.

Conformational sensitivity of conjugated poly(ethylene oxide)-poly(amidoamine) molecules to cations adducted upon electrospray ionization - a mass spectrometry, ion mobility and molecular modeling study.

PubMed

Tintaru, Aura; Chendo, Christophe; Wang, Qi; Viel, Stéphane; Quéléver, Gilles; Peng, Ling; Posocco, Paola; Pricl, Sabrina; Charles, Laurence

2014-01-15

Tandem mass spectrometry and ion mobility spectrometry experiments were performed on multiply charged molecules formed upon conjugation of a poly(amidoamine) (PAMAM) dendrimer with a poly(ethylene oxide) (PEO) linear polymer to evidence any conformational modification as a function of their charge state (2+ to 4+) and of the adducted cation (H(+)vs Li(+)). Experimental findings were rationalized by molecular dynamics simulations. The G0 PAMAM head-group could accommodate up to three protons, with protonated terminal amine group enclosed in a pseudo 18-crown-6 ring formed by the PEO segment. This particular conformation enabled a hydrogen bond network which allowed long-range proton transfer to occur during collisionally activated dissociation. In contrast, lithium adduction was found to mainly occur onto oxygen atoms of the polyether, each Li(+) cation being coordinated by a 12-crown-4 pseudo structure. As a result, for the studied polymeric segment (Mn=1500gmol(-1)), PEO-PAMAM hybrid molecules exhibited a more expanded shape when adducted to lithium as compared to proton. Copyright © 2013 Elsevier B.V. All rights reserved.

Fabrication of Pt/Au concentric spheres from triblock copolymer.

PubMed

Koh, Haeng-Deog; Park, Soojin; Russell, Thomas P

2010-02-23

Dispersion of an aqueous H(2)PtCl(6) solution into a trifluorotoluene (TFT) solution of a polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) triblock copolymer produced an emulsion-induced hollow micelle (EIHM), comprising a water nanodroplet stabilized by PEO, H(2)PtCl(6)/P2VP, and PS, sequentially. The following addition of an aqueous LiAuCl(4) solution into the dispersion led to a coordination of LiAuCl(4) and PEO. The resulting spherical EIHM structure was transformed to a hollow cylindrical micelle by the fusion of spherical EIHM with the addition of methanol. This structural transition was reversible by the alternative addition of methanol and TFT. Oxygen plasma was used to generate Pt/Au concentric spheres and hollow cylindrical Pt/Au nano-objects.

Carbon Nanotubes Embedded in Oriented Polymer Nanofibers by Electrospinning

NASA Astrophysics Data System (ADS)

Cohen, Yachin; Dror, Yael; Khalfin, Rafail L.; Salalha, Wael; Yarin, Alexander L.; Zussman, Eyal

2004-03-01

The electrospinning process was used successfully to fabricate nanofibers of poly(ethylene oxide) [PEO] in which carbon nanotubes, either multi-walled (MWCNT) or single-walled (SWCNT) are embedded. MWCNTs were dispersed in water using SDS or Gum Arabic - a highly branched polyelectrolyte. Aqueous dispersion of SWCNT's was achieved using an alternating copolymer of styrene and maleic anhydride, hydrolyzed with NaOH. The focus of this work is on the development of axial orientations in the multi-component nanofibers. The degree of orientation of polymers, surfactants and nanotubes was studied using X-ray diffraction and transmission electron microscopy. Individual nanotubes were successfully embedded in the polymer nanofibers with good axial alignment. A high degree of alignment of PEO crystals and SDS layers was also found in the electrospun nanofibers containing SWCNT's. Oriented ropes of the nanofibers were fabricated in a converging electric field by a rotating disc with a tapered edge. These results can lead to further usage of the nanofibers with embedded carbon nanotubes in applications such as nano-scale energy storage devices.

Bone-like apatite growth on controllable macroporous titanium scaffolds coated with microporous titania.

PubMed

Rao, Xi; Li, Jing; Feng, Xue; Chu, Chenglin

2018-01-01

In this study, a simple, cost-effective approach of polymeric foam replication was used to produce three-dimensionally macroporous titanium scaffolds with controllable porosities and mechanical properties. Two kinds of porous titanium scaffolds with different porosities (74.7% and 87.6%) and pore sizes (360µm and 750µm) were fabricated. Both of the scaffolds exhibit good compressive strength (24.5MPa and 13.5MPa) with a low elastic modulus (0.23GPa and 0.11GPa), approximating the mechanical properties of nature human cancellous bone (E = 10-50MPa, σ = 0.01-3.0GPa). Thereafter, the scaffolds were surface modified using plasma electrolyte oxidation (PEO) process to gain a bioactive porous titania ceramic coating. The SBF immersion test indicates PEO treated scaffolds show excellent bioactivity as the apatite rapidly nucleates and grows on the scaffold surface during 3-28 days. The results suggest that the highly porous titanium scaffolds with titania bioactive coatings are promising in cancellous bone replacement. Copyright © 2017 Elsevier Ltd. All rights reserved.

Enhancing surface properties of breast implants by using electrospun silk fibroin.

PubMed

Valencia-Lazcano, A A; Román-Doval, R; De La Cruz-Burelo, E; Millán-Casarrubias, E J; Rodríguez-Ortega, A

2017-08-24

In the present study, a new electrospun silk fibroin coating of silicone breast implants with improved biocompatibility and mechanical properties was obtained. Fibrous scaffolds were produced by electrospinning a solution containing silk fibroin, derived from Bombyx mori cocoons, and polyethylene oxide (PEO) to be used as a coating of breast implants. A randomly oriented structure of fibroin/PEO was electrospun on implants as assessed by SEM analysis, roughness measurements and ATR-FTIR spectroscopy. The scaffold showed 0.25 µm diameter fibres, 0.76 µm size superficial pores, arithmetic roughness of 0.632 ± 0.12 µm and texture aspect ratio of 0.893 ± 0.04. ATR-FTIR spectroscopy demonstrates the presence of PEO and fibroin in the coating. The mechanical characterisation of the implants before and after being coated with fibroin/PEO demonstrated that the fibroin/PEO scaffold contributes to the increase in the elastic modulus from 0.392 ± 0.02 to 0.560 ± 0.03 MPa and to a more elastic behaviour of the breast implants. Using the fibroin/PEO coating, human fibroblasts seeded on this matrix increased viability up to 30% compared to conventional breast implants. Electrospun silk fibroin could represent a clinically compatible, viable form to coat breast implants. Low cytotoxicity by the fibroin coating and its physico-chemical and mechanical properties may find application in improving breast implants biocompatibility. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2017. © 2017 Wiley Periodicals, Inc.

Mechanical and transport properties of the poly(ethylene oxide)-poly(acrylic acid) double network hydrogel from molecular dynamic simulations.

PubMed

Jang, Seung Soon; Goddard, William A; Kalani, M Yashar S

2007-02-22

We used atomistic molecular dynamics (MD) simulations to investigate the mechanical and transport properties of the PEO-PAA double network (DN) hydrogel with 76 wt % water content. By analyzing the pair correlation functions for polymer-water pairs and for ion-water pairs and the solvent accessible surface area, we found that the solvation of polymer and ion in the DN hydrogel is enhanced in comparison with both PEO and PAA single network (SN) hydrogels. The effective mesh size of this DN hydrogel is smaller than that of the SN hydrogels with the same water content and the same molecular weight between the cross-linking points (Mc). Applying uniaxial extensions, we obtained the stress-strain curves for the hydrogels. This shows that the DN hydrogel has a sudden increase of stress above approximately 100% strain, much higher than the sum of the stresses of the two SN hydrogels at the same strain. This arises because PEO has a smaller Mc value than PAA, so that the PEO in the DN reaches fully stretched out at 100% strain that corresponds to 260% strain in the PEO SN (beyond this point, the bond stretching and the angle bending increase dramatically). We also calculated the diffusion coefficients of solutes such as D-glucose and ascorbic acid in the hydrogels, where we find that the diffusion coefficients of those solutes in the DN hydrogel are 60% of that in the PEO SN and 40% of that in the PAA SN due to its smaller effective mesh size.

Complex coacervate core micelles with a lysozyme-modified corona.

PubMed

Danial, Maarten; Klok, Harm-Anton; Norde, Willem; Stuart, Martien A Cohen

2007-07-17

This paper describes the preparation, characterization, and enzymatic activity of complex coacervate core micelles (C3Ms) composed of poly(acrylic acid) (PAA) and poly(N-methyl-2-vinyl pyridinium iodide)-b-poly(ethylene oxide) (PQ2VP-PEO) to which the antibacterial enzyme lysozyme is end-attached. C3Ms were prepared by polyelectrolyte complex formation between PAA and mixtures containing different ratios of aldehyde and hydroxyl end-functionalized PQ2VP-PEO. This resulted in the formation of C3Ms containing 0-40% (w/w) of the aldehyde end-functionalized PQ2VP-PEO block copolymer (PQ2VP-PEO-CHO). Chemical conjugation of lysozyme was achieved via reductive amination of the aldehyde groups, which are exposed at the surface of the C3M, with the amine groups present in the side chains of the lysine residues of the protein. Dynamic and static light scattering indicated that the conjugation of lysozyme to C3Ms prepared using 10 and 20% (w/w) PQ2VP-PEO-CHO resulted in the formation of unimicellar particles. Multimicellar aggregates, in contrast, were obtained when lysozyme was conjugated to C3Ms prepared using 30 or 40% (w/w) PQ2VP-PEO-CHO. The enzymatic activity of the unimicellar lysozyme-C3M conjugates toward the hydrolysis of the bacterial substrate Micrococcus lysodeikticus was comparable to that of free lysozyme. For the multimicellar particles, in contrast, significantly reduced enzymatic rates of hydrolysis, altered circular dichroism, and red-shifted tryptophan fluorescence spectra were measured. These results are attributed to the occlusion of lysozyme in the interior of the multimicellar conjugates.

Nanofiber mats composed of a chitosan-poly(d,l-lactic-co-glycolic acid)-poly(ethylene oxide) blend as a postoperative anti-adhesion agent.

PubMed

Ko, Jae Eok; Ko, Young-Gwang; Kim, Won Il; Kwon, Oh Kyoung; Kwon, Oh Hyeong

2017-10-01

Postoperative tissue adhesion causes serious complications and suffering in 90% of patients after peritoneum surgery, while commercial anti-adhesion agents cannot completely prevent postoperative peritoneal adhesions. This study demonstrates electrospining of a blended solution of chitosan, poly(d,l-lactic-co-glycolic acid) (PLGA), and poly(ethylene oxide) (PEO) to fabricate a chitosan-based nanofibrous mat as a postoperative anti-adhesion agent. Rheological studies combined with scanning electron microscopy reveal that the spinnability of the chitosan-PLGA solution could be controlled by adjusting the blend ratio and concentration with average fiber diameter from 634 to 913 nm. Biodegradation of the nanofiber specimens showed accelerated hydrolysis by chitosan. Proliferation of fibroblasts and antimicrobial activity of nanofibers containing chitosan was analyzed. Abdominal defects with cecum adhesion in rats demonstrated that the blend nanofiber mats were effective in preventing tissue adhesion as a barrier (4 weeks after abdominal surgery) by coverage of exfoliated peritoneum and insufficient wound sites at the beginning of the wound healing process. Chitosan-PLGA-PEO blend nanofiber mats will provide a promising key as a postoperative anti-adhesion agent. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1906-1915, 2017. © 2016 Wiley Periodicals, Inc.

Theoretical study of binding and permeation of ether-based polymers through interfaces.

PubMed

Samanta, Susruta; Hezaveh, Samira; Roccatano, Danilo

2013-11-27

We present a molecular dynamics simulation study on the interactions of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and their ABA-type block copolymer, poloxamers, at water/n-heptane and 1,2-dimyristoyl-sn-glycero-3-phospatidycholine (DMPC) lipid bilayer/water interfaces. The partition coefficients in water/1-octanol of the linear polyethers up to three monomers were calculated. The partition coefficients evidenced a higher hydrophobicity of the PPO in comparison to PEO. At the water/n-heptane interface, the polymers tend to adopt elongated conformations in agreement with similar experimental ellipsometry studies of different poloxamers. In the case of the poloxamers at the n-heptane/water interface, the stronger preference of the PPO block for the hydrophobic phase resulted in bottle-brush-type polymer conformations. At lipid bilayer/water interface, the PEO polymers, as expected from their hydrophilic nature, are weakly adsorbed on the surface of the lipid bilayer and locate in the water phase close to the headgroups. The free energy barriers of permeation calculated for short polymer chains suggest a thermodynamics propensity for the water phase that increase with the chain length. The lower affinity of PEO for the hydrophobic interior of the lipid bilayer resulted in the spontaneous expulsion within the simulation time. On the contrary, PPO chains and poloxamers have a longer residence time inside the bilayer, and they tend to concentrate in the tail region of the bilayer near the polar headgroups. In addition, polymers with PPO unit length comparable to the thickness of the hydrophobic region of the bilayer tend to span across the bilayer.

Biocompatible Polysiloxane-Containing Diblock Copolymer PEO-b-PγMPS for Coating Magnetic Nanoparticles

PubMed Central

Chen, Hongwei; Wu, Xinying; Duan, Hongwei; Wang, Y. Andrew; Wang, Liya; Zhang, Minming; Mao, Hui

2009-01-01

We report a biocompatible polysiloxane containing amphiphilic diblock copolymer, poly(ethylene oxide)-block-poly(γ-methacryloxypropyltrimethoxysilane) (PEO-b-PγMPS), for coating and stabilizing nanoparticles for biomedical applications. Such amphiphilic diblock copolymer which comprises both a hydrophobic segment with “surface anchoring moiety” (silane group) and a hydrophilic segment with PEO (Mn=5000 g/mol) was obtained by the reversible addition fragmentation chain transfer (RAFT) polymerization using the PEO macromolecular chain transfer agent. When used for coating paramagnetic iron oxide nanoparticles (IONPs), copolymers were mixed with hydrophobic oleic acid coated core size uniformed IONPs (D=13 nm) in co-solvent tetrahydrofuran. After being aged over a period of time, resulting monodispersed IONPs can be transferred into aqueous medium. With proper PγMPS block length (Mn=10,000 g/mol), polysiloxane containing diblock copolymers formed a thin layer of coating (~3 nm) around monocrystalline nanoparticles as measured by transmission electron microscopy (TEM). Magnetic resonance imaging (MRI) experiments showed excellent T2 weighted contrast effect from coated IONPs with a transverse relaxivity r2=98.6 mM−1s−1 (at 1.5 Tesla). Such thin coating layer has little effect on the relaxivity when compared to that of IONPs coated with conventional amphiphilic copolymer. Polysiloxane containing diblock copolymer coated IONPs are stable without aggregation or binding to proteins in serum when incubated for 24 h in culture medium containing 10% serum. Furthermore, much lower level of intracellular uptake by macrophage cells was observed with polysiloxane containing diblock copolymers coated IONPs, suggesting the reduction of non-specific cell uptakes and antibiofouling effect. PMID:20161520

Investigation of a new thermosensitive block copolymer micelle: hydrolysis, disruption, and release.

PubMed

Pelletier, Maxime; Babin, Jérôme; Tremblay, Luc; Zhao, Yue

2008-11-04

Thermosensitive polymer micelles are generally obtained with block copolymers in which one block exhibits a lower critical solution temperature in aqueous solution. We investigate a different design that is based on the use of one block bearing a thermally labile side group, whose hydrolysis upon heating shifts the hydrophilic-hydrophobic balance toward the destabilization of block copolymer micelles. Atom transfer radical polymerization was utilized to synthesize a series of diblock copolymers composed of hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly(2-tetrahydropyranyl methacrylate) (PTHPMA). We show that micelles of PEO-b-PTHPMA in aqueous solution can be destabilized as a result of the thermosensitive hydrolytic cleavage of tetrahydropyranyl (THP) groups that transforms PTHPMA into hydrophilic poly(methacrylic acid). The three related processes occurring in aqueous solution, namely, hydrolytic cleavage of THP, destabilization of micelles, and release of loaded Nile Red (NR), were investigated simultaneously using 1H NMR, dynamic light scattering, and fluorescence spectroscopy, respectively. At 80 degrees C, the results suggest that the three events proceed with a similar kinetics. Although slower than at elevated temperatures, the disruption of PEO-b-PTHPMA micelles can take place at the body temperature (approximately 37 degrees C), and the release kinetics of NR can be adjusted by changing the relative lengths of the two blocks or the pH of the solution.

Improving Educational Objectives of the Industrial and Management Systems Engineering Programme at Kuwait University

ERIC Educational Resources Information Center

Aldowaisan, Tariq; Allahverdi, Ali

2016-01-01

This paper describes the process of developing programme educational objectives (PEOs) for the Industrial and Management Systems Engineering programme at Kuwait University, and the process of deployment of these PEOs. Input of the four constituents of the programme, faculty, students, alumni, and employers, is incorporated in the development and…

Design of Hybrid Solid Polymer Electrolytes: Structure and Properties

NASA Technical Reports Server (NTRS)

Bronstein, Lyudmila M.; Karlinsey, Robert L.; Ritter, Kyle; Joo, Chan Gyu; Stein, Barry; Zwanziger, Josef W.

2003-01-01

This paper reports synthesis, structure, and properties of novel hybrid solid polymer electrolytes (SPE's) consisting of organically modified aluminosilica (OM-ALSi), formed within a poly(ethylene oxide)-in-salt (Li triflate) phase. To alter the structure and properties we fused functionalized silanes containing poly(ethylene oxide) (PEO) tails or CN groups.

Iridescent cellulose nanocrystal/polyethylene oxide composite films with low coefficient of thermal expansion

Treesearch

Jairo A. Diaz; Julia L. Braun; Robert J. Moon; Jeffrey P. Youngblood

2015-01-01

Simultaneous control over optical and thermal properties is particularly challenging and highly desired in fields like organic electronics. Here we incorporated cellulose nanocrystals (CNCs) into polyethylene oxide (PEO) in an attempt to preserve the iridescent CNC optical reflection given by their chiral nematic organisation, while reducing the composite thermal...

Poly(ethylene oxide) surfactant polymers.

PubMed

Vacheethasanee, Katanchalee; Wang, Shuwu; Qiu, Yongxing; Marchant, Roger E

2004-01-01

We report on a series of structurally well-defined surfactant polymers that undergo surface-induced self-assembly on hydrophobic biomaterial surfaces. The surfactant polymers consist of a poly(vinyl amine) backbone with poly(ethylene oxide) and hexanal pendant groups. The poly(vinyl amine) (PVAm) was synthesized by hydrolysis of poly(N-vinyl formamide) following free radical polymerization of N-vinyl formamide. Hexanal and aldehyde-terminated poly(ethylene oxide) (PEO) were simultaneously attached to PVAm via reductive amination. Surfactant polymers with different PEO:hexanal ratios and hydrophilic/hydrophobic balances were prepared, and characterized by FT-IR, 1H-NMR and XPS spectroscopies. Surface active properties at the air/water interface were determined by surface tension measurements. Surface activity at a solid surface/water interface was demonstrated by atomic force microscopy, showing epitaxially molecular alignment for surfactant polymers adsorbed on highly oriented pyrolytic graphite. The surfactant polymers described in this report can be adapted for simple non-covalent surface modification of biomaterials and hydrophobic surfaces to provide highly hydrated interfaces.

Hierarchically Ordered Nanopatterns for Spatial Control of Biomolecules

PubMed Central

2015-01-01

The development and study of a benchtop, high-throughput, and inexpensive fabrication strategy to obtain hierarchical patterns of biomolecules with sub-50 nm resolution is presented. A diblock copolymer of polystyrene-b-poly(ethylene oxide), PS-b-PEO, is synthesized with biotin capping the PEO block and 4-bromostyrene copolymerized within the polystyrene block at 5 wt %. These two handles allow thin films of the block copolymer to be postfunctionalized with biotinylated biomolecules of interest and to obtain micropatterns of nanoscale-ordered films via photolithography. The design of this single polymer further allows access to two distinct superficial nanopatterns (lines and dots), where the PEO cylinders are oriented parallel or perpendicular to the substrate. Moreover, we present a strategy to obtain hierarchical mixed morphologies: a thin-film coating of cylinders both parallel and perpendicular to the substrate can be obtained by tuning the solvent annealing and irradiation conditions. PMID:25363506

Robust solid polymer electrolyte for conducting IPN actuators

NASA Astrophysics Data System (ADS)

Festin, Nicolas; Maziz, Ali; Plesse, Cédric; Teyssié, Dominique; Chevrot, Claude; Vidal, Frédéric

2013-10-01

Interpenetrating polymer networks (IPNs) based on nitrile butadiene rubber (NBR) as first component and poly(ethylene oxide) (PEO) as second component were synthesized and used as a solid polymer electrolyte film in the design of a mechanically robust conducting IPN actuator. IPN mechanical properties and morphologies were mainly investigated by dynamic mechanical analysis and transmission electron microscopy. For 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide (EMITFSI) swollen IPNs, conductivity values are close to 1 × 10-3 S cm-1 at 25 ° C. Conducting IPN actuators have been synthesized by chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) within the PEO/NBR IPN. A pseudo-trilayer configuration has been obtained with PEO/NBR IPN sandwiched between two interpenetrated PEDOT electrodes. The robust conducting IPN actuators showed a free strain of 2.4% and a blocking force of 30 mN for a low applied potential of ±2 V.

Fabrication of Ordered Nanopattern by using ABC Triblock Copolymer with Salt in Toluene.

PubMed

Huang, Hailiang; Zhong, Benbin; Zu, Xihong; Luo, Hongsheng; Lin, Wenjing; Zhang, Minghai; Zhong, Yazhou; Yi, Guobin

2017-08-15

Ordered nanopatterns of triblock copolymer polystyrene-block-poly(2-vinylpyridine)-block- poly (ethylene oxide)(PS-b-P2VP-b-PEO) have been achieved by the addition of lithium chloride (LiCl). The morphological and structural evolution of PS-b-P2VP-b-PEO/LiCl thin films were systematically investigated by varying different experimental parameters, including the treatment for polymer solution after the addition of LiCl, the time scale of ultrasonic treatment and the molar ratio of Li + ions to the total number of oxygen atoms (O) in PEO block and the nitrogen atoms (N) in P2VP block. When toluene was used as the solvent for LiCl, ordered nanopattern with cylinders or nanostripes could be obtained after spin-coating. The mechanism of nanopattern transformation was related to the loading of LiCl in different microdomains.

Poly(2-vinyl pyridine)-block-poly(ethylene oxide) featuring a furan group at the block junction-synthesis and functionalization.

PubMed

Rudolph, Tobias; Barthel, Markus J; Kretschmer, Florian; Mansfeld, Ulrich; Hoeppener, Stephanie; Hager, Martin D; Schubert, Ulrich S; Schacher, Felix H

2014-05-01

Furfuryl glycidyl ether (FGE) represents a highly versatile monomer for the preparation of reversibly cross-linkable nanostructured materials via Diels-Alder reactions. Here, the use of FGE for the mid-chain functionalization of a P2VP-b-PEO diblock copolymer is reported. The material features one furan moiety at the block junction, P2VP68 -FGE-b-PEO390 , which can be subsequently addressed in Diels-Alder reactions using maleimide-functionalized counterparts. The presence of the FGE moiety enables the introduction of dyes as model labels or the formation of hetero-grafted brushes as shell on hybrid Au@Polymer nanoparticles. This renders P2VP68 -FGE-b-PEO390 , a powerful tool for selective functionalization reactions, including the modification of surfaces. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast Lithium-Ion Transportation in Crystalline Polymer Electrolytes.

PubMed

Fu, Xiao-Bin; Yang, Guang; Wu, Jin-Ze; Wang, Jia-Chen; Chen, Qun; Yao, Ye-Feng

2018-01-05

Fast lithium-ion transportation is found in the crystalline polymer electrolytes, α-CD-PEO n /Li + (n=12, 40), prepared by self-assembly of α-cyclodextrin (CD), polyethylene oxide (PEO) and Li + salts. A detailed solid-state NMR study combined with the X-ray diffraction technique reveals the unique structural features of the samples, that is, a) the tunnel structure formed by the assembled CDs, providing the ordered long-range pathway for Li + ion transportation; b) the all-trans conformational sequence of the PEO chains in the tunnels, attenuating significantly the coordination between Li + and the EO segments. The origin of the fast lithium-ion transportation has been attributed to these unique structural features. This work demonstrates the first example in solid polymer electrolytes (SPEs) for "creating" fast ion transportation through material design and will find potential applications in the design of new ionconducting SPE materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microscopic mechanism for the effect of adding salt on electrospinning by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Wang, Bing-Bing; Wang, Xiao-Dong; Wang, Tian-Hu

2014-09-01

Adding salts into polymer solution has been found to modulate the fiber structure and significantly improve the solution spinnability in electrospinning. However, the mechanisms have not been fully understood. This work adopted molecular dynamics method to investigate the dynamic behavior of poly(ethylene oxide) (PEO)/water droplet with or without dissolved NaCl salt under high-voltage electric field. Our simulation results agreed with the previous experimental reports well. We observed that some daughter droplets detach from the mother droplet due to the ions evaporation and hydration effect, which significantly accelerates the water evaporation and hence improves the solution spinnability. We also observed that some sodium ions are always coordinated with the ether oxygen group in the PEO chain. When these ions are accelerated by the electric field, the PEO chain segments follow the motion of the ions, inevitably stretching the chain and improving the fiber morphology.

Molecular dynamics study of linear and comb-like polyelectrolytes in aqueous solution: effect of Ca2+ ions

NASA Astrophysics Data System (ADS)

Tong, Kefeng; Song, Xingfu; Sun, Shuying; Xu, Yanxia; Yu, Jianguo

2014-08-01

All-atom molecular dynamics simulations were employed to provide microscopic mechanism for the salt tolerance of polyelectrolytes dispersants. The conformational variation of polyelectrolytes and interactions between COO- groups and counterions/water molecules were also studied via radius of gyration and pair correlations functions. Sodium polyacrylate (NaPA) and sodium salts of poly(acrylic acid)-poly(ethylene oxide) (NaPA-PEO) were selected as the representative linear and comb-like polyelectrolyte, respectively. The results show that Ca2+ ions interact with COO- groups much stronger than Na+ ions and can bring ion-bridging interaction between intermolecular COO- groups in the NaPA systems. While in the NaPA-PEO systems, the introduced PEO side chains can prevent backbone chains from ion-bridging interactions and weaken the conformational changes. The present results can help in selecting and designing new-type efficient polyelectrolyte dispersants with good salt tolerance.

Polymer Ni-MH battery based on PEO-PVA-KOH polymer electrolyte

NASA Astrophysics Data System (ADS)

Yang, Chun-Chen

An alkaline polymer electrolyte film has been prepared by a solvent-casting method. Poly(vinyl alcohol), PVA is added to improve the ionic conductivity of the electrolyte. The ionic conductivity increases from 10 -7 to 10 -2 S cm -1 at room temperature when the weight percent ratio of poly(ethylene oxide), PEO to PVA is increased from 10:0 to 5:5. The activation energy of the ionic conductivity for the PEO-PVA-KOH polymer electrolyte is 3-8 kJ mol -1. The properties of the electrolyte film are characterized by a wide variety of techniques and it is found that the film exhibits good mechanical stability and high ionic conductivity at room temperature. The application of such electrolyte films to nickel-metal-hydride (Ni-MH) batteries is examined and the electrochemical characteristics of a polymer Ni-MH battery are obtained.

Hierarchically Ordered Nanopatterns for Spatial Control of Biomolecules

DOE PAGES

Tran, Helen; Ronaldson, Kacey; Bailey, Nevette A.; ...

2014-11-04

We present the development and study of a benchtop, high-throughput, and inexpensive fabrication strategy to obtain hierarchical patterns of biomolecules with sub-50 nm resolution. A diblock copolymer of polystyrene-b-poly(ethylene oxide), PS-b-PEO, is synthesized with biotin capping the PEO block and 4-bromostyrene copolymerized within the polystyrene block at 5 wt %. These two handles allow thin films of the block copolymer to be postfunctionalized with biotinylated biomolecules of interest and to obtain micropatterns of nanoscale-ordered films via photolithography. The design of this single polymer further allows access to two distinct superficial nanopatterns (lines and dots), where the PEO cylinders are orientedmore » parallel or perpendicular to the substrate. Moreover, we present a strategy to obtain hierarchical mixed morphologies: a thin-film coating of cylinders both parallel and perpendicular to the substrate can be obtained by tuning the solvent annealing and irradiation conditions.« less

Block copolymer with simultaneous electric and ionic conduction for use in lithium ion batteries

DOEpatents

Javier, Anna Esmeralda K; Balsara, Nitash Pervez; Patel, Shrayesh Naran; Hallinan, Jr., Daniel T

2013-10-08

Redox reactions that occur at the electrodes of batteries require transport of both ions and electrons to the active centers. Reported is the synthesis of a block copolymer that exhibits simultaneous electronic and ionic conduction. A combination of Grignard metathesis polymerization and click reaction was used successively to synthesize the block copolymer containing regioregular poly(3-hexylthiophene) (P3HT) and poly(ethylene oxide) (PEO) segments. The P3HT-PEO/LiTFSI mixture was then used to make a lithium battery cathode with LiFePO.sub.4 as the only other component. All-solid lithium batteries of the cathode described above, a solid electrolyte and a lithium foil as the anode showed capacities within experimental error of the theoretical capacity of the battery. The ability of P3HT-PEO to serve all of the transport and binding functions required in a lithium battery electrode is thus demonstrated.

Photophysics of Ru(II)— and Os(II)—polypyridine complexes in poly(ethyleneoxide) matrices

NASA Astrophysics Data System (ADS)

Campagna, Sebastiano; Bartolotta, Antonino; Marco, Gaetano Di

1993-04-01

Photophysical properties of Ru(bpy) 32+, Ru(bpy) 2(biq) 2+, and Os(bpy) 32+ (bpy=2,2'-bipyridine; biq=2,2'-biquinoline) in poly(ethyleneoxide) matrices (PEO) constituted by (CH 2CH 2O) repeating units, with average molecular weight 400 (PEO-400, a highly viscous fluid) and 600000 dalton (PEO-600000, a semicrystalline solid) have been studied at room temperature and 77 K. Comparison with similar systems is made. The absorption spectra, luminescence spectra and lifetimes at room temperature of the three complexes in both matrices are in agreement with the typical features reported for the same complexes in fluid solutions, and indicate that fast excited state relaxation via solvent reorganization occurs in both PEO matrices at room temperature. Such behaviour is not usual for solid matrices and is attributed to the microheterogeneous nature of PEO-600000 and to the ability of the solid PEO amorphous region to stabilize polar species within the timescale of radiative relaxation. The results suggest that PEO-600000 is a promising medium for studying electron and energy transfer processes having mild driving forces in the solid state at room temperature.

Lithium batteries using poly(ethylene oxide)-based non-aqueous electrolytes

DOEpatents

Chen, Zonghai; Amine, Khalil

2015-09-08

Lithium-air cells employing poly(ethyleneoxide) phosphate-based electrolytes may be prepared and exhibit improved charge carrying capacity. Such PEO phosphates generally have the formulas IIa, IIb, IIc, where: ##STR00001##

In-situ preparation of poly(ethylene oxide)/Li3PS4 hybrid polymer electrolyte with good nanofiller distribution for rechargeable solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Chen, Shaojie; Wang, Junye; Zhang, Zhihua; Wu, Linbin; Yao, Lili; Wei, Zhenyao; Deng, Yonghong; Xie, Dongjiu; Yao, Xiayin; Xu, Xiaoxiong

2018-05-01

Nano-sized fillers in a polymer matrix with good distribution can play a positive role in improving polymer electrolytes in the aspects of ionic conductivity, mechanical property and electrochemical performance of Li-ion cells. Herein, polyethylene oxide (PEO)/Li3PS4 hybrid polymer electrolyte is prepared via a new in-situ approach. The ionic conductivities of the novel hybrid electrolytes with variable proportions are measured, and the optimal electrolyte of PEO-2%vol Li3PS4 presents a considerable ionic conductivity of 8.01 × 10-4 S cm-1 at 60 °C and an electrochemical window up to 5.1 V. The tests of DSC and EDXS reveal that the Li3PS4 nanoparticles with better distribution, as active fillers scattering in the PEO, exhibit a positive effect on the transference of lithium ion and electrochemical interfacial stabilities. Finally, the assembled solid-state LiFePO4/Li battery presents a decent cycling performance (80.9% retention rate after 325 cycles at 60 °C) and excellent rate capacities with 153, 143, 139 and 127 mAh g-1 at the discharging rate of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C. It is fully proved that it is an advanced strategy to preparing the new organic/inorganic hybrid electrolytes for lithium-ion batteries applications.

Anxiety-like behaviour in mice exposed to tannery wastewater: The effect of photoelectrooxidation treatment.

PubMed

Siqueira, Ionara Rodrigues; Vanzella, Cláudia; Bianchetti, Paula; Rodrigues, Marco Antonio Siqueira; Stülp, Simone

2011-01-01

The leather industry is a major producer of wastewaters and releases large quantities of many different chemical agents used in hide processing into the environment. Since the central nervous system is sensitive to many different contaminants, our aim was to investigate the neurobehavioral effects of exposure of mice to tannery effluents using animal models of depression and anxiety, namely forced swim and elevated plus-maze. In order to propose a clean technology for the treatment of this effluent, we also investigated the exposure of mice to effluents treated by photoelectrooxidation process (PEO). Adult male Swiss albino mice (CF1 strain) were given free access to water bottles containing an effluent treated by a tannery (non-PEO) or PEO-treated tannery wastewater (0.1 and 1% in drinking water). Exposure to tannery wastewater induced behavioural changes in the mice in elevated plus-maze. Exposure to non-PEO 1% decreased the percentage of time spent in the open arms, indicating anxiety-like behaviour. Exposure to tannery wastewater did not alter immobility time in the forced swim test, suggesting that tannery effluents did not induce depression-like behaviour in the mice. These behavioural data suggest that non-PEO tannery effluent has an anxiogenic effect, whereas PEO-treated tannery effluents do not alter anxiety levels. Copyright © 2011 Elsevier Inc. All rights reserved.

Hollow carbon nanospheres using an asymmetric triblock copolymer structure directing agent.

PubMed

Li, Yunqi; Tan, Haibo; Salunkhe, Rahul R; Tang, Jing; Shrestha, Lok Kumar; Bastakoti, Bishnu Prasad; Rong, Hongpan; Takei, Toshiaki; Henzie, Joel; Yamauchi, Yusuke; Ariga, Katsuhiko

2016-12-20

We introduce a simple method to prepare hollow carbon nanospheres (HCNs) by using triblock copolymer poly(styrene-b-2-vinylpyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) micelles as a new class of soft-templates. Simply by changing the solvent we can prepare ultra-small sized micelles of the triblock copolymer PS-b-P2VP-b-PEO soft template to obtain HCNs with ultra-small diameters (43 nm) and hollow cores (19 nm). Furthermore, we use these HCNs to make electric double-layer capacitors (EDLCs) that exhibit superior performance.

Core-Shell-Corona Micelles with a Responsive Shell.

PubMed

Gohy, Jean-François; Willet, Nicolas; Varshney, Sunil; Zhang, Jian-Xin; Jérôme, Robert

2001-09-03

A reactor for the synthesis of gold nanoparticles is one of the uses of a poly(styrene)-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) triblock copolymer (PS-b-P2VP-b-PEO) which forms core-shell-corona micelles in water. Very low polydispersity spherical micelles are observed that consist of a PS core surrounded by a pH-sensitive P2VP shell and a corona of PEO chains end-capped by a hydroxyl group. The corona can act as a site for attaching responsive or sensing molecules. © 2001 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Colloidal behavior of aqueous montmorillonite suspensions in the presence of non-ionic polymer

NASA Astrophysics Data System (ADS)

Gareche, M.; Azri, N.; Allal, A.; Zeraibi, N.

2015-04-01

In this paper we characterized at first, the rheological behavior of the bentonite suspensions and the aqueous solutions of polyethylene oxide (PEO), then we were investigated the influence of this polymer in a water-based drilling fluid model (6% of bentonite suspension). The objective is to exhibit how the non ionic polymer with molecular weight 6×103 g/mol. of varying concentration mass (0.7%, 1%, 2% et 3%) significantly alter the rheological properties (yield stress, viscosity, loss and elastic modulus) of the bentonite suspensions. The rheological measurements made in simple shear and in dynamic on the mixture (water-bentonite-PEO), showed rheological properties of bentonite suspensions both in the presence and absence of non-ionic polymer. The PEO presents an affinity for the bentonite particles slowing down their kinetic aggregation. The analysis by X-rays diffraction also allowed understanding the structure of this mixture. It had revealed the intercalation between of the clay platelets on one hand, and the links bridges assured by the chains of polymer between bentonite particles beyond a critical concentration in PEO on the other hand. The Herschel- Bulkley rheological model is used for the correlation of our experimental results.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

NASA Astrophysics Data System (ADS)

Costa, Luciano T.; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

2015-07-01

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li+ coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSIṡ1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend.

PubMed

Costa, Luciano T; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

2015-07-14

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li(+) coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Adsorption and Exchange Dynamics in Aging Hydroxyethylcellulose Layers on Silica.

PubMed

Mubarekyan; Santore

2000-07-15

The adsorption kinetics of hydroxyethylcellulose (HEC) on silica and relaxations in adsorbed HEC layers were probed using total internal reflectance fluorescence and near-Brewster reflectivity. Like many random-coil polymers, HEC was found to adsorb at the transport-limited rate. Relaxations occurred at nearly constant interfacial mass when HEC layers were exposed to aqueous solvent, causing the subsequent exchange of chains between the layer and the free solution to become increasingly hindered. Eventually, on the time scale of a day, layers became immobilized and unable to accommodate chains from free solution. A continued fluorescence decay, beyond time scales that could be probed with self exchange, suggested further relaxations of the adsorbed HEC. The polydisperse HEC system (with an average molecular weight near 450,000) behaved qualitatively similar to molecular weight standard polyethylene oxide (PEO) layers on silica. For instance, relaxations in PEO layers occurred on a time scale of 10-20 h, like the HEC layers. Young layers of the latter, however, exhibited self-exchange kinetics that were an order of magnitude slower than PEO layers of similar age. This difference in adsorbed layer dynamics was attributed to HEC's stiffer backbone, compared with flexible PEO. Copyright 2000 Academic Press.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

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

Costa, Luciano T., E-mail: ltcosta@id.uff.br; Sun, Bing; Jeschull, Fabian

2015-07-14

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li{sup +} coordination and transportation were studied in the ternary electrolyte system, i.e., PEO{sub 16}LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generatedmore » significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.« less

Investigation of particle lateral migration in sample-sheath flow of viscoelastic fluid and Newtonian fluid.

PubMed

Yuan, Dan; Zhang, Jun; Yan, Sheng; Peng, Gangrou; Zhao, Qianbin; Alici, Gursel; Du, Hejun; Li, Weihua

2016-08-01

In this work, particle lateral migration in sample-sheath flow of viscoelastic fluid and Newtonian fluid was experimentally investigated. The 4.8-μm micro-particles were dispersed in a polyethylene oxide (PEO) viscoelastic solution, and then the solution was injected into a straight rectangular channel with a deionised (DI) water Newtonian sheath flow. Micro-particles suspended in PEO solution migrated laterally to a DI water stream, but migration in the opposite direction from a DI water stream to a PEO solution stream or from one DI water stream to another DI water stream could not be achieved. The lateral migration of particles depends on the viscoelastic properties of the sample fluids. Furthermore, the effects of channel length, flow rate, and PEO concentration were studied. By using viscoelastic sample flow and Newtonian sheath flow, a selective particle lateral migration can be achieved in a simple straight channel, without any external force fields. This particle lateral migration technique could be potentially used in solution exchange fields such as automated cell staining and washing in microfluidic platforms, and holds numerous biomedical applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The development and characterization of degradable poly(vinyl ester) and poly(vinyl ester)/PEO block copolymers

NASA Astrophysics Data System (ADS)

Lipscomb, Corinne Elizabeth

The development of biodegradable materials is a challenging and important problem in polymer science. A review of the state of the art in degradable materials is presented, which reveals that current biodegradable materials do not exhibit the thermal or mechanical properties necessary for widespread applications. One strategy for toughening polymeric materials, which has previously been applied to non-degradable thermoplastics and thermoplastic elastomers, is the formation of block copolymers. Poly(vinyl esters) (PVE) homopolymers are known to have a wide range of properties, but PVE block copolymers comprise a class of inexpensive and (bio)degradable materials that were previously unknown. Therefore, the synthesis and properties of these block copolymers were explored in an effort to develop robust degradable materials. This thesis research probes the reaction conditions necessary for the reversible-addition fragmentation chain transfer (RAFT) polymerization and chain extension reactions of vinyl ester monomers. PVE di- and triblock copolymers are synthesized and studied, and the triblock copolymers display extremely poor toughness due to their relatively low molecular weights in light of the high entanglement molecular weight of the poly(vinyl acetate) center block. Attempts to improve the mechanical properties of these materials focus on the incorporation of poly(ethylene oxide) (PEO) as a low entanglement molecular weight and biocompatible center block in PVE-containing triblock copolymers. Depending on the choice of PVE endblocks and the overall polymer composition, crystallization of the PEO block can be controlled, confined, or inhibited. Polymers in which PEO crystallization is completely inhibited exhibit enhanced mechanical properties and behave as weak thermoplastics. In order to understand the relationship between the inhibition of PEO crystallization and the mechanical properties of PVE/PEO materials, these polymers were studied using dynamic mechanical spectroscopy, wide angle X-ray scattering, small angle X-ray scattering, differential scanning calorimetry, and uniaxial tensile tests. By combining insights gained from these techniques, a complex picture emerges that explains the enhanced mechanical properties of these materials based on the type and location of thermal transitions, amorphous PEO entanglements, and the strain-induced crystallization of PEO. This work represents an important step toward developing robust materials with tunable properties containing (bio)degradable components.

Putting HR outsourcing into practice.

PubMed

Berger, Michael

2007-01-01

Faced with the time-consuming responsibility of human resources (HR) management, a growing number of medical practices are outsourcing their HR to professional employer organizations (PEOs) so they can concentrate on their core business. A PEO functions as an HR department-minus the high overhead-managing daily administrative tasks such as payroll processing and related tax filings, employee benefits, and workers' compensation coverage and claims resolution. PEOs help physicians' offices keep up with the piles of paperwork that never seem to shrink, freeing doctors to focus on patient care and building their practice. Because of their volume buying power, PEOs are able to offer employees of small medical practices big-company benefits-everything from health, dental, and vision coverage to long-term disability insurance and tuition assistance. A fledgling industry only a decade ago, HR outsourcing has morphed into a blossoming industry. Enlisting the services of a PEO is now considered de rigueur in many small business circles.

Controlled lecithin release from a hierarchical architecture on blood-contacting surface to reduce hemolysis of stored red blood cells.

PubMed

Shi, Qiang; Fan, Qunfu; Ye, Wei; Hou, Jianwen; Wong, Shing-Chung; Xu, Xiaodong; Yin, Jinghua

2014-06-25

Hemolysis of red blood cells (RBCs) caused by implant devices in vivo and nonpolyvinyl chloride containers for RBC preservation in vitro has recently gained much attention. To develop blood-contacting biomaterials with long-term antihemolysis capability, we present a facile method to construct a hydrophilic, 3D hierarchical architecture on the surface of styrene-b-(ethylene-co-butylene)-b-styrene elastomer (SEBS) with poly(ethylene oxide) (PEO)/lecithin nano/microfibers. The strategy is based on electrospinning of PEO/lecithin fibers onto the surface of poly [poly(ethylene glycol) methyl ether methacrylate] [P(PEGMEMA)]-modified SEBS, which renders SEBS suitable for RBC storage in vitro. We demonstrate that the constructed 3D architecture is composed of hydrophilic micro- and nanofibers, which transforms to hydrogel networks immediately in blood; the controlled release of lecithin is achieved by gradual dissolution of PEO/lecithin hydrogels, and the interaction of lecithin with RBCs maintains the membrane flexibility and normal RBC shape. Thus, the blood-contacting surface reduces both mechanical and oxidative damage to RBC membranes, resulting in low hemolysis of preserved RBCs. This work not only paves new way to fabricate high hemocompatible biomaterials for RBC storage in vitro, but provides basic principles to design and develop antihemolysis biomaterials for implantation in vivo.

The effect of microgeometry, implant thickness and polyurethane chemistry on the foreign body response to subcutaneous implants.

PubMed

Ward, W Kenneth; Slobodzian, Emily P; Tiekotter, Kenneth L; Wood, Michael D

2002-11-01

We addressed the effect of implant thickness, implant porosity, and polyurethane (PU) chemistry on angiogenesis and on the foreign body response in rats. The following materials were implanted subcutaneously for 7 weeks then excised for histologic analysis: a solid PU; a solid polyurethane with silicone and polyethylene oxide (PU-S-PEO); porous expanded polytetrafluoroethylene (ePTFE); and porous polyvinyl alcohol sponge (PVA). Two thicknesses of PU-S-PEO were compared: 300 microns (thin) and 2000 microns (thick). Foreign body capsule (FBC) thickness was much less in PU-S-PEO implants than in PU implants. In addition, FBC were thinner in thin implants than in thick implants. FBC was much more dense in solid implants than in porous implants. As compared with solid implants, porous implants (PVA and ePTFE) led to a marked increase in the number of microvessels that developed adjacent to the implant, as observed both with hematoxylin/eosin staining and with an immunohistochemical anti-endothelial stain. We conclude that the polyethylene oxide and silicone moieties in PU reduce the thickness of the subsequent FBC. In addition, thin implants lead to a thin FBC. Porous implants (PVA and ePTFE) cause more angiogenesis than solid implants. These results may have implications for the measurement of blood-derived analytes by biosensors.

Comparison study of morphology and crystallization behavior of polyethylene and poly(ethylene oxide) on single-walled carbon nanotubes.

PubMed

Zheng, Xiaoli; Xu, Qun

2010-07-29

In this work, we provided a comparison study of morphology and crystallization behavior of polyethylene (PE) and poly(ethylene oxide) (PEO) on single-walled carbon nanotubes (SWNTs) with assistance of supercritical CO(2). The resulting polymer/SWNT nanohybrids were characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectra, wide-angle X-ray diffraction, and differential scanning calorimetry. SWNT small bundles were decorated by PE lamellar crystals, forming nanohybrid "shish-kebab" (NHSK) structure, whereas SWNTs were only wrapped by a thin amorphous polymer coating in the case of PEO. The varying morphologies of the nanohybrids were found to depend on the molecular conformation and the interactions between polymer chains and SWNTs. Nonisothermal experiments showed that SWNTs provided heterogeneous nucleation sites for PE crystallization, while the NHSK structure hindered polymer chain diffusion and crystal growth. Also, SWNTs played antinucleation effect on PEO. In addition, the formation mechanism analysis indicated that PE chains preferred to form a homogeneous coating along the tube axis before proceeding to kebab crystal growth. The purpose of this work is to enlarge the area of theoretical understanding of introducing precisely hierarchical structures on carbon nanotubes, which are important for functional design in nanodevice applications.

Tenofovir Containing Thiolated Chitosan Core/Shell Nanofibers: In Vitro and in Vivo Evaluations.

PubMed

Meng, Jianing; Agrahari, Vivek; Ezoulin, Miezan J; Zhang, Chi; Purohit, Sudhaunshu S; Molteni, Agostino; Dim, Daniel; Oyler, Nathan A; Youan, Bi-Botti C

2016-12-05

It is hypothesized that thiolated chitosan (TCS) core/shell nanofibers (NFs) can enhance the drug loading of tenofovir, a model low molecular weight and highly water-soluble drug molecule, and improve its mucoadhesivity and in vivo safety. To test this hypothesis, poly(ethylene oxide) (PEO) core with TCS and polylactic acid (PLA) shell NFs are fabricated by a coaxial electrospinning technique. The morphology, drug loading, drug release profiles, cytotoxicity and mucoadhesion of the NFs are analyzed using scanning and transmission electron microscopies, liquid chromatography, cytotoxicity assays on VK2/E6E7 and End1/E6E7 cell lines and Lactobacilli crispatus, fluorescence imaging and periodic acid colorimetric method, respectively. In vivo safety studies are performed in C57BL/6 mice followed by H&E and immunohistochemical (CD45) staining analysis of genital tract. The mean diameters of PEO, PEO/TCS, and PEO/TCS-PLA NFs are 118.56, 9.95, and 99.53 nm, respectively. The NFs exhibit smooth surface. The drug loading (13%-25%, w/w) increased by 10-fold compared to a nanoparticle formulation due to the application of the electrospinning technique. The NFs are noncytotoxic at the concentration of 1 mg/mL. The PEO/TCS-PLA core/shell NFs mostly exhibit a release kinetic following Weibull model (r 2 = 0.9914), indicating the drug release from a matrix system. The core/shell NFs are 40-60-fold more bioadhesive than the pure PEO based NFs. The NFs are nontoxic and noninflammatory in vivo after daily treatment for up to 7 days. Owing to their enhanced drug loading and preliminary safety profile, the TCS core/shell NFs are promising candidates for the topical delivery of HIV/AIDS microbicides such as tenofovir.

Addressable Direct-Write Nanoscale Filament Formation and Dissolution by Nanoparticle-Mediated Bipolar Electrochemistry.

PubMed

Crouch, Garrison M; Han, Donghoon; Fullerton-Shirey, Susan K; Go, David B; Bohn, Paul W

2017-05-23

Nanoscale conductive filaments, usually associated with resistive memory or memristor technology, may also be used for chemical sensing and nanophotonic applications; however, realistic implementation of the technology requires precise knowledge of the conditions that control the formation and dissolution of filaments. Here we describe and characterize an addressable direct-write nanoelectrochemical approach to achieve repeatable formation/dissolution of Ag filaments across a ∼100 nm poly(ethylene oxide) (PEO) film containing either Ag + alone or Ag + together with 50 nm Ag-nanoparticles acting as bipolar electrodes. Using a conductive AFM tip, formation occurs when the PEO film is subjected to a forward bias, and dissolution occurs under reverse bias. Formation-dissolution kinetics were studied for three film compositions: Ag|PEO-Ag + , Ag|poly(ethylene glycol) monolayer-PEO-Ag + , and Ag|poly(ethylene glycol) monolayer-PEO-Ag + /Ag-nanoparticle. Statistical analysis shows that the distribution of formation times exhibits Gaussian behavior, and the fastest average initial formation time occurs for the Ag|PEO-Ag + system. In contrast, formation in the presence of Ag nanoparticles likely proceeds by a noncontact bipolar electrochemical mechanism, exhibiting the slowest initial filament formation. Dissolution times are log-normal for all three systems, and repeated reformation of filaments from previously formed structures is characterized by rapid regrowth. The direct-write bipolar electrochemical deposition/dissolution strategy developed here presents an approach to reconfigurable, noncontact in situ wiring of nanoparticle arrays-thereby enabling applications where actively controlled connectivity of nanoparticle arrays is used to manipulate nanoelectronic and nanophotonic behavior. The system further allows for facile manipulation of experimental conditions while simultaneously characterizing surface conditions and filament formation/dissolution kinetics.

Ion transport mechanisms in lamellar phases of salt-doped PS-PEO block copolymer electrolytes.

PubMed

Sethuraman, Vaidyanathan; Mogurampelly, Santosh; Ganesan, Venkat

2017-11-01

We use a multiscale simulation strategy to elucidate, at an atomistic level, the mechanisms underlying ion transport in the lamellar phase of polystyrene-polyethylene oxide (PS-PEO) block copolymer (BCP) electrolytes doped with LiPF 6 salts. Explicitly, we compare the results obtained for ion transport in the microphase separated block copolymer melts to those for salt-doped PEO homopolymer melts. In addition, we also present results for dynamics of the ions individually in the PEO and PS domains of the BCP melt, and locally as a function of the distance from the lamellar interfaces. When compared to the PEO homopolymer melt, ions were found to exhibit slower dynamics in both the block copolymer (overall) and in the PEO phase of the BCP melt. Such results are shown to arise from the effects of slower polymer segmental dynamics in the BCP melt and the coordination characteristics of the ions. Polymer backbone-ion residence times analyzed as a function of distance from the interface indicate that ions have a larger residence time near the interface compared to that near the bulk of lamella, and demonstrates the influence of the glassy PS blocks and microphase segregation on the ion transport properties. Ion transport mechanisms in BCP melts reveal that there exist five distinct mechanisms for ion transport along the backbone of the chain and exhibit qualitative differences from the behavior in homopolymer melts. We also present results as a function of salt concentration which show that the mean-squared displacements of the ions decrease with increasing salt concentration, and that the ion residence times near the polymer backbone increase with increasing salt concentration.

Polymer dynamics under nanoscopic constraints: the "corset effect" as revealed by NMR relaxometry and diffusometry.

PubMed

Fatkullin, Nail; Fischer, Elmar; Mattea, Carlos; Beginn, Uwe; Kimmich, Rainer

2004-06-21

A spinodal demixing technique was employed for the preparation of linear poly(ethylene oxide) (PEO) confined in nanoscopic strands, which in turn are embedded in a quasi-solid methacrylate matrix impenetrable to PEO. Both the molecular weight of the PEO and the mean diameter of the strands are variable to a certain degree. Chain dynamics of the PEO in the molten state were examined with the aid of field-gradient NMR diffusometry and field-cycling NMR relaxometry. The dominating mechanism for translational displacements in the nanoscopic strands is shown to be reptation. A formalism for the evaluation of NMR diffusometry is presented, which permits the estimation of the mean PEO strand diameter. Samples of different composition revealed diameters in the range 9-58 nm, in reasonable agreement with electron micrographs. The time scale of the diffusion measurements was 10-300 ms. On the much shorter time scale of field-cycling NMR relaxometry, 10(-9)-10(-4)s, a frequency dispersion of the spin-lattice relaxation time characteristic for reptation clearly showed up in all samples. An effective tube diameter of only 0.6 nm was found even when the strand diameter was larger than the radius of gyration of the PEO chain random coils. The finding that the tube diameter effective on the short time scale of field-cycling NMR relaxometry is much smaller than the diameter of the confining structure is termed the "corset effect", and is traced back to the lack of local free-volume fluctuation capacity under nanoscale confinements. The order of magnitude of the 'pore' diameter, at which the cross-over from confined to bulk chain dynamics is expected, is estimated.

Molecular dynamics study of the encapsulation capability of a PCL-PEO based block copolymer for hydrophobic drugs with different spatial distributions of hydrogen bond donors and acceptors.

PubMed

Patel, Sarthak K; Lavasanifar, Afsaneh; Choi, Phillip

2010-03-01

Molecular dynamics simulation was used to study the potential of using a block copolymer containing three poly(epsilon-caprolactone) (PCL) blocks of equal length connected to one end of a poly(ethylene oxide) (PEO) block, designated as PEO-b-3PCL, to encapsulate two classes of hydrophobic drugs with distinctively different molecular structures. In particular, the first class of drugs consisted of two cucurbitacin drugs (CuB and CuI) that contain multiple hydrogen bond donors and acceptors evenly distributed on their molecules while the other class of drugs (fenofibrate and nimodipine) contain essentially only clustered hydrogen bond acceptors. In the case of cucurbitacin drugs, the results showed that PEO-b-3PCL lowered the Flory-Huggins interaction parameters (chi) considerably (i.e., increased the drug solubility) compared to the linear di-block copolymer PEO-b-PCL with the same PCL/PEO (w/w) ratio of 1.0. However, the opposite effect was observed for fenofibrate and nimodipine. Analysis of the intermolecular interactions indicates that the number of hydrogen bonds formed between the three PCL blocks and cucurbitacin drugs is significantly higher than that of the linear di-block copolymer. On the other hand, owing to the absence of hydrogen bond donors and the clustering of the hydrogen bond acceptors on the fenofibrate and nimodipine molecules, this significantly reduces the number of hydrogen bonds formed in the multi-PCL block environment, leading to unfavourable chi values. The findings of the present work suggest that multi-hydrophobic block architecture could potentially increase the drug loading for hydrophobic drugs with structures containing evenly distributed multiple hydrogen bond donors and acceptors. (c) 2009 Elsevier Ltd. All rights reserved.

Formation and stability of water-soluble, molecular polyelectrolyte complexes: effects of charge density, mixing ratio, and polyelectrolyte concentration.

PubMed

Shovsky, Alexander; Varga, Imre; Makuska, Ricardas; Claesson, Per M

2009-06-02

The formation of complexes with stoichiometric (1:1) as well as nonstoichiometric (2:1) and (1:2) compositions between oppositely charged synthetic polyelectrolytes carrying strong ionic groups and significantly different molecular weights is reported in this contribution. Poly(sodium styrenesulfonate) (NaPSS) was used as polyanion, and a range of copolymers with various molar ratios of the poly(methacryloxyethyltrimethylammonium) chloride, poly(METAC), and the nonionic poly(ethylene oxide) ether methacrylate, poly(PEO45MEMA), were used as polycations. Formation and stability of PECs have been investigated by dynamic and static light scattering (LS), turbidity, and electrophoretic mobility measurements as a function of polyelectrolyte solution concentration, charge density of the cationic polyelectrolyte, and mixing ratio. The data obtained demonstrate that in the absence of PEO45 side chains the 100% charged polymer (polyMETAC) formed insoluble PECs with PSS that precipitate from solution when exact stoichiometry is achieved. In nonstoichiometric complexes (1:2) and (2:1) large colloidally stable aggregates were formed. The presence of even a relatively small amount of PEO45 side chains (25%) in the cationic copolymer was sufficient for preventing precipitation of the formed stoichiometric and nonstoichiometric complexes. These PEC's are sterically stabilized by the PEO45 chains. By further increasing the PEO45 side-chain content (50 and 75%) of the cationic copolymer, small, water-soluble molecular complexes could be formed. The data suggest that PSS molecules and the charged backbone of the cationic brush form a compact core, and with sufficiently high PEO45 chain density (above 25%) molecular complexes are formed that are stable over prolonged times.

Polymer Nanocomposite Films: Dispersion of Polymer Grafted Nanorods and Optical Properties

NASA Astrophysics Data System (ADS)

Composto, Russell

2013-03-01

The thermodynamic factors that affect the dispersion of polymer-brush grafted gold nanorods (NR) in polymer matrix films have been studied by experiment and theory. When brush and matrix have a favorable interaction, such as poly(ethylene oxide) (PEO)-NR/ poly(methyl methacrylate) (PMMA) and polystyrene (PS)-NR / poly(2,6-dimethyl-p-phenylene oxide) (PPO), nanorods are uniformly dispersed. For PEO-NRs in PMMA, the NRs are regularly spaced and well dispersed, independent of the ratio of the degree of polymerization of the matrix (P) to that of the brush (N), namely P/N. As the NR volume fraction increases, the local orientation of the nanorods increases, whereas the macroscopic orientation remains isotropic. When the brush and matrix are similar (i.e., PS-NR / PS and PEO-NR / PEO), the nanorods randomly disperse for P/N < 2 (i.e., wet brush), but align side-by-side in aggregates for P/N > 2. UV-visible spectroscopy and discrete dipole approximation (DDA) calculations demonstrate that surface plasmon coupling leads to a blue shift in the longitudinal surface plasmon resonance (LSPR) as P/N increases. For P/N > 2, self-consistent field theory (SCFT) calculations and Monte Carlo (MC) simulations indicate that nanorod aggregation is caused by depletion-attraction forces. Starting with a dry brush system, namely, a PS matrix where P/N = 30, these attractive forces can be mediated by adding a compatibilizing agent (e.g., PPO) that drives the NRs to disperse. Finally, dry and wet brush behavior is observed for NR aspect ratios varying from 2.5 to 7. However, compared at the same volume fraction, long rods for the dry case exhibit much better local order than lower aspect ratio nanorods, suggesting that long rods may exhibit nematic-like ordering at higher loadings. NSF Polymer and CEMRI Programs.

Nanosized amorphous calcium carbonate stabilized by poly(ethylene oxide)-b-poly(acrylic acid) block copolymers.

PubMed

Guillemet, Baptiste; Faatz, Michael; Gröhn, Franziska; Wegner, Gerhard; Gnanou, Yves

2006-02-14

Particles of amorphous calcium carbonate (ACC), formed in situ from calcium chloride by the slow release of carbon dioxide by alkaline hydrolysis of dimethyl carbonate in water, are stabilized against coalescence in the presence of very small amounts of double hydrophilic block copolymers (DHBCs) composed of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blocks. Under optimized conditions, spherical particles of ACC with diameters less than 100 nm and narrow size distribution are obtained at a concentration of only 3 ppm of PEO-b-PAA as additive. Equivalent triblock or star DHBCs are compared to diblock copolymers. The results are interpreted assuming an interaction of the PAA blocks with the surface of the liquid droplets of the concentrated CaCO3 phase, formed by phase separation from the initially homogeneous reaction mixture. The adsorption layer of the block copolymer protects the liquid precursor of ACC from coalescence and/or coagulation.

Physicochemical properties of micelles of poly(styrene-b-[3-(methacryloylamino)propyl]trimethylammonium chloride-b-ethylene oxide) in aqueous solutions.

PubMed

Liu, Jingjing; Liu, Dian; Yokoyama, Yuuichi; Yusa, Shin-Ichi; Nakashima, Kenichi

2009-01-20

Polymeric micelles from a new triblock copolymer, polystyrene-block-poly[(3-(methacryloylamino)propyl)trimethylammonium chloride]-block-poly(ethylene oxide) (PS-b-PMAPTAC-b-PEO), were prepared in aqueous solutions and characterized by various techniques including dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fluorescence spectroscopy. The micelle consists of a PS core, PMAPTAC shell, and PEO corona. It was revealed by SEM and DLS measurements that the micelles have a spherical structure with a hydrodynamic diameter about 75 nm. The addition of tungstate to the micellar solution caused a morphological change in the micelles from extended to shrunken spheres, which can be attributed to the fact that electrostatic repulsion among the cationic PMAPTAC blocks is canceled by the negative charge of the bound tungstate ions. Effective incorporation of tungstate ions into the micelles were confirmed by TEM and zeta-potential measurements.

Molecular dynamics simulation of the polymer electrolyte poly(ethylene oxide)/LiClO(4). II. Dynamical properties.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2006-12-07

The dynamical properties of the polymer electrolyte poly(ethylene oxide) (PEO)LiClO(4) have been investigated by molecular dynamics simulations. The effect of changing salt concentration and temperature was evaluated on several time correlation functions. Ionic displacements projected on different directions reveal anisotropy in short-time (rattling) and long-time (diffusive) dynamics of Li(+) cations. It is shown that ionic mobility is coupled to the segmental motion of the polymeric chain. Structural relaxation is probed by the intermediate scattering function F(k,t) at several wave vectors. Good agreement was found between calculated and experimental F(k,t) for pure PEO. A remarkable slowing down of polymer relaxation is observed upon addition of the salt. The ionic conductivity estimated by the Nernst-Einstein equation is approximately ten times higher than the actual conductivity calculated by the time correlation function of charge current.

Fragmentation-based QM/MM simulations: length dependence of chain dynamics and hydrogen bonding of polyethylene oxide and polyethylene in aqueous solutions.

PubMed

Li, Hui; Li, Wei; Li, Shuhua; Ma, Jing

2008-06-12

Molecular fragmentation quantum mechanics (QM) calculations have been combined with molecular mechanics (MM) to construct the fragmentation QM/MM method for simulations of dilute solutions of macromolecules. We adopt the electrostatics embedding QM/MM model, where the low-cost generalized energy-based fragmentation calculations are employed for the QM part. Conformation energy calculations, geometry optimizations, and Born-Oppenheimer molecular dynamics simulations of poly(ethylene oxide), PEO(n) (n = 6-20), and polyethylene, PE(n) ( n = 9-30), in aqueous solution have been performed within the framework of both fragmentation and conventional QM/MM methods. The intermolecular hydrogen bonding and chain configurations obtained from the fragmentation QM/MM simulations are consistent with the conventional QM/MM method. The length dependence of chain conformations and dynamics of PEO and PE oligomers in aqueous solutions is also investigated through the fragmentation QM/MM molecular dynamics simulations.

Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

NASA Astrophysics Data System (ADS)

Tudryn, Gregory J.

A sequential study of ion-containing polymers capable of ion solvation with varied ion content, dielectric constant, and counterions is presented in this dissertation in order to compare ion transport properties in ionomers with various ionic interactions. Structure-property relationships in these ion containing polymers are defined using x-ray scattering, rheology and dielectric spectroscopy, enabling the quantification of ion transport dynamics. Poly(ethylene oxide), (PEO) based ionomers are investigated in order to probe the relation between ion conduction and segmental relaxation, and copolymers of PEO and Poly(tetramethylene oxide), (PTMO) further develop an understanding of the trade-off between ion solvation and segmental dynamics. Ionomers with ionic liquid counterions probe diffuse charge interactions and steric effects on ion transport, and incorporation of ionic liquids into ionomer membranes such as Nafion provides desirable thermal and ion conducting properties which extend the use of such membranes for electroactive devices. PEO ionomers exhibit a strong relation between ionic conductivity and segmental dynamics, providing insight that the glass transition temperature, Tg, dominates the ion conduction mechanism. Increasing temperature induces aggregation of ionic groups as evidenced by the static dielectric constant and X-ray scattering as a function of temperature, revealing the contribution of ionic dipoles in the measured dielectric constant. The trade-off between ion solvation and fast polymer segmental dynamics are quantified in copolymer ionomers of PEO and lower Tg PTMO. While conducting ion content remains nearly unchanged, conductivity is lowered upon incorporation of PTMO, because the vast majority of the PTMO microphase separates from the PEO-rich microdomain that remains continuous and contributes most of the ion conduction. Dielectric constants and X-ray scattering show consistent changes with temperature that suggest a cascading aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used to predict and design advanced ion-containing polymers to be used in battery membranes and a variety of electroactive devices, including actuators and electromechanical sensors.

Synthesis of bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles

PubMed Central

Li, Xue-Mei; Liu, Hong-Ling; Liu, Xiao; Fang, Ning; Wang, Xian-Hong; Wu, Jun-Hua

2015-01-01

Bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles were synthesized by a modified nanoemulsion process using poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The morphology and crystal structure of the nanoparticles were studied by TEM/HRTEM and XRD. The nanoparticles manifest soft ferromagnetic and/or near superparamagnetic behavior with a small coercivity of ~19 Oe at room temperature. The corresponding magnetic hysteresis curves were elucidated by the modified Langevin equation. The FTIR study confirms the PEO-PPO-PEO molecules on the surface of the nanoparticles. The UV-vis and PL results reveal the well-behaved absorption bands including surface plasmon resonance and multiple visible fingerprint photoluminescent emissions of the nanoparticles dispersed in both hydrophilic and hydrophobic solvents. Moreover, the processes of solvent dispersion-collection of the nanoparticles were demonstrated for application readiness of such core-shell nanostructures. PMID:26548369

Synthesis of bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles

NASA Astrophysics Data System (ADS)

Li, Xue-Mei; Liu, Hong-Ling; Liu, Xiao; Fang, Ning; Wang, Xian-Hong; Wu, Jun-Hua

2015-11-01

Bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles were synthesized by a modified nanoemulsion process using poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The morphology and crystal structure of the nanoparticles were studied by TEM/HRTEM and XRD. The nanoparticles manifest soft ferromagnetic and/or near superparamagnetic behavior with a small coercivity of ~19 Oe at room temperature. The corresponding magnetic hysteresis curves were elucidated by the modified Langevin equation. The FTIR study confirms the PEO-PPO-PEO molecules on the surface of the nanoparticles. The UV-vis and PL results reveal the well-behaved absorption bands including surface plasmon resonance and multiple visible fingerprint photoluminescent emissions of the nanoparticles dispersed in both hydrophilic and hydrophobic solvents. Moreover, the processes of solvent dispersion-collection of the nanoparticles were demonstrated for application readiness of such core-shell nanostructures.

Characteristics and in vitro response of thin hydroxyapatite–titania films produced by plasma electrolytic oxidation of Ti alloys in electrolytes with particle additions

PubMed Central

Yeung, W. K.; Sukhorukova, I. V.; Shtansky, D. V.; Levashov, E. A.; Zhitnyak, I. Y.; Gloushankova, N. A.; Kiryukhantsev-Korneev, P. V.; Petrzhik, M. I.; Matthews, A.

2016-01-01

The enhancement of the biological properties of Ti by surface doping with hydroxyapatite (HA) is of great significance, especially for orthodontic applications. This study addressed the effects of HA particle size in the electrolyte suspension on the characteristics and biological properties of thin titania-based coatings produced on Ti–6Al–4V alloy by plasma electrolytic oxidation (PEO). Detailed morphological investigation of the coatings formed by a single-stage PEO process with two-step control of the electrical parameters was performed using the Minkowski functionals approach. The surface chemistry was studied by glow discharge optical emission spectroscopy and Fourier transform infrared spectroscopy, whereas mechanical properties were evaluated using scratch tests. The biological assessment included in vitro evaluation of the coating bioactivity in simulated body fluid (SBF) as well as studies of spreading, proliferation and osteoblastic differentiation of MC3T3-E1 cells. The results demonstrated that both HA micro- and nanoparticles were successfully incorporated in the coatings but had different effects on their surface morphology and elemental distributions. The micro-particles formed an irregular surface morphology featuring interpenetrated networks of fine pores and coating material, whereas the nanoparticles penetrated deeper into the coating matrix which retained major morphological features of the porous TiO2 coating. All coatings suffered cohesive failure in scratch tests, but no adhesive failure was observed; moreover doping with HA increased the coating scratch resistance. In vitro tests in SBF revealed enhanced bioactivity of both HA-doped PEO coatings; furthermore, the cell proliferation/morphometric tests showed their good biocompatibility. Fluorescence microscopy revealed a well-organised actin cytoskeleton and focal adhesions in MC3T3-E1 cells cultivated on these substrates. The cell alkaline phosphatase activity in the presence of ascorbic acid and β-glycerophosphate was significantly increased, especially in HA nanoparticle-doped coatings. PMID:27019704

Adsorption and association of a symmetric PEO-PPO-PEO triblock copolymer on polypropylene, polyethylene, and cellulose surfaces.

PubMed

Li, Yan; Liu, Hongyi; Song, Junlong; Rojas, Orlando J; Hinestroza, Juan P

2011-07-01

The association of a symmetric polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO(19)-PPO(29)-PEO(19)) triblock copolymer adsorbed from aqueous solutions onto polypropylene (PP), polyethylene (PE), and cellulose surfaces was probed using Atomic Force Microscopy (AFM). Significant morphological differences between the polyolefin substrates (PP and PE) and the cellulose surfaces were observed after immersion of the films in the PEO(19)-PPO(29)-PEO(19) solutions. When the samples were scanned, while immersed in solutions of the triblock copolymer, it was revealed that the structures adsorbed on the polyolefin surfaces were smoothed by the adsorbed PEO(19)-PPO(29)-PEO(19). In contrast, those structures on the hydrophilic cellulose surfaces were sharpened. These observations were related to the roughness of the substrate and the energy of interaction between the surfaces and the PEO and PPO polymer segments. The interaction energy between each of the blocks and the surface was calculated using molecular dynamics simulations. It is speculated that the associative structures amply reported in aqueous solution at concentrations above the critical micelle concentration, CMC, are not necessarily preserved upon adsorption; instead, it appears that molecular arrangements of the anchor-buoy type and hemimicelles prevail. The reported data suggests that the roughness of the surface, as well as its degree of hydrophobicity, have a large influence on the nature of the resulting adsorbed layer. The reported observations are valuable in explaining the behavior of finishing additives and lubricants commonly used in textile and fiber processing, as well as the effect of the morphology of the boundary layers on friction and wear, especially in the case of symmetric triblock copolymers, which are commonly used as antifriction, antiwear additives.

Understanding the interaction of block copolymers with DMPC lipid bilayer using coarse-grained molecular dynamics simulations.

PubMed

Hezaveh, Samira; Samanta, Susruta; De Nicola, Antonio; Milano, Giuseppe; Roccatano, Danilo

2012-12-13

In this paper, we present a computational model of the adsorption and percolation mechanism of poloxamers (poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) triblock copolymers) across a 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayer. A coarse-grained model was used to cope with the long time scale of the percolation process. The simulations have provided details of the interaction mechanism of Pluronics with lipid bilayer. In particular, the results have shown that polymer chains containing a PPO block with a length comparable to the DMPC bilayer thickness, such as P85, tends to percolate across the lipid bilayer. On the contrary, Pluronics with a shorter PPO chain, such as L64 and F38, insert partially into the membrane with the PPO block part while the PEO blocks remain in water on one side of the lipid bilayer. The percolation of the polymers into the lipid tail groups reduces the membrane thickness and increases the area per lipid. These effects are more evident for P85 than L64 or F38. Our findings are qualitatively in good agreement with published small-angle X-ray scattering experiments that have evidenced a thinning effect of Pluronics on the lipid bilayer as well as the role of the length of the PPO block on the permeation process of the polymer through the lipid bilayer. Our theoretical results complement the experimental data with a detailed structural and dynamic model of poloxamers at the interface and inside the lipid bilayer.

Osseointegration improvement by plasma electrolytic oxidation of modified titanium alloys surfaces.

PubMed

Echeverry-Rendón, Mónica; Galvis, Oscar; Quintero Giraldo, David; Pavón, Juan; López-Lacomba, José Luis; Jiménez-Piqué, Emilio; Anglada, Marc; Robledo, Sara M; Castaño, Juan G; Echeverría, Félix

2015-02-01

Titanium (Ti) is a material frequently used in orthopedic applications, due to its good mechanical properties and high corrosion resistance. However, formation of a non-adherent fibrous tissue between material and bone drastically could affect the osseointegration process and, therefore, the mechanical stability of the implant. Modifications of topography and configuration of the tissue/material interface is one of the mechanisms to improve that process by manipulating parameters such as morphology and roughness. There are different techniques that can be used to modify the titanium surface; plasma electrolytic oxidation (PEO) is one of those alternatives, which consists of obtaining porous anodic coatings by controlling parameters such as voltage, current, anodizing solution and time of the reaction. From all of the above factors, and based on previous studies that demonstrated that bone cells sense substrates features to grow new tissue, in this work commercially pure Ti (c.p Ti) and Ti6Al4V alloy samples were modified at their surface by PEO in different anodizing solutions composed of H2SO4 and H3PO4 mixtures. Treated surfaces were characterized and used as platforms to grow osteoblasts; subsequently, cell behavior parameters like adhesion, proliferation and differentiation were also studied. Although the results showed no significant differences in proliferation, differentiation and cell biological activity, overall results showed an important influence of topography of the modified surfaces compared with polished untreated surfaces. Finally, this study offers an alternative protocol to modify surfaces of Ti and their alloys in a controlled and reproducible way in which biocompatibility of the material is not compromised and osseointegration would be improved.

Solid state nuclear magnetic resonance investigation of polymer backbone dynamics in poly(ethylene oxide) based lithium and sodium polyether-ester-sulfonate ionomers.

PubMed

Roach, David J; Dou, Shichen; Colby, Ralph H; Mueller, Karl T

2013-05-21

Polymer backbone dynamics of single ion conducting poly(ethylene oxide) (PEO)-based ionomer samples with low glass transition temperatures (T(g)) have been investigated using solid-state nuclear magnetic resonance. Experiments detecting (13)C with (1)H decoupling under magic angle spinning (MAS) conditions identified the different components of the polymer backbone (PEO spacer and isophthalate groups) and their relative mobilities for a suite of lithium- and sodium-containing ionomer samples with varying cation contents. Variable temperature (203-373 K) (1)H-(13)C cross-polarization MAS (CP-MAS) experiments also provided qualitative assessment of the differences in the motions of the polymer backbone components as a function of cation content and identity. Each of the main backbone components exhibit distinct motions, following the trends expected for motional characteristics based on earlier Quasi Elastic Neutron Scattering and (1)H spin-lattice relaxation rate measurements. Previous (1)H and (7)Li spin-lattice relaxation measurements focused on both the polymer backbone and cation motion on the nanosecond timescale. The studies presented here assess the slower timescale motion of the polymer backbone allowing for a more comprehensive understanding of the polymer dynamics. The temperature dependences of (13)C linewidths were used to both qualitatively and quantitatively examine the effects of cation content and identity on PEO spacer mobility. Variable contact time (1)H-(13)C CP-MAS experiments were used to further assess the motions of the polymer backbone on the microsecond timescale. The motion of the PEO spacer, reported via the rate of magnetization transfer from (1)H to (13)C nuclei, becomes similar for T≳1.1 T(g) in all ionic samples, indicating that at similar elevated reduced temperatures the motions of the polymer backbones on the microsecond timescale become insensitive to ion interactions. These results present an improved picture, beyond those of previous findings, for the dependence of backbone dynamics on cation density (and here, cation identity as well) in these amorphous PEO-based ionomer systems.

Engineering Nanostructures by Decorating Magnetic Nanoparticles onto Graphene Oxide Sheets to Shield Electromagnetic Radiations.

PubMed

Mural, Prasanna Kumar S; Pawar, Shital Patangrao; Jayanthi, Swetha; Madras, Giridhar; Sood, Ajay K; Bose, Suryasarathi

2015-08-05

In this study, a minimum reflection loss of -70 dB was achieved for a 6 mm thick shield (at 17.1 GHz frequency) employing a unique approach. This was accomplished by engineering nanostructures through decoration of magnetic nanoparticles (nickel, Ni) onto graphene oxide (GO) sheets. Enhanced electromagnetic (EM) shielding was derived by selectively localizing the nanoscopic particles in a specific phase of polyethylene (PE)/poly(ethylene oxide) (PEO) blends. By introduction of a conducting inclusion (like multiwall carbon nanotubes, MWNTs) together with the engineered nanostructures (nickel-decorated GO, GO-Ni), the shielding efficiency can be enhanced significantly in contrast to physically mixing the particles in the blends. For instance, the composites showed a shielding efficiency >25 dB for a combination of MWNTs (3 wt %) and Ni nanoparticles (52 wt %) in PE/PEO blends. However, similar shielding effectiveness could be achieved for a combination of MWNTs (3 wt %) and 10 vol % of GO-Ni where in the effective concentration of Ni was only 19 wt %. The GO-Ni sheets facilitated in an efficient charge transfer as manifested from high electrical conductivity in the blends besides enhancing the permeability in the blends. It is envisioned that GO is simultaneously reduced in the process of synthesizing GO-Ni, and this facilitated in efficient charge transfer between the neighboring CNTs. More interestingly, the blends with MWNTs/GO-Ni attenuated the incoming EM radiation mostly by absorption. This study opens new avenues in designing polyolefin-based lightweight shielding materials by engineering nanostructures for numerous applications.

FETs Based on Doped Polyaniline/Polyethylene Oxide Fibers

NASA Technical Reports Server (NTRS)

Theofylaktos, Noulie; Robinson, Daryl; Miranda, Felix; Pinto, Nicholas; Johnson, Alan, Jr.; MacDiarmid, Alan; Mueller, Carl

2006-01-01

A family of experimental highly miniaturized field-effect transistors (FETs) is based on exploitation of the electrical properties of nanofibers of polyaniline/ polyethylene oxide (PANi/PEO) doped with camphorsulfonic acid. These polymer-based FETs have the potential for becoming building blocks of relatively inexpensive, low-voltage, highspeed logic circuits that could supplant complementary metal oxide/semiconductor (CMOS) logic circuits. The development of these polymerbased FETs offers advantages over the competing development of FETs based on carbon nanotubes. Whereas it is difficult to control the molecular structures and, hence, the electrical properties of carbon nanotubes, it is easy to tailor the electrical properties of these polymerbased FETs, throughout the range from insulating through semiconducting to metallic, through choices of doping levels and chemical manipulation of polymer side chains. A further advantage of doped PANi/PEO nanofibers is that they can be made to draw very small currents and operate at low voltage levels, and thus are promising for applications in which there are requirements to use many FETs to obtain large computational capabilities while minimizing power demands. Fabrication of an experimental FET in this family begins with the preparation of a substrate as follows: A layer of silicon dioxide between 50 and 200 nm thick is deposited on a highly doped (resistivity 0.01 W.cm) silicon substrate, then gold electrodes/contact stripes are deposited on the oxide. Next, one or more fibers of camphorsulphonic acid-doped PANi/PEO having diameters of the order of 100 nm are electrospun onto the substrate so as to span the gap between the gold electrodes (see Figure 1). Figure 2 depicts measured current-versus-voltage characteristics of the device of Figure 1, showing that saturation channel currents occur at source-todrain potentials that are surprisingly low, relative to those of CMOS FETs. The hole mobility in the depletion regime in this transistor was found to be 1.4 10(exp -4) sq cm/(V.s), while the one-dimensional charge density at zero gate bias was estimated to be approximately one hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (approx. 10(exp -3) S/cm). Reducing or eliminating the PEO content of the fibers is expected to enhance the properties of future versions of this transistor.

Recyclable magnetic nanocluster crosslinked with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) copolymer for adsorption with antibody.

PubMed

Prai-In, Yingrak; Boonthip, Chatchai; Rutnakornpituk, Boonjira; Wichai, Uthai; Montembault, Véronique; Pascual, Sagrario; Fontaine, Laurent; Rutnakornpituk, Metha

2016-10-01

Surface modification of magnetic nanoparticle (MNP) with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) (PEO-b-PVDM) diblock copolymers and its application as recyclable magnetic nano-support for adsorption with antibody were reported herein. PEO-b-PVDM copolymers were first synthesized via a reversible addition-fragmentation chain-transfer (RAFT) polymerization using poly(ethylene oxide) chain-transfer agent as a macromolecular chain transfer agent to mediate the RAFT polymerization of VDM. They were then grafted on amino-functionalized MNP by coupling with some azlactone rings of the PVDM block to form magnetic nanoclusters with tunable cluster size. The nanocluster size could be tuned by adjusting the chain length of the PVDM block. The nanoclusters were successfully used as efficient and recyclable nano-supports for adsorption with anti-rabbit IgG antibody. They retained higher than 95% adsorption of the antibody during eight adsorption-separation-desorption cycles, indicating the potential feasibility in using this novel hybrid nanocluster as recyclable support in cell separation applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Controlling block copolymer phase behavior using ionic surfactant

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

Ray, D.; Aswal, V. K.

2016-05-23

The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO{sub 26}PO{sub 39}EO{sub 26})] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle–surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at highermore » temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.« less

Mesoscopic Simulations of Adsorption and Association of PEO-PPO-PEO Triblock Copolymers on a Hydrophobic Surface: From Mushroom Hemisphere to Rectangle Brush.

PubMed

Song, Xianyu; Zhao, Shuangliang; Fang, Shenwen; Ma, Yongzhang; Duan, Ming

2016-11-08

The dissipative particle dynamics (DPD) method is used to investigate the adsorption behavior of PEO-PPO-PEO triblock copolymers at the liquid/solid interface. The effect of molecular architecture on the self-assembled monolayer adsorption of PEO-PPO-PEO triblock copolymers on hydrophobic surfaces is elucidated by the adsorption process, film properties, and adsorption morphologies. The adsorption thicknesses on hydrophobic surfaces and the diffusion coefficient as well as the aggregation number of Pluronic copolymers in aqueous solution observed in our simulations agree well with previous experimental and numerical observations. The radial distribution function revealed that the ability of self-assembly on hydrophobic surfaces is P123 > P84 > L64 > P105 > F127, which increased with the EO ratio of the Pluronic copolymers. Moreover, the shape parameter and the degree of anisotropy increase with increasing molecular weight and mole ratio of PO of the Pluronic copolymers. Depending on the conformation of different Pluronic copolymers, the morphology transition of three regimes on hydrophobic surfaces is present: mushroom or hemisphere, progressively semiellipsoid, and rectangle brush regimes induced by decreasing molecular weight and mole ratio of EO of Pluronic copolymers.

Final Report for DE-FG02-93ER14376,Ionic Transport in Electrochemical Media

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

J. W. Halley

This project was a molecular dynamics study of the relevant issues associated with the structure and transport of lithium in polymer electrolytes such as polyethylene oxide(PEO). In close collaboration with quantum chemist Larry Curtiss and neutron scatterers David Lee Price and Marie-Louise Saboungi at Argonne, we used molecular dynamics to study the local structure and dynamics and ion transport in the polymer. The studies elucidated the mechanism of Li transport in PEO, revealing that the rate limiting step is extremely sensitive to the magnitude of the torsion forces in the backbone of the polymer. Because the torsion forces are difficultmore » to manipulate chemically, this makes it easier to understand why improving the conductivity of PEO based electrolytes has proven to be very difficult. We studied the transport properties of cations in ionic liquids as possible additives to polymer membranes for batteries and fuel cells and found preliminary indications that the transport is enhanced near phase separation in acid-ionic liquid mixtures.« less

DNA-polymer micelles as nanoparticles with recognition ability.

PubMed

Talom, Renée Mayap; Fuks, Gad; Kaps, Leonard; Oberdisse, Julian; Cerclier, Christel; Gaillard, Cédric; Mingotaud, Christophe; Gauffre, Fabienne

2011-11-25

The Watson-Crick binding of DNA single strands is a powerful tool for the assembly of nanostructures. Our objective is to develop polymer nanoparticles equipped with DNA strands for surface-patterning applications, taking advantage of the DNA technology, in particular, recognition and reversibility. A hybrid DNA copolymer is synthesized through the conjugation of a ssDNA (22-mer) with a poly(ethylene oxide)-poly(caprolactone) diblock copolymer (PEO-b-PCl). It is shown that, in water, the PEO-b-PCl-ssDNA(22) polymer forms micelles with a PCl hydrophobic core and a hydrophilic corona made of PEO and DNA. The micelles are thoroughly characterized using electron microscopy (TEM and cryoTEM) and small-angle neutron scattering. The binding of these DNA micelles to a surface through DNA recognition is monitored using a quartz crystal microbalance and imaged by atomic force microscopy. The micelles can be released from the surface by a competitive displacement event. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mass Spectrometry and Ion Mobility Characterization of Bioactive Peptide-Synthetic Polymer Conjugates.

PubMed

Alalwiat, Ahlam; Tang, Wen; Gerişlioğlu, Selim; Becker, Matthew L; Wesdemiotis, Chrys

2017-01-17

The bioconjugate BMP2-(PEO-HA) 2 , composed of a dendron with two monodisperse poly(ethylene oxide) (PEO) branches terminated by a hydroxyapatite binding peptide (HA), and a focal point substituted with a bone growth stimulating peptide (BMP2), has been comprehensively characterized by mass spectrometry (MS) methods, encompassing matrix-assisted laser desorption ionization (MALDI), electrospray ionization (ESI), tandem mass spectrometry (MS 2 ), and ion mobility mass spectrometry (IM-MS). MS 2 experiments using different ion activation techniques validated the sequences of the synthetic, bioactive peptides HA and BMP2, which contained highly basic amino acid residues either at the N-terminus (BMP2) or C-terminus (HA). Application of MALDI-MS, ESI-MS, and IM-MS to the polymer-peptide biomaterial confirmed its composition. Collision cross-section measurements and molecular modeling indicated that BMP2-(PEO-HA) 2 exists in several folded and extended conformations, depending on the degree of protonation. Protonation of all basic sites of the hybrid material nearly doubles its conformational space and accessible surface area.

Ordered Materials via Additive Driven Assembly and Reaction using Surfactant-Based Templates

NASA Astrophysics Data System (ADS)

Beaulieu, Michael R.; Daga, Vikram K.; Lesser, Alan J.; Watkins, James J.

2011-03-01

We recently reported (1) the ordering behavior of Pluronic surfactant melts through the addition of aromatic additives with hydrogen bond donating groups, which exhibit selective interactions with the polyethylene oxide (PEO) block. The ordered blends had domain sizes ranging from 12 to 16 nm at additive loadings up to 80%.The goal of this work is to utilize condensation chemistries based on the functionality of similar additives, to yield ordered composite materials that could be used for applications involving membranes or dielectric materials. The structure of the blends and composites are determined by small angle x-ray scattering, which indicates that the ordered structure is preserved following reaction of the additives. Differential scanning calorimetry indicates that an increase in additive loading causes a decrease in the melting temperature and enthalpy of melting of the PEO, which demonstrates that the interaction between the PEO segments and the additive is strong. (1) Daga, V.K., Watkins, J. J. Macromolecules, ASAP.

Chitosan Nanofibers for Transbuccal Insulin Delivery

PubMed Central

Lancina, Michael G.; Shankar, Roopa Kanakatti; Yang, Hu

2017-01-01

Purpose In this work, we aimed at producing chitosan based nanofiber mats capable of delivering insulin via the buccal mucosa. Methods Chitosan was electrospun into nanofibers using poly (ethylene oxide) (PEO) as a carrier molecule in various feed ratios. The mechanical properties and degradation kinetics of the fibers were measured. Insulin release rates were determined in vitro using an ELISA assay. The bioactivity of released insulin was measured in terms of Akt activation in pre-adipocytes. Insulin permeation across the buccal mucosa was measured in an ex-vivo porcine transbuccal model. Results Fiber morphology, mechanical properties, and in vitro stability were dependent on PEO feed ratio. Lower PEO content blends produced smaller diameter fibers with significantly faster insulin release kinetics. Insulin showed no reduction in bioactivity due to electrospinning. Buccal permeation of insulin facilitated by high chitosan content blends was significantly higher than that of free insulin. Conclusions Taken together, our work demonstrates chitosan based nanofibers have the potential to serve as a transbuccal insulin delivery vehicle. PMID:28000386

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

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

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Magnetic hydrogels from alkyne/cobalt carbonyl-functionalized ABA triblock copolymers

DOE PAGES

Jiang, Bingyin; Hom, Wendy L.; Chen, Xianyin; ...

2016-03-09

A series of alkyne-functionalized poly(4-(phenylethynyl)styrene)- block-poly(ethylene oxide)- block-poly(4-(phenylethynyl)styrene) (PPES-b-PEO-b-PPES) ABA triblock copolymers was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. PES n[Co 2(CO) 6] x-EO 800-PES n[Co 2(CO) 6] x ABA triblock copolymer/cobalt adducts (10–67 wt % PEO) were subsequently prepared by reaction of the alkyne-functionalized PPES block with Co 2(CO) 8 and their phase behavior was studied by TEM. Heating triblock copolymer/cobalt carbonyl adducts at 120 °C led to cross-linking of the PPES/Co domains and the formation of magnetic cobalt nanoparticles within the PPES/Co domains. Magnetic hydrogels could be prepared by swelling the PEO domains of the cross-linkedmore » materials with water. Furthermore, swelling tests, rheological studies and actuation tests demonstrated that the water capacity and modulus of the hydrogels were dependent upon the composition of the block copolymer precursors.« less

PEO-b-P4VP/Yttrium Hydroxide Hybrid Nanotubes as Supporter for Catalyst Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Yang, Qian; Chen, Dao-yong

2012-06-01

The adsorption of poly (ethylene oxide)-b-poly(4-vinylpyridine)(PEO-b-P4VP) micelles onto the surface of yttrium hydroxide nanotubes (YNTs) resulted in the hybrid nanotubes with a dense P4VP inner layer and a stretched PEO outer layer surrounding YNTs. The dense P4VP layer was further stabilized by the crosslinking using 1,4-dibromobutane as the crosslinker. Then, the crosslinked hybrid nanotubes (CHNTs) were used as a novel nano supporter for loading the catalyst gold nanoparticles (GNPs) within the crosslinked P4VP layer. The resultant GNPs/CHNTs (GNTs loaded on CHNTs) were applied to catalyze the reduction reaction of p-nitrophenol. The results indicate that this novel nano supporter has advantages such as good dispersity in the suspension, high capacity in loading GNPs (0.87 mmol/g), high catalytic activity of the loaded GNPs (12.9 μmol-1min-1), and good reusability of GNTs/CHNTs.

A study of degradation resistance and cytocompatibility of super-hydrophobic coating on magnesium.

PubMed

Zhang, Yufen; Feyerabend, Frank; Tang, Shawei; Hu, Jin; Lu, Xiaopeng; Blawert, Carsten; Lin, Tiegui

2017-09-01

Calcium stearate based super-hydrophobic coating was deposited on plasma electrolytic oxidation (PEO) pre-treated magnesium substrate. The pre-treated magnesium and super-hydrophobic coating covered sample were characterized by scanning electron microscopy, X-ray diffraction and electrochemical corrosion measurements. The cytocompatibility and degradation resistance of magnesium, pre-treated magnesium and super-hydrophobic coating were analysed in terms of cell adhesion and osteoblast differentiation. The results indicate that the calcium stearate top coating shows super-hydrophobicity and that the surface is composed of micro/nanostructure. The super-hydrophobic coating covered sample shows higher barrier properties compared with the PEO pre-treated magnesium and bare magnesium. Human osteoblast proliferation, but not differentiation is enhanced by the PEO coating. Contrary, the super-hydrophobic coating reduces proliferation, but enhances differentiation of osteoblast, observable by the formation of hydroxyapatite. The combination of corrosion protection and cell reaction indicates that this system could be interesting for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

DOE PAGES

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.; ...

2015-07-10

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes.

PubMed

Savoie, Brett M; Webb, Michael A; Miller, Thomas F

2017-02-02

Solid polymer electrolytes (SPEs) have the potential to increase both the energy density and stability of lithium-based batteries, but low Li + conductivity remains a barrier to technological viability. SPEs are designed to maximize Li + diffusivity relative to the anion while maintaining sufficient salt solubility. It is thus remarkable that poly(ethylene oxide) (PEO), the most widely used SPE, exhibits Li + diffusivity that is an order of magnitude smaller than that of typical counterions at moderate salt concentrations. We show that Lewis-basic polymers like PEO favor slow cation and rapid anion diffusion, while this relationship can be reversed in Lewis-acidic polymers. Using molecular dynamics, polyboranes are identified that achieve up to 10-fold increases in Li + diffusivities and significant decreases in anion diffusivities, relative to PEO in the dilute-ion regime. These results illustrate a general principle for increasing Li + diffusivity and transference number with chemistries that exhibit weaker cation and stronger anion coordination.

Multivalent Ion Transport in Polymers via Metal-Ligand Coordination

NASA Astrophysics Data System (ADS)

Sanoja, Gabriel; Schauser, Nicole; Evans, Christopher; Majumdar, Shubhaditya; Segalman, Rachel

Elucidating design rules for multivalent ion conducting polymers is critical for developing novel high-performance materials for electrochemical devices. Herein, we molecularly engineer multivalent ion conducting polymers based on metal-ligand interactions and illustrate that both segmental dynamics and ion coordination kinetics are essential for ion transport through polymers. We present a novel statistical copolymer, poly(ethylene oxide-stat-imidazole glycidyl ether) (i.e., PEO-stat-PIGE), that synergistically combines the structural hierarchy of PEO with the Lewis basicity of tethered imidazole ligands (xIGE = 0.17) required to coordinate a series of transition metal salts containing bis(trifluoromethylsulfonyl)imide anions. Complexes of PEO-stat-PIGE with salts exhibit a nanostructure in which ion-enriched regions alternate with ion-deficient regions, and an ionic conductivity above 10-5 S/cm. Novel normalization schemes that account for ion solvation kinetics are presented to attain a universal scaling relationship for multivalent ion transport in polymers via metal-ligand coordination. AFOSR MURI program under FA9550-12-1.

Reciprocated suppression of polymer crystallization toward improved solid polymer electrolytes: Higher ion conductivity and tunable mechanical properties

DOE PAGES

Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; ...

2015-08-06

Solid polymer electrolytes based on lithium bis(trifluoromethanesulfonyl) imide and polymer matrix were extensively studied in the past due to their excellent potential in a broad range of energy related applications. Poly(vinylidene fluoride) (PVDF) and polyethylene oxide (PEO) are among the most examined polymer candidates as solid polymer electrolyte matrix. In this paper, we study the effect of reciprocated suppression of polymer crystallization in PVDF/PEO binary matrix on ion transport and mechanical properties of the resultant solid polymer electrolytes. With electron and X-ray diffractions as well as energy filtered transmission electron microscopy, we identify and examine the appropriate blending composition thatmore » is responsible for the diminishment of both PVDF and PEO crystallites. Laslty, a three-fold conductivity enhancement is achieved along with a highly tunable elastic modulus ranging from 20 to 200 MPa, which is expected to contribute toward future designs of solid polymer electrolytes with high room-temperature ion conductivities and mechanical flexibility.« less

Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes

PubMed Central

2015-01-01

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials. PMID:27162971

Development of electrospun nanofibers containing chitosan/PEO blend and phenolic compounds with antibacterial activity.

PubMed

Kuntzler, Suelen Goettems; Costa, Jorge Alberto Vieira; Morais, Michele Greque de

2018-05-31

Electrospun nanofibers can be formed with chitosan as the polymers found in biological sources have antibacterial ability. The objective of this work was to evaluate whether chitosan/polyethylene oxide (PEO) blend nanofibers containing microalgal phenolic compounds exhibit antibacterial activity. Nanofibers produced with a 3% chitosan/2% PEO blend containing 1% phenolic compounds had an average diameter of 214 ± 37 nm, which resulted in a high temperature of maximum degradation, an important parameter for food packaging. The potential antibacterial activity of this nanofibers was confirmed by their inhibition of Staphylococcus aureus ATCC 25923 (6.4 ± 1.1 mm) and Escherichia coli ATCC 25972 (5.5 ± 0.4 mm). The polymeric nanofibers produced from chitosan and containing phenolic compounds have properties that therefore allow their application as active packaging. In addition, chitosan is an excellent polymer for packaging as it presents biodegradability, biocompatibility and, non-toxicity. Copyright © 2018. Published by Elsevier B.V.

Degradation of cyanotoxins (microcystin) in drinking water using photoelectrooxidation.

PubMed

Garcia, A C A; Rodrigues, M A S; Xavier, J L N; Gazulla, V; Meneguzzi, A; Bernardes, A M

2015-05-01

The discharge of sewage and industrial effluents containing high concentrations of pollutants in water bodies increases eutrophication. Cyanobacteria, some of the organisms whose growth is promoted by high nutrient concentrations, are resistant and produce several types of toxins, known as cyanotoxins, highly harmful to human beings. Current water treatment systems for the public water supply are not efficient in degradation of toxins. Advanced oxidation processes (AOP) have been tested for the removal of cyanotoxins, and the results have been positive. This study examines the application of photoelectrooxidation in the degradation of cyanotoxins (microcystins). The performance of the oxidative processes involved was evaluated separately: Photocatalysis, Electrolysis and Photoelectrooxidation. Results showed that the electrical current and UV radiation were directly associated with toxin degradation. The PEO system is efficient in removing cyanotoxins, and the reduction rate reached 99%. The final concentration of toxin was less than 1 µg/L of microcystin in the treated solution.

A mechanistic investigation of thrombotic microangiopathy associated with IV abuse of Opana ER.

PubMed

Hunt, Ryan; Yalamanoglu, Ayla; Tumlin, James; Schiller, Tal; Baek, Jin Hyen; Wu, Andrew; Fogo, Agnes B; Yang, Haichun; Wong, Edward; Miller, Peter; Buehler, Paul W; Kimchi-Sarfaty, Chava

2017-02-16

Since 2012, a number of case reports have described the occurrence of thrombotic microangiopathy (TMA) following IV abuse of extended-release oxymorphone hydrochloride (Opana ER), an oral opioid for long-term treatment of chronic pain. Here, we present unique clinical features of 3 patients and investigate IV exposure to the tablet's inert ingredients as a possible causal mechanism. Guinea pigs were used as an animal model to understand the hematopathologic and nephrotoxic potential of the inert ingredient mixture (termed here as PEO+) which primarily contains high-molecular-weight polyethylene oxide (HMW PEO). Microangiopathic hemolytic anemia, thrombocytopenia, and acute kidney injury were found in a group of 3 patients following recent injection of adulterated extended-release oxymorphone tablets. Varying degrees of cardiac involvement and retinal ischemia occurred, with TMA evident on kidney biopsy. A TMA-like state also developed in guinea pigs IV administered PEO+. Acute tubular and glomerular renal injury was accompanied by nonheme iron deposition and hypoxia-inducible factor-1α upregulation in the renal cortex. Similar outcomes were observed following dosing with HMW PEO alone. IV exposure to the inert ingredients in reformulated extended-release oxymorphone can elicit TMA. Although prescription opioid abuse shows geographic variation, all physicians should be highly inquisitive of IV drug abuse when presented with cases of TMA.

Molecular Dynamics Simulations of Star Polymeric Molecules with Diblock Arms, a Comparative Study.

PubMed

Swope, William C; Carr, Amber C; Parker, Amanda J; Sly, Joseph; Miller, Robert D; Rice, Julia E

2012-10-09

We have performed all atom explicit solvent molecular dynamics simulations of three different star polymeric systems in water, each star molecule consisting of 16 diblock copolymer arms bound to a small adamantane core. The arms of each system consist of an inner "hydrophobic" block (either polylactide, polyvalerolactone, or polyethylene) and an outer hydrophilic block (polyethylene oxide, PEO). These models exhibit unusual structure very close to the core (clearly an artifact of our model) but which we believe becomes "normal" or bulk-like at relatively short distances from this core. We report on a number of temperature-dependent thermodynamic (structural/energetic) properties as well as kinetic properties. Our observations suggest that under physiological conditions, the hydrophobic regions of these systems may be solid and glassy, with only rare and shallow penetration by water, and that a sharp boundary exists between the hydrophobic cores and either the PEO or water. The PEO in these models is seen to be fully water-solvated at low temperatures but tends to phase separate from water as the temperature is increased, reminiscent of a lower critical solution temperature exhibited by PEO-water mixtures. Water penetration concentration and depth is composition and temperature dependent with greater water penetration for the most ester-rich star polymer.

Loss of efficiency of polymeric drag reducers induced by high Reynolds number flows in tubes with imposed pressure

NASA Astrophysics Data System (ADS)

Soares, Edson J.; Sandoval, Gustavo A. B.; Silveira, Lucas; Pereira, Anselmo S.; Trevelin, Renata; Thomaz, Fabricio

2015-12-01

This paper studies the loss of efficiency of polymeric drag reducers induced by high Reynolds number flows in tubes. The overall pressure was fixed and the apparatus was built so as to minimize the polymer degradation. We used three kinds of polymers: two flexible and one rigid. We conducted our tests to take into account the drag reduction (DR) for a wide range of concentrations of each polymer. The main results are displayed for the DR as a function of the number of passes through the apparatus. The mechanism of the loss of efficiency for the Xanthan Gum (XG) solutions (the rigid one) seems to be completely different from that observed for Poly (ethylene oxide) (PEO) and Polyacrylamide (PAM) (the flexible materials). While the PEO and PAM mechanically degrade by the action of the turbulent flow, the XG seems to remain intact, even after many passes through the pipe flow apparatus. From the practical point of view, it is worth noting that the PAM solutions are clearly more efficient than the PEO and XG. Another practical point that deserves attention is concerned with the asymptotic drag reduction found for XG. Although its maximum DR was significantly smaller than that found for PEO, the final value for both polymers were quite the same, which is obviously related to the intensified mechanical molecule scission in the PEO solutions. Our results for the relative drag reduction (the current value of DR divided by its maximum obtained at the first pass) was quite well fitted by the decay function proposed in our previous paper [A. S. Pereira and E. J. Soares, "Polymer degradation of dilute solutions in turbulent drag reducing flows in a cylindrical double gap rheometer device," J. Non-Newtonian Fluid Mech. 179, 9-22 (2012)], in which a rotating apparatus was used. This strongly suggests that the physical mechanism that governs the degradation phenomenon is independent of the geometry. We also used a degradation model for PEO proposed by Vonlanthen and Monkewitz ["Grid turbulence in dilute polymer solution: Peo in water," J. Fluid Mech. 730, 76-98 (2013)] to fit our data of relative drag reduction for PEO and PAM.

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. I. Structural properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2006-05-14

Molecular dynamics (MD) simulations have been performed for prototype models of polymer electrolytes in which the salt is an ionic liquid based on 1-alkyl-3-methylimidazolium cations and the polymer is poly(ethylene oxide), PEO. The MD simulations were performed by combining the previously proposed models for pure ionic liquids and polymer electrolytes containing simple inorganic ions. A systematic investigation of ionic liquid concentration, temperature, and the 1-alkyl- chain length, [1,3-dimethylimidazolium]PF6, and [1-butyl-3-methylimidazolium]PF6, effects on resulting equilibrium structure is provided. It is shown that the ionic liquid is dispersed in the polymeric matrix, but ionic pairs remain in the polymer electrolyte. Imidazolium cations are coordinated by both the anions and the oxygen atoms of PEO chains. Probability density maps of occurrences of nearest neighbors around imidazolium cations give a detailed physical picture of the environment experienced by cations. Conformational changes on PEO chains upon addition of the ionic liquid are identified. The equilibrium structure of simulated systems is also analyzed in reciprocal space by using the static structure factor, S(k). Calculated S(k) display a low wave-vector peak, indicating that spatial correlation in an extended-range order prevail in the ionic liquid polymer electrolytes. Long-range correlations are assigned to nonuniform distribution of ionic species within the simulation box.

Hard Pd Nanorods in the Soft Surfactant Mixture of CTAB and Pluronics: Seedless Synthesis and Their Self-Assembly.

PubMed

Song, Hyon-Min; Zink, Jeffrey I

2018-04-10

Seedless synthesis of Pd nanorods and their self-assembly into the layered smectic ordering are described. Aqueous Pluronic triblock copolymers (14.3-35.7%) are used as a soft template along with cetyltrimethylammonium bromide for inducing one-dimensional growth of Pd nanorods. Pluronic triblock copolymers are probably the most used polymer surfactants, and they are composed of poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO triblocks. Neither pH adjustment nor AgNO 3 and other additives, such as poly(vinyl pyrrolidone) and ethylene glycol, are required to obtain Pd nanorods. Sonochemical synthesis at 43 °C, followed by thermal annealing for 1 h at 65 °C produces Pd nanorods with the aspect ratio from 3.1 (17.9%, Pluronic L-64) to 6.7 (35.7%, Pluronic P-123). Two-dimensional self-assembly of the nanorods is observed, and both nematic ordering between the mesogens and smectic ordering between the layers is identified. Micellar hydrophobic PPO with hydrated PEO coronas are known to self-assemble into many crystalline orders, including cubic, hexagonal, lamellar, and inverse hexagonal mesophases, which extend into cylindrical micelles with increasing temperature. Relatively small size of Pluronic copolymers with regard to general polymers, but rather large size of their micelles and their tendency to organize into crystalline mesophases are thought to contribute to the anisotropic growth of Pd nanorods.

Synthesis of high molecular weight PEO using non-metal initiators

DOEpatents

Yang, Jin; Sivanandan, Kulandaivelu; Pistorino, Jonathan; Eitouni, Hany Basam

2015-05-19

A new synthetic method to prepare high molecular weight poly(ethylene oxide) with a very narrow molecular weight distribution (PDI<1.5) is described. The method involves a metal free initiator system, thus avoiding dangerous, flammable organometallic compounds.

Tablet coating by injection molding technology - Optimization of coating formulation attributes and coating process parameters.

PubMed

Desai, Parind M; Puri, Vibha; Brancazio, David; Halkude, Bhakti S; Hartman, Jeremy E; Wahane, Aniket V; Martinez, Alexander R; Jensen, Keith D; Harinath, Eranda; Braatz, Richard D; Chun, Jung-Hoon; Trout, Bernhardt L

2018-01-01

We developed and evaluated a solvent-free injection molding (IM) coating technology that could be suitable for continuous manufacturing via incorporation with IM tableting. Coating formulations (coating polymers and plasticizers) were prepared using hot-melt extrusion and screened via stress-strain analysis employing a universal testing machine. Selected coating formulations were studied for their melt flow characteristics. Tablets were coated using a vertical injection molding unit. Process parameters like softening temperature, injection pressure, and cooling temperature played a very important role in IM coating processing. IM coating employing polyethylene oxide (PEO) based formulations required sufficient room humidity (>30% RH) to avoid immediate cracks, whereas other formulations were insensitive to the room humidity. Tested formulations based on Eudrajit E PO and Kollicoat IR had unsuitable mechanical properties. Three coating formulations based on hydroxypropyl pea starch, PEO 1,000,000 and Opadry had favorable mechanical (<700MPa Young's modulus, >35% elongation, >95×10 4 J/m 3 toughness) and melt flow (>0.4g/min) characteristics, that rendered acceptable IM coats. These three formulations increased the dissolution time by 10, 15 and 35min, respectively (75% drug release), compared to the uncoated tablets (15min). Coated tablets stored in several environmental conditions remained stable to cracking for the evaluated 8-week time period. Copyright © 2017 Elsevier B.V. All rights reserved.

Liquid eutectic GaIn as an alternative electrode for PTB7:PCBM organic solar cells

NASA Astrophysics Data System (ADS)

Thanh Hau Pham, Viet; Kieu Trinh, Thanh; Tam Nguyen Truong, Nguyen; Park, Chinho

2017-04-01

Conventional vacuum deposition process of aluminum (Al) is costly, time-consuming and difficult to apply to the large-scale production of organic photovoltaic devices (OPV). This paper reports a vacuum-free fabrication process of poly[[4,8-bis(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b‧]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thienophenediyl]:[6,6]-phenyl C71 butyric acid methyl ester (PTB7:PCBM) bulk heterojunction organic solar cell with liquid eutectic gallium-indium (EGaIn) electrode as an alternative to the common Al electrode. The insertion of a thin poly(ethylene oxide) (PEO) layer after depositing organic photoactive layer could help prevent the diffusion of liquid EGaIn into the active layer and allow the deposition of the EGaIn electrode. The PEO interfacial layer was formed by spin-coating from a mixed solvent of alcohol and water. Among different alcohol+water (methanol, ethanol, ethylene glycol, n-propanol, isopropanol, and isobutanol) mixed solvent tested, the n-propanol+water mixed solvent showed the greatest enhancement to the performance of OPVs. The improved device performance was attributed to the reactivity of mixed solvent n-propanol+water toward the surface of PTB7:PCBM active layer, which could help optimize surface morphology.

Study of Polymer Crystallization by Physical Vapor Deposition

NASA Astrophysics Data System (ADS)

Jeong, Hyuncheol

When a polymer is confined under the submicron length scale, confinement size and interfaces can significantly impact the crystallization kinetics and resulting morphology. The ability to tune the morphology of confined polymer systems is of critical importance for the development of high-performance polymer microelectronics. The wisdom from the research on confined crystallization suggests that it would be beneficial to have a processing route in which the crystallization of polymers is driven by interface and temperature effects at a nanometer-scale confinement. In practice, for atomic and small-molecular systems, physical vapor deposition (PVD) has been recognized as the most successful processing route for the precise control of the film structure at surface utilizing confinement effects. While standard PVD technologies are not generally applicable to the deposition of the chemically fragile macromolecules, the development of matrix-assisted pulsed laser evaporation (MAPLE) now enables the non-destructive PVD of high-molecular weight polymers. In this thesis work, we investigated the use of MAPLE for the precise control of the crystallization of polymer films at a molecular level. We also sought to decipher the rules governing the crystallization of confined polymers, by using MAPLE as a tool to form confined polymer systems onto substrates with a controlled temperature. We first explored the early stages of film growth and crystallization of poly(ethylene oxide) (PEO) at the substrate surface formed by MAPLE. The unique mechanism of film formation in MAPLE, the deposition of submicron-sized polymer droplets, allowed for the manifestation of confinement and substrate effects in the crystallization of MAPLE-deposited PEO. Furthermore, we also focused on the property of the amorphous PEO film formed by MAPLE, showing the dependence of polymer crystallization kinetics on the thermal history of the amorphous phase. Lastly, we probed how MAPLE processing affected the semi-crystalline structure in MAPLE-deposited polyethylene (PE) films. Depositing PE at various temperatures remarkably allowed for the tunability of the melting temperature and crystallinity of the PE films, thus manipulating the semi-crystalline structure. By comparing the structure of PE formed by different processing routes, i.e., MAPLE and melt-crystallization, we discussed how processing routes affect the development of semi-crystalline phase in polymer films.

Understanding ion association states and molecular dynamics using infrared spectroscopy

NASA Astrophysics Data System (ADS)

Masser, Hanqing

A molecular level understanding of the ion transport mechanism within polymer electrolytes is crucial to the further development for advanced energy storage applications. This can be achieved by the identification and quantitative measurement of different ion species in the system and further relating them to the ion conductivity. In the first part of this thesis, research is presented towards understanding the ion association states (free ions, ion pairs and ion aggregates) in ionomer systems, and the correlation of ion association states, ion conduction, polymer dynamics, and morphology. Ion conductivity in ionomers can be improved by lowering glass transition temperature, increasing polymer ion solvation ability, and adjusting ionomer structural variables such as ion content, cation type and side chain structure. These effects are studied in three ionomer systems respectively, using a combination of characterization methods. Fourier Transform Infrared Spectroscopy (FTIR) identifies and quantifies the ion association states. Dielectric Spectroscopy (DRS) characterizes ion conductivity and polymer and ion dynamics. X-ray scattering reveals changes in morphology. The influence of a cation solvating plasticizer on a polyester ionomer is systematically investigated with respect to ion association states, ion and polymer dynamics and morphology. A decrease in the number ratio of ion aggregates with increased plasticizer content and a slight increase at elevated temperature are observed in FTIR. Similar results are also detected by X-ray scattering. As determined from dielectric spectroscopy, ion conductivity increases with plasticizer content, in accordance with the decrease in glass transition temperature. Research on copolymer of poly(ethylene oxide) (PEO) and poly(tetramethylene oxide) (PTMO) based ionomers further develops an understanding of the trade-off between ion solvation and segmental dynamics. Upon the incorporation of PTMO, the majority of the PTMO microphase separates from the PEO-rich microphase, and ionic groups are preferentially solvated by PEO chains and reside in the PEO-rich microphase. As the ratio of PTMO increases, the fraction of aggregates increases, resulting in more highly coordinated aggregation states. Results on ion association states are in good agreement with previous results on ion conductivity, polymer dynamics and morphology. The effects of ion content, cation type and ionic side chain structure on ion association states are systemically studied in a series of ionomers with short ethylene oxide and ionic sulfonated styrene side chains, and then correlated to the ion and polymer dynamic characterization. It is found that ionomers with modest ion content, large cation and styrene ionic side chain have the most "free ions" and ion pairs, and highest ion conductivity. Ion conduction in ionomers is optimized by systematically changing their chemical structures. In addition to knowledge of ion association states, a IR band shape also contains information on molecular dynamics. In companion investigation, the vibrational relaxation and dynamic transitions of conformationally insensitive normal modes in two different polymer systems (atactic polystyrene and deuterated poly(methyl methacrylate)) are studied. The information on vibrational relaxations is resolved by conducting precisely controlled FTIR experiments, applying specialized curve resolving data analysis, and calculating time correlation functions through numerical Fourier transformation. The vibrational relaxations of these modes can be described by a two process model: a fast process on the time scale of 0.01 ps, which is inhomogeneously broadened by a slow process on the time scale of picoseconds.

Synthesis and Characterization of Hydrophilic-Hydrophobic Poly(Arylene Ether Sulfone) Random and Segmented Copolymers for Membrane Applications

NASA Astrophysics Data System (ADS)

Nebipasagil, Ali

Poly(arylene ether sulfone)s are high-performance engineering thermoplastics that have been investigated extensively over the past several decades due to their outstanding mechanical properties, high glass transition temperatures (Tg), solvent resistance and exceptional thermal, oxidative and hydrolytic stability. Their thermal and mechanical properties are highly suited to a variety of applications including membrane applications such as reverse osmosis, ultrafiltration, and gas separation. This dissertation covers structure-property-performance relationships of poly(arylene ether sulfone) and poly(ethylene oxide)-containing random and segmented copolymers for reverse osmosis and gas separation membranes. The second chapter of this dissertation describes synthesis of disulfonated poly(arylene ether sulfone) random copolymers with oligomeric molecular weights that contain hydrophilic and hydrophobic segments for thin film composite (TFC) reverse osmosis membranes. These copolymers were synthesized and chemically modified to obtain novel crosslinkable poly(arylene ether sulfone) oligomers with acrylamide groups on both ends. The acrylamideterminated oligomers were crosslinked with UV radiation in the presence of a multifunctional acrylate and a UV initiator. Transparent, dense films were obtained with high gel fractions. Mechanically robust TFC membranes were prepared from either aqueous or water-methanol solutions cast onto a commercial UDELRTM foam support. This was the first example that utilized a water or alcohol solvent system and UV radiation to obtain reverse osmosis TFC membranes. The membranes were characterized with regard to composition, surface properties, and water uptake. Water and salt transport properties were elucidated at the department of chemical engineering at the University of Texas at Austin. The gas separation membranes presented in chapter three were poly(arylene ether sulfone) and poly(ethylene oxide) (PEO)-containing polyurethanes. Poly(arylene ether sulfone) copolymers with controlled molecular weights were synthesized and chemically modified to obtain poly(arylene ether sulfone) polyols with aliphatic hydroxyethyl terminal functionality. The hydroxyethyl-terminated oligomers and a,u-hydroxy-terminated PEO were chain extended with a diisocyanate to obtain polyurethanes. Compositions with high poly(arylene ether sulfone) content relative to the hydrophilic PEO blocks were of interest due to their mechanical integrity. The membranes were characterized to analyze their compositions, thermal and mechanical properties, water uptake, and molecular weights. These membranes were also evaluated by collaborators at the University of Texas at Austin to explore single gas transport properties. The results showed that both polymer and transport properties closely related to PEO-content. The CO2/CH4 gas selectivity of our membranes were improved from 25 to 34 and the CO2/N2 gas selectivity nearly doubled from 25 to 46 by increasing PEO-content from 0 to 30 wt.% in polyurethanes. Chapter four also focuses on polymers for gas separation membranes. Disulfonated poly(arylene ether sulfone) and poly(ethylene oxide)-containing polyurethanes were synthesized for potential applications as gas separation membranes. Disulfonated polyols containing 20 and 40 mole percent of disulfonated repeat units with controlled molecular weights were synthesized. Poly(arylene ether sulfone) polyols and alpha,o-hydroxy-terminated poly(ethylene oxide) were subsequently chain extended with a diisocyanate to obtain polyurethanes. Thermal and mechanical characterization revealed that the polyurethanes had a phase-mixed complex morphology.

Core-shell-corona micelles by PS-b-P2VP-b-PEO copolymers: focus on the water-induced micellization process.

PubMed

Willet, Nicolas; Gohy, Jean-François; Auvray, Loïc; Varshney, Sunil; Jérôme, Robert; Leyh, Bernard

2008-04-01

It is now well established that amphiphilic PS-b-P2VP-b-PEO linear triblock copolymers can form multilayered assemblies, thus core-shell-corona (CSC) micelles, in water. Micellization is triggered by addition of a small amount of water into a dilute solution of the PS-b-P2VP-b-PEO copolymer in a non-selective organic solvent. However, the phenomena that take place at the very beginning of this process are poorly documented. How these copolymer chains are perturbed by addition of water was investigated in this work by light and neutron scattering techniques and transmission electron microscopy. It was accordingly possible to determine the critical water concentration (CWC), the compactness of the nano-objects in solution, their number of aggregation, and their hydrodynamic diameter at each step of the micellization process.

Low-temperature roll-to-roll coating procedure of dye-sensitized solar cell photoelectrodes on flexible polymer-based substrates

NASA Astrophysics Data System (ADS)

Tinguely, Jean-Claude; Solarska, Renata; Braun, Artur; Graule, Thomas

2011-04-01

A new approach for the large-scale production of flexible photoelectrodes for dye-sensitized solar cells (DSSCs) is presented by roll-to-roll coating of a titanium dioxide nanodispersion containing the block copolymer 'Pluronic®' (PEOx-PPOy-PEOx, PEO: poly(ethylene oxide), PPO: poly(propylene oxide)). Functional DSSCs were assembled and the different coating procedures compared with respect to their solar power conversion efficiency. It is shown that the binder 'Pluronic' can be removed at processing temperatures as low as 140 °C, thus aiding achievement of sufficient adhesion to the ITO-PET support, higher porosity of the TiO2 layer and decreased crack appearance. Further optimization of this method is particularly promising when combined with other known low-temperature methods.

Characterization of the organic ligand shell of semiconductor quantum dots by fluorescence quenching experiments.

PubMed

Boldt, Klaus; Jander, Sebastian; Hoppe, Kathrin; Weller, Horst

2011-10-25

We present the characterization of the organic ligand shell of CdSe/Cd(x)Zn(1-x)S/ZnS nanoparticles by means of fluorescence quenching experiments. Both electron scavengers and acceptors for resonance energy transfer were employed as probes. Different quenching behavior for short and long chain thiol ligands in water was found. It could be shown that poly(ethylene oxide) (PEO)-capping of the particles comprises a densely packed inner shell and a loosely packed outer shell in which ions and small molecules diffuse unhindered. A quantitative uptake of quencher molecules into the PEO shell was observed, through which the particle volume including the ligand sphere could be determined.

Composite polymer-containing coatings on Mg alloys perspective for industry and implant surgery

NASA Astrophysics Data System (ADS)

Gnedenkov, S. V.; Sinebryukhov, S. L.; Mashtalyar, D. V.; Imshinetskiy, I. M.; Gnedenkov, A. S.; Minaev, A. N.

2017-09-01

In order to improve the corrosion resistance of magnesium alloys the ways of composite protective coating formation were developed by means of plasma electrolytic oxidation (PEO) as well as electrophoretic deposition methods. Electrochemical, corrosion, tribological, and morphological properties of the MAS magnesium alloy composite coatings were studied. The composite polymer-containing coating decrease the corrosion current density values by three orders of magnitude (Ic = 2.0 . 10-10 A/cm2), in comparison with the base PEO-layer. These polymer-containing layers enable one to expand the practical usage area of Mg alloys. The application of such coatings provides the increasing the bioactivity and regulate the corrosion rate of resorbable magnesium implants.

High shear microfluidics and its application in rheological measurement

NASA Astrophysics Data System (ADS)

Kang, Kai; Lee, L. James; Koelling, Kurt W.

2005-02-01

High shear rheology was explored experimentally in microchannels (150×150 μm). Two aqueous polymer solutions, polyethylene oxide (viscoelastic fluid) and hydroxyethyl cellulose (viscous fluid) were tested. Bagley correction was applied to remove the end effect. Wall slip was investigated with Mooney’s analysis. Shear rates as high as 106 s-1 were obtained in the pressure-driven microchannel flow, allowing a smooth extension of the low shear rheological data obtained from the conventional rheometers. At high shear rates, polymer degradation was observed for PEO solutions at a critical microchannel wall shear stress of 4.1×103 Pa. Stresses at the ends of the microchannel also contributed to PEO degradation significantly.

Size and space controlled hexagonal arrays of superparamagnetic iron oxide nanodots: magnetic studies and application

PubMed Central

Ghoshal, Tandra; Maity, Tuhin; Senthamaraikannan, Ramsankar; Shaw, Matthew T.; Carolan, Patrick; Holmes, Justin D.; Roy, Saibal; Morris, Michael A.

2013-01-01

Highly dense hexagonally arranged iron oxide nanodots array were fabricated using PS-b-PEO self-assembled patterns. The copolymer molecular weight, composition and choice of annealing solvent/s allows dimensional and structural control of the nanopatterns at large scale. A mechanism is proposed to create scaffolds through degradation and/or modification of cylindrical domains. A methodology based on selective metal ion inclusion and subsequent processing was used to create iron oxide nanodots array. The nanodots have uniform size and shape and their placement mimics the original self-assembled nanopatterns. For the first time these precisely defined and size selective systems of ordered nanodots allow careful investigation of magnetic properties in dimensions from 50 nm to 10 nm, which delineate the nanodots are superparamagnetic, well-isolated and size monodispersed. This diameter/spacing controlled iron oxide nanodots systems were demonstrated as a resistant mask over silicon to fabricate densely packed, identical ordered, high aspect ratio silicon nanopillars and nanowire features. PMID:24072037

Preparation of Proton Exchange Membranes and Lithium Batteries from Melamine-containing Ormosils

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Kinder, James D.; Meador, Mary Ann; Waldecker, James; Bennett, William R.

2004-01-01

Our laboratory has recently reported a series of rodcoil polymers for lithium batteries that display dimensionally stable films with good ionic conductivity. The rod segments consist of rigid linear and branched polyimides and the coil segments are polyethylene oxides (PEO). It has been proposed that good mechanical and transport properties are due to phase separation between the rod and coil segments. It was also observed that increased branching and molecular weight lead to increased conductivity. The following study was undertaken to assess the effects of phase separation in polyalkylene oxides connected by melamine linkages. Melamine was chosen as the linking unit because it provides a branching site, cation binding sites to help ionic transport between polymer chains, and the opportunity for self assembly through hydrogen bonding. Polymers were made by the reaction of cyanuric chloride with a series of amine-terminated alkylene oxides. A linear polymer was first made, followed by reaction of the third site on cyanuric chloride with varying ratios of monofunctional Jeffamine and (3-aminopropyl)triethoxysilane. The lithium trifluoromethane sulfonamide-doped polymers are then crosslinked through a sol-gel process to form free-standing films. Initial results have shown mechanically strong films with lithium conductivities on the order of 2 x 10(exp -5) S/cm at ambient temperature. In a separate study, organically modified silanes (Ormosils) that contain sulfonic acid derivatized melamines have been incorporated into proton exchange membranes. The membranes are made by reaction of the primary amine groups of various ratios of melamine derivative and difunctional Jeffamine (MW = 2000) with the epoxide group of (3-Glycidyloxypropyl)trimethoxysilane. The films were then cross-linked through a sol-gel process. Resulting sulfuric acid doped films are strong, flexible, and have proton conductivities on the order of 2 x l0(exp -2) S/cm (120 C, 25% relative humidity). Our best results have been observed when films contain 60% PEO and 40% sulfonated melamine.

Effect of chain length on binding of fatty acids to Pluronics in microemulsions.

PubMed

James-Smith, Monica A; Shekhawat, Dushyant; Cheung, Sally; Moudgil, Brij M; Shah, Dinesh O

2008-03-15

We investigated the effect of fatty acid chain length on the binding capacity of drug and fatty acid to Pluronic F127-based microemulsions. This was accomplished by using turbidity experiments. Pluronic-based oil-in-water microemulsions of various compositions were synthesized and titrated to turbidity with concentrated Amitriptyline, an antidepressant drug. Sodium salts of C(8), C(10), or C(12) fatty acid were used in preparation of the microemulsion and the corresponding binding capacities were observed. It has been previously determined that, for microemulsions prepared with sodium caprylate (C(8) fatty acid soap), a maximum of 11 fatty acid molecules bind to the microemulsion per 1 molecule of Pluronic F127 and a maximum of 12 molecules of Amitriptyline bind per molecule of F127. We have found that with increasing the chain length of the fatty acid salt component of the microemulsion, the binding capacity of both the fatty acid and the Amitriptyline to the microemulsion decreases. For sodium salts of C(8), C(10) and C(12) fatty acids, respectively, a maximum of approximately 11, 8.4 and 8.3 molecules of fatty acid molecules bind to 1 Pluronic F127 molecule. We propose that this is due to the decreasing number of free monomers with increasing chain length. As chain length increases, the critical micelle concentration (cmc) decreases, thus leading to fewer monomers. Pluronics are symmetric tri-block copolymers consisting of propylene oxide (PO) and ethylene oxide (EO). The polypropylene oxide block, PPO is sandwiched between two polyethylene oxide (PEO) blocks. The PEO blocks are hydrophilic while PPO is hydrophobic portion in the Pluronic molecule. Due to this structure, we propose that the fatty acid molecules that are in monomeric form most effectively diffuse between the PEO "tails" and bind to the hydrophobic PPO groups.

A Combination Tissue Engineering Strategy for Schwann Cell-Induced Spinal Cord Repair

DTIC Science & Technology

2016-10-01

block copolymer consisting of polyethylene oxide (PEO) and polypropylene oxide (PPO). It has thermoreversible gelation properties when used at...high; Zeus Inc., Orangeburg, SC) were placed on top of the aligned and random fibrous PVDF-TrFE disks in 96-well polypropylene plates to prevent them...2011. Preparation of spinal cord injured tissue for light and electron microscopy including preparation for immunostaining. In: Lane LE , Dunnett BS

Electrospinning chitosan/poly(ethylene oxide) solutions with essential oils: Correlating solution rheology to nanofiber formation.

PubMed

Rieger, Katrina A; Birch, Nathan P; Schiffman, Jessica D

2016-03-30

Electrospinning hydrophilic nanofiber mats that deliver hydrophobic agents would enable the development of new therapeutic wound dressings. However, the correlation between precursor solution properties and nanofiber morphology for polymer solutions electrospun with or without hydrophobic oils has not yet been demonstrated. Here, cinnamaldehyde (CIN) and hydrocinnamic alcohol (H-CIN) were electrospun in chitosan (CS)/poly(ethylene oxide) (PEO) nanofiber mats as a function of CS molecular weight and degree of acetylation (DA). Viscosity stress sweeps determined how the oils affected solution viscosity and chain entanglement (Ce) concentration. Experimentally, the maximum polymer:oil mass ratio electrospun was 1:3 and 1:6 for CS/PEO:CIN and:H-CIN, respectively; a higher chitosan DA increased the incorporation of H-CIN only. The correlations determined for electrospinning plant-derived oils could potentially be applied to other hydrophobic molecules, thus broadening the delivery of therapeutics from electrospun nanofiber mats. Copyright © 2015 Elsevier Ltd. All rights reserved.

Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

2016-02-01

The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

The diffusion and conduction of lithium in poly(ethylene oxide)-based sulfonate ionomers

NASA Astrophysics Data System (ADS)

LaFemina, Nikki H.; Chen, Quan; Colby, Ralph H.; Mueller, Karl T.

2016-09-01

Pulsed field gradient nuclear magnetic resonance spectroscopy and dielectric relaxation spectroscopy have been utilized to investigate lithium dynamics within poly(ethylene oxide) (PEO)-based lithium sulfonate ionomers of varying ion content. The ion content is set by the fraction of sulfonated phthalates and the molecular weight of the PEO spacer, both of which can be varied independently. The molecular level dynamics of the ionomers are dominated by either Vogel-Fulcher-Tammann or Arrhenius behavior depending on ion content, spacer length, temperature, and degree of ionic aggregation. In these ionomers the main determinants of the self-diffusion of lithium and the observed conductivities are the ion content and ionic states of the lithium ion, which are profoundly affected by the interactions of the lithium ions with the ether oxygens of the polymer. Since many lithium ions move by segmental polymer motion in the ion pair state, their diffusion is significantly larger than that estimated from conductivity using the Nernst-Einstein equation.

Polyethylene Oxide Films Polymerized by Radio Frequency Plasma-Enhanced Chemical Vapour Phase Deposition and Its Adsorption Behaviour of Platelet-Rich Plasma

NASA Astrophysics Data System (ADS)

Hu, Wen-Juan; Xie, Fen-Yan; Chen, Qiang; Weng, Jing

2008-10-01

We present polyethylene oxide (PEO) functional films polymerized by rf plasma-enhanced vapour chemical deposition (rf-PECVD) on p-Si (100) surface with precursor ethylene glycol dimethyl ether (EGDME) and diluted Ar in pulsed plasma mode. The influences of discharge parameters on the film properties and compounds are investigated. The film structure is analysed by Fourier transform infrared (FTIR) spectroscopy. The water contact angle measurement and atomic force microscope (AFM) are employed to examine the surface polarity and to detect surface morphology, respectively. It is concluded that the smaller duty cycle in pulsed plasma mode contributes to the rich C-O-C (EO) group on the surfaces. As an application, the adsorption behaviour of platelet-rich plasma on plasma polymerization films performed in-vitro is explored. The shapes of attached cells are studied in detail by an optic invert microscope, which clarifies that high-density C-O-C groups on surfaces are responsible for non-fouling adsorption behaviour of the PEO films.

Triblock copolymer-mediated synthesis of catalytically active gold nanostructures

NASA Astrophysics Data System (ADS)

Santos, Douglas C.; de Souza, Viviane C.; Vasconcelos, Diego A.; Andrade, George R. S.; Gimenez, Iara F.; Teixeira, Zaine

2018-04-01

The design of nanostructures based on poly(ethylene oxide)-poly(propylene)-poly(ethylene oxide) (PEO-PPO-PEO) and metal nanoparticles is becoming an important research topic due to their multiple functionalities in different fields, including nanomedicine and catalysis. In this work, water-soluble gold nanoparticles have been prepared through a green aqueous synthesis method using Pluronic F127 as both reducing and stabilizing agents. The size dependence (varying from 2 to 70 nm) and stability of gold nanoparticles were systematically studied by varying some parameters of synthesis, which were the polymer concentration, temperature, and exposure to UV-A light, being monitored by UV-Vis spectroscopy and TEM. Also, an elaborated study regarding to the kinetic of formation (nucleation and growth) was presented. Finally, the as-prepared Pluronic-capped gold nanoparticles have shown excellent catalytic activity towards the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride, in which a higher catalytic performance was exhibited when compared with gold nanoparticles prepared by classical reduction method using sodium citrate. [Figure not available: see fulltext.

Effect of blending and nanoparticles on the ionic conductivity of solid polymer electrolyte systems

NASA Astrophysics Data System (ADS)

Manjunatha, H.; Damle, R.; Kumaraswamy, G. N.

2018-05-01

In the present work, a polymer electrolyte blend containing polymers Poly ethylene oxide (PEO) and Poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) was prepared. The polymer blend was complexed with potassium trifluoromethanesulfonate (KCF3SO3), and titanium oxide nanoparticles (TiO2) (10nm size) were dispersed in to the complex at different weight percentages. The conductivity due to ions in the blend is determined by Ac impedance measurements in the frequency range of 10Hz-1MHz. The nano composite polymer blend containing 5wt% of TiO2 shows a conductivity of 7.95×10-5Scm-1, which is almost 1.5 orders more than polymer electrolyte with PEO as a polymer. XRD studies show a decrease in the coherence length of XRD peaks on addition of nanoparticles, which is due to increase the amorphous phase in the systems. Temperature dependence conductivity studies of the systems shows that, activation energy decreases with increase in the percentage of nanoparticles in the blend.

Metal adsorption of gamma-irradiated carboxymethyl cellulose/polyethylene oxide blend films

NASA Astrophysics Data System (ADS)

El-Naggar, Amal A.; Magida, M. M.; Ibrahim, Sayeda M.

2016-03-01

Blend films of different ratios of carboxymethyl cellulose (CMC)/polyethylene oxide (PEO) were prepared by the solution casting method. To investigate the effect of irradiation on all properties of prepared blend, it was exposed to different gamma irradiation doses (10, 20, and 30 kGy). Physical properties such as gel fraction (GF) (%) and swelling (SW) (%) were investigated. It was found that the GF (%) increases with increasing irradiation dose up to 20 kGy, while SW (%) decreases with an increase in the irradiation doses for all blend compositions. Moreover, the structural and mechanical properties of the prepared films were studied. The results of the mechanical properties obtained showed that there is an improvement in these properties with an increase in both CMC and irradiation dose up to 20 kGy. The efficiency of metal ions uptake was measured using a UV spectrophotometer. The prepared films showed good tendency to absorb and release metal ions from aqueous media. Thus, the CMC/PEO film can be used in agricultural domain.

Comparison of Different Ion Mobility Setups Using Poly (Ethylene Oxide) PEO Polymers: Drift Tube, TIMS, and T-Wave

NASA Astrophysics Data System (ADS)

Haler, Jean R. N.; Massonnet, Philippe; Chirot, Fabien; Kune, Christopher; Comby-Zerbino, Clothilde; Jordens, Jan; Honing, Maarten; Mengerink, Ynze; Far, Johann; Dugourd, Philippe; De Pauw, Edwin

2018-01-01

Over the years, polymer analyses using ion mobility-mass spectrometry (IM-MS) measurements have been performed on different ion mobility spectrometry (IMS) setups. In order to be able to compare literature data taken on different IM(-MS) instruments, ion heating and ion temperature evaluations have already been explored. Nevertheless, extrapolations to other analytes are difficult and thus straightforward same-sample instrument comparisons seem to be the only reliable way to make sure that the different IM(-MS) setups do not greatly change the gas-phase behavior. We used a large range of degrees of polymerization (DP) of poly(ethylene oxide) PEO homopolymers to measure IMS drift times on three different IM-MS setups: a homemade drift tube (DT), a trapped (TIMS), and a traveling wave (T-Wave) IMS setup. The drift time evolutions were followed for increasing polymer DPs (masses) and charge states, and they are found to be comparable and reproducible on the three instruments. [Figure not available: see fulltext.

Dependence on sphere size of the phase behavior of mixtures of rods and spheres

NASA Astrophysics Data System (ADS)

Urakami, Naohito; Imai, Masayuki

2003-07-01

By the addition of chondroitin sulfate (Chs) to the aqueous suspension of tobacco mosaic virus (TMV), the aggregation of TMV occurs at very dilute TMV concentration compared with the addition of polyethylene oxide (PEO). The difference of physical behavior between Chs and PEO is the chain conformation in solution. The Chs chain has a semirigid nature, whereas the PEO chain has a flexible nature. In this study, the Chs and PEO chains are simplified to spherical particles having different size, and we use the spherocylinder model for TMV particle. The effect of the sphere size on the phase behaviors in the mixtures of rods and spheres is investigated by Monte Carlo simulations. By the addition of small spheres, the system transforms from the miscible isotropic phase to the miscible nematic phase. On the other hand, by the addition of large spheres, the system changes from the miscible isotropic phase to the immiscible nematic phase through the immiscible isotropic phase. The different phase behaviors between the small and the large spheres originate from the difference of overlapping volume of the depletion zone. In addition, we perform the Monte Carlo simulations in the case that semirigid chains are used as the Chs chain models. The same phase behaviors are observed as the mixtures of rods and large spheres. Thus the sphere model captures the phase behaviors of rod and polymer mixture systems.

Dual aging behaviour in a clay-polymer dispersion.

PubMed

Zulian, Laura; Augusto de Melo Marques, Flavio; Emilitri, Elisa; Ruocco, Giancarlo; Ruzicka, Barbara

2014-07-07

Clay-polymer compounds have recently attracted increasing attention due to their intriguing physical properties in colloidal science and their rheological non-trivial behaviour in technological applications. Aqueous solutions of Laponite clay spontaneously age from a liquid up to an arrested state of different nature (gel or glass) depending on the colloidal volume fraction and ionic strength. We have investigated, through dynamic light scattering, how the aging dynamics of Laponite dispersions at fixed clay concentration (Cw = 2.0%) is modified by the addition of various amounts of poly(ethylene oxide) (PEO) (CPEO = (0.05 ÷ 0.50) %) at two different molecular weights (Mw = 100 kg mol(-1) and Mw = 200 kg mol(-1)). A surprising and intriguing phenomenon has been observed: the existence of a critical polymer concentration C that discriminates between two different aging dynamics. With respect to pure Laponite systems the aging will be assisted (faster) or hindered (slower) for PEO concentrations respectively lower (CPEO < C) or higher (CPEO > C) than the critical concentration. In this way a control on the aging dynamics of PEO-Laponite systems is obtained. A possible explanation based on the balance of competitive mechanisms related to the progressive saturation of the clay surface by polymers is proposed. This study shows how a real control on the aging speed of the PEO-Laponite system is at hand and renders possible a real control of the complex interparticle interaction potential.

Self-assembled mesoporous TiO2/carbon nanotube composite with a three-dimensional conducting nanonetwork as a high-rate anode material for lithium-ion battery

NASA Astrophysics Data System (ADS)

Wang, Jie; Ran, Ran; Tade, Moses O.; Shao, Zongping

2014-05-01

Mesoporous three-dimensional (3D) TiO2/carbon nanotube conductive hybrid nanostructures can be successfully developed using polyethylene oxide (PEO) to modify the surfaces of carbon nanotubes (CNTs). During the synthesis process, PEO acts as not only "bridges" to connect the TiO2 nanoparticles to the CNT surfaces but also as "hosts" to accommodate and stabilize the in situ generated TiO2 particles. As the electrodes for lithium-ion batteries, such mesoporous 3D TiO2/CNT hybrids, demonstrate high Li storage capacity, superior rate performance and excellent long-term cycling stability. They exhibit a reversible specific capacity of 203 mA h g-1 at 100 mA g-1 and a stable capacity retention of 91 mA h g-1 at 8000 mA g-1 (47.6 C) over 100 cycles; they also retain approximately 90% (71 mA h g-1) of their initial discharge capacity after 900 cycles at an extremely high rate of 15,000 mA g-1 (89 C). This facile synthetic strategy to construct mesoporous 3D TiO2/CNT conductive hybrids provides a convenient route that efficiently assembles various inorganic oxide components on the CNTs' surfaces and enables the formation of heterogeneous nanostructures with novel functionalities. In particular, utilizing a conductive 3D CNT network can serve as a promising strategy for developing high-performance electrodes for Li secondary batteries and supercapacitors.

Conductivity and Thermal Studies on Plasticized Nano-Composite Solid Polymer Electrolyte, Peo: Ec: LiTf: Al2O3

NASA Astrophysics Data System (ADS)

Pitawala, H. M. J. C.; Dissanayake, M. A. K. L.; Seneviratne, V. A.

2006-06-01

Poly (ethylene oxide)-(PEO)-based composite polymer electrolytes are of great interest for solid-state-electrochemical devices. This paper presents the results of a preliminary study on electrical conductivity and thermal behavior (DSC) of composite polymer electrolytes (CPEs) containing PEO: LiCF3SO3 complexed with plasticizer (EC) and incorporating nano-sized particles of the ceramic filler Al2O3. Ionic conductivity enhancement in these electrolytes has been obtained by optimizing the combined effect of the plasticizer and the ceramic filler. Nano-composite, plasticized polymer electrolyte films (400-600μm) were prepared by common solvent casting method. It was revealed that the presence of the Al2O3 filler in PEO: LiTf polymer electrolyte significantly enhanced the ionic conductivity in the temperature range of interest, giving the maximum conductivity for (PEO)9LiTf+15 wt.% Al2O3 CPE [σRT (max)=2×10-5 S cm-1]. It was also observed that the addition of plasticizer (EC) to this electrolyte up to a concentration of 50 wt. % EC, showed a further conductivity enhancement [σRT (max) = 1.5×10-4 S cm-1]. It is suggested that the conductivity is enhanced mainly by two mechanisms. The plasticizer (EC) would directly contribute by reducing the crystallinity and increasing the amorphous phase content of the polymer electrolytes. The ceramic filler (Al2O3) would contribute to conductivity enhancement by creating additional sites to migrating ionic species through transient bonding with O/OH groups in the filler surface. The decrease of Tg values of plasticized CPE systems seen in the DSC thermograms points towards the improved segmental flexibility of polymer chains, increasing the mobility of conducting ions.

Molecular dynamics and a spectroscopic study of sulfur dioxide absorption by an ionic liquid and its mixtures with PEO.

PubMed

Hoher, Karina; Cardoso, Piercarlo F; Lepre, Luiz F; Ando, Rômulo A; Siqueira, Leonardo J A

2016-10-19

An investigation comprising experimental techniques (absorption capacity of SO 2 and vibrational spectroscopy) and molecular simulations (thermodynamics, structure, and dynamics) has been performed for the polymer poly(ethylene oxide) (PEO), the ionic liquid butyltrimethylammonium bis(trifluoromethylsulfonyl)imide ([N 4111 ][Tf 2 N]) and their mixtures as sulfur dioxide (SO 2 ) absorbing materials. The polymer PEO has higher capacity to absorb SO 2 than the neat ionic liquid, whereas the mixtures presented intermediary absorption capacities. The band assigned to the symmetric stretching band of SO 2 at ca. 1140 cm -1 , which is considered a spectroscopic probe for the strength of SO 2 interactions with its neighborhood, shifts to lower wavenumbers as more negative total interaction energy values of SO 2 were evaluated from the simulations. The solvation free energy of SO 2 , ΔG sol , correlates linearly with the absorption capacity of SO 2 . The negative values of ΔG sol are due to negative and positive values of enthalpy and entropy, respectively. In the ionic liquid, SO 2 weakens the cation-anion interactions, whereas in the mixture with a high content of PEO these interactions are slightly increased. Such effects were correlated with the relative population of cisoid and transoid conformers of Tf 2 N anions as revealed by Raman spectroscopy. Moreover, the presence of SO 2 in the systems provokes the increase of diffusion coefficients of the absorbing species in comparison with the systems without the gas. Proper to the slow dynamics of the polymer, the diffusion coefficient of ions and SO 2 diminishes with the increase of the PEO content.

The black and white coatings on Ti-6Al-4V alloy or pure titanium by plasma electrolytic oxidation in concentrated silicate electrolyte

NASA Astrophysics Data System (ADS)

Han, Jun-xiang; Cheng, Yu-lin; Tu, Wen-bin; Zhan, Ting-Yan; Cheng, Ying-liang

2018-01-01

Black TiO2 has triggered scientific interest due to its unique properties such as enhanced solar-driven photocatalytic activity. In this paper, plasma electrolytic oxidation (PEO) treatment of Ti-6Al-4V alloy has been carried out in concentrated sodium silicate electrolyte. Silica-based black and white TiO2 coatings respectively have been obtained by controlling the oxidation time. The black coating, which was formed with a short treatment time, shows good corrosion resistance and the black appearance can be attributed to the presence of Ti2+ and Ti3+ in the coating. The lower valence titanium ions are absent in the white coatings and they also contain relatively higher Na content compared to the black coatings. The white coatings have great surface roughnesses and super hydrophilicity. The bonding strengths of the black and white coatings on the Ti-6Al-4V alloy are ∼14.4 and 4.3 MPa, respectively. The vanadium contributes little to the black appearance of the coating on Ti6Al4V alloy, since the same phenomena occur for the PEO of a pure titanium substrate.

Nanostructures and surface hydrophobicity of self-assembled thermosets involving epoxy resin and poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) amphiphilic diblock copolymer.

PubMed

Yi, Fangping; Zheng, Sixun; Liu, Tianxi

2009-02-19

Poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) (PTFEA-b-PEO) amphiphilic diblock copolymer was synthesized via the reversible addition-fragmentation transfer polymerization of 2,2,2-triffluroethyl acrylate with dithiobenzoyl-terminated poly(ethylene oxide) as a chain-transfer agent. The amphiphilic diblock copolymer was incorporated into epoxy resin to prepare the nanostructured epoxy thermosets. The nanostructures were investigated by means of atomic force microscopy, small-angle X-ray scattering, and dynamic mechanical analysis. In terms of the miscibility of the subchains of the block copolymer with epoxy after and before curing reaction, it is judged that the formation of the nanostructures follows the mechanism of self-assembly. The static contact angle measurements indicate that the nanostructured thermosets containing PTFEA-b-PEO diblock copolymer displayed a significant enhancement in surface hydrophobicity as well as a reduction in surface free energy. The improvement in surface properties was ascribed to the enrichment of the fluorine-containing subchain (i.e., PTFEA block) of the amphiphilic diblock copolymer on the surface of the nanostructured thermosets, which was evidenced by surface atomic force microscopy and energy-dispersive X-ray spectroscopy.

Systematic understanding of corrosion behavior of plasma electrolytic oxidation treated AZ31 magnesium alloy using a mouse model of subcutaneous implant.

PubMed

Jang, Yongseok; Tan, Zongqing; Jurey, Chris; Collins, Boyce; Badve, Aditya; Dong, Zhongyun; Park, Chanhee; Kim, Cheol Sang; Sankar, Jagannathan; Yun, Yeoheung

2014-12-01

This study was conducted to identify the differences between corrosion rates, corrosion types, and corrosion products in different physiological environments for AZ31 magnesium alloy and plasma electrolytic oxidation (PEO) treated AZ31 magnesium alloy. In vitro and in vivo tests were performed in Hank's Balanced Salt Solution (HBSS) and mice for 12 weeks, respectively. The corrosion rates of both AZ31 magnesium alloy and PEO treated AZ31 magnesium alloy were calculated based on DC polarization curves, volume of hydrogen evolution, and the thickness of corrosion products formed on the surface. Micro X-ray computed tomography (Micro-CT), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) were used to analyze morphological and chemical characterizations of corrosion products. The results show that there is more severe localized corrosion after in vitro test in HBSS; however, the thicknesses of corrosion products formed on the surface for AZ31 magnesium alloy and PEO treated AZ31 magnesium alloy in vivo were about 40% thicker than the thickness of corrosion products generated in vitro. The ratio of Ca and P (Ca/P) in the corrosion products also differed. The Ca deficient region and higher content of Al in corrosion product than AZ31 magnesium alloy were identified after in vivo test in contrast with the result of in vitro test. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of nanoparticles on the compatibility of PEO-PMMA block copolymers.

PubMed

Mu, Dan; Li, Jian-Quan; Li, Wei-Dong; Wang, Song

2011-12-01

The compatibility of six kinds of designed poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers was studied at 270, 298 and 400 K via mesoscopic modeling. The values of the order parameters depended on both the structures of the block copolymers and the simulation temperature, while the values of the order parameters of the long chains were higher than those of the short ones; temperature had a more obvious effect on long chains than on the short ones. Plain copolymers doped with poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA) homopolymer showed different order parameter values. When a triblock copolymer had the same component at both ends and was doped with one of its component polymers as a homopolymer (such as A5B6A5 doped with B6 or A5 homopolymer), the value of its order parameter depended on the simulation temperature. The highest order parameter values were observed for A5B6A5 doped with B6 at 400 K and for A5B6A5 doped with A5 at 270 K. A study of copolymers doped with nanoparticles showed that the mesoscopic phase was influenced by not only the properties of the nanoparticles, such as the size and density, but also the compositions of the copolymers. Increasing the size of the nanoparticles used as a dopant had the most significant effect on the phase morphologies of the copolymers.

Stealth properties of poly(ethylene oxide)-based triblock copolymer micelles: a prerequisite for a pH-triggered targeting system.

PubMed

Van Butsele, K; Morille, M; Passirani, C; Legras, P; Benoit, J P; Varshney, S K; Jérôme, R; Jérôme, C

2011-10-01

Evaluation of the biocompatibility of pH-triggered targeting micelles was performed with the goal of studying the effect of a poly(ethylene oxide) (PEO) coating on micelle stealth properties. Upon protonation under acidic conditions, pH-sensitive poly(2-vinylpyridine) (P2VP) blocks were stretched, exhibiting positive charges at the periphery of the micelles as well as being a model targeting unit. The polymer micelles were based on two different macromolecular architectures, an ABC miktoarm star terpolymer and an ABC linear triblock copolymer, which combined three different polymer blocks, i.e. hydrophobic poly(ε-caprolactone), PEO and P2VP. Neutral polymer micelles were formed at physiological pH. These systems were tested for their ability to avoid macrophage uptake, their complement activation and their pharmacological behavior after systemic injection in mice, as a function of their conformation (neutral or protonated). After protonation, complement activation and macrophage uptake were up to twofold higher than for neutral systems. By contrast, when P2VP blocks and the targeting unit were buried by the PEO shell at physiological pH, micelle stealth properties were improved, allowing their future systemic injection with an expected long circulation in blood. Smart systems responsive to pH were thus developed which therefore hold great promise for targeted drug delivery to an acidic tumoral environment. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effect of methyl red dye on dielectric and conductivity properties of PEO/CdCl{sub 2} electrolytes

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

Kamath, Archana; Devendrappa, H., E-mail: dehu2010@gmail.com

2016-05-06

In this report the conductivity and dielectric properties of polyethylene oxide-cadmium chloride (PEO/CdCl{sub 2}) polymer electrolyte films doped with an azo dye methyl red (MR) are discussed. The films were prepared by solution casting technique at different concentrations of the dye in PEO/CdCl{sub 2} electrolyte. The thermal behavior, chemical interaction of the dye with the electrolyte and surface morphology were studied by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) respectively. The conductivity and dielectric properties were measured as a function of composition and temperature using complex impedance spectroscopy. The temperature dependent electrical conductivitymore » of the films exhibited Arrhenius type behavior. Conductivity and dielectric results also signify the enhancement in the amorphous phase of the polymer electrolyte dye systems. The value of highest conductivity observed is 1.21x10{sup −4} at 343K and the conductivity of the film was enhanced by a three orders of magnitude.« less

Studies on the thermal and electrical properties of polyethylene oxide/polyvinyl alcohol blend by incorporating of Cesium Chloride

NASA Astrophysics Data System (ADS)

Ragab, H. M.

The composites PVA/PEO filled with various concentrations of CsCl samples, which were prepared for using a solvent casting technique and studied via Fourier transform infrared spectroscopy (FTIR), ultraviolet - visible (UV-Vis), X-ray spectroscopy, Scanning electron microscopy (SEM), AC conductivity and dielectric properties to use as sensor in electronic devices. The FTIR indicated the interaction between PVA/PEO and CsCl. From data of UV. Vis. was observed band gap (Eg) reduces with addition CsCl to polymer blend. The XRD shows the degree of crystallinity (χ%) decreasing with increasing concentration of CsCl from 2.93 to 2.45. The SEM of the surface of composite PVA/PEO filled with various concentrations of CsCl in magnification 1500 times its change with compare of pure blend. From TGA was observed improvement in the thermal stability of the samples after addition of CsCl. The AC conductivity rise more rapidly with temperature and associated with activation energy Ea, for conduction and enhanced with increasing both temperature and frequency.

Lithium Dendrite Suppression and Enhanced Interfacial Compatibility Enabled by an Ex Situ SEI on Li Anode for LAGP-Based All-Solid-State Batteries.

PubMed

Hou, Guangmei; Ma, Xiaoxin; Sun, Qidi; Ai, Qing; Xu, Xiaoyan; Chen, Lina; Li, Deping; Chen, Jinghua; Zhong, Hai; Li, Yang; Xu, Zhibin; Si, Pengchao; Feng, Jinkui; Zhang, Lin; Ding, Fei; Ci, Lijie

2018-06-06

The electrode-electrolyte interface stability is a critical factor influencing cycle performance of All-solid-state lithium batteries (ASSLBs). Here, we propose a LiF- and Li 3 N-enriched artificial solid state electrolyte interphase (SEI) protective layer on metallic lithium (Li). The SEI layer can stabilize metallic Li anode and improve the interface compatibility at the Li anode side in ASSLBs. We also developed a Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 -poly(ethylene oxide) (LAGP-PEO) concrete structured composite solid electrolyte. The symmetric Li/LAGP-PEO/Li cells with SEI-protected Li anodes have been stably cycled with small polarization at a current density of 0.05 mA cm -2 at 50 °C for nearly 400 h. ASSLB-based on SEI-protected Li anode, LAGP-PEO electrolyte, and LiFePO 4 (LFP) cathode exhibits excellent cyclic stability with an initial discharge capacity of 147.2 mA h g -1 and a retention of 96% after 200 cycles.

On the Role of Specific Interactions in the Diffusion of Nanoparticles in Aqueous Polymer Solutions

PubMed Central

2013-01-01

Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(N-vinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions. PMID:24354390

On the role of specific interactions in the diffusion of nanoparticles in aqueous polymer solutions.

PubMed

Mun, Ellina A; Hannell, Claire; Rogers, Sarah E; Hole, Patrick; Williams, Adrian C; Khutoryanskiy, Vitaliy V

2014-01-14

Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(N-vinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions.

Segmental dynamics of polymers in nanoscopic confinements, as probed by simulations of polymer/layered-silicate nanocomposites.

PubMed

Kuppa, V; Foley, T M D; Manias, E

2003-09-01

In this paper we review molecular modeling investigations of polymer/layered-silicate intercalates, as model systems to explore polymers in nanoscopically confined spaces. The atomic-scale picture, as revealed by computer simulations, is presented in the context of salient results from a wide range of experimental techniques. This approach provides insights into how polymeric segmental dynamics are affected by severe geometric constraints. Focusing on intercalated systems, i.e. polystyrene (PS) in 2 nm wide slit-pores and polyethylene-oxide (PEO) in 1 nm wide slit-pores, a very rich picture for the segmental dynamics is unveiled, despite the topological constraints imposed by the confining solid surfaces. On a local scale, intercalated polymers exhibit a very wide distribution of segmental relaxation times (ranging from ultra-fast to ultra-slow, over a wide range of temperatures). In both cases (PS and PEO), the segmental relaxations originate from the confinement-induced local density variations. Additionally, where there exist special interactions between the polymer and the confining surfaces ( e.g., PEO) more molecular mechanisms are identified.

Force fields for describing the solution-phase synthesis of shape-selective metal nanoparticles

NASA Astrophysics Data System (ADS)

Zhou, Ya; Al-Saidi, Wissam; Fichthorn, Kristen

2013-03-01

Polyvinylpyrrolidone (PVP) and polyethylene oxide (PEO) are structure-directing agents that exhibit different performance in the polyol synthesis of Ag nanostructures. The success of these structure-directing agents in selective nanostructure synthesis is often attributed to their selective binding to Ag(100) facets. We use first-principles, density-functional theory (DFT) calculations in a vacuum environment to show that PVP has a stronger preference to bind to Ag(100) than to Ag(111), whereas PEO exhibits much weaker selectivity. To understand the role of solvent in the surface-sensitive binding, we develop classical force fields to describe the interactions of the structure-directing (PVP and PEO) and solvent (ethylene glycol) molecules with various Ag substrates. We parameterize the force fields through force-and-energy matching to DFT results using simulated annealing. We validate the force fields by comparisons to DFT and experimental binding energies. Our force fields reproduce the surface-sensitive binding predicted by DFT calculations. Molecular dynamics simulations based on these force fields can be used to reveal the role of solvent, polymer chain length, and polymer concentration in the selective synthesis of Ag nanostructures.

Chitosan(PEO)/silica hybrid nanofibers as a potential biomaterial for bone regeneration.

PubMed

Toskas, Georgios; Cherif, Chokri; Hund, Rolf-Dieter; Laourine, Ezzeddine; Mahltig, Boris; Fahmi, Amir; Heinemann, Christiane; Hanke, Thomas

2013-05-15

New hybrid nanofibers prepared with chitosan (CTS), containing a total amount of polyethylene oxide (PEO) down to 3.6wt.%, and silica precursors were produced by electrospinning. The solution of modified sol-gel particles contained tetraethoxysilane (TEOS) and the organosilane 3-glycidyloxypropyltriethoxysilane (GPTEOS). This is rending stable solution toward gelation and contributing in covalent bonding with chitosan. The fibers encompass advantages of biocompatible polymer template silicate components to form self-assembled core-shell structure of the polymer CTS/PEO encapsulated by the silica. Potential applicability of this hybrid material to bone tissue engineering was studied examining its cellular compatibility and bioactivity. The nanofiber matrices were proved cytocompatible when seeded with bone-forming 7F2-cells, promoting attachment and proliferation over 7 days. These found to enhance a fast apatite formation by incorporation of Ca(2+) ions and subsequent immersion in modified simulated body fluid (m-SBF). The tunable properties of these hybrid nanofibers can find applications as active biomaterials in bone repair and regeneration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Chitosan nanofibers for transbuccal insulin delivery.

PubMed

Lancina, Michael G; Shankar, Roopa Kanakatti; Yang, Hu

2017-05-01

In this work, they aimed at producing chitosan based nanofiber mats capable of delivering insulin via the buccal mucosa. Chitosan was electrospun into nanofibers using poly(ethylene oxide) (PEO) as a carrier molecule in various feed ratios. The mechanical properties and degradation kinetics of the fibers were measured. Insulin release rates were determined in vitro using an ELISA assay. The bioactivity of released insulin was measured in terms of Akt activation in pre-adipocytes. Insulin permeation across the buccal mucosa was measured in an ex-vivo porcine transbuccal model. Fiber morphology, mechanical properties, and in vitro stability were dependent on PEO feed ratio. Lower PEO content blends produced smaller diameter fibers with significantly faster insulin release kinetics. Insulin showed no reduction in bioactivity due to electrospinning. Buccal permeation of insulin facilitated by high chitosan content blends was significantly higher than that of free insulin. Taken together, the work demonstrates that chitosan-based nanofibers have the potential to serve as a transbuccal insulin delivery vehicle. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1252-1259, 2017. © 2017 Wiley Periodicals, Inc.

Biomedical applications of ferulic acid encapsulated electrospun nanofibers.

PubMed

Vashisth, Priya; Kumar, Naresh; Sharma, Mohit; Pruthi, Vikas

2015-12-01

Ferulic acid is a ubiquitous phytochemical that holds enormous therapeutic potential but has not gained much consideration in biomedical sector due to its less bioavailability, poor aqueous solubility and physiochemical instability. In present investigation, the shortcomings associated with agro-waste derived ferulic acid were addressed by encapsulating it in electrospun nanofibrous matrix of poly (d,l-lactide-co-glycolide)/polyethylene oxide. Fluorescent microscopic analysis revealed that ferulic acid predominantly resides in the core of PLGA/PEO nanofibers. The average diameters of the PLGA/PEO and ferulic acid encapsulated PLGA/PEO nanofibers were recorded as 125 ± 65.5 nm and 150 ± 79.0 nm, respectively. The physiochemical properties of fabricated nanofibers are elucidated by IR, DSC and NMR studies. Free radical scavenging activity of fabricated nanofibers were estimated using di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium (DPPH) assay. 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay confirmed the cytotoxicity of ferulic acid encapsulated nanofibers against hepatocellular carcinoma (HepG2) cells. These ferulic acid encapsulated nanofibers could be potentially explored for therapeutic usage in biomedical sector.

Structurally Stable Attractive Nanoscale Emulsions with Dipole-Dipole Interaction-Driven Interdrop Percolation.

PubMed

Shin, Kyounghee; Gong, Gyeonghyeon; Cuadrado, Jonas; Jeon, Serim; Seo, Mintae; Choi, Hong Sung; Hwang, Jae Sung; Lee, Youngbok; Fernandez-Nieves, Alberto; Kim, Jin Woong

2017-03-28

This study introduces an extremely stable attractive nanoscale emulsion fluid, in which the amphiphilic block copolymer, poly(ethylene oxide)-block-poly(ϵ-caprolactone) (PEO-b-PCL), is tightly packed with lecithin, thereby forming a mechanically robust thin-film at the oil-water interface. The molecular association of PEO-b-PCL with lecithin is critical for formation of a tighter and denser molecular assembly at the interface, which is systematically confirmed by T 2 relaxation and DSC analyses. Moreover, suspension rheology studies also reflect the interdroplet attractions over a wide volume fraction range of the dispersed oil phase; this results in a percolated network of stable drops that exhibit no signs of coalescence or phase separation. This unique rheological behavior is attributed to the dipolar interaction between the phosphorylcholine groups of lecithin and the methoxy end groups of PEO-b-PCL. Finally, the nanoemulsion system significantly enhances transdermal delivery efficiency due to its favorable attraction to the skin, as well as high diffusivity of the nanoscale emulsion drops. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring solute interactions with poly(ethylene oxide)-modified colloidal silica nanoparticles via fluorescence anisotropy decay.

PubMed

Tleugabulova, Dina; Duft, Andy M; Brook, Michael A; Brennan, John D

2004-01-06

The fluorescence-based nanosize metrology approach, proposed recently by Geddes and Birch (Geddes, C. D.; Birch, D. J. S. J. Non-Cryst. Solids 2000, 270, 191), was used to characterize the extent of binding of a fluorescent cationic solute, rhodamine 6G (R6G), to the surface of silica particles after modification of the surface with the hydrophilic polymer poly(ethylene oxide) (PEO) of various molecular weights. The measurement of the rotational dynamics of R6G in PEO solutions showed the absence of strong interactions between R6G and PEO chains in water and the ability of the dye to sense the presence of polymer clusters in 30 wt % solutions. Time-resolved anisotropy decays of polymer-modified Ludox provided direct evidence for distribution of the dye between bound and free states, with the bound dye showing two decay components: a nanosecond decay component that is consistent with local motions of bound probes and a residual anisotropy component due to slow rotation of large silica particles. The data showed that the dye was strongly adsorbed to unmodified silica nanoparticles, to the extent that less than 1% of the dye was present in the surrounding aqueous solution. Addition of PEO blocked the adsorption of the dye to a significant degree, with up to 50% of the probe being present in the aqueous solution for Ludox samples containing 30 wt % of low molecular weight PEO. The addition of such agents also decreased the value and increased the fractional contribution of the nanosecond rotational correlation time, suggesting that polymer adsorption altered the degree of local motion of the bound probe. Atomic force microscopy imaging studies provided no evidence for a change in the particle size upon surface modification but did suggest interparticle aggregation after polymer adsorption. Thus, this redistribution of the probe is interpreted as being due to coverage of particles with the polymer, resulting in lower adsorption of R6G to the silica. The data clearly show the power of time-resolved fluorescence anisotropy decay measurements for probing the modification of silica surfaces and suggest that this method should prove useful in characterization of new chromatographic stationary phases and nanocomposite materials.

Periodic organosilica hollow nanospheres as anode materials for lithium ion rechargeable batteries

NASA Astrophysics Data System (ADS)

Sasidharan, Manickam; Nakashima, Kenichi; Gunawardhana, Nanda; Yokoi, Toshiyuki; Ito, Masanori; Inoue, Masamichi; Yusa, Shin-Ichi; Yoshio, Masaki; Tatsumi, Takashi

2011-11-01

Polymeric micelles with core-shell-corona architecture have been found to be the efficient colloidal templates for synthesis of periodic organosilica hollow nanospheres over a broad pH range from acidic to alkaline media. In alkaline medium, poly (styrene-b-[3-(methacryloylamino)propyl] trimethylammonium chloride-b-ethylene oxide) (PS-PMAPTAC-PEO) micelles yield benzene-silica hollow nanospheres with molecular scale periodicity of benzene groups in the shell domain of hollow particles. Whereas, an acidic medium (pH 4) produces diverse hollow particles with benzene, ethylene, and a mixture of ethylene and dipropyldisulfide bridging functionalities using poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) micelles. These hollow particles were thoroughly characterized by powder X-ray diffraction (XRD), dynamic light scattering (DLS), thermogravimetric analysis (TG/DTA), Fourier transformation infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), magic angle spinning-nuclear magnetic resonance (29Si MAS NMR and 13CP-MAS NMR), Raman spectroscopy, and nitrogen adsorption/desorption analyses. The benzene-silica hollow nanospheres with molecular scale periodicity in the shell domain exhibit higher cycling performance of up to 300 cycles in lithium ion rechargeable batteries compared with micron-sized dense benzene-silica particles.Polymeric micelles with core-shell-corona architecture have been found to be the efficient colloidal templates for synthesis of periodic organosilica hollow nanospheres over a broad pH range from acidic to alkaline media. In alkaline medium, poly (styrene-b-[3-(methacryloylamino)propyl] trimethylammonium chloride-b-ethylene oxide) (PS-PMAPTAC-PEO) micelles yield benzene-silica hollow nanospheres with molecular scale periodicity of benzene groups in the shell domain of hollow particles. Whereas, an acidic medium (pH 4) produces diverse hollow particles with benzene, ethylene, and a mixture of ethylene and dipropyldisulfide bridging functionalities using poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) micelles. These hollow particles were thoroughly characterized by powder X-ray diffraction (XRD), dynamic light scattering (DLS), thermogravimetric analysis (TG/DTA), Fourier transformation infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), magic angle spinning-nuclear magnetic resonance (29Si MAS NMR and 13CP-MAS NMR), Raman spectroscopy, and nitrogen adsorption/desorption analyses. The benzene-silica hollow nanospheres with molecular scale periodicity in the shell domain exhibit higher cycling performance of up to 300 cycles in lithium ion rechargeable batteries compared with micron-sized dense benzene-silica particles. Electronic supplementary information (ESI) available: FTIR, Raman spectral data, additional TEM pictures, N2 adsorption and physical characteristics of hollow particles data, and cycling performance of dense silica particles. See DOI: 10.1039/c1nr10804b

Heat transfer and thermal management studies of lithium polymer batteries for electric vehicle applications

NASA Astrophysics Data System (ADS)

Song, Li

The thermal conductivities of the polymer electrolyte and composite cathode are important parameters characterizing heat transport in lithium polymer batteries. The thermal conductivities of lithium polymer electrolytes, including poly-ethylene oxide (PEO), PEO-LiClO4, PEO-LiCF3SO 3, PEO-LiN(CF3SO2)2, PEO-LiC(CF 3SO2)3, and the thermal conductivities of TiS 2 and V6O13 composite cathodes, were measured over the temperature range from 25°C to 150°C by a guarded heat flow meter. The thermal conductivities of the electrolytes were found to be relatively constant for the temperature and for electrolytes with various concentrations of the lithium salt. The thermal conductivities of the composite cathodes were found to increase with the temperature below the melting temperature of the polymer electrolyte and only slightly increase above the melting temperature. Three different lithium polymer cells, including Li/PEO-LiCF3 S O3/TiS2, Li/PEO-LiC(CF3 S O2)3/V6 O13, and Li/PEO-LiN(CF3 S O2)2/ Li1+x Mn2 O4 were prepared and their discharge curves, along with heat generation rates, were measured at various galvanostatic discharge current densities, and at different temperature (70°C, 80°C and 90°C), by a potentiostat/galvanostat and an isothermal microcalorimeter. The thermal stability of a lithium polymer battery was examined by a linear perturbation analysis. In contrast to the thermal conductivity, the ionic conductivity of polymer electrolytes for lithium-polymer cell increases greatly with increasing temperature, an instability could arise from this temperature dependence. The numerical calculations, using a two dimensional thermal model, were carried out for constant potential drop across the electrolyte, for constant mean current density and for constant mean cell output power. The numerical calculations were approximately in agreement with the linear perturbation analysis. A coupled mathematical model, including electrochemical and thermal components, was developed to study the heat transfer and thermal management of lithium polymer batteries. The results calculated from the model, including temperature distributions, and temperatures at different stages of discharge are significantly different from those calculated from the thermal model. The discharge curves and heat generation rates calculated by the electrochemical-thermal model were in agreement with the experimental results. Different thermal management approaches, including a variable conductance insulation enclosure were studied.

Electrospinning of doxorubicin loaded silica/poly(ɛ-caprolactone) hybrid fiber mats for sustained drug release

NASA Astrophysics Data System (ADS)

El Gohary, Mohammed I.; El Hady, Bothaina M. Abd; Saeed, Aziza A. Al; Tolba, Emad; El Rashedi, Ahlam M. I.; Saleh, Safaa

2018-06-01

Loading of anticancer drugs into electrospun fiber matrices is a portentous approach for clinical treatment of diseased tissues or organs. In this study, doxorubicin hydrochloride (DOX) is added to silica nanoparticles () during the formation of via the sol-gel approach. The obtained nanoparticles are then added to poly(-caprolactone) (PCL) and poly(ethylene oxide) (PEO) blend before electrospinning process via different methods. The effects of DOX addition as a free form or as nanoparticles on physical and chemical properties of obtained PCL-PEO fibers, as well as release profiles are evaluated to give a continual DOX release for several days. The morphology observed with scanning electron microscope (FESEM) revealed significant changes in the average diameter of obtained fibers ranging from 2164 nm to 659 nm and distribution of drug-loaded nanoparticles in the final mats according to the mode of additions. With the same manner, the releasing performances of obtained mats are quite different. Therefore, fabrication of drug loaded mats would offer a powerful approach to minimize serious side effects for clinical patients and allows us to control the drug concentration in the bloodstream.

Intravenous injections of soluble drag-reducing polymers reduce foreign body reaction to implants.

PubMed

Marascalco, Philip J; Blair, Harry C; Nieponice, Alejandro; Robinson, Lisa J; Kameneva, Marina V

2009-01-01

We tested whether soluble viscoelastic drag-reducing polymers (DRPs), which modify blood flow in the macro- and microcirculation, affect host response to implanted biomaterials and control biodegradation and tissue ingrowth processes. Porous poly(L-lactate) (PLLA) implants, which are naturally hydrolyzed by foreign body giant cells, were used to evaluate differences in host response. Intravenous DRPs, high-molecular weight poly(ethylene oxide) (PEO) or poly(mannose) (PMNN), were given biweekly at 0.3-0.4 nM in saline (equivalent volumes of saline in controls) to rats with subcutaneous PLLA implants. After 7 weeks, there was no difference in weight gain or behavior between control and DRP-injected groups. Implanted PLLA scaffolds in controls were almost totally degraded and replaced by giant cell granulomas. On the contrary, PEO- or PMNN-treated animals retained a significant part of the implanted scaffold (p < 0.0001 vs. controls). The foreign body reaction was markedly decreased, and there was an increase in well-oriented collagen deposition within the implanted scaffold area in the animals treated with DRPs. The DRP-mediated effects observed in this study potentially reflect alteration in inflammatory events in response to implanted bioengineered materials, and, thus, warrant further investigation.

Design of sustained release tablet containing fucoidan.

PubMed

Tran, Thao Truong-Dinh; Ngo, Dai Kieu-Phuong; Vo, Toi Van; Tran, Phuong Ha-Lien

2015-01-01

The study introduced a new therapeutic agent, fucoidan, which can offer potential medical treatments including anti-inflammatory and anti-coagulant activities, as well as anti-proliferative effects on cancer cells. Fucoidan was included in sustained release formulations expected for an effective plasma drug concentration for approximately 24 h. The matrices based on the two polymers hydroxypropyl methycellulose (HPMC) and polyethylene oxide (PEO) were prepared with various ratios between the polymers and fucoidan. The dissolution profiles of various matrix tablets performed in enzyme-free simulated intestinal fluid (pH 6.8) for 24 h indicated a higher potential of PEO-based matrix tablets in sustaining release of fucoidan. The swelling and erosion of the tablets were also characterized to elucidate the difference among those dissolution profiles.

On the Interfacial Properties of Polymers/Functionalized Single-Walled Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Ansari, R.; Rouhi, S.; Ajori, S.

2016-06-01

Molecular dynamics (MD) simulations is used to study the adsorption of polyethylene (PE) and poly(ethylene oxide) (PEO) on the functionalized single-walled carbon nanotubes (SWCNTs). The effects of functionalization factor weight percent on the interaction energies of polymer chains with nanotubes are studied. Besides, the influences of different functionalization factors on the SWCNT/polymer interactions are investigated. It is shown that for both types of polymer chains, the largest interaction energies associates with the random O functionalized nanotubes. Besides, increasing temperature results in increasing the nanotube/polymer interaction energy. Considering the final shapes of adsorbed polymer chains on the SWCNTs, it is observed that the adsorbed conformations of PE chains are more contracted than those of PEO chains.

Molecular dynamics simulations of amphiphilic graft copolymer molecules at a water/air interface.

PubMed

Anderson, Philip M; Wilson, Mark R

2004-11-01

Fully atomistic molecular dynamics simulations of amphiphilic graft copolymer molecules have been performed at a range of surface concentrations at a water/air interface. These simulations are compared to experimental results from a corresponding system over a similar range of surface concentrations. Neutron reflectivity data calculated from the simulation trajectories agrees well with experimentally acquired profiles. In particular, excellent agreement in neutron reflectivity is found for lower surface concentration simulations. A simulation of a poly(ethylene oxide) (PEO) chain in aqueous solution has also been performed. This simulation allows the conformational behavior of the free PEO chain and those tethered to the interface in the previous simulations to be compared. (c) 2004 American Institute of Physics.

Crystallization in diblock copolymer thin films at different degrees of supercooling

NASA Astrophysics Data System (ADS)

Darko, C.; Botiz, I.; Reiter, G.; Breiby, D. W.; Andreasen, J. W.; Roth, S. V.; Smilgies, D.-M.; Metwalli, E.; Papadakis, C. M.

2009-04-01

The crystalline structures in thin films of polystyrene- b -poly(ethylene oxide) (PS- b -PEO) diblock copolymers were studied in dependence on the degree of supercooling. Atomic force microscopy showed that the crystalline domains (lamellae) consist of grains, which are macroscopic at low and intermediate degrees of supercooling, but of submicrometer size for strong supercooling. Using grazing-incidence wide-angle x-ray scattering, we could determine the grain orientation distribution function which shows that the chain stems are perpendicular to the lamellae at low supercooling, but tilted at intermediate and strong supercooling. These results suggest that, at intermediate and strong supercooling, the crystalline PEO lamellae do not grow homogeneously, but by the formation of small crystallites at the growth front.

Field Effect Transistor Behavior in Electrospun Polyaniline/Polyethylene Oxide Nanofibers

NASA Technical Reports Server (NTRS)

Miranda, Felix A.; Theofylaktos, Noulie; Mueller, Carl H.; Pinto, Nicholas J.

2004-01-01

Novel transistors and logic devices based on nanotechnology concepts are under intense development. The potential for ultra-low-power circuitry makes nanotechnology attractive for applications such as digital electronics and sensors. For NASA applications, nanotechnology offers tremendous opportunities for increased onboard data processing, and thus autonomous decision-making ability, and novel sensors that detect and respond to environmental stimuli with little oversight requirements. Polyaniline (PANi) is an intriguing material because its electrical conductivity can be changed from insulating to metallic by varying the doping levels and conformations of the polymer chain, and when combined with polyethylene oxide (PEO), can be formed into nanofibers with diameters ranging from approximately 50 to 500 nm (depending on the deposition conditions). The initial goal of this work was to demonstrate transistor behavior in these nanofibers, thus creating a foundation for future logic devices.

Formation and self-organization kinetics of alpha-CD/PEO-based pseudo-polyrotaxanes in water. A specific behavior at 30 degrees C.

PubMed

Travelet, Christophe; Schlatter, Guy; Hébraud, Pascal; Brochon, Cyril; Lapp, Alain; Hadziioannou, Georges

2009-08-04

alpha-Cyclodextrins (alpha-CDs) have the ability to form inclusion complexes with poly(ethylene oxide) (PEO) polymer chains. These pseudo-polyrotaxanes (PPRs) can be obtained by quenching an alpha-CD/PEO mixture in water from 70 degrees C down to a lower temperature (typically in the range from 5 to 30 degrees C) thanks to favorable interactions between alpha-CD cavities and PEO chains. Moreover, starting from a liquid alpha-CD/PEO mixture at a total mass fraction of 15% w/w at 70 degrees C, the formation of PPRs with time at a lower temperature induces a white physical gel with time, and phase separation is observed. We established that PPR molecules are exclusively found in the precipitated phase although unthreaded alpha-CD molecules and unthreaded PEO chains are in the liquid phase. At 30 degrees C, the physical gel formation is much slower than at 5 degrees C. At 30 degrees C, we established that, in a first step, alpha-CDs thread onto PEO chains, forming PPR molecules which are not in good solvent conditions in water. At a higher length scale, rapid aggregation of the PPR molecules occurs, and threaded alpha-CD-based nanocylinders form (cylinder length L = 5.7 nm and cylinder radius R = 4.7 nm). At a higher length scale, alpha-CD-based nanocylinders associate in a Gaussian way, engendering the formation of precipitated domains which are responsible for the high turbidity of the studied system. At the end of this first step (i.e., after 20 min), the system still remains liquid and the PPRs are totally formed. Then, in a second step (i.e., after 150 min), the system undergoes its reorganization characterized by a compacity increase of the precipitated domains and forms a physical gel. We found that PPRs are totally formed after 20 min at 30 degrees C and that the system stays in a nongel state up to 150 min. This opens new perspectives regarding the PPR chemical modification: between these two characteristic times, we can easily envisage an efficient chemical modification of the PPR molecules in water, as for instance an end-capping reaction leading to the synthesis of polyrotaxanes.

Simultaneous improvement in ionic conductivity and flexibility of solid polymer electrolytes for thin film lithium ion batteries

NASA Astrophysics Data System (ADS)

Ji, Jianying

Solid polymer electrolytes (SPEs) provide advantages over liquid electrolytes in terms of safety, reliability, less temperature sensitive, and simplicity of design. With the use of a SPE in lithium batteries, high specific energy and specific power, safe operation, flexibility in packaging, and low cost of fabrication can be expected. However, after 30 years, SPEs have rarely found commercial success due to the low ionic conductivity and/or insufficient mechanical properties, both of which are related to the movement of the polymer chains. Many physical/chemical methods have been exploited to simultaneously create enhancement in ionic conductivity and mechanical properties, and some suggested ways have shown promise. However, the complex strategies have always introduced other challenge issues and incurred extra costs for manufacturing. In such a context, the development of dry solid state electrolytes is the central challenge to be faced worldwide. This thesis deals with the approaches to improving ionic conductivity and mechanical properties simultaneously. The method is to apply two kinds of controllable organic fillers: copolymer and protein. Our work revealed that the commercial available copolymer, poly (ethylene oxide)- block-polyethylene (PEO-b-PE), possesses a capability for enhancing the multiple performances of poly(ethylene oxide)(PEO)-based polymer electrolyte. And the effects of composition and molecular weight of the copolymers on performance of the resulting SPEs were examined. It was found that increasing the PE block percentage in the copolymer resulted in a significant increase in both ionic conductivity and mechanical properties, while increasing the molecular weight of the copolymer resulted in better mechanical properties, and an identical ionic conductivity. A rubber-like, soy protein-based SPE (s-SPE)was obtained by employing soy protein isolate (SPI), a soy product usually used as rigid fillers for enhancing mechanical properties of polymers, blended with poly(ethylene oxide)(PEO). The results indicated that the s-SPE with 55 wt% of SPI possesses a fully amorphous uniform structure having low Tg, in contrast with crystalline PEO-based SPE having discernable Tg and Tm. The conductivity and elasticity are both significantly improved with SPI involvement. Remarkably, this film has been elongated up to 100% without loss of ionic conductivity and 700% without mechanical damage.

Novel Hydrogels from Telechelic Polymers

NASA Astrophysics Data System (ADS)

Taribagil, Rajiv R.

The last two decades have seen telechelic polymers support an increasing number of applications as stabilizers and flow modifiers in fields as varied as pharmaceutics, paints and oil recovery. Mainly consisting of a long hydrophilic block end-capped with hydrophobic blocks, these polymers form gels at modest concentrations, comprising hydrophobic junctions with hydrophilic blocks bridging these junctions. This thesis examines two different types of telechelic polymer hydrogels: concentrated dispersions of telechelic triblock copolymers and dilute solutions of wormlike micelles cross-linked by hydrophobically end-capped polymers. Aqueous gels of telechelic poly(ethylene oxide) (PEO)-based triblock polymers, with homo and hetero combinations of 1,2-polybutadiene (PB) and poly(perfluoropropylene oxide) (PFPO) as hydrophobic end-blocks, were investigated using a combination of cryogenic scanning electron microscopy and small-angle neutron scattering. The PB-b-PEO-b-PB copolymers formed networks of spherical micelles at all concentrations as expected, albeit with significant spatial heterogeneity that diminished with increasing concentration. The PFPO-b-PEO-b-PFPO copolymers also formed networks by aggregation of the end-blocks, but the PFPO blocks tended to adopt disk-like or even sheet-like structures. This is attributed to the extremely high interfacial tension of PFPO with water and is consistent with the "super-strong" segregation regime behavior. The heterotelechelic PB-b-PEO- b-PFPO terpolymers adopted a quite different structure, namely an intricate bicontinuous open-cell foam, with cells on the order of 500 nm in size and cell walls composed of PFPO disks embedded in PB sheets. These various network structures illustrate the potential of using end-block chemistry to manipulate both the morphology and the physical properties of polymer gels. Dilute aqueous solutions containing 1 wt% cetyltrimethylammonium tosylate, a surfactant well recognized to form wormlike micelles, and low concentrations of hydrophobically end-capped poly(ethylene oxide), were investigated using dynamic mechanical spectroscopy and small-angle neutron scattering. The detailed examination shows that addition of as little as 0.1 wt% of the polymer to the dilute wormlike micelle solution leads to a massive enhancement in its viscoelastic response. This phenomenon raises the possibility of significantly reducing the amount of additive required to achieve a desired rheological profile, with concomitant advantages in both cost and environmental impact.

Mg2B2O5 Nanowire Enabled Multifunctional Solid-State Electrolytes with High Ionic Conductivity, Excellent Mechanical Properties, and Flame-Retardant Performance.

PubMed

Sheng, Ouwei; Jin, Chengbin; Luo, Jianmin; Yuan, Huadong; Huang, Hui; Gan, Yongping; Zhang, Jun; Xia, Yang; Liang, Chu; Zhang, Wenkui; Tao, Xinyong

2018-05-09

High ionic conductivity, satisfactory mechanical properties, and wide electrochemical windows are crucial factors for composite electrolytes employed in solid-state lithium-ion batteries (SSLIBs). Based on these considerations, we fabricate Mg 2 B 2 O 5 nanowire enabled poly(ethylene oxide) (PEO)-based solid-state electrolytes (SSEs). Notably, these SSEs have enhanced ionic conductivity and a large electrochemical window. The elevated ionic conductivity is attributed to the improved motion of PEO chains and the increased Li migrating pathway on the interface between Mg 2 B 2 O 5 and PEO-LiTFSI. Moreover, the interaction between Mg 2 B 2 O 5 and -SO 2 - in TFSI - anions could also benefit the improvement of conductivity. In addition, the SSEs containing Mg 2 B 2 O 5 nanowires exhibit improved the mechanical properties and flame-retardant performance, which are all superior to the pristine PEO-LiTFSI electrolyte. When these multifunctional SSEs are paired with LiFePO 4 cathodes and lithium metal anodes, the SSLIBs show better rate performance and higher cyclic capacity of 150, 106, and 50 mAh g -1 under 0.2 C at 50, 40, and 30 °C. This strategy of employing Mg 2 B 2 O 5 nanowires provides the design guidelines of assembling multifunctional SSLIBs with high ionic conductivity, excellent mechanical properties, and flame-retardant performance at the same time.

Polymer chain dynamics under nanoscopic confinements.

PubMed

Kimmich, Rainer; Fatkullin, Nail; Mattea, Carlos; Fischer, Elmar

2005-02-01

It is shown that the confinement of polymer melts in nanopores leads to chain dynamics dramatically different from bulk behavior. This so-called corset effect occurs both above and below the critical molecular mass and induces the dynamic features predicted for reptation. A spinodal demixing technique was employed for the preparation of linear poly(ethylene oxide) (PEO) confined to nanoscopic strands that are in turn embedded in a quasi-solid and impenetrable methacrylate matrix. Both the molecular weight of the PEO and the mean diameter of the strands were varied to a certain degree. The chain dynamics of the PEO in the molten state was examined with the aid of field-gradient NMR diffusometry (time scale, 10(-2)-10(0) s) and field-cycling NMR relaxometry (time scale, 10(-9)-10(-4) s). The dominating mechanism for translational displacements probed in the nanoscopic strands by either technique is shown to be reptation. On the time scale of spin-lattice relaxation time measurements, the frequency dependence signature of reptation (i.e., T1 approximately nu(3/4)) showed up in all samples. A "tube" diameter of only 0.6 nm was concluded to be effective on this time scale even when the strand diameter was larger than the radius of gyration of the PEO random coils. This corset effect is traced back to the lack of the local fluctuation capacity of the free volume in nanoscopic confinements. The confinement dimension is estimated at which the crossover from confined to bulk chain dynamics is expected.

Physical properties and application in the confined geometrical systems

NASA Astrophysics Data System (ADS)

Pak, Hunkyun

Surface viscoelasticity of a vitamin E modified polyethylene glycol (vitamin E-TPGS) monolayers at the air/water interface is deduced by the surface light scattering method and Wilhelmy plate method. It was found that the viscoelasticity of vitamin E-TPGS monolayer is similar to that of PEO monolayer at the surface pressure lower than the collapse pressure of the polyethylene oxide (PEO). However, at higher surface pressure than the collapse pressure of PEO, it deviates from the viscoelastic behavior of PEO. Lateral diffusion constants of a probe lipid (NBD-PC) in a binary monolayer of L-a-dilauroylphosphatidylcholine (DLPC) and poly-(di-isobutylene-alt-maleic acid) (PDIBMA) were determined by the fluorescence recovery after photobleaching (FRAP) method at the air/pH 7 buffer interface as a function of composition. The diffusion constant is found to retard down to less than one hundredth to that at pure DLPC monolayers as the mole fraction of PDIBMA increased. The free area model was used to interpret the probe diffusion retardation. Translational diffusion constants of a probe molecule, 4-octadecylamino-7-nitrobenzo-2-oxa-1,3-diazole (C18-NBD), in thin polyisoprene (PI) and polydimethyl siloxane (PDMS) films, spin coated on methylated and propylyaminated silicon wafers, are studied by the FRAP method as a function of film thickness. Reduction of the diffusion constant is observed as thickness of the films is decreased. Two empirical models, the two-layer model and the continuous layer model are proposed to account for the diffusion constant dependence on the film thickness vs. thickness. It was observed that the diffusion profiles in the films are dependet on the nature of the substrate surfaces. Self-assembled patterns of magnetic particles were made and fixed by applying magnetic field on the particles dispersed at the air/liquid interface, followed by gelling of the liquid subphase. With this method, the large patterns with controllable lattice constant can be made. The fixation of the subphase enhances the stability of the patterns. Further, three-dimensional self-assembled patterns can be made by this method when the fixation process is incorporated.

A new method to analyze copolymer based superplasticizer traces in cement leachates.

PubMed

Guérandel, Cyril; Vernex-Loset, Lionel; Krier, Gabriel; De Lanève, Michel; Guillot, Xavier; Pierre, Christian; Muller, Jean François

2011-03-15

Enhancing the flowing properties of fresh concrete is a crucial step for cement based materials users. This is done by adding polymeric admixtures. Such additives have enabled to improve final mechanicals properties and the development of new materials like high performance or self compacting concrete. Like this, the superplasticizers are used in almost cement based materials, in particular for concrete structures that can have a potential interaction with drinking water. It is then essential to have suitable detection techniques to assess whether these organic compounds are dissolved in water after a leaching process or not. The main constituent of the last generation superplasticizer is a PolyCarboxylate-Ester copolymer (PCE), in addition this organic admixture contains polyethylene oxide (free PEO) which constitutes a synthesis residue. Numerous analytical methods are available to characterize superplasticizer content. Although these techniques work well, they do not bring suitable detection threshold to analyze superplasticizer traces in solution with high mineral content such as leachates of hardened cement based materials formulated with superplasticizers. Moreover those techniques do not enable to distinguish free PEO from PCE in the superplasticizer. Here we discuss two highly sensitive analytical methods based on mass spectrometry suitable to perform a rapid detection of superplasticizer compounds traces in CEM I cement paste leachates: MALDI-TOF mass spectrometry, is used to determine the free PEO content in the leachate. However, industrial copolymers (such as PCE) are characterized by high molecular weight and polymolecular index. These two parameters lead to limitation concerning analysis of copolymers by MALDI-TOFMS. In this study, we demonstrate how pyrolysis and a Thermally assisted Hydrolysis/Methylation coupled with a triple-quadrupole mass spectrometer, provides good results for the detection of PCE copolymer traces in CEM I cement paste leachates. Copyright © 2011 Elsevier B.V. All rights reserved.

Morphological characterization of microspheres, films and implants prepared from poly(lactide-co-glycolide) and ABA triblock copolymers: is the erosion controlled by degradation, swelling or diffusion?

PubMed

Witt, C; Kissel, T

2001-05-01

Erosion of biodegradable parenteral delivery systems (PDS) based on ABA copolymers consisting of poly(L-lactide-co-glycolide) (PLGA) A-blocks attached to polyethylene oxide (PEO) B-blocks, or PLGA is important for the release of macromolecular drugs. The degradation behavior of four types of PDS, namely extruded rods, tablets, films and microspheres, was studied with respect to molecular weight, mass, polymer composition and shape and microstructure of the PDS. For each device the onset time of bulk erosion (t(on)) and the apparent rate of mass loss (k(app)) were calculated. In the case of PLGA, the t(on) was 16.2 days for microspheres, 19.2 days for films and 30.1 days for cylindrical implants and tablets. The k(app) was 0.04 days(-1) for microspheres, 0.09 days(-1) for films, 0.11 days(-1) for implants and 0.10 days(-1) for tablets. The degradation rates were in the same range irrespective of the geometry and the micrographs of eroding PDS demonstrated pore formation; therefore, a complex pore diffusion mechanism seems to control the erosion of PLGA devices. In contrast, PDS based on ABA copolymers showed swelling, followed by a parallel process of molecular weight degradation and polymer erosion, independent of the geometry. The contact angles of ABA films increased either with decreasing PEO content or with increasing chain length of the PEO B-blocks. In summary, the insertion of a hydrophilic B-block leads to an erosion controlled by degradation of ABA copolymers, whereas for PLGA a complex pore diffusion of degradation products controls the rate of bulk erosion.

Synthesis and characterization of PEO-PCL-PEO triblock copolymers: effects of the PCL chain length on the physical property of W(1)/O/W(2) multiple emulsions.

PubMed

Cho, Heui Kyoung; Cho, Kwang Soo; Cho, Jin Hun; Choi, Sung Wook; Kim, Jung Hyun; Cheong, In Woo

2008-08-01

A series of poly(ethylene glycol)-block-poly(epsilon-caprolactone)-block-poly(ethylene glycol) (PEO-PCL-PEO) triblock copolymers were prepared and then used for the investigation of the effects of the ratio of epsilon-caprolactone to poly(ethylene glycol) (i.e., [CL]/[EO]) on the physical properties of water-in-oil-in-water (W(1)/O/W(2)) multiple emulsions containing a model reagent, ascorbic acid-2-glucoside (AA2G). In the synthesis, the [CL]/[EO] was varied from 0.11 to 0.31. The molecular weights and compositions of PEO-PCL-PEO were determined by GPC and (1)H NMR analyses. Thermal behavior and crystal formation were studied by DSC, XRD, FT-IR, and polarized optical microscopy (POM). Aggregate behavior of PEO-PCL-PEO was confirmed by DLS, UV, and (1)H NMR. Morphology and relative stiffness of the W(1)/O/W(2) multiple emulsions in the presence of PEO-PCL-PEO were studied by confocal laser scanning microscopy (CLSM) and rheometer. Variation in the [CL]/[EO] significantly affects the crystalline temperature and spherulite morphology of PEO-PCL-PEO. As the [CL]/[EO] increases, the CMCs of PEO-PCL-PEO decreases and the slope of aggregate size reduction against the copolymer concentration becomes steeper except for the lowest [CL]/[EO] value of PEO-PCL-PEO (i.e., P-222). P-222 significantly increases the viscosity of continuous (W(2)) phase, which implies the copolymer would exist in the W(2) phase. On the other hand, the triblock copolymers with relatively high [CL]/[EO] ratios mainly contribute to the size reduction of multiple emulsions and the formation of a firm wall structure. The particle size of the multiple emulsion decreases and the elastic modulus increased as [CL]/[EO] increases, confirmed by microscopic and rheometric analyses.

Mg-containing hydroxyapatite coatings on Ti-6Al-4V alloy for dental materials

NASA Astrophysics Data System (ADS)

Yu, Ji-Min; Choe, Han-Cheol

2018-02-01

In this study, Mg-containing hydroxyapatite coatings on Ti-6A1-4 V alloy for dental materials were researched using various experimental instruments. Plasma electrolytic oxidation (PEO) was performed in electrolytes containing Mg (symbols of specimens: CaP, 5M%, 10M%, and 20M%) at 280 V for 3 min. The electrolyte used for PEO was produced by mixing Ca(CH3COO)2·H2O, C3H7NaCaO6P, and MgCl2·6H2O. The phases and composition of the oxide films were evaluated by X-ray diffraction and field-emission scanning electron microscopy with energy dispersive X-ray spectrometry. The irregularity of the surface, pore size, and number of pores decreased as the Mg concentration increased. The ratio of the areas occupied and not occupied by pores decreased as the Mg concentration increased, with the numbers of both large and small pores decreasing with increasing Mg concentration. The number of particles on the internal surfaces of pores was increased as the Mg content increased. Mg content of all samples containing Mg ions showed higher in the pore outside than that of pore inside, whereas the Ca content was higher inside the pores. The P content of samples with the addition of Mg ions showed higher values inside the pores than outside. The Ca/P and [Mg + Ca]/P molar ratios in the PEO films decreased with Mg content. The crystallite size of anatase was increased with increasing Mg concentration in the solution.

Noninvasive Fluorescence Resonance Energy Transfer Imaging of in vivo Premature Drug Release from Polymeric Nanoparticles

PubMed Central

Zou, Peng; Chen, Hongwei; Paholak, Hayley J.; Sun, Duxin

2013-01-01

Understanding in vivo drug release kinetics is critical for the development of nanoparticle-based delivery systems. In this study, we developed a fluorescence resonance energy transfer (FRET) imaging approach to noninvasively monitor in vitro and in vivo cargo release from polymeric nanoparticles. The FRET donor dye (DiO or DiD) and acceptor dye (DiI or DiR) were individually encapsulated into poly(ethylene oxide)-b-polystyrene (PEO-PS) nanoparticles. When DiO (donor) nanoparticles and DiI (acceptor) nanoparticles were co-incubated with cancer cells for 2 h, increased FRET signals were observed from cell membranes, suggesting rapid release of DiO and DiI to cell membranes. Similarly, increased FRET ratios were detected in nude mice after intravenous co-administration of DiD (donor) nanoparticles and DiR (acceptor) nanoparticles. In contrast, another group of nude mice i.v. administrated with DiD/DiR co-loaded nanoparticles showed decreased FRET ratios. Based on the difference in FRET ratios between the two groups, in vivo DiD/DiR release half-life from PEO-PS nanoparticles was determined to be 9.2 min. In addition, it was observed that the presence of cell membranes facilitated burst release of lipophilic cargos while incorporation of oleic acid-coated iron oxide into PEO-PS nanoparticles slowed the release of DiD/DiR to cell membranes. The developed in vitro and in vivo FRET imaging techniques can be used to screening stable nano-formulations for lipophilic drug delivery. PMID:24033270

Block Copolymer Nanocomposites with High Refractive Index Contrast for One-Step Photonics.

PubMed

Song, Dong-Po; Li, Cheng; Li, Wenhao; Watkins, James J

2016-01-26

Photonic crystals (PhCs) prepared using the self-assembly of block copolymers (BCPs) offer the potential for simple and rapid device fabrication but typically suffer from low refractive index contrast (Δn ≤ 0.1) between the phase-segregated domains. Here, we report the simple fabrication of BCP-based photonic nanocomposites with large differences in refractive index (Δn > 0.27). Zirconium oxide (ZrO2) nanoparticles coated with gallic acid are used to tune the optical constants of the target domains of self-assembled (polynorbornene-graft-poly(tert-butyl acrylate))-block-(polynorbornene-graft-poly(ethylene oxide)) (PtBA-b-PEO) brush block copolymers (BBCPs). Strong hydrogen-bonding interactions between the ligands on ZrO2 and PEO brushes of the BBCPs enable selective incorporation and high loading of up to 70 wt % (42 vol %) of the ZrO2 nanoparticles within the PEO domain, resulting in a significant increase of refractive index from 1.45 to up to 1.70. Consequently, greatly enhanced reflection at approximately 398 nm (increases of ∼250%) was observed for the photonic nanocomposites (domain spacing = 137 nm) relative to that of the unmodified BBCPs, which is consistent with numeric modeling results using transfer matrix methods. This work provides a simple strategy for a wide range tuning of optical constants of BCP domains, thereby enabling the design and creation of high-performance photonic coatings for various applications. The large refractive index contrast enables high reflectivity while simultaneously reducing the coating thickness necessary, compared to pure BCP systems.

Cellulose Nanocrystals vs. Cellulose Nanofibrils: A Comparative study on Their Microstructures and Effects as Polymer Reinforcing Agents

Treesearch

Xuezhu Xu; Fei Liu; Long Jiang; J.Y. Zhu; Darrin Haagenson; Dennis P. Wiesenborn

2013-01-01

Both cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) are nanoscale cellulose fibers that have shown reinforcing effects in polymer nanocomposites. CNCs and CNFs are different in shape, size and composition. This study systematically compared their morphologies, crystalline structure, dispersion properties in polyethylene oxide (PEO) matrix, interactions...

Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Tigelaar, Dean M.; Chapin, Kara; Bennett, William R.

2007-01-01

Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

Tailored Design of Bicontinuous Gyroid Mesoporous Carbon and Nitrogen-Doped Carbon from Poly(ethylene oxide-b-caprolactone) Diblock Copolymers.

PubMed

Chu, Wei-Cheng; Bastakoti, Bishnu Prasad; Kaneti, Yusuf Valentino; Li, Jheng-Guang; Alamri, Hatem R; Alothman, Zeid A; Yamauchi, Yusuke; Kuo, Shiao-Wei

2017-10-04

Highly ordered mesoporous resol-type phenolic resin and the corresponding mesoporous carbon materials were synthesized by using poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) diblock copolymer as a soft template. The self-assembled mesoporous phenolic resin was found to form only in a specific resol concentration range of 40-70 wt % due to an intriguing balance of hydrogen-bonding interactions in the resol/PEO-b-PCL mixtures. Furthermore, morphological transitions of the mesostructures from disordered to gyroid to cylindrical and finally to disordered micelle structure were observed with increasing resol concentration. By calcination under nitrogen atmosphere at 800 °C, the bicontinuous mesostructured gyroid phenolic resin could be converted to mesoporous carbon with large pore size without collapse of the original mesostructure. Furthermore, post-treatment of the mesoporous gyroid phenolic resin with melamine gave rise to N-doped mesoporous carbon with unique electronic properties for realizing high CO 2 adsorption capacity (6.72 mmol g -1 at 0 °C). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning thin-film electrolyte for lithium battery by grafting cyclic carbonate and combed poly(ethylene oxide) on polysiloxane.

PubMed

Li, Jie; Lin, Yue; Yao, Hehua; Yuan, Changfu; Liu, Jin

2014-07-01

A tunable polysiloxane thin-film electrolyte for all-solid-state lithium-ion batteries was developed. The polysiloxane was synthesized by hydrosilylation of polymethylhydrosiloxane with cyclic [(allyloxy)methyl]ethylene ester carbonic acid and vinyl tris(2-methoxyethoxy)silane. (1) H NMR spectroscopy and gel-permeation chromatography demonstrated that the bifunctional groups of the cyclic propylene carbonate (PC) and combed poly(ethylene oxide) (PEO) were well grafted on the polysiloxane. At PC/PEO=6:4, the polysiloxane-based electrolyte had an ionic conductivity of 1.55 × 10(-4) and 1.50 × 10(-3)  S cm(-1) at 25 and 100 °C, respectively. The LiFePO4 /Li batteries fabricated with the thin-film electrolyte presented excellent cycling performance in the temperature range from 25 to 100 °C with an initial discharge capacity at a rate of 1 C of 88.2 and 140 mA h g(-1) at 25 and 100 °C, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design and characterisation of a polyethylene oxide matrix with the potential use as a teat insert for prevention/treatment of bovine mastitis.

PubMed

Bhattarai, Sushila; Alany, Raid G; Bunt, Craig R; Abdelkader, Hamdy; Rathbone, Michael J

2015-01-01

This manuscript reports (for the first time) on antibiotic-free polymeric inserts for the prevention and/or treatment of bovine mastitis. Polyethylene oxide (PEO)-based inserts were prepared using different concentrations of various hydrophilic polymers and water-soluble and water-insoluble drug-release-modifying excipients. A simple and scalable melt-extrusion method was employed to prepare the inserts. The prepared inserts were characterised for their dimension, rheological and mechanical properties. The in vitro release of a model bacteriostatic drug (salicylic acid) from the prepared inserts was studied to demonstrate the effectiveness and reproducibility of the melt-extrusion manufacturing method. Further, the in vitro stability of the inserts was evaluated using gel permeation chromatography (GPC) to monitor any change in molecular weight under real-time and accelerated storage conditions. The investigated inserts were stable at accelerated storage conditions over a period of 6 months. PEO inserts have the potential to serve a dual purpose, act as a physical barrier against pathogens invading the teat canal of cows and possibly control the release of a drug.

Study of the dynamics of poly(ethylene oxide) by combining molecular dynamic simulations and neutron scattering experiments

NASA Astrophysics Data System (ADS)

Brodeck, M.; Alvarez, F.; Arbe, A.; Juranyi, F.; Unruh, T.; Holderer, O.; Colmenero, J.; Richter, D.

2009-03-01

We performed quasielastic neutron scattering experiments and atomistic molecular dynamics simulations on a poly(ethylene oxide) (PEO) homopolymer system above the melting point. The excellent agreement found between both sets of data, together with a successful comparison with literature diffraction results, validates the condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASS) force field used to produce our dynamic runs and gives support to their further analysis. This provided direct information on magnitudes which are not accessible from experiments such as the radial probability distribution functions of specific atoms at different times and their moments. The results of our simulations on the H-motions and different experiments indicate that in the high-temperature range investigated the dynamics is Rouse-like for Q-values below ≈0.6 Å-1. We then addressed the single chain dynamic structure factor with the simulations. A mode analysis, not possible directly experimentally, reveals the limits of applicability of the Rouse model to PEO. We discuss the possible origins for the observed deviations.

Study of the dynamics of poly(ethylene oxide) by combining molecular dynamic simulations and neutron scattering experiments.

PubMed

Brodeck, M; Alvarez, F; Arbe, A; Juranyi, F; Unruh, T; Holderer, O; Colmenero, J; Richter, D

2009-03-07

We performed quasielastic neutron scattering experiments and atomistic molecular dynamics simulations on a poly(ethylene oxide) (PEO) homopolymer system above the melting point. The excellent agreement found between both sets of data, together with a successful comparison with literature diffraction results, validates the condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASS) force field used to produce our dynamic runs and gives support to their further analysis. This provided direct information on magnitudes which are not accessible from experiments such as the radial probability distribution functions of specific atoms at different times and their moments. The results of our simulations on the H-motions and different experiments indicate that in the high-temperature range investigated the dynamics is Rouse-like for Q-values below approximately 0.6 A(-1). We then addressed the single chain dynamic structure factor with the simulations. A mode analysis, not possible directly experimentally, reveals the limits of applicability of the Rouse model to PEO. We discuss the possible origins for the observed deviations.